Chemical Management in Textiles and Fashion (The Textile Institute Book Series) [1 ed.] 012820494X, 9780128204948

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Chemical Management in Textiles and Fashion

The Textile Institute Book Series Incorporated by Royal Charter in 1925, The Textile Institute was established as the professional body for the textile industry to provide support to businesses, practitioners, and academics involved with textiles and to provide routes to professional qualifications through which Institute Members can demonstrate their professional competence. The Institute’s aim is to encourage learning, recognize achievement, reward excellence, and disseminate information about the textiles, clothing and footwear industries and the associated science, design and technology; it has a global reach with individual and corporate members in over 80 countries. The Textile Institute Book Series supersedes the former “Woodhead Publishing Series in Textiles” and represents a collaboration between The Textile Institute and Elsevier aimed at ensuring that Institute Members and the textile industry continue to have access to high caliber titles on textile science and technology. Books published in The Textile Institute Book Series are offered on the Elsevier website at: store. elsevier.com and are available to Textile Institute Members at a substantial discount. Textile Institute books still in print are also available directly from the Institute’s website at: www.textileinstitute.org To place an order, or if you are interested in writing a book for this series, please contact Matthew Deans, Senior Publisher: [email protected] Recently Published and Upcoming Titles in the Textile Institute Book Series: Handbook of Natural Fibres: Volume 1: Types, Properties and Factors Affecting Breeding and Cultivation, 2nd Edition, Ryszard Kozlowski Maria Mackiewicz-Talarczyk, 978-0-12-818398-4 Handbook of Natural Fibres: Volume 2: Processing and Applications, 2nd Edition, Ryszard Kozlowski Maria Mackiewicz-Talarczyk, 978-0-12-818782-1 Advances in Textile Biotechnology, Artur Cavaco-Paulo, 978-0-08-102632-8 Woven Textiles: Principles, Technologies and Applications, 2nd Edition, Kim Gandhi, 978-0-08-102497-3 Auxetic Textiles, Hong Hu, 978-0-08-102211-5 Carbon Nanotube Fibres and Yarns: Production, Properties and Applications in Smart Textiles, Menghe Miao, 978-0-08-102722-6 Sustainable Technologies for Fashion and Textiles, Rajkishore Nayak, 978-0-08-102867-4 Structure and Mechanics of Textile Fibre Assemblies, Peter Schwartz, 978-0-08-102619-9 Silk: Materials, Processes, and Applications, Narendra Reddy, 978-0-12-818495-0 Anthropometry, Apparel Sizing and Design, 2nd Edition, Norsaadah Zakaria, 978-0-08-102604-5 Engineering Textiles: Integrating the Design and Manufacture of Textile Products, 2nd Edition, Yehia Elmogahzy, 978-0-08-102488-1 New Trends in Natural Dyes for Textiles, Padma Vankar Dhara Shukla, 978-0-08-102686-1 Smart Textile Coatings and Laminates, 2nd Edition, William C. Smith, 978-0-08-102428-7 Advanced Textiles for Wound Care, 2nd Edition, S. Rajendran, 978-0-08-102192-7 Manikins for Textile Evaluation, Rajkishore Nayak Rajiv Padhye, 978-0-08-100909-3 Automation in Garment Manufacturing, Rajkishore Nayak and Rajiv Padhye, 978-0-08-101211-6 Sustainable Fibres and Textiles, Subramanian Senthilkannan Muthu, 978-0-08-102041-8 Sustainability in Denim, Subramanian Senthilkannan Muthu, 978-0-08-102043-2 Circular Economy in Textiles and Apparel, Subramanian Senthilkannan Muthu, 978-0-08-102630-4 Nanofinishing of Textile Materials, Majid Montazer Tina Harifi, 978-0-08-101214-7 Nanotechnology in Textiles, Rajesh Mishra Jiri Militky, 978-0-08-102609-0 Inorganic and Composite Fibers, Boris Mahltig Yordan Kyosev, 978-0-08-102228-3 Smart Textiles for In Situ Monitoring of Composites, Vladan Koncar, 978-0-08-102308-2 Handbook of Properties of Textile and Technical Fibres, 2nd Edition, A. R. Bunsell, 978-0-08-101272-7 Silk, 2nd Edition, K. Murugesh Babu, 978-0-08-102540-6

Chemical Management in Textiles and Fashion Edited by

Dr. Subramanian Senthilkannan Muthu Director & Head of Sustainability, SgT, API & Qualspec, Hong Kong

Woodhead Publishing is an imprint of Elsevier The Officers’ Mess Business Centre, Royston Road, Duxford, CB22 4QH, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States The Boulevard, Langford Lane, Kidlington, OX5 1GB, United Kingdom Copyright © 2021 Elsevier Ltd. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 978-0-12-820494-8 (print) ISBN: 978-0-12-820497-9 (online) For information on all Woodhead Publishing publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Matthew Deans Acquisitions Editor: Brian Guerin Editorial Project Manager: Emma Hayes Production Project Manager: Anitha Sivaraj Cover Designer: Mark Rogers Typeset by MPS Limited, Chennai, India

Contents

List of Contributors

ix

1

1

2

3

Chemical management system in textiles C. Jo¨nsson, S. Roos and J. Hildenbrand 1.1 Introduction 1.2 Chemical management system 1.3 Restricted substance list and manufacturing restricted substance list 1.4 Regulation and labeling schemes 1.5 Practical feasibilities and challenges 1.6 Knowledge and awareness 1.7 Available tools 1.8 Implementation of a chemical management system in textile supply chains: example of a tool development 1.9 Tool development 1.10 Conclusion 1.11 Future trends 1.12 Recommendations for further studies References Chemical hazards in textiles Parthiban Manickam and Deepthi Vijay 2.1 Introduction 2.2 Hazardous chemicals 2.3 Routes of exposure 2.4 Human toxicity 2.5 Impact of restricted substance list in chemical management 2.6 Regulatory aspects 2.7 Hazard control through regulatory norms 2.8 Hazard control and management 2.9 Conclusion References Chemical risk assessment in textile and fashion Subhankar Maity, Kunal Singha and Pintu Pandit 3.1 Introduction 3.2 Chemical risk analysis

1 3 3 4 5 5 7 8 9 14 15 16 16 19 19 19 26 35 37 39 41 42 50 50 53 53 55

vi

Contents

3.3

Chemical substances in textiles and garments and their release and exposure 3.4 Release of toxic chemicals from textiles 3.5 Hazardous chemical in textile products 3.6 Method of assessment of potential risk of hazardous textile chemicals 3.7 Conclusion References 4

5

Challenges in dyeing of cellulosics with reactive dyes and practical sustainable feasibilities A.S.M. Raja, A. Arputharaj, G. Krishnaprasad, Sujata Saxena and P.G. Patil 4.1 Introduction 4.2 Cellulosic fibers 4.3 Cellulosic fiber consumption 4.4 Chemistry of cellulose 4.5 Chemical processing of cellulosic fibers 4.6 History of reactive dyes 4.7 Common structure of reactive dyes 4.8 Classification of reactive dyes 4.9 Mechanism of reactive dyeing of cellulosics 4.10 Factors affecting reactive dyeing of cellulosics 4.11 Application techniques of reactive dyes to cellulosic fibers 4.12 Ecological aspects of reactive dyeing 4.13 Ecological problem due to chemicals, auxiliaries, and water 4.14 Current technologies for improvement 4.15 Unconventional reactive dyeing (ultrasound, microwave, foam, plasma, supercritical) 4.16 Conclusion References Essentials of chemical management system for textiles Nishita Ivy 5.1 Introduction 5.2 Chemical management system 5.3 Essential elements of the chemical management system 5.4 The implementation process of Chemical Management System in textiles 5.5 Tackling challenges on Chemical Management System in textiles 5.6 Conclusion and recommendation References

58 60 65 71 73 74

79

79 80 80 82 83 84 84 85 85 86 88 89 91 92 93 95 96 99 99 99 100 109 110 111 111

Contents

6

7

Hazardous, restricted, and manufacturing restricted substances in textiles and clothing supply chain M. Gobalakrishnan, Subrata Das and D. Saravanan 6.1 Introduction 6.2 Restricted substances 6.3 Importance of restricted substances list (RSL) 6.4 Criteria for a substance to be included in a restricted substances list 6.5 Purpose of brand restricted substances list 6.6 Scope of brand restricted substances lists 6.7 Contents of a restricted substances list document (MBDC, 2012; Rev, 2014) 6.8 Basic terms in restricted substances list document (Das, 2015) 6.9 Major risk areas for restricted substances 6.10 Restricted substances list for Calvin Klein 6.11 Introduction to manufacturing restricted substances list (MRSL) 6.12 Difference between manufacturing restricted substances list (MRSL) and restricted substances list (RSL) 6.13 Scope of a manufacturing restricted substances list 6.14 Implementation of a manufacturing restricted substances list in a facility (ZHDC Group, 2015) 6.15 Role of MRSL to ensure RSL compliance of a finished product 6.16 Restricted chemical groups mentioned in brand RSL and MRSL documents 6.17 Important terms and definitions used in a typical MRSL document (ZHDC Group, 2015; ZDHC, 2015) 6.18 Structure of a manufacturing restricted substances list document 6.19 Global legislations on harmful chemicals in textiles 6.20 Practical challenges in managing RSL and MRSL in a textile mill 6.21 Conclusion References Chemical compliance and regulations in textiles and fashion G. Prasannamedha and P. Senthilkumar 7.1 Introduction to chemical compliance in textile industry 7.2 Overview of chemicals used in textile industry 7.3 Identification of hazardous chemicals in textiles 7.4 Categorization of hazardous chemicals 7.5 Need for chemical compliance in textile sector 7.6 Compliance requirements

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113 113 114 114 114 115 115 115 116 117 120 124 125 125 125 126 126 126 127 129 132 132 132 135 135 136 137 138 138 142

viii

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Contents

7.7 Life cycle of chemicals used in textile and fashion industries 7.8 Regulations promoted for hazardous chemicals 7.9 Compliance monitoring 7.10 Consumer Product Safety Law 7.11 Chemical regulations in India 7.12 Conclusion 7.13 Future scope and needs References

145 145 150 151 151 152 153 153

Life cycle assessment and textile chemicals S. Roos and C. Jo¨nsson 8.1 Introduction 8.2 Life cycle assessment in textile chemicals 8.3 Challenges in life cycle assessment studies of textile chemicals 8.4 Case studies 8.5 Conclusion 8.6 Future trends 8.7 Recommendations for further study References

155

Green chemistry in textile and fashion Pintu Pandit, Kunal Singha and Subhankar Maity 9.1 Introduction 9.2 Application of natural dyeing in textile and fashion 9.3 Application of green flame retardants in textile and fashion 9.4 Application of antibacterial finishes in textile and fashion 9.5 Green chemistry approach for ultraviolet protection in textile and fashion 9.6 Aroma finishing of textile and fashion 9.7 Mosquito repellency finish for textile and fashion 9.8 Applications of graphene in textile 9.9 Application of plasma technology in textile and fashion 9.10 Application of green reducing agent for synthesis of nanoparticles 9.11 Green synthesis of nanofibers and nanoparticles for textile finishing 9.12 Future and challenges of green chemistry in textile and fashion 9.13 Conclusion References

177

Index

155 158 160 164 169 170 171 171

177 180 182 183 184 185 186 187 189 192 193 195 197 198 205

List of Contributors

A. Arputharaj ICAR Mumbai, India

Central Institute for Research on Cotton Technology,

Subrata Das Department of Fashion Technology, Bannari Amman Institute of Technology, Sathyamangalam, India M. Gobalakrishnan Department of Textile Technology, Bannari Amman Institute of Technology, Sathyamangalam, India J. Hildenbrand RISE IVF AB, Materials and Production Division, Mo¨lndal, Sweden Nishita Ivy PhD Student, Nalanda University, Rajgir, Bihar, India C. Jo¨nsson RISE IVF AB, Materials and Production Division, Mo¨lndal, Sweden G. Krishnaprasad ICAR Mumbai, India

Central Institute for Research on Cotton Technology,

Subhankar Maity Department of Textile Technology, Uttar Pradesh Textile Technology Institute, Kanpur, India Parthiban Manickam Department of Fashion Technology, PSG College of Technology, Coimbatore, India Pintu Pandit Department of Textile Design, National Institute of Fashion Technology, Ministry of Textiles, Government of India, Patna, India P.G. Patil ICAR India

Central Institute for Research on Cotton Technology, Mumbai,

G. Prasannamedha Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Kalavakkam, India A.S.M. Raja ICAR Mumbai, India

Central Institute for Research on Cotton Technology,

x

List of Contributors

S. Roos RISE IVF AB, Materials and Production Division, Mo¨lndal, Sweden D. Saravanan Department of Textile Technology, Kumaraguru College of Technology, Coimbatore, India Sujata Saxena ICAR Mumbai, India

Central Institute for Research on Cotton Technology,

P. Senthilkumar Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Kalavakkam, India Kunal Singha Department of Textile Design, National Institute of Fashion Technology, Ministry of Textiles, Government of India, Patna, India Deepthi Vijay Department of Fashion Technology, PSG College of Technology, Coimbatore, India

Chemical management system in textiles

1

C. Jo¨nsson, S. Roos and J. Hildenbrand RISE IVF AB, Materials and Production Division, Mo¨lndal, Sweden

1.1

Introduction

The textile value chain is long and complex, containing many different process steps, where wet treatment and finishing dominate the chemical use. Fig. 1.1 presents the process steps along the textile supply chain and the different chemicals that are handled in each of them. The textile materials are sourced according to the specification of the final customer. During yarn spinning, fabric manufacturing (knitting, warping, and weaving), and garment making low amounts of chemicals are added in the process. Some of them are intended to become part of the product, whereas others are auxiliaries and are removed afterward, not always without leaving remnants in or on the fabric. Raw material production, fiber production, wet treatment, and finishing are process steps where both high amounts and a large variety of chemicals are used. The chemicals are in their turn sourced either from a formulator at a local market or via global suppliers. The production of garments uses roughly between 1 and 4 kg of chemicals per kg garment (Olsson et al., 2009). New innovative wet treatments such as supercritical carbon dioxide and dope dye technology drastically decrease the chemical usage (Johannesson, 2016). The actual amount is dependent both on garment type and supply chain performance, such as process conditions. Chemicals in this context include for instance detergents, salts, emulsifiers, pigments/colorants, finishing agents, and solvents. In the manufacturing of textiles, a variety of chemicals are used, often in large amounts (Olsson et al., 2009). Some textile-related chemicals are harmful to health and/or the environment, with properties such as sensitizing, human toxic, ecotoxic, persistent, or bio-accumulative (Swedish Chemicals Agency, 2014) (see Fig. 1.2). Textile-relevant hazardous chemicals are currently considered under European Union (EU) law such as Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) (European Commission, 2006), persistent organic pollutants (POP) (European Commission, 2019), and biocidal products regulation (European Commission, 2012), which require from market participants provision of information that in turn can be used by customers to evaluate the chemical content of articles. Some of these legislations have corresponding regulations in North America (Canadian Environmental Protection Act in Canada; CEPA, 1999), toxic substances control act in the United States (US EPA, 1976), and other regions). In theory, Chemical Management in Textiles and Fashion. DOI: https://doi.org/10.1016/B978-0-12-820494-8.00001-0 © 2021 Elsevier Ltd. All rights reserved.

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Figure 1.1 Chemicals use and possible issues in the textile supply chain. Source: Illustration from Roos, S., Jo¨nsson, C., Posner, S., 2017a. Labelling of chemicals in textiles Nordic Textile Initiative. Nordic Working Paper. NA2017:915. Copenhagen. doi: 10.6027/NA2017-915.

Figure 1.2 Illustration of chemical substances in society. A small share of all substances is classified as hazardous and of these, a small fraction is restricted in some way. Textilerelevant substances can be found both among nonclassified, classified, and restricted substances. Note that the proportions of the figure are not to scale. Source: © RISE IVF AB and Stefan Posner.

Chemical management system in textiles

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important chemical information would be possible to retrieve where market participants follow their compliance obligations. Textile supply chains are at the same time among the longest and most complicated in manufacturing industry, with many actors responsible for different substeps (Kogg, 2009). Quite often, part of the production may be executed by subcontractors without the final customer’s knowledge. The industry’s task to obtain specific chemical information about hazardous chemicals used and emitted in practice is challenging due to the length and complexity of the supply chain (Bo¨rjeson et al., 2015).

1.2

Chemical management system

In order to comply with existing legislation and to fulfill customer demands, a chemical management system (CMS) is utilized by all textile actors on the market. Current CMS are designed and intended to handle the obstacles described above that occur due to the complexity of the supply chain. Textile brands and companies use a variety of tools and routines to manage potential risks of chemical use in their supply chain (Fransson and Molander, 2013). These elements are in short: business agreements (business to business contracts), restricted substance list (RSL), audits at plant or mill, routines for material testing, and dialog and collaborations to enable mutual understanding of risks with handling chemicals both for the environment but also for workers and users. Information regarding chemicals are communicated via trade names, chemicals company names, unique chemical identification number (chemical abstracts service registration numbers (CAS RN); American Chemical Society, 2016), and color index (SDC and AATCC, 2016). Information may be shared via dialog, email, excel sheets, business systems, contracts, and transaction receipts.

1.3

Restricted substance list and manufacturing restricted substance list

Many companies rely on contracts and RSL as their core tool in the chemical management system. The RSL normally consists of chemical names as well as CAS numbers of the specific substances. In some cases, the lists also give guidance to where the chemicals may be found in the production or provide information on the function (Swedish Chemicals Group/Swedish Textile Importer’s Association, 2016). Substances included in such lists mainly consist of restricted substances, often but not always related to the textile materials. Some front runners occasionally and additionally include substances in their RSLs that may be, but not yet are, regulated, together with already regulated. Such RSLs in the textile area include regularly substances of very high concern (SVHC) and skin sensitizers (allergenic). To our knowledge, no companies use RSLs that only include requirements based on hazard properties, for example, a restriction of all carcinogenic substances without

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specifying CAS numbers. This practice is logical since the companies need requirements that are possible to follow up and legal classification can vary between countries for a specific substance even though the harmonized classification system is used (United Nations, 2011). More specifically, it is challenging in audit and dialog situations upstream when the requirements are only based on classification and hazard properties according to classification, packaging and labelling directive (European Commission, 2008). Chemical products used in the manufacturing process are added according to analog or digitized recipes. Chemical used in formulations and as additives may influence humans and the surrounding environment during the production phase as emissions to air and water within the mill or from the mill to the surrounding environment. Chemical products that are intended to be providing functions may also be present at sufficiently high quantities in the final product to be emitted during use or during the end-of-life phase. If formulations, additives or other chemical products or materials of concern have been identified, it would be a proactive approach to substitute them. In a manufacturing RSL, risk materials and chemical products can be restricted and thus excluded altogether. Thereby a certain risk chemical may be managed. This however implies good knowledge on materials and chemical formulations.

1.4

Regulation and labeling schemes

The awareness of problematic substances in textile production is rising among Western consumers, companies, and authorities, for instance resulting in regulation in the European chemicals legislation REACH (European Commission, 2006) and under the UNEP POPs convention (UN Environment, 2017). Hazardous textilerelevant chemicals of transnational concern are specified in labeling and/or declaration schemes (ZDHC, 2014; Nordic Ecolabelling, 2016; BLUESIGNs, 2017; OEKO-TEXs Association, 2017). Addition to such schemes is an ongoing process, and not all chemicals with hazardous potential are already identified and evaluated. Such schemes, though they are not complete and updated over time, support industry to enhance and improve this critical communication and possibly result in the phase-out of hazardous chemicals and introduction of less hazardous alternatives where technically feasible and economically viable (Stro¨mbom et al., 2015). Use of a trademark label such as OEKO-TEX (OEKO-TEXs Association, 2017) assures the consumer that the textile product contains hazardous chemicals only in low concentrations under the limits that are transparently communicated and independently tested in certified laboratories. The “detox catwalk” campaign by Greenpeace (Choi et al., 2011; Brigden et al., 2012), targets specific hazardous chemicals, which they call priority chemicals and which are found in high-street fashion sold in developed countries. The campaign names brands that comply with detox commitments and uses a “name and shame” approach; brands that fail to make any detox commitment or are seen as “green-washers” and do not fulfill their commitments are listed on the campaign website. Note that the campaign is not solely focused on hazardous chemicals, but also evaluates transparency and CSR aspects.

Chemical management system in textiles

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5

Practical feasibilities and challenges

Traditional tools and routines that are used within a homogenous organization are challenging to implement in complex supply chains leading to deficiency in the chemical management. More specifically, the challenges comprise organizational issues, linguistic obstacles, and lack of knowledge. These challenges relate to the fact that textile production is global and participants do not always understand each other’s language and do not even have a “lingua franca,” as the proficiency in English is limited. The level of education and training differs from country to country, which is why information of different kinds may be difficult to assimilate, and actions, routines, and toolsets to react to information are not established. Cultural differences including religion and attitudes also add to the lack of common understandings and point of view. The lack of knowledge in the supply chain is especially problematic since upstream actors that are handling chemicals (textile manufacturers and their suppliers) are not necessarily trained in chemistry and chemicals management (Munn, 2011; Roos, 2016). Since the supply chain is long, complex, and global, it is difficult for European brands importing textiles from mainly Asian countries to know exactly which substances are present in a ready-made textile product (Roos, 2015). The information exchange in the textile value chain is illustrated in a simplified manner in Fig. 1.3, starting from chemical suppliers, raw material producers down to the retailer. Information along this chain will be transferred between actors in two directions as indicated by red arrows. However, with the obstacles stated above, important chemical information is easily lost, inhibiting comprehensive information exchange. It shall also be emphasized that the chain is divided upstream into two streams; one that may have direct contact with the textile company, namely the raw material producer, and one stream that owns the chemical information but does not necessarily have contact with the final business to business customer (as can be seen in the illustration in Fig. 1.3). Furthermore, European downstream actors (i.e., brands and retailers) need information about restricted or unwanted chemicals in order to comply with legislation, but they often lack sufficient information on which chemicals are actually being used in the production countries. These chemicals may include substances that are restricted in the EU, but may be allowed in the location of upstream suppliers. An agency report by the Swedish Chemicals Agency estimated based on registration data that 3500 different chemicals can be used in textiles, and approximately 10% of them might be particularly hazardous (Swedish Chemicals Agency, 2016).

1.6

Knowledge and awareness

A study by Subic et al. (2012) examines the sustainability knowledge and capability among first and second-tier suppliers of sports apparel and footwear. The study

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Chemical Management in Textiles and Fashion

Figure 1.3 Simplified illustration of the textile value chain and the information exchange routes between actors. Source: Illustration from Roos, S., Jo¨nsson, C., Posner, S., 2017a. Labelling of chemicals in textiles Nordic Textile Initiative. Nordic Working Paper. NA2017:915. Copenhagen. doi: 10.6027/NA2017-915.

shows that there are several knowledge gaps that can be classified in two groups, namely insufficient capability to identify which processes are resource and/or emission-intensive and why that is the case and insufficient capability of selecting the most sustainable option based on the economic, environmental, and social criteria. Different knowledge levels regarding sustainability issues are commonly established among different actors in the supply chain. A possible explanation can be found in the approaches to technical change within different industries. Pavitt (1984) suggests a taxonomy, in which chemical industry is described as “sciencebased,” with a high potential and demand to constantly innovate, whereas in textile industry innovations are supplier-dominated and are introduced from outside of the company. Supplier dominated companies are characterized as small and with weak in-house R&D and engineering capabilities. This distinction aims to explain observed differences for innovation, but we suggest applying it also to understand the need for comprehensive and applicable information and education for actors from textile industry who are less used to technical innovation. Moreover, as chemical industry and textile industry fall into the two most opposite categories of sectors, interaction between stakeholders from those two sectors can be hampered. As an effect observed in practice, textile companies rely on chemical suppliers for choice of products and application recipes (Fransson, 2012), and in turn chemical

Chemical management system in textiles

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suppliers might not always correctly identify the specific needs of textile companies and suggest generic solutions that are not resource-efficient. Apart from specialists, a range of roles in an apparel brand’s organization will typically come in contact with issues related to chemical, water, and energy use. For instance, product developers may be interested in making low-impact design choices, buyers may be tasked with collecting resource usage and output information from suppliers and subsuppliers, and communicators may need to proactively and/or reactively describe how the brand is dealing with chemical, water, and energy risks. Likewise, these roles will often be confronted with issues and questions related to an even broader spectrum of environmental issues, including safeguard objects such as biodiversity, specific air emissions, and greenhouse gases that contribute to climate change. In parallel, social risks are recognized for textile production including child labor, forced labor, and occupational risks for workers. Thus enlightened apparel organizations need effective access to educational material covering a wide and evolving range of sustainability topics. Given these preconditions, it is obvious that communication and information exchange along the supply chain is important in order to minimize the exposure of factory workers, local environment, as well as final consumers to hazardous chemicals. However, this type of communication is still very difficult in practice due to organizational issues and other obstacles, such as language (Roos et al., 2017b). But a basic requirement is the need to raise the level of knowledge and awareness. This emphasizes the demand for user-friendly learning tools, which can be used by individuals with different background knowledge on chemicals and chemicals management. New types of tools are needed in order to spread knowledge along the whole textile supply chain and facilitate substitution of hazardous chemicals in production processes in practice. In this paper we investigate the possibilities for learning tools to increase the knowledge level and consider chemicals in all tiers of the textile supply chain.

1.7

Available tools

A variety of tools for chemicals management in textile products exists today, that are different in purpose and aimed for different users. Tools can generally be divided after the purpose of the tool, which can be to enlighten, spur, steer, or control the user (Renstro¨m et al., 2013). Chemicals management tools in the textile supply chain can further be divided according to the expertise in chemistry required from their intended users—from chemical experts, process engineers to procurers and even consumers. Chemicals management tools can be classified according to the type of information content: 1. Management routine tools that address the administrative routines around the chemical’s management; 2. RSLs type tools that compile lists of substances that are declarable or prohibited, either in the product or at the manufacturing sites; or

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Chemical Management in Textiles and Fashion

3. Chemical substance information tools that inform about properties and available alternatives for specific chemicals.

Several management routines tools (Type I tools) addressing the administrative routine around chemicals in textile products are in use in the textile industry. They can be linked to organizations and initiatives that also certify that companies apply the tools as intended. One important recent initiative is the Outdoor Industry Association and the Sustainable Apparel Coalition (SAC) who developed the Chemicals Management Module (Outdoor Industry Association, 2014) which was integrated into SAC’s Higg Index FEM 3.0 (SAC, 2019). Another leading initiative, combining Type I and Type II is the AFIRM Supplier Toolkit (AFIRM, 2015). The second type of tool, based on RSLs (Type II), is the historically most dominant type of tool used in the textile industry. OEKO-TEX, a label ensuring the consumer that substances hazardous for health are not present in a product above a specified limit, is today the largest textile trademark with environmental focus on the market (OEKO-TEXs Association, 2017). In the outdoor industry, the use of BlueSign (2017) is widely spread, building on the philosophy of restricting the input chemicals to the textile production processes. Also, the Roadmap to Zero Discharge of Hazardous Compounds (ZDHC) (2014) that emerged as a response to the “Toxic threads” campaign from Greenpeace in 2012 (Brigden et al., 2012) and the American Apparel & Footwear Association RSL (AAFA, 2015) are other widely used Type II tools. Several Type III management tools addressing specific chemicals are available through the Substitution and Alternatives Assessment Toolbox (SAAT), which is promoted by OECD (2015) as a collection of existing online resources and tools. A tools selector helps potential users identify suitable tools for different levels of expertise, some of which are available free of charge whereas others require a fee. One tool that previously featured on this list with clear connection to the textile industry is the ChemicAll database, which was developed by the Swedish Chemicals Group at RISE, where a majority of the Swedish textile companies are members (RISE, 2018). While several of the Type I and Type II tools address and encourage collaborative work in the supply chain, the Type III tools, informing about properties and available alternatives for specific chemicals, do seldom take this approach. How widespread the use in the textile industry might be the most important indicator for a tool, giving a hint of the usefulness in practice.

1.8

Implementation of a chemical management system in textile supply chains: example of a tool development

To overcome challenges related to managing a priority substance, a tool was developed supporting the exchange of important chemical information between actors in

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9

the project Forward Learning (Swerea et al., 2015). The tool focuses on creating a basis for common understanding and enhancing competence. For the design of the tool, several aspects were considered from observations in practice, such as a lack of knowledge regarding who is the contact person and what is their level of knowledge and awareness; a lack of expert knowledge between communicators; weak precision regarding textile relevance of chemicals included in RSLs; or a general refusal to share and exchange critical chemicals information, which may be considered confidential. Often presence of hazardous regulated and/or unwanted chemicals may also lead to negative publicity for the producer and is thus seen as reputational risk, for instance, if it is included in a campaign such as “detox catwalk” (Brigden et al., 2012). To overcome the lack of knowledge, an interactive, web-based learning tool was created, which is combining learning activities, assessment of achievements and knowledge status, and support of networking. The tool uses elements of gamification to keep the interest and was cocreated by academia, education companies, and textile brands. An underlying study highlighted in particular the challenge that compliancebased activities in the supply chain often emphasize solely the motives and problems of the final part of the chain (the retailer or brand). Any activities that guarantee producing a product compliant with legal or customer demand are generally accepted. Beyond that, best-practice, efficient, and eco-innovative processes should be preferred, however, such development is not supported or specifically encouraged. A strong focus on properties of the final product and the retailer or brand perspective to some extent puts a lid on the potential of education to foster knowledge transfer in the supply chain, innovation, efficiency, and competitive insight. As illustrated above chemical substances used for textile production processes can lead to environmental and health problems, both for workers in factories who potentially use them in high concentrations as well as for final consumers who are in direct contact with a treated product for long periods of time. One example of a class of chemical substances with textile relevance and known adverse effects on the environment and human health is nonylphenol ethoxylates (NPEO). In the environment, NPEO is a precursor for nonylphenols, which are endocrine-disrupting chemicals, meaning they interfere with the hormonal system and are linked to feminization and disruption of the development of male offspring in fish. Nonylphenols also have a direct ecotoxic potential (ECHA, 2013). NPEO is a surfactant and can be used in several textile processing steps, for instance as detergent in finishing processes. NPEO was used as an example substance to develop the learning tool related to chemical management and will be used in the remainder of this text as an illustrative example.

1.9

Tool development

The main goal for the construction of a learning tool was to provide knowledge about chemicals, chemicals management, and specifically a substitution process

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Chemical Management in Textiles and Fashion

enabling phase-out actions of prioritized hazardous chemicals. Because the use of NPEO is widespread, the substitution is potentially required in several stages in the supply chain and involves different actors; thus the tool should be available for the whole textile supply chain. A rough outline of a substitution process is illustrated in Fig. 1.4, where the first step represents identification of a need to substitute. The need for chemical substitution cannot be related to external drivers such as legislation or customer demands, but also to company internal decisions to regulate beyond legislation when environmental and health impact due to emissions or workplace human exposure is suspected. At the start of a substitution process, it is not always known whether, where and how the chemicals in question are used, and which is why a background mapping is needed as an initial step. Because of the well-established legislation in the European Union, for instance, REACH, the substitution need is often identified and driven by brands in Europe. The actual substitution needs, however, to be executed in producing countries, which are often located in Southeast Asia. Thus the substitution usually needs to involve different supply chain actors for implementation in practice. When the specific function and an unambiguous identifier of a chemical (i.e., CAS number) are established, the identification of suitable alternatives with comparable functionality can be initiated. When proper alternatives are identified, information related to health and environmental impacts as well as legal status needs to be collected and assessed to avoid a regrettable substitution with an alternative that has itself negative properties. Together with relevant actors, technical performance needs to be evaluated. The last step is to replace the chemical with feasible alternatives, according to the model for chemical substitution proposed by Jo¨nsson et al. (2018). To reach different target groups, the tool should provide flexibility in terms of who is the audience, and in which context the information content is to be used. Therefore a modularized tool was designed, both in relation to different parts in the substitution process but also regarding the level of details in the information. For the example of NPEO, the tool provides information on the process and also includes some specific guidance and information about where the chemical can be used and what alternatives may be suitable to provide required functions. While the tool is designed for NPEO, general substitution steps as described in the following and guidance in relation to type of information are supposed to be applicable for other chemicals of concern.

Figure 1.4 Step-by-step illustration of a substitution process.

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The development work was divided into six main steps described below. Step 1: Formulation of learning objectives The learning objectives were formulated in close cooperation with textileimporting companies in Sweden through members of the network Chemicals Group at RISE (2018). Also, transcripts from interviews with experts and practitioners within the industry were evaluated and together form a core of subject matter including a source of prioritization, as well as an indication of meaningful levels of learning. The goal was to enable a proactive approach to chemicals management by including companies and through interaction with authorities. It was concluded that both general routines and information regarding chemicals management as well as substance-specific information to facilitate substitution was of large importance. The learning objectives must relate to the specific user/information receiver. Step 2: Development of learning tool structure For the substitution learning tool, the structure was divided stepwise and customized to knowledge level (1 3) of the intended user groups according to the following procedure: 1. 2. 3. 4. 5.

Select chemical for substitution (level 1 3) Understand the problem (level 1 3) Inventory at site level and in supply chain (level 1 3) Phase-out (level 1 3) Creation of good examples to inspire others

Level 1 represents a high level of knowledge, whereas level 3 addresses individuals with low competence level within the area. Interviews with key persons were carried out and recorded and transformed into short educational films. An animated film illustrating NPEO issues was created based on collected material. Detailed explanatory background materials were mostly added to level 3 for more inexperienced learners with a low level of preknowledge (Fig. 1.5). Step 3: Development of learning tool content The objective of the pilot course was to build knowledge and consensus about chemicals and related concerns in the textile value chain. Therefore information about general chemicals management practices and RSLs was included in the course content via the generic part of the structure in different modules. From an

Figure 1.5 Illustration of the levels and themes for the learning tool.

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initial mapping of prioritized topics into course modules and lessons, relevant experts and practitioners were identified; interview questions drafted, and interviews conducted and recorded, with a duration of typically 1 h. Interview settings were either face to face or online. In addition to a more generic part on CMS and RSL, one module for the specific chemical group NPEO was created. The underlying information regarding the course content was to a large extent already available as a result of several years of industry-based research, network activities in the Chemicals Group at RISE (2018) and governmental assignments, which was complemented with literature studies and interviews with experts and companies. Step 4: Format of initial course content The course modules were initially created as slideshow presentations for easy transformation into a web-based tool and other communication formats. The included modules of information were general chemicals management, information about RSLs, and specific chemical information regarding NPEO. More precisely, the information about NPEO contained possible uses of NPEO, potential hazards associated to the chemicals and alternative, less hazardous chemicals. The information was presented in different forms including recorded interviews, short animations, and text. The level of details was sorted from a top level, with introductory parts, a second level with some information, and a third level that contained detailed information. In this way the user can choose the level depending on their expertise, knowledge, and competence in relation to the specific substitution step. Step 5: Resulting tool Based on the experiences from a field trip to visit upstream suppliers, two webbased learning tools, customized for supply chain communication were developed. One is focusing on chemicals management and the other is focusing on substitution with NPEO as an illustrative example. The development was iterative and made in close cooperation with representatives from three Swedish textile-importing companies who were also involved in the goal and scope definition. The draft slideshow presentations and course contents were further refined. A series of draft animated videos was produced that use a “talking head” setting, generally between 5 and 15 min in duration for each video. Keywords and phrases were inserted to emphasize and anchor important points. Videos and still images were used together both to enhance the understanding of topics and points being described and create variety in the material and keep the interest for online material. Illustrations and graphs were also included—sometimes animated—to add clarity where needed. The enhanced video material was then typically separated into logical sequences, which are generally not more than 1 3 min in length. These sequences are forming the bulk of a full lesson object. Learning checkpoints were created in relation to the video-based material, primarily to emphasize and anchor key learning points, but also when needed to create variety and change of pace in the flow via interaction. The course content as well as the actual chemicals handling compared to the state of the art in certain factories was evaluated during field trips to textile producers in China and Portugal. In total, five dye houses and finishing, coating, and

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printing factories were visited. Textile brand partners participated and facilitated the plant visits. On plant level, dye house staffs, laboratory staff, production staff, and production managers were all taking part in the visit. Before the visit, several documents, including documents translated to Chinese, were communicated to the contact persons at the factories. In the documents, the purpose and expectations of the visit were communicated as well as discussion points and the presentations to be held. The presentations/tested course material was: 1. Introduction to the complex life cycle of chemicals in textiles; 2. Awareness of chemicals used in processes and chemicals that will be part of the final product; 3. General introduction of textile-related chemical impact on the environment and on humans, on local scale in relation to production site as well as for consumers; 4. Chemicals management, for instance, RSL and European legislation (REACH); 5. Introduction to Forward Learning; 6. Module approach; 7. Discussion around NPEO; 8. Good examples of NPEO substitution.

During the visits, the awareness and knowledge of environmental and health impacts from use of NPEO were tested, as well as awareness of NPEO use in the process. In addition, good examples of substitution of NPEO were collected in the visited supply chains. Step 6: Evaluation of learning module Evaluation of the tool was carried out by looking into the aspects of usability and relevance, together with knowledge creation. For the substitution tool, these aspects were evaluated among the members of the Chemicals Group at RISE (2018). The finalized tool was again tested with 10 companies in their (overseas) supply chains as a support in dialog concerning chemicals management and substitution. For the chemical management tool, feedback on the content, scope, structure, and educational value, along with technical quality, was captured via three main vehicles: 1. Comprehensive evaluation form via online survey; 2. Self-assessment learning objects within each module, structured as a series of questions for the learners to consider; 3. Occasional focus group sessions with learners to give and receive more detailed feedback.

The chemicals management education part of the tool has been used by approximately 700 learners from 30 organizations, which are predominantly Western apparel brands. Some important learnings from these educations are that the format encourages group discussions and collaboration, something that is seen as a key point for learning, especially when multiple colleagues from the same organization take the course. Also, the eclectic style, for example, that the template and the structure of the course vary and that real people and examples are included, helps to keep the course interesting and energizing. It was also seen that the content of the learning was much more important than having uniform graphical formats.

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Another important point was to identify time- or trend-sensitive content early on and put that in modules that are easily replaceable. The substitution modules of the learning tool were tested and evaluated by brands participating in the project and were seen as a tool that is user-friendly and with clear information on the right knowledge level for the users. Some comments on key insights from the company representatives are: 1. The project has succeeded to take a very complicated subject into an easily understandable level. 2. The methodology is very easy and clear to understand. 3. The tool has an attractiveness that creates a “Want to learn more” need.

The different information films included in the substitution tool have been used a lot by the participating companies since they are flexible and easy to bring to suppliers. The slideshow presentations that were made as background to the films have been extensively used, and these two instruments are by many users seen as a good combination to use. They were also regarded as easy to implement in each company’s own work routines. The learning tool as such is considered to be more complicated to use in practice, since it is not always compatible with the companies’ existing web solutions. Companies used the tool in their value chain as well as for different roles with the same purpose, to reach common ground and common view regarding chemicals issues and NPEO.

1.10

Conclusion

A new approach to encourage and activate professionals in the textile industry to participate in acquiring and sharing knowledge about chemicals based on an innovative chemicals management and substitution educational tool was created. The results from the study show that it is possible to combine knowledge status, learning, and networking in an online learning tool. During the project, communication gaps along the supply chain were revealed and an approach to overcome them was developed. In the tool, it is possible to adjust the knowledge level, language, and type of information (e.g., written texts or video animations and interviews) depending on the users’ background and understanding of the subject. This makes the content approachable also for an inexperienced user. One drawback with the tool is that for some companies it can be difficult to implement that type of tool in their existing IT and administrative systems. It was also concluded that the content of the information was of much larger importance for the user than the features of the learning tool. This implies that access to clear and transparent information is the most important issue for retailers who want to work actively with chemicals management. Since there already are several other web-based tools established for different types of environmental management, including chemicals management (e.g.,

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modules within the Higg Index; SAC, 2019), companies might be reluctant to use yet another tool. On the other hand, level-customized films and slideshow presentations including relevant content are flexible in their use, making them easily accessible. For example, companies may show such information to suppliers and select an appropriate format and content in order to customize the information for each supplier. The learning tool is shown to be suitable for chemicals management and since it is easy to forward, it should function well in a complex supply chain. If the aim of a retailer is to substitute a known hazardous chemical, this kind of tool is well suited to contribute to a joint phase-out action. For long-term improvement of chemicals handling, it is necessary that the awareness level for both suppliers and retailers is raised. The platform with the learning tool does not yet exist commercially, as the competition with other tools on the market was fatal. It was created to visualize what could be possible to communicate for an example with NPEO and can serve as inspiration for future tool development.

1.11

Future trends

Chemical management initiatives are strongly connected to customer and legal demands as well as the landscape of different policies. Current chemical management approaches have focused on control of restricted or regulated chemicals. However, there have been recent changes in policy actions related to chemical information. More focus is put on having complete information about actual chemical content rather than emphasizing the absence of a specific content. Examples of European initiatives include the database, which will contain the submitted information on the presence in articles of SVHCs on the Candidate List (ECHA, 2019b) and ECHA’s Ask REACH project (ECHA, 2019a). In a communication letter by the European Commission from 2018, the importance of sharing of chemical information to support circular flows was stressed (European Commission, 2018). Thus future trends include traceability and transparency in the value chains, including the textile value chain. This calls out for new chemical management routines and tools. As described earlier, focus has been previously on tools and approaches such as: G

G

G

G

G

RSL contracts material tests dialog collaboration

To meet future demands, more emphasis will most likely be put on areas related to creating common views, having similar targets, and common goals. Additionally, new business models are developed that create incentives for sharing critical chemical information within a protected node of the supply chain, as well as establishing effective ways to share information.

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Chemical Management in Textiles and Fashion

Recommendations for further studies

The authors see three important parts that need to be further researched in order to create feasible information sharing systems allowing all actors to attain control over the chemical content. These are: 1. Supporting common goals and common viewpoints. This may be done by educational systems related to chemicals and chemical management for actors in the textile value chain. Extra focus on actors and roles with different cultural, linguistic, and educational background is recommended. This also allows for common understanding even when the legal background for different locations of production sites is different. 2. Effective information sharing system for traceability and transparency in the textile value chain as well as for enabling circular flows of the material. This can be executed by digital information carriers. Such carriers can be loaded with important information related to chemical input. This information can then be transferred to actors in the end-of-life handling of textiles. Note that the implications of adding electronic tags to textile products need to be evaluated. 3. Business models supporting information sharing. There is a need to create business models that allow companies to share information in an economically beneficial manner. Increased or saved market shares, customer loyalties and trust, and service systems where information is key, may be important incentives for companies to mine “information” in the upstream value chain and then share information with downstream partners.

References AAFA, 2015. AAFA restricted substance list. Available at: ,https://www.wewear.org/rsl/. (accessed 26.10.15.). AFIRM, 2015. AFIRM supplier toolkit. Available at: ,http://www.afirm-group.com/.. American Chemical Society, 2016 CAS Registry. Available at: ,http://www.cas.org/content/ chemical-substances.. BLUESIGNs, 2017. BLUESIGNs. Available at: ,http://www.bluesign.com/. (accessed 24.08.13.). Bo¨rjeson, N., Gilek, M., Karlsson, M., 2015. Knowledge challenges for responsible supply chain management of chemicals in textiles as experienced by procuring organisations. J. Clean. Prod. 107, 130 136. Available from: https://doi.org/10.1016/j. jclepro.2014.03.012. Brigden, K., et al., 2012. Toxic Threads : The Big Fashion Stitch-Up. Greenpeace International, Amsterdam. Available at. Available from: http://www.greenpeace.org/ international/en/campaigns/detox/. CEPA, 1999. Canadian Environmental Protection Act. Canada Gazette. Available at: ,http:// laws-lois.justice.gc.ca/eng/acts/C-15.31/.. Choi, J., et al., 2011. Dirty Laundry unravelling the corporate connections to toxic water pollution in China. Greenpeace International, Amsterdam. ECHA, 2013. Annex XV dossier: identification of 4-nonylphenols as SVHC. Helsinki, Finland. ECHA, 2019a. Ask REACH. Available at: ,https://www.askreach.eu/. (accessed 27.09.19.).

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ECHA, 2019b. SCIP database. Available at: ,https://echa.europa.eu/scip-database. (accessed 27.09.19.). European Commission, 2006. Regulation (EC) No. 1907/2006 of the European Parliament and the Council of 18 December 2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), establishing a European Chemicals Agency, amending Directive 1999/45/E, Official Journal of the European Union, L396 (30/12/2006), pp. 0001 0851. European Commission, 2008. Regulation (EC) No. 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/ EC, and amending Regulation (EC). Official Journal of the European Union L, 353/1, 353(1). European Commission, 2012. Regulation (EU) No. 528/2012 of the European Parliament and of the Council of 22 May 2012 concerning the making available on the market and use of biocidal products. Official Journal of the European Union, 55(L167). European Commission, 2018. Communication from the Commission to the European Parliament, the Council, the European Economic and Social Committee and the Committee of the regions on the implementation of the circular economy package: options to address the interface between chemical. Strasbourg. European Commission, 2019. Regulation (EU) 2019/1021 of the European Parliament and of the Council of 20 June 2019 on persistent organic pollutants. Official Journal of the European Union, (L169). Fransson, K., 2012. Chemical Risk Information in Product Chains. The Cases of Paint and Textiles. Licentiate dissertation, Chalmers University of Technology, Gothenburg. Fransson, K., Molander, S., 2013. Handling chemical risk information in international textile supply chains. J. Environ. Plan. Manag. 56, 345 361. Johannesson, C., 2016. Emerging Textile Production Technologies Sustainability and Feasibility Assessment and Process LCA of Supercritical CO2 Dyeing. Chalmers University of Technology. Available at. Available from: http://publications.lib.chalmers. se/records/fulltext/241201/241201.pdf. Jo¨nsson, C., Posner, S., Roos, S., 2018. Sustainable chemicals: a model for practical substitution. In: Muthu, S.S. (Ed.), The Detox Fashion Cleaning Up Fashion Sector, second ed. Springer, Singapore. Available from: https://dx.doi.org/10.1007/978-981-10-4876-0. Kogg, B., 2009. Responsibility in the Supply Chain Interorganisational Management of Environmental and Social Aspects in the Supply Chain Case Studies from the Textile Sector. IIIEE, Lund University, Lund, Sweden. Munn, K., 2011. The chemicals in products project : case study of the textiles sector. Geneva, Switzerland. Nordic Ecolabelling, 2016. Nordic Ecolabelling of textiles, hides/skins and leather. Version 4.3. Copenhagen, Denmark. OECD, 2015. Substitution and alternatives assessment toolbox (SAAT). Available at: ,www.oecdsaatoolbox.org/. (accessed 26.10.15.). OEKO-TEXs Association, 2017. OEKO-TEXs Standard 100. Available at: ,https://www. oeko-tex.com. (accessed 24.08.13.). Olsson, E., et al., 2009. Kartl¨aggning av kemikalieanv¨andning i kl¨ader. Mo¨lndal, Sweden. Outdoor Industry Association, 2014. Chemicals Management Module (CMM). Available at: ,https://outdoorindustry.org/advocacy/corporate-responsibility/chemicals-managementmodule/. (accessed 01.06.16.).

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Pavitt, K., 1984. Sectoral patterns of technical change: towards a taxonomy and a theory. Res. Policy 13, 343 373. Renstro¨m, S., et al., 2013. Target the use phase! Design for sustainable behaviour. In: The 6th International Conference on Life Cycle Management. Gothenburg, pp. 1 4. RISE, 2018. Kemikaliegruppen. The Swedish Chemicals Group. Available at: ,www.kemikaliegruppen.se. (accessed 26.10.15.). Roos, S., 2015. Towards Sustainable Use of Chemicals in the Textile Industry: How Life Cycle Assessment Can Contribute. Chalmers University of Technology, Gothenburg. Roos, S., 2016. Advancing Life Cycle Assessment of Textile Products to Include Textile Chemicals. Inventory Data and Toxicity Impact Assessment. Chalmers University of Technology. Available at. Available from: http://publications.lib.chalmers.se/publication/246361. Roos, S., Jo¨nsson, C., Posner, S., 2017a. Labelling of chemicals in textiles Nordic Textile Initiative. Nordic Working Paper. NA2017:915. Copenhagen. doi: 10.6027/NA2017915. Roos, S., Jo¨nsson, C., Posner, S., 2017b. Nordic Textile Initiative report on labelling of chemicals in textiles. Copenhagen, Denmark. SAC, 2019. Sustainable Apparel Coalition (SAC). Available at: ,http://apparelcoalition.org/ the-higg-index/. (accessed 01.05.19.). SDC, AATCC, 2016. Colour index. Society of Dyers and Colourists & AATCC. Available at: ,http://www.colour-index.com/. (accessed 02.06.16.). Stro¨mbom, S., et al., 2015. Chemicals management in the textile sector dialogue between authorities, research institutes and retailers leading to concrete actions. In: 7th International Conference on Life Cycle Management, 30th August to 2nd September. Bourdeaux, p. 631. Subic, A., et al., 2012. Capability framework for sustainable manufacturing of sports apparel and footwear. Sustainability 4 (9), 2127. Available from: https://doi.org/10.3390/ su4092127. Swedish Chemicals Agency, 2014. Chemicals in textiles risks to human health and the environment. KemI Report 6/14. Stockholm, Sweden. Available at: ,https://www.kemi. se/files/8040fb7a4f2547b7bad522c399c0b649/report6-14-chemicals-in-textiles.pdf.. Swedish Chemicals Agency, 2016. Hazardous chemical substances in textiles proposals for risk management measures Report from a government assigment. Stockholm, Sweden. Swedish Chemicals Group/Swedish Textile Importer’s Association, 2016. Chemicals guidance. Mo¨lndal, Sweden. Available at: ,http://www.kemikaliegruppen.se/.. Swerea, SFA, Lexicon, 2015. Forward Learning. Available at: ,http://forwardlearning.sustainablefashionacademy.org/. (accessed 08.11.16.). UN Environment, 2017. Stockholm Convention on Persistent Organic Pollutions (POPs). United Nations, 2011. Globally Harmonized System of Classification and Labelling of Chemicals (GHS), fourth ed., US Environmental Agency, Arlington, USA, fourth revised ed. United Nations, New York and Geneva. Available at: ,http://www.unece. org/trans/danger/publi/ghs/ghs_rev06/06files_e.html#c38156. (accessed 06.09.13). US EPA, 1976. Toxic Substances Control Act (TSCA). ZDHC, 2014. Roadmap to Zero Discharge of Hazardous Chemicals (ZDHC). Available at: ,http://www.roadmaptozero.com/. (accessed 01.06.14).

Chemical hazards in textiles

2

Parthiban Manickam and Deepthi Vijay Department of Fashion Technology, PSG College of Technology, Coimbatore, India

2.1

Introduction

Textiles make up a very broad category of products and are used in a way that consumers, including children, are directly or indirectly exposed to their chemical content. Chemicals in textiles can have adverse effects, not only on the health of the consumers, but also on the environment by long-term effects from persistent or bioaccumulating substances. India’s textiles and clothing industry is one of the mainstays of the national economy. Textile industry contributes 30% of India’s export. It produces over 400 million meters of cloth and around 1000 million kg of yarn per annum. Textile sector is labor-intensive and nearly a million of workers are associated with various unit operations. Textile wet processing activities contribute about 70% of pollution in textile industry. Right from cotton cultivation and manufacture of fibers, spinning, weaving, processing, and finishing, more than 14,000 dyes and chemicals are used and a significant quantity of these goes in the solid, liquid, and air wastes, thereby polluting air, land, and water. To deal with the problems posed by hazardous chemicals in textiles, there is a need for regulation of chemical content in textile products.

2.2

Hazardous chemicals

Chemicals play an inevitable role in all the processes involved in textile production, starting from the cultivation of raw material, to finishing of the end product. Right from the pesticides used, the role of chemicals extends to sizing, desizing, dyeing, printing, and specialized finishes.

2.2.1 Pesticides in cotton cultivation Large quantities of most toxic fertilizers and pesticides are used in conventional cotton cultivation since cotton is a highly pest-prone crop. The proportion of global pesticide consumption for cotton is 11% on an average. In addition to insecticides, an enormous amount of herbicides, fungicides, defoliants, and synthetic fertilizers Chemical Management in Textiles and Fashion. DOI: https://doi.org/10.1016/B978-0-12-820494-8.00002-2 © 2021 Elsevier Ltd. All rights reserved.

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are used in cotton cultivation. Nitrogenous and phosphoric fertilizers are widely used. This residual nitrates and phosphates present in agricultural drainage cause water pollution and damage to aquatic life. Groundwater gets toxic due to seepage from the surface. The additions of chemicals reduce the fertility and production capacity of the soil. Toxic insecticides kill useful soil bacteria that are important for plant growth. Chlorinated pesticides convert to dioxins that are poisonous. Some pesticides are also carcinogenic to man and animals. Throughout various stages, the pesticides are harmful to the environment through soil, air, and water pollution.

2.2.2 Dyeing and printing The dyeing of textiles is done using dyes and pigments. Almost all dyes used in textile industry are synthetic organic compounds. Colorizing with dyes is based on physical-chemical equilibrium processes, namely diffusion and sorption of the dye molecules or ions. These processes may be followed by chemical reactions in the fibers. In a well-managed dyeing process, 70%
95% of the dyeing agents attach to the fiber and the rest are channeled to wastewater treatment. Pigments are attached into the fabric using a binding agent or applied using a printing method. Approximately half of all textile printing is performed using pigment printing technology, in which the pigment has no affinity with the fiber. For this reason, a binder and fixating agent must be added to the printing paste. The type and quantity of dyes, chemicals, and auxiliaries (surfactants, dispersing agents, etc.) depend on the product quality (Zameer Ul Hassan et al., 2013).

2.2.3 Sensitizing and allergic dyes The main functions of clothes are protecting from environmental injuries and helping to regulate skin temperature and moisture. Natural and synthetic fabrics used in the manufacture of clothing cause almost no skin problems. Clothing dermatitis is generally attributed to chemicals and dyes added to these fibers during their manufacture and assembly into garments. In particular, responsible agents are represented by finishes, dyes, metals, rubber, and glues. Also optical whitener, biocides, flame retardants, and other agents are occasionally recognized as causative substance. Any location where the clothing is held more tightly against the skin is a likely spot for textile dermatitis. Sometimes, other sites not directly exposed to sensitizing substances, such as face and hands, can be involved as well. Not all garment-related allergy trouble can be attributed only to the dyestuffs used but also many other factors; however, attention should be paid as some dyestuffs do contain allergenic (sensitizing) properties. Parameters influencing the risk of sensitization in textile dyes include not only the allergenicity of dye molecule but also the fastness of the dye, that is, how well it is bound to the fabric and the percutaneous absorption. An allergic skin reaction requires re-exposure or continuous exposure to the allergen, the substance causing the allergy. The first exposure “sensitizes” the person and the later exposure “elicits” the reaction. The hypersensitivity to an allergen can be immediate (Type I)—a sometimes-hazardous response

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that occurs within minutes to an hour of contact with the allergen—or delayed (Type IV), appearing at 24
72 h (Islam and Arun, 2013).

2.2.3.1 Disperse dyes Textile dyes are causes of acute dermatitis with rapid onset. Among textile dyes, disperse dyes are considered the most responsible. Literature data report their prevalence of sensitization ranging between 3.1% and 5.2%. In particular, disperse blue dyes were recently selected as “contact allergens of the year” for 2000. Patch tests with disperse dyes performed on children with suspected acid reduction clearing agent (ACD) and/or atopic dermatitis have shown a positivity of 4.6%: the most common sensitizer was Disperse Yellow 3. Both animal tests and human patch test studies have shown significant potential for sensitization to disperse blue 35, 106, and 124. The above dyes have been reported to cause an ACD to a variety of garments that include underwear, blouses, pants, swimsuits, etc. There is evidence that at least 15 disperse dyes are contact allergens particularly those applied to garments made of synthetic fiber and worn skin-tight. In the 1970s this phenomenon was called as “stockings dye allergy” and in the 1990s as “leggings allergy” (Su and Zhang, 2011).

2.2.3.2 Basic and acid dyes The basic dyes are the next most common allergens. They are mainly used to dye wool, silk, cotton, cellulosics, and polyacrylonitriles. Basic Red 46, Basic Brown 1, Basic Black 1, Brilliant Green, and Turquoise have been reported to cause textile dermatitis. Acid dyes, also indicated as textile allergens, are used to color wool, other protein fibers, and some man-made fibers (nylon). They include monoazoic, diazoic, triphenylmethane, and anthraquinone compounds. Acid Yellow 23, Supramine Yellow and Red, and Acid Violet 17 belong to this class.

2.2.3.3 Direct dyes Direct dyes are directly applied on fibers, most often wool, cotton, flax, and leather. Water-soluble direct dyeing agents are bound to the fibers by depositing in cavities. Binding is not very strong, which means that the colorfastness is only moderate. However, these agents are characterized by a low absorption through the skin. Direct Black 38, a triazoic compound dye, has been reported to be an allergen.

2.2.3.4 Vat dyes Vat dyes are water-insoluble dyes applied in a reduced soluble form and then reoxidized to the original insoluble form once absorbed into the fiber. They are used for cellulosics and some wool principally. Anthraquinone or indigoids are the chemical groups used. Vat dyes are relatively hypoallergenic although Vat Green 1, an

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anthraquinone derivative, has been reported to cause five cases of contact dermatitis from blue uniforms in nurses.

2.2.3.5 Reactive dyes With an azo or anthraquinone structure, connected to a reactive group, capable of linking through covalent bonds to amine or sulfhydryl groups, these dyes are used for coloring natural fibers such as cotton, silk, and wool and are also applied for polyamides. Asthma and contact dermatitis have been described after occupational exposure to reactive dyes. A study conducted on 1813 subjects patch tested with 12 reactive dyes has revealed 18 patients sensitized to these dyes. Most of them showed dermatitis localized to the trunk, upper limbs, and/or hands; only one patient, occupationally exposed, presented dermatitis localized to the face. The dyes most frequently responsible for positive patch tests were Red Cibacron CR (Reactive Red 238) and Violet Remazol 5R (Reactive Violet 5). A further study performed with five other reactive dyes patch tested on 312 patients showed no positive allergic or irritant reactions.

2.2.3.6 Azo dyes Azo dyes are one of the main types of dye used by the textile industry. However, these dyes break down during use and release chemicals known as aromatic amines, some of which are carcinogenic. The EU has banned the use of these azo dyes that release cancer-causing amines in any textiles that come into contact with human skin. Regulations for azo dyestuffs are actually for certain azo dyestuffs that produce amine classified as carcinogenic due to reduction decomposition. In the present context specific azo dyes releasing any of the 20 harmful amines have been banned as per the German Legislation. Azo dyes are manufactured from aromatic amines. It is important to note that some of them can split off carcinogenic amines, such as benzidine, which may be absorbed through skin and the respiratory and intestinal tract (Li et al., 2011).

2.2.4 Regulated chemicals 2.2.4.1 Alkylphenols Commonly used alkylphenol compounds include nonylphenols (NPs) and octylphenols and their ethoxylates, particularly nonylphenol ethoxylates. NPs are widely used in the textiles industry in cleaning and dyeing processes. They are toxic to aquatic life, persist in the environment, and can accumulate in body tissue and biomagnify (increase in concentration through the food chain). Their similarity to natural estrogen hormones can disrupt sexual development in some organisms, most notably causing the feminization of fish. NPs are heavily regulated in Europe and since 2005 there has been an EU-wide ban on major applications.

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2.2.4.2 Phthalates Phthalates are a group of chemicals most commonly used to soften PVC (the plastic polyvinyl chloride). In the textile industry they are used in artificial leather, rubber, and PVC, and in some dyes. There are substantial concerns about the toxicity of phthalates such as DEHP [bis(2-ethylhexyl) phthalate], which is reprotoxic in mammals, as it can interfere with development of the testes in early life. The phthalates DEHP and DBP (dibutyl phthalate) are classed as “toxic to reproduction” in Europe and their use restricted.

2.2.4.3 Brominated and chlorinated flame retardants Many brominated flame retardants (BFRs) are persistent and bioaccumulative chemicals that are now present throughout the environment. Polybrominated diphenyl ethers (PBDEs) are one of the most common groups of BFRs and have been used to fireproof a wide variety of materials, including textiles. Some PBDEs are capable of interfering with the hormone systems involved in growth and sexual development. Under EU law the use of some types of PBDE is tightly restricted and one PBDE has been listed as a “priority hazardous substance” under EU Water Law, which requires that measures be taken to eliminate its pollution of surface waters.

2.2.4.4 Organotin compounds Organotin compounds are used in biocides and as antifungal agents in a range of consumer products. Within the textile industry they have been used in products such as socks, shoes, and sport clothes to prevent odor caused by the breakdown of sweat. One of the best-known organotin compounds is tributyltin (TBT). One of its main uses was in antifouling paints for ships, until evidence emerged that it persists in the environment, builds up in the body, and can affect immune and reproductive systems. Its use as an antifouling paint is now largely banned. TBT has also been used in textiles and is listed as a “priority hazardous substance” under EU regulations that require measures to be taken to eliminate its pollution of surface waters in Europe.

2.2.4.5 Perfluorinated chemicals Perfluorinated chemicals (PFCs) are man-made chemicals widely used by industry for their nonstick and water-repellent properties. In the textile industry they are used to make textile and leather products both water and stain-proof. Evidence shows that many PFCs persist in the environment and can accumulate in body tissue and biomagnify (increasing in levels) through the food chain. Once in the body some have been shown to affect the liver as well as acting as hormone disruptors, altering levels of growth and reproductive hormones. The best known of the PFCs is perfluorooctane sulfonate (PFOS), a compound highly resistant to degradation; it is expected to persist for very long periods in the environment. PFOS is one of the “persistent organic pollutants” restricted under the

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Stockholm Convention, a global treaty to protect human health and the environment, and PFOS is also prohibited within Europe and in Canada for certain uses.

2.2.4.6 Chlorobenzenes Chlorobenzenes are persistent and bioaccumulative chemicals that have been used as solvents and biocides, in the manufacture of dyes and as chemical intermediaries. The effects of exposure depend on the type of chlorobenzene; however, they commonly affect the liver, thyroid, and central nervous system. Hexachlorobenzene (HCB), the most toxic and persistent chemical of this group, is also a hormone disruptor. Within the EU, pentachlorobenzene and HCB are classified as “priority hazardous substances” under regulations that require measures to be taken to eliminate their pollution of surface waters in Europe. They are also listed as “persistent organic pollutants” for global restriction under the Stockholm Convention, and in line with this they are prohibited or scheduled for reduction and eventual elimination in Europe.

2.2.4.7 Chlorinated solvents Chlorinated solvents—such as trichloroethane (TCE)—are used by textile manufacturers to dissolve other substances during manufacturing and to clean fabrics. TCE is an ozone-depleting substance that can persist in the environment. It is also known to affect the central nervous system, liver, and kidneys. Since 2008 the EU has severely restricted the use of TCE in both products and fabric cleaning.

2.2.4.8 Chlorophenols Chlorophenols are a group of chemicals used as biocides in a wide range of applications, from pesticides to wood preservatives and textiles. Pentachlorophenol (PCP) and its derivatives are used as biocides in the textile industry. PCP is highly toxic to humans and can affect many organs in the body. It is also highly toxic to aquatic organisms. The EU banned production of PCP-containing products in 1991 and now also heavily restricts the sale and use of all goods that contain the chemical.

2.2.4.9 Short-chain chlorinated paraffins Short-chain chlorinated paraffins (SCCPs) are used in the textile industry as flame retardants and finishing agents for leather and textiles. They are highly toxic to aquatic organisms, do not readily break down in the environment, and have a high potential to accumulate in living organisms. Their use has been restricted in some applications in the EU since 2004.

2.2.5 Heavy metals: cadmium, lead, mercury, and chromium (VI) Heavy metals such as cadmium, lead, and mercury have been used in certain dyes and pigments used for textiles. These metals can accumulate in the body over time and are

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highly toxic, with irreversible effects including damage to the nervous system (lead and mercury) or the kidneys (cadmium). Cadmium is also known to cause cancer. Uses of chromium (VI) include certain textile processes and leather tanning: it is highly toxic even at low concentrations, including to many aquatic organisms. Within the EU cadmium, mercury, and lead have been classified as “priority hazardous substances” under regulations that require measures to be taken to eliminate their pollution of surface waters in Europe. Uses of cadmium, mercury, and lead have been severely restricted in Europe for some time, including certain specific uses of mercury and cadmium in textiles (Zhiyuan et al., 2008).

2.2.5.1 Heavy metal content Heavy metals are constituents of some dyes and pigments. They can also be found in natural fibers due to absorption by plants through soil. Metals may also be introduced into textiles through dyeing and finishing processes. After chemical processing of textiles, wastewater contains many impurities as well as chemicals. Each year the global textile industry discharges 40,000
50,000 tons of dye into our rivers, and more than 200,000 tons of salt. Effluent from textile dyeing process contains heavy metals. These metals are toxic as their ions or compounds are soluble in water and may be readily absorbed into living organisms. These heavy metals that have transferred to the environment are highly toxic and can bio-accumulate in the human body, aquatic life, natural water-bodies, and also possibly trapped in the soil. Once absorbed by humans, heavy metals tend to accumulate in internal organs such as the liver or kidney. The effects on health can be tremendous when high levels of accumulation are reached. For example, high levels of lead can seriously affect the nervous system. After absorption, even in small amounts these metals bind to structural proteins, enzymes, and nucleic acids causing health effects. The toxicity of metal pollution is slow and long-lasting as these metal ions are nondegradable. Among the different heavy metals iron, copper, aluminum, and tin are considered more safe compared to lead, chromium, cadmium, and mercury. Heavy metals very often refer to antimony (Sb), arsenic (As), lead (Pb), cadmium (Cd), mercury (Hg), copper (Cu), chromium (Cr), cobalt (Co), and nickel (Ni). Both cadmium and lead are classified as carcinogens. There are no legal limits for heavy metal contents in textiles. However, eco-labels and buyers have adopted limits of drinking water for textile end products. Maximum permissible limits of heavy metals in drinking water according to Indian Standards are less than 1 ppm in almost all the cases. Prolonged exposure to heavy metals may cause health problems such as kidney failure, emphysema, allergies, and even cancer. Copper causes irritation of mucous membrane. Iron when contact with skin and eyes causes severe burns. Manganese causes symptoms of Parkinson’s disease. Aluminum is a probable cause for Alzheimer’s and Parkinson’s disease. Zinc causes gastrointestinal problems and damage to kidneys. Selenium causes nausea, diarrhea, fatigue, and hair loss. Lead affects the central nervous system. Mercury affects central nervous system and the areas associated with visual and auditory functions. Cadmium

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causes kidney failure. Nickel induces irritation of skin and eyes and dermatitis. Long continuous exposure to chromium may lead to liver and kidney disease and even cancer (Li et al., 2016).

2.3

Routes of exposure

Toxicity can be defined as the relative ability of a substance to cause adverse effects in living organisms. This “relative ability” is dependent upon several conditions. As Paracelsus suggests, the quantity or the dose of the substance determines whether the effects of the chemical are toxic, nontoxic, or beneficial. In addition to dose, other factors may also influence the toxicity of the compound, such as the route of entry, duration and frequency of exposure, variations between different species (interspecies), and variations among members of the same species (intraspecies). To apply these principles to hazardous materials response, the routes by which chemicals enter the human body will be considered first. Knowledge of these routes will support the selection of personal protective equipment (PPE) and the development of safety plans. The second section deals with dose
response relationships. Since dose
response information is available in toxicology and chemistry reference books, it is useful to understand the relevance of these values to the concentrations that are actually measured in the environment (Gomathi et al., 2017). The third section of this chapter includes the effects of the duration and frequency of exposure, interspecies variation and intraspecies variation on toxicity. Finally, toxic responses associated with chemical exposures are described according to each organ system. There are four routes by which a substance can enter the body: inhalation, skin (or eye) absorption, ingestion, and injection. G

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Inhalation: For most chemicals in the form of vapors, gases, mists, or particulates, inhalation is the major route of entry. Once inhaled, chemicals are either exhaled or deposited in the respiratory tract. If deposited, damage can occur through direct contact with tissue or the chemical may diffuse into the blood through the lung
blood interface. Upon contact with tissue in the upper respiratory tract or lungs, chemicals may cause health effects ranging from simple irritation to severe tissue destruction. Substances absorbed into the blood are circulated and distributed to organs that have an affinity for that particular chemical. Health effects can then occur in the organs, which are sensitive to the toxicant. Skin (or eye) absorption: Skin (dermal) contact can cause effects that are relatively innocuous such as redness or mild dermatitis; more severe effects include destruction of skin tissue or other debilitating conditions. Many chemicals can also cross the skin barrier and be absorbed into the blood system. Once absorbed, they may produce systemic damage to internal organs. The eyes are particularly sensitive to chemicals. Even a short exposure can cause severe effects to the eyes or the substance can be absorbed through the eyes and be transported to other parts of the body causing harmful effects. Ingestion:

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Chemicals that inadvertently get into the mouth and are swallowed do not generally harm the gastrointestinal tract itself, unless they are irritating or corrosive. Chemicals that are insoluble in the fluids of the gastrointestinal tract (stomach, small, and large intestines) are generally excreted. Others that are soluble are absorbed through the lining of the gastrointestinal tract. They are then transported by the blood to internal organs where they can cause damage. Injection: Substances may enter the body if the skin is penetrated or punctured by contaminated objects. Effects can then occur as the substance is circulated in the blood and deposited in the target organs. Once the chemical is absorbed into the body, three other processes are possible: metabolism, storage, and excretion. Many chemicals are metabolized or transformed via chemical reactions in the body. In some cases, chemicals are distributed and stored in specific organs. Storage may reduce metabolism and therefore increase the persistence of the chemicals in the body. Various excretory mechanisms (exhaled breath, perspiration, urine, feces, or detoxification) rid the body, over a period of time, of the chemical. For some chemicals elimination may be a matter of days or months; for others, the elimination rate is so low that they may persist in the body for a lifetime and cause deleterious effects. The dose
response relationship: In general, a given amount of a toxic agent will elicit a given type and intensity of response. The dose
response relationship is a fundamental concept in toxicology and the basis for measurement of the relative harmfulness of a chemical. A dose
response relationship is defined as a consistent mathematical and biologically plausible correlation between the number of individuals responding and a given dose over an exposure period. Dose terms: In toxicology, studies of the dose given to test organisms are expressed in terms of the quantity administered: Quantity per unit mass (or weight). Usually expressed as milligram per kilogram of body weight (mg/kg). Quantity per unit area of skin surface. Usually expressed as milligram per square centimeter (mg/cm2). Volume of substance in air per unit volume of air. Usually given as microliters of vapor or gas per liter of air by volume (ppm). Particulates and gases are also given as milligrams of material per cubic meter of air (mg/m3).

The period of time over which a dose has been administered is generally specified. For example, 5 mg/kg/3 days is 5 mg of chemical per kilogram of the subject’s body weight administered over a period of three days. For dose to be meaningful it must be related to the effect it causes. For example, 50 mg/kg of chemical “X” administered orally to female rats has no relevancy unless the effect of the dose, say sterility in all test subjects, is reported (Sivakumar et al., 2011).

2.3.1 Health effects Human health effects caused by exposure to toxic substances fall into two categories: short-term and long-term effects. Short-term effects (or acute effects) have a relatively quick onset (usually minutes to days) after brief exposures to relatively high concentrations of material (acute exposures). The effect may be local or

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systemic. Local effects occur at the site of contact between the toxicant and the body. This site is usually the skin or eyes, but includes the lungs if irritants are inhaled or the gastrointestinal tract if corrosives are ingested. Systemic effects are those that occur if the toxicant has been absorbed into the body from its initial contact point, transported to other parts of the body, and cause adverse effects in susceptible organs. Many chemicals can cause both local and systemic effects. Long-term effects (or chronic effects) are those with a long period of time (years) between exposure and injury. These effects may occur after apparent recovery from acute exposure or as a result of repeated exposures to low concentrations of materials over a period of years (chronic exposure). Health effects manifested from acute or chronic exposure are dependent upon the chemical involved and the organ it affects. Most chemicals do not exhibit the same degree of toxicity for all organs. Usually the major effects of a chemical will be expressed in one or two organs. These organs are known as target organs, which are more sensitive to that particular chemical than other organs(https://www.blcchemicaltesting.com/chemical-testing/ heavy-metals-testing-and-analysis/). The organs of the body and examples of effects due to chemical exposures are listed below.

2.3.1.1 Respiratory tract The respiratory tract is the only organ system with vital functional elements in constant, direct contact with the environment. The lung also has the largest exposed surface area of any organ on a surface area of 70
100 m2 versus 2 m2 for the skin and 10 m2 for the digestive system. The respiratory tract is divided into three regions: 1. Nasopharyngeal—extends from nose to larynx. These passages are lined with ciliated epithelium and mucous glands. They filter out large inhaled particles, increase the relative humidity of inhaled air, and moderate its temperature. 2. Tracheobronchial—consists of trachea, bronchi, and bronchioles and serves as conducting airway between the nasopharyngeal region and alveoli. These passageways are lined with ciliated epithelium coated by mucous, which serves as an escalator to move particles from deep in the lungs back up to the oral cavity so they can be swallowed. These ciliated cells can be temporarily paralyzed by smoking or using cough suppressants. 3. Pulmonary acinus—is the basic functional unit in the lung and the primary location of gas exchange. It consists of small bronchioles which connect to the alveoli. The alveoli, of which there are 100 million in humans, contact the pulmonary capillaries. Inhaled particles settle in the respiratory tract according to their diameters: a. 5
30-micron particles are deposited in the nasopharyngeal region. b. 1
5-micron particles are deposited in the tracheobronchial region. c. Less than 1-micron particles are deposited in the alveolar region by diffusion and Brownian motion. In general, most particles 5
10 microns in diameter are removed. However, certain small inorganic particles settle into smaller regions of the lung and kill the cells which attempt to remove them. The result is fibrous lesions of the lung. Many chemicals used or produced in industry can produce acute or chronic diseases of the respiratory tract when they are inhaled. The toxicants can be classified according to how they affect the respiratory tract. d. Asphyxiants: gases that deprive the body tissues of oxygen.

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e. Simple asphyxiants are physiologically inert gases that at high concentrations displace air leading to suffocation. Examples: nitrogen, helium, methane, neon, and argon. f. Chemical asphyxiants are gases that prevent the tissues from getting enough oxygen. Examples: carbon monoxide and cyanide. Carbon monoxide binds to hemoglobin 200 times more readily than oxygen. Cyanide prevents the transfer of oxygen from blood to tissues by inhibiting the necessary transfer enzymes. g. Irritants: chemicals that irritate the air passages. Constriction of the airways occurs and may lead to edema (liquid in the lungs) and infection. Examples: hydrogen fluoride, chlorine, hydrogen chloride, and ammonia. h. Necrosis producers: chemicals that result in cell death and edema. Examples: ozone and nitrogen dioxide. i. Fibrosis producers: chemicals that produce fibrotic tissue which, if massive, blocks airways and decreases lung capacity. Examples: silicates, asbestos, and beryllium. j. Allergens: chemicals that induce an allergic response characterized by bronchoconstriction and pulmonary disease. Examples: isocyanates and sulfur dioxide. k. Carcinogens: chemicals that are associated with lung cancer. Examples: cigarette smoke, coke oven emissions, asbestos, and arsenic. Not only can various chemicals affect the respiratory tract, but the tract is also a route for chemicals to reach other organs. Solvents, such as benzene and tetrachloroethane, anesthetic gases, and many other chemical compounds can be absorbed through the respiratory tract and cause systemic effects (http://textilelibrary.blogspot.in/2009/03/disperse-dye.html).

2.3.1.2 Skin The skin is, in terms of weight, the largest single organ of the body. It provides a barrier between the environment and other organs (except the lungs and eyes) and is a defense against many chemicals. The skin consists of the epidermis (outer layer) and the dermis (inner layer). In the dermis are sweat glands and ducts, sebaceous glands, connective tissue, fat, hair follicles, and blood vessels. Hair follicles and sweat glands penetrate both the epidermis and dermis. Chemicals can penetrate through the sweat glands, sebaceous glands, or hair follicles. Although the follicles and glands may permit a small amount of chemicals to enter almost immediately, most pass through the epidermis, which constitutes the major surface area. The top layer is the stratum corneum, a thin cohesive membrane of dead surface skin. This layer turns over every 2 weeks by a complex process of cell dehydration and polymerization of intracellular material. The epidermis plays the critical role in skin permeability (http://www.pulcra-chemicals.com/zdhc). Below the epidermis lies the dermis, a collection of cells providing a porous, watery, nonselective diffusion medium. Intact skin has a number of functions: G

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Epidermis: prevents absorption of chemicals and is a physical barrier to bacteria. Sebaceous glands: secrete fatty acids that are bacteriostatic and fungistatic. Melanocytes (skin pigment): prevent damage from ultraviolet radiation in sunlight. Sweat glands: regulate heat. Connective tissue: provides elasticity against trauma. Lymph-blood system: provides immunologic responses to infection. The ability of skin to absorb foreign substances depends on the properties and health of the skin and the chemical properties of the substances. Absorption is enhanced by:

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Breaking top layer of skin by abrasions or cuts; Increasing hydration of skin; Increasing temperature of skin that causes sweat cells to open up and secrete sweat, which can dissolve solids; Increasing blood flow to skin; Increasing concentrations of the substance; Increasing contact time of the chemical on the skin; Increasing the surface area of affected skin; Altering the skin’s normal pH of 5; Decreasing particle size of substance; Adding agents that will damage skin and render it more susceptible to penetration; Adding surface-active agents or organic chemicals; Inducing ion movement by an electrical charge. Absorption of a toxic chemical through the skin can lead to local effects through direct contact, such as irritation and necrosis and systemic effects. Many chemicals can cause a reaction with the skin, resulting in inflammation called dermatitis. These chemicals are divided into three categories: Primary irritants: Act directly on normal skin at the site of contact (if chemical is in sufficient quantity for a sufficient length of time). Skin irritants include acetone, benzyl chloride, carbon disulfide, chloroform, chromic acid and other soluble chromium compounds, ethylene oxide, hydrogen chloride, iodine, methyl ethyl ketone, mercury, phenol, phosgene, styrene, sulfur dioxide, picric acid, toluene, and xylene. Photosensitizers Increase in sensitivity to light, which results in irritation and redness. Photosensitizers include tetracyclines, acridine, creosote, pyridine, furfural, and naphtha. Allergic sensitizers: May produce allergic-type reaction after repeated exposures. They include formaldehyde, phthalic anhydride, ammonia, mercury, nitrobenzene, toluene diisocyanate, chromic acid and chromates, cobalt, and benzoyl peroxide.

2.3.1.3 Eyes The eyes are affected by the same chemicals that affect skin, but the eyes are much more sensitive. Many materials can damage the eyes by direct contact (http://www. centexbel.be/files/brochure-pdf/allergens_eng.pdf). G

Acids: Damage to the eye by acids depends on pH and the protein-combining capacity of the acid. Unlike alkali burns, the acid burns that are apparent during the first few hours are a good indicator of the long-term damage to be expected. Some acids and their properties are: Sulfuric acid—It simultaneously removes water and generates heat; Picric acid and tannic acid—No difference in damage they produce in entire range of acidic pHs; Hydrochloric acid—Severe damage at pH 1, but no effect at pH 3 or greater. Alkalies: Damage that appears mild initially but can later lead to ulceration, perforation, and clouding of the cornea or lens. The pH and length of exposure have more bearing on the amount of damage than the type of alkali. Some problematic alkalies are: Sodium hydroxide (caustic soda) and potassium hydroxide; G

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Ammonia penetrates eye tissues more readily than any other alkali; calcium oxide (lime) forms clumps when it contacts eye tissue and is very hard to remove. Organic solvents: Organic solvents (e.g., ethanol, toluene, and acetone) dissolve fats, cause pain, and dull the cornea. Damage is usually slight unless the solvent is hot. Lacrimators: Lacrimators cause instant tearing at low concentrations. They are distinguished from other eye irritants (hydrogen chloride and ammonia) because they induce an instant reaction without damaging tissues. At very high concentrations lacrimators can cause chemical burns and destroy corneal material. Examples are chloroacetophenone (tear gas) and mace. In addition, some compounds act on eye tissue to form cataracts, damage the optic nerve, or damage the retina. These compounds usually reach the eye through the blood having been inhaled, ingested, or absorbed rather than direct contact (http://www.pulcrachemicals.com/zdhc). Examples of compounds that can provide systemic effects damaging to the eyes are: Naphthalene: cataracts and retina damage, Phenothiazine (insecticide): retina damage, Thallium: cataracts and optic nerve damage, and Methanol: optic nerve damage. G

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2.3.1.4 Central nervous system Neurons (nerve cells) have a high metabolic rate but little capacity for anaerobic metabolism. Subsequently, inadequate oxygen flow (anoxia) to the brain kills cells within minutes. Some may die before oxygen or glucose transport stops completely. Because of their need for oxygen, nerve cells are readily affected by both simple asphyxiants and chemical asphyxiants. Also, their ability to receive adequate oxygen is affected by compounds that reduce respiration and thus reduce oxygen content of the blood (barbiturates, narcotics). Other examples are compounds such as arsine, nickel, ethylene chlorohydrin, tetraethyl lead, aniline, and benzene that reduce blood pressure or flow due to cardiac arrest, extreme hypotension, hemorrhaging, or thrombosis. Some compounds damage neurons or inhibit their function through specific action on parts of the cell. The major symptoms from such damage include dullness, restlessness, muscle tremor, convulsions, loss of memory, epilepsy, idiocy, loss of muscle coordination, and abnormal sensations. Examples are: G

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Fluoroacetate: rodenticide, Triethyltin: ingredient of insecticides and fungicides, Hexachlorophene: antibacterial agent, Lead: gasoline additive and paint dye ingredient, Thallium: sulfate used as a pesticide and oxide or carbonate used in manufacture of optical glass and artificial gems, and Tellurium: pigment in glass and porcelain. Organomercury compounds: Methyl mercury, used as a fungicide, is also a product of microbial action on mercury ions. Organomercury compounds are especially hazardous because of their volatility and their ability to permeate tissue barriers. Some chemicals are noted for producing weakness

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of the lower extremities and abnormal sensations (along with previously mentioned symptoms): Acrylamide: soil stabilizer and waterproofer; Carbon disulfide: solvent in rayon and rubber industries; n-Hexane: used as a cleaning fluid and solvent. Its metabolic product, hexanedione, causes the effects. Organophosphorus compounds: Often used as flame retardants (triorthocresyl phosphate) and pesticides (Leptofor and Mipafox). Agents that prevent the nerves from producing proper muscle contraction and may result in death from respiratory paralysis are dichlorodiphenyltrichloroethane (DDT), lead, botulinum toxin, and allethrin (a synthetic insecticide). DDT, mercury, manganese, and monosodium glutamate also produce personality disorders and madness (http://www. pulcra-chemicals.com/zdhc). G

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2.3.1.5 Liver Liver injury induced by chemicals has been known as a toxicologic problem for hundreds of years. It was recognized early that liver injury is not a simple entity, but that the type of lesion depends on the chemical and duration of exposure. Three types of response to hepatotoxins can be identified: G

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Acute Cell death from carbon tetrachloride: solvent and degreaser; Chloroform: used in refrigerant manufacture solvent; Trichloroethylene: solvent, dry cleaning fluid, and degreaser; Tetrachloroethane: paint and varnish remover and dry cleaning fluid; Bromobenzene: solvent and motor oil additive; Tannic acid: ink manufacture; Kepone: pesticide.

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Cirrhosis: a progressive fibrotic disease of the liver associated with liver dysfunction and jaundice. Among agents implicated in cirrhosis cases are carbon tetrachloride, alcohol, and aflatoxin. Carcinomas: malignant, growing tissue. For example, vinyl chloride (used in polyvinyl chloride production) and arsenic (used in pesticides and paints) are associated with cancers. Biotransformation of toxicants. The liver is the principal organ that chemically alters all compounds entering the body. For example, ethanol!acetaldehyde!acetic acid!water 1 carbon dioxide This metabolic action by the liver can be affected by diet, hormone activity, and alcohol consumption.

Biotransformation in the liver can also lead to toxic metabolities, for example, carbon tetrachloride!chloroform

2.3.1.6 Kidneys The kidney is susceptible to toxic agents for several reasons: 1. The kidneys constitute 1% of the body’s weight, but receive 20%
25% of the blood flow (during rest). Thus large amounts of circulating toxicants reach the kidneys quickly.

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2. The kidneys have high oxygen and nutrient requirements because of their workload. They filter one-third of the plasma reaching them and reabsorb 98%
99% of the salt and water. As they are reabsorbed, salt concentrates in the kidneys. 3. Changes in kidney pH may increase passive diffusion and thus cellular concentrations of toxicants. 4. Active secretion processes may concentrate toxicants. 5. Biotransformation is high. A number of materials are toxic to the kidneys: a. Heavy metals may denature proteins as well as produce cell toxicity. Heavy metals (including mercury, arsenic, gold, cadmium, lead, and silver) are readily concentrated in the kidneys, making this organ particularly sensitive. b. Halogenated organic compounds, which contain chlorine, fluorine, bromine, or iodine. Metabolism of these compounds, like that occurring in the liver, generates toxic metabolites. Among compounds toxic to the kidneys are carbon tetrachloride, chloroform, 2,4,5-T (a herbicide), and ethylene dibromide (a fumigant). c. Miscellaneous, including carbon disulfide (solvent for waxes and resins) and ethylene glycol (automobile antifreeze).

2.3.1.7 Blood The blood system can be damaged by agents that affect blood cell production (bone marrow), the components of blood (platelets, red blood cells, and white blood cells), or the oxygen-carrying capacity of red blood cells.

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Arsenic, used in pesticides and paints (http://www.texanlab.com/documents/downloads/ 15.pdf); Bromine, used to manufacture gasoline antiknock compounds, ethylene dibromide, and organic dyes; Methyl chloride, used as a solvent, refrigerant, and aerosol propellant; Ionizing radiation, produced by radioactive materials and X-rays is associated with leukemia; Benzene, a chemical intermediate associated with leukemia.

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Aspirin, which inhibits cloning; Benzene, which decreases the number of platelets; Tetrachloroethane, which increases the number of platelets.

Leukocytes (white blood cells) are primarily responsible for defending the body against foreign organisms or materials by engulfing and destroying the material or by producing antibodies. Chemicals that increase the number of leukocytes include naphthalene, magnesium oxide, boron hydrides, and tetrachloroethane. Agents that decrease the number of leukocytes include benzene and phosphorous. Erythrocytes

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(red blood cells) transport oxygen in the blood. Chemicals that destroy (hemolyze) red blood cells include arsine (a gaseous arsenic compound and contaminant in acetylene), naphthalene (used to make dyes), and warfarin (a rodenticide). Oxygen transport. Some compounds affect the oxygen-carrying capabilities of red blood cells. A notable example is carbon monoxide that combines with hemoglobin to form carboxyhemoglobin. Hemoglobin has an affinity for carbon monoxide 200 times greater than that for oxygen. While carbon monoxide combines reversibly with hemoglobin, some chemicals cause the hemoglobin to change such that it cannot combine reversibly with oxygen. This condition is called methemoglobinemia. Some chemicals that can cause this are: G

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Sodium nitrite is an important basic material for the dyeing of textiles and is used in the chemical, pharmaceutical, and metal industries. Aniline: Azo dyes are used in dyeing textile fibers, particularly cotton but also silk, wool, viscose, and synthetic fibers. Nitrobenzene and dinitrobenzene are used in manufacture of dyestuffs and explosives. Mercaptans are used in manufacture of pesticides and as odorizers for hazardous odorless gases. 2-Nitropropane is used as a solvent (http://www.texanlab.com/documents/downloads/15. pdf).

2.3.2 Classification of factors influencing toxicity Factors related to the concern of chemical G

G

G

G

G

G

G

G

G

G

Chemical composition (salt, free base, etc.), Physical characteristics (particle size, liquid, solid, etc.), Physical properties (volatility, solubility, etc.), Presence of impurities, Break down products, Carrier, Exposure dose, Concentration, Route of exposure (ingestion, skin absorption, injection, inhalation), and Duration of exposure.

Factors related to the person exposed which addresses. Factors related to environment which addresses (air, water, food, soil); additional chemical present (synergism, temperature); air pressure (http://www.pulcra-chemicals.com/zdhc). G

Routes of exposure

Biological results can be different for the same dose, depending on whether the chemical is inhaled, ingested, applied to the skin, or injected. Natural barriers impede the intake and distribution of material once in the body. These barriers can attenuate the toxic effects of the same dose of a chemical. The effectiveness of these barriers is partially dependent upon the route of entry of the chemical.

Chemical hazards in textiles

2.4

35

Human toxicity

The human toxicity potential (HTP) is a quantitative toxic equivalency potential (TEP) that has been introduced previously to express the potential harm of a unit of chemical released into the environment. HTP includes both inherent toxicity and generic source-to-dose relationships for pollutant emissions. Three issues associated with the use of HTP in life cycle impact assessment are evaluated here. First is the use of regional multimedia models to define source-to-dose relationships for the HTP. Second is uncertainty and variability in source-to-dose calculations. And third is model performance evaluation for TEP models. Using the HTP as a case study, we consider important sources of uncertainty/ variability in the development of source-to-dose models—including parameter variability/uncertainty, model uncertainty, and decision rule uncertainty. Once sources of uncertainty are made explicit, a model performance evaluation is appropriate and useful and thus introduced. Model performance evaluation can illustrate the relative value of increasing model complexity, assembling more data, and/or providing a more explicit representation of uncertainty. This work reveals that an understanding of the uncertainty in TEPs as well as a model performance evaluation are needed to (1) refine and target the assessment process and (2) improve decision making. The emission of some substances (such as heavy metals) can have impacts on human health. Assessments of toxicity are based on tolerable concentrations in air and water, air quality guidelines, tolerable daily intake, and acceptable daily intake for human toxicity. Impacts to air and water have been combined in the rating tables. Characterization factors, expressed as HTPs, are calculated using USES-LCA, as with ecotoxicity, which describes fate, exposure, and effects of toxic substances for an infinite time horizon. For each toxic substance HTPs are expressed using the reference unit, kg 1,4-dichlorobenzene (1,4-DB) equivalent (Shukla, 2006).

2.4.1 Ecotoxicity Ecotoxicity to fresh water and land: kg 1,4 dichlorobenzene (1,4-DB) eq. Environmental toxicity is measured as two separate impact categories that examine fresh water and land respectively. The emission of some substances, such as heavy metals, can have impacts on the ecosystem. Assessment of toxicity has been based on maximum tolerable concentrations in water for ecosystems (Kebschull). Ecotoxicity potentials are calculated with the USES-LCA, which is based on EUSES, the EU’s toxicity model. This provides a method for describing fate, exposure, and the effects of toxic substances on the environment (Mathur et al., 2005). Characterization factors are expressed using the reference unit, kg 1,4-dichlorobenzene equivalent (1,4-DB), and are measured separately for impacts of toxic substances on: G

G

Freshwater aquatic ecosystems Terrestrial ecosystems

Table 2.1

36

Chemical Management in Textiles and Fashion

Table 2.1 Method impact categories and their units expressed in equivalence factor (Hatch and Maibach, 2000). Impact category

Unit

Abiotic depletion Acidification Eutrophication Global warming (GWP100) Ozone layer depletion (ODP) Human toxicity Freshwater aquatic ecotoxicity Marine aquatic ecotoxicity Terrestrial ecotoxicity Photochemical oxidation

kg Sb eq kg SO2 eq kg PO4 eq kg CO2 eq kg CFC-11 eq kg 1,4-DB eq kg 1,4-DB eq kg 1,4-DB eq kg 1,4-DB eq kg C2H4 eq

2.4.2 Environmental factors Young et al. developed environmental impact factors calculated using the waste reduction algorithm (Manzini, 1996). These factors encompass (1) physical potential impacts (acidification of soil, greenhouse enhancement, ozone depletion, and photochemical oxidant depletion), (2) human toxicity effects (air, water, and soil), and (3) ecotoxicity effects (aquatic and terrestrial) (Hatch and Maibach, 2000). The important parameters are as follows: G

G

G

G

G

G

G

G

Human toxicity potential by ingestion, Human toxicity potential by exposure, both dermal and inhalation, Terrestrial toxicity potential, Aquatic toxicity potential, Global warming potential, Ozone depletion potential (ODP), Photochemical oxidation potential, and Acidification potential.

As the preceding names imply, detailed information is needed about the impact potential of chemicals to estimate these parameters. Currently such detailed information is not available for most of the chemicals used in the chemical and allied industries (Nadiger, 2001). Several tools and methodologies are available for measuring environmental impact, including . G

G

G

G

G

G

G

G

Life cycle assessment, Material input per unit service (MIPS), Environmental risk assessment, Materials flow accounting (MFA), Cumulative energy requirements analysis (CERA), Material input per delivered function analysis (MFA), Environmental input-output analysis, Eco-design,

Chemical hazards in textiles

G

G

G

37

Life-cycle costing, Total cost accounting, and Cost-benefit analysis.

Long-term effects of chemicals on the ecology and fauna are very difficult to obtain. Thus we have to make several assumptions and approximations while using these impact factors. In addition, the line connecting the indicators to the environment and the economic growth and/or social development needs to be developed. These indicators should also be relevant to diverse groups such as industries, public, NGOs, government agencies, etc. There are several unifying or common factors, such as the availability of resources, energy, land, water, clean air, and environmental diversity. Examples of indicators based on this principle include MIPS, MFA, the energy-based indices such as CERA and the energy-based sustainability index developed by Dewulf et al. The area of land and that of water are limiting factors that can be used to develop a sustainable process index. For example, the electronic and semiconductor industries require large quantities of clean water, and the choice of the location will depend on that water’s uninterrupted availability. Depletion of groundwater could be a disadvantage for setting up such manufacturing plants. The petrochemical and oil industries require large areas of land, preferably near the coastal area. Atomic power plants are located near the coast, so that the seawater is used for cooling the reactor core. Industries would like to evaluate technologies using money-based indices such as total cost accounting, cost-benefit analysis, shareholders’ value, and value addition. Countries below the poverty line would not mind compromising on many of these resources to provide enough food, clothing, and shelter to its residents. That is one of the reasons why several hazardous manufacturing industries have been relocated in Third World countries in the 1980s (Manzini, 1996)

2.5

Impact of restricted substance list in chemical management

The restricted substance list (RSL) was created by a special working group of the American Apparel & Footwear Association’s (AAFA) Environmental Task Force (https://www.academia.edu/5284474/ Adoption_of_Sustainable_Risk_Management_A_Study_of_Chemical_Exposure_in_Textile_Industry_in_Nigeria). The RSL is intended to provide apparel and footwear companies with information related to regulations and laws that restrict or ban certain chemicals and substances in finished home textile, apparel, and footwear products around the world. The RSL was developed to serve as a practical tool to help those individuals in textile, apparel, and footwear companies and their suppliers, responsible for environmental compliance throughout the supply chain, to become more aware of various national and international regulations governing the amount of substances that are permitted in finished home textile, apparel, and footwear products. The RSL will be updated on a regular basis and will be

38

Chemical Management in Textiles and Fashion

supplemented with additional resources to help officials in these companies undertake responsible chemical management practices in the afore-mentioned finished products (https://onlinelibrary.wiley.com/doi/abs/10.1111/j.1600-0536.1991. tb01718.x).

2.5.1 Methodology The RSL includes only those materials, chemicals, and substances that are restricted or banned in finished home textile, apparel, and footwear products because of a regulation or law. In each case, the RSL identifies the most restrictive regulation. The RSL does not include regulations that restrict the use of substances in production processes or in the factory; rather the focus is on whether or not the substance can be found in finished home textile, apparel, and footwear products at a certain level (https://onlinelibrary.wiley.com/doi/abs/10.1111/j.1478-4408.1969.tb02865.x).

2.5.1.1 Structure For each substance, the RSL identifies the following features: 1. CAS number 2. Common chemical or color name 3. Information on the restriction/limit on final product or tested component a. Restriction level, b. Country where that restriction/limit is found, c. Test method (where no test method is stipulated in the regulation, the GAFTI column may suggest one), d. Other countries that maintain equal or less restrictions, and e. Comments (if applicable).

2.5.1.2 What is included and what is not The RSL is not intended to address product safety regulations outside the chemical management area—such as Consumer Product Safety Commission (CPSC) regulations related to small parts. Moreover, it is not structured to cover toys, automotive textiles, or other industrial textiles. This list (https://www.twosistersecotextiles.com/ pages/azo-dyes) does not include restrictions related to use of substances in packaging or related materials. The following legislation is not listed because there are no regulatory concentration limits but may warrant evaluation for applicability. The US Environmental Protection Agency (EPA), following the Montreal Protocols, promulgated legislation on ozone-depleting compounds. Class I and Class II listed chemicals used in the process of manufacturing of product or packaging requires special labeling as detailed in the regulation. Residuals of the chemical components in the product or package are not necessary to trigger the requirement. Minor usage in textiles as a spot cleaner is acceptable (http://www.greenpeace.org/ eastasia/campaigns/toxics/science/eleven-flagship-hazardous-chemicals/; https:// www.researchgate.net/project/Green-Chemistry-16).

Chemical hazards in textiles

39

California Proposition 65 requires a “clear and reasonable” warning label for all products sold in the state of California containing one or more chemicals known to the state to cause cancer or reproductive toxicity. Labeling requirements are dependent on consumer exposure to the chemical [measured in micrograms (µg)/day] not the concentration in the product. To comply with the law, manufacturers must either ensure that consumer exposure to regulated chemicals in their products does not exceed the established safe harbor levels or label their products. Chemical nomenclature can take several forms. Technical chemical names may take numerous forms. It is the responsibility of the user to verify synonyms of any regulated chemicals referenced. It is possible that regulated components may be present in raw materials below the levels that require reporting on material safety data sheets (MSDS). Care should be taken to verify the presence of all regulated ingredients regardless of the concentration (http://www.jocpr.com/articles/ study-the-effect-of-the-duration-exposure-for-lethal-and-sublethal-concentrations-oforganophosphorus-chlorpyrifos-pesti.pdf; https://nepis.epa.gov/Exe/ZyNET.exe/ 2000GIVM.txt?ZyActionD 5 ZyDocument&Client 5 EPA&Index 5 1995%20Thru %201999&Docs 5 &Query 5 &Time 5 &EndTime 5 &SearchMethod 5 1 &Toc Restrict 5 n&Toc 5 &TocEntry 5 &QField 5 &QFieldYear 5 &QFieldMonth 5 &QFieldDay 5 &UseQField 5 &IntQFieldOp 5 0&ExtQFieldOp 5 0&XmlQuery 5 &File 5 D%3A%5CZYFILES%5CINDEX%20DATA%5C95THRU99%5CTXT% 5C00000017%5C2000GIVM.txt&User 5 ANONYMOUS&Password 5 anonymous &SortMethod 5 h%7C-&MaximumDocuments 5 1&FuzzyDegree 5 0 &Image Quality 5 r75g8/r75g8/x150y150g16/i425&Display 5 hpfr&DefSeekPage 5 x&Search Back 5 ZyActionL&Back 5 ZyActionS&BackDesc 5 Results%20page&Maximum Pages 5 1&ZyEntry 5 134&slide) (Table 2.2).

2.6

Regulatory aspects

Textile industry persists globally and is a major economic contributor. The employment opportunities are numerous in the textile industry. The textile and apparel supply chain is long and involves many complicated production processes. Now, the making of textiles has become dangerous, which urged the government to manage the textile industry with specific laws and regulations. The laws and regulations vary from country to country across the world.

2.6.1 Textile regulation by different countries G

European Union (EU) REACH Regulation No 1907/2006 Annex XVII Textile Regulation (EU) No 1007/2011 Short-chain chlorinated paraffins (SCCPs) Regulation (EC) No. 850/2004 and Regulation (EU) No. 519/2012 Substances of very high concern (SVHC) in candidate list G

G

G

G

40

Chemical Management in Textiles and Fashion

Table 2.2 List of chemical substances under the RSL. Change log from RSL 20 to RSL 21 Arylamines Asbestos Dioxins and Furans Disperse dyes Flame retardants Fluorinated greenhouse gases Metals Misc. Organotin compounds Pesticides Phthalates Solvents Appendix I: reporting Appendix II: labeling

G

G

G

G

G

G

G

G

G

G

G

G

G

as specified under RSL 20 Update of PFOS regulation to (EU) 2019/1021 on persistent organic pollutants (recast) as specified under RSL 20 as specified under RSL 20 Added South Korea (Standards Notice No. 2019-0352) on BBP, DBP, and DEHP as specified under RSL 20 Addition of five new SVHC chemicals to EU REACH Addition of Colorado Revised Statutes 24-33.5-1234 on PFAS in firefighting personal protective equipment

Canada CCPSA, restriction of lead on surface coating material in children’s product (SOR/ 2005-109) CCPSA, restriction of lead content in children’s product (SOR/2010-273) CCPSA, restriction of phthalates in children’s product (SOR/2010-298) United States Consumer Product Safety Act (CPSA) Consumer Product Safety Improvement Act (CPSIA) Federal Hazardous Substances Act (FHSA) Toxic Substances Control Act (TSCA) Japan Act on Control of Household Products Containing Harmful Substances (Act No. 112 of October 12, 1973) India Textiles (Consumer Protection) Regulation 1988 Environment (Protection) Act, 1986: prohibition of 112 azo- and benzidine-based dyes China GB 18401 National General Safety Technical Code for Textile Products GB 31701 The Safety Technical Code for Infants and Children Textile Products GB 5296.4 Instructions for Use of Products of Consumer Interest

Part 4: Textiles and Apparel GB 20400 Leather and Fur

Limit of Harmful Matter GB 21550 The Restriction of Hazardous Materials in Polyvinyl Chloride Artificial Leather G

G

as specified under RSL 20 as specified under RSL 20 as specified under RSL 20 as specified under RSL 20 as specified under RSL 20 as specified under RSL 20

G

G

G

G

G

Chemical hazards in textiles

2.7

41

Hazard control through regulatory norms

Textile materials mean the different fiber, yarn, and fabric materials used in the manufacture of apparel, home textiles, technical textiles, etc. These materials are of different types and find various end uses. Classification of these materials is complex and for the purpose of testing the eco-friendliness and fixing the safe limits for certain hazardous substances are provided by Oeko-Tex Standard 100 categorized under four product classes as shown in Table 2.3. This classification aids in fixing the safer limits for the use or presence of hazardous substances in the product, for example, the product class I sets very stringent regulation and lower limits of hazardous substances since this includes products for babies and toddlers who are very sensitive and delicate. Product class II is also crucial because they are in direct contact with the skin; longer exposure may increase the impact of hazards (https://www.slideshare.net/gauravhtandon1/environmentaltoxicology-32480341). Product classes III and IV are comparatively liberal in setting limits since their skin contact and exposure to the consumer are less compared to product classes I and II (https://books.google.co.in/books?id 5 9BnHzvCeZPQC &pg 5 RA6-PA22&lpg 5 RA6-PA22&dq 5 %22The 1 respiratory 1 tract 1 is 1 the 1 only 1 organ 1 system 1 with 1 vital 1 functional 1 elements 1 in 1 constant, 1 direct 1 contact-with 1 the 1 environment.%22&source 5 bl&ots 5 CCPES7cL 1h&sig 5 AC fU3U3RdYHbipmtXdMJKSo4-_ethzTVtw&hl 5 en&sa 5 X&ved 5 2ahUKEwjS5LiGu 9flAhUKso8KHZN9CI8Q6AEwAHoECAQQAQ#v 5 onepage&q 5 %22The%20 respiratory%20tract%20is%20the%20only%20organ%20system%20with%20vital %20functional%20elements%20in%20constant%2C%20direct%20contact-with%20 the%20environment.%22&f 5 false).

Table 2.3 Classification of textile products by Oeko-Tex Standard 100. Product class

Description

Examples

I

Textiles and textile toys for babies and small children up to the age of three Textiles which, when used as intended, have a large part of their surface in direct contact with the skin Textiles which, when used as intended, have no or only a little part of their surface in direct contact with the skin Furnishing materials for decorative purposes

Underwear, romper suits, bed linen, bedding, soft toys, etc. Underwear, bed linen, terry cloth items, shirts, blouses, etc.

II

III

IV

Jackets, coats, facing materials, etc. Table linen and curtains, textile wall and floor coverings, etc.

42

Chemical Management in Textiles and Fashion

2.7.1 Hazard management in textiles Importances of hazard management in textiles are as follows: 1. 2. 3. 4. 5.

Ensures safety of consumer. Aids in eco-labeling of products. Serves as an eco-passport for international trade of textile and apparel products. Gives indication of the pollution level. Helps in the eco-management of the textile industry.

2.8

Hazard control and management

2.8.1 Residual pesticides Pesticides are widely used in cotton cultivation and wool production (https://ehs. unl.edu/documents/tox_exposure_guidelines.pdf). Though the fiber undergoes many processes to be made into a garment, the garment contains residual pesticides. When exposed to direct skin contact, these pesticides have a tendency to enter the human body through the pores in the skin and also orally, in case of sucking of garments by children (https://books.google.co.in/books?id 5 9BnHzvCeZPQC &lpg 5 RA6-PA25&ots 5 CCPES7dG-e&dq 5 %22Act%20directly%20on%20normal%20 skin%20at%20the%20site%20of%20contact%20(if%20chemical%20is%20in%20 sufficient%20quantity%20for%20a%20sufficient%20length%20of%20time.%22&pg 5 PP1#v 5 twopage&q&f 5 false; https://www.scribd.com/doc/316760737/Tox-ExposureGuidelines). Then the poisoning occurs with symptoms such as headache, nausea, dizziness, and vomiting. Hence the use of pesticides is regulated in many countries. Certain chlorinated pesticides such as aldrin, dieldrin, chlordane, endrin, heptachlor, hexachlorobenzene, mirex, toxaphene, and hexachlorocyclohexane are banned from use (https://link.springer.com/article/10.1007/BF02977846). A study by Zameer Ul Hassan et al. used Soxhlet extraction method and ultrasound-assisted extraction for extraction of residual pesticides from cotton fiber. Then the extract was analyzed using biosensor toxicity analyzer by the measurement of bioelectrical signals caused by enzymatic inhibition of acetyl cholinesterase (AChE) for the detection of pesticides. Cryogenic homogenization was carried out for sample pretreatment (https://www.openlca.org/wp-content/uploads/2016/08/ LCIA-METHODS-v.1.5.5.pdf).

2.8.2 Phthalates Phthalates are group of chemicals used as plasticizers to improve the softness and flexibility of plastics, especially PVC. They are esters of ortho-phthalic acid and are used in making accessories, decorative items, and plastic packaging. Phthalates are reported to be carcinogenic and endocrine disruptors in humans and animals. The use of phthalates is restricted in plasticized materials in toys and childcare

Chemical hazards in textiles

43

Table 2.4 List of restricted phthalates. Name (phthalate)

CAS number

Di-(2-ethylhexyl) phthalate (DEHP) Dibutyl phthalate (DBP) Butyl benzyl phthalate (BBP) Di-isononyl phthalate (DINP) Di-isodecyl phthalate (DIDP) Di-n-octyl phthalate (DNOP) Di-isobutyl phthalate (DIBP) Di-isohexyl phthalate (DIHP) Dipentyl phthalate (DPP) Dimethoxyethyl phthalate (DMEP)

117-81-7 84-74-2 85-67-2 28553-12-0 and 68515-48-0 26761-40-0 and 68515-49-1 114-84-0 84-69-5 68515-50-4 131-18-0 117-82-8

articles and apparel with plasticized materials (https://studyres.com/doc/2661173/ characterisation). BS EN 15777:2009 was the first method for determination of phthalate content in textile products. Later in 2014, a new standard ISO 14389 was issued and it supersedes the old standard BS EN 15777:2009. The old method employed Soxhlet extraction with hexane as solvent, while the new method employs ultrasonic extraction method with tetrahydrofuran (THF) solvent. The extraction time is 1 and 4 h for the old and new methods, respectively. Then the extract is analyzed using gas chromatography
mass spectrometry (GC-MS) and the phthalate content is calculated based on the ratio of the mass of the print or coating to the mass of the whole sample (Table 2.4).

2.8.3 Chlorinated phenols Chlorinated phenols are a group of substances with 1
5 chlorines covalently bonded to phenol and they include all isomers of mono-, di-, tri-, tetra-, and pentachlorophenol (http://www.greenpeace.org/eastasia/campaigns/toxics/science/ eleven-flagship-hazardous-chemicals/). They are widely used as pesticides and preservatives for textiles. They are found in textile and leather materials, dyes, and print pastes. Pentachlorophenol (PCP) and tetrachlorophenol (TeCP) are among the widely used chlorophenols and find application in making of apparel, footwear, and accessories (https://www.researchgate.net/project/Green-Chemistry16). Pentachlorophenol (CAS No. 87-86-5) is used as a preservative in textiles to protect from fungus, mold, and insects. It finds major use in sizing starch preparation for warp beam. It is also used as a preservative in pigment emulsions, adhesives, glues, vegetable, and mutton tallow. PCP is used as a biocide when textiles are to be stored or transported in humid conditions. Traces of PCP may be found in elastic rubber accessories and natural rubber latex
based finishes. PCP released from products and dispersed into the environment can result in human exposure by breathing, eating, drinking, or absorbing the substance through the skin.

44

Chemical Management in Textiles and Fashion

Pentachlorophenol is very toxic, persistent, and bio-accumulates in organisms. PCP is classified as “toxic in humans in contact with skin and if swallowed” and as “very toxic by inhalation.” Damages have been recorded in the cardiovascular system, blood, and liver when inhaled by humans. Tests on animals have shown that PCP has impacts on the immune system and central nervous system. It has also been classified as a carcinogen. Additionally, PCP is very toxic to many fish species. Dioxins and furans are formed as by-products in the production of PCP, which is the reason products containing PCP are usually contaminated with dioxins and furans. PCP is an important source of emission of dioxins, furans, and hexachlorobenzene (https://www.sciencedirect.com/topics/engineering/human-toxicity-potential). All these three substance groups have serious effects on health and the environment and are therefore strictly regulated. The processes involved in the analysis of PCP are extraction, purification, separation, identification, and quantification. ISO 17070 is a standard method for determination of PCP in leather and no standard method is available for textiles. A study by Su and Zhang (2011) devised a method for accurate measurement of PCP in textiles by liquid chromatography- mass spectrometric detection using isotope dilution (LC-IDMS). Samples were pretreated with acid and then with n-hexane and then measured based on isotope dilution LC-IDMS. The precision of this method is in the range of 0.80%
1.40%. The method can trace to mass (https://www.sciencedirect.com/topics/engineering/environmental-impact-factor).

2.8.4 Formaldehyde Formaldehyde is a volatile compound that is naturally present in small quantities. Human blood is said to have traces of formaldehyde. When formaldehyde is present in large quantities, it may cause skin allergy or irritation, respiratory inflammation, and eye irritation. The uses of formaldehyde in textiles include antishrinkage treatments, resin finishes for wrinkle or crease resistance, and as dye fixing agents. Formaldehyde was first restricted in Japan, and then Finland regulated the use with limiting values. Now, many European countries have limited the use of formaldehyde. Two different test methods are performed to test the formaldehyde and are expressed as either free or hydrolyzed formaldehyde or released formaldehyde. Free formaldehyde is a measure of the amount of formaldehyde present in the textile material, while released formaldehyde is a measure of the amount of formaldehyde released by the material into the atmosphere. A common method employed for the determination of free formaldehyde in textile material is pentane-2,4-dione method, which is also known as acetyl acetone method. The test procedure is as follows: G

G

Prepare standard formaldehyde solution by diluting 2.5 mL of standard solution (containing 1500 µg/mL formaldehyde) with water to 50 mL in a volumetric flask. This solution contains 75 µg/mL of formaldehyde. From the test sample prepare two test specimens that weigh 2.5 g each at an accuracy of 10 mg. Cut the test specimen into small pieces and transfer into a 250 mL flask with stopper.

Chemical hazards in textiles

G

G

G

G

45

Add 100 mL of water to the flask and close tightly with the stopper. Place the flask in an ultrasonic bath at 40 C for 30 min. Then filter the solution and collect in another flask. Take 5 mL of the filtered solution in a test tube and 5 mL of standard formaldehyde solution in other test tubes. Add 5 mL of acetyl acetone reagent into each tube and shake well. Place the test tubes in a water bath at (40 6 2) C for (30 6 5) min. Then keep at ambient temperature for (30 6 5) min. Add 5 mL of acetyl acetone reagent solution to 5 mL of water and treat it the same way as the blank reagent. Measure the absorbance values in a 10 mm absorption cell at a wavelength of 412 nm against water in a UV-Vis spectrophotometer and report the detected formaldehyde in mg/kg. If the concentration of formaldehyde is less than 20 mg/ kg, then the result is reported as “not detectable.”

The method used to test the released formaldehyde (during storage and ironing) is steam absorption or gas phase method. The procedure to test the released formaldehyde by vapor absorption method is as follows: G

G

G

Take 1.0 g of test specimen from the textile sample and put it in a glass flask. Add water to the jar and seal it. Place the jar in an oven at 49 C for 20 h. Then the extract is analyzed for the amount of formaldehyde vapor released by the material in water (https://www.sciencedirect.com/topics/earth-and-planetary-sciences/ozonedepletion-potential).

2.8.5 Extractable heavy metals A heavy metal is a chemical element whose specific gravity is at least five times the specific gravity of water. Heavy metals are employed in various industrial applications such as the manufacture of pesticides, batteries, alloys, electroplated metal parts, textile dyes, and steel. It is manageable when smaller amount of these heavy metals are present in the environment, while larger amounts may cause acute or chronic toxicity. Toxicity caused by heavy metals includes damage in central nervous function and damage of vital organs such as lungs, kidneys, and liver. Longterm exposure results in neurological degenerative processes similar to Alzheimer’s, Parkinson’s disease, muscular dystrophy, and multiple sclerosis. Allergy and carcinogenicity are also caused by repeated exposure to heavy metals. Traces of heavy metals are often present in different textile processes such as metal complex dyes, dye stripping agents, oxidizing compounds, antifungal, odorpreventive agents, and mordant. The restricted heavy metals in textiles are antimony, arsenic, barium, cadmium, chromium, cobalt, copper, lead, mercury, nickel, selenium, tin, and zinc. Heavy metals are the most commonly legislated chemicals globally. Different analytical methods can be applied for the determination of heavy metals present in and on textile materials, in textile wastewaters, as well as in different reagent solutions used in textile processing. The process involves two basic steps: 1. Microwave digestion or extraction by acidic artificial perspiration solution/saliva solution 2. Analysis

46

Chemical Management in Textiles and Fashion

The test procedure for extraction process is as follows: G

G

G

G

G

G

G

G

G

G

G

Dry the textile sample in an oven at 105 C 6 2 C at least for 4 h. Prepare the artificial perspiration solution as per the standard EN ISO 105-E04: In a 1000 mL glass flask, take 1000 mL of water and accurately weigh the following chemicals and add to the water and mix well: 0.5 g L-histidine monohydrochloride 1-hydrate, 5.0 g sodium chloride, and 2.2 g sodium dihydrogen phosphate 2-hydrate. Adjust the pH of the solution to 5.5 6 0.2 with dilute sodium hydroxide or dilute hydrochloric acid. From the test sample cut a specimen of 1 g and record the mass to the nearest 1 mg. If the test sample is heterogeneous, different parts are included as a composite specimen with equal parts of the material. Take the test specimen in a 100 mL flask and add 50 mL of the prepared artificial perspiration solution and shake by hand to ensure complete wetting. Then the specimen is shaken for 1 h at (37 6 2) C in a shaker. Set the shaking frequency to 60 cycles per minute if using a horizontal shaker or 30 cycles per minute if using a circular shaker. A magnetic stirrer may also be used as an alternative. After the specified time, filter the extract so that solid textile particles and fluff are removed. The filtered solution is analyzed by microwave plasma atomic emission spectroscopy (https://www.slideshare.net/gauravhtandon1/environmental-toxicology-32480341).

The test procedure for microwave digestion method is as follows: G

G

From the test sample, prepare a specimen of 1 g and digest with 6 mL of 65% nitric acid (HNO3) and 2 mL of 30% hydrogen peroxide (H2O2) in a microwave digestion system and diluted to 10 mL with deionized water. The advantage of microwave digestion is that it is a closed system. Then the digested solution is analyzed by atomic absorption spectrometry (AAS) and the concentration of heavy metals is expressed in µg/g or mg/kg (http://www.urbnvendor. com/us/wp-content/uploads/sites/2/2015/06/AAFA-RSL-18th-Edition.pdf).

2.8.6 Nickel Nickel is used in metal accessories such as zippers, rivets, belt buckles, buttons, and fashion jewelry. It is a highly allergenic heavy metal. Presence of nickel may pierce the skin and cause skin allergy such as contact dermatitis and hence the release of nickel by metal accessories is regulated and restricted. Test for nickel is done by three different ways as follows: 1. Nickel release per day 2. Nickel release per week (µg/cm2) 3. Nickel spot test

The original standard EN 1811:2011 was found to have uncertainty in measurement and hence the standard was amended on January 15, 2015 as EN 1811:2011 1 A1:2015. The test procedure is as follows: G

The material to be tested is first cleaned and degreased.

Chemical hazards in textiles

G

G

47

Artificial sweat solution is prepared and the material is placed in it and the temperature maintained at 30 C for a week (168 h). Then the extract is analyzed using AAS or inductively coupled plasma spectroscopy.

In case of metal-coated items, the release value should not exceed 0.5 µg/cm2/ week for a period of 2 years of normal use of the item. The method for simulating 2 years of normal wear is defined by the standard EN12472:2009. Another method for nickel test uses the standard PD CR 12471:2002. Screening tests for nickel release from alloys and coatings in items that come into direct and prolonged contact with the skin. The property of the nickel iron that forms colored complex, when comes in contact with dimethylglyoxime or dithiooxamide, is made use of in testing the nickel. To simulate the influence of sweat when in direct contact with the skin the material is pretreated with artificial sweat. This is a quick screening method that provides guidance in evaluation of nickel release (https:// www.aafaglobal.org/AAFA/Solutions_Pages/Restricted_Substance_List).

2.8.7 Dimethylformamide N,N-Dimethylformamide (DMF) is a polar aprotic solvent, miscible with water and majority of organic fluids. DMF is used in production of acrylic fibers and polyurethane products. It is also used in the manufacture of artificial leather, films, and coatings. DMF is harmful if inhaled and while in direct contact with the skin. It is classified as a carcinogenic, mutagenic, and reprotoxic substance and is being included in the candidate list of SVHCs (https://www.sciencedirect.com/topics/ earth-and-planetary-sciences/photochemical-oxidant).

2.8.8 Chlorinated organic carriers Chlorinated organic carriers are a class of compounds comprising of chlorotoluenes and chlorobenzenes with different substitution patterns of chlorine substitution. These compounds are used as carriers in disperse dyeing of synthetic fibers such as polyester acetates, and polyacrylic polyamides. These substances are toxic and found to affect the nervous system and may cause skin irritation. They may induce liver malfunction and irritation to mucus membrane. Hexachlorobenzene is classified as carcinogenic group 2 and 1,4-dichlorobenzene is classified as carcinogenic group 3. Table 2.5 lists the chlorinated organic carriers used in textile dyeing (https://studylib.net/doc/18335875/aafa-restricted-substances-list--rsl-) (Table 2.5). The method DIN 54232 employs extraction of chlorinated organic carriers from textiles by methylene chloride and detected with GC-MS.

2.8.9 Hazard management in textile industry To manage risks, the first thing is to identify the hazards that could give rise to risks, followed by eliminating the risks as practicable. If it is not reasonably practicable to eliminate the risk, then minimize the risk. Implementing control measure is one of the important steps in managing risks in a factory (https://mhdetox.com/pcp/).

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Table 2.5 List of chlorinated organic carriers. Compounds

CAS number

2-Chlorotoluene 3-Chlorotoluene 4-Chlorotoluene 2,3-Dichlorotoluene 2,4-Dichlorotoluene 2,5-Dichlorotoluene 2,6-Dichlorotoluene 3,4-Dichlorotoluene 2,3,6-Trichlorotoluene 2,4,5-Trichlorotoluene Pentachlorotoluene 1,2-Dichlorobenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2,3-Trichlorobenzene 1,2,4-Trichlorobenzene 1,3,5-Trichlorobenzene 1,2,3,4-Tetrachlorobenzene 1,2,3,5-Tetrachlorobenzene 1,2,4,5-Tetrachlorobenzene Pentachlorobenzene Hexachlorobenzene

95-49-8 108-41-8 106-43-4 32768-54-0 95-73-8 19398-61-9 118-69-4 95-75-0 2077-46-5 6639-30-1 877-11-2 95-50-1 541-73-1 106-46-7 87-61-6 120-82-1 108-70-3 634-66-2 634-90-2 95-94-3 608-93-5 118-74-1

It is important to remember that if you are not competent of any aspect of managing chemicals safely in your workplace, you must involve a competent person who can guide you on understanding the key elements of chemicals management. There are three basic steps for managing risks of chemicals: 1. Identify the chemicals you have in your workplace and the hazards associated with them. 2. Assessing the risks from chemicals used in processes and workplace. 3. Control measures to mitigate risk: Include various recognized control measures to eliminate or reduce the risks.

While managing risks, following factors should be taken into considerations: G

G

G

Intrinsic hazardous properties of chemicals used in the processes and workplace; Potentially hazardous reaction between two chemicals (e.g., sodium hydrosulfite, when it comes in contact with moisture, can lead to a high risk of explosion or fire since it generates oxygen for combustion based on a chemical reaction with moisture); Workplace activities associated with hazardous chemical.

The control measures are required to be implemented in a factory to ensure chemical safety. The recommended hierarchy of control measures is given here as a guideline.

Chemical hazards in textiles

1. 2. 3. 4. 5.

49

Eliminate the hazardous chemical. Substitute with a less hazardous chemical. Install engineering controls. Put administrative controls in place. Use PPE.

2.8.10 Finding information about chemical hazards The most important sources of information on the hazards of your chemicals are the label and the safety data sheet (SDS). Labels: It should be ensured that any chemical is supplied with a label attached on container. The label gives information on the chemical or product name, the chemical hazards and the precautions you should take into account to ensure safe handling and use (http://www.eftasurv.int/media/notification-of-dtr/2010-9017Impact-assessment-.pdf). SDSs: It is must to have a SDS for each hazardous chemical that is used in the process and workplace. It is your duty to ensure that chemical supplier provides you an SDS for chemical product. These SDSs should be kept at identifiable place where it can be accessed from employees and emergency services in case of chemical accident (http://www.asbestosremovalz.com/asbestos/). You must ensure that all employees are aware of where the SDSs are stored and they have read and understood the SDS. The management should ensure that periodic trainings are conducted to impart knowledge on SDS and how to interpret the same for hazard identification and measures to mitigate these hazards (https://www. scribd.com/document/156713353/TN2-Determination-of-Formaldehyde-in-Textile). SDS should: G

G

G

G

G

G

G

G

Be provided for all chemicals used at the workplace, especially those which are classified as hazardous. Contain 16 headings/sections. Be prepared by a competent person (MSDS/SDS-author). Be clear and understandable. Be provided free of charge. Be provided no later than at the time of first delivery of chemical product. Be provided upon update or revision to every user. Be dated and the pages numbered.

Chemical safety is important to prevent hazards at source by elimination and substitution of hazardous chemicals to the best extent possible. If this is not possible, protective measures such as PPE, storage measures, and engineering controls should be put in place to minimize worker’s exposure to these hazards (https:// www.blcchemicaltesting.com/chemical-testing/heavy-metals-testing-and-analysis/). Developing chemical safety program is must to prevent risks from hazardous chemicals. Some of the important activities of chemical safety program may include (https://www.scribd.com/document/72123157/En-CR12471-1996-Screening-Testsfor-Nickel-Release-From-Alloys-and-Coatings-in-Items-That-Come-Into-Direct-andProlonged-Contact-With-the-Skin):

50

G

G

G

G

Chemical Management in Textiles and Fashion

Mapping chemicals for hazards, Planning actions on hazards, Communication of hazards (labeling, training on SDS), and Implementing standard operating procedures.

Mapping of chemical hazards is beneficial because a dynamic database of all chemicals used in the factory is developed, and this database is very useful to identify the hazardous chemicals used in high volumes (https://www.tuv-sud.in/in-en/ resource-centre/publications/technical-guidance-insights/technical-guidance-onchlorinated-organic-carriers). Mapping of chemicals helps to identify the missing documents such as MSDS/SDS and supplier declaration. Duplication of chemicals can be avoided by identifying the unnecessary chemicals used in the processes. As a result of mapping of chemicals, a clear action plan to phase out hazardous chemicals can be devised. Communication of hazards of chemicals to workers is the most prioritized activity in chemical safety program. Workers must know the hazards of the chemicals they are handling (https://mnsgarmentsprinting.com/ chemical-safety/). Chemical safety program is a basic need in textile mills and a contributing factor for effective textile production, as with the help of proper systems and programs in place there are less chances of accidents and can improve upon productivity. The textile industry can encourage the implementation of chemical safety programs through spreading awareness and training.

2.9

Conclusion

A clear and profound understanding of the hazards caused by some of the dyes and auxiliaries used in textile production, especially the wet processing sector paved the way to regulations by governments of countries across the globe and introduction of eco-label, both by the government and the industry. Now brands have become conscious about the need for eco-label and eco-friendly products. Thus the testing of textile products for the presence of various banned or regulated substance is accomplished by eco-testing. In conclusion though chemicals and textiles are inseparable, sustainable approaches should be encouraged and implemented throughout the sector. So that, at least in the near future textile industry would be able to achieve a status of nonpolluting and eco-friendly sector. The future definitely will be a darker one if the chemical hazards are out of control in the present. Therefore from the day 1 onward the textile industry should take serious initiatives and reforms for a better and brighter future for everyone.

References Gomathi, E., Rathika, G., Santhini, E., 2017. Physico-chemical parameters of textile dyeing effluent and its impacts with case study. Int. J. Res. Chem. Environ. 7, 17
24.

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Hatch, K.L., Maibach, H.I., 2000. Textile dye allergic contact dermatitis prevalence. Contact Dermatitis. 42, 187
195. http://textilelibrary.blogspot.in/2009/03/disperse-dye.html.. http://www.asbestosremovalz.com/asbestos/.. http://www.centexbel.be/files/brochure-pdf/allergens_eng.pdf.. http://www.eftasurv.int/media/notification-of-dtr/2010-9017-Impact-assessment-.pdf.. http://www.greenpeace.org/eastasia/campaigns/toxics/science/eleven-flagship-hazardous-chemicals/.. http://www.jocpr.com/articles/study-the-effect-of-the-duration-exposure-for-lethal-and-sublethal-concentrations-of-organophosphorus-chlorpyrifos-pesti.pdf.. http://www.pulcra-chemicals.com/zdhc.. http://www.texanlab.com/documents/downloads/15.pdf.. http://www.urbnvendor.com/us/wp-content/uploads/sites/2/2015/06/AAFA-RSL-18th-Edition. pdf.. https://books.google.co.in/books?id 5 9BnHzvCeZPQC&lpg 5 RA6-PA25&ots 5 CCPES 7dG-e&dq 5 %22Act%20directly%20on%20normal%20skin%20at%20the%20site% 20of%20contact%20(if%20chemical%20is%20in%20sufficient%20quantity%20for%20a %20sufficient%20length%20of%20time).%22&pg 5 PP1#v 5 twopage&q&f 5 false.. https://books.google.co.in/books?id 5 9BnHzvCeZPQC&pg 5 RA6-PA22&lpg 5 RA6PA22&dq 5 %22The 1 respiratory 1 tract 1 is 1 the 1 only 1 organ 1 system 1 with 1 vital 1 functional 1 elements 1 in 1 constant, 1 direct 1 contact-with1 the 1 environment.%22&source 5 bl&ots 5 CCPES7cL1h&sig 5 ACfU3U3RdYH bipmtXdMJKSo4-_ethzTVtw&hl 5 en&sa 5 X&ved 5 2ahUKEwjS5LiGu9flAhUKso8 KHZN9CI8Q6AEwAHoECAQQAQ#v 5 onepage&q 5 %22The%20respiratory%20tract %20is%20the%20only%20organ%20system%20with%20vital%20functional%20elements%20in%20constant%2C%20direct%20contact-with%20the%20environment.% 22&f 5 false.. https://ehs.unl.edu/documents/tox_exposure_guidelines.pdf.. https://link.springer.com/article/10.1007/BF02977846.. https://mhdetox.com/pcp/.. https://mnsgarmentsprinting.com/chemical-safety/.. https://nepis.epa.gov/Exe/ZyNET.exe/2000GIVM.txt?ZyActionD 5 ZyDocument&Client 5 EPA&Index 5 1995%20Thru%201999&Docs 5 &Query 5 &Time 5 &EndTime 5 & SearchMethod 5 1&TocRestrict 5 n&Toc 5 &TocEntry 5 &QField 5 &QFieldYear5 &QFieldMonth 5 &QFieldDay 5 &UseQField 5 &IntQFieldOp 5 0&ExtQFieldOp5 0&XmlQuery 5 &File 5 D%3A%5CZYFILES%5CINDEX%20DATA%5C95THRU 99%5CTXT%5C00000017%5C2000GIVM.txt&User 5 ANONYMOUS&Password 5 anonymous&SortMethod 5 h%7C-&MaximumDocuments 5 1&FuzzyDegree 5 0& ImageQuality 5 r75g8/r75g8/x150y150g16/i425&Display 5 hpfr&DefSeekPage 5 x& SearchBack 5 ZyActionL&Back 5 ZyActionS&BackDesc 5 Results%20page& MaximumPages 5 1&ZyEntry 5 134&slide.. https://onlinelibrary.wiley.com/doi/abs/10.1111/j.1478-4408.1969.tb02865.x.. https://onlinelibrary.wiley.com/doi/abs/10.1111/j.1600-0536.1991.tb01718.x.. https://studylib.net/doc/18335875/aafa-restricted-substances-list--rsl-.. https://studyres.com/doc/2661173/characterisation.. https://www.aafaglobal.org/AAFA/Solutions_Pages/Restricted_Substance_List.. https://www.academia.edu/5284474/Adoption_of_Sustainable_Risk_Management_A_Study_ of_Chemical_Exposure_in_Textile_Industry_in_Nigeria.. https://www.blcchemicaltesting.com/chemical-testing/heavy-metals-testing-and-analysis/..

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https://www.blcchemicaltesting.com/chemical-testing/heavy-metals-testing-and-analysis/.. https://www.openlca.org/wp-content/uploads/2016/08/LCIA-METHODS-v.1.5.5.pdf.. https://www.researchgate.net/project/Green-Chemistry-16.. https://www.sciencedirect.com/topics/earth-and-planetary-sciences/ozone-depletionpotential.. https://www.sciencedirect.com/topics/earth-and-planetary-sciences/photochemical-oxidant.. https://www.sciencedirect.com/topics/engineering/environmental-impact-factor.. https://www.sciencedirect.com/topics/engineering/human-toxicity-potential.. https://www.scribd.com/doc/316760737/Tox-Exposure-Guidelines.. https://www.scribd.com/document/156713353/TN2-Determination-of-Formaldehyde-inTextile.. https://www.scribd.com/document/72123157/En-CR12471-1996-Screening-Tests-for-NickelRelease-From-Alloys-and-Coatings-in-Items-That-Come-Into-Direct-and-ProlongedContact-With-the-Skin.. https://www.slideshare.net/gauravhtandon1/environmental-toxicology-32480341.. https://www.tuv-sud.in/in-en/resource-centre/publications/technical-guidance-insights/technical-guidance-on-chlorinated-organic-carriers.. https://www.twosistersecotextiles.com/pages/azo-dyes.. Islam, A., Arun, K.G., 2013. Removal of pH, TDS and color from textile effluent by using coagulants and aquatic/non aquatic plants as adsorbents. Resour. Environ. 3 (5), 101
114. Kebschull, D. The challenge of eco-friendly textiles exports to Germany and Europe: eco friendly textiles
challenges to the textile industry. Textile Committee Publication. Li, X., et al., 2016. Determination of polycyclic aromatic hydrocarbons in textiles by gas chromatography
mass spectrometry. AATCC J. Res. 3 (6), 6
11. Li, Y., et al., 2011. Determination of organotin compounds in textile auxiliaries by gas chromatography-mass spectrometry. Se Pu 29 (4), 353
357. Manzini, B.M., Motolese, A., Conti, A., Ferdani, G., Seidenari, S., 1996. Sensitization to reactive textile dyes in patients with contact dermatitis. Contact Dermatitis 34, 172
175. Mathur, N., Bhatnagar, P., Bakre, P., 2005. Assessing mutagenicity of textile dyes from Pali (Rajasthan) using Ames bioassay. Appl. Ecol. Environ. Res. 4, 111
118. Nadiger, G.S., 2001. Azo ban, econorms and testing. Indian J. Fibre Text. Res. 26, 55
60. Shukla, S.R., 2006. Heavy metals. Colourage LIII (9
12), 66. Sivakumar, K.K., et al., 2011. Assessment studies on wastewater pollution by textile dyeing and bleaching industries at Karur, Tamil Nadu. Rasayan J. Chem. 4 (2), 264
269. Su, F., Zhang, P., 2011. Accurate analysis of trace pentachlorophenol in textiles by isotope dilution liquid chromatography-mass spectrometry. J. Sep. Sci. 34 (5), 495
499. Zameer Ul Hassan, S., Militky, Jiri, Krejci, Jan, 2013. A qualitative study of residual pesticides on cottoners, Conference Papers in Science, vol. 2013. Hindawi Publishing Corporation. Zhiyuan, W., et al., 2008. Determination of organotin compounds in textiles and leather by GC/MS. China Leather 13, 011.

Chemical risk assessment in textile and fashion

3

Subhankar Maity1, Kunal Singha2 and Pintu Pandit2 1 Department of Textile Technology, Uttar Pradesh Textile Technology Institute, Kanpur, India, 2Department of Textile Design, National Institute of Fashion Technology, Ministry of Textiles, Government of India, Patna, India

3.1

Introduction

Various chemicals are present in textile products and garments or used during production of the same in large quantities. Use of these chemicals has many advantages that will modify or improve vital qualities and performance of the textiles and garments. However, there are risks and negative side effects of using these chemicals as well as their presence in textile production that should not be overlooked. The risks or harmful effects of these chemicals may occur during various stages of production and processing of the textiles such as dyeing, printing, and finishing, as well as during the use by consumers. In order to handle risks concerned with these chemicals throughout all stages of the production chain as mentioned above, chemical risk assessment (CRA) is required. There are a large number of synthetic chemicals used in textile and fashion industries at present, and the number is increasing day by day. But, we do not have safety information about using and presence of all these chemicals in consumer products. As there is risk with many of these chemicals that already suspected and reported by many, there is a need for more and better information about safety concern of these chemicals. The concern about assessment of chemical risks has led to test activities performed by many companies in global scenario keeping in mind the environmental concern. For example, the Swedish Chemical Agency prepared an action plan of obtaining everyday toxic-free environment under the aegis of the Swedish Government in the year 2011 2014. (Krishnan, 2011; Swedish Chemicals Agency, 2011a,b; Posner and Jo¨nsson, 2014). The CRA is affected by external factors such as legislation and the regulations of chemicals started in the context of criminal law regarding the use of chemicals identified to be toxic. Since last few decades, legislation has been developed in many countries to minimize, ban, or control the hazardous chemicals used in industries such as pharmaceuticals, textiles, papers, water, and food (Bengtsson, 2010). Recently, more attention has been paid to chemicals present in consumer products (Massey et al., 2008; Rude´n and Hansson, 2009; Chemitecs, 2012). NGOs in the United States have established consumers’ right to know the details of chemicals used during manufacturing of products that should be made publicly available, which will help the consumer to take Chemical Management in Textiles and Fashion. DOI: https://doi.org/10.1016/B978-0-12-820494-8.00003-4 © 2021 Elsevier Ltd. All rights reserved.

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the decision of buying a product (Iles, 2007). In the advent of globalization, the risks of chemicals associated with a product are often spread over several countries. There are various stages of life cycle of textiles starting from fiber to ending at consumer products like a garment. Textile fibers such as cotton, wool, silk, polyester, acrylic, and viscose are the starting or raw materials of the textile industry. These fibers either solely or in combinations are spun into yarns, which are in most cases processed by knitting or weaving into textile fabrics. Textile fabrics are the starting materials of garment and fashion industries. There are more alternative specific processes and routes for producing textile consumer products. Majority of the textile materials are manufactured today in blended or mixed form such as with a variety of mixtures of fibers and yarns. This blending generally improves strength, durability, and performance of the textiles compromising the cost. To improve esthetic appeal of the garment textile components are dyed and printed with colors. Dyeing processes in fiber, yarn, and fabric stage are available and fabric dyeing is getting more popularity along with fabric printing. The gray fabrics prepared from raw natural and synthetic fibers require pretreatment processes prior to dyeing, printing, and finishing processes. The use and maintenance of textiles require washing with various soaps and detergents. A flow chart of textile processes is shown in Fig. 3.1. These processes involve chemicals associated with risk that need to be assessed and informed. In the present chapter, various harmful chemicals of textiles and clothings that are identified as potential risk are reported with their harmful effects. Various

Figure 3.1 Textile process flow chart.

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55

methods of releasing toxic chemicals from textile products are presented with all possible human and environmental exposure of the same. Allergic, carcinogenic, and reproductive toxicity effects of the textile chemicals are informed. Methods of risk assessment and controllable use of the chemicals are discussed.

3.2

Chemical risk analysis

Hazard and risk are not synonymous. Hazard can be defined as inherent property of a chemical having the potential to cause harm when organisms, vegetation, or human beings are exposed to that chemical. Risk is the probability of the harmful effect or hazard occurring. Risk of a chemical depends on inherent toxicity of the chemical (hazard) and its exposure. It means the amount of a chemical present in an environmental medium (e.g., water, air, and soil) and how much contact a person or ecological receptor has with the chemical (exposure). A hazardous chemical has no risk if there is no exposure. The relationship between risk, hazard, and exposure is shown in Fig. 3.2. The objective of CRA is comprehensive understanding of the nature, magnitude, and probability of a potential health hazard or adverse environmental effect of a chemical. Therefore both hazard and exposure are taken into account for the assessment. Such risk assessment is the basis of regulatory decisions by the authorized body or government for regulatory use of industrial chemicals, food additives, pharmaceuticals, pesticides, and cosmetics, as well as chemicals used in textile and fashion industries. The CRA consists of three steps: hazard characterization, exposure assessment, and risk characterization as illustrated in Fig. 3.3. Hazard characterization is based on dose-response determination that determines the relationship between the magnitude of exposure to a hazard and the probability and severity of harmful effects. In the process of exposure assessment the extent to which exposure

Figure 3.2 Risk, hazard, and exposure defined.

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Figure 3.3 Procedure of chemical risk assessment under REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) by the European Union (EU) Regulation.

actually occurs is estimated or measured. Process of combination of information from hazard characterization and exposure assessment to draw a conclusion about nature and magnitude of risk is called risk characterization.

3.2.1 Chemical legislation based on chemical risk analysis The aim of the formulation of chemical legislation is to prevent hazardous effects of the same on human health as well as environment. There are different modes of legislation that regulate different stages of the life cycle of a textile product. The legislation also covers some specific chemicals allowed in the textile processing. However, there is probably not a single legislation that covers and regulates all the chemical substances used in various stages of manufacturing and processing, and use of textiles and garments in order to protect humans beings, as well as environment from the hazardous exposure of the chemicals (Posner and Jo¨nsson, 2014).

3.2.2 European Union Regulation: Registration, Evaluation, Authorisation and Restriction of Chemicals Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) and the Regulation on Classification, Labelling and Packaging (CLP) are the two fundamental community acts established for governing chemical substances in the European Union (EU). The REACH regulation has many restrictions of using of hazardous chemical substances. But, REACH was not specifically designed to account for chemical substances in products such as textiles and garments. The fundamental principle of REACH is that the companies dealing with chemicals are

Chemical risk assessment in textile and fashion

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obliged to take responsibility for the chemicals they released in the market ensuring that they are safe for humans and environment. Manufacturers and importers have to register the chemicals manufactured or imported to the European Chemicals Agency (ECHA) and report the test and assessment data of the hazardous properties of the chemicals. The report also includes intended use of the chemicals. If the quantity of chemicals manufactured or imported exceeds 10 tonnes per year, a special risk assessment is required to be carried out for each intended use of the chemicals. The chemical safety report issued by ECHA regarding the way the chemicals should be used safely for human beings as well as for environment. However, many chemicals that are used in the textile and fashion industries might not fall under the obligation for registration because their quantity does not exceed one tonne per year. But most serious issue is that there is very poor information about the use of chemicals in various textile and fashion materials. This lack of information affects the quality and risk assessment of the product. The chemical registration is verified with adequate information and is randomly evaluated. The evaluation is necessary to establish whether the chemical can impose a health hazard or environmental risk during its incorporation into textiles or use (Fransson, 2012).

3.2.3 Assessment of risk and controlled use The use of a chemical must be controlled efficiently when it is launched in the market. The adequate control can be achieved through registering the chemical by the launching company and by presenting all handling instructions and safety measures, with all information about the hazardous properties and scope of the chemical. If these exposure guidelines are followed during use, the use of the product is considered to be adequately controlled and the same product is not then required to assess for risk for human health and environment. If it is not possible to attain adequately controlled use of a chemical through these measures, then risk management steps are essential to implement in the form of authorization or restrictions of the same. A standard model is established by REACH about the expected adequately controlled use of a chemical. This model is based on a ratio of calculated level of a chemical present in the environment to the maximum concentration of the chemical that is not expected to lead to any toxic or harmful effect on living beings. This ratio is defined as risk factor and if its value is less than 1, the use of concerned chemical is considered to be safe. For exposure point of view, the risk is assessed to be adequately controlled if the risk factor between calculated exposures to a predicted exposure is found less than 1 as shown in Fig. 3.3. However, there is always some uncertainty for assessment of risk in spite of the available method and tools. The adequately controlled exposure levels of textile chemicals that are determined by risk factors as discussed above for both human being and environment are established based on available data concerning the harmful effects of the same chemicals. In this regard, the amount of reliable available data is collected by REACH by some volume-based surveys and studies. To mitigate uncertainties and deviation in the collected data for the risk assessment of a chemical substance standard assessment factors are generally implied for accounting unknown variations to

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improve sensitivity among groups of exposed people. The category and importance of the risk, the extent of the exposure, and the quality and range of the available data also affect the values obtained. We have to rely on such modeled data to estimate the extent of chemical exposure of humans as well as environment, to provide reasonable, but presumed extreme exposure in worst case. It can be understood that there will be always an uncertainty of both the calculated exposure levels and the estimated relevant exposure level obtained using certain methodologies. Quotient between these two quantities becomes even more uncertain, and an absolute value of the quotient is obtained less than 1 the particular exposure situation is to be regarded as “safe” from the health and the environment point of view. Rather the procedure can be described as a scientifically substantiated policy decision. This means that assessments that produce a risk factor of less than 1 in many cases need to be refined by further information being obtained based on harmful effects and exposure. An alternative to this is to tighten the conditions for use, which provides a modified exposure scenario. In the modified exposure scenario, certain conditions must be fulfilled for use to be regarded as adequately controlled. The conditions include risk management measures and maintaining operating conditions like requirements for the use of some protective clothing such as gloves, masks, and gowns, as well as ventilation, respiratory protection, etc. The conditions may also include the method of application and maximum volume or period of exposure. The standard model for risk assessment is applied to chemicals that are having a threshold or limiting effect on human health and environment, where it is possible to establish a minimum level of exposure at which the effects can occur. In other methods, there are high environmental concerns of some categories of chemicals without a threshold. The exposure scenarios are only dealing with exposure to a single chemical from a single source and do not take account of combination effects of two or more chemicals. Therefore it is not relevant to deal with several aspects of the total exposure of many chemicals for both human beings and environment. The deficiencies and limitations in both the risk assessment and risk management models guide us about the precautionary principle that should be adopted to improve the protection of human health and the environment.

3.3

Chemical substances in textiles and garments and their release and exposure

There are many kinds of textile and clothing products manufactured by industry and used by consumers for personal or environmental protection, which are either directly or indirectly exposed to their chemical content. Large quantities of chemicals are used in textile and clothing industries from processing stages to finishing stage. The chemicals can remain or retain in textile product intentionally or unintentionally. It is important to know the exact kinds of chemicals retained, its amount, or concentration level. This information is difficult to obtain due to long supply chain of the product. The information regarding the chemicals retained in textiles is

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generally decreasing from top to bottom of the supply chain. Many chemicals and substances are hazardous and have harmful effect on human health as well as environment.

3.3.1 Chemicals used in production and finishing of textile and clothing The chemicals that are used during manufacturing and finishing of textiles and clothing can be classified into three categories, namely (1) functional chemicals, (2) auxiliary chemicals, and (3) nonintentionally added chemical substances. Functional chemicals are added to improve the performance of the textiles. Some examples of such chemicals are dyes and pigments, oil, soil, and water repellents, antishrinking agents, crease-resistant agents, plasticizers, flame retardants, and biocides for specific functionalities in the garment.

3.3.1.1 Functional chemicals These functional chemicals are supposed to retain in the textile substrate in a sufficient quantity to achieve a desirable property throughout the life cycle of the product. The key requirement for these functional chemicals is their compatibility with the textile substrates. They should have good solubility in available solvent for easy applicability and ability to form physical or chemical bond of sufficient strength for better durability or fastness. For attaining chemical bonds with textile substrates some functional chemicals react with the substrate fibers after application but they still retain their function. For example, the flame retardant tetrabromobisphenol A (TBBPA) reacts with textile substrate during its application and still retains its function as flame retardant due to the presence of the bromine.

3.3.1.2 Auxiliary chemicals Auxiliary chemicals are used during various chemical treatment processes of textiles to accelerate or retard the process so as to improve the quality of the product. These chemicals are not retained by finished goods and do not develop any desired quality in the product. These chemicals are therefore necessary to remove by washing after the successful processing of the textiles. Some examples of auxiliary chemicals are surfactants, organic solvents, softeners, acids, bases, and salts.

3.3.1.3 Nonintentionally added chemicals Nonintentionally added chemical substances are those chemicals that are not intended to remain in the finished articles, such as contaminants and chemicals for degradation. These chemicals have no role in the process of textile production and finishing. These chemicals do not remain in the final product or often retain in a relatively low concentration or quantity compared with the concentrations of functional chemicals. However, these chemicals with little amount can be sufficient for affecting human health and environment. Few examples of such nonintentionally

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added chemical substances include toxic metals (e.g., heavy metals), polyaromatic hydrocarbons (PAH) impurities in paralyzed products, for example, carbon black, formaldehyde released from certain reactive resins, arylamines derived from certain azo dyes and pigments due to impurities from the raw material, etc. Remnants of the auxiliary chemical substances, as well as nonintentionally added chemical substances, may, however, be found in the finished articles and can cause health and/or environmental problems.

3.3.2 Nature and effect of textile chemicals The properties of the chemicals may affect the properties and performance of the textiles up to a certain extent depending upon the amount and extent of chemical remains in the textile product. The water-soluble chemicals are removed during the washing processes either completely or to a certain extent. The volatile chemicals are evaporated during or after finishing treatment of textile products. The auxiliary chemical substances should be removed by washing after the processing stage. The role of these auxiliary chemicals is to facilitate by accelerating or retarding the wet processes of textiles. Surfactants, chemical detergents, emulsifiers, and other watersoluble chemicals such as inorganic salts, alkalis, and acids are washed out by hot or cold washing prior to launching these products in market ready for the consumers. For effective washing out of these chemicals the washing process is critical and various standard washing methods are applied with the help of designated instruments such as launderometer.

3.4

Release of toxic chemicals from textiles

Chemicals that are incorporated into textiles and garments during their manufacturing, processing, and finishing can release in several ways during their use by the consumers as shown in Fig. 3.4. Therefore there will be a subsequent exposure of the released chemicals to humans being as well as environment. In course of dayto-day use there will be regular wear and tear of the textiles and garments. After the prolonged use till the end of its life, a product is disposed as waste. The ingredient chemicals present in the product are then released by various mechanisms such as migration, leaching, evaporation, and particulate releases. The amount and the rate of release depend on various factors viz. (i) inherent chemical/physical properties of the material, (ii) method of incorporation of the chemicals into the textiles, (iii) type of fiber/substrate, (iv) handling and the duration of use of the textiles, (v) chemical and physical properties of the chemicals, (vi) the environment or media that support the release of the chemicals such as surrounding vapor pressure, humidity, and pH, (vii) time available for the release, and (viii) solubility of the chemicals in water. The release of a chemical substance can occur in molecular form and/or in particle form in association with agglomerated molecules bonded by each other by physical or chemical means. The particulate releases that consist of

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Figure 3.4 Chemical release pattern from textiles.

fiber fragments occur during wear and tear in daily use and washing of the clothes. The nature and strength of bonds between the chemicals and textile fiber may influence the form of the releasing chemicals. Molecular release occurs when chemicals are loosely bound to the textile surface. The release of plasticizers, stabilizing agents, direct dyes, etc., follows such types of release. In case of strongly bound chemicals which are characterized by strong chemical bonds, are released in particulate form with fiber fragments. The examples of such chemicals are reactive dyes, durable crease resistant agent, etc. Some residues of process chemicals, external impurities, and contaminants are often loosely bonded to the material. The bond strength depends on various factors such as humidity, temperature, ultraviolet (UV) radiation, and physical stress (Inoue et al., 2004). A considerable amount of silver, triclosan, and triclocarban is released from biocide-treated textiles after few washing cycles (Inoue et al., 2004). The release of such active substances during daily use and disposal should be accounted for in risk assessments (Repon et al., 2017). Many reports are available in literature about the potential environmental hazards caused by textile and clothing due to release of toxic chemicals during production (China, 2011). Also few reports are published regarding the toxicity of textile wastewaters contaminated with various process chemicals (Verma, 2008; Villegas-Navarro et al., 2001; Go´mez et al., 2008). There is limited information available in literature about the potential risks relating to release of hazardous chemicals from textile products by leaching and laundering (Dave and Aspegren, 2010). Printed cotton and cotton/linen textiles are reported to be more toxic than that of unprinted materials. While the opposite result is found in case of synthetic textiles where printed textiles are found to be less toxic than unprinted textiles (Lithner, 2011). Acute toxicity of water leachates from synthetic textiles made of different synthetic fibers is investigated and observed that 9 out of 25 textile fibers leach enough chemicals to cause acute toxicity during short-term test of 3 days

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leaching in water at 50 C. The toxic leachates are reported to be technical textiles, furniture covers, and upholstery. The most toxic leachates identified in literature are acrylic fiber impregnated with long-chain fluorinated water and oil repellents and a polyester fiber coated with plasticized polyvenyle chloride (PVC). These are hydrophobic organic polymers proved as potential toxic compounds. Use of silver zinc zeolite as a biocide product in textiles is proved to be risky by reporting Member State under the work program for review of active substances in biocidal products under Directive 98/8/EC, Sweden (Posner and Jo¨nsson, 2014). The risk assessment is conducted based on cumulative exposure to silver. For the purpose of environmental exposure assessment, biocidal silver products are divided into different parts where treated textiles are the same. Assuming the average life of the textile as 2 years, all silver content in the treated textiles is allowed to release by 2 years. The risk assessment showed that the use of silver zinc zeolite in textiles contributed to potential risk giving a risk factor of .1. However, it is worth mentioning here that the identified risk can be refined by a long-term test with sediment organisms. Finally, it can be understood that the use of silver as a biocide in textiles is a potential risk.

3.4.1 Exposure to chemical substances from textiles and cloths: human exposure As textiles and clothes are loaded with various chemicals the everyday use of them may lead to the exposure of the chemical content in textiles to the wearers. Therefore if textile products contain hazardous substances above a certain level, then there exist detrimental health effects by a certain degree of human exposure. The exposure can have an extensive effect on mankind. Human exposure to chemicals in textiles mainly occurs through skin contact. However, the chemicals may release out of textiles fibers and cause exposure through inhalation and unintended ingestion of dust. Unintended ingestion of dust and oral exposure through sucking or chewing of textiles by small children are considered to be significant exposure routes. The textile and clothing comprises a large sector covering all surfaces in the indoor environment including floors, ceiling, windows, doors, etc., with the products such as carpets, wall hangings, curtains, sofa covers, mats, towels, wipes, etc. All these textile products are used in huge quality in indoors in comparison to garments. These home textiles are suffering from rigorous wear and tear in daily used and contributed much to human exposure. Other garment accessories such as shoes, toys, covers, bags, and draperies also have chemicals contributing to exposure. The exposure scenario is presented in Fig. 3.5.

3.4.2 Dermal exposure Textile cloths such as garments, bed linens, towels, etc., are used in close contact with skin that cause skin or dermal exposure. This can be called as a central exposure pathway because there is direct touch of the chemicals with human skin

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Figure 3.5 Various modes of exposure to textile chemicals.

affecting the wearer as well as the retail workers who are handling and managing the clothes in stores. When cloths are in direct contact with human skin, chemicals present in the cloth can migrate from the cloth to human skin. There is then quite possibility of that chemical to penetrate inside human body through skin causing skin irritation and other health hazards. This dermal exposure depends on many factors such as types of textile material, amount of available chemicals in textile, physicochemical properties of the chemical, solubility in water and other solvents, and skin penetration rate. If toxic chemicals are present in the textiles and the skin of the wearer is sensitive, thin, or damaged, then the chemical can readily penetrate inside the body causing severe problems. However, dermal exposure is particularly serious for sensitizing chemicals and contact allergy that is a well-known issue related to the chemicals used for processing and finishing of the textiles and cloths.

3.4.3 Oral exposure Oral exposure is a minor pathway of human exposure that is the activity of mouthing of textiles normally performed by minor children who often put the cloths in their mouths and that leads to significant oral exposure. Chemicals present in the textile and cloths can transfer from cloths to saliva of the victim and the degree of migration of the chemical is dependent on the type of textile materials, amount of available chemicals, physicochemical properties of the chemical, solubility to water and oil, mechanical stress, etc. (ECHA, 2012a,b). Water-soluble chemicals are more dangerous that mix easily with the saliva consumed by body during chewing by the minors. In course of daily use, the garments experience wear and tear making release of fibers containing chemicals that mix with indoor atmosphere as dust

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in large extent causing direct inhalation and affecting health. It is necessary to assess the extent of oral exposure and detrimental effect of the related chemicals that are bound to textile fibers in dust. The assessment is really difficult (Van Engelen et al., 2009). Small children often stay close to the floor and consume dust due to their inherent mouthing behaviors that is an important source of oral exposure for children (Bjo¨rklund, 2011). Indirect oral exposure via diet is also a contributing exposure pathway for humans to hazardous chemicals in textiles. Textile chemicals are released to water by daily laundering and during waste treatment processes. Foods and drinking water are contaminated with unwanted chemicals and becoming another pathway of oral exposure to textile chemicals.

3.4.4 Inhalation exposure Chemicals or fibers associated with chemicals are released from the textiles and contaminate atmosphere so as to reach the breathing zone of human beings causing inhalation exposure. Volatile compounds are easily released from textiles with a very fast release rate (ECHA, 2012a,b). The amount or level of volatile chemicals to be released depends on the final stage of textile finishing by heating, drying, and curing. The release of the volatiles is generally affected by the heating process. Volatile chemicals are intentionally added to textiles in order to obtain certain qualities of the functional textiles. For example, addition of fragrances is a practice for preparation of cosmetic textiles. We may be exposed to such volatile chemicals through inhalation of textile fibers that are released from the garments and textile products during daily wear and tear (ECHA, 2012a,b). Retail workers who are working in retail garment stores and handling new garments are adversely affected by such chemical exposure through inhalation. The exposure becomes severe in poorly ventilated stores where a huge quantity of textiles are stocked. Textile warehouses, upholstery stores, furniture stores, clothing stores, and other public facilities with a lot of textile furnishing are examples of places where inhalation of chemicals odour from textiles can be serious threat to human health.

3.4.5 Environmental exposure Environmental exposure of chemicals coming out of textile and clothing is mainly occurred via leaching of chemicals after laundering, tearing out of dyed textile fibers due to daily wear and tear, and from the waste generated by textile industries. A lot of wastewater is released during processing and finishing of textiles. Laundering and dry cleaning centers also release wastewater and discharges. The chemical agents that were used during processing and finishing of textiles, emitted from the textiles during washing and reach to or sustain in water. In most industries, wastewater is sent to treatment plants and if the chemicals are not degradable, the water is released as treated wastewater effluents or produce sludge. The treated wastewater and sludge when mix with soil and other part in the environment then human being are exposed to the chemicals via the environment. Environmental risks associated with chemicals present in textile products mainly occur through the

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aquatic environment. Other sources of environmental risk are through air when evaporation of certain chemicals from textiles occurs during the finishing treatment of textiles, drying, home-dyeing, domestic chlorine bleaching, water-resistant impregnation, curing, etc. During washing or laundering chemicals are leached from the textile materials and mix with municipal wastewater and end up in treatment plants followed by exposure of the chemicals to the degrading organisms present in water. If the chemicals are not retained in the sludge, the chemicals are evaporated or degraded in the treatment plant and are released to the environment as effluent and aquatic ecosystems are exposed. Moreover, when the sludge is mixed with soil the organisms present in the terrestrial ecosystems are exposed. When chemicals that mix in soils are taken up by crop plants subsequently and reach to edible part of the crop, resulting in exposure of humans via food. There is a certain degree of fiber loss from textiles during domestic use of cloths by consumers. The chemicals that bind strongly to the lost textile fibers follow the same fate of the fibers. Textile fibers after releasing may mix up in the wastewater and spoil the environment as described above. Otherwise, the fibers are associated with household dust and disposed of via vacuum cleaning dust bags and deposited in dumps or landfills or burned ultimately. In case of waste disposals via water, the chemicals are exposed to aquatic organisms by leachate formation. If the waste is incinerated, all ecosystems may be exposed to the combustion gases. In case recycling of textiles, the chemicals are fed into the recycling system and end up in new products unless they are removed from recycling system. There is a lack of knowledge in supply chain about existence of a chemical and its quantity in a textile product until the end-of-life of the product. Generally, most of the process chemicals are washed out from the textile product before it becomes waste. Whereas, in case of functional textiles the chemicals are strongly bound to textile fibers and are not coming out of the product during daily use. Examples of such functional chemicals are bromine-contained flame retardant agents, water, oil, and soil-repellent agents, crease-resistant agent, dyes, etc. The effect of consumer use of textiles as a source of the toxic and harmful chemicals is largely unknown to us.

3.5

Hazardous chemical in textile products

There are studies reported in literature about various hazardous textile chemicals and their detrimental health effects and environmental effects associated with exposure of the same. There are published documents in literature about various chemical substances that are required for textile wet processing as shown in Fig. 3.6. Also, some chemicals are applied to textile surface and intentionally retained for performance enhancement, for example, silver, nonylphenol ethoxylates, and highly fluorinated polymers. The identification of potential risks with these hazardous chemicals in textile articles is required. However, identification of the same in textiles is not well studied and there is a lack of information in literature about potential risks from these hazardous substances or chemicals present in textiles that are

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Figure 3.6 Various chemicals used during textile wet processing and their detrimental effects.

responsible for the human and environment exposure as discussed above (Xu et al., 2013). It has been reported that textile dyes, textile finishing resins, and some other textile-related chemicals can cause allergic skin irritation (Gu¨ngo¨rdu¨ et al., 2013). The potential link between exposure to such sensitizing chemicals present in textiles and their allergic effect has also investigated (Gu¨ngo¨rdu¨ et al., 2013). There is a lack of information about the amount of allergic chemicals added to the textile during processing and retained after the finishing process. Such information is not produced by manufacturers and it is not regularly practiced by the industry. Therefore it is difficult to decide if there is a link between hazardous chemicals in finished textiles and contact dermatitis.

3.5.1 Irritation and allergy caused by textile chemicals Textile chemicals and fibers sometimes cause irritation and reaction with skin upon direct or indirect contact. Such type of skin reaction is called textile dermatitis that is typically characterized by itchiness, redness, and inflammation. This occurs mainly with synthetic materials such as nylon, polyester, and polyvenylene chloride. When such synthetic fibers are used in garments such as trousers, skirts, underwear, shirts, stockings, and sportswear, then such skin irritation may occur (Lisi et al., 2014). Two types of textile dermatitis are reported, namely allergic dermatitis and irritant dermatitis. Both these types often coexist from similar garments and show similar symptoms or characteristics (Ale and Maibach, 2010). Allergic textile dermatitis is caused by some specific activation of the immune system of human body by a foreign chemical that penetrates into skin. Allergic dermatitis is

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specific to the individual and caused by a specific chemical or substance. Therefore some chemicals and substances may be more allergenic than others. Assessment of prediction of such allergic textile dermatitis is very difficult. There are two phases of development of an allergic reaction, namely sensitization phase and elicitation phase. In the first or sensitization phase immune system recognizes the chemical and gives a response, whereas in the second or elicitation phase the immune system produces an allergic reaction, which means that the symptoms of allergic textile dermatitis develop with time after the allergen chemical comes in contact with human skin. If textile chemicals and substances directly damage the skin and cause irritation as soon as they come in contact with skin, then such type of reaction is called irritant textile dermatitis. These types of irritants are easy to detect due to the inherent hazardous characteristics of the chemical/substance. However, it is difficult to distinguish allergic and irritant chemicals in any clinical set-up (Ale and Maibach, 2010). Contact allergy to disperse dyes was reported by European patients, which was clinically tested as well. In this study, it was also stated that women are more sensitive to textile dyes causing allergic reactions than men and allergy is found more common in southern Europe than in the northern parts (Lisi et al., 2014). The textile dermatitis is reported mostly for upper part of the body due to wearing of tight clothing made of synthetic fibers (Lisi et al., 2014; Malinauskiene et al., 2013). Occupational exposure is also reported especially when hand lesions occur from wearing work gloves (Lisi et al., 2014). There was a clinical study conducted among 858 patients in Sweden and Belgium for assessing contact allergy of synthetic textiles and it was found that 18% of the patients developed positive symptoms or skin problems (Ryberg et al., 2006; Ryberg et al., 2009). The allergy is dependent on various factors. The allergic results were found to be dependent on the patient selection, study design, types of cloths, material of the cloth, chemicals present in the cloth, etc. (Ryberg et al., 2006; Ryberg et al., 2009; Malinauskiene et al., 2013; Malinauskiene et al., 2012). Many epidemiological studies also reported inconsistency in allergic results. However, there are several publications where it is reported that the allergic problem is growing with use of uncontrolled and unethical use of many chemicals (Malinauskiene et al., 2013). It is not possible to diagnose patients today if they are allergic to textile dyes or chemicals by using the commercial patch tests that are used routinely in clinics. Presently, contact dermatitis in patients is normally diagnosed by using the European baseline series that do not include any textile dyes or chemicals, with the exception of formaldehyde (Birhanlı and Ozmen, 2005). Therefore allergy to textile chemicals can only be diagnosed in patients by clinical studies. In rare cases doctor specifically suspect a textile chemical as the allergen, and even in those cases only a limited number of dyes and finishes are included in the patch tests (Wentworth et al., 2012; Malinauskiene et al., 2012; Caliskaner et al., 2012; Nygaard, Kralund, and Sommerlund, 2013; Wong et al., 2009). It is quite possible that the chemical that is used for diagnostic purpose in clinical laboratory may differ greatly both by composition and purity from the substances used in textile production, making it even

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more difficult to identify the true allergen. It is thus quite possible that the contact allergy to textile chemicals remain undiagnosed in the clinics.

3.5.2 Exposure to textile dyes Among the textile dyes, disperse dyes are reported to be potential textile dermatitis. Disperse dyes are used to color synthetic fibers such as polyamide, polyester, polypropylene, and acetate; they are suitable for dyeing of natural fibers such as cotton, wool, and silk. The disperse dye molecules are lipophilic in nature and consist of azobenzene or anthraquinone with a functional group attached to its chemical structure. Fastness of the disperse dye to synthetic fibers is generally good, but it is very poor in case of natural fibers. Even if the dyeing conditions and process are not followed properly during dyeing of synthetic fibers the dye molecules can come out of the fiber easily during washing or perspiration and can migrate into skin of the wearer causing irritation. Various disperse dyes such as Disperse Blue 106, Disperse Blue 124, and Disperse Yellow 3 are reported to be very problematic with more than 1% prevalence in screening studies at dermatology clinics (Malinauskiene et al., 2013). There are various case studies reported in literature showing the hazardous effect of various disperse dyes present in textile products tested clinically (Caliskaner et al., 2012; Nygaard et al., 2013; Valladares-Narganes et al., 2013; Hession and Scheinman, 2010; Dawes-Higgs and Freeman, 2004). It is reported that 25% of patients are tested positive for contact allergy to disperse dyes, though these patients are not responsive to the dye molecule but to other substances in the dye. This reveals that the commercial dyes may contain some substances that cause hazardous effects and are unknown to us. There are 19 types of dispersion dyes that are pointed out as allergens by the EU ecolabel and some of these are also mentioned by the Oeko-Tex Standard 100 criteria (Villegas-Navarro et al., 2001; Go´mez et al., 2008). The EU ecolabel and the Oeko-Tex Standard are followed many manufacturers, importers, and retailers to conform to a decreased use of the most well-known allergenic disperse dyes. As a result, today there are very rare instances of cloths available in market dyed with allergenic disperse dyes (Dave and Aspegren, 2010). There are only a few instances reported in literature about textile dermatitis caused by other kinds of textile dyes such as direct dyes, reactive dyes, vat dyes, acid dyes, basic dyes, mordant dyes, sulfur dyes, and pigments (Ryberg et al., 2006; Ryberg et al., 2009; Repon et al., 2017). However, there are random reports of textile dermatitis caused by reactive and basic dyes in clothing that are available in literature (Moreau and Goossens, 2005; Curr and Nixon, 2006). Few epidemiological studies reveal that some basic, reactive, and acid dyes have positive test results as textile dermatitis (Lisi et al., 2014; Wentworth et al., 2012; Slodownik et al., 2011).

3.5.3 Exposure to textile finishing resins Resins are cross-linking agents used in textile finishing for achieving shrink, crease, or wrinkle resistance. These resins are used widely in industry to improve

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quality, texture, appearance, and overall performance of the garments. Such finishing resins may release formaldehyde that is a potential volatile product causing textile dermatitis. This is a common problem with all formaldehyde resins finished clothes reported by many consumers (De Groot et al., 2010a; De Groot et al., 2010b). Today, many EU countries have national regulations regarding the use of formaldehyde in textiles in order to minimize the risk to human health (Lithner, 2011). In many countries there are strong legislation and voluntary restrictions that led to the controlled and minimized use of formaldehyde resins in textiles. However, there are few recent reports where it is published that formaldehyde is no longer considered to be a problem for consumer health and indicated that formaldehyde resins can be considered for finishing of textiles. There are only 2.3% 8.2% textile dermatitis patients who are sensitized to formaldehyde reported by epidemiological studies from 2004 to 2014. The formaldehyde allergy is found to be more common among workers wearing work wear treated with the resin (Lisi, et al., 2014; Lazarov, 2004; Wentworth et al., 2012; Slodownik et al., 2011). Joint Research Centre carried out a survey of formaldehyde in textile products in 2007 and reported that about 11% of the products can produce skin hazards, which contained more than 30 mg formaldehyde per kg of textiles and are in direct contact with the skin. The EU ecolabel and Oeko Tex therefore defined this concentration of 30 mg formaldehyde per kg of textiles as limiting value or allowable level. Statistical reports from the EU and Rapid Alert System for Exchange warned a serious health risk for consumers stating that formaldehyde alone represents about 3% of all notifications of hazardous chemicals in textile products from 2009 to 2014. Other than dyes and resins there are many chemicals used for chemical finishing of textiles. They include water repellents, softeners, flame retardants, antimicrobial agents, etc. However, there are rare instances of dermatitis caused by these substances reported in literature. One of the instances is textile dermatitis caused by sodium metabisulfite that is present in a pair of blue jeans as reported by a case study (Aerts et al., 2014).

3.5.4 Respiratory allergy caused by textiles There are some substances in textiles that can cause respiratory allergy and irritation such as asthma and bronchitis. However, these respiratory sensitizers are limited in nature and are associated with certain chemicals and to certain respondents who are working in a specific environment (Lensen et al., 2007). Such respiratory allergy is most likely to be reported in closed environment or workplace such as airways, though there is hardly any reported case of such problem among consumers in airways. This respiratory problem is identified as a major occupational problem due to closed occupational exposure in textile industry and other working places. Textile dye powder, size particles in weaving, and fly in spinning are few potential respiratory sensitizers (Chaari et al., 2011). However, such sensitizers are active or available in workplace only during manufacturing of textiles, and normal consumers are remain unaffected in outside atmosphere.

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3.5.5 Carcinogenic effects of textile chemicals Carcinogenic chemicals are substances that can cause tumors, assists growth of tumor cells and/or malignancy, and accelerate tumor occurrence. Such types of abnormal growth in human tissue are called chemically induced carcinogenesis. It consists of mutagenic and genotoxic events as well as nongenotoxic events. Mutagenicity is the induction of permanent changes of the DNA molecule, whereas genotoxicity is a broader term that refers to all types of alterations of the genetic material including structural changes and segregation of DNA. The carcinogenic effects of the textile chemicals are mainly coming from occupational exposure in the textile industry. Exposure to textile dust, chemicals, and fiber parts as fly are causing much higher risk of cancer for workers in the textile industry. However, the risk is much lower for downstream consumers outside of production house. There is little information in literature about carcinogenic issues from the consumers exposed to textile chemicals during regular downstream use of garments as well as from the workers handling large volumes of such garments. Several studies have reported on carcinogenicity and mutagenicity due to exposure to dyes present in textile and cloths. Azo dyes constitute the major part of the reported exposure. Most of the carcinogenic issues are reported when there is a skin contact of the clothing that have such toxic chemicals. Several azo dyes as well as other types of textile dyes such as anilines and anthraquinones are identified as carcinogenic and/or mutagenic. It is revealed that both azo dyes in pure form and azo dyes contaminated with industrial effluents can cause mutagenic and genotoxic effects in cultured cells (Tsuboy et al., 2007; Prasad and Rao, 2013; Carita´ and MarinMorales, 2008). It is proved by an experimental setting that azo dyes can migrate from cotton fibers to artificial sweat and can cause mutagenic event (Leme et al., 2014). The carcinogenic and mutagenic properties of the azo dyes are attributed to aromatic amines, which is released from the dye molecules after structural disintegration of dye molecules. There are some reports of carcinogenic and mutagenic effects of other types of dyes having chromium metals such as mordant dyeing with chromium salts or other techniques using chromium as oxidation or fixing agents (Zeng et al., 2013). Other than dye molecules, nanoparticles, which are recently used in many functional finishing of textiles, are reported to be harmful. Titanium dioxide (TiO2) that is used widely for achieving UV protection and delusterant is reported to be mutagenic and genotoxic for human cells. Silver nanoparticles which are a multipurpose finishing agent for textiles are also found to produce mutagenic and genotoxic effects in cultured cells (Roszak et al., 2013; Wa˛sowicz et al., 2011).

3.5.6 Reproductive toxicity of textile chemicals Reproductive toxicity is caused by endocrine-disrupting substances with a direct attack on reproductive organs and system. The reproductive toxicity is mainly caused by exposure to textile products that are categorized by four types. These are brominated flame retardants, fluorinated water and stain repellents, phthalates, and antibacterial agents. Exposure to brominated flame retardants causes neurobehavioral and developmental disorders, reproductive health effects, and malfunctioning of thyroid of human beings (Kim et al., 2014). Reproductive toxicity related to

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the exposure of brominated flame retardants is also reported in case of animals (Miyaso et al., 2012; Lema et al., 2007; Eriksson et al., 2006; Talsness et al., 2005; Branchi et al., 2005; Eriksson et al., 2010). Highly fluorinated polymeric water and stain repellents used in textiles possess reproductive toxicity for animals (Viberg et al., 2013; Wolf et al., 2006). There is no association observed between human levels in maternal or umbilical cord blood and reproductive effects such as congenital cryptorchidism, birth weight, and thyroid hormones (Jensen et al., 2014; Monroy et al., 2008; Inoue et al., 2004). Exposure to several different phthalates present in textiles has harmful reproductive effects. The reproductive effects are related to antiandrogenic mode of action and have combined effects due to the exposure to phthalates (Howdeshell et al., 2008; Hannas et al., 2011). Popular antimicrobial agents used on textiles are Triclosan, triclocarban, and silver nanoparticles. There are harmful effects of exposure to triclosan as reproductive toxicity and thyroid malfunctioning (Oliveira et al., 2009; Ishibashi et al., 2004; Dann and Hontela, 2011). Silver nanoparticle exposure has significant effects on neuronal development and functioning (Xu et al., 2013). Textile azo dyes also possess reproductive toxicity with varying potency depending upon available concentration (Gu¨ngo¨rdu¨ et al., 2013; Birhanlı and Ozmen, 2005). Due to occupational exposure of synthetic and natural fibers in textile manufacturing, the textile women workers are suffering from increased risk of miscarriages (Wong, et al., 2009).

3.5.7 Development of antibiotic resistance from antibacterial biocides Antimicrobial textiles are produced by the application of various antimicrobial agents on to textiles, which are called as biocides. The biocides are increasingly used nowadays to get protection from microbes and bacteria. These biocides can prevent bacterial growth and odor in casual and sportswear. Silver, triclosan, and triclocarban are the common biocides used in textiles. These biocides are released gradually from textiles during domestic washing and mixed in water. The continual release of them into water in low concentration creates the suitable environment for bacteria to develop resistance against the biocides. Even very low concentrations of antibacterial agents may create a selection pressure for resistant bacteria. The growth and reproduction of the sensitive wild-type bacteria are inhibited, while bacteria with decreased sensitivity survived and can pass on their resistance genes. In this way, resistance is sustained and increases gradually over bacteria generations. Thus resistance caused by the antimicrobial agent accelerates the resistance of antibiotics. The role of antibacterial biocides in antibiotic resistance has been identified as newly identified health risks.

3.6

Method of assessment of potential risk of hazardous textile chemicals

Potential risks of textile chemicals and substances are analyzed by expert judgment. In this method hazardous effects of a chemical are examined by experts and hazard

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score from 1 to 10 are given. These scores represent hazardous potential of the chemical, which are prioritized for this assignment. A chemical with a health hazard score of 8 10 or an environmental hazard score of 6 10 is considered to be highly objectionable and possessing potential risk. Carcinogenicity, reproductive toxicity, endocrine disruption, mutagenicity, sensitization as well as chronic aquatic toxicity, persistence, and bioaccumulating properties are the general effects of such high hazard chemicals and substances. A brief description of the different prioritization of judgment process is given below.

3.6.1 Prioritization of chemicals based on relevance of textile products Chemicals with a health hazard score of 8 10 or an environmental hazard score of 6 10 are required to be evaluated further for the assessment of presence of the chemicals in textiles with relevant concentration or quantity. It is required to understand the source of such chemicals during textile manufacturing and finishing processes. If such functional chemicals are found with a relatively high concentration in the final textile article, then they are prioritized for further analysis.

3.6.2 Prioritization of chemicals based on probable release from textiles Potential hazardous textile chemicals are assessed based on the probable release of the same from textiles. In this process, the chemical is divided into three groups based on high, moderate, or low probability of release from textiles. Chemicals that are loosely bound to textile fibers can easily release to environment and mix with air in volatile form or mingle with water in soluble form. Chemicals with a moderate bonding strength with textile fiber are semivolatile in nature and have limited water solubility. Chemicals that are strongly bonded with textile fibers with covalent or electrovalent bonds are mainly released from textiles in fiber-bound form.

3.6.3 Prioritization of chemicals based on hazardous properties The environmental hazard score of 6 10 and human health hazard score of 8 10 are considered to be high risk. Such chemicals are considered to be high hazard elements and are prioritized for extensive process of risk assessment. The selection criteria are developed to identify chemicals with the following health hazard properties, namely carcinogenicity, mutagenicity, toxic to reproduction, endocrine disrupting properties, and sensitization. Also, the possibility of the chemicals for bioaccumulation in food chain can be evaluated.

3.6.4 Prioritization of chemicals based on relevance for textile end-products High hazard chemicals can be grouped based on their relevance for textile endproducts and the functional chemicals are prioritized for further analysis. In this

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method functional chemicals are intentionally added to the textiles and are expected to remain in the finished end-products with sufficiently high concentrations. Examples of such environmentally hazardous chemicals are nonylphenol ethoxylates and nonylphenol.

3.6.5 Prioritization of chemicals based on probability of release from textiles Chemicals are grouped based on the probability of release from the textiles. They can be prioritized as high release chemicals, moderate release chemicals, and low release chemicals in their molecular form via migration to waster or emission in air from textile products. Low probability of release of substances generally occurs in fiber-bound form in the form of dust, fly, or waste. The chemicals are scored based on probability of release from the textiles to understand potential risk to human health and the environment.

3.7

Conclusion

Various chemicals and substances that are present in textile products and garments may have potential risks or negative side effects that should not be overlooked. The risks or harmful effect of these chemicals may arise during various stages of production of the textiles such as dyeing, printing, and finishing, as well as during consumer use. There are different modes of legislation that regulate the use of specific chemicals in the textile manufacturing process and different stages of the life cycle of a textile product. REACH and CLP are the two fundamental community acts established for governing the use of chemical substances in the EU. The chemicals that are used during manufacturing and finishing of textiles and clothing can be classified into three categories: functional chemicals, auxiliary chemicals, and nonintentionally added chemical substances. Functional chemicals are added to improve the performance of the textiles, such as dyes and pigments, crease-resistant agents, antishrinking agents, oil, soil, and water repellents, plasticizers, flame retardants, and biocides. Auxiliary chemicals are used during various chemical treatment processes of textiles to accelerate or retard the process so as to improve the quality of the product and washed off from the finished products. Examples of such chemicals are organic solvents, surfactants, softeners, salts, acids, and bases. Nonintentionally added chemical substances are those chemicals that are unintentionally added to and remained in the finished article like contaminants. Some examples of such nonintentionally added chemical substances are formaldehyde resins, PAH impurities from paralyzed products, for example, carbon black, arylamines derived from certain azo dyestuffs and pigments, toxic metals (e.g., heavy metals) due to impurities from the raw material, etc. The ingredient chemicals present in textiles are released by various mechanisms such as migration, leaching, evaporation, and particulate releases. The release of a chemical substance can occur in molecular form and/or in particle form in association with agglomerated

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molecules bonded by each other by physical or chemical means. There are various modes of exposure of textile chemicals such as human exposure, dermal exposure, oral exposure, inhalation exposure, and environmental exposure. One of the serious hazardous chemicals associated with textile products is called as textile dermatitis, causing skin reaction typically characterized by inflammation, redness, and itching of the skin after direct contact with textiles. These materials are mainly synthetic materials such as nylon, polyester, and polyvinyl chloride present in trousers, skirts, underwear, shirts, stockings, and sportswear. Two types of dermatitis are reported in literature, namely allergic dermatitis and irritant dermatitis. Few disperse dyes are reported to be potential dermatitis. Formaldehyde resin is also a potential volatile product causing textile dermatitis. Respiratory allergy from textiles is most likely to be reported in closed environment or workplaces such as airways or retail shops. Exposure to textile dust, chemicals, and fiber parts as fly causes much higher risk of cancer for workers in the textile industry. Several studies are reported on carcinogenicity and mutagenicity due to exposure to dyes present in textile and cloths. Azo dyes constitute the major part of the reported exposure. TiO2 and silver nanoparticles are also found to produce mutagenic and genotoxic effects in cultured cells. The reproductive toxicity is mainly caused by exposure to textile products from brominated flame retardants, fluorinated water and stain repellents, phthalates, and antibacterial agents. The role of antibacterial biocides in antibiotic resistance has been identified as newly identified health risks. Potential risks of textile chemicals and substances can be analyzed by expert judgment assigning hazard score from 1 to 10. A chemical with a health hazard score of 8 10 or an environmental hazard score of 6 10 is considered to be highly objectionable and possessing potential risk. These scores represent hazardous properties of the chemical that are prioritized for this assignment. Various bases of prioritizations are hazardous properties of the chemicals, relevance for textile end-products, and probability of release from textiles. In many cases risk assessment may find significant hazards of chemicals, which is required to identify and control to save us and environment. Therefore it is required to establish regulatory board, law and methods of assessment, and tools by the developing nations.

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Disperse Blue 291 in the human hepatic cell line HepG2. Toxicol. In Vitro 21 (8), 1650 1655. Valladares-Narganes, L.M., Sanchez-Sambucety, P., Ruiz-Gonzalez, I., Otero-Rivas, M., Rodriguez-Prieto, M.A., 2013. Lymphomatoid dermatitis caused by contact with textile dyes. Contact Dermatitis 68 (1), 62 64. Van Engelen, J.G.M., van der Zee Park, M., Janssen, P.J.C.M., Oomen, A.G., Brandon, E.F. A., Bouma, K., et al., 2009. Chemicals in toys. A general methodology for assessment of chemical safety of toys with a focus on elements. RIVM rapport 320003001. Verma, Y., 2008. Acute toxicity assessment of textile dyes and textile and dye industrial effluents using Daphnia magna bioassay. Toxicol. Ind. Health 24 (7), 491 500. Viberg, H., Lee, I., Eriksson, P., 2013. Adult dose-dependent behavioral and cognitive disturbances after a single neonatal PFHxS dose. Toxicology 304, 185 191. Villegas-Navarro, A., Ramı´rez-M, Y., Salvador-SB, M.S., Gallardo, J.M., 2001. Determination of wastewater LC50 of the different process stages of the textile industry. Ecotoxicol. Environ. Saf. 48 (1), 56 61. Wa˛sowicz, W., Cie´slak, M., Palus, J., Sta´nczyk, M., Dziubałtowska, E., Ste˛pnik, M., et al., 2011. Evaluation of biological effects of nanomaterials. Part I. Cyto- and genotoxicity of nanosilver composites applied in textile technologies. Int. J. Occup. Med. Environ. Health 24 (4), 348 358. Wentworth, A.B., Richardson, D.M., Davis, M.D., 2012. Patch testing with textile allergens: the mayo clinic experience. Dermatitis 23 (6), 269 274. Wolf, C.J., Fenton, S.E., Schmid, J.E., Calafat, A.M., Kuklenyik, Z., Bryant, X.A., et al., 2006. Developmental toxicity of perfluorooctanoic acid in the CD-1 mouse after crossfoster and restricted gestational exposures. Toxicol. Sci. 95 (2), 462 473. Wong, E.Y., Ray, R.M., Gao, D.L., Wernli, K.J., Li, W., Fitzgibbons, E.D., et al., 2009. Dust and chemical exposures, and miscarriage risk among women textile workers in Shanghai, China. Occup. Environ. Med. 66 (3), 161 168. Xu, F., Piett, C., Farkas, S., Qazzaz, M., Syed, N.I., 2013. Silver nanoparticles (AgNPs) cause degeneration of cytoskeleton and disrupt synaptic machinery of cultured cortical neurons. Mol. Brain 6 (1), 29. Zeng, M., Xiao, F., Zhong, X., Jin, F., Guan, L., Wang, A., et al., 2013. Reactive oxygen species play a central role in hexavalent chromium-induced apoptosis in Hep3B cells without the functional roles of p53 and caspase-3. Cell. Physiol. Biochem. 32 (2), 279 290.

Challenges in dyeing of cellulosics with reactive dyes and practical sustainable feasibilities

4

A.S.M. Raja, A. Arputharaj, G. Krishnaprasad, Sujata Saxena and P.G. Patil ICAR
Central Institute for Research on Cotton Technology, Mumbai, India

4.1

Introduction

Sustainable development is a complex multidimensional concept concerning the environment, economy, human health, and social impact. Due to the increase in population and constant depletion of natural resources, these days lot of importance is given to sustainability. The currently used processes are also undergoing sustainability tests for their continuation. Any existing process if it fails in the sustainability issue needs to be modified suitably or to be replaced by a new sustainable process. Sustainability cannot be compromised even a process is able to meet the intended requirements. Reactive dye is one of the major classes of dyestuff used by the textile industry for dyeing of cotton, wool, silk, viscose, and other cellulosic fibers. The reactive dye is major class of dyestuff for cellulosic fibers due to its ability to produce brilliant colors with reasonably good fastness properties. The advantages of factors such as ease of application of dyestuff on the cellulosic and requirement of cheap chemicals for exhaustion and fixation of dyes make reactive dye as a number one dye for the dyers of cellulosic fibers. Reactive dyes constitute about 25% of total dyestuffs produced worldwide by major producers such as China, India, Taiwan, and Pakistan. Recently several dyestuff-producing industries in China were closed due to enforcement of tougher environmental regulations. Cellulosic fibers such as cotton and viscose are the important fibers in the market and constitute approximately 40% of the total fiber production. The importance of natural cellulosic fibers is improved further due to the ocean plastic problem mainly due to the release of nonbiodegradable microfibers mainly from clothing materials made from synthetic fibers such as polyester and acrylic. Based on the above the present study briefly outlines some basic information about cellulosic fibers, history and chemistry of reactive dye development, different types of reactive dyes, method of application, ecological aspects of reactive dyes, unconventional dyeing methods for reactive dyes, sustainability challenges in the reactive dyes, current technologies for improvement of sustainability of reactive dyes, and feasibilities for improvement. Chemical Management in Textiles and Fashion. DOI: https://doi.org/10.1016/B978-0-12-820494-8.00004-6 © 2021 Elsevier Ltd. All rights reserved.

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Cellulosic fibers

Cellulosic fibers are defined as fibers containing cellulose as the major polymeric substance. Cotton is an important member of the natural cellulosic fibers and is associated with human right from birth to the last breath. The oldest recorded discoveries of cotton textiles date back to 5000 BCE. Remains of cotton balls, woven textiles, fabrics, and fragment of handspun yarn have been excavated from caves in Mexico and from the ruins of the Indus Valley Civilization dating back to some 5000 BCE. Cotton finds mention in the oldest scriptures of the Hindus, the “Rig Veda.” Cotton as an industrial crop played vital role in the history of mankind and civilization. Currently, India is the largest producer of cotton among 90 cottonproducing countries in the world. India, China, and the United States account for a combined 63% of global cotton production in 2017
18. Cellulosic fibers can be classified on the basis of source into natural and regenerated fibers (Fig. 4.1). Regenerated cellulosic fibers are produced by dissolving cellulose in specific solvents and regenerating by precipitating in an aqueous medium. It was the first man-made fiber used in the textile industry and in the early days of its development had the popular name “artificial silk.” Physical and chemical properties of natural and regenerated fibers vary, which depend on nature of the source and method of regeneration. Viscose rayon, cuprammonium rayon, and acetate rayon were amongst the first-generation regenerated cellulose fibers. A relatively recent entry to the rayon family is Lyocell, trade named Tencel, which is produced from Nmethylene morpholine oxide (NMMO) (Chen, 2015).

4.3

Cellulosic fiber consumption

Before the invention of synthetic fibers, only natural fibers were being used for the human needs. However, after the introduction of synthetic fibers, especially

Figure 4.1 Classification of cellulosic fibers.

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81

polyester in 1950s, the contribution of cellulosic fibers in the total mill consumption has been steadily declining (Fig. 4.2). As given in Fig. 4.3 currently the total mill consumption of cellulosic fiber is around 34%, which includes regenerated cellulosic fibers (https://waterfootprint.org/ media/downloads/Viscose_fibres_Sustainability.pdf). It is also very clear that cotton is dominant natural fiber among all natural fibers in terms of percentage consumption. Globally, textile and clothing sector makes significant contribution to the increase in

Figure 4.2 Production of cotton and polyester fibers. Source: ICAC, Washington.

Figure 4.3 Global fiber consumption (https://waterfootprint.org/media/downloads/ Viscose_fibres_Sustainability.pdf).

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carbon footprint. Apparel and textiles account for approximately 10% of the total carbon impact in the world. Carbon footprints of natural fibers such as cotton and flax are comparatively much lower than synthetic fibers such as polyester and nylon. The embodied energy of synthetic fibers is much more than natural fibers. Production of natural fibers such as hemp and jute reduces the carbon footprints. The world today has rapidly turned its attention toward the natural fibers that are environment-friendly and biodegradable due to sustainable issues with synthetic fibers.

4.4

Chemistry of cellulose

Cellulose is a polysaccharide and most abundant of all naturally occurring organic polymers on Earth, being produced by photosynthesis. Cellulose and starch are having similar chemical structure but vary very differently in their physical and chemical properties. Cellulose is made up of repeating 1,4 β-anhydroglucose units connected to each other by ether linkages (Fig. 4.4), while starch has 1,4 α-anhydroglucose units. The long linear chains of cellulose permit the hydroxyl (OH) functional groups on each anhydroglucose unit to interact with OH groups on adjacent chains through hydrogen bonding and Van der Waals forces. These strong intermolecular forces between chains, coupled with the high linearity of the cellulose molecule, account for the crystalline nature of cellulosic fibers (Shore, 1995). Free rotation of the anhydrogluco-pyranose C
O
C link is stopped by steric effects. There are three
OH groups attached to each anhydroglucose. One
OH group is attached at C-6 and two others at C-2 and C-3 positions. Due to the presence of
OH groups and the chain conformation, there are many more bonds possible (inter- and intramolecular). Such bonds make the cellulosic fibers more rigid by increasing the rigidity of the structure of cellulose (Gordon and Hsieh, 2006). There exist regions of low order (so-called amorphous regions) and of very high order (so-called crystalline regions) in same cellulose (Hearle, 1958). The degree of crystallinity of cellulosic fibers is estimated in the range of 50%
80% which is highest in natural cellulosic fibers. Five allomorphic forms of cellulose have been identified (Rowland and Roberts, 1972). These are denoted as cellulose I to cellulose V. Native crystalline cellulose that is present in natural fibers is cellulose I, having a unit cell of the crystal lattice phases with dimensions approximately a 5 0.82, b 5 0.79, c (fiber axis) 5 1.034 nm with two antiparallel cellobiose chain segments running in opposite directions along the fiber axis (Haigler, 1985; Meyer and Misch, 1937).

Figure 4.4 Chemical structure of cellulose.

Challenges in dyeing of cellulosics with reactive dyes and practical sustainable feasibilities

4.5

83

Chemical processing of cellulosic fibers

Chemical processing is the most important operation in the manufacturing of textile products. It not only adds value to the textile products, but also improves the comfort and esthetic properties. Cellulosic materials have undergone chemical processing since time immemorial. In all the years, the basic objectives of chemical processing, that is, coloring and finishing, have not changed, but in recent times this field has expanded and diversified (Arputharaj et al., 2016). The fundamental purpose of chemical processing is to remove the impurities and prepare the material for further processing. Cellulosic fibers have to be prepared before the dyeing process to make them accessible for dye molecules and other finishing chemicals. For cotton and bast fibers through scouring and bleaching is required to remove natural impurities such as oils,waxes etc. Regenerated fibers will not require severe scouring and bleaching due to their inherent purity. Mercerization is being carried out to increase the dye uptake of cellulosic fibers. Currently for the dyeing of cellulosic fibers different classes of dyes are commercially available, namely direct, reactive, vat, and sulfur. Naphthol color (azoic) is also used at significant level especially in printing of cellulosics (Burkinshaw and Salihu, 2019) (Fig. 4.5). Each class of dyes has its own advantages and limitations. Various classes of dyes for cellulosics have continued to compete with one another. Reactive dyes have edge over other classes of dyes in terms of all round fastness, vivid colors, wide range of availability in different temperature range, and suitability of different dyeing techniques (Lewis, 2011). Due to this consumption of reactive dyes has increased significantly while other classes of dyes are showing a declining trend.

Figure 4.5 Percentage consumption of different dyes for cellulosics (Burkinshaw and Salihu, 2019).

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Chemical Management in Textiles and Fashion

History of reactive dyes

The dyeing of cellulosics is a craft that originated many years ago. In 18th and at the beginning of 19th centuries mostly mordant method of dyeing was used for the dyeing of cotton using the colors obtained from natural sources such as madder and logwood. W.H. Perkin mauve invention in 1856 lead to synthesis of first synthetic dye Magenta by French chemist F.E. Verguin in 1859. However, these dyes required mordant for the dyeing of cotton. The most remarkable landmark in the development of synthetic dye was the discovery of diazotization process of amines by German scientist Peter Griess in 1858 (Peters, 1975). Congo red, the first direct synthetic bis azo dye which will not require any mordanting for dyeing of cotton was invented in 1883 by Paul Bo¨ttiger. However, it was not the easy task for the chemists and colorists to develop high wash fast dyes on textile material by forming a covalent bond between the dye molecules and cellulose, though developments happened in the synthesis of vat and sulfur dyes. This is due to ambiguity in understanding physicochemical structure of cellulose till the 1920s. It was focused to develop reactive dyes for wool rather than cotton. Cross and Bevan (1895) obtained dyed cellulose with arylazobenzoyl, by multistage conversions. Later, many investigations were carried out to obtain colored cellulose ethers and esters. In 1920
30 many inventions were patented for dyes capable of forming chemical bonds with fibrous materials, but nothing find commercial exploitation because these methods required severe treatment conditions causing heavy damage to the fiber polymers (Peters, 1975). Fundamental work on investigation of the mechanism of interaction of cyanuric chloride with cellulose is a breakthrough research in the development of reactive dyes (Lewis, 2011). In 1954, a patent was granted to the chemists of ICI (Ratee and Stephan) for reactive dyes that were water-soluble dyes containing a dichlorotriazine (DCT) group that can be applied to cellulosic fibers in a neutral dye bath and by increasing the pH of dye bath, covalent bonds can be formed between a triazine carbon atom and an
OH group of a cellulose (Shore, 1995). In 1956, ICI manufactured the first reactive DCT dyes under the brand name of Procion. After that, many other reactive systems were introduced by different dyestuff manufacturers (Khatri et al., 2015).

4.7

Common structure of reactive dyes

The common structure of reactive dyes can be written as follows:

where W represents the water-soluble group, mostly
SO3Na group; C represents the chromogenic group of the dye molecule; BG represents the bridging group; RG represents reactive group (RG); L represents the leaving atom of the RG.

Challenges in dyeing of cellulosics with reactive dyes and practical sustainable feasibilities

4.8

85

Classification of reactive dyes

Reactive dyes can be classified on the basis of dyeing temperature, reactivity and affinity. However, classification using functional group will be more meaningful than other ways of classification. Fig. 4.6 shows the different types of commercially used reactive systems (Shore, 1995) (Gopalakrishnan et al., 2018).

4.9

Mechanism of reactive dyeing of cellulosics

Reactive dyes undergo mostly two types of reaction with
OH group of cellulose (Johnson, 1989; Renfrew, 1999):

4.9.1 Type 1. Nucleophilic substitution reaction First heterocyclic carbon of the RG is activated by the heteroatoms in the aryl ring due to electronegativity, followed by attack on the heterocyclic carbon of the RG by the most basic form of the nucleophilic group that will eliminate the leaving

Figure 4.6 Classification of reactive dyes on the basis of reactive groups.

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group and form the covalent bond. In the case of dyeing the nucleophilic group will be cellulosate anions (CellO2) of cellulose. The equilibrium concentration of CellO2, has to be increased for the formation of the dye
fiber bond, which is achieved by increasing pH of the dye bath.

4.9.2 Type 2. Nucleophilic addition reaction This is a two-step reaction. The first step is alkali-catalyzed 1,2 β-elimination of precursor group to form the vinyl sulfone system. The second step is addition of the nucleophilic group of the substrate to a C 5 C double bond on the RG. In the case of dyeing, the nucleophilic group will be, CellO2 of cellulose. An important difference between the fixation mechanisms of Type 1 and Type 2 is that with Type 1 dyes the CellO2 ion participates in the addition as well as in the elimination step, while with Type 2 dyes the first elimination step is independent of concentration of CellO2 ion (Johnson, 1989).

4.10

Factors affecting reactive dyeing of cellulosics

4.10.1 Reactivity The reactivity may be defined by the speed of reaction of RG with the nucleophilic group at certain temperatures and pH of the medium (Johnson, 1989). It is the main characteristic that determines the dyeing method and the fastness properties of reactive dyes. It primarily depends on the structure of the dye and the nature of the RG and its leaving group. The reactivity may increase with temperature and the bath pH. This is achieved by adding alkalis such as sodium carbonate and sodium hydroxide. DCT dyes are the most reactive and are able to interact with cellulose fiber even at room temperature at a pH 5 10.5. Trichloro pyrimidine dyes are the least reactive dyes that require higher pH. The reactivity of other dyes such as Levafix E, Remazol, Cibacron and Procion HX is in between DCT and tri choloro pyrimidine dyes. It is very important to assure the dye molecule reaction with CellO2 ion not with OH2 ion. It is very essential to understand that why should reactive dyes react with cellulose not with water? Reaction of reactive dyes with OH2 ion will lead to hydrolysis of dyes. Hydrolysis of reactive dye is the major issue in reactive dyeing. It can be explained by the following example (Vickerstaff, 1954; Sadov et al., 1978). The rate of hydrolysis and formation of covalent bond formation can be given as follows: Rw 5 Kw ½HO2  ½DX

(4.1)

Rc 5 Kc ½CellO2  ½DX1 

(4.2)

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where Kw is the constant of the speed of dye reaction with water, Kc is the constant of the speed of reaction with cellulose, [HO2] is the concentration of OH ions, [DX] is the concentration of reactive dye in solution, [DX1] is the concentration of reactive dye in the fiber, and [CellO2] is the concentration of CellO2 ions in solution. The ratio of the rates of reactive dye reactions with cellulose and water is Rc Kc ½CellO2  ½DX1  5 1:30:136 5 4080 U 5 U Rw Kw ½HO2  ½DX By considering high ionization of
OH in cellulose as compared with water 2  ½DX 1  Kc
OH ½CellO  30, ½HO2 Kw 5 1, and ½DX 2  5 136 This shows that when a reactive dye is exhausted on a cellulosic substrate, the concentration of the dye inside a fiber being considerably higher than in the surrounding aqueous medium, dye combines with cellulose polymer hundreds of times quicker than with water. If the dye is highly reactive, chances of hydrolysis are also higher (Sadov et al., 1978). The stability of dye
fiber bond depends upon the reactive system. In general, dyes that undergo nucleophilic substitution reaction have poor acid hydrolysis, while dyes that undergo nucleophilic addition have poor alkali fastness (Shore, 1995).

4.10.2 Substantivity Substantivity is defined as “selective attraction between textile substrate and dye molecule in which the latter is precisely extracted by substrate in the dyeing medium” (Shamey, 2013). The substantivity of the dye is characterized by the amount of dye exhausted during the dyeing process. Many factors influence the substantivity of the reactive dye: 1. Solubility of the dye Highly water-soluble dyes are having less substantivity toward cellulosic fiber because of the more affinity toward water. Mostly reactive dyes are more water-soluble (with two to four groups) than direct class dyes. That is why reactive dyes require more amount of electrolyte to increase the exhaustion. Addition of electrolytes reduces the water solubility of dyes; thereby affinity toward cellulose is increased. Electrolytes also reduce the zeta potential developed during the exhaustion of dyes. This is achieved by adding electrolytes such as sodium chloride or Glauber’s salt (Khatri et al., 2015). 2. Temperature At higher temperature solubility of dyes gets increased and substantivity is reduced. However due to increase in the diffusion coefficient of dyes at higher temperature the total exhaustion of dyes gets increased. Reactive dyes with lower reactivity normally require larger chromogens in order to provide sufficient substantivity for the substrate at high-temperature dyeing. 3. pH

The pH of the dyeing medium has an insignificant effect on the substantivity of reactive dyes because of the interval that is used practically, that is, pH 5 7
10.8.

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However, at a pH higher than 11, the substantivity may be reduced because of increase in the cellulose fiber negative charge due to the ionization of the
OH group (Johnson, 1989). In the case of nucleophilic addition reaction, the first step is alkali-catalyzed 1,2 β-elimination of precursor group to form the vinyl sulfone system that reduces the water solubility of dyes due to removal of
SO3Na group and thereby increases the substantivity.

4.11

Application techniques of reactive dyes to cellulosic fibers

Reactive dyes are highly versatile than other classes of dyes in terms of application. A wider range of substantivity levels is feasible in reactive class (40%
80%). Mostly three kinds of methods are being used for the application of reactive dyes to cellulosic fibers: 1. 2. 3. 1.

Batch-wise or exhaustion Semicontinuous Fully continuous Exhaustion methods Basic steps involved in the application of reactive dyes using exhaustion methods remain same irrespective of type of cellulosic fibers and type of machinery (Koh, 2011). a. Application of reactive dye solution to the material in the pH of 6.5
7.5 in the presence of electrolyte, b. Fixation of reactive dye to cellulose in the pH of 10
10.5 in the presence of alkali, c. Neutralization of dye bath using acidic solutions, and d. Washing off treatment to remove the unfixed/hydrolyzed dyes.

Concentration of electrolyte and alkali depends upon the following parameters: G

G

G

G

Substantivity of the dye; Reactivity of the RG; Material to liquor ratio employed in the dyeing. Electrolyte concentration is to be increased in long liquor ratio. Alkali concentration is to be reduced in low liquor ratio; Nature of salt and alkali.

Dyes with higher substantivity are chosen for the exhaustion technique. 2. Continuous methods

In continuous methods the fabric is padded with dye solution, after that fixed with alkaline solution. This is highly suitable for 100% cotton-woven fabric (Fig. 4.7). In continuous dyeing process medium to high-reactive dyes are used. For padbatch application, high-reactive dyes are used. For fully continuous methods, medium reactive dyes are preferred. Since higher concentration of dyes is to be used, highly water-soluble dyes are used; otherwise, higher quantity of urea is to be used, which is considered as noneco-friendly. Vinyl sulfone dyes are not preferred

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Figure 4.7 Classification of continuous methods of reactive dyeing.

for pad-dry-bake process due to their tendency to undergo reaction with urea, which will deactivate them to react with cellulose. To prevent migration of dyes during alkali padding, electrolytes are added in the alkaline bath. Low substantive dyes pose higher migration problem. In pad-batch method after silicate padding the fabric is batched for 12
16 h. The pad-batch method is the best available method for the reactive dyeing of cotton fabric in terms of energy and economical aspects.

4.12

Ecological aspects of reactive dyeing

The application of reactive dyes on cellulosic materials requires different chemicals for exhaustion as well as fixation of dyes. The role of different chemicals in the reactive dye is dealt in the following subsections.

4.12.1 Electrolyte While dyeing cotton with reactive dyes, large quantity of metal salts such as sodium chloride and sodium sulfate is added for exhausting the dyes. The reason behind the addition of salt during dyeing is that when the cotton material is immersed in water, it acquires week negative charge due to ionization of hydroxyl groups present in its structure. The reactive dye is also anionic in nature and acquires negative charge when dissolved in water. During dyeing, cotton and dye repel each other due to the same charge on their surface. If the salt is not added in the dye bath, the dye tends to react more with water than with cotton and loses its dyeability. A schematic diagram of the above mechanism is given in Fig. 4.8. The addition of salt during dyeing serves two purposes: G

G

To neutralize the weak negative charge developed on the cotton substrate and make it positive so that dye can react with cotton and form covalent bond, and To prevent unnecessary reaction of reactive dye with water that leads to the loss of covalent bond formation tendency of dye with cotton.

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Figure 4.8 Schematic diagram of salt requirement during dyeing of cellulosic fiber.

4.12.2 Alkali Use of alkali is inevitable in the reactive dyeing process. It aides the formation of covalent bond between hydroxyl group of cellulosic material and reactive dye. Different alkalis such as sodium carbonate, sodium hydroxide, and potassium hydroxide are used during the dyeing process for maintaining the optimum pH.

4.12.2.1 Miscellaneous chemicals and auxiliaries Urea is used during the dyeing of reactive dyes with cellulosic to aid dye dissolution and fiber swelling. It also prevents dye evaporation in the bath. Urea is also used during printing as well as continuous dyeing processes of cellulosic materials with reactive dyes (Sheth and Musale, 2004). Apart from the above chemicals, wetting agent,sequestering agent, leveling agent, lubricants, dye-fixing agent, sodium alginate etc., are also being used in the dyeing bath as auxiliaries.

4.12.2.2 Residual dye The fixation percentage of reactive dyes is dependent on various factors such as nature of reactive system, chromophore group, molecular weight, and absorption coefficient. In general, the fixation percentage of reactive dyes is between 70% and 85%. On an average, it is expected that about 15%
20% of the reactive dye will remain as such in the bath and also in the form of unfixed/hydrolyzed dyes on the fabric. The presence of residual dye in the effluent has to be removed by employing suitable treatment process.

4.12.2.3 Water Reactive dye is applied on cellulosic material using water as a medium. However, due to the exhaustion and fixing nature of reactive dye, the dyed fabric has to be

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subjected to different washing sequences to remove the unfixed dyes in order to get the good wash durability on the fabric. In general, there are 4
6 washing cycles consisting of cold wash, hot wash, soaping, and neutralization steps. The continuous dyeing process of reactive dyes also requires different washing steps to get required fastness properties.

4.13

Ecological problem due to chemicals, auxiliaries, and water

The effluent coming out of reactive dyeing process contains high amount of total dissolved solids (TDS), alkalinity, suspended solids, residual dyes, etc., which needs to be treated before releasing in the land or river or sea. In the case of zero liquid discharge (ZLD) also, the above substances in the effluent have to be removed to bare minimum amount in order to reuse it. For dyeing 1 kg of cellulosic materials with reactive dye by exhaust method, approximately 0.25
0.6 kg of electrolyte is added during dyeing depending upon the depth of color shade and material to liquor ratio used in dyeing. In one sense salt is used only as intermediate auxiliary to reduce the surface charge of cotton. Once dyeing is over, the whole amount of salts is removed during subsequent washing along with unutilized dye as effluent. The salt content in the effluent drastically increases the TDS content of the final effluent. The TDS of the reactive dye bath effluent will be around 60,000
80,000 ppm without dilution for darker shades. If the dilution of electrolyte content due to different wash cycles is taken into consideration, the TDS of the reactive dye effluent is in the range of 12,000
16,000 ppm. As per the pollution control board norms, the TDS content of treated effluent should be less than 2100 ppm before releasing into inland water bodies because the salt water has the tendency to affect the soil health and its fertility and also the quality of groundwater. However, several countries including India have implemented ZLD norms in which it is absolutely necessary to completely recycle the electrolyte and reuse the same for dyeing purpose. The ZLD system does not allow the solid waste due to recycling for disposal. Instead, it advocates the reuse of recycled electrolytes. At present, the sea disposal of treated effluent does not prescribe any limit for the TDS content. In future, there is a likelihood/possibility of stringent norms for seawater disposal, also considering the complex and sensitive ecosystem in the sea. The common effluent treatment processes such as precipitation, decolorization, biological treatment, and photo-oxidation do not reduce the TDS content of the reactive dye effluent. The most commonly used method to remove the salt from the effluent is through reverse osmosis (RO) process and evaporation of RO rejects using multieffect evaporator in order to separate the salts. Both processes are highly energy, time, and cost-intensive. Due to this, industries are facing enormous pressure and losing their competitiveness to other countries where there are no stringent environmental laws for such reduction in TDS. Several industries are facing the problem of nonability to comply with the strict environmental laws, especially TDS problem.

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4.14

Current technologies for improvement

4.14.1 Development in dyes—bifunctional and polyfunctional dyes As the name implies, bifunctional and polyfunctional reactive dyes have more than one RG in their structure. There are two RG in bifunctional dyes, for example, homo bifunctional reactive dyes in which two identical reactive groups are present and hetero bifunctional reactive dyes in which two different reactive systems such as monochloro triazine groups and sulfatoethyl sulfone groups are present. These dyes are developed with an aim to achieve G

G

G

G

G

High exhaustion and fixing percentage Level dyeing Full and bright colors Excellent fastness properties Batch-batch reproducibility

4.14.2 Low salt reactive dyes Several dyestuff manufacturers have attempted to produce reactive dyes that require less amount of salt. NOVACRON LS dyes are innovative bireactive dyes that require only 25% the salt of conventional reactive dyes. They have very strong buildup and high fixation, resulting in outstanding reproducibility and less pollution (http://www.huntsman.com/textile_effects/a/Products/Dyes/Cellulosics/Reactive% 20dyes%20for%20Exhaust%20Processes). Attempt has been made to reduce the amount of salt used during dyeing by using cationic liposomes as carrier for reactive dye (Ru et al., 2018).

4.14.3 Use of organic electrolyte The use of organic salts in place of inorganic salts such as sodium chloride and sodium sulfate has been proposed by many researchers. Cotton fabrics dyed with reactive dyes with sodium citrate showed satisfactory results with significant reduction in TDS (Prabu and Sundrarajan, 2002). Similarly organic salts such as sodium edate, trisodium nitrilotriacetate, and sodium oxalate have been used as an alternative to sodium chloride for dyeing of cotton successfully (Ahmed, 2005; Khatri et al., 2013).

4.14.4 Development of machineries Developments in the textile machinery for dyeing of cotton with reactive dyes mostly focus on the reduction of water usage in the dyeing process and uniform dyeing. Nowadays ultralow liquor ratio (ULLR) dyeing equipment for both knitted and woven fabrics are available for both batch and continuous processes. One such development in dyeing machinery is Econtrol process. Monforts in collaboration

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with Dystar introduced Econtrol dyeing process in ITMA 1995. This technique differs from other reactive dyeing methods in terms of fixation process where drying and fixation take place in same step. According to Montfort, the E-control climate inside the fixation chamber ensures a perfect dyeing result during the drying process. By using this process cotton, viscose, Tencel, and linen can be dyed. It is claimed that this process uses less energy, water, and chemical than conventional process (Yu et al., 2014; Ali et al., 2012). German company M/S Then has introduced new dyeing machine Airflow Synergy/G2 to get better reduction of water and energy during the wet processing (Nair, 2011). M/S Thies GmbH & Co. KG, Germany, introduced iMaster H2O dyeing machine for the piece dyeing process. M/ S Thies claims that this type of machinery will be helpful for the dyer for better adaptability and flexibility (http://www.thiestextilmaschinen.com/index.php/fuseaction/download/lrn_file/imaster_h2o.pdf). Globally many such machinery suppliers are available who can supply both batch-wise and continuous processing equipment, which will require less energy and water.

4.14.5 Modification of cellulosic fiber In this area of research cellulosic materials are treated with different cationic substances in order to produce reactive site on the surface by which they can be dyed without using salt. Most of the studies in the field of salt-free reactive dyeing used cationic agents such as quaternary ammonium
based chemical for imparting positive charge on cotton fabrics. The agents are organic in nature and considered as producing minimum pollution load. The cationic agents used are 1-amino-2-hydroxy-3-trimethylammoniumpropane chloride (Wang et al., 2009), 3-chloro-2-hydroxypropyl trimethyl ammonium chloride(CHTAC) along with 40 gpl sodium hydroxide (Hashem, 2007). Several studies were conducted to use cationic polymers instead of cationic agents to impart cationic nature to cotton. Generally, the process employed for coating polymers is pad-dry process. The used polymers are dimethylamino ethylmethacrylate, polyepichlorohydrin dimethylamine, polyamide-epichlorohydrin resin, poly(4-vinylpyridine) quaternary ammonium compound—1% on the weight of the material (OWM), dendrimers, amino-terminated polymers (Arputharaj et al., 2016). Chitosan along with assisting agents for penetration and starch derivatives has been used through pretreatment before dyeing with reactive dyes without salt. Chitosan and its derivatives, amino acids derived from soybean hulls, and glycine have been used by different researchers for dyeing of cotton in place of inorganic salts (Asaye and Nalankilli, 2018; Kannan et al., 2006; Samanta et al., 2015).

4.15

Unconventional reactive dyeing (ultrasound, microwave, foam, plasma, supercritical)

Several unconventional dyeing techniques have been reported in the literature for increasing the efficiency of reactive dyeing process on cellulosic materials.

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Ultrasonic energy was used during cold pad-batch dyeing process, which reduced the batching time and alkali requirement. It was also used to improve the fixation properties of different fixing agents used during dyeing of cotton (Khatri et al., 2011; Akalin et al., 2004). Microwave irradiation technique has been used by several researchers as an alternative to conventional heating to reduce dyeing time material to liquor ratio, salt concentration, and dyeing time of reactive dyeing process of cellulosic materials (Haggag et al., 2014; Kiran et al., 2018; Irfan et al., 2018). Foam dyeing technique developed during 19th century also finds renewed interest nowadays for dyeing cotton with reactive dyes. This technology is used with the conventional pad-batch dyeing process, which reduced the amount of dyes and chemicals considerably during dyeing process (Yu et al., 2014). It is also attempted to dye cellulosic material with poly(ethylene glycol)-based reverse micelle system in nonaqueous alkane medium of heptane, octane, and nonane. Solvent-based dyeing process for cellulosic material using reactive dye is also attempted. The miscibility of the solvents is temperature-dependent, which facilitates dyeing and also recyclability of solvents (Wang et al., 2016; Tang et al., 2018; Deng et al., 2019). Plasma-based surface modification process has been used to develop sustainable reactive dyeing process for cotton. Air plasma and dichlorodifluoromethane (DCFM) plasmas have been used for improving the dye uptake on cotton. Another study used plasma to improve the adhesion of chitosan on cotton fabric that facilitated salt-free dyeing process (Bhat et al., 2011; Haji et al., 2016). Supercritical fluid
based dyeing process uses liquid carbon dioxide as a medium of dyeing in place of water. This process is one of the sustainable dyeing processes that eliminate the water and related effluent treatment process. Several attempts have been made to use supercritical fluid dyeing of cotton by development of new dyes, solvents, and process modification. However, the hydrophilic nature of cellulosic fibers due to the presence of polar groups makes the process unsuitable for industrial adoption (Cid et al., 2007; Zhang et al., 2017).

4.15.1 Development in effluent management The different stages of conventional and ZLD effluent treatment processes are given Table 4.1. The conventional treatment consists of collection and homogenization of effluent, neutralization, and secondary effluent treatments such as flocculation, primary and secondary clarification, ultraviolet treatment, activated carbon filtration followed by release of effluent in the sea or river bodies. In the conventional water treatment, there is no limit prescribed for TDS content in the effluent. However, the chemical oxygen demand of the effluent should be less than 250 for sea discharge and less than 100 for river discharge. In the ZLD-based effluent treatment processes the effluent needs to be recycled and reused for further processing. ZLD refers to installation of facilities and system that will enable industrial effluents for absolute recycling of permeate and converting solute (dissolved organic and inorganic compounds/salts) into residue in the solid form by adopting method of concentration and thermal evaporation.

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Table 4.1 Conventional and ZLD-based effluent treatments. S. no.

Conventional effluent treatment

Zero liquid discharge

1 2 3 4 5 6

Collection sump Flash mixing Neutralization and settling Aeration tank Primary and secondary clarifier Dual media filter and activated carbon filter Release of effluent into river bodies

Collection sump Flash mixing Neutralization and settling Aeration tank Primary and secondary clarifier Ultrafiltration

7 8 9

Reverse osmosis (RO) Recovery of permeate and RO reject Multieffect evaporator, solar evaporation pan of RO reject to recover salt

The ZLD-based effluent treatment process is costly and energy-intensive due to additional RO and evaporation methods for separation of solids from the effluents. In India, ZLD is made as mandatory for textile bleaching and dyeing industries except for industries located in the areas where sea disposal facilities are available. For sea disposal of effluent, there is a stringent norm for chemical and biological oxygen demand parameters. In view of the stringent effluent norms, most of the dyeing industries using reactive dyes are required to adopt ZLD-based effluent treatment processes. Alternative cheap effluent treatment processes have to be developed to deal with TDS content arising out of reactive dyeing processes. There is a need to adopt uniform effluent treatment norms for all the countries irrespective of disposal methods. Precise water can be recovered by adopting ZLD-based effluent treatment process even in the case of sea disposal.

4.16

Conclusion

The invention of reactive dye is one of the important milestones in the cellulosic chemistry research after mercerization process. The cellulosic materials dyed with reactive dyes are able to meet both esthetic and functional requirements such as brilliant colors, and fastness properties. The only problem associated with dyeing of cellulosic materials with reactive dye is requirement of high amount of salt and alkali to facilitate the reaction between hydroxyl group of the cellulose and reactive dye. During the development of reactive dyes in the 1950s, the current problems related to pollution and water scarcity were not the important criteria. However, at present world is facing different sustainability issues due to population increase and industrialization. The use of water and chemicals for textile processing should be a bare minimum to address the sustainability. Reactive dye in the present form is not

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considered as sustainable due to the requirements of large amount of chemicals and water. Over the years, several new developments have made in the reactive dyes such as introduction of new reactive systems, high exhaustion, low salt, ULLR machines, and cationization of cellulose. However, still more research is required to develop a new reactive dyeing system by which cellulosic materials can be dyed at neutral conditions without addition of salt. In the case of effluent management, it is very important to adopt uniform ZLD-based effluent treatment process for dyeing industries worldwide irrespective of the disposal methods since sustainability is the global issue and not a local one. The dyeing industries are burdened with pollution issues unequally without any alternate sustainable reactive dyes. The dyestuff manufacturing industries need to share the responsibility and come up with new reactive dyes to address the sustainability challenges faced by the dyeing industries.

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7. Tang, A.Y.L., Lee, C.H., Wang, Y., Kan, C.W., 2018. Dyeing properties of cotton with reactive dye in nonane nonaqueous reverse micelle system. ACS Omega 3 (3), 2812
2819. Vickerstaff, T., 1954. Physical Chemistry of Dyeing. Wang, L., Ma, W., Zhang, S., Teng, X., Yang, J., 2009. Preparation of cationic cotton with two-bath pad-bake process and its application in salt-free dyeing. Carbohydr. Polym. 78 (3), 602
608. Wang, Y., Lee, C.-H., Tang, Y.-L., Kan, C.-W., 2016. Dyeing cotton in alkane solvent using polyethylene glycol-based reverse micelle as reactive dye carrier. Cellulose 23, 965
980. Available from: https://doi.org/10.1007/s10570-015-0831-8. Yu, B., Wang, W.M., Cai, Z.S., 2014. Application of sodium oxalate in the dyeing of cotton fabric with reactive red 3BS. J. Text. Inst. 105 (3), 321
326. Yu, H., Wang, Y., Zhong, Y., Mao, Z., Tan, S., 2014. Foam properties and application in dyeing cotton fabrics with reactive dyes. Color. Technol. 130 (4), 266
272. Zhang, J., Zheng, L.J., Su, Y.H., Liu, M., Yan, J., Xiong, X.Q., 2017. Dyeing behavior prediction of cotton fabrics in supercritical CO2. Therm. Sci. 21 (4), 1739
1744.

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Nishita Ivy PhD Student, Nalanda University, Rajgir, Bihar, India

5.1

Introduction

Textile industry plays an important role in the economic growth as well as human’s attire all around the world. Textile products accounted for 88.5 million tons that have been produced globally by the textile industry in the year 2012 (Yacout et al., 2015). However, textiles need different types of chemicals in huge quantities for manufacturing various textile products. Over 8000 chemicals are being used in different processes of manufacturing textiles nowadays (Kant, 2012). Therefore, it is necessary to manage different chemicals effectively for the textile industry because improper management of chemical waste can cause negative impacts on human health as well as on the environment. Furthermore, a variety of potential hazards is associated with the handling and application of chemicals. Hazards may occur during storing, transferring, and handling chemicals if appropriate methods of storage, transfer, and use are not followed. Exposure to chemicals can also be considered as a threat to human life. On the other hand, spillage of chemicals or inappropriate disposal of waste containing harmful chemicals can utterly pollute the environment. There are many other risks such as fire, accidental leakage, explosion, and so on, which may occur due to improper management of chemicals. If textile industries develop and implement an effective system of chemical management, the occurrence of possible hazards will be minimized. Moreover, the environmental impacts of using chemicals can also be reduced. Textile industry can implement efficient chemical management system (CMS) for them by following necessary steps, national and international standards, rules, and regulations thoroughly. In this chapter, different elements, as well as the implementation of a CMS, will be discussed further.

5.2

Chemical management system

A CMS can be defined as a set of guidelines that are used from procuring to disposal of chemicals for ensuring a safe and environmentally friendly way of using chemicals. Textile industry requires to manage different aspects of using chemicals in their manufacturing as well as other operational processes. In this regard, a wellestablished CMS helps them to manage all those aspects effectively. However, Chemical Management in Textiles and Fashion. DOI: https://doi.org/10.1016/B978-0-12-820494-8.00005-8 © 2021 Elsevier Ltd. All rights reserved.

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textile industry can be able to get several benefits from the successful implementation of the CMS. Such benefits include: G

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Protection of workers’ health and safety; Compliance with environmental standards; Reduction of costs and waste through using fewer chemicals; Increase of company reputation; Satisfaction from buyers, customers, and legislative bodies; Tracking all kinds of chemicals across the supply chain; Ensuring compliance with restricted substance list (RSL) and manufacturing restricted substance list (MRSL); Increasing efficiency of operations; Production of safe and environmental-friendly textile products for customers.

5.3

Essential elements of the chemical management system

A methodical approach is requisite to follow for establishing CMS successfully. Plan-do-check-act model is an established and well-accepted approach worldwide and this model can be applied for any type of management systems whether for the environment, chemicals, or quality management (Cahn and Clifford, 2014). Therefore, this model can be used for the development and implementation of the CMS as well (Fig. 5.1). Proper planning is necessary first of all for establishing and maintaining an operative CMS. After that, taking actions according to plan is required. Monitoring and reviewing the effectiveness of different actions regularly assist the factories in identifying current status of CMS, gaps between current outcomes and expected outcomes, and further needs for successful implementation of CMS. Performing accordingly through taking corrective and preventive actions after checking performance is another important step of plan-do-check-act cycle. However, CMS in the textile industry comprises several essential elements ranging from the system of procuring

Figure 5.1 A simple diagram of plan-do-check-act model (Bernal, 2014).

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chemicals to final disposal system of chemical waste that are required to consider significantly. The different essential elements of CMS are described below:

5.3.1 Procurement system of chemicals Purchasing chemicals is an imperative step for the textile industry before using chemicals on the production floor. The textile industry uses different kinds of chemicals in its manufacturing processes as well as in other processes. Therefore, the industry must need to choose chemicals that are less hazardous and environmentalfriendly for their manufacturing processes before purchasing chemicals. Moreover, factories also require to consider compliance with RSL and MRSL of brands and Zero Discharge of Hazardous Chemicals (ZDHC) before procuring any chemical. RSL refers to the list of harmful chemicals that are restricted under a definite threshold limit for final products and MRSL refers to the list of harmful chemicals that are restricted under a definite threshold limit for manufacturing textiles, garments, or footwear (Hossain, 2018). For ensuring compliance with RSL and MRSL, establishing a procurement system for purchasing appropriate chemicals from authentic sources is effective for the textiles. For developing an effective procurement system of chemicals, formulation and maintaining a purchasing policy are prerequisite. Formulating and upholding a chemicals purchasing policy assist the textile industry to show organizational commitment towards procuring chemicals along with consideration of environmental and economic benefits. Besides, creating a responsible position for procuring chemicals such as purchasing manager is also indispensable. Appointing a competent person for this position helps the textiles for ensuring the purchase of comparatively less hazardous and right chemicals through initiating appropriate purchasing procedure. The responsible person, as well as the management part of textiles, must take into consideration several factors before procuring chemicals or dyes. First of all, the quality of chemicals or dyes can be varied significantly from suppliers to suppliers. Reputed suppliers are generally aware of conformity with rules and regulations for ensuring high quality of the chemicals. Therefore, textile industries must need to consider recognized suppliers for purchasing high quality and less hazardous chemicals. Secondly, textiles should be aware of national and international rules and regulations such as Registration, Authorization, and Restriction of Chemicals (REACH) for avoiding banned chemicals and ensuring regulatory compliance. Furthermore, the designated person must need to carry out an inventory of chemicals for assessing the current stocks as well as further required quantity of different categories of chemicals. Besides, the management body should focus on environmentally friendly chemicals for reducing environmental impacts from their manufacturing processes. On the other hand, possible hazards with using targeted chemicals may also be required to assess before purchasing those chemicals. Chemical purchase manager can also initiate lab test of sample chemicals. If the chemicals fail to pass the lab test, those chemicals are needed to exclude from purchasing (Rahman, 2016a).

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5.3.2 Collection, maintaining, reviewing, and updating material safety data sheets Material safety data sheet (MSDS) or safety data sheet (SDS) of a substance is mainly prepared by its manufacturer or supplier that comprises of thorough and inclusive information on the substance as well as possible hazards such as fire, reactivity health, and environmental hazards that are associated with the substance. It also contains information on specific safety requirements, handling procedures, and emergency process for using the material (Canadian Centre for Occupational Health and Safety, 2019; Eastlake et al, 2012). According to the US Occupational Safety and Health Administration (OSHA), MSDSs must be prepared on the basis of 16 sections format that consists of categories of information as (1) identification, (2) identification of hazards, (3) composition of the substance, (4) first-aid procedures, (5) measures of fire-fighting, (6) measures for accidental release, (7) storage and handling procedures, (8) personal protection or exposure control measures, (9) chemical and physical properties, (10) reactivity and stability, (11) information on toxicity, (12) ecological information, (13) disposal procedures, (14) information on transportation, (15) regulatory information, and (16) other information (OSHA, n.d.a). On the other hand, an MSDS is required to prepare and deliver for a chemical substance or mixture of substances according to GHS (Globally Harmonized System of classification and labeling of chemicals) classification criteria. The characteristics and associated hazards of a chemical and mixture of chemicals are determined by using GHS classification criteria. There are three types of hazards associated with different chemicals, which are physical, health, and environmental. All the hazards related to a chemical or mixture of chemicals are required to include in the MSDS by following the GHS classification criteria. However, GHS is a standard for classifying and labeling chemicals. This standard was adopted by the United Nations in 2003 and includes approaches for classifying chemicals according to physical, health, and environmental hazards (OHSA, n.d.b). Most of the countries such as Australia, Canada, Brazil, China, the United States, Korea, Japan, and the countries of the European Union have been implementing the system (GHS, 2016). Textiles must need to collect MSDSs of all the purchased chemicals from the suppliers. Collecting and preserving MSDSs of all the chemicals will assist the factory to ensure safe handling of chemicals as well as taking necessary protective measures for using the chemicals. It also helps the factory to educate employees properly on handling procedures, personal protection from hazards, as well as safe use of the chemicals. Textiles must need to share information of MSDSs of chemicals that are handled by the employees through confirming easy accessibility of MSDSs to them. Moreover, it is a responsibility of the employer to label chemicals in appropriate way along with relevant hazard signage according to the physicochemical, health, and/or environmental hazards that are included in the MSDSs of the chemicals. However, many workers may not be able to read MSDSs if these have been written in a foreign language. Therefore, textiles should also require to ensure the availability of MSDSs in the native language for employees. On the

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other hand, An MSDS must be reviewed and updated after every 3 years from its preparation or revision date. It is also necessary to check the collected MSDSs regularly to ensure that the facility has updated MSDS for every chemical item. However, it is the responsibility of the suppliers to provide the latest MSDSs after bringing every update to their customers.

5.3.3 Inventory system for chemicals Different chemicals and dyes are essential materials for manufacturing processes of textiles. For ensuring safe handling of chemicals and dyes, inventory of chemicals is significantly important for textiles to assess the current stock of all the chemicals as well as further required quantity of chemicals. Moreover, it is also helpful to find out and maintain lists of all the different chemicals that are used in the factory. Textiles must need to include all kinds of chemicals and dyes including chemicals that are used for other purposes instead of manufacturing processes such as cleaners, machine oils, and paints. Moreover, specific information of each chemical such as nature (flammable, reactive, explosive, corrosive, and so on), quantity, location, and use must be needed to include in the chemical inventory. Besides, chemical inventory must be required to update regularly to ensure lists of all chemicals used currently are available in case of emergencies such as fire and chemical spills. In this regard, factories should add all the newly arrived chemicals immediately. Moreover, they also require to remove the name of the chemicals that are going to be disposed from the inventory. Furthermore, inventory of chemicals must be readily accessible into the workplace area for employees who handle these chemicals. A typical form of chemical inventory is shown in Table 5.1.

5.3.4 Storage of chemicals Storing chemicals properly is one of the most important components of CMS. Chemicals are required to store in specific locations that are designed and built in this regard. Effective practices of chemical storage can reduce environmental, health, and safety-related risks. These practices are discussed below:

5.3.4.1 Safety measures of storing chemicals The area of storing chemicals should be kept protected and roofed adequately. Moreover, the temperature of the chemical storage areas should be controlled and direct sunlight must be avoided for the chemical storage areas. However, impervious floor surface of the areas must be needed to ensure. Furthermore, a particular type of ventilation system such as exhaust fans may also be required in the storage areas. Besides, spill kits should be available in the storage areas for controlling accidental release or spill of any chemical. In this regard, personal protective

Table 5.1 Inventory of chemicals. Name of chemical

Chemical Composition

Content CAS No.

Name of Supplier

Address, Contact Name and Number of supplier

Use Volume Date of Used purchase

Expire Date

Location of storage

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equipment (PPE) for the employees of chemical storage areas should also be made available. Moreover, equipment for fire-fighting, fire extinguishers, and fire hoses are also required to keep in a designated location of the storage areas. Signs specifying the spots of PPE, spill kits, fire extinguishers, and so on, are required to post in noticeable locations. Routes of forklifts and aisles are needed to mark noticeably as well (Outdoor Industry Association, 2017a). For storing flammable chemicals, sources of ignition such as smoking, high temperature, hot machines, and so on, must be needed to prohibit. On the other hand, reactive type of chemicals is necessary to keep away from any source of reaction such as water and excessive humidity. Chemical containers should not be stored above man’s shoulder height or above 1.5 m because accidents may occur during picking up or picking out the chemical containers if these are stored above this height. MSDS of each chemical should also be required to attach with the containers of the chemicals. Besides, inventory records of all chemicals should be readily available in the chemical storage location (Rahman, 2016b).

5.3.4.2 Storing incompatible chemicals Textile factories should be aware of incompatible chemicals and these are required to store separately for certain chemicals. For example, organic peroxides are required to isolate completely from other groups of chemicals. On the other hand, certain incompatible chemicals can be stored separately in the same storage area by maintaining as a minimum 5 m distance. For instance, corrosive type of chemicals should be kept minimum 5 m away from the flammable type of chemicals. Again, some other incompatible chemicals can be kept in the same area of storing by maintaining minimum 3 m distance. For example, oxidizing agent should be kept minimum 3 m away from both flammable and nonflammable gases. Textile factories can use chemical compatibility chart for storing chemicals appropriately. However, chemical compatibility chart gives overall guidance on storing different groups of chemicals according to their consistency (Fig. 5.2).

5.3.4.3 Using secondary containment Each chemical container must be needed to keep in secondary containment. Secondary containment prevents leakage or spills of chemicals into the surface and the volume of secondary containment must be minimum of 110% of the volume of the largest chemical container of the storage area (Cahn and Clifford, 2014).

5.3.4.4 Labeling chemical containers All the chemical containers including secondary containment should be properly labeled along with hazard signs according to GHS labeling. There are three main components of the GHS labeling. The first component is hazard pictogram that involves a sign to denote a specific type of physical, health, or environmental hazard according to GHS hazard class and hazard category. The second component is

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Figure 5.2 Chemical compatibility chart (Outdoor Industry Association, 2017a).

using signal words such as danger and/or warning for indicating the level of related hazards with the chemical. The third component is a hazard statement that includes homogenous and consigned phrases describing hazards according to the GHS classification of hazard such as “toxic if ingested.” Despite from these three components precautionary statement (measures for minimizing harmful effects of chemicals), product identifier (number or name for a chemical according to SDS), supplier identification (name, telephone number, and contact address of the supplier of a chemical), and supplementary information can also be included during labeling chemicals (UNECE, 2017). Chemicals that are present in the storage area as well as in other locations such as production floor, generator room, effluent treatment plant (ETP), and so on, should be labeled properly according to the GHS labeling.

5.3.5

Transportation of chemicals

Chemicals are required to transfer from storage to production floor or in other locations within a facility of the textile industry. If chemicals are not transported appropriately, it can cause environmental or health problems due to accidental release or spillage of chemicals. For that reason, the factory should focus on appropriate transportation of chemicals. Textiles can also adapt their internal system for the transportation of chemicals. Responsible employees should use suitable PPE during transporting chemicals into the production floor or other areas. During transportation, chemical containers must be needed to label properly as well as required to transport by authorized or designated persons only. Chemicals should be transferred

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carefully to avoid accidental leakage or puncturing by using suitable vehicles and/ or manual equipment such as trolley and pallet jack. Chemicals should be needed to keep into the secondary containment during transferring for avoiding accidental release or spills into the surface as well. On the other hand, transportation of imported or purchased chemicals from the suppliers to the factory should be followed by nationals and international standards, rules and regulations of transporting hazardous materials (CITA, 2017).

5.3.6 Chemical handling procedures Textiles must need to ensure safe handling of chemicals and therefore, they must need to develop safe chemical handling procedures of chemicals. Safe handling of chemicals can minimize the chemical exposure to the employees. Workers are required to provide sufficient training and awareness on safe chemical handling procedures. Furthermore, factories must need to provide appropriate PPE for every employee who works with chemicals if control methods are not available or adequate. PPE should be selected carefully for protecting workers from different health hazards. MSDS of each chemical provides necessary information on working procedures including PPE, first-aid measures and emergency procedures. Therefore, factories can use MSDSs of chemicals for selecting appropriate PPE as well as for getting other necessary information on handling particular chemicals. There are several kinds of PPE that have particular applications and requirements of use. Longlasting boots are generally suitable to protect foot and leg against spillage of chemicals. On the other side, hands and fingers can be protected by using gloves during working with chemicals. Gloves that are resistant to chemicals are generally made from rubber, polyvinyl chloride (PVC), neoprene, nitrile, polyethylene, or other materials. Materials of gloves should be required to select on the basis of chemicals that employees are anticipated to work. Supplier of gloves may provide a chart of gloves from which appropriate protective materials of gloves can be selected (Outdoor Industry Association, 2017a). Protecting body effectively is helpful to block hazards that are associated with particles, chemicals, and aerosols. In this regard, workers need to wear aprons, gowns, coats, or full bodysuits that can be made from synthetics, rubber, or leather. Besides, eye and face protection must be required to consider for avoiding risks of contacting chemicals with worker’s face and eyes. Face shields can protect the face and neck as well as are suitable for transferring, mixing, or cleaning chemicals. Besides, goggles and safety glasses are used for protecting eyes that can be selected according to the nature of working. Furthermore, respirators are necessary for the workers to keep themselves protected from breathing contaminated air containing fumes, mists, vapors, gases, and so on (Wastradowski, n.d.; Outdoor Industry Association, 2017a). The employer must be required to provide necessary training on how to use PPE to the workers for ensuring their safety. Workers who have specific health issues or pregnant workers should not be deployed on works that are related to chemicals handling. Besides, the standard operating procedure should be needed to prepare and inform the

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employees on different processes related to chemicals. However, evaluating health status of workers who work with chemicals on regular basis is a good practice for the textile industry. The work areas where chemicals are being used should be kept arranged and clean for eradicating possibility of accidents, fires, or explosions. Besides, strict prohibition of taking foods, drinking, or smoking near chemicals must be needed to ensure in the factory premises. Indoor air may be contaminated from volatile organic and inorganic compounds, mists, vapors, and gases because of using chemicals. Odor may also be produced in the textile industry because of using chemicals in dyeing and other finishing processes. Therefore, textiles must need to consider purification of indoor air to ensure good indoor air quality. In this regard, textiles may require to install particular control technologies such as exhaust hoods and scrubbers. On the other hand, keeping working floors clean, neat, and dry prevents injuries related to slip and fall. Moreover, keeping spill kits such as absorbent pads and wipers in the areas where employees work with chemicals helps the staff to clear out spills immediately. Using necessary signs, posting necessary instructions on handling chemicals and labeling chemical pots and containers appropriately make employees aware of safe chemical handling. Moreover, it is also similarly essential to make eyewash stations, showers, first-aid kits, and fire extinguishers easily accessible so that employees can use these apparatuses properly during chemical exposure related emergency situations (Hamel, 2011).

5.3.7 Disposal system for chemical waste Different types of chemical-related hazardous waste can be generated during or after use of chemicals such as waste liquid chemicals, empty chemical or dye containers and/or cans, cut fabrics containing chemicals, residues of finishing chemicals, expired chemicals, and so on (Yacout et al., 2015). Chemicals-related waste must be required to collect and dispose of separately. On the other hand, liquid chemicals as well as wastewater mixed with chemicals must be needed to treat in ETP before discharging into the environment. Moreover, sludge and treated wastewater should be tested to meet the local standards of discharging wastewater and sludge disposal. Besides, solid waste that contains chemicals is required to collect and dispose of separately to avoid contamination of nonhazardous general waste by chemicals. Bins that are used to store chemical waste must be labeled properly. On the other side, chemical containers are required to empty and wash appropriately by following the instructions of MSDS before storing for disposal. Chemicals-related waste should be stored prior to disposal in a secured and separate designated area that has impermeable surface as well as sufficient arrangement to prevent entering rainwater. Expired chemicals should be sent back to the supplier. Moreover, all the chemicals-related waste should be disposed according to applicable national and international rules and regulations. Textile industry can also select and assign authorized contractor for disposing chemical waste. However, reducing usage of

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chemicals and dyes as well as choosing chemicals that cause less harm to the environment can minimize the generation of harmful chemical waste from the manufacturing processes of textiles (Rahman, 2016b).

5.3.8 Restricted Substances List (RSL) and Manufacturing Restricted Substances List (MRSL) RSL contains a list of several harmful chemicals that are restricted under a specific threshold limit for final textile products. On the other hand, MRSL provides a list of several hazardous chemicals that can be used under certain limits in the manufacturing processes of textiles, garments, and footwear industries but cannot be present in the final products. The aim of complying with RSL and MRSL for textile industry is to control hazardous chemical substances that are used in the production processes of textiles as well as to ensure safe and legitimately compliant textile products. Textile industries must need to have a systematic process of addressing and tracing substances as well as complying with RSL and MRSL for ensuring inclusive compliance with their CMS. Various companies and brands that have serious concerns on chemical management establish their own RSL and MRSL. On the other hand, there are several allied textile initiatives at present such as ZDHC, American Apparel and Footwear Association (AAFA) and Apparel and Footwear International RSL Management Working Group (AFIRM) which have set RSL and/or MRSL for the textile industry (Textile Guide, 2019). ZDHC provides MRSL for textiles, apparel, and footwear industries, which includes a wide group of chemicals such as alkylphenol (AP) and alkylphenol ethoxylates (APEOs), chlorobenzenes and chlorotoluenes, chlorophenols, azo dyes and other groups of dyes, flame retardants, glycols, halogenated solvents, organotin compounds, polycyclic aromatic hydrocarbons (PAHs), perfluorinated and polyfluorinated chemicals, phthalates, heavy metal and volatile organic chemicals (ZDHC, n.d.). On the other hand, Bluesign RSL provides a widespread list of substances along with related test methods and limit values considering all the perspectives of the manufacturing process and user safety. Besides, the OEKO-TEX STANDARD 100 RSL provides standards and methods of testing as well as limit values for numerous regulated chemical substances and also gives information on several hazardous chemicals that are not regulated (Outdoor Industry Association, 2017b; Gunar and Yucel, 2005).

5.4 The implementation process of Chemical Management System in textiles For implementing a CMS, it is crucial to make an organizational commitment from management body on taking necessary initiatives such as reviewing purchasing practices, documenting policy and procedures of chemicals management, assessing

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regulatory requirements, and safe handling and disposal procedures. Another important part of the implementation of the CMS is to establish a team that is responsible for ensuring chemical management. Roles and responsibilities of each member of the CMS team must be required to create. On the other hand, every member of the CMS team should be aware of their roles and responsibilities. Management body needs to provide necessary training as well as all the available information and guidance on chemical management to the members of the CMS team. Members of CMS team should include environment, safety, and health manager, purchasing department, ETP manager, quality and production departments. The purchasing department should ensure procuring chemicals that are relatively safe and have compliance with MRSL, brand standards, and regulatory requirements. Inventory of chemicals is also required to update on a regular basis and all types of chemicals are essential to include in the inventory. Moreover, a comprehensive risk assessment should be needed to carry out to identify, control, and mitigate the harmful effects of chemicals in the manufacturing processes as well as in other processes where chemicals are being used. On the other side, providing different pieces of training on safe handling procedures, using PPE, safe disposal of chemical waste, and so on, to various internal and external stakeholders is also important. Furthermore, carrying out external and internal audits to assess the performance and effectiveness of existing chemicals management system is helpful for the factories to identify gaps and areas of improvement (Apparel Online, 2017).

5.5 Tackling challenges on Chemical Management System in textiles A huge volume of chemicals is used in the textile industry, so effective chemical management can be a big challenge for the industry. Chemicals and hazards associated with these chemicals must be required to identify efficiently. In this regard, assigning a competent CMS team to carry out different activities is significantly important. On the other hand, chemicals can contain harmful substances beyond MRSL even after purchasing those from reputed suppliers. For that reason, the textile industry should ask the suppliers to provide a Conformity Declaration indicating their responsibility and obligation on supplying chemicals (SGS, 2013). However, maintaining a chemical inventory by listing all kinds of chemicals is another challenge for the textile industry because of using many different colors, dyes, and other chemicals with huge quantities in various manufacturing processes. In this case, textiles can utilize technological advancement to tackle this challenge. There are many chemical inventory tools nowadays such as chemical inventory management software that can be used by the textiles for tracking all sorts of chemicals (Lonhrey, n.d.). Textiles can face different problems in establishing, implementing, and maintaining an effective CMS. If the factories can ensure a systematic procedure of addressing nonconformities, taking corrective and preventive actions, as well as other issues along with a competent team, then it will be helpful for them to

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tackle different problems regarding CMS. Moreover, reviewing the team performance regularly and identifying different areas of improvement are also essential. Providing necessary training and developing skills of the team members are also effective for establishing a competent CMS team. Furthermore, documentation is an important part of CMS. Creating and maintaining documents on all the elements and related activities of CMS will be helpful for the factories to ensure presence of sufficient evidence of achieving the goals of CMS (Cahn and Clifford, 2014).

5.6

Conclusion and recommendation

Chemical management is a serious concern for the textile industry. If factories could not able to manage chemicals appropriately, it may cause serious threats to the employees and public health as well as for the environment. Therefore, factories need to establish CMS effectively. A robust obligation from the factory management towards ensuring safe and environmental-friendly manufacturing processes of textiles is fruitful to launch and uphold an effective CMS. Moreover, the management part of factories can monitor and evaluate the effectiveness of existing CMS and initiate necessary steps to improve the CMS on regular basis. On the other hand, the use of chemicals and potential hazards associated with chemicals may have alteration over the period of time depending on the types and groups of chemicals and industrial processes. Therefore, regular update of different changes is required to consider for ensuring the expected outcome from CMS. If the management of factories has a strong commitment to the safe use of chemicals for their production, the CMS can be implemented much more successfully.

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Gunar, M., Yucel, O., 2005. Environmental protection and waste management in textile and apparel sectors. J. Appl. Sci. 5 (10), 1843 1849. Available from: https://scialart.net/fulltextmobile/?doi 5 jas.2005.1843.1849 (accessed 30.08.19.). Hamel, K.D., 2011. Eight tips for chemical safety. ,https://ohsonline.com/Articles/2011/08/ 01/Eight-Tips-for-Chemical-Safety.aspx?m 5 1. (accessed 30.08.19.). Hossain, R., 2018. RSL-MRSL promise and reality. ,https://www.textiletoday.com.bd/rslmrsl-promise-reality/. (accessed 10.11.19.). Kant, R., 2012. Textile dyeing industry an environmental hazard. Nat. Sci. 4 (1), 22 26. Available from: https://doi.org/10.4236/ns.2012.41004 (accessed 23.08.19.). Lonhrey, n.d. Chemical inventory requirements. ,https://smallbusiness.chron.com/chemicalinventory-requirement-78196.html. (accessed 30.08.19.). OSHA, n.d.a. Hazard communication standard: safety data sheets. ,https://www.osha.gov/ Publications/OSHA3514.html. (accessed 25.08.19.). OSHA, n.d.b. The globally harmonized system for hazard communication. ,https://www. osha.gov/dsg/hazcom/global.html. (accessed 27.08.19.). Outdoor Industry Association, 2017a. Chemical management guide and training for manufacturers. ,https://outdoorindustry.org/chemicals-manuals/1/en/topic/. (accessed 10.12.19.). Outdoor Industry Association, 2017b. Chemicals management. ,https://outdoorindustry.org/ sustainable-business/chemicals-management/. (accessed 30.08.19.). Rahman, K.M., 2016a. Chemical purchase policy. ,https://autogarment.com/chemical-purchase-industrial-suppliers/. (accessed 23.08.19.). Rahman, K.M., 2016b. Chemical management system. ,https://autogarment.comchemicalmanagement-system/. (accessed 23.08.19.). SGS, 2013. Chemical safety issues and solutions for the textile industry. ,https://www.sgs. com/en/news/2013/10/chemical-safety-issues-and-solutions-for-the-textile-industry. (accessed 30.08.19.). Textile Guide, 2019. Setting up an RSL/mRSL. ,https://textileguide.chemsec.org/act/settingup-an-rsl/. (accessed 28.08.19.). UNECE, 2017. Globally harmonised system of classification and labelling of chemicals (GHS). ,www.unece.org/trans/danger/publi/ghs/ghs_rev07/07files_e0.html#c61353. (accessed 26.08.19.). Yacout, D.M.M., El-Kawi, M.A.A., Hassouna, M.S., 2015. Applying waste management in textile industry: case study an Egyptian plant. Open. Conf. Proc. J. 6, 35 40. Available from: https://pdfs.semanticscholar.org/7a4ec0e96e142af83aa027134f49d0b54ed4.pdf (accessed 27.08.19.). Wastradowski, M., n.d. Choosing PPE to protect against poisons in the workplace. ,https:// www.graphicproducts.com/articles/choosing-ppe-to-protect-against-poisons-in-the-workplace/. (accessed 28.09.19.). ZDHC, n.d. Chapter 1 MRSL for textiles and coated fabrics processing. ,https://www.roadmaptozero.com/mrsl_online/?fbclid 5 lwAR0SK-_5fV2SokbDQG_cb8sh2-o4K-bLFahm UnyggEUqZzF9olCyQ7xURbY. (accessed 03.09.19.).

Hazardous, restricted, and manufacturing restricted substances in textiles and clothing supply chain

6

M. Gobalakrishnan1, Subrata Das2 and D. Saravanan3 1 Department of Textile Technology, Bannari Amman Institute of Technology, Sathyamangalam, India, 2Department of Fashion Technology, Bannari Amman Institute of Technology, Sathyamangalam, India, 3Department of Textile Technology, Kumaraguru College of Technology, Coimbatore, India

6.1

Introduction

It is well known that a wide variety of chemicals are used in the production of textile raw materials and articles to respond to a wide range of performance, aesthetic and functional requirements (Deshpande, 2001). Pesticides are frequently used in natural fiber production and dyes, processing chemicals, water or stain repellents, performance-enhancing coatings or treatments, flame retardants, and other chemicals are commonly employed in producing a finished article (Kant, 2012; Bhatt and ¨ zkara et al., 2016). Some of these are either fixed on end product and Rani, 2013; O remain as residual chemicals and/or discharged into wastewater after their intended function. Most chemical finishes applied in functional finishing are also intended to remain in the finished articles. The issue of eco-friendly textiles first arose after Germany passed its Food and Consumer Goods Act in 1986, which prohibits the use of azo-dyestuffs in textiles and consumer goods because they contain cancer-causing aromatic amines (Act, 1986). Since then legislative bodies and various governments along with manufacturers and suppliers of consumer goods started taking a more serious approach in consumer safety in their own domestic markets. Many brands and retailers also started taking an active role by issuing restricted substances list (RSL) to their supply base to indicate which chemicals are restricted or prohibited in their merchandise. Since then RSL has been the subject of constant revision and several other reputed brands have adopted a similar approach and improved on it in terms of chemical detail, methods of testing and auditing of textile products and laboratories. In this chapter, the following points were discussed: G

definition of restricted substances;

Chemical Management in Textiles and Fashion. DOI: https://doi.org/10.1016/B978-0-12-820494-8.00006-X © 2021 Elsevier Ltd. All rights reserved.

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G

G

G

G

G

G

G

G

G

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importance of restricted substances; criteria, scope, purpose, content, and content basic terms in RSL document; major risk areas of restricted substances; example of brand RSL; introduction of manufacturing restricted substances list (MRSL); difference between RSL and MRSL; scope, implementation, basic terms of MRSL; structure of MRSL document; chemical management of restricted substances/chemical; and global legislations on harmful chemicals in textiles.

6.2

Restricted substances

Restricted substances are chemicals, which are banned or restricted for use and are monitored for their presence in an end product such as finished apparel, home textiles, footwear, and other goods. RSL is a comprehensive list of substances restricted for use and monitored for their presence in finished articles by brands and retailers (Brown, 2012). RSLs are regularly updated by brands based on global legislations, eco-label criteria, and nongovernmental organization (NGO) concerns (Olson, 2014; Rev, 2014; MBDC, 2012; REACH, n.d.).

6.3

Importance of restricted substances list (RSL)

A brand creates an RSL to ensure that no substance listed in the RSL is present on the end product in the interest of consumer safety. The textile supply chain is very complex with many stages in production. These substances could be used at any stage and hence communication of the RSL through the entire supply chain is necessary. Suppliers and vendors of brands need to be aware of and understand the substances and accordingly use input chemicals in their production processes (Das, 2015). Restricted substances are banned for the following reasons: G

G

Effect on human health: The substances can have harmful effects on human health. They can be carcinogenic, mutagenic, or toxic to reproduction, or the substances can act as endocrine disruptors. Additionally, certain chemicals can be allergenic or skin sensitizers. Effect on environment: The substances can pose harm to the environment as they can be persistent, bioaccumulative, and/or toxic to aquatic organisms.

6.4

Criteria for a substance to be included in a restricted substances list

There are four main criteria for including a substance in an RSL (Das, 2015).

Hazardous, restricted, and manufacturing restricted substances in textiles and clothing supply chain

G

G

G

G

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Legislations: Government bodies have created appropriate laws and legislations to regulate and control toxic chemicals. For example, REACH regulation in the EU and TSCA in the United States (REACH n.d.). Toxicological studies: The data obtained from toxicological studies on substances performed by reputed research organizations are considered for inclusion in RSLs. These studies form the basis of NGO campaigns that challenge the industry and government to take positive actions. Eco-labels: Industry associations and government bodies have promoted voluntary standards in the form of eco-labels, such as Global Organic Textile Standard or GOTS, OEKO-TEX 100, and the EU Flower. The substances listed in the criteria of these ecolabels are also considered for including a substance in a brand RSL (KEMI, 2014). Precautionary principle: The precautionary principle applies to any chemical, which might have the potential to be harmful to either human health and/or the environment even if such studies do not firmly establish the harmful effects of the chemical. Such chemicals are also considered for inclusion in brand RSL.

6.5

Purpose of brand restricted substances list

The purpose of brand RSL is to: G

G

G

G

Inform suppliers of substances that are restricted or banned for use. Build and maintain a positive image of the brand as an organization that takes the responsibility for consumer safety. Ensure the protection of human health and environment. Ensure compliance with different global legislations.

6.6 G

G

G

G

Scope of brand restricted substances lists

The substances that are banned in the RSL should not be detected in a finished article. The amount of restricted substances detected in the finished article should not exceed the limits stated in the RSL document. The detection of restricted substances is done only by testing the finished articles, which are sampled and tested as per the specified standard test method. RSLs are not monitored in wastewater and sludge discharged from a manufacturing facility.

6.7

Contents of a restricted substances list document (MBDC, 2012; Rev, 2014)

A typical RSL manual contains the following: G

G

chemical group; substance name or analyte in each chemical group;

116

G

G

G

G

G

G

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CAS number of each analyte; limit values of each restricted chemical group or analyte; technical terms such as “not detected” and “detection limit”; test methods for detecting the presence of a restricted substance in the finished article; units of measurement for each restricted chemical group; and regulations under which the chemical group is restricted.

6.8

Basic terms in restricted substances list document (Das, 2015)

CAS number is a unique numerical identifier that is assigned by the Chemical Abstracts Service (CAS) to every chemical described in the open scientific literature. The CAS number is convenient for database searches. Example: CAS number of formaldehyde is 50-00-0. Detection limit specifies the detection sensitivity as per the specified test method that a laboratory is able to achieve when measuring the chemical substance in an article. Example: Detection limit of a laboratory for detecting alkylphenol ethoxylates (APEOs) could be 10 ppm, that is, the lab can detect APEO in a finished article as low as 10 ppm. Reporting limit (RL) specifies the minimum concentration of a restricted substance that has to be reported by the testing laboratory. Example: If the RL of APEOs is 30 ppm, the laboratory only has to report all values detected above 30 ppm. Not detected (ND): If a substance is detected below “RL” of the laboratory, the laboratory will report it as not detected or “ND.” For example, if the APEO in a finished garment is 20 ppm, the laboratory will report it as ND in the test report. Usage ban/prohibited: This prohibits the intentional use of a chemical during any stage of product manufacture. However, the RSL document gives allowance for trace, that is, unavoidable residues of these restricted substances under the criteria “trace residues (TR).” Example: There is a usage ban on APEO; however, unavoidable contaminations in the form of TR are considered in many RSL documents. Limit value: This is the maximum allowable concentration of the restricted substance in an RSL compliant article. It is expressed in the following units: G

G

G

G

G

G

G

mg/kg; µg/kg; mg/L (for disperse dyes); µg/cm2/week (for nickel release); µg/m2 or µg/cm2 (for PFCs); ppm (parts per million); and ppb (parts per billion).

Milligram per kilogram (mg/kg): The amount of restricted substance in milligrams per kilogram of substrate. For example, 1 mg of a substance on 1 kg of the article will be 1 mg/kg.

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Microgram per kilogram (µg/kg): The amount of restricted substance in micrograms per kilogram of substrate. For example, 1 µg of a substance on 1 kg of the article will be 1 µg/kg. Milligram per liter (mg/L): This is the amount of substance measured in milligrams found in 1 L of extract. For example, this unit is used for the analysis of allergenic disperse dyes in extract. µg/cm2/week (microgram per square centimeter per week): This is a unit for expressing the amount of a substance released in extraction per square centimeter of an article per week. The calculation is based on the area of exposure of the article to the human skin during use. For example, this is used in test methods for releasable metal content (e.g., nickel release). Parts per million (ppm): 1 ppm is an abbreviation of parts per million. It is a value that represents a part of a whole number in units of 1/1,000,000. “ppm” is a ratio of two quantities of the same unit (e.g., mg/kg or mL/m3). Parts per billion (ppb): It is 1000 times smaller than ppm.

6.9

Major risk areas for restricted substances

The risk areas for restricted substances can be divided into six major segments based on the end products and a typical textile supply chain (NimkarTek Technical Services Private Limited, 2015; Luongo, 2015): G

G

G

G

G

G

dyehouses or fabric mills, garment washing units, printers, leather processing, footwear manufacturing, and trims and accessories.

Dyehouse/fabric mills S. no.

Process/stage

Restricted substances group

Applications/sources

1.

Pretreatment (singeing, scouring, bleaching, and mercerization)

APEOs

Wetting, scouring, and lubricating agent Preservative in enzymes

2.

Dyeing and printing

Biocides (isothiazolinone) PCP and TeCP Unreacted monomers (acrylates) Banned amines Disperse dyes

Preservative in starch sizes Polyacrylate-based sizes

Part of the dyestuffs and pigments Dyeing/printing Part of dyes and pigments (Continued)

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(Continued) S. no.

Process/stage

Restricted substances group Heavy metals (Cu, Cr, Ni, Cd, Pb, Hg, and Co) Chlorinated aromatics Formaldehyde APEOs

3.

Finishing and coating

Formaldehyde APEOs PFCs (PFOS and PFOA) Flame retardants Isocyanates

Unreacted monomers Organotins

Applications/sources

Carrier in dyeing of polyester, dyes, pigments, and mineral turpentine oil Dye-fixing agent, binders, and fixers Dyes, washing agents, dispersants, and lubricants Resins used for easy care and durable press finish Silicone softeners and PE emulsions Oil and water repellent finish Flame retardant finishing polyurethane (PU) dispersions, resin/crosslinker/polymer Polyacrylamide and acrylonitrile-based coatings Stabilizer for polyvinyl chloride (PVC), antimicrobial agent

Garment laundry S. no.

Process/stage

Restricted substances group

Applications/sources

1.

Desizing, bleaching/fading, tinting/overdyeing, washing, softening, and specialty finishes

Formaldehyde

Resin used for Wrinklefree effect Part of dyes used for tinting and overdyeing PU softeners and PU coatings Detergent in washing, silicone softeners, and antibackstaining agents (isothiazolinone)

Banned amines Isocyanates APEOs

Biocides Preservative in enzymes used for fading and biopolishing

Hazardous, restricted, and manufacturing restricted substances in textiles and clothing supply chain

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Printers S. no.

Process/stage

Restricted substances group

Applications/sources

1.

Plastisol printing, pigment printing, and reactive printing

Heavy metals Phthalates

Part of dyes and pigments In plastisol inks used for garment printing Washing agents Plastisol paste and coatings based on PU and PVC Binder and fixer in pigment printing Binder and adhesives in pigment printing

APEOs Organotins Formaldehyde Unreacted monomers

Leather processing S. no.

Process/stage

Restricted substances group

Applications/sources

1.

Tanning, bating, fatliquoring, dyeing, and finishing

Chromium VI

Tanning agent, chrome, or metalcomplex dyes Fatliquoring agent

short chain chlorinated paraffins Banned amines APEOs Biocides (isothiazolinone) Formaldehyde PFCs (PFOA and PFOS)

Part of direct dyes, acid dyes, and pigments Washing agents, dyes Preservative in enzymes used in bating process Syntans and tanning agents Oil and water repellent finishing agents

Footwear manufacturing S. no.

Process/stage

Restricted substances group

Applications

1.

Footwear manufacturing processes

Isocyanates APEOs

PU units and synthetic leather Fabric linings and natural leather components Synthetic leather PU and PVC components Colored natural leather Adhesives and resins PVC Natural leather

Solvents Organotins Banned amines Formaldehyde Phthalates Chromium VI

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Trims and accessories S. no.

Process/stage

Restricted substances group

Applications

1.

Various trims and accessories

Heavy metals

Button, rivets, zippers, and other metallic accessories Plastic buttons and lacquers used on metallic buttons Plastic and PVC buttons Dyed polyester buttons, dyed laces, and colored zipper fabric

Phthalates Organotins Banned amines

6.10

Restricted substances list for Calvin Klein

In connection with the manufacture of clothing, the manufacturer shall not utilize or permit any subcontractors or suppliers to utilize in the manufacture or treatment of any of the products manufactured here under any restricted substances.

6.10.1 Azo dyes All fabrics, trims, and accessories must be free of the azo dyes (including blue colorant #611-070-00-2) and pigments that are banned by some European countries. This also applies to leather and other components. Azo testing is not required as the signed manufacturer’s agreement/supplier certification is needed to confirm the mill is using azo-free products. Azo dyes and pigments that can be split into any of the 22 amines listed below must not be used in any products manufactured for Calvin Klein irrespective as to where these products will be sold. These azo dyes and pigments have been found to be carcinogenic. S. no.

Name of the azo dye

CAS number

S. no.

Name of the azo dye

CAS number

1.

4-Aminobiphenyl

92-67-1

13.

838-88-0

2. 3.

Benzidine 4-Chloro-o-toluidine

92-87-5 95-69-2

14. 15.

91-59-8 97-56-3 99-55-8 106-47-8 615-05-4 101-77-9

16. 17. 18. 19. 20. 21

3,30 -Dimethyl-4,40 diaminodiphenylmethane p-Cresidine 4,40 -Methylene-bis(2-chloroaniline) 4,40 -Oxydianiline 4,40 -Thiodianiline o-Toluidine 2,4-Toluylenediamine 2,4,5-Trimethylaniline 4-Aminoazobenzene

101-80-4 139-65-1 95-53-4 95-80-7 137-17-7 60-09-3

9194-1 119-90-4 119-93-7

22. 23. 24.

o-Anisidine 2,4-Xylidine 2,6-Xylidine

90-04-0 95-68-1 87-62-7

4. 5. 6. 7. 8 9.

2-Naphthylamine o-Aminoazotoluene 2-Amino-4-nitrotoluene p-Chloroaniline 2,4-Diaminoanisole 4,40 Diaminodiphenylmethane 10. 3,30 -Dichlorobenzidine 11. 3,30 -Dimethoxybenzidine 12. 3,30 -Dimethylbenzidine

120-71-8 101-14-4

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6.10.2 Disperse dyes S. no.

Disperse dyes

CAS number

1. 2. 3. 4. 5. 6. 7. 8. 9.

Disperse Blue 1 Disperse Blue 35 Disperse Blue 106 Disperse Blue 124 Disperse Orange 3 Disperse Orange 37/59/76 Disperse Blue 3 Disperse Red 1 Disperse Yellow 3

2475-45-8 12222-75-2 12223-01-7 61951-51-7 730-40-5 13301-61-6 2475-46-9 2872-52-8 2832-40-8

Enforcement of this policy will include G

G

G

All suppliers must guarantee in writing that they will not use any of these dyes and pigments for fabric, trims, and accessories used in garments supplied to Calvin Klein as a condition of our manufacturing agreement. This includes leather and other materials. All suppliers to Calvin Klein must obtain a guarantee from the manufacturer of their dyestuffs and chemicals as to their compliance with these requirements. Calvin Klein may randomly test for above restricted substances through an independent laboratory. Failure to comply can be a breach of contract and can result in fines.

6.10.3 Other restricted substances Required test

Method

Phthalates

CPSC-CH-C100109-3 (solvent extraction 1 GCMS)

Formaldehyde

Textiles JIS L-1041 Leather ISO 17226

Standard

Adults— , 75 ppm Children: not detected.— 024 months , 20 ppm—all others

Comments Di-(iso-nonyl) phthalate (DINP), diethylhexyl phthalate (DEHP) Mandatory US testing required in addition to the supplier’s written guarantee Example: can be found in resins

Phenols incl.: (Continued)

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(Continued) Required test

Method

Standard

PCP—CAS# 87-865 (pentachloraphenols) TeCP (tetrachlorophenols) Cleavable arylamines (azo)

LFGB y 64 BVL B 82.02.08

Below 3 years ,0.05 ppm Above 3 years ,0.5 ppm

Textiles—ISO 14362-1/2 Leather ISO 143621 4-Amino azobenzene— LFGB 64 BVL B 80 02 9 DIN 54231

Detection limit: 5 ppm

Carcinogenic dyes (a.o. navy blue) Allergenic disperse dyes

DIN 54231

Nickel release test

“Spot test”/EN 12471 If dispute use: EN 1811/12472, for simulation of wear and corrosion Paint/ink/surface coating CPSCCH-E1003-09.1

Lead content

Lead content

Lead substrate CPSC-CHE1002-08.1

Comments

MAK class III, categories 1 and 2

Carcinogen dyes required: not detected Allergen dyes required: 5 mg/ L ,0.5 µg/m2/week

No more than 90 ppm lead content based on the weight of the dried paint or coating film

Apparel/clothing; plastic materials 30 ppm Handbags/belts/ footwear 200 ppm

Example: painted buttons, snaps, zippers, etc. Pigment prints and dyes, coating and lamination on fabric Mandatory US testing required in addition to the supplier’s written guarantee California Proposition 65 Mandatory US testing required in addition to the supplier’s (Continued)

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(Continued) Required test

Method

Lead substrate Nonmetal: CPSC-CH-E100208.1 Lead substrate Metal: CPSC-CH-E100108.1

Chromium VI

ISO17075

Cadmium

Balance; acid digestion 1 ICP/ AAS

Organotins (such as triphenyltin, dibutyltin, dioctyltin, tributyltin)

Solvent extraction, gas chromatography mass spectrometry (GC-MS) analysis liquid chromatography mass spectrometry ( LC-MS) LC-MS

Perfluorooctanesulfonates (PFOS)

Perfluorooctane acids (PFOA)

Standard Metals on handbags/belts/ footwear 300 ppm 100 ppm

Prohibited Detection limit: 3 ppm Limit: ,75 ppm

Comments written guarantee

Other materials, for example, textile/ leather, metal AAFA—RSL most updated version Mandatory US testing required in addition to the supplier’s written guarantee Mostly found in leather Can be found in PVC, PU, neoprene, and plastic-coated trims (such as buttons, buckles, and zippers) Mandatory US testing required in addition to the supplier’s written guarantee

Nondetectable

1 µg/m2

Can be found in fabric protectors and stain repellants

1 µg/m2

Can be found in fabric protectors (Continued)

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(Continued) Required test

Method

Standard

Comments

Dimethyl fumarate

GC-MS

0.1 mg/kg EU legislation only

Cobalt dichloride

substances of very high concern (SVHC) screening

Prohibited EU legislation only

and stain repellants Can be found in silica gel packets, leather, natural materials (e.g., straw), etc. Can be found in silica gel packets

6.10.4 Banned substances and processes Flame retardants

CAS number

Octabromodiphenyl ether (OctaBDE) Pentabromodiphenyl ether (PentaBDE) Polybrominated biphenyls (PBB) Tris (aziridinyl) phosphine oxide (TEPA) Tri-(2,3-dibromopropyl)-phosphate (TRIS) Deca (BDE) Hexabromocyclododecane (HBCDD) Alpha-hexabromocyclododecane

32536-52-0 32534-81-9 59536-65-1 5455-55-1

Beta-hexabromocyclododecane Gamma-hexabromocyclododecane

Solvent extraction and analysis by GC-MS or LC-MS

126-72-7 1163-19-5 25637-99-4 134237-506 134237-517 134237-528

Tris(2-chloroethyl) phosphate (TCEP) Note that the substances and processes listed in the table are banned on all Calvin Klein products.

6.11

Introduction to manufacturing restricted substances list (MRSL)

The MRSL or manufacturing restricted substances list is an approach to control and monitor hazardous and restricted substances used in the manufacturing process of textile, footwear, and trim materials. It is a list of substances subjected to a usage ban, while allowing for reasonably expected manufacturing impurities or unintentional contaminations that should be consistently achievable by responsible chemical manufacturers (Das, 2015; ZDHC, 2015).

Hazardous, restricted, and manufacturing restricted substances in textiles and clothing supply chain

6.12

125

Difference between manufacturing restricted substances list (MRSL) and restricted substances list (RSL)

The RSL restricts the presence of residues of restricted substances only in the finished article, while the MRSL puts limits for unintentional residues of restricted substances in chemical formulations used and discharged during manufacturing. The MRSL takes into consideration both process and functional chemicals used to make products as well as sundry chemicals such as those used for maintenance and cleaning of equipment and facilities. It addresses the entire range of chemicals used within the four walls of a manufacturing facility.

6.13

Scope of a manufacturing restricted substances list

The scope of an MRSL covers all chemical substances potentially used on an article and/or discharged into the environment during manufacturing or related processes —not just those substances that could be present in the finished article. These are ingredients potentially used in cleaners, solvents, adhesives, stabilizers, paints, inks, detergents, dyes, pigments, auxiliaries, coatings, and finishing agents used for wet processing, maintenance, wastewater treatment, sanitation, and even pest control in a facility (ZDHC, 2015). The substances listed in an MRSL are those that may be used or found in commercially available chemical formulations—not those from early stages of chemical synthesis. Brands expect material suppliers and factories to communicate this MRSL document to all their chemical suppliers and ensure that the listed substances are not present in their commercial chemical formulations above the limits specified in the document.

6.14

Implementation of a manufacturing restricted substances list in a facility (ZHDC Group, 2015)

The following steps can be followed: G

G

G

G

G

Map the inventory of all chemicals used in the facility for direct application as well as Sundry Chemicals, along with the details of the suppliers. Communicate the MRSL to all chemical suppliers. Get the declaration of conformance to the MRSL limits from chemical suppliers for all chemicals used in the facility. Prepare a list of chemicals that do not conform to the MRSL limits and “phase out” these chemicals by procuring safer alternatives. Implement the safer alternatives after evaluating for performance and cost considerations.

126

6.15

Chemical Management in Textiles and Fashion

Role of MRSL to ensure RSL compliance of a finished product

The MRSL bans intentional use of restricted substances in input chemical formulations and details limits for unintentional contaminations that may be expected as impurities in commercial formulations. Thus, compliance by a chemical manufacturer to the MRSL will definitely ensure your compliance to brand RSL requirements. However, the MRSL does not replace legal or brand-specific restrictions of hazardous substances in finished products.

6.16

Restricted chemical groups mentioned in brand RSL and MRSL documents

The chemical groups covered in both RSL and MRSL documents are the same. However, the limits for individual analytes may differ. This is because RSL limits are for residual contaminations in a finished article, while MRSL limits are for unintentional contaminations in commercial chemical formulations. In some MRSL documents, additional chemical groups such as glycols and volatile organic compounds or VOCs are included. Also, in an MRSL, the limit values are always expressed as milligram per kilogram, while in an RSL document, there are also other units of measurement such as mg/L (for disperse dyes and other dyes), microgram/cm2/week (for nickel release), µg/m2, or µg/cm2 (for PFCs).

6.17

Important terms and definitions used in a typical MRSL document (ZHDC Group, 2015; ZDHC, 2015)

Substance: It is a chemical element and its compounds in the natural state or obtained by any manufacturing process. A substance is usually identifiable by a unique, single chemical abstracts number (CAS) or by a color index number. Commercial chemical formulation: It is usually a proprietary blend of several substances that is available for purchase from chemical suppliers under their own trade name. Usage ban: It indicates that the MRSL-listed substance or a group of substances may not be used to achieve a desired function or effect. In other words, there should be no intentional use of the substance in the production of the chemical formulation. However, due to the presence of manufacturing impurities, a minor or trace amount of the restricted substance is permitted up to certain specified limits.

Hazardous, restricted, and manufacturing restricted substances in textiles and clothing supply chain

6.18

127

Structure of a manufacturing restricted substances list document

A typical MRSL tabulation will comprise the following columns: The MRSL chemical groups (e.g., phthalates, organotins, APEOs, etc.). Substance name, that is, the list of analytes in each MRSL chemical group. CAS number of the substance. Criteria: For chemical suppliers, the criteria are the limits prescribed for unintentional contaminations. For example, under APEOs, the limit for nonylphenol and octylphenol ethoxylates could be 500 ppm. This means that a commercial chemical formulation should not contain unintentional contaminations of these substances beyond 500 ppm. 5. Potential uses in the apparel and footwear manufacturing processes. 6. General techniques for analyzing these substances in the chemical formulations. It is important to know that since there are no standard test methods currently available for testing of restricted substances in chemical formulations, only test equipment details are mentioned in an MRSL. However, some brand MRSL documents have listed chemical test methods. 1. 2. 3. 4.

Chemical management for restricted chemicals/substances in textile supply chain: For ensuring RSL compliance of finished articles, the following best practices can be implemented in the factory (Das, 2015): appointment of a compliance manager; implementing right purchase practices; understanding of chemical-related documentation; screening of inputs (including new chemicals) for restricted substances; testing of finished articles for restricted substances; training for internal team and chemical suppliers on restricted substances; and preparing a database of RSL noncompliance with corrective actions. Appointment of a compliance manager The first important step to implement the best practices for RSL compliance is “appointment of a compliance manager” who will be responsible for all the RSL-related issues in the factory. The compliance manager should have the following qualifications and capabilities: He should have an educational background in chemistry and/or textile processing. He should have good interpersonal skills to provide training at all levels. He should have the ability to establish programs and to collect, analyze, and communicate substance-related data effectively. Important roles and responsibilities of a compliance manager are: collection, analysis, and communication of RSL-related documentation and recordkeeping; implementation of chemical management systems at the facility; and training of internal staff on restricted substances and safe work practices. 2. Implementing right purchase practices Right purchase practices should be implemented in the factory for ensuring RSL compliance. You should only purchase goods and products which conform to brand RSL requirements. For this, the purchase department must communicate your RSL

1. 2. 3. 4. 5. 6. 7. 1.

G

G

G

G

G

G

G

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requirements to all your chemical and raw material suppliers. Then you must get proper RSL compliance declarations for all the chemicals and raw materials from all the suppliers. Last, you must maintain and update all chemical-related documents such as brand RSLs, material safety data sheet (MSDS), and technical data sheet (TDS). Chemical-related documentation It is also important to maintain proper records of all the chemical-related documents at the factory. Such documents include brand RSL documents, MSDS, TDS, RSL compliance supplier declaration, and RSL test reports from the laboratories. You must ensure that: All the brand RSL documents are updated as and when a brand makes changes in its document. All the MSDSs are complete and studied to analyze the hazards in the chemicals. All the TDS are kept in the production department and the instructions therein rigorously followed. RSL compliance declarations are collected from all the chemical and raw material suppliers and these are reviewed for making action plans on phase-out and substitution of chemicals containing restricted substances. Test reports on finished articles tested for restricted substances are maintained with details on corrective actions taken for any RSL noncompliance. Screening of inputs for restricted substances The next best practice for the RSL compliance is “screening of inputs for restricted substances.” Input chemicals (including new chemicals) and raw materials must be screened for restricted substances through supplier declarations and laboratory testing, wherever required. You must get supplier declarations for every chemical and raw material entering your facility. You should ensure that all the supplier declarations cover all the RSL chemical groups and also cover unintentional contaminations. Input chemicals and raw materials can also be tested randomly for unintentional contamination or the presence of restricted substances. Testing of finished articles for restricted substances In addition to input chemicals and raw materials, finished articles should also be tested and monitored for reduction and elimination of restricted substances. You should develop a testing plan for finished articles based on the type of process, substrate, and chemicals used. Training for internal team and chemical suppliers Training is an important action to be performed in your facility. For internal team and chemical suppliers, you must conduct training on: restricted substances and risk areas and chemical management systems For workers, training should be conducted on: safe handling and use of chemicals; use of personal protective equipment; safe practices in the workplace for chemical handling; and mock drills on fire and medical emergency, first aid, and response to spillages or leakages of chemicals. Preparing a database of RSL noncompliance, with corrective actions G

G

G

G

G

4.

5.

6.

G

G

G

G

G

G

7.

You should prepare and maintain a database of any RSL noncompliance occurring in your facility. You should conduct a root cause analysis of an RSL

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noncompliance and record the corrective/preventive actions to prevent recurrence of the noncompliance in future.

6.19

Global legislations on harmful chemicals in textiles

Chemicals have become an integral part of our lives. We interact with chemicals from the time we wake up in the morning until the time we go back to bed at night. Man lived sustainably and harmoniously with nature, till the discovery of oil. Soon, man learned to create synthetic chemicals and materials using petroleum products extruded from the earth. This led to enormous growth in man-made articles such as plastics, synthetic fibers, and synthetic colorants and garments. The exponential growth in human population led to various environmental problems such as contamination of soil, air, and water (NimkarTek Technical Services Private Limited, 2015). Some chemicals and colorants used in the manufacture of textiles have a negative impact on the human body on exposure. Hence, there was a need for legislation on chemicals. The first initiative was taken in 1960 by the World Health Organization (WHO) followed by the United States and Nordic countries to regulate the use and production of chemicals. From 1960 to 2000, many conventions, protocols, agreements were made to regulate the chemicals until, a very important legislation, called the REACH was enacted by the EU parliament in 2006. The first three chemicals in textiles that were regulated are formaldehyde, carcinogenic amines released from certain azo dyes, and pentachlorophenol. The brief summary of country-wise regulations is described below (NimkarTek Technical Services Private Limited, 2015). In the United States, there are two systems for legislations: 1. Federal laws and 2. State laws.

Federal laws are applicable to the people living in all the territories of the United States and State laws are applicable to people living in a particular state in the United States. The Consumer Product Safety Improvement Act (CPSIA) is considered to be one of the most important federal laws in the United States for consumer products, especially designed for children. As per the CPSIA, it is mandatory for domestic manufacturer or importer of children’s products designed or intended primarily for children 12 years of age or younger to: 1. Issue a written Children’s Product Certificate that provides evidence of the product’s compliance to the law to his distributors and retailers. 2. Be tested for compliance by a CPSC-accepted accredited laboratory. 3. Have permanent tracking information affixed to the product and its packaging where practicable.

In case of nonchildren’s products, the CPSIA requires domestic manufacturers or importers of nonchildren’s products to issue a General Certificate of Conformity

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(GCC). The CPSIA regulates specific substances such as lead and phthalates in children’s products, including children’s apparel and sleepwear. The specific restriction with limit values has been covered in the module. The second federal law in the United States is “Federal Insecticide, Fungicide, and Rodenticide Act,” also referred to by the acronym “FIFRA,” which was enacted to regulate the distribution, sale, and use of pesticides to protect human health and the environment. As per FIFRA, the antibacterial chemicals or finishes used in the manufacture of textiles are considered to be pesticides. And hence, this law applies to textiles that are treated with antibacterial chemicals. The state law “California Proposition 65” is the original name for the Safe Drinking Water and Toxic Enforcement Act. As per Cal Prop 65, it is the responsibility of the importer to prove to the Office of Environmental Health Hazard Assessment (OEHHA) that an article does not contain any of the listed chemicals. If it contains any of the listed chemicals, then a warning label must be put on the product stating that “This product contains a chemical known to the State of California to cause cancer, birth defects, or other reproductive harm.” Washington Children’s Safe Product Act (WCSPA) was enforced in April 2008, to reduce the risk posed by the toxic chemicals in children’s products. This law is applicable only to the State of Washington and is implemented in two parts. G

G

Part I: Restriction on children’s products containing lead, cadmium, and phthalates Part II: Notification on Chemicals of High Concern to Children (CHCC)

The children’s products are allowed for manufacture and sale provided it contains lead # 90 ppm, cadmium # 40 ppm, and eight phthalates # 1000 ppm individually or in combination. If a CHCC is intentionally added or present as a contaminant above 100 ppm in children’s products such as garment, toys, and jewelry, then the manufacturers or distributors must provide notice to the Department of Ecology (NimkarTek Technical Services Private Limited, 2015). In the European Union (EU), an important regulation is the REACH. It stands for Registration, Evaluation, Authorization, and Restriction of Chemicals. The REACH law applies to pure substances, mixtures, and articles. Compliance to REACH regulation for textile articles is required in three ways: 1. Communication or notification is applicable if an SVHC on the Candidate List is used in an article produced or imported into the EU. It is an obligation for EU producers and importers of articles. 2. Authorization is applicable if an SVHC listed in Annexure 14 of REACH must be used in an article produced in the EU, but not imported into the EU. 3. Restriction is applicable if chemical listed in Annexure 17 of REACH is used in a substance, preparation, or an article produced or imported into the EU.

The second regulation applicable to textiles is the Biocidal Product Regulation EU 528/2012 that concerns the placing on the market and use of biocidal products. As per this regulation, treated articles should not be placed on the market unless all “active substances” contained in the biocidal product with which they were treated are approved in accordance with the regulation.

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In Korea, textiles are regulated under two important laws. These are: 1. Self-Regulatory Safety Confirmation Act and 2. Safety Quality Mark.

The textile products that are intended for infants of less than or equal to 36 months are covered under Self-Regulatory Safety Confirmation Act. General textile products such as innerwear, mid-wear, outerwear, and bedding are covered under Safety Quality Mark Act. As on January 2015, the restricted substances included under Self-Regulatory Safety Confirmation Act for infant clothing and textile products are formaldehyde, azo dyes, phthalates, organotin compounds, dimethyl fumarate, flame retardants, lead, and allergenic disperse dyes. Similarly, the limits for children’s and adult textile products have been covered under the Safety Quality Mark Act. In Taiwan, the Bureau of Standards, Metrology, and Inspection (BSMI) has implemented an inspection regime for chemicals in textile products, based on the Chinese National Standards, that is, CNS 15290 Safety of Textiles. According to BSMI, there are two main categories of textile products. These are: 1. babies garments and clothing accessories under 24 months of age or height less than 86 cm; 2. general textile products such as towels, sweaters, garments, swimwear, underwear, hosiery, and bedding.

Taiwan BSMI has set limit values for chemicals that may be present in the textile products sold in the Taiwanese market. BSMI requires manufacturers to comply with these limits. Textile products sold in Taiwanese markets must also bear a safety mark called Commodity Inspection Mark. In China, there are two types of regulatory standards. 1. mandatory national standards prefixed by GB or GB/T (GB standards) and 2. product-specific standards prefixed by FZ (voluntary).

The GB 18401-2010 is applicable to textiles that are divided into three categories: infant products, skin contact products, and nonskin contact products. Currently, GB 18401-2010 standard covers product safety in terms of formaldehyde content, pH of the aqueous extract, colorfastness to water, perspiration, rubbing, and saliva, odor, and dyestuffs cleaved into arylamines from azoic colorants. An important voluntary standard for infant clothing is FZ/T 81014-2008.This standard is applicable to all textile woven fabrics as the main raw material and apparel products for infants and young children of age less than or equal to 24 months. The other regulations that are applicable to textiles are listed below. 1. 2. 3. 4.

Consumer Product Safety Act, Canada The Act on Control of Household Products containing Harmful Substances, Japan The Chemical Risk Reduction Ordinance, Switzerland Regulations on limitations of Substances in Products, Norway

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Practical challenges in managing RSL and MRSL in a textile mill

The manufacture of textile articles uses hundreds of input chemicals in various processes but some of these chemicals can affect the health of the end consumer. For example, these chemicals can cause allergies and eczema on contact with the skin. Some chemicals used in the process are volatile and are released into the air, impacting the health of the workers. For example, solvents used for dry cleaning and removal of stains on fabrics are volatile and cause eye irritation to workers. Chemicals such as sodium hydrosulfite can be a spontaneous ignition risk if it comes in contact with oxidizing agents such as hydrogen peroxide or with moisture. It is thus imperative to store such chemicals separately. The effluent discharged from a textile mill contains many polluting chemicals that can affect aquatic life and human health. Some toxic chemicals such as APEOs used widely in textile processes can be toxic to fish. Other chemicals such as urea and some sequestering agents contain phosphates, which when discharged into the effluent, cause eutrophication, that is, excessive growth of algae in lakes and river surfaces that prevent sunlight and air penetration, resulting in the death of aquatic species.

6.21

Conclusion

Most of the brand RSLs only take care of the residual chemicals on their end products by restricting/prohibiting “harmful” or “toxic” substances residual chemicals as required by legislation but not those discharged into the environment. Further, chemicals find their way into RSLs to comply with the regulations on consumer goods to protect. However, since regulations vary from country to country, there is inconsistency among the brand RSL requirements. For example, some of them include chemicals because it is illegal to use them in manufacturing to control occupational exposures to protect workers. There are many chemicals that are known to be harmful humans, wildlife, or the environment but, to date, they have escaped being made the subject of specific legislation, either in terms of use or of sale. Most reputable brands include such chemicals on their RSLs despite not being obliged to do so. Consumer and media assurance is an unavoidable part of the chemical landscape nowadays and some substances are on RSLs because brands have to take a position on a substance. However, a comprehensive list of restricted chemicals and auxiliaries across the sectors related to textiles with suitable substitutes could help the manufacturers in a big way.

References Act, T.C.P., 1986. The Consumer Protection Act, 1986 & rules. Bhatt, P., Rani, A., 2013. Textile dyeing and printing industry: an environmental hazard. Asian Dyer 10 (6), 5154.

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Brown, V.J., 2012. Why is it so difficult to choose safer alternatives for hazardous chemicals? Environ. Health Perspect. 120 (7), 359361. Das, S., 2015. Product Safety and Restricted Substances in Apparel. Woodhead Publishing India Pvt. Ltd., New Delhi. Deshpande, S.D., 2001. Ecofriendly dyeing of synthetic fibres. Indian. J. Fibre Text. Res. 26 (12), 136142. Kant, R., 2012. Textile dyeing industry an environmental hazard. Nat. Sci. 4 (1), 2226. KEMI, 2014, Chemicals in Textiles: Risks to Human Health and the Environment. Swedish Chemicals Agency Report. pp. 1142. Luongo, G., 2015. Chemicals in textiles: a potential source for human exposure and environmental pollution. MBDC, LLC, 2012. Banned Lists of Chemicals. NimkarTek Technical Services Private Limited, 2015. Guide Book of Chemical Management for Textile & Garment Industry. NimkarTek Technical Services Private Limited. Olson S.S., 2014. International Environmental Standards Handbook. ¨ zkara, A., Akyil, D., Konuk, M., 2016, Pesticides, environmental pollution, and health. In: O Environmental Health Risk  Hazardous Factors to Living Species. pp. 328. REACH, n.d. Restricted substance list. Available from: ,https://echa.europa.eu/substancesrestricted-under-reach.. Rev, U., 2014. The Ericsson Lists of Banned and Restricted Substances, no. November. pp. 016. ZDHC, 2015. MRSL for Textiles and Coated Fabrics Processing. ZDHC. Available from: ,https://www.roadmaptozero.com/mrsl_online/.. ZHDC Group, 2015. Manufacturing restricted substances list implementation framework.

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G. Prasannamedha and P. Senthilkumar Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Kalavakkam, India

7.1

Introduction to chemical compliance in textile industry

India is one of the fastest-growing economical countries with GDP rate of 6.6%. Textile sector is one of the oldest industries in the Indian economy consisting of two major segments, namely; traditional and modern sectors. Traditional sector includes handlooms, handicrafts, and sericultures, whereas the modern segment includes spinning and composite mills with fresh and restructured concepts. It is estimated that a total of 9.3 million metric tons of chemicals are used throughout the world per year. In the existing textile and fashion industry, health and environmental hazards not merely lie in use of chemicals in manufacturing processes but complete chain of processes that are involved in nailing the final products from preliminary stage till finish. There are two types of chemicals used in weaving textiles in industrial sector. They are hazardous and nonhazardous chemicals. Each chemical has different functional role that depends on structural and chemical groups present in it. Toxicity of each chemical depends on its strength of functional groups and its bonding nature with the substrate. Apart from the chemical nature, pH, temperature, presence of inorganic ions, and other substances define its toughness before involving them in built-up system. Hazardous refers to exposure of living being to danger or chance of harm or risk. Identification of chemical and its range of toxicity is the preliminary stage in farming regulation and laws. Chemical compliance is a term that defines the standards to maintain moderate working environment. Here standard denotes rules and laws to be followed for using chemicals in textile industries as they have direct effects on workers such as inducing allergic reactions or persistent accumulating in biota. As the data about chemicals are not transparent, it is mandatory to gain knowledge about them, thereby reducing its level of wastage (Textile Learner, 2015; Textile Fashion Study, 2012; Textile Today, 2017). Toxicity of chemical is identified by consumers through different ecolabels such as Bluesign, EU Ecolabel, Oeko-Tex, GOTS, Fair Trade SA 8000, and many more. Apart from labels, different governments have enforced laws and legislation to protect ecosystem and human health (Fibre2Fashion.Com). Some of them are Consumer Product Safety Improvement Act (CPSIA), the Toxic Substance Chemical Management in Textiles and Fashion. DOI: https://doi.org/10.1016/B978-0-12-820494-8.00007-1 © 2021 Elsevier Ltd. All rights reserved.

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Control Act (TSCA), Washington Children’s Safe Product Act (CSPA), California Proposition 65 (Cal Prop 65), China GB 18401-2010, and Japan Law 112. With the view of the above-discussed points, this chapter briefs the importance of chemical compliance in the textile sectors along with enforced laws and legislations for reducing/preventing the impacts caused due to the unconditional use of chemicals (Fibre2Fashion.Com).

7.2

Overview of chemicals used in textile industry

Some of the chemicals that are used in manufacturing of textile products are given below (United Nations Environment Program DTIE/Chemical Branch, 2011) (Table 7.1). The above-discussed chemicals are some of them that are used in textile industry. Mostly, processes such as dyeing/printing and finishing require and yield more chemicals that can be witnessed in environmental components. The nature of chemicals that are found in the finished textile depends on its specific physical and chemical properties. During the processing of textile products, there should not be Table 7.1 List of chemicals used in textiles. Substance

Functional role

Release pathway

Nonylphenol ethoxylates (NPEs)

Detergents and auxiliaries water, oil, stain, and wrinkle-resistant coatings Fire retardant

Water

Perflourinated compounds (PFCs, including PFOs, PFNA, and FTOH) Poly-brominated diphenyl ethers (PBDEs), hexabromocyclododecone (HBCD) Short-chain chlorinated paraffins (SCCPs) Asbestos Phthalates Heavy metals (e.g., lead, cadmium, organotins) Silver Triclosan Dimethyl fumarate (DMF) Heavy metals (e.g., mercury, cadmium, and lead) Azo dyes (which can cleave into carcinogenic aromatic amines in the presence of external factors) Chromium SCCPs Heavy metals Nonylphenol ethoxylates

Plastic coatings Antibacterial and antimold agents

Water

Water Water Air Water Water Water Water

dyes and colorants

Water Water

Footwear and leather products Others

Water Water Water Water

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any chemicals that are left in finished textiles. The presence of residual chemicals depends on its water solubility and persistent parts that are found in the chemical structure.

7.3

Identification of hazardous chemicals in textiles

Hazardous chemicals refer to chemicals with properties such as toxic, corrosive, explosive, combustible, combustion-supporting, flammable, and irritant. The Swedish Chemicals Agency (KEMI) investigated about the list of chemicals that are hazardous in textile production along with their properties. According to the chemical survey in textile industry during 2005 12, perfluorinated compounds, phthalates, heavy metals, flame retardants, isocyanates, organic tin compounds, antibacterial substances, free acrylamides from dyes, formaldehyde, and glycols were identified to hazardous compounds (Hazardous chemicals in textile, Swedish Chemical Agency) (Table 7.2). Generally, hazardous substances in textile are classified as carcinogenic, mutagenic, and toxic for reproduction. This agency has chosen only the classified substance of CLP regulation (EC) No 1272/2008. The database contains classification, labeling, and information on notified chemicals that are reported by importers and manufacturers. Table 7.2 List of hazardous chemicals based on KEMI (2013). S. no.

Compound

Functional role in textile

Risk assessed

1

1-Vinyl-2-pyrrolidone

Risk is negligible

2 3

o-Anisidine Acrylonitrile

Ultraviolet curing for ink and coatings Pigments or dyes Used in the production of acrylic and modacrylic textile fibers

4

Tris(2-chloroethyl) phosphate (TCEP) Decabromodiphenyl ether (DecaBDE) Antimony trioxide Hydrogen peroxide

5 6 7

8 9

Hexabromocyclododecane (HBCDD) Alkanes, C10 13, chloro (SCCP)

Flame retardant Plasticizer Flame retardant Flame retardant Textile bleaching by consumers Textile coating agent, flame retardant Flame retardant, water repellent

Dermal or oral issues Dermal and inhalation. It is a nonthreshold carcinogen Inhalation, dermal, and oral risk Dermal Dermal Dermal, inhalation, irritation to eye, corrosivity Oral, inhalation Oral, inhalation

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Categorization of hazardous chemicals

Various global and national regulations and laws define hazardous chemicals in different terms depending on particular legislation. European Union and the United States had used globally harmonized system (GHS) for categorizing various harmful chemicals in systematic manner. GHS is defined as uniform system of classification, ranking, and way of communicating information about hazardous chemicals. It uses pictograms and symbols for representing hazardous chemicals. There are nine symbols among which four representing physical hazard, one representing environmental hazards, and four representing health hazards (Cahn and Clifford, 2014) (Table 7.3).

7.5

Need for chemical compliance in textile sector

The aim of chemical compliance is to protect human health and environment from hazardous chemicals. Textile industry uses a number of chemical substances such as solvents, pigments, dye, etc., which need to undergo registration, evaluation, and authorization. Textile manufacturing is a big chain that includes authorities such as stakeholders, chemical manufacturers, governmental and nongovernmental organizations. Establishing a better place in global industrial platform, stringent laws are enforced for chemicals. Performing chemical test for supplied chemicals and finished products may help in complying with laws enforced, but this procedure is not effective when taken for long-term analysis. Profound chemical management is the best possible way for controlling risk and toxicity assessed due to use of hazardous chemical substances. Through better compliance of chemicals, it is easy to manage the supply chain for better understanding of chemical composition in the final product and introduce product in the market. Various laws have been enforced for chemical management in the textile industries to meet compliance. Compliance includes obeying regulatory and voluntary standards.

7.5.1 Regulatory standards Some of the regulatory standards to be followed for authorizing chemicals that are used and found in final products of textile and clothing industries are (DyStar): 1. Chemical control legislation—REACH 2. Pollution control legislation— integrated pollution prevention and control (IPPC) 3. Consumer product safety legislation—CPSIA

REACH—It is an EU regulation expanded as Registration, Evaluation, Authorisation, and Restriction of Chemicals. It targets all manufacturers and importers of chemicals to identify all chemical compounds, which industry manufacture and market that pose risk to human and environment. This is an important

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Table 7.3 GHS symbols for hazardous chemicals. S. no.

GHS symbols (image source: www.ec.europa.eu)

GHS term

Physical hazardous chemicals 1 Explosive and reactive compounds

Hazardous nature

It includes explosives and extremely reactive chemicals such as organic peroxides, water-reactive, selfreactive chemicals

2

Flammable substances

It includes flammable liquids, solids, and gases such as pyrophorics, selfreactive chemicals, and chemicals that release flammable gases

3

Gases

Gases under pressure such as LPG and compressed gases in cylinders

4

Oxidizers

They need not to be combustible, but upon combustion, it may yield rapid oxygen that may cause combustion to other materials

5

Toxicity

It is categorized to be acute toxicity. It is a poison for consumers

6

Corrosive

Corrosive to skins, eyes, and metals

7

Moderate toxicity

Irritation to skin, eye, allergic effects, and nervous systems such as drowsiness and dizziness

8

Serious toxicity

Cancer, reproductive, respiratory toxicity, and target organ infection

Health hazardous chemicals

(Continued)

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Table 7.3 (Continued) S. no.

GHS symbols (image source: www.ec.europa.eu)

GHS term

Hazardous nature

Physical hazardous chemicals

Environmental hazardous chemicals 9

Hazardous to aquatic bodies

Fishes, plants, and bioaccumulative

legislation to be followed by textile and fashion industries for complying with the toxicity of chemicals.

7.5.2 Voluntary standards It denotes labels/certificates/standard schemes operated on voluntary basis by NGOs, not-for-profit, testing laboratories, consultancies, or consortia. Some of the important labels in textiles and clothing industry from environment/chemical point are: G

G

G

G

G

Oeko-Tex STANDARD 100 EU Ecolabel Global Organic Textile Standard (GOTS) Bluesign Cradle-2-Cradle (C2C)

7.5.2.1 Oeko-Tex STANDARD 100 STANDARD 100 is a testing and certificate system for textile products by OekoTex. This test is performed for all harmful chemicals that are prone to be harmful to human health. The tested chemical or product is allocated to one of the four STANDARD 100 classes based on its end use. The certificate is valid for 1 year and renewed as often as required.

7.5.2.2 Global Organic Textile Standard GOTS is a standard followed for processing organic fibers from harvesting till final products. It is followed by most of the manufacturers all around the world, hence it is the most approved certificate in the globe. It requires social compliance in addition to environmental compliance. Dyes, chemicals, and reagents used in the process of manufacturing fabric should meet both environmental and toxicological criteria (Amutha and Muthu, 2017).

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Product categories All the textile and allied materials along with its products are categorized into 19 categories. They are: Accessories

Ladies wear

Technical textiles

Baby wear Children wear Fabrics Garments Home textiles Hygiene products

Leisure wear Men’s wear Nonwovens Raw fibers Socks Sportswear

Toys Underwear Yarn Others

Types of Global Organic Textile Standard label There are two label grades for textile products, namely Label grade 1: “Organics” and Label grade 2: “made with X% organics.”

7.5.2.3 Bluesign It was founded in Switzerland in 2000. The main aim of this certificate is to provide comprehensive production control system to prevent harmful to human and environmental impacts. Almost 80% of the international testing companies in the world follow Bluesign. This standard is based on five principles of sustainability: resource productivity, consumer safety, air emission, water emission, and occupational health and safety. Here preproduction audit is performed at each phase within production chain to ensure compliance with sustainability principle. There are three tools in the Bluesign concept. Bluetool: It is a chemical evaluation tool. Bluefinder: Database of approved chemicals and dyes. Blueguide: Catalog containing approved textile products.

7.5.2.4 Cradle-2-Cradle C2C design is a tool promoted by Dr. Michael Braungart of EPEA, Hamburg. It stands for innovation, quality, and good design of products. It describes the safe and potential use of materials in cycle. There are two nutrient cycles followed in C2C design concept, namely biological and technical cycles. In biological cycle, material is taken back to biosphere from where new material is generated, whereas in technical cycle, materials that are not used as product can be reprocessed and allowed them to use as new product. This design concept relies on principles of an ideal circular economy. It allows the companies to present their products not only for sale but also for use. After the use of products, the materials are allowed to take bake in the reprocessing system,

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thereby maintaining the circulation system (EPEA—Part of Drees & Sommer, M. Braungart).

7.5.2.5 EU ecolabels It was launched by the European Commission in 1992. This is a voluntary scheme that rewards products and services that are less harmful to the biosphere. It is an idea of encouraging manufacturers to go beyond regulations and legislation in reducing the environmental impact due to the formed product. Manufacturer can label the product only after verified by national authority. It encourages company to develop products that are durable, easy to repair and recycle. It promotes sustainable economy by encouraging producers to generate less waste and CO2 during the manufacturing process. Few reasons for opting EU Ecolabel is, it works in accordance with ISO Standard 14024 for reliable way to communicate environmental information to consumers. Hence it can also be termed as Type I label. It creates a favorable climate for marketing green products among consumers (European Commission, Environment, Industry).

7.6

Compliance requirements

Compliance is defined as chemical management practices. It is the foundation for every company selling or manufacturing products to meet the requirements framed by legislative bodies (Cattlemole Consulting Inc). The need for compliance of chemicals in textile industry is (1) address the hazards associated with chemicals that are used on manufacturing process, (2) take responsibilities for health and welfare of existing and future generation, and (3) address the concern from buyers, stakeholders, consumers. With respect to the above demand, there are few associations that work in framing safer chemical management practices. By implementing chemical management practices, there will be the reduction in excessive purchase of chemicals and release of the same to environment (Chemical Management for the Textile Industry).

7.6.1 Zero discharge of hazardous chemicals It is zero discharge of hazardous chemicals (ZDHC). The main aim of ZDHC is to enable textile industries to implement sustainable chemical management to promote zero discharge of hazardous chemicals. It is a road map to zero program, collaboration of major fashion brands, value chain affiliates, and associations which began in 2011. In 2014, ZDHC Manufacturing Restriction Substance List (ZDHC MRSL) version 1 with chemical guidance sheet was released. The same was updated in 2015 as ZDHC MRSL version 1.1 by including leather and coated fabrics. This established a clear vision on sustainable chemistry, driving innovation, and better practices in the industry to protect and prevent workers, consumers, and

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environment. In 2015, focus and crossing areas were formed to optimize impacts and praise the work of all industrial associations and nongovernmental organizations. Again all focus areas were restructured for better tackling of leather, textile, and footwear chain. During the up-gradation, few documents were released that relate standardized procedure and tools for reducing the workload and promote simplicity in manufacturing processes. It includes documents such as: G

G

G

G

framework for prioritizing chemicals of concern, that is, hazardous chemicals; chemical guideline sheet including 11 classes of hazardous chemicals; ZDHC MSRL; and chemical list that does not have an alternative (Cattlemole Consulting Inc).

There are three focus areas that work on three segments: (1) creating proper and systematic standards for industry, (2) effective implementation, and (3) involving all stakeholders for amplifying changes throughout the industrial production chain. The following are the three important steps (Zero Discharge of Hazardous Chemicals).

Standard setting guidelines

Collaborative implementation

Engagement of all stakeholders

7.6.1.1 Input focus area It focuses on restricting input chemicals instead of removing them from effluents. This includes ZDHC MSRL list, ZDHC Gateway—Chemical Module, ZDHC ChemCheck report, and ZDHC InCheck report.

7.6.1.2 Process focus area Focuses on tools and guidelines designed to assist chemical management practices harmonized execution of ZDHC Tools.

7.6.1.3 Output focus area It includes maintenance and guidelines for ZDHC wastewater effluents and its related tools are ZDHC Gateway—Wastewater Module and ZDHC ClearStream report.

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Figure 7.1 Three focus areas of ZDHC.

7.6.1.4 ZDHC MSRL This is a priority chemical list that should not be used intentionally and must be maintained within permissible concentration limit even in commercial chemical formulation. It is a living guide that is reviewed regularly and updated to meet the challenges in managing chemicals in textile, fashion, and footwear industries. The main objectives of ZDHC MSRL are listed below. G

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Transparency—It denotes the use of publicly transparent process for evaluating chemicals with respect to ZDHC MSRL. Inclusivity—It is meant to involve stakeholders from ZDHC contributors. Best available information on degree of hazardous and extent of exposure. To reduce hazardous effects and impacts of chemicals. Efficient use of ZDHC organizational resources.

The pictorial representation shown in Fig. 7.1 relates the three focus areas that are concentrated by ZDHC. ZDHC MSRL includes all those hazardous chemicals that are involved in textile, fashion, and footwear industries for which alternative replacements are chemicals that are commercially, economically and technically available in the market. In companies or private organizations, sections such as environment, health and safety, purchase team, and quality control are responsible for identifying toxicity and nontoxicity nature of chemicals with respect to its concentration in industrial applications. To ensure safety in textile industries, chemical safety program is essential.

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Life cycle of chemicals used in textile and fashion industries

Chemical compliance requires management of chemicals based on its life cycle with respect to industrial applications. This management of chemicals may reduce the negative impacts of certain hazardous chemicals. It involves the following steps that describe the process involved from the purchase of chemicals till the end of disposal. G

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selection of chemicals, purchase of chemicals, filling the data sheets with necessary information, delivery with receipt for chosen chemicals, storage of chemicals, transport of chemicals from yard to processing site, usage of chemicals, disposal of chemicals, and emptying the containers held chemicals.

7.8

Regulations promoted for hazardous chemicals

Some of the important regulations are implemented to regulate the use of chemical substances at various steps in textile processing industries. There are regulations that are directly linked to textiles such as REACH and indirectly linked such as IPPC, CPSIA, and TSCA. REACH—Registration, Evaluation, Authorisation and Restriction of Chemicals: This regulation is applied to all chemical substances used in industries and consumers’ applications. It enforces companies to demonstrate how they are managing potential risks and how chemicals are stored and handled with safety measures. TSCA: This regulates both new chemicals as well as existing chemicals used in the industries (Transparency One, 2019). The following section will elaborate on the regulations in brief.

7.8.1 REACH Reach regulation EC No. 1907/2006 is the European Union chemical regulation that ensures high-level protection of human health and environment along with free circulation of chemicals in the market while enhancing competitiveness in chemical industry. It enforces companies to identify risk and manage the same. Also it underlines the importance of safe handling procedures of chemicals and must communicate the risk management measures to the users. In case if the risk cannot be managed by the producers, REACH can restrict them from its use in many ways.

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7.8.2 How do REACH function? REACH provides some list of procedures for collecting and assessing information about properties and hazardous nature of substances that are used/produced by industries. This list provided to companies should register their substance to legislation. After registration, compliance for the substance is uploaded. European Chemical Agency (ECHA) receives the complied report for the prescribed substance and evaluates, further EU identifies the negative effects of substance on health and environment. At last the committee assesses whether the risk of the substance can be managed or not. If risks are unmanageable, authorities can ban the substances (European Chemical Agency). During the registration process, manufacturer or importer of chemicals having 1 tonne or more than 1 year, legal entity has to be registered in ECHA. ECHA has some 138 lists of chemicals in the candidate list. Candidate list is defined as a list of substances that cause serious and long effects on human health and environment (i.e., substance of very high concern, SVHC). Once a chemical is added to candidate list, it will have two phases, namely, short and long term. Short-term impacts are just needed to add in the information, whereas long-term impacts will be mentioned in prohibition list used in the textile industries (Hazardous chemicals in textile, Swedish Chemical Agency). The following are the steps involved in REACH.

7.8.2.1 Registration Registration applies to chemicals that industry own or mixture of chemicals. It is based on “one substance, one registration” principle which means that manufacturers and importers of the same chemicals should submit their registration jointly. Analytical and spectral information provided should be constant and plenty to confirm the substance identity. Information about impacts, risk and hazardous nature of chemicals are provided in registration dossier that is further communicated to ECHA.

7.8.2.2 Evaluation ECHA and members of community evaluate the quality of information provided in registration dossier, testing methodologies, and notify the toxic impacts of substances. Evaluation takes place at three different points. G

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Testing proposals submitted by registrants. Cross-examination of compliance check provided by registrants. Substance examination. After the completion of evaluation, registrant is asked to submit further information.

7.8.2.3 Authorisation This process defines the SVHC chemicals and ensures the replacement of chemicals of high concern by less dangerous chemicals. A chemical is categorized as SVHC after public consultation carried for 45 days. After identifying a chemical as SVHC,

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it is included in candidate list. Inclusion in candidate list follows safety data sheets, safe use of chemicals. The following properties are defined a chemical to fit in SVHC category. G

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Substance termed to be carcinogenic, mutagenic, or toxic in accordance with CLP regulation. Persistent, bioaccumulative, and toxic (PBT) or very persistent, very bioaccumulative (vPvB). Chemicals that are equal to PBT and vPvB.

7.8.2.4 Restriction It is the process of protecting human and environment from negative impacts caused by hazardous chemicals. It also denotes ban or avoids supply and use of toxic substance taking human as a concern. Few substances are exempted from restriction list offered by REACH such as on-site isolated intermediates, substances such as cosmetics, and substances used in scientific research and development.

7.8.2.5 Enforcement It is defined as group action taken by national authority to verify the compliance of duty holders with legislation such as checking whether chemical is registered or not registered, verifying the correctness of data in safety sheets. It is the responsibility of national-level committees such as EU members for laying down legislation compliance and inducing penalties for noncompliance with respect to this regulation.

7.8.3 REACH regulation 7.8.3.1 Consolidated version of REACH regulations The consolidated version of the Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the REACH incorporates all of the amendments and corrigenda to REACH till the date marked in the first sheet of regulation. This consolidated version does not include recitals. The recitals can be found in the REACH initial text.

7.8.3.2 REACH initial text Regulation (EC) No 1907/2006 of the European Parliament and the Council of 18 December 2006 concerning the REACH, amending Directive 1999/45/EC, and repealing Council Regulation (EEC) No 793/93 and Commission Regulation (EC) No 1488/94, as well as Council Directive 76/769/EEC and Commission Directives 91/155/EEC, 93/67/EEC, 93/105/EC, and 2000/21/EC.

7.8.3.3 Amendment not included in consolidated version EU Commission 2018/675 to Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the REACH are regarded as CMR substance.

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The following are few regulations that come under REACH legislation: G

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regulation on joint submission of data or data sharing, regulation on test methods, and regulation on fees.

Efficiency in achieving REACH lies in cooperation with authorities and stakeholders by enhancing and combining knowledge, avoiding gaps, providing support for testing strategies, and assessments of impacts for chemicals. By working together, information on particular group of chemicals can be shared, and transparency and predictability of regulatory activities can be ensured (European Chemical Agency).

7.8.4 Toxic Substance Control Act TSCA was organized by Environmental Protection Agency (EPA) in 1976. This act provides authority to report, record keeping, testing requirement, and restrictions related to chemical substances and mixtures. Substances such as food, drugs, cosmetics, and pesticides are excluded from TSCA. It addresses some of the important chemicals such as asbestos, radon, lead-based paints, and polychlorinated biphenyls (PCBs) in their production, import process, use, and disposal. TSCA provides authorities with the following details. To protect the environment and human health, EPA works with federal, legal, and state tributary partners to assure compliance for chemical substances in accordance with regulation and law. TSCA is one of the major laws governing such chemical substances. G

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Notification for new chemicals before manufacturing. Testing of chemicals by manufacturers, importers, and processors, where risk and impacts arising due to chemicals are found. Nearly 83,000 chemicals are found in TSCA list. Once a new chemical is discovered, it is placed in this list. Maintaining record by person about importing, using of chemicals. Any person who manufactures or imports chemical substances and obtains information about toxicity arising from chemicals to human health and environment must inform EPA (US Environmental Protection Agency).

7.8.5 Globally harmonized system of classification and labeling of chemicals GHS is framed for classifying chemicals globally by providing standardized classification and communication. It aims in improving the safety precautions for the workers, consumers, and environment by providing consistent information on hazardous nature of chemicals throughout the world. Communication about type and nature of hazard induced by chemical is done through labels and safety data sheets. GHS also provides a path for harmonization of rules and regulations on chemicals at national, regional, and worldwide for trade facilitation (UNECE).

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7.8.6 Waste, chemical, and clean-up enforcement Waste enforcement is related to impacts generated due to waste coming from industrial sectors. EPA enforces impacts causing from use and disposal of chemicals such as pesticides and PCBs. It enforces requirement under emergency planning and community right-to-know Act (EPCRA) about emergencies related to chemicals and reports on toxic nature (US Environmental Protection Agency).

7.8.7 Integrated pollution prevention and control Directive 2008/1/EC concerning IPPC deals with pollution coming from large industries. According to this directive, industries require to permit all its activities with high pollution prevention. According to this, directive companies are responsible for reduction in pollution. This is a minimum directive, which means each member has the right to impose stricter rules (Hazardous chemicals in textile, Swedish Chemical Agency).

7.8.7.1 Best available technique Under IPPC, best available technique (BAT) is a new technique that can be adopted by industries for pollution prevention. BAT should be developed for implementation of technology in industrial sector in economical and feasible way, considering cost and benefits (Hazardous chemicals in textile, Swedish Chemical Agency).

7.8.7.2 The industrial emission directives IPPC directive is one of the directives that will be included in industrial emission directives (IED). IED is one of the directives that hold seven directives in one regulation. IED involves tightening the application of BAT and reducing the industrial emission-like pollutants from large combustion plants (Hazardous chemicals in textile, Swedish Chemical Agency).

7.8.8 The biocidal product regulation Biocidal products are the products used to protect biota from pests and microorganisms. This regulation entered into operation from September 2013. It will replace Biocidal Products Directive (BPD). Previously, textiles were not regulated by biocides; now effective implementation of BPR has paved the way for preventing unacceptable risk for human health (Hazardous chemicals in textile, Swedish Chemical Agency).

7.8.9 General product safety directive General product safety directive (GPSD) 2001/95/EC states that all products such as textiles placed in market should be safe. This directive applies to all goods and services sold by traders. It does not provide any information related to

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chemicals or safety requirement instead poses a fact that goods should not cause risk to human health. Consumers must be guaranteed that their health is not endangered because of the product they purchase from the market. RAPEX is an informative system used in EU countries for sharing information about products with each other that are sold in the market (Hazardous chemicals in textile, Swedish Chemical Agency).

7.9

Compliance monitoring

Compliance monitoring is an important component in EPA that ensures all the communities obey environmental laws and regulations. It includes: G

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formulation and implementation of compliance strategies; off-site compliance monitoring such as inspection, evaluation, and investigation; on-site compliance monitoring such as data collection, report, review, and support; inspection training and credentials.

EPA facilitates compliance incentives and auditing that encourages finding out any violations in the community and communicating with agencies. Compliance monitoring is a key parameter of any effective environmental compliance and enforcement program. The main aims of compliance monitoring are: G

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assessing and documenting compliance with permits and regulation, supporting the enforcement process through evident collection, creating prevention, and providing feedbacks on implementing enforcement.

There are various compliance monitoring programs for the environmental components of air, water, waste, chemical, and clean-up environment. Some of the compliance monitoring regulations are: G

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Clean Air Act (CAA) Compliance Monitoring Comprehensive Environment Response Compensation and Liability Act (CERCLA) Compliance Monitoring Clean Water Act (CWA) Compliance Monitoring Federal Insecticides, Fungicide and Rodenticide Act (FIFRA) Compliance Monitoring Resource Conservation and Recovery Act (RCRA) Compliance Monitoring Safe Drinking Water Act Compliance (SDWA) Monitoring TSCA compliance Monitoring Good Laboratory Practices Standards Compliance Monitoring Program (US Environmental Protection Agency)

Among all compliance monitoring programs listed, TSCA is one of the key components for textile and fashion industries, as they use numerous quantities of chemicals. TSCA has been discussed in Section 7.8.

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Consumer Product Safety Law

7.10.1 Consumer Product Safety Improvement Act This was amended in 2008 with new significant regulatory and enforcement tools as a segment of amending and enhancing several consumer product safety acts. It generally defines “children products” with the following credentials. G

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Obey all children’s product safety rules. Should be tested for compliance by accredited laboratory. Should hold a written children product safety certificate as evidence for product compliance. Need permanent tracking information for the product. CPSIA also requires domestic manufacturer and importer to issues general certificate of conformity for children’s products.

Some of the regulations that come under CPSIA are: G

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phthalate limit in toy and children care products under Section 108 of CPSIA; lead limits in paints and substrates under Section 101 of CPSIA; testing and certificating under parts 1107 and 1109; and product registration cards part 1130 (US Consumer Product Safety Commission, Regulation Laws & Standards, CPSIA).

7.11

Chemical regulations in India

There are two major chemical regulations followed in India. They are (ChemsafetyPro): G

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Manufacture, Storage and Import of Hazardous Chemical Amendment Rules, 1989, 1994, 2000 Ozone Depleting Substance (R&C) Rules, 2000

7.11.1 Manufacture, Storage and Import of Hazardous Chemical Amendment Rules, 1989 This enforcement was enacted in 1989 by MOEF and CC and further amended in 1994, 2000. It ensures manufacture, storage, and import of hazardous chemicals in India. Import of chemicals should follow Motor Vehicle Act 1988. Hazardous chemicals contain three schedules, namely: G

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Schedule 1—chemicals listed in part I of this schedule Schedule 2—chemicals listed in column 2 of Schedule 2 Schedule 3—chemicals listed in column 2 of Schedule 3

7.11.1.1 Regulations on Schedule 1 hazardous chemicals It includes the following criteria for listed chemicals:

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Toxic chemicals—oral LD50 , 200 mg/kg, dermal LD50 , 2000 mg/kg, and inhalation LC50 , 10 mg/L Flammable gases—gases that are ignitable when in a mixture of 13% or less by volume with air Flammable liquids—liquids with a flash point less than 90 C Explosives

7.11.1.2 Regulations on Schedules 2 and 3 hazardous chemicals It includes chemicals that have threshold quantities. When chemicals with higher threshold quantities are handled in site, then the site is called as major accident hazards (MAHs).

7.11.2 Ozone Depleting Substance (R&C) Rules, 2000 This regulation completely controls the production, import, and use of oxygen depleting substances (ODS) in India. Most of the ODS are banned in India because of its toxicity. Complete regulation has been listed by MOEF and CC.

7.12

Conclusion

This chapter gives an overview of chemicals that are hazardous in textile industries along with compliance requirements. Different types of chemicals are used in textile industries such as hazardous and nonhazardous chemicals. While the use of hazardous chemicals during fabrication of fabric compliance is mandatory to assess the safety identity of chemicals involved. Compliance is a factor that helps to abide by rules and regulations framed by national and international authorities for preventing the risk imposed by the use of toxic and hazardous chemicals in textile and fashion industries. REACH is one of the international legislations that promotes need for compliance and safety aspects with respect to the risk identified for chemicals. Also it facilitates the alternative for toxic chemicals. REACH is a direct legislation linked with textile industries. Apart from REACH, various other legislations that are indirectly linked with textile industries also help in controlling the toxicity level of hazardous chemicals used in single or mixture in the textile brand. Eco-friendly labels that denote the safe chemicals such as GOTS, Bluesign, and C2C are discussed. As a suggestion, ZDHC has been highlighted for preventing the environmental pollution. Various international countries have successfully used ZDHC at different segments of industrial process such as effluent treatment plant, mining, and chemical manufacturing. Hence zero discharge can be effectively adopted in textile industries as this is the major source for discharge of azo dyes and other organic pollutants that are difficult to degrade chemically or biologically. Prevention of emission of such pollutants will conserve this environment from further damage.

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Future scope and needs

In 2011, MOEF and CC published a draft on hazardous substance classification, labeling, and packaging rules which is not fully used in trend but can be adopted for preparing safety data sheets that are used for assessing the risk or impacts associated with the use of toxic chemicals. Likewise, different laws and regulations were framed by small and large communities at national and international levels, which help in monitoring compliance process for safer industrial activities. Some of factors that are considered while compliance are manufacturing of chemicals, transportation of chemicals, consumer interest, protection of health and environment. Evolution of global labeling and classification of chemicals such as GHS framed visual effects in identifying the toxic nature of substances. Although effective laws are used in the Indian system, there are few drawbacks such as: G

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No single agency or ministry ensures proper implementation of existing regulations. Only primary effects are carried out in identifying the effects of chemicals on environment and health safety. Only few data are available on accidental issues identified during manufacturing, transportation, and use of chemicals. None of the ministries have prepared database on chemicals identified by them.

Hence it is mandatory to address the above issues using single nodal agency for comprehensive use of legislation. Merging of different existing regulations in one umbrella policy can be encouraged. Some of the information like risk, impacts and toxicity of chemicals should be allowed reach public for gaining enough knowledge.

References Amutha, K., 2017. Sustainable practices in textile industry: standards and certificates. In: Muthu, S. (Ed.), Sustainability in the Textile Industry. Textile Science and Clothing Technology. Springer, Singapore. Cahn, D., Clifford, R., 2014. Best practices in chemical management for textile manufacturing, 2014. Environmental Safeguards Units (VPS/EPG). ,http://www.thecahngroup. com/uploads/6/4/2/1/64212261/2014-12-chemical-management-textile-manufacturing. pdf.. Cattlemole Consulting Inc, Chemical Management Consultancy. ,https://www.cattermoleconsulting.com/what-is-the-zero-discharge-of-hazardous-chemicals-zdhc-program/.. Chemical Management for the Textile Industry, Module 1, road map to ZDHC. ,https:// www.roadmaptozero.com/fileadmin/layout/media/downloads/en/CMModule1.pdf? fref 5 ts.. ChemsafetyPro, Overview of chemical regulations in India. ,https://www.chemsafetypro. com/Topics/India/Overview_of_Chemical_Regulations_in_India.html.. DyStar, Sustainability, compliance. ,https://www.dystar.com/compliance/.. EPEA—Part of Drees & Sommer, M. Braungart. ,https://epea-hamburg.com/michael-braungart/..

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European Chemical Agency, ECHA, legislation, REACH. ,https://echa.europa.eu/regulations/reach/legislation.. European Commission, Environment, Industry. ,https://ec.europa.eu/environment/ecolabel/.. Fibre2Fashion.Com, Textile industry news, articles and market intelligence. ,www.fibre2fashion.com.. Hazardous chemicals in textile, Swedish Chemical Agency. ,https://www.kemi.se/global/ rapporter/2016/report-8-16-hazardous-chemical-substances-in-textiles.pdf.. Textile Fashion Study, 2012. Compliance in garment industry. ,http://textilefashionstudy. com/what-is-compliance-compliance-in-garment-industry/.. Textile Learner, 2015. Importance to understand chemical compliance in textile and apparel industry. ,https://textilelearner.blogspot.com/2015/03/importance-to-understand-chemical. html.. Textile Today, 2017. Sustainability impacts of chemicals used in Textiles. ,https://www.textiletoday.com.bd/sustainability-impacts-chemicals-used-textiles/.. Transparency One, 2019. More sustainable use of chemicals in the textile industry. ,https:// www.transparency-one.com/sustainable-chemicals-textile-industry/.. UNECE, Legal Instrumentation and Recommendation, GHS. ,http://www.unece.org/trans/ danger/publi/ghs/ghs_welcome_e.html.. United Nations Environment Program DTIE/Chemical Branch, 2011. The chemicals in products project case study of the textile sector. US Consumer Product Safety Commission, Regulation Laws & Standards, CPSIA. ,https:// www.cpsc.gov/Regulations-Laws--Standards/Statutes/The-Consumer-Product-SafetyImprovement-Act.. US Environmental Protection Agency, Laws & Regulations, summary of Toxic Substance Control Act. ,https://www.epa.gov/laws-regulations/summary-toxic-substances-controlact.. US Environmental Protection Agency, Enforcement, waste, chemical and cleanup. ,https:// www.epa.gov/enforcement/waste-chemical-and-cleanup-enforcement.. Zero Discharge of Hazardous Chemicals, ZDHC. ,https://www.roadmaptozero.com/about/..

Life cycle assessment and textile chemicals

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S. Roos and C. Jo¨nsson RISE IVF AB, Materials and Production Division, Mo¨lndal, Sweden

8.1

Introduction

This chapter investigates the discrepancies between the observed damage of textile chemicals in reality and the omission of textile chemicals when assessing impacts of textiles in life cycle assessment (LCA).

8.1.1 Textile industry uses large amounts of chemicals and has large emissions Beyond chemical manufacturers themselves, the biggest industrial users of chemicals are the rubber, plastics, textiles, and construction sectors. At the global level, the textile industry comes at second place (after the rubber and plastics industry) with 5.3% of the total sales of chemical products (ICCA, 2019). Cotton cultivation is infamous for its use of pesticides, using 25% of the world consumption of insecticides on a land area which is only 2.4% of total agriculture, as an example of how chemical-intensive this industry is (B¨arlocher et al., 1999). In the textile supply chain, chemicals are used in all the steps of the production (see Fig. 8.1). To take some examples of why chemicals are used; they can be applied as sizing agents to prevent tear of the thread during weaving, or as biocides to prevent mold during boat transports (Olsson et al., 2009). To produce 1 kg of garment it has been estimated that between 1.5 and 6.9 kg of chemicals are needed, which means that the weight of the chemicals used in the production process is larger than that of the finished garment itself (Olsson et al., 2009). Many of the chemicals are used at the dyehouse, in the pretreatment, dyeing, and finishing of yarns and fabrics. In contrast to most other sectors, the textile sector (and especially the dyehouses in the wet treatment processes) uses chemicals in open systems. The chemicals are mixed with incoming water and washed out with the wastewater from the processes. It has been reported that the wastewater is far from always treated; a study in Bangladesh found that only 108 of the 466 inspected textile wet processing facilities had installed effluent treatment plants whereof 56 were actually being used (Ecotextile News, 2016). This direct pollution of the process water with chemicals is not common in other sectors; there are large amounts of water used also in other industrial processes but then usually as cooling water (SFA/Ecotextile News, 2018). Thus the textile industry has both a large usage Chemical Management in Textiles and Fashion. DOI: https://doi.org/10.1016/B978-0-12-820494-8.00008-3 © 2021 Elsevier Ltd. All rights reserved.

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Figure 8.1 Generalized model for the life cycle of a textile product in terms of raw material extraction, production process, use, and end of life.

of chemicals and also large emissions of chemicals to the environment comparatively to other sectors. In countries where the textile sector dominates the industrial landscape, pollution is also dominated by the emissions from textile factories (San et al., 2018). San et al. (2018) studied the shares of pollution from different industries in Cambodia and noted that the textiles and apparel sector had such a dominant share that in the light of it other sectors’ shares were negligible in comparison.

8.1.2 The effects on humans and the environment from textile chemicals The fact that the textile industry pollutes the watersheds where wastewater is emitted is well documented. Several sources point to how the neighboring inhabitants to recipients of textile wastewaters notice how the rivers or streams change color “after the fashion in Paris” or similar stories (CBC News, 2017). Also, effects on workers in textile factories in terms of respiratory diseases and cancer cases (Singh and Chadha, 2016; Ghani et al., 2018) and/or effects on nearby populations in terms of developmental damage to children as well as environmental impacts are documented (Stenborg, 2013). Below are given some examples of known effects of different groups of textile-related chemicals. Today, alkylphenol ethoxylates (APEO) are still a commonly occurring group of surfactants used in all steps of the textile supply chain, as detergents, dispersants, and emulsifiers. In the environment, APEO breaks down to alkylphenols (APs). Nonylphenol (NP, one of the APs) is listed a substance of very high concern in the

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European REACH legislation (European Commission, 2006) due to that NP is both an endocrine disrupter and an environmental toxin (ECHA, 2013). Fish are especially sensitive to nonylphenol exposure, which has been shown to impair reproduction as well as complete sex reversal of three different fish species, resulting in all-female populations. Per- and polyfluoroalkyl substances (PFAS) are another highlighted group of textile-related chemicals, whereof several have been identified as persistent organic pollutants (POP) by the United Nations (UNEP, 2016). They are extensively used as water- and oil-repellent agents on outdoor garments (so-called durable water repellent treatment), but they are also used in digital printing processes to prevent bleed-through of the fabric. PFAS are, or transform into, persistent substances, meaning that they resist degradation in the environment. They also bioaccumulate, meaning that their concentration in organisms can become higher than that of the surrounding environment. Such substances have been detected in the blood of small children, adults, and other mammals, as well as in the ground and water in remote areas, such as the Arctic (Posner et al., 2013). PFAS have been linked to adverse health effects, such as low birth weight, delayed puberty onset, elevated cholesterol levels, reduced immunologic responses to vaccination, and overrepresentation of attention-deficit/hyperactivity disorder in children (Bergman et al., 2013). In fact, several textile chemicals cause cancer and/or harm the human reproductive system. Benzidine-based dyes metabolize in the human body to carcinogenic substances (US EPA, 2017). Several solvents are either carcinogenic such as trichloroethylene, or reproduction toxic such as dimethylformamide (European Commission, 2008). A cocktail of hazardous substances is emitted daily to air, water, and soil from the textile industry. Textile chemicals are also in general designed to be long-lived, persistent, so, for example, the color stays year after year in the garment. When emitted into the environment, these chemicals do not degrade but the concentrations build up in the soil, in the groundwater as well as surface water, and in the air for volatile substances. Some chemicals are transported far beyond their original point of emission (Choi et al., 2011). The situation makes emissions of chemicals in the textile industry one of the major sustainability issues for the industry. Emissions of toxic textile chemicals are causing the damage described above, but also nontoxic chemicals cause damage due to the contribution to eutrophication and acidification, which is not further treated in this book chapter.

8.1.3 Mitigation measures by authorities, nongovernmental organizations, and industry There have been several measures taken at governmental level to reduce the adverse impacts of textile chemicals on the environment and human health, building on the Strategic Approach to International Chemicals Management (SAICM) (UNEP, 2006). The European chemicals legislation REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) (European Commission, 2006) and the Consumer Product Safety Improvement Act (US CPSC, 2008) are

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examples of legislation applicable to chemicals in textile products on the European Union (EU) respective US markets. The fact that textile production processes are geographically located mostly outside the EU or the US jurisdictional areas adds a challenge to the environmental management of textile products via legislative actions. In the production countries, legislation is growing regarding textile chemicals, for example, in China, Korea, and India (China Ministry of Environmental Protection (MEP), 2010; South Korean Ministry of the Environment, 2011; Government of India, 2012). Also regulations regarding wastewater emission are implemented in practice where Tirupur, a textile cluster in India, was among the first to shift to “zero liquid discharge” in a systematic manner (Gro¨nwall and Jonsson, 2017). Similarly, several nongovernmental environmental organizations have reacted on the emissions from the textile industry, as they have been measuring toxic contaminants in the wastewater (Choi et al., 2011; Brigden et al., 2012; IPE, 2014). The burden from the pollution of the textile industry is also reflected in the concentration of requirements for chemicals in voluntary ecolabeling schemes for textiles (European Commission, 2006, 2010b; Dodd et al., 2012; Nordic Ecolabelling, 2016; OEKO-TEXs Association, 2017) as well as in the industry initiatives in the area (ZDHC, 2014). Concludingly, the damage caused by pollution of textile chemicals is a wellknown phenomenon. However, it is not reflected in the practices and methods of LCA (Roos et al., 2015), which is detailed in the next section.

8.2

Life cycle assessment in textile chemicals

8.2.1 The holistic perspective of life cycle assessment LCA is a technique to assess environmental impacts associated with all the stages of a product’s life from cradle to grave, that is, from raw material extraction through materials processing, product manufacture, distribution, use, and maintenance, to waste treatment via disposal or recycling (ISO, 2006a). Fig. 8.1 shows a generalized life cycle for a textile product. LCA also takes the holistic perspective in terms of environmental impacts from inflows and outflows from the different life cycle stages: global warming, water use, toxicity, among others. Thus different technology solutions for producing textile products can be evaluated without risking burden shifting in terms of optimizing one life cycle stage with the consequence of increasing the total life cycle impact or reducing the burden from one environmental aspect at the expense of increasing the burden from other aspects.

8.2.2 Inclusion of chemicals in life cycle inventory and life cycle impact assessment The LCA result builds on the life cycle inventory (LCI) of all the resources used and all the emissions occurring during the life cycle. Then the inflows and outflows

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Figure 8.2 The damage to a species from a chemical depends on emission, fate, exposure, and cause effect relations.

from the LCI are translated via characterization factors (CFs) into indicators for a variety of impact categories that reflect potential environmental and health impacts as well as resource scarcity impacts (Hauschild and Huijbregts, 2015), rendering a quantitative score for the total impact, the life cycle impact assessment (LCIA). The CFs for emissions of chemicals are generally calculated using models for environmental fate of chemicals, impact pathways (deciding which species are exposed), and cause effect relations leading to damage to humans and the environment (see Fig. 8.2). LCA has traditionally been applied extensively for reporting carbon footprints, that is, one of the impact categories. This has had the consequence that many studies have reduced the workload of the LCI work to inventorying inflows and outflows related only to energy use and other sources to greenhouse gases (Beck et al., 2000). When chemicals are inventoried, it is often focused on the climate effects from chemicals manufacturing. LCA is intended to be a tool that includes all relevant aspects of a product (ISO, 2006b) wherefore the environmental effects of textile chemicals should be included due to the relevance shown in the Introduction. To do this, textile chemicals need to be included both in the LCI and the LCIA. This is, however, scarcely done; in an overview of the state-of-the-art specifically for textile LCA studies it was found that textile chemicals were included in the LCI in only seven of the 58 published LCA studies of textile products (Roos et al., 2015). But only including chemicals in the inventory will not mean that a quantitative score for the environmental impact is rendered; a CF is needed for each of the individual substances. However, of the seven studies that were found to include textile chemicals in the LCI, only four matched the inventoried textile chemicals with CFs in the LCIA: Beck et al. (2000), Schulze et al. (2001), Hellweg et al. (2005), and Saouter and van Hoof (2002).

8.2.3 Life cycle assessment’s ability to reflect the environmental impacts in reality The consequence of not including the environmental effects of textile chemicals in an LCA of textile products is that the LCA result does not reflect the reality. Fig. 8.3 shows schematically the data that are generally available in an LCA study, and data gaps that are significant in a textile LCA study for the case of textile wet treatment. It is the direct emission of chemicals to air, water, and soil that gives rise to the pollution and damage to humans and the environment described in Chapter 1, Chemical Management System in Textiles. Not including these direct emissions is to set their impact to zero.

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Figure 8.3 Several types of data are generally available in LCA. The figure highlights the parts where there are usually significant data gaps in LCA studies of textiles. Inventoried inputs and outputs are generally related to energy production according to Beck et al. (2000).

Even though system analysis methods such as LCA are known to be difficult to validate (Miser and Quade, 1988), the conclusion of the LCA in this case: water emissions from textile wet treatment have zero toxic effects

and observations in reality: water emissions from textile wet treatment have documented significant toxic effects

differ fundamentally. Beck et al. (2000) concluded that the chemical substances included most comprehensively in LCI databases are chemicals related to energy production, since inventories for energy production have been compiled intensively. Thus there is a risk that the results from the LCA study lead to erroneous conclusions, such as that yarn spinning with its high energy consumption has larger impact on toxicity than wet treatment. As this does not reflect the observations in reality, the trust in and relevance of LCA can be questioned.

8.3

Challenges in life cycle assessment studies of textile chemicals

There are two major challenges in including textile chemicals in the LCA of textile products: 1. The inventory of chemicals (inflows as well as outflows) in LCI.

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The inventory of chemicals in general has long been known to be challenging (Hauschild et al., 2011). Since 2011, some pieces of work have been published in the area of LCI of textile chemicals (Manda Krishna et al., 2015; Pourzahedi and Eckelman, 2015; Roos et al., 2017). However, there are still very few studies that include textile chemicals in both the LCI part and have matching CFs in the impact assessment part in LCA studies of textile products. The challenge with LCI of textile chemicals lies on the practice side rather than model or method deficiencies. The textile supply chains contain a large variety of materials and technologies (Munn, 2011). The mixture of agricultural, chemical, and mechanical processes can be a challenge per se. But perhaps the most critical point is that inflows are sometimes not equal to outflows as chemicals in many processes react (and are intended to react in order to function) into other substances (Van Zelm et al., 2010), which is a big challenge for an LCA practitioner not trained in chemistry. Methods for support and advancing the practice seem therefore to be needed. This is further elaborated on in the next section. 2. The calculation of toxicity impact in LCIA is often questioned due to both model and data uncertainties in the CFs for toxicity impact categories (Parisi et al., 2015).

The model uncertainties stem from the fact that a model is always a simplification of the reality, and the sort of simplification made decides the model uncertainty (European Commission, 2011). It has been shown that the most commonly used methods for LCIA often render different toxicity scores for the same emissions, as a consequence of the different choices in modeling (Owsianiak et al., 2014). In addition, the current models do not fit all substances, such as very persistent organic pollutants (Roos et al., 2017) or nanosized particles (Ettrup et al., 2017), and do not handle combined toxicity from exposure to multiple substances (Fantke et al., 2018). On the data uncertainty side, the data gaps are large both on the physical and chemical properties but especially on the effect side. Recent developments include attempts to use in silico data generation, for example, using quantitative structureactivity relationship models (Holmquist et al., 2018).

8.3.1 Data about textile chemical inflows and outflows To start with, the term textile chemical is a rather vague concept. In Fig. 8.4, the textile chemical is an input chemical: a “chemical product,” directly applied to the textile in the textile wet treatment process. A chemical product can be a “pure” substance [with a specific CAS registration number (American Chemical Society, 2016)], or more commonly, a mixture of substances. However, the actual content of a chemical product is seldom 100% of the desired substance or substances; there are usually aid substances: solvents (in many cases water), preservatives, stabilizers, etc. that are added deliberately in the production of the chemical product to enhance the function and usability. Further, chemical products have to some extent unintended substances present: residues from production, contaminants, or breakdown products of the intentionally added substances. During the development of the CHEM-IQ tool it was discovered that the full content of a chemical product

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Figure 8.4 The inflows and outflows of chemicals in the textile wet treatment process.

is not even always known to the compounder of the textile chemicals (VF Corporation, 2014). Many chemicals are designed to react or dissociate during their usage, for example, acids, reactive dyestuff, and cross-binders. In Fig. 8.4, transformation products are added to the outflows of chemicals. In many cases it is not the desired substances in a chemical product that cause damage to humans and/or the environment. Instead it is the aid substances, residues from production, contaminants, breakdown products, and reaction products that need to be caught in the LCA in order to properly catch the impact on toxicity. Data on the full recipe of the input textile chemicals (inflows) is sometimes difficult to inventory by the LCA practitioner, sometimes due to reluctance from the textile factory’s side to expose information about the chemical products used, but more often due to the difficulties in finding out the content of the chemical products. To the list of substances present in the input chemicals it is sometimes relevant to add well-known breakdown products of these substances in order to catch the full environmental impact. One example is azo dyestuff that is per se harmless substances but can be broken down to carcinogenic arylamines, as described in the Introduction to this chapter.

8.3.2 Data needs for calculating toxic impacts in life cycle assessment The inventory data is matched with CF as described in the section above. There are several models available to develop CFs. One source to uncertainty in the application of toxicity scores in LCA is the different scores these models sometimes render for the same substance (due to differences in the choices for how to model fate, exposure, and effect), that is, they score the comparative significance of different substances (Owsianiak et al., 2014). USEtox, the consensus model (Rosenbaum et al., 2008) that has been recommended by the International Reference Life Cycle Data System handbook (European Commission, 2011) and chosen for the Product

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Environmental Footprint (PEF) framework (European Commission, 2013) is the model that will be discussed in this chapter. In USEtox, the CF for a substance is derived from the product of three matrices (Huijbregts et al., 2015c), including fate factors (FF), exposure factors (XF), and toxicological effect factors (EF): CF 5 EF 3 XF 3 FF. The FF and the XF are derived from physicochemical data for the substance properties and model data for different environmental compartments. Hence they describe “what the environment does to the substance,” that is, where it ends up. The EF is derived from inherent toxicity properties of the substance, and describes “what the substance does to its environment.” Calculating CFs is a data-intensive work, and many chemicals lack data. For instance, toxicity tests for the EF are both expensive and many times not practically feasible as live animal testing is ethically questioned. Saouter et al. have put extensive effort in trying to retrieve the necessary data for USEtox CFs from the REACH registration database (Saouter et al., 2017a,b).

8.3.3 Data about toxic impacts from textile chemicals The toxicity data availability for the substances emitted from textile processing is complicated by two reasons: 1. The human and environmental damage is often caused by other substances present than the desired ones in the chemical product, and hence reported ones. The consequence is that many substances relevant for impact calculations will never be registered for any intended use; hence toxicity data will not be collected automatically within regulatory frameworks such as the registration duty under EU REACH (ECHA, 2019). 2. Some types of textile processing are done exclusively in countries where the ingredients of a chemical product will never be registered within any regulatory framework (such as EU REACH). The majority of textile production is made in developing countries today. Also in the cases when the garment making (cut and sew) is made within the EU or the United States (and the textile product is labeled as made in an EU country/in the United States), the wet treatment part is often executed in developing countries.

Still, the tool LCA needs to be able to describe the environmental effects of activities regardless of jurisdictional scope, and some toxic substances will at least in the near future need to be manually checked for inclusion in the LCIA model.

8.3.4 Conceptual challenges in toxicity modeling in life cycle assessment There are two main conceptual challenges with toxicity modeling in LCA. First, impacts depend both on intrinsic properties of a substance and the fate of the substance in the environment. Thus there is a need to make a model of an inherently complex technical and natural system, where chemicals move in and between various environmental compartments (indoor air, urban air, rural air, continental freshwater, etc.) exposing different species. Second, toxicity properties are with some

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exceptions measured for a single substance under laboratory conditions, which are then estimated or extrapolated to the LCA-relevant ecotoxicological endpoints, not considering the effects from a mixture of substances (Fantke et al., 2018).

8.4

Case studies

The industry initiative Higg Index by SAC (2018a) and the European Commission’s development of the PEF respective Organization Environmental Footprint (OEF) (European Commission, 2017) provide two recent examples of the challenges with handling chemicals information in LCA. The SAC has decided to use qualitative questions for the Higg material sustainability index to assess chemistry until USEtox proves more relevant for the apparel, footwear, and home textile industries, though the USEtox methodology will continue to be considered as it matures (SAC, 2019). USEtox, if applied strictly as implemented in common LCA software (GreenDelta, 2019; PRe´ Consultants, 2019; ThinkStep International, 2019), suffers from a lack of precision (i.e., a large uncertainty of two to three orders of magnitude) as well as lack of coverage in the textile chemicals area (SAC, 2018b). For the PEF, USEtox is the reference model to characterize life cycle chemical emissions in terms of their potential human toxicity and freshwater aquatic ecotoxicity. In order to address the lack of toxicity data, the European Commission designed two case studies to analyze the influence of input data source on EF results and to compare official USEtox EF with ecotoxicity effect indicators used in the context of the European chemicals regulation, respectively (Saouter, 2017a,b), summarized below. The relevance of the USEtox model to the textile industry would increase if uncertainties could be handled by a more detailed description of how to apply the model in practice. For example, creating consensus about what data sources to select for toxic effects would increase the precision of the model. The lack of inventory data is the other main challenge in including textile chemicals in LCA of textile products. Simplification and proxies have been proposed as a way to manage the deficiency in the Mistra Future Fashion methodology (Roos, 2016) that is described in detail further down in this chapter.

8.4.1 Filling the data gaps in life cycle impact assessment with data from the REACH registration database The lack of toxicity data is one of the aspects for which the European Commission’s work with chemicals legislation has led to several improvements (Fantke et al., 2018). As described above the CF is the product of the FF, XF, and EF. USEtox bases the EF on the chronic hazard concentration (HC50) value for a chemical calculated as the arithmetic mean of all logarithmized geometric means of species-specific

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chronic median lethal or effect concentrations (LC50 respective EC50). However, the availability of chronic LC50 and EC50 data is scarce, leading to that a large number of CFs are based on extrapolation from acute to chronic toxicity (Saouter et al., 2017a). In the first case study, a comparison of the USEtox EF with the classification of substances in the context of the European chemicals regulation, discrepancies were found between the systems. It is suggested to evaluate whether what is already classified as ecotoxic in EU and global chemical legislation is also considered toxic in a PEF/OEF context, and if not, what the reasons for this are (model differences, data differences). The aim of the second case study was to explore the extent to which the new available data in the REACH registration database (ECHA, 2019) can be used as input for USEtox and to discuss how this would influence the quantification of FF and XF. Initial results show that the choice of data source and the parameters selected can greatly influence FF and XF, leading to potentially different rankings and relative contributions of substances to overall human toxicity and ecotoxicity impacts (Saouter et al., 2017b). To conclude, the REACH registration database offers a means to fill many data gaps in LCA; however, how this is done will influence the results.

8.4.2 Mistra Future Fashion methodology The textile research program Mistra Future Fashion started in 2011 with an explicit aim of clarifying the concept of sustainable fashion via LCA (Sandin et al., 2019). Seeing that inclusion of chemicals in LCA of textile products being handled unsatisfactory and having good experience of chemicals’ functions thinking within the Swedish Chemicals Group at Swerea IVF (RISE, 2018) for reducing complexity in textile chemistry, a methodology was developed (Roos, 2016). The Mistra Future Fashion methodology helps to add a textile chemical recipe to the LCI and USEtox CFs to the LCIA for a quantitative impact assessment. This way the comparative significance of textile chemicals will be known. The chemicals related to the use and end-of-life phases are currently not addressed in the framework as they were considered to be less challenging. The methodology is built on two main components: G

G

An inventory “database” for textile production processes (“database” for process recipes) A Generic Chemical Products Inventory (“database” for textile chemicals, including USEtox factors for LCIA)

Step 1—Completion of the inventory with textile chemicals The completion of the inventory with inflows and outflows of relevant substances contains three steps, described in Fig. 8.5: 1. Recipe of the input textile chemicals (inflows) For each step in the textile supply chain, the use of chemicals is inventoried in the LCA: fiber production, yarn spinning, fabric making, wet treatment, finishing,

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Figure 8.5 The three steps in creating the inventory with relevant substances. confectioning, and packaging. For the LCA practitioner that is not an expert in textile processing, it can be challenging to collect data about the use of chemicals in each step, especially in the wet treatment step. The LCI framework in the Mistra Future Fashion method provides an inventory “database” for textile production processes (a “database” for process recipes). In this database is found examples of 30 textile production processes for which LCI datasets have been created (Roos et al., 2019, supplementary material, sheets 1 30). The LCI datasets are selected to cover the most commonly occurring textile production processes, equipment,

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and textile-related substances. In the absence of primary data from textile production processes, these datasets can be used for screening LCA studies that do not require specific data. In many cases, the recipes of the input chemicals are very generic, and the chemical products in the datasets are representative for a large number of processes, for example, for weaving and knitting. The general structure of the datasets, with a description of the function of the chemicals and suggested amounts can also be used as data collection templates in more detailed LCA studies. Note that the production of input materials such as polymers, production of chemicals such as acetic acid, and production of fuels such as diesel are not considered textile processes and are not included in the framework. The inventory framework also provides five examples of garment level modeling to illustrate how the different processes are combined to create a product (Roos et al., 2019, supplementary material, sheets 31 35). 2. Full content of the chemical products As stated above, the content of the chemical product is seldom 100% of the desired substance or substances, while the main contributors to environmental impact might be other substances present. The full content of the chemical product is to a lesser degree important for the modeling of upstream production of chemicals, but crucial in order to model outflows to air, water and soil correctly. This step can be very challenging as the full content of chemical products is seldom exposed by the chemicals’ manufacturers, especially for LCA practitioners that are nonchemists. The LCI framework in the Mistra Future Fashion method addresses this challenge by providing a Generic Chemical Products Inventory (a “database” for textile chemicals, including USEtox factors for LCIA). For each chemical product in the Generic Chemical Products Inventory is inventoried if there are any aid substances (auxiliary additives) such as solvents, preservatives, and stabilizers that are added deliberately in the production of the chemical product (Roos et al., 2019, Supplementary Material, Sheet 36). These aid substances are deliberately added to the chemical product and are many times listed in the material safety data sheet (MSDS) of the chemical product. Further, it is inventoried whether the chemical products have to some extent unintended substances present: residues from production, contaminants, or breakdown products of the intentionally added substances. These unintended substances are sometimes listed in the SDS; if they are hazardous and present in concentrations above 1%, they have to be reported according to EU legislation (European Commission, 2006). Other substances are known from literature to be present in certain mixtures, and modeled in the Generic Chemical Products Inventory based on literature data. 3. Other relevant substances present in the outflows

The chemicals in the inflow to a process are not always the same as in the outflow. Many chemicals are designed to react or dissolve during their usage, for example, acids, reactive dyestuff, and cross-binders, releasing “leaving groups” (condensation products) such as formaldehyde. Sometimes it is the transformation products (breakdown products and reaction products) that need to be caught in the LCA in order to properly catch the impact on toxicity (Van Zelm et al., 2010). In the Generic Chemical Products Inventory, each chemical product and its content have been modeled to fit the subsequent LCIA step. In addition, the substances are matched with a USEtox CF. This means that the content and subsequent emission data are time-integrated, including both original content and, when relevant, transformation products. Speaking in general terms, it means that the model is

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made as if all substances were immediately transformed into their long-term transformation products on the USEtox’s in principle indefinite time horizon (European Commission, 2010a). For example, nonylphenol ethoxylates are broken down to nonylphenols immediately in the model, although this is in reality occurring over a longer time. Table 8.1 shows the example of the content of a wetting agent. When the recipe for each production step, the full content of the chemical products and possible transformation products are added, the inventory of textilerelevant substances is complete (see Fig. 8.5 for the entire procedure). Step 2—Matching the inventory with LCIA For the 72 textile-related substances included in the Generic Chemical Products Inventory, USEtox CFs are available (Roos et al., 2019, supplementary material, Sheet 36). First, the CFs were retrieved from the USEtox (2.01) database (USEtox, 2019), second from the COSMEDE database (ADEME, 2015), and third, new CFs were calculated using the USEtox methodology (Huijbregts et al., 2015b). The matching of the chemicals in the LCI with LCIA contains five steps:

Table 8.1 Full content of a chemical product, a wetting agent in this case, representing an average performance level. Nonylphenol

Timeintegrated chemical content

Fatty methylester sulfonates (R16) sodium salt

Isooctyl alcohol

Nonylphenol ethoxylates (NPEO)

Amount per kg input chemical product (kg) Emissions to air (per kg used chemical product) (kg) Emissions to river water (per kg used chemical product) (kg) Documentation

0.6

0.2

0.1

0.0002

0.0001

0.06

0.02

0.01

0.00001

MSDS Nonvolatile 10% emitted to water

MSDS 10% emitted to water.

MSDS 10% emitted to water.

0.1% of the content is modeled to be degraded to common breakdown products

Nonreported content is water.

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1. Build recipe from chemical products in the Generic Chemical Products Inventory. In screening LCA studies, the inventoried chemical products can be used as proxies for others. Thus it is recommended to first see whether the existing chemical products in the inventory can represent the ones used in reality. If so, the only measure needed is to insert the relevant quantities of consumed chemical products per process in the Supplementary Material excel sheet from Roos et al. (2019) (see Step 5). 2. Build chemical products from substances in the Generic Chemical Products Inventory. In the absence of primary data on textile chemicals, these inventories of chemical products can be used as proxies for generic textile chemicals. In many cases, two similar chemical products contain the same ingredients, and the proxy is a good representative. One example is hydrogen peroxide, which is a substance that can be used both as bleach and as oxidizing agent in vat dyeing. If a model bleach based on hydrogen peroxide has been created, it can be reused for modeling the oxidizing agent. 3. Add substances to the Generic Chemical Products Inventory. The models for the substances can be reused for modeling more chemical products. The general structure of the inventory, with a description of the time-integrated chemical content, emissions to air per kg used chemical product, and emissions to water per kg used chemical product, can be reused when inventorying new substances. The data on the function of the chemicals and suggested amounts can also be used as data collection templates in more detailed LCA studies. 4. Calculate own CFs. If there is a need to calculate own USEtox CFs, this is done in accordance to the latest version of the USEtox manuals (Huijbregts, et al., 2015a,b,c). A data source selection strategy was developed to guide the LCA practitioner when filling in the parts where the USEtox manuals leave room for variation, in order to increase the repeatability of the CF calculations. This strategy enables use of publicly available data in a transparent and scientifically sound manner, aiming for consistency with the existing USEtox CFs and at the same time covering as many substances as possible. The data source selection strategy was developed during the data collection for the 25 textile-related chemicals in the inventory for which CFs have been manually calculated (Roos et al., 2017). 5. Calculate results

When all substances have been matched with USEtox CFs, and provided with an emission scenario for air and water emission, the relevant quantities of consumed chemical product per process are inserted in the Supplementary Material excel sheet from Roos et al. (2019) and a toxicity score is calculated.

8.5

Conclusion

This chapter has described both the challenges and the recent achievements in the area of LCA studies of textile chemicals. The main benefit of using LCA to assess the toxicity impact of textile chemicals lies in the potential for expressing the environmental performance quantitatively, in comparison to qualitative, semiquantitative, and management routine-focused methods. The information about the comparative importance of different emissions can

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guide toward a total reduction in environmental impact from textile production, including also the toxicity impacts from textile chemicals. The recent advancements in the method development and data availability enable LCA to be used in practice for guiding stakeholders of the textile sector in macrolevel decisions regarding the effectiveness of different impact reduction interventions, as well as for guiding on-site decisions in textile manufacturing.

8.6

Future trends

Recently, a task force under the Life Cycle Initiative hosted at the United Nations Environment Programme performed an evaluation on the state of the science in modeling chemical exposure of organisms and resulting ecotoxicological effects for use in LCIA (Fantke et al., 2018). The guidance and recommendations for changes to the existing practice in exposure and effect modeling in ecotoxicity characterization include, for example, (1) to consider additional environmental compartments and impact pathways and (2) the relevance of effect metrics other than the currently applied geometric mean of toxicity effect data across species. Another ongoing work at the strategic level is the development of the EU chemicals policy for 2030 where more and better data on human health and environmental exposure and on hazardous chemicals use have been highlighted (European Union, 2019). Especially, insects and birds species are declining, male fertility is decreasing at an alarming rate, and cancers and neurological diseases are on the rise, with chemicals pointed out as one of the sources to these problems. Also, with the circular economy, achieving nontoxic material loops was pointed out as a priority. Toxic chemicals used in the production of textiles are emitted to air, water, and soil and are distributed over neighbor estates and watersheds (Brigden et al., 2012) that are classic exposure routes for the fate modeling in LCA. However, textile workers are directly exposed to toxic chemicals via skin contact and inhaling contaminated air in the working environment (Hesperian, 2015). The inclusion of these routes are under development (Ernstoff et al., 2016; Fantke et al., 2016) and is expected to mature within the coming years, leading to improved accuracy in LCA of textiles. Finally, another exposure route for toxins recently highlighted is via shedding of fibers, the so-called microplastics, that can act as carriers of contaminants, for example, as indoor dust and dispersed particles in the aquatic environment (Browne et al., 2011; Jo¨nsson et al., 2018). This issue is still to be decided if it will be treated as an exposure route or an indicator. Micro-sized polymeric particles do not have any harmful intrinsic properties per se. In contrast to nanosized particles they cannot pass cell membranes. Thus it seems as far as the current scientific community is aware that the contribution to environmental and health impact is solely due to their function as carriers of toxins, rather than being toxins themselves (Eriksson Andin, 2018). However, it has been suggested to create a separate microplastics

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indicator (Laitala et al., 2018). Regardless, addressing the large amounts of microsized fibers occurring in the working environment of the “dry” steps of textile production will be essential to reduce the human health effects.

8.7

Recommendations for further study

In the life cycle perspective, emissions from the textile production processes dominate the toxicity impact of textile products. For some chemicals, however, also emissions at the chemicals production plant or emission at the end of life are connected to severe impacts. In addition, textile chemicals have also other environmental impacts than toxicity: eutrophication, acidification, and greenhouse gas effects to take some examples. To make use of the holistic approach of LCA will be very important for future studies. There are still large data gaps both on the LCI side and the LCIA side. More case studies are expected, in order to build up a critical mass of studies that can better and better represent the large variation of processes in the textile industry. If textile-relevant substances can start to be included in the commercial databases this will lead to a spread of knowledge and more inventory data generated. On the LCIA side, improvements in and extended use of in silico modeling will be needed for textile-relevant substances as these are difficult to fit in the legal framework where data are generated at high speed today (ECHA, 2019). The recommendations are given for the field of LCA on textile products, but apply to several other industries where chemicals are an important contributor to health and environmental impacts in the life cycle perspective, for example, toys, food packaging, and metal products.

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Green chemistry in textile and fashion

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Pintu Pandit1, Kunal Singha1 and Subhankar Maity2 1 Department of Textile Design, National Institute of Fashion Technology, Ministry of Textiles, Government of India, Patna, India, 2Department of Textile Technology, Uttar Pradesh Textile Technology Institute, Kanpur, India

9.1

Introduction

The release of distressing volumes of greenhouse gases in the environment, disappearing natural resources of clean water, fossil fuel reserves, and increasing pollution by industrial effluents have made every single industrial process come under examination for its value of sustainability. It is for this reason, efforts are being undertaken to reduce the burden on earth by finding the best solution from waste. Functional properties such as coloration, antibacterial, ultraviolet (UV) protection, flame retardant, mosquito repellency, aroma finishing, etc., using the green chemistry from natural resources such as coconut shell, Sterculia foetida fruit shell, Delonix regia stem shell, peanut husk, etc., are utilized for major applications in textile and fashion materials (Teli and Pandit, 2017a,b; Pandit et al., 2018; Teli and Pandit, 2018a). The green coconut shell is widely available in India and all other developing countries, and it is discarded as a waste product while cutting green coconut for obtaining the nutritional water as a drink. Thus, natural biomolecules derived from different plant, coconut shell extract, fruit shell extract, stem shell extract, etc. has been explored as functional finishes for textile materials and it is critically surveyed for valuable effects in terms of different functional properties on textile fabrics for sustainable fashion garments. Increasing global competition has led to rapid growth in value-added textiles and eco-friendly methods delivering functionality requirements for the application of multifunctional finishes using green chemistry. Among them, antimicrobial textiles and UV protection have a significant share in the market to fulfill the requirements for a healthy, hygienic, and comfortable lifestyle with advances in green chemistry. Tree species, tree part, age, harvest season, and geographic location of the tree are important factors affecting the chemical composition and amount of the extracts. Using green chemistry natural coloration has been carried out by using extracts from natural resources such as tamarind seed coat, soya bean seed waste, and flower waste from the temple and Emblica Officinalis G. fruit (amla) (Prabhu et al., 2011; Teli et al., 2013; Pandit et al., 2018). Natural products derived from plants do not affect the natural ecological balance, as their residue is easily degradable and thus it is a good alternative for control and maintenance of the ecosystem. Chemical Management in Textiles and Fashion. DOI: https://doi.org/10.1016/B978-0-12-820494-8.00009-5 © 2021 Elsevier Ltd. All rights reserved.

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Plasma technology is one of the great innovations of science and technology and it depends on factors such as nature of gas used, gas flow rate, system pressure, discharge power, duration of treatment, aging of plasma-treated surface and temperature change during the plasma treatment. Atmospheric pressure plasma is costeffective and could easily be integrated with the existing textile processes (Teli et al., 2015a; Teli et al., 2015b; Teli et al., 2015). Hence, it is becoming popular in the research community for various industrial applications. In the last few decades, numerous finishing agents for making antimicrobial textile have been formulated based on the development of a range of synthetic antimicrobial chemicals. However, these products possess sufficient toxicity to cause effluent problems, water pollution, etc. Present-day consumers are more conscious about eco-friendly consumption through advancement of using green chemistry synthesis of functional textiles. Recently there has been a lot of attention focused on producing a hygienic fabric with products based on natural resources involving green chemistry. Herbal products such as tea tree oil, tulsi leaf, Aloe vera, coconut shell extract, chitosan, Sterculia foetida fruit shell extract, and Delonix regia stem shell extract have also been used to get the natural antibacterial effect in the application of textile fabrics. Development of UVprotective textile materials achieved by using different plant sources such as manjistha, babool, annatto, coconut shell extract, Delonix regia (Gulmohar) shell extract, Sterculia foetida fruit shell extract, peanut husk extract, and ratan jot (Prabhu et al., 2011; Teli and Pandit, 2017c,d; Teli and Pandit, 2017a; Pandey et al., 2017; Pandit et al., 2018). Textile and fashion materials widely used in home furnishing, hospitals, railway, and aircraft constitute a valuable sector of mass consumables. However, being cellulosic and lignocellulosic in nature, the textile material rapidly catches fire and thus causes many serious accidents. Flame retardant textiles are increasingly in demand and numerous approaches have been taken to make textile material ecofriendly flame retardant. The most commonly used chemicals for imparting flame retardant property to textile material are borax-boric acid combination, phosphorous and nitrogen-based condensate such as di-ammonium hydrogen phosphate, and urea for making flame retardant cellulosic and lignocellulosic textile using a mechanism involved of green chemistry that is safe to use and apply on fabric (Horrocks and Price, 2001; Horrocks, 2011; Basak and Ali, 2016; Basak and Wazed Ali, 2018). Researchers are exploring the green chemistry approach to use sustainable routes to make the materials flame retardant and have revealed different natural resources as flame retardant alternatives to satisfactorily substitute for synthetic chemicals. In this direction DNA, casein, whey proteins, hydrophobins, starch, chicken feather, banana pseudostem sap, spinach leaves, etc., were reported to be used for flame retardant finishing on textile fabric (Alongi et al., 2014; Malucelli, Bosco, et al., 2014; Basak, Patil, et al., 2016; Basak, Samanta, et al., 2016). Requirement of water in wet processing of textile represented with the process flow diagrams for woven fabric finishing, knit fabric finishing, stock or yarn dyeing and finishing is shown in Fig. 9.1. In textile wet processing water is required in every stage with help of synthetic chemicals which results in effluent problems and

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Figure 9.1 Requirement of water in wet processing of textile.

thus the aim of the chapter is to depict the suitable green chemistry in textile and fashion. In this chapter green chemistry used in application of natural dyeing in textile and fashion has been depicted and discussed. Green flame retardants in textile and fashion has also been discussed in-depth using plant, animal, and clay sources, which can be an alternative for synthetic chemicals. Antibacterial finishing mostly important for garments and clothing that have been exposed in weather and also used for in-house home textile applications. Apparel textiles such as shirtings, trousers, and sari (directly come in contact with skin) used by the people also need hygienic finishes, discussed in this chapter. Applications of UV protection in textile and fashion have a different protective capability depending on their structural composition and chemicals measured in terms of ultraviolet protection factor (UPF) has depicted in this chapter using natural resources. Clothing styles and popular apparel fashions rapidly change, and the fashion world is continuously inundated with innovations and fly-by-night fads. Green chemistry used in application of mosquito repellents and aroma finished fabric using citronella oil, castor oil, clove oil, cedar oil, rosemary oil, peppermint oil, lemongrass oil, geranium oil, chrysanthemum, etc., also discussed in this chapter. Emerging technology such as graphene, plasma, nanofibers application in textile using green chemistry also discussed. Graphene has emerged as a revolutionary material in the field of material science and physics due to its extraordinary properties. Nanofibers prepared by using ecological solvents or naturally occurring biodegradable polymers are discussed in detail. Moreover,

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Future of green chemistry in textile and fashion using nanomaterials in an environmentally safe manner, nanobiological interactions that are mediated by chemical functionalities, green technologies for synthesis of nanomaterials, graphene, plasma, green fire retardant, natural aroma, and green mosquito repellent textile have been covered in this chapter.

9.2

Application of natural dyeing in textile and fashion

The concept of green chemistry is the design of chemical products or processes that can reduce or eliminate the use or generation of hazardous substances. Green chemistry applies across the life cycle of a chemical product, including its design, manufacture, use, and ultimate disposal. The coloration of textile materials is possible with different natural resources of plants. D. regia stem shell extract, S. foetida fruit shell extract, coconut shell extract, marigold, pomegranate, tea, etc., can be successfully employed natural dyeing of textile materials as a natural source of colorant. The concept of using green chemistry with natural resources such as plants, animal, and clay in dyeing, printing, and finishing of textile materials is relatively old but its applications with the advanced technology and synthesis are increasing nowadays. National and international awareness about diminution of natural resources, ecological imbalance, pollution problem, and disturbed environment due to the ample usage of hazardous chemicals and synthetic dyes forced environmentalists to think in terms of natural and green products. These factors have brightened the scope of utilization of natural dyes. The process of natural dyeing may be divided into three phases: (1) adsorption of the dyestuff at the fiber surface, (2) diffusion of the dyestuff through the internal structure of the fiber, and (3) fixation or “anchoring” of the dye molecule at a suitable location or dye site. Natural dyes are so called because they are obtained from natural resources. Colorants obtained from natural resources such as plants, animals, minerals, and microbial origins are used for coloration of textile substrates. Natural dyes again have gained importance because of their easy availability, the simple process of application, shade uniformity, and better fastness properties. Natural dyes are ecofriendly as they are renewable, biodegradable, skin-friendly, and could be beneficial to the health of the wearer. Kermes is animal origin crimson red dye derived from the insect Kermes ilicis, used to color wool/silk fibers though inferior to cochineal in fastness. Lac dye for coloration of protein fibers is obtained as a byproduct during the production of shellac, from insect exudate. It has been additionally used (Wheeler, 1931) to color cotton, as it is freely available. Textile fibers, mainly cellulosic, do not have much affinity for most natural dyes and hence these are treated with a mordant salt. Carthamin from safflower (Carthamus tinctorius) petals and bark extracts gave a strong and fast red color. The root extract of ratan jot (Onosma echioides), also containing Carthamin gave a similar color. Coloring matter from the roots of Indian madder (Rubia cordifolia) and European madder (Rubia tinctorum) also conferred

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red color on the cotton fabric. But these dyes required the use of mordants. Lac dye, derived from the resin secreted by the Laccifer lacca previously used for dyeing of proteinous wool and silk fabrics, has now been applied to chitosan-pretreated cotton fabric to produce a violet color (Joshi et al., 2007; Samanta and Konar, 2011; Ali et al., 2014). Yellow color dye from turmeric and rhizomes of the plant Curcuma longa, has been reported to be the most popular choice for textile coloration. Fruit pulp of annatto contains two major carotenoids (colorants), bixin and norbixin, that also produce orange-yellow color on textiles. Orange flower of Tesu (Butea monosperma), onion (Allium cepa) skins, and marigold (Tagetes patula) have been explored to produce a yellow color on the cellulosic cotton textiles (Samanta and Agarwal, 2009; Samanta and Konar, 2011). Organic cotton, harvesting technique is different from the traditional cotton, which is grown without use of industrial pesticides. Woolen fabrics are soft, fuzzy, and thick; they are warmer than worsted wool fabrics. Napping gives woolens a soft surface, which acts as a protection against objectionable luster. Worsted fabrics are firm, wrinkle less and hold creases and shape and become shiny with the use. They are appropriate for tailored and dressy purposes, spring and summer coats and suits, and for tropical coats too. Linen is a textile derived from the fibers of the flax plant. Linen is tedious to manufacture, but the fiber is very absorbent and garments made of linen benefit the wearer with exceptional coolness and freshness in hot weather. Linen fabric feels cool due to its higher thermal conductivity. It is smooth, giving lint-free finished fabric, and gets softer with numerous washings (Teli and Pandit, 2017a; Teli and Pandit, 2017a; Teli and Pandit, 2018b). Usage of banana pseudostem sap for dyeing of cotton fabric mordanted by tannic acid and alum at boil temperature for 30 min. It was also reported that the cotton fabric showed attractive Khaki color in alkaline condition. Moreover, due to the mordanting process, dyed fabric showed good wash durability, light fastness, rubbing fastness, and weathering durability (Basak et al., 2016). Indigo a natural dye that provides blue color is obtained from the plant of genus Indigofera. Indigo has good overall fastness and is mostly used for dyeing cotton denim. It provides blue color with a reddish tone due to the presence of trace amount of indirubin. Woad (Isatis tinctoria) is also an Indigo source to produce blue color in cellulosic cotton and jute fabric with good fastness properties. Plant extracts that contain a high amount of tannin generally produce brown to black shades. Catechu (Acacia catechu) produces dark brown color on cotton. Logwood, Harda, and custard apple are also rich tannin sources (Samanta et al., 2011). Tannin-rich brown to black color dyes are suitable for coloration of both cellulosic and protein fibers. One major advantage of these groups of dyes is that no mordanting process is necessary as these dyes act as mordant. Natural dyes have also been used for dyeing of lignocellulosic fibers and protein-based wool and silk fibers. Lignin present in the jute fabric helps to uptake the natural dye at neutral to alkaline pH. Natural dye extracted from jackfruit leaf, annatto, myrobalan, manjistha, and ratan jot has been utilized for dyeing of jute, whereas kenduka, haritaki, and lodhra extract has been used as bio-mordants. On the contrary, amine ( NH2) and carboxylic acid ( COOH) group present in the wool polymer helps to uptake

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Table 9.1 Nominal proportion of mordants used for natural dyeing of textile. Mordant type

Proportion used in dyeing (w/w)

Harda Aluminum sulfate Ferrous sulfate Tin chloride Copper sulfate Potassium dichromate

10% 5% 5% 3% 2% 2%

Mordant is a chemical, which has affinity toward textile fiber, metallic mordant (alum, ferrous sulfate, stannous chloride, potassium dichromate, copper sulfate), and bio-mordants (tannic acid, citric acid).

the natural dye in the pH range of 4.5 5 (isoelectric point of the wool polymer). Almost all natural dyes can be used for dyeing wool polymer because of its amphoteric nature (Samanta et al., 2015). Mordant forms a chemical bond with fiber and natural dye in different ways, and the extent of bonding depends on the functional and ionic groups present in the fiber and natural dye. Nominal proportion of mordants used for natural dyeing of textile is mentioned in Table 9.1. In metallic mordants, namely alum, aluminum ion is a trivalent cation and it initially binds with either the negative charge present on the surface of fibers or the natural dye anion. Afterward functional groups present in the natural dye molecule ( OH, .C 5 O) and aluminum ion form them coordinated complex inside the fiber. Tannins are water-soluble phenolic compounds with higher molecular weights form chemical bonds with fiber between the hydroxyl/ phenolic groups of mordant and amino/amido/hydroxyl/carboxyl groups of fiber or ionic bond between charged anionic groups of mordant and cationic groups of fiber.

9.3

Application of green flame retardants in textile and fashion

Eco-friendly flame retardant finishing is important, among various functional finishing of textile materials, as it protects against a common and major human health hazard. In recent years, research in the field of eco-friendly flame retardancy in textile materials has increased to find a sustainable route to reducing the carbon footprint. Efforts have been made, especially in the last 5 7 years, to use various eco-friendly biomolecules extracted from plant (sap and grain-based) and animal (protein and polysaccharide-based) natural resources for making thermally stable textile materials. There have been effective researches for green solutions identifying natural flame retardant resources for application in textile materials. Flame and fire retardancy are achieved because the plant extract and waste plant products are composed of elements of phosphorous and other positive metal ions,

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inorganic salt biomolecules, metal oxides, etc., which could confer flame retardant finishing of cellulosic, lignocellulosic, and protein fiber based textile materials. Flame retardancy effect with plant-based biomolecules has been found with coconut shell extract, banana pseudostem sap, spinach juice, starch, and pomegranate rind extract applied mostly on cellulosic, lignocellulosic, and protein textile materials. Nitrogen and ammonium sulfamate has been used recently for making fire retardant cellulosic and lignocellulosic substrates. However, most of the conventional flame retardant chemicals are not eco-friendly and are often not wash-durable (Horrocks, 1986; Horrocks and Price, 2001). It is quite clear from an extensive review that the major challenge is to develop more low-cost, environment-friendly, and sustainable fire retardant formulations. In this regard, Katovi´c et al. attempted to decrease the volume of formaldehyde released from fire retardant fabrics by using binding agent butane tetracarboxylic acid instead of the usual formaldehydebased resins. El-Hady et al. used nano-zinc oxide based fire retardant formulation (Katovi´c et al., 2012; El-Hady et al., 2013). Application of new phosphorus-based flame retardants have been reported innumerous publications and patents (Ravey et al., 1998; Wilkie and Morgan, 2009). Flame retardancy of the textile material using casein, whey proteins, DNA, hydrophobins, starch, chicken feather, etc. are reported as thermal stabilizing agents. However, the sources used were not available in abundant and extraction process was also complex (Bosco et al., 2013; Malucelli, Carosio, et al., 2014; Wang et al., 2014). There exists a distinct difference in degradation behavior of both the cellulose and starch biomolecule even though both contain the same glucosidic linkage in their structural backbone. Application of Starch by layer-by-layer (LBL) method to the different g/m2 cotton fabric (100, 200, and 400) is reported in literature. The surface of the cotton fabric was initially activated by polyacrylic acid and then alternately dipped into the positively charged starch solution and negatively charged polyphosphoric acid solution. All starch treated cotton fabric showed lower burning rate and more formation of black char residue after flammability test (Carosio et al., 2015). Chicken feather protein (CFP)-based phosphorous-nitrogen containing flame retardant was used to obtain fire retardancy on cotton. Using a general pad-dry-cure finishing method, 250 gpl CFP treated cotton fabric gave an limiting oxygen index value of 30 and extinguished the flame in 7 s in vertical flammability test. But afterglow was present for 180 s, and the sample was burnt completely with a slow burning rate. CFP-treated cotton fiber produced char that was thick, compact, and bulky on the fiber, whereas CFP with boric acid and borax treated fabric showed the fine dispersion of even granules on the fiber surface (Wang et al., 2014).

9.4

Application of antibacterial finishes in textile and fashion

Antimicrobial finishes are mostly important for garments and clothing that have been exposed to weather and also used for home textile applications. Apparel

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textiles such as shirtings, trousers, and sari (directly come in skin contact) used by the people also need hygienic finishes. Presently, a large number of synthetic antimicrobial agents are available in the market to make the textile antimicrobial, antibacterial, and antifungal. Among those chemicals formalin solutions, tributyl tin oxide, dihydroxy dichlorodiphenyl methane, and triclosan have been used widely as antibacterial agents for many decades. Quaternary ammonium compounds have been used as the most effective and popular antimicrobial agent for its positive ammonium ion. However, all of these chemicals are water-soluble and cannot provide durability of the finish to the end-products. The advantages of using plantbased antimicrobial agents are eco-friendly, biodegradability, and economy, as they are produced from renewable and diversified sources of plants and herbs. Green chemistry using the herbal and plant products, such as chitosan, Aloe vera, neem, tea oil, eucalyptus oil, and tulsi leaf extracts showed excellent antimicrobial activity on various textile substrates. Neem-chitosan nanocomposite was used to make cotton textile antimicrobial. Chitosan has also been used in LBL process with another negatively charged polymeric materials for improving the antimicrobial efficacy and durability (Rajendran et al., 2012). Neem, pomegranate, and prickly chaff flower have the active antimicrobial ingredient that can control the growth of microbes. Pomegranate rind extract contains different nitrogenous compounds and the positively charged aminoguanidine. This chemical is interacted with and destroys the negatively charged bacterial cell wall (Thilagavathi and Kannaian, 2010; Basak and Ali, 2017). Hena and juglone obtained from the walnut contain naphthoquinone that acts as antibacterial and antifungal agents. Recently, Aloe vera gel has been applied to cotton textile to improve the antibacterial activity against Staphylococcus aureus bacteria (Banupriya and Maheshwari, 2013). Onion peel, marigold flower, and green coconut shell extract have been used for making multifunctional cotton, silk, and wool fabric. It is a waste product and rich in tannin, saponin, and flavonoid content. This extract-treated cotton fabric showed excellent antimicrobial efficacy against gram-positive and the gram-negative bacteria. The fabrics dyed with catechu dye showed high antibacterial activity towards both gram-positive and gram negative bacteria as a result it can be used as wound dressing material. Antimicrobial fabric, finished with herbal extract was found to be effective for the people those are suffering with skin allergies, eczema and psoriasis (Prabhu et al., 2011; Teli et al., 2017; Pandit et al., 2018).

9.5

Green chemistry approach for ultraviolet protection in textile and fashion

Textile materials have different protective capability depending on their structural composition. Cotton, jute, and silk suffer from very poor UPF. Many chemicals are available at the market for enhancing the UPF of the fabric such as phenyl salicylates, benzophenones, benzotriazole, oxalic acid, and dianilide derivative. However, these chemicals are not eco-friendly. Various plant extracts such as babool,

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manjistha, ratan jot, and annatto have been used by the researchers for getting the UV-protective effect. Recently plant sources such as marigold flower, sapan wood, tamarind seed coat, coconut shell extract, S. foetida fruit shell extract, and D. regia stem shell extract have been reported to be used for enhancing the UPF of the lightweight cotton, silk, linen, organic cotton, wool, jute and other natural fabrics. Dye with Acacia catechu and Rubia cardifolia has shown excellent and good UV property respectively of the nettle fabric without mordanting (Chattopadhyay et al., 2013; Teli et al., 2017; Teli et al., 2018). UV-protective finishing of the textile materials using nano-based titanium dioxide, zinc oxide, and selenium dioxide finish formulations have been used more popularly by the researchers. A few recent studies have reported that some of the natural dyes have the active molecules that can absorb UV light and block its passage through the fabric. Dyes extracted from the madder, knotgrass, fenugreek and marigold possess very good UV-protective property. Linen, hemp, and silk fabrics were dyed with those natural plant extracts. The linen fabric was dyed with Indian madder that showed UPF rating of more than 50, which is considered as excellent as far as the UV protection is concerned. Dyeing of cotton with madder and Indigo could also improve the UV-protective performance. It was observed that by increasing the percentage of natural dye from 2% to 6%, the UPF value was found to increase to 50 (Sun and Tang, 2011). The UPF of a fabric is depending on a number of factors such as type of natural fiber, fabric construction, thickness of fabric, chemical constitution of natural dye, depth of the shade, type of mordant used and absorption characteristics of the natural dye in the UV region.

9.6

Aroma finishing of textile and fashion

The aroma quality or other substances arises from their fragrance or agreeable odor. Clothing styles and popular apparel fashions rapidly change, and the fashion world is continuously inundated with runway innovations and fly-by-night fads. Table 9.2 lists the sources and their respective odors applied in fragrance finishing using natural resources. Applying fragrances to textiles has been often done using fabric conditioners in the wash and during tumble-drying. Irrespective of the technique used to introduce the fragrance, its effect is temporary, not lasting beyond one or two wash cycles (Inoue et al., 1991). All types of textiles are excellent substrates for emanating fragrance compounds and enhance the comfort level, especially of sports persons wearing activewear, depending on their fragrance preference and intensity. Fragrance of choice for sportswear may be orange or lemon that would keep them energized for a longer time. Microencapsulation can effectively modulate the release load of the fragrance compounds and essential oils as required, while also ensuring the stability and limiting the dosage of volatile substances (Inoue et al., 1991).

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Table 9.2 Natural resources of aroma and its odor categories. S. no.

Natural resources

Representative odor categories

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

Citrus lemon Orange Floral carnation Gardenia Geranium Lilac Lily Rose Violet Fruity apple Apricot Banana Grape Peach Strawberry Herbaceous clove Minty Sweet anise Cinnamon Honey Sweet Vanilla

Citral, citronellal Mandarin oil, decyl acetate Phenethyl salicylate Nonyl acetate Citronellol Anisyl acetate Hydroxycitronellal Rose absolute Costus oil, methyl-2-nonenoate Benzyl acetate Allyl butyrate Amyl acetate Isobutyl isobutyrate Allyl butyrate Benzyl benzoate Eugenyl acetate l-Carveol, l-carvone, l-menthol Ethyl acetate, methyl sorbate Cinnamaldehyde Allyl phenoxyacetate Acetanisole Anisyl acetate

9.7

Mosquito repellency finish for textile and fashion

There are various natural mosquito repellents, which include citronella oil, castor oil, clove oil, cedar oil, rosemary oil, peppermint oil, lemongrass oil, geranium oil, chrysanthemum, etc. Among all the mentioned natural repellents, chrysanthemum was found to be the most effective. The significant feature of chrysanthemum is that it does not lose its action toward mosquitoes for a long period of time even when it gets exposed to the environment, that is, it retains activity and stability. This is not in the case with the other mentioned natural repellents, because they deteriorate on exposure to sun, heat, and rain. Some of the chemical repellents are DEET (diethyl-meta-toluamide), allethrin, permethrin (synthetic analog of pyrethrum), and malathion. There are different types of testing methods for evaluation of mosquito repellent textiles such as cone test, wire-ball test, cylinder test, and field test. In the case of cone test exposed mosquitoes might spend more time resting on the cone, not on the treated surface. In case of wire-ball test the treated fabric, which is to be tested, is wrapped around a wireframe, and mosquitoes introduced into this ball. In case of cylinder test, inside of a test cylinder is covered with the textile. The field test is especially performed in such a location where the

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flood water mosquitoes are rich. The mosquito repellent textiles can be used as antimosquito garment, bedsheets, wide-mesh netting jackets, head nets, bands and anklets, repellent ropes, bed nets, bed curtains, window curtains, and bathroom curtains (Nuchuchua et al., 2009; Pandit et al., 2018). Chrysanthemum genus (Asteraceae) has been suggested for many years in folk medicine and has been widely used for the prevention of migraine headaches and arthritis, and as antiinflammatory agents (Jo´zefczyk et al., 1999). Aerial parts of Chrysanthemum indicum were used to treat various medical conditions such as vertigo, hypertensive, and also some infectious diseases such as pneumonia, colitis, stomatitis, etc. The chemical composition of essential oil extracted from air-dried C. indicum flowers were studied and its antibacterial activity has also been confirmed against S. aureus, E. coli, and Streptococcus pneumoniae (Shunying et al., 2005). Chrysanthemum oil extracted from fresh and dried flowers and leaves of C. indicum by steam distillation have components such as borneol, chrysanthenone, and bornyl acetate. It was found that oil extracted from leaf had a larger number and amount of sesquiterpenoids than monoterpenoids (Stoianova-Ivanova et al., 1983). Chrysanthemum oil could be used with different oils and the composition can be applied to the skin for repelling mosquitoes. Another researcher also developed the application technique of chrysanthemum oil nanoemulsion for making nylon net fabric mosquito repellent. The net fabric treated with chrysanthemum oil emulsion exhibited wash fastness and was durable up to 25 washes and also showed excellent mosquito repellent property (Plummer and Plummer, 1993). Some researchers also found pyrethrins as an insecticide from Chrysanthemum cinerariaefolium flowers. The compound was extracted using organic solvents and detection by high-performance liquid chromatography proved that the extract contained Pyrethrin I and Pyrethrin II. The extract from flowers showed an active biological effect against beetle flour Tribolium castanum (Khazaal and Shawkat, 2011). Chrysanthemum morifolium Ramat is one of the utmost important attractive flowers in the floriculture industry. Due to its aromatherapy effect for the treatment or mitigation of headaches, blood hypertension, allergies, eye-related diseases and inflammation, it was used as cigarette flavor. One of the studies reported that flavonoids from C. morifolium L. can be used as anti-AIDS agents. Researchers also found that the presence of chrysanthemum oil in composition gives refreshment effect and has better effects on listlessness, amnesia, and other symptoms caused by various discomforts. Chrysanthemum oil also has antiinflammatory activity against acute and chronic inflammation. The safety of chrysanthemum oil was also tested and confirmed (Hwang and Kim, 2013; Chun-Ping et al., 2015).

9.8

Applications of graphene in textile

Textile fabrics offer potential advantages compared with sheet materials, such as high surface area, mechanical properties, and flexibility, which can make them

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attractive substrates onto which other functional materials can be deposited. Graphene has emerged as a revolutionary material in the field of material science and physics due to its extraordinary properties. It can produce a conductive platform that can be integrated into textiles by means of chemical deposition, by producing graphene woven fabrics, or by integrating conductive fibers of graphene into the fabrics. A lot of work has been done with graphene-based fibers. The applications of this kind of materials include UV protection, conductive fabrics, antistatic fabrics, hydrophobicity, sensors, heat generation, thermal conduction, photocatalytic and electrolytic activity, antimicrobial, fuel and solar cells, field emission devices, energy storage, etc (Choi et al., 2010; Meng et al., 2015; Xu and Gao, 2015). Graphene coated woven fabrics of high conductivity can be obtained by a chemical vapor deposition method. Due to the high conductivity obtained, this method can be employed for the high conductivity applications such as sensors —one of the main uses of these types of textile structures. The high sensitivity of these fabrics as strain sensors having very high gauge factors opens the door to new applications such as voice recognition, movement sensors, and breath and pulse sensors. Regarding future developments, more efforts shall be devoted to increasing the adhesion of graphene coatings on the textile substrates. The development in the area of energy applications will definitely be explored in more depth in the future and more applications will be ideated. These applications may include flexible supercapacitors composed of graphene; their development will allow the implementation of electronic textiles with various functionalities. The applications of graphene as an electrode material for energy applications also include Li-ion batteries, Li-sulfur batteries, Li-air/oxygen batteries, fuel cells, or solar cells (Brownson et al., 2011; Sun et al., 2015). Application of semiconducting nanoparticles (NPs) based graphene fabrics studied in depth using titanium dioxide NPs (Zhu et al., 2014; Karimi et al., 2015; Molina et al., 2015). Graphene functionalised fabrics can be employed as photocatalytic materials or can be integrated into solar cells to increase the energy conversion efficiency. Owing to its organic nature, it can be easily modified with organic dyes through π π interactions or hydrophobic interactions and can be used as a good approach to extend the bandwidth energy absorbance of graphene materials that usually absorb radiation in the UV region, to the visible region where dyes absorb. This approach will also lead to an increase in energy conversion efficiency in solar cells (Li et al., 2012; Meng et al., 2012; Liang et al., 2014). Graphene is a very strong, stiff, and lightweight material. Currently, aerospace engineers are incorporating carbon fiber in the manufacture of aircraft as it is also very strong and light but not more than graphene. It is being utilized to replace carbon fiber and steel in the aircraft, improving fuel efficiency, range, and reducing weight. Owing to its high electric properties it can also be used to coat aircraft surface material to prevent electrical damage caused by thunder strikes. Graphene coating can also be used to measure strain rate, notifying the pilot of any changes in the stress levels of aircraft wings. High strength requirement for body armors of military personnel and vehicles is a challenging requirement for the application of graphene (Pandit et al., 2018).

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189

Application of plasma technology in textile and fashion

Textiles are manufactured to execute a number of functions. While manufacturing, fabric has to go through various stages. Water and energy are consumed in nearly every step of the process chain of textile manufacturing. The water thus required is taken from various sources. Main pollution in textile wastewater comes from manufacturing of regenerated fibers and textile wet processing especially, dyeing and finishing processes. With increasing industrial pollution and consequent governmental regulations, the need to provide “green” processes to prevent pollution, reduce wastewater, and utilize environment-friendly resources has become an important issue. The water thus required is taken from various sources. Main pollution in textile wastewater comes from manufacturing of regenerated fibers and textile wet processing especially, dyeing and finishing processes. The longer the processing sequences, higher will be the quantity of water required. Immense water is utilized in washing at the end of each process (Manivaskam, 1995). With increasing industrial pollution and consequent governmental regulations, the need to provide “green” processes to prevent pollution, reduce wastewater, and utilize environment-friendly resources has become an important issue. The plasma treatment of textiles only modifies the surface with different valueadded functionalities, such as water, stain and oil repellent, hydrophilic, antimicrobial, flame retardant, UV-protective, dirt-repellent, antistatic properties, electromagnetic radiation (EMF) protective, and improvements in dyeing, printing, bio-compatibility, and adhesion can be achieved by modifying the fiber surface at nanometer level (Samanta et al., 2010; Kale and Desai, 2011; Teli et al., 2015a; Teli et al., 2015). Plasma polymerization or plasma-enhanced chemical vapor deposition enables the deposition of very thin films of polymers that possess highly cross-linked structures onto textile surface. Examples of different plasma gases commonly applied and their effects are given in Table 9.3. Atmospheric pressure plasma treatment of textile is being investigated as an alternative for enhancement of conventional processing technology. A wide variety of plasma processing effects on textile substrates have been demonstrated. The applications are widespread and encompass enhancement of flame retardency, Table 9.3 Various common plasma gases. Type of gas

Type of property

Helium Argon Oxygen, nitrogen

Increased hydrophilicity Increased surface roughness Modification of surface functional groups, increased hydrophilicity Polymerization, increased hydrophobicity Modification of surface functional groups

Fluorocarbons Ammonia, carbon dioxide

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antimicrobial property, water and oil resistance, adhesion and barrier properties, among others (Shenton et al., 2001). Active molecular fragments such as free radicals are generated when the chemical bonds are cleaved by the 0 5 eV energy spectrum of cold plasma. Atmospheric pressure nonequilibrium plasma can be used to produce large area and uniform surface modification of materials under continuous process conditions. Polymer surface modifications that use various plasma methods have received significant attention. The chief advantage of modifying textile surfaces with plasma is the ability to alter the surface (altering the reactivity of surface) without changing the structure and bulk properties. Extension of atmospheric plasma application to graft copolymerization is a novel technique that provides permanent covalent bonding of polymers onto fabrics. Plasma treatment improved the dyeability and color strength of the plasmatreated silk fabric; degummed silk fabrics were plasma-treated in O2, N2, and H2 atmosphere for 5 min and were dyed with Remazol reactive dye with M:L-1:50 at 50 C for 90 min. In all the cases K/S of the treated fabric improved significantly compared to the control silk fabric. It was found that in the 5 min plasma-treated and dyed fabric at 6% shade exhibited equal color strength when the control sample was dyed with 10% shade. This might be because plasma treatment might have helped in the formation of more number of active sites for the dye (Iriyama, 2003). Nonpolymerizing gases such as O2, N2, H2, He, and Ar have mainly been used for improving hydrophilic property and coloration of silk textile. However, to impart other functional properties, plasma reaction has to be carried out using a polymerizing precursor. Researchers used SF6 cold plasma to impart high degree hydrophobic functionality in the Bombyx mori silk fabric (Nimmanpipug et al., 2008). Plasma treatment can be applied to silk to improve the surface properties of the fabrics. However, it should be noted that different parameters used may have different effects on the degree of improvement. Due to formation of more numbers of NH2 group and surface oxidation, the N and O content in the treated fabric increased by 16% and 39%, respectively. Surface oxidation of wool fiber was confirmed by measuring the shift in binding energy of sulfur from 163 eV in the control fabric to 168 eV in plasma-treated fabric (X-ray photoelectron spectroscopy analysis). This helped in formation of sulfonic acid due to oxidation of disulfide linkage upon plasma treatment. As a result of this, S atomic percentage reduced from 2.58 to 2.23 in the untreated to plasma-treated samples (El-Zawahry et al., 2006). Similar result was also observed when the wool was plasma-treated in the presence of oxygen (O2) atmosphere. However, there were two more physicochemical changes observed in oxygen plasma such as (1) additional formation of C 5 O, OH, and COOH groups that are responsible for enhanced dye uptake and dye fiber interaction and (2) slight improvement in crystallinity of the plasmatreated sample. In these two plasmas, the C/N atomic ratio decreased from 7.39 (O2 plasma) to 6.70 (N2 plasma) and O/C atomic ratio increased significantly in both cases compared to the untreated wool (Kan, 2007). Atomic force microscopy observation showed formation of widened striations and rough bark-like appearance with

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the presence of small pits and microcraters non-uniformly distributed over the wool scale surface for 2 min of O2 plasma treatment. This plasma-enhanced surface etching leads to an increase in surface area from 0.1 to 0.35 m2/g (Ho¨cker, 2002). It was found that plasma treatment breaks down the scales and oxidizes the upper fatty hydrophobic layer and helps in producing shrink-proof wool. Dielectric barrier discharge plasma treatment on cotton, wool, and polypropylene changed the hydrophobic character to hydrophilic. Specific surface areas significantly increased from 0.1 to 0.35 m2/g in cotton and wool, increasing percentage of dye uptake (Ho¨cker, 2002). Dyeing of plasma pretreated cotton-woven fabrics showed deeper and brighter color shades than untreated sample. Plasma helps the cotton textiles to absorb more dye from dyeing bath, but has little effect on colorfastness of textile material. Plasma treatment on cotton in presence of air or oxygen increases both the rate of dyeing and the direct dye uptake of Chloramine Fast Red K, in the absence of electrolyte in the dye bath. This effect depends more on the oxygen component of air than the nitrogen component. Oxygen plasma treatment was more effective than air plasma treatment (Spitzl and Hildegard, 2003). Plasma treatment with nitrogen under a pressure of 2 mbar induced in situ polymerization of acrylic acid 10% 20% w/w on polyester, polyamide, and polypropylene (PP) fabrics for 5 15 min exposure to 25, 50, and 75 W plasma power. The overall color strength obtained was significantly higher. The wash fastness was acceptable on polyamide and unsatisfactory on polyester and polypropylene fabrics as grafting of polyacrylic acid had taken place only on the surface of the polyester and polypropylene fibers, but in case of polyamide the interior of the fiber was also modified. The spectral value (K/S) of the dyed polyester fabric increased by about 50%, and relative dye uptake also increased by about 18% after the treatment. The improvement of the dyeability does not degrade the dyeing fastness of the material. The treated fabrics were dyed with a reactive dye (Remazol Black B); color yield and fastness properties of the fabrics were studied. The K/S values improved by 15% 20% when compared to the untreated fabric (Ferrero et al., 2004). Hydrophobic textiles are important in many applications because liquids are around us in the form of rainwater, food, beverages, chemicals, and pesticides. Hydrophobic finishing of cotton textile was studied by treatment with siloxane or perfluorocarbon plasma. Hexamethyldisiloxane-derived plasma polymers are used for the hydrophobic finishing of cotton textiles leading to a smooth surface showing water contact angles up to 130 degrees without changing its water vapor transmission rate (Kale and Desai, 2011; Teli et al., 2015). Plasma polymerization with gaseous hydrocarbon monomers such as methane (CH4), ethylene (C2H4), or acetylene (C2H2) can deposit film-like coatings of cross-linked amorphous hydrocarbon layers, which show hydrophobic properties. Plasma treatments using CF4 and C3F6 on cotton denim fabrics in low-pressure plasma were found to increase the surface hydrophobicity as indicated by the increasing contact angle. For cotton, the contact angle changes from 30 degrees for the untreated sample to 90 150 degrees for the plasma-treated sample depending upon the pressure in the reactor and treatment time. Overall hydrophobicity of treated desized denim fabrics was found to be higher than that of treated sized denim fabrics, indicating that the sizing on the denim

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fabric plays a role in determining surface wettability even after fluorination in a CF4, and C3F6 plasma treatments (McCord et al., 2003). Superhydrophobic finishing of textile and other substrates to impart lotus effect on the substrates, has taken the attention in the research community. This would help the material to be self-cleaned and may also be dust repellent. Selection of the appropriate method to create surface roughness and lower down the surface energy depends on the mechanical and physicochemical properties of the substrate. Making a superhydrophobic material from cellulose would help to serve the advance applications, while maintaining its fundamental comfort properties. It was observed that roughness was not sufficient to establish superhydrophobicity and hydrophilic cellulose fibers must also be hydrophobized by a fluorocarbon/hydrocarbon coating (Balu et al., 2008). A mixture of hexafluoroethane (C2F6) and hydrogen was investigated as barrier against hydrolysis of aramid fabric such as Nomex. The deposition of a thin layer leaves the fibers intact by immersion in 85% H2SO4 solution (20 h at RT), while a conventional fluorocarbon finishing shows a significant shrinkage of fibers and loss of properties. Plasma treatment on cotton fabric using O2 gas in presence of hexafluoroethane resulted hydrophobic finished cotton fabric (Ho¨cker, 2002).

9.10

Application of green reducing agent for synthesis of nanoparticles

A new route to green synthesis of silver NPs through a single step of silver reduction by an eco-friendly reducing agent such as tannic acid, forming uniform NPs having diameter in the range of 18 30 nm was reported (Doshi and Reneker, 1995). A simple and green approach for the synthesis of silver NPs utilizing aqueous leaf extract of Azadirachta indica was also reported in the literature. The plant extract was used as a reducing agent and also a capping agent. Silver NPs obtained were well dispersed and mostly spherical with a diameter of 34 nm. The silver NPs exhibited antibacterial activity when exposed to both gram-positive (Staphylococcus aureus) and gram-negative (Escherichia coli) bacteria. Their result provided a facile, fast, single-step, eco-friendly, and nontoxic method, which needs just 15 min to convert silver ions into silver NPs at room temperature, without using any hazardous reagents (Ahmed et al., 2016). Quasispherical silver NPs using hot water olive leaf extract (OLE), as both reductant and stabilizer with silver nitrate as a precursor. The silver NPs were mostly spherical with a diameter of 20 25 nm. The antibacterial activity of synthesized AgNPs relative to aqueous OLE was measured by well diffusion method. Silver NPs showed higher antibacterial efficacy against multidrug-resistant S. aureus, Pseudomonas aeruginosa, and E. coli compared to OLE extract (Khalil et al., 2014). Synthesis of silver NPs using silver nitrate as a precursor from the leaf portion of the plants, Musa balbisiana (banana), A. indica (neem), and Ocimum tenuiflorum (black tulsi) was reported in the literature. It showed significantly

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higher antimicrobial activities both against E. coli and Bacillus sp. in presence of both silver nitrate and raw plant extracts. The toxicity of silver NPs was evaluated by seed germination technique, performed on seeds of mung bean and chickpea. The seeds treated with silver NPs showed better rates of germination indicating low toxic nature of silver NPs (Banerjee et al., 2014).

9.11

Green synthesis of nanofibers and nanoparticles for textile finishing

Nanofibers prepared by using ecological solvents or naturally occurring biodegradable polymers have found a niche use in medical devices for wound healing and controlled drug release, especially due to high surface area and membrane-like structure. Electrospun nanofiber mats have been synthesized using hydroxypropyl cellulose (HPC) separately or by addition of fiber-forming polymer such as poly (vinyl alcohol) (PVA) or polyvinylpyrrolidone (PVP) to improve the mechanical strength of the nanofibers mats. The blend of HPC with PVA/PVP increased the favorable properties such as thermal stability, visual appearance, and mechanical properties. Drug loading on such nanofibers allowed for sustained release of drug, when tested in vitro (El-Newehy et al., 2018). A green nanofiber was prepared by using H2O2-assisted dissolution of chitosan/ polyvinyl alcohol in water, a green solvent. This is necessary to replace organic solvents used to solubilize water-insoluble polymers, with aqueous spinnable solutions. It is essential for end applications of nanofibers in environmental solutions or in biological systems that no toxic chemicals be used in their processing. The method developed produce uniform nanofibers, with PVA, polyvinyl alcohol, as a supporting polymer and chitosan made water-soluble by a heterogeneous reaction (Pervez and Stylios, 2018). Carbon nanofibers (CNF) have been commonly prepared from synthetic carbon polymer precursors, and organic solvents such as methylene dichloride and dimethylsulfoxide used to dissolve these are toxic and hazardous. But their preparation from naturally available precursors with benign solvents is less common. Thermal treatment for stabilization, at 350 C, followed by reduction to carbon at higher temperature of 950 C, formed graphite-like CNF. In situ doping of Ag NPs at 0.1 wt. % in CNF increased electrical conductivity by one order of magnitude (Chakravarty et al., 2017). Conventional textile finishes that impart advantages such as water repellency and stain repellency to the fabric are rarely durable to frequent laundering. NPs with their characteristic large surface area and high surface energy bind to fabrics, with greater strength conferring better durability of the desired textile property (Kathirvelu et al., 2009). NPs provide functional applications such as chromic behavior, antibacterial properties, self-cleaning, and UV protection, but most significant to textile use are antibacterial, UV-protective, and coloration properties. Odor control, stain control, and restricting spread of infection in densely populated areas (clean human environment being a civilizational need), all of these require

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antibacterial coatings on medical devices, hygienic products, medical surgery equipment, textile, storage materials, etc. Hygiene finishes protect textile users from pathogenic or odor-causing microorganisms in common textile garments. Preventing damage to textile by fungi or rot-producing microbes is another goal. Quaternary ammonium compounds act against gram-negative and gram-positive bacteria and are often used as additives in laundering formula (Fouda, 2012). Natural antibacterial compounds such as chitosan [poly-(1 4)-D-glucosamine], a cationic polysaccharide and a major component in crustacean shells, are produced by deacetylation of chitin with an alkali (Ye et al., 2006). Silver is the most biocidal against different pathogenic bacteria. Immobilization of silver NPs on synthetic and natural fibers for odor control and biocidal activity has been achieved (Rivero et al., 2015). The antibacterial effect is obtained at extremely low loads of the silver component. The AATCC Technical Manual 12 contains numerous test methods to evaluate antimicrobial finishes on textiles. The frequency of occurrence of skin cancer has risen worldwide due to increased exposure to UV rays of sunlight. The longer wavelength (320 400 nm) UV rays (UVA) cause pigmentation of skin with more melanin, while higher energy UV rays (UV-B) penetrate skin surface, causing acute chronic skin eruption and damages such as skin reddening (erythema) or sunburn (Das, 2010). Textile clothing treated with NPs of zinc, zinc oxide, and TiO2 act as UV protection barriers on skin. NPs of TiO2, ZnO, and metallic zinc in size of 20 50 nm are photostable and offer broad-spectrum protection, but skin sensitivity and allergic reactions have to be considered, for optimum load of UV-protective finishing on fabric (Manaia et al., 2013). Coloration of textile is achieved by dyeing with either natural dyes or synthetic dyes but color changes due to UV light damage, repeated washing, and surface abrasion during wear are factors that deteriorate the colorfastness and overall quality of the fabrics and textile. Colorfastness is essential for high-quality fabrics and textiles for high-value products (Johnston et al., 2008). Colored metallic NPs, whose color depends on the particle size, can be prepared. The stability to UV light that is possessed by metallic NPs makes them suitable to color textiles that may undergo exposure to extreme levels of UV light. Gold and silver NPs exhibit localized surface plasmon resonance (LSPR) phenomenon that gives bright colors and also act as catalysts (Tang et al., 2011). The coloration of fibers has been done through the LSPR effect of silver and gold NPs, which also provide UV protection and antibacterial action (Johnston et al., 2008; Tang et al., 2015). Gold and silver NPs with different size provide stable colorfast colorants that can be applied in high-quality fabrics and textiles (Tang et al., 2012). LBL technique, involving the principle of self-assembly of nano-layers, can produce a thin-layer film on numerous types of surfaces. LBL process allows control of film thickness and also the choice of molecule as precursors can direct the formation of the layered assembly. Electrostatic self-assembly is favored for its simplicity and efficiency. In LBL method to coat textile fabric, suitable polyelectrolytes with opposite charges were deposited alternately, interrupted with wash steps in between to remove excess unbound polyelectrolyte, on the fabric surface. The thickness is

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determined by the number of cycles of adsorption. LBL technique enabled deposition of a thin nanocomposite on the fabric surface and different properties such as color, hydrophobicity, fire retardancy, and UV photoprotection have been imparted to fabric (Srikulkit et al., 2017). Studies on durability indicate stability even after repeated washes. This technique is an economical, eco-friendly, and zero energy consuming process. Therefore it can be implemented at grass level (Dubas et al., 2006). Engineered nanomaterials are a crucial component of sustainable solutions to challenges in the field of nonfossil fuel based energy generation, storage and saving, maintaining a clean environment, recycling wastewater, rapid and cheap mass transportation, and applications in health care such as lab-on-chip diagnosis, fulfilling infrastructure and food security needs for a huge population. Nanomaterials also are specialized complex structures that require specific handling and usage conditions, such that functionality is retained. Better knowledge of the toxicity of nanomaterials in biological systems would help in the establishment of guidelines for their use in applications.

9.12

Future and challenges of green chemistry in textile and fashion

The application of nanomaterials in an environmentally safe manner requires a sufficiently deep understanding of the complexities of nano-biological interactions that are mediated by chemical functionalities on cell surfaces and the functional reactivity, which is also shape and size-dependent of the nanomaterial. They often involve dynamic interactions at solid liquid interfaces that have implications in different areas of application such as drug release, filtration and adsorption, material resistance to corrosion and damage, and mechanical strength of composite materials. Green technologies for synthesis of nanomaterials also require successful scale-up and adaptability to current manufacturing modes. Research in advanced materials is progressing toward competent solutions to resolve these obstacles (Hamers, 2017). In the recent past, the demand for different multifunctional textiles with properties such as self-cleaning and antibacterial was high. In order to obtain textile materials with functional performances, many procedures are used for impregnation of NPs on the fibrous material such as conventional techniques such as pad-dry-cure, coating with the help of binders, and nonconventional processes such as grafting through plasma treatment. Plasma is a mixture of varying concentrations of charged particles such as ions, electrons, neutrons, and uncharged or partially charged species such as photons, free radicals, metastable excited species, molecular and polymer fragments, which is electrically neutral when considered in total. Plasma can be created under low pressure or atmospheric pressure. It is a good tool to modify the structure and topography of the surface of different bulk materials. Plasma treatment processes involving plasmas with driving frequencies in the radio frequency to microwave range have been used in cleaning of surfaces, by removal of coating impairing

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substances to achieve better deposition and the subsequent loading of NPs on the surface of textile fibers (Kiumarsi et al., 2017). This technique can reduce the usage of water and solvents resulted in minimize chemical usage to achieve the same level of effective coating as conventional wet methods. Grafting is a surface modification technique, which deposits NPs by creating polar groups on textile substrate. But this technique consumes costly and hazardous chemicals and solvents. This has led to greener methods of processing of textiles with the development of new technologies for deposited of NPs on textiles such as LBL technology or polyelectrolyte multilayer. Recently, superhydrophobic finishing of textile and other substrates to impart lotus effect on the substrates has caught the attention of the research community. This would help the material to be self-cleaned and may also be dust repellent. Cellulose is a biodegradable, renewable, flexible, inexpensive biopolymer, which is abundantly present in nature. Therefore making a superhydrophobic material from cellulose using green process would help to serve the advanced applications, while maintaining its fundamental comfort properties. If it is rendered superhydrophobic by modifying its surface in nanoscale, it could have applications in a vast array of products, for microwavable food and fast food packages, beverage containers, selfcleaning cartons and textiles, labels, paper boards, heat-transfer surfaces (to remove condensed water quickly), and membranes with low degrees of surface fouling. Graphene has emerged as a revolutionary material in the field of material science and physics due to their extraordinary properties. It can produce a conductive platform that can be integrated into textiles by means of chemical deposition, by producing graphene-woven fabrics, or by integrating conductive fibers of graphene in the fabrics. The applications of this kind of materials include UV protection, conductive fabrics, antistatic fabrics, hydrophobicity, sensors, heat generation, thermal conduction, photocatalytic and electrolytic activity, antimicrobial, fuel and solar cells, field emission devices, energy storage, etc., which can be used in textile and fashion industry. Effluent problems in the textile industry might be due to dye, high dissolved solids, heavy metals, high chemical oxygen demand, low biochemical oxygen demand, alkaline pH, suspended matter generated from textile wet processing unit as shown in Fig. 9.2. Sources of water pollution in textile industry generated a huge waste that causes effluent problems. Sources of such water pollution waste are process waste from sizing and chemical processing waste from desizing, scouring, bleaching, mercerizing, dyeing, printing, and finishing. Wastewater generated after rinsing and washing step of textile wet processing. Wastage of water generated in textile industries can also be from cooling water, boiler blowdown, floor and machine washing, spills, leaks, etc. Textile industry consumes a large amount of water in various processing operations. Consumption of water in the mechanical processing (spinning and weaving) is very small as compared to textile wet processing (scouring, bleaching, dyeing, printing, finishing) where water is used extensively. Almost all dyes and chemicals are applied to textile substrates from water bath. The actual amount of water used is not an important fact to think for textile processing industries, but besides this, the

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Figure 9.2 General layout of textile wet processing.

used water is not “cleaned up” by the textile industry before discharge, which generates effluent to our ecosystem. Common effluent from textile industry is chemically filled with phthalates, organochlorines, lead, and a host of other chemicals that have been proven to cause a variety of human health issues. Felted fabrics processes are more water-intensive as compared to other processing categories such as wovens, knits, carpets, nonwovens, etc. Thus, the green chemistry approach will be useful for the reduction of effluent generation, reduction of process-water consumption and discharge, sustainable effluent treatment, refraining the use of inorganic and harmful chemicals, and development of eco-friendly alternative process and chemicals.

9.13

Conclusion

The major contribution to the pollution in textile wastewater comes from the manufacturing of regenerated fibers and textile wet processing, especially, dyeing and finishing processes. The longer the processing sequences, higher will be the quantity of water required. Large amount of water is utilized in washing at the end of each process. With increasing industrial pollution and consequent governmental regulations, the need to provide “green” processes to prevent pollution, reduce

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wastewater, and utilize environmental-friendly resources has become an important issue. Graphene has emerged as a revolutionary material in the field of material science and physics due to its extraordinary properties. The green process of plasma treatment of textiles only modifies the surface of the material without altering the bulk properties to increase the uptake of dyes and finishes or to impart unique functionality. Natural coloration in textile materials mostly use substances derived from flowers, roots, bark, etc. Recently, various attempts have been taken to extract biomolecules from various natural wastes such as D. regia stem shell extract, S. foetida fruit shell extract, coconut shell extract, and temple waste flower for coloration and functional finishing of textile materials for the development of sustainable fashion products.

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Index

Note: Page numbers followed by “f” and “t” refer to figures and tables, respectively. A Acetyl acetone method, 44 Acetyl cholinesterase (AChE), 42 AChE. See Acetyl cholinesterase (AChE) Acid dyes, 21 Acid reduction clearing agent (ACD), 21 Acids, 30 Active molecular fragments, 190 Adequate control, 57 58 Air plasma, 93 94 Alkali, 90 91 miscellaneous chemicals and auxiliaries, 90 residual dye, 90 Alkylphenol ethoxylates (APEO), 116, 156 157 Alkylphenols, 22 Allergic dyes, 20 22 azo dyes, 22 basic and acid dyes, 21 direct dyes, 21 disperse dyes, 21 reactive dyes, 22 vat dyes, 21 22 Allergic sensitizers, 30 Allergic textile dermatitis, 66 67 Aluminum, 25 26 1-Amino-2-hydroxy-3trimethylammoniumpropane chloride, 93 Amorphous regions, 82 Aniline, 34 Anthraquinone, 21 22 Antibacterial finishes, in textile and fashion, 183 184 Antimicrobial textiles, 71 APEO. See Alkylphenol ethoxylates (APEO) Aroma finishing, of textile and fashion, 185

Artificial silk, 80 Arylazobenzoyl, 84 Asphyxiants, 28 Atomic power plants, 37 Authorisation, of REACH, 146 147 Authorities, mitigation measures by, 157 158 Auxiliary chemicals, 59 60, 73 74 Awareness, 4 7 Azadirachta indica, 192 Azo dyes, 22, 70 71, 120 Azo-dyestuffs in textiles, 113 Azo-free products, 120 121 B Basic dyes, 21 BAT. See Best available technique (BAT) Benzidine-based dyes metabolize, 157 Best available technique (BAT), 149 BFRs. See Brominated flame retardants (BFRs) Bifunctional reactive dyes, 92 Biocidal product regulation (BPR), 1 3, 149 Biocidal Product Regulation EU 528/2012, 130 Biocide product, 71 in textiles, 61 62 Biotransformation of toxicants, 32 Bis(2-ethylhexyl) phthalate (DEHP), 23 Blood, 33 34 components, 33 34 marrow, 33 Bluesign, 8, 141 Bone marrow, 33 Brand restricted substances list documents, 126 purpose of, 115 scope of, 115

206

Brominated flame retardants (BFRs), 23, 70 71 BS EN 15777:2009 standard, 43 BSMI. See Bureau of Standards, Metrology, and Inspection (BSMI) Bureau of Standards, Metrology, and Inspection (BSMI), 131 Business models supporting information sharing, 16 Butane tetracarboxylic acid, 183 C Cadmium, 24 26 California Proposition 65, 130 Calvin Klein, restricted substances list for, 120 124 azo dyes, 120 banned substances and processes, 124 disperse dyes, 121 other, 121 124 Carbon footprints, 81 82 Carbon nanofibers (CNF), 193 Carcinogenic effects, of textile chemicals, 70 CAS number. See Chemical abstracts service (CAS) number Catechu (Acacia catechu), 181 Cationic liposomes, 92 C2C design. See Cradle-2-Cradle (C2C) design CellO, 85 86 Cellulose, 84, 196 chemical structure of, 82f chemistry of, 82 reactive dye reactions with, 87 Cellulosic fibers, 79 80 chemical processing of, 83 classification, 80f consumption, 80 82 crystallinity of, 82 dyeing of, 83 84, 83f, 90f hydrophilic nature of, 93 94 modification of, 93 reactive dyes. See Reactive dyes, cellulosic fibers Central exposure pathway, 62 63 Central nervous system, 31 32 Characterization factors (CFs), 35, 158 159 Chemical abstracts service (CAS) number, 116, 126

Index

Chemical compliance, 135 136 in textile sector, 138 142 Chemical enforcement, 149 Chemical hazards in textiles, 19, 49 50 and clothing industry, 19 hazard control. See Hazard control hazard management in, 42 hazardous chemicals. See Hazardous textile chemicals human toxicity, 35 37 ecotoxicity, 35 environmental factors, 36 37 equivalence factor, 36t regulation by different countries, 39 40 regulatory aspects, 39 40 routes of exposure, 26 34 factors influencing toxicity, classification of, 34 health effects. See Health effects wet processing, 19 Chemical legislation, on chemical risk assessment, 56 Chemical management, 138, 142 restricted substance list in, 37 39 Chemical management system (CMS), 3, 99 100. See also Chemicals chemical handling procedures, 107 108 disposal system for chemical waste, 108 109 essential elements of, 100 101 implementation, 8 9, 99 100, 109 110 inventory system for, 103, 104t manufacturing restricted substance list, 109 material safety data sheet (MSDS), 102 103 procurement system of, 101 restricted substance list, 109 storage of chemicals, 103 106 incompatible chemicals, 105 labeling chemical containers, 105 106 safety measures of, 103 105 using secondary containment, 105 tackling challenges on, 110 111 transportation of chemicals, 106 107 Chemical oxygen demand, 94 Chemical processing, of cellulosic fibers, 83 Chemical product, 161 162, 168t

Index

Chemical regulations, in India. See India, chemical regulations in Chemical-related hazardous waste, 108 109 Chemical risk assessment/analysis (CRA), 53, 55 58 chemical legislation based on, 56 European Union regulation, 56 57 objective, 55 56 under REACH, 56 57, 56f release of toxic chemicals, 60 65 risk and controlled use, assessment of, 57 58 textiles and garments, chemical substances in, 58 60. See also Textile chemicals Chemicals compatibility chart, 106f purchasing, 101 storage of, 103 106 transportation of, 106 107 Chemical safety program, 49 50 CHEM-IQ tool, 161 162 Chicken feather protein (CFP), 183 Children products, 151 Chitosan, 93, 184 Chlorinated flame retardants, 23 Chlorinated organic carriers, 47, 48t Chlorinated pesticides, 19 20, 42 Chlorinated phenols, 43 44 Chlorinated solvents, 24 Chlorobenzenes, 24 3-Chloro-2-hydroxypropyl trimethyl ammonium chloride(CHTAC), 93 Chlorophenols, 24 Chromium, 24 26, 70 Chrysanthemum cinerariaefolium, 187 Chrysanthemum genus (Asteraceae), 187 Chrysanthemum indicum, 187 Chrysanthemum morifolium, 187 Chrysanthemum oil, 187 Cirrhosis, 32 Classification, Labelling and Packaging (CLP), 56 57 Clean-up enforcement, 149 Clothing, chemicals used in, 59 60 auxiliary chemicals, 59 dermal exposure, 62 63 environmental exposure, 64 65 functional chemicals, 59

207

human exposure, 62 inhalation exposure, 64 nonintentionally added chemical substances, 59 60 oral exposure, 63 64 skin contact of, 70 Clothing dermatitis, 20 Clothing industry, 19 CMS. See Chemical management system (CMS) Coating polymers, 93 Colorfastness, 194 Commercial chemical formulation, 126 Commodity Inspection Mark, 131 Communication, 7, 148 Compliance, 142 requirements, 142 144 zero discharge of hazardous chemicals, 142 144 Compliance monitoring, 150 Consumer Product Safety Commission (CPSC) regulations, 38 Consumer Product Safety Improvement Act (CPSIA), 129, 151, 157 158 Consumer Product Safety Law, 151 Contact allergy, 67 68 Continuous methods, 88, 89f Control measures, 47 49 Conventional effluent treatment, 94, 95t COSMEDE database, 168 Cotton cultivation, pesticides in, 19 20 Cotton fibers, 80 dyed with reactive dyes, 92 93 production of, 81f Covalent bond formation, 86 87, 90 CPSIA. See Consumer Product Safety Improvement Act (CPSIA) CRA. See Chemical risk assessment/analysis (CRA) Cradle-2-Cradle (C2C) design, 141 142 Criminal law, 53 54 Cryogenic homogenization, 42 Crystalline regions, 82 Curcuma longa, 180 181 Cyanuric chloride with cellulose, 84 D DBD plasma treatment, 191 DCT. See Dichlorotriazine (DCT)

208

Delonix regia stem shell, 177 178, 180 Dermal exposure, 62 63 Dermatitis, 30 Dermis, 29 30 Detection limit, 116 “Detox catwalk”, 4, 8 9 Dibutyl phthalate (DBP), 23 1,4 Dichlorobenzene (1,4-DB), 35, 47 Dichlorodifluoromethane (DCFM), 93 94 Dichlorodiphenyltrichloroethane (DDT), 32 Dichlorotriazine (DCT), 84 N,N-Dimethylformamide (DMF), 47, 157 Dimethylglyoxime/dithiooxamide, 47 Direct dyes, 21 Disperse dyes, 21, 67 68, 121 Disposal system for chemical waste, 108 109 DMF. See N,N-Dimethylformamide (DMF) Documentation, 110 111 Dope dye technology, 1 Dose response relationships, 26 27 Dry cleaning, 64 65 Durable water repellent treatment, 157 Dye fiber bond, 87 Dyehouse/fabric mills, 117 118 Dyeing of cellulosics, 83f, 84, 90f of cotton, 84 mordant method of, 84 of textiles, 20 Dyestuff for cellulosic fibers, 79 E ECHA. See European Chemical Agency (ECHA) Eco-friendly flame retardant finishing, 182 183 Eco-friendly textiles, 113 Eco-labels, 115 Ecological aspects, of reactive dyeing alkali, 90 91 electrolyte, 89 Econtrol dyeing process, 92 93 Ecotoxicity, 35 Effluent management, development in, 94 95 Effluent treatment plant (ETP), 105 106, 152 Electrolytes, 87, 89, 91

Index

Electrospun nanofiber, 193 Electrostatic self-assembly, 194 195 Elicitation phase, 66 67 Energy-based sustainability index, 37 Enforcement, of REACH, 147 EN 1811:2011 standard, 46 47 EN12472:2009 standard, 47 Environmental exposure, 61 62, 64 65 Environmental factors, 36 37 Environmental hazard, 72 Environmental Protection Agency (EPA), 148 Epidermis, 29 30 Erythrocytes, 33 34 ETP. See Effluent treatment plant (ETP) EU ecolabels, 142 European Chemical Agency (ECHA), 56 57, 146 European Union regulation, 56 57 Evaluation, of REACH, 146 Exhaustion methods, 88, 91 Exposure assessment, 55 56, 55f Eyes, 30 31 F Face shields, 107 108 Fashion industries. See Textile and fashion industries Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA), 130 Federal laws, 129 Fibers, textile, 54, 64 65 dyeing processes in, 54 Fire retardant textiles, 182 183 Flame retardant textiles, 178, 182 183 Fluorinated polymeric water, 70 71 Foam dyeing technique, 93 94 Food and Consumer Goods Act in 1986, 113 Footwear manufacturing, 119 120 Formaldehyde, 44 45, 167 resin, 67 69, 73 74 Fragrance compounds, 185 Free/hydrolyzed formaldehyde, 44 Fully continuous methods, 88 89 Functional chemicals, 59, 72 74 G Garments accessories, 62

Index

chemical substances in, 58 60 laundry, 118 119 production, 1 Gas chromatography mass spectrometry (GC-MS), 43 GB 18401-2010, 131 GCC. See General Certificate of Conformity (GCC) General Certificate of Conformity (GCC), 129 130 General product safety directive (GPSD), 149 150 Generic Chemical Products Inventory, 167 169 Genotoxicity, 70 GHS. See Globally harmonized system (GHS) Global fiber consumption, 81f Globally harmonized system (GHS), 138 of classification and labeling of chemicals, 148 classification criteria, 102, 105 106 components of, 105 106 symbols for hazardous chemicals, 139t Global Organic Textile Standard (GOTS), 115, 140 141 Gloves, 107 108 GOTS. See Global Organic Textile Standard (GOTS) GPSD. See General product safety directive (GPSD) Graphene, in textile, 187 188, 196 Gray fabrics, 54 Green chemistry in application of antibacterial finishes, 179 180, 183 184 of aroma finishing, 185 of graphene, 187 188 of green flame retardants, 182 183 of green reducing agent, 192 193 mosquito repellency finish, 186 187 of nanofibers and nanoparticles, 193 195 of natural dyeing, 180 182 of plasma technology, 189 192 for ultraviolet protection, 184 185 concept of, 180 future and challenges of, 195 197

209

in wet processing of textile, 179f Green coconut shell, 177 Green flame retardants, in textile and fashion, 182 183 Greenhouse gases (GHGs), 7 Green nanofiber, 193 Green synthesis, 193 195 Groundwater, 19 20, 37 H Hair follicles, 29 30 Harmful chemicals in textiles, 129 131 Hazard control chemical, 49 50 and management, 42 50 chlorinated organic carriers, 47, 48t chlorinated phenols, 43 44 extractable heavy metals, 45 46 formaldehyde, 44 45 nickel, 46 47 phthalates, 42 43 residual pesticides, 42 in textile industry, 47 49 through regulatory norms, 41 42 Hazardous Chemical Amendment Rules, 1989, 151 152 Hazardous textile chemicals, 4, 19 26, 53 54, 65 71, 135 137, 137t allergic dyes. See Allergic dyes assessment of potential risks of, 71 73 carcinogenic effects of, 70 categorization, 138 dyeing and printing, 20 finishing resins, 68 69 GHS of classification and labeling of, 148 symbols for, 139t heavy metals, 24 26 integrated pollution prevention and control, 149 irritation and allergy caused by, 66 68 pesticides in cotton cultivation, 19 20 prioritization of chemicals based on hazardous properties, 72 based on probability of release from textiles, 73 based on probable release from textiles, 72

210

Hazardous textile chemicals (Continued) based on relevance for textile endproducts, 72 73 based on relevance of textile products, 72 REACH. See REACH regulated chemicals, 22 24 alkylphenols, 22 brominated and chlorinated flame retardants, 23 chlorinated solvents, 24 chlorobenzenes, 24 chlorophenols, 24 organotin compounds, 23 perfluorinated chemicals, 23 24 phthalates, 23 short-chain chlorinated paraffins, 24 regulations and laws, 138 regulations promoted for, 145 150 reproductive toxicity, 70 71 respiratory allergy caused by, 69 sensitizing dyes, 20 22 textile dyes, 68 textile-relevant, 1 3 Toxic Substance Control Act, 148 waste, chemical, and clean-up enforcement, 149 Hazards, 55f, 99 characterization, 55 56 chemicals and, 110 111 management, 42 50. See also Hazard control and risk, 55 by textile and clothing, 61 62 HCB. See Hexachlorobenzene (HCB) Health effects, 27 34 blood system, 33 34 central nervous system, 31 32 eyes, 30 31 kidneys, 32 33 liver injury, 32 respiratory tract, 28 29 skin, 29 30 Heavy metals, 24 26 extractable, 45 46 Hemoglobin, 34 Hepatotoxins, 32 Heterocyclic carbon of RG, 85 86 Hexachlorobenzene (HCB), 24, 47

Index

Hexafluoroethane, 192 Hexamethyldisiloxane-derived plasma polymers, 191 192 HPC. See Hydroxypropyl cellulose (HPC) HTP. See Human toxicity potential (HTP) Human exposure, 62 Human toxicity, 35 37 ecotoxicity, 35 environmental factors, 36 37 Human toxicity potential (HTP), 35 Hydrogen peroxide, 132 Hydrolysis of reactive dye, 86 Hydrophobic textiles, 191 192 Hydroxyl (OH) functional groups, 82 Hydroxyl groups, 89 90 Hydroxypropyl cellulose (HPC), 193 I Ideal circular economy, 141 142 IED. See Industrial emission directives (IED) Immense water, 189 Incompatible chemicals, 105 India, chemical regulations in, 151 152 Hazardous Chemical Amendment Rules, 1989, 151 152 Ozone Depleting Substance (R&C) Rules, 2000, 152 Indigo, 181 Indigofera, 181 Indigoids, 21 22 Indirect oral exposure, 63 64 Industrial emission directives (IED), 149 Indus Valley Civilization, 80 Information sharing systems, 16 Ingestion, 26 27 Ingredient chemicals, 60 61 Inhalation, 26 Injection, 27 Inorganic salts, 92 Intact skin, 29 30 Integrated pollution prevention and control (IPPC), 149 best available technique, 149 biocidal product regulation, 149 general product safety directive, 149 150 industrial emission directives, 149 Inventory system, for chemicals, 103

Index

IPPC. See Integrated pollution prevention and control (IPPC) Irritant textile dermatitis, 67 ISO 14389 standard, 43 K KEMI. See Swedish Chemicals Agency (KEMI) Kermes ilicis, 180 Kidneys, 32 33 Knowledge and awareness, 5 7 L Labeling chemical containers, 105 106 Laccifer lacca, 180 181 Lacrimators, 31 Laundering chemicals, 64 65 Launderometer, 60 LCI. See Life cycle inventory (LCI) LCIA. See Life cycle impact assessment (LCIA) LC-IDMS. See Liquid chromatography-mass spectrometric detection using isotope dilution (LC-IDMS) Lead, 24 26 Learning tools, 11f, 15 development, 9 14 levels and themes for, 11f substitution modules of, 14 Leather processing, 119 Leggings allergy, 21 Legislations, 53 54, 56, 115, 157 158 REACH, 148 systems for, 129 Leukocytes, 33 34 Life cycle assessment (LCA), 155, 158 159, 160f calculating toxic impacts in, 162 163 future trends, 170 171 generalized model for, 156f Mistra Future Fashion methodology, 165 169 in textile chemicals, 158 160 challenges in, 160 164 environmental impacts in reality, 159 160 holistic perspective, 158 life cycle inventory and, 158 159 toxicity modeling in, 163 164

211

Life cycle impact assessment (LCIA), 158 159, 163, 170 data gaps in, 164 165 Life cycle inventory with, 168 169 Life cycle inventory (LCI), 158 159 Linen fabric, 181, 185 Lingua franca, 5 Liquid chromatography-mass spectrometric detection using isotope dilution (LC-IDMS), 44 Liver injury, 32 Localized surface plasmon resonance (LSPR), 194 Long-term effects, 27 28, 37 Low salt reactive dyes, 92 M Machineries development, 92 93 MAHs. See Major accident hazards (MAHs) Main pollution, in textile wastewater, 189, 197 198 Major accident hazards (MAHs), 152 Management, hazard control and, 42 50 chlorinated organic carriers, 47, 48t chlorinated phenols, 43 44 extractable heavy metals, 45 46 formaldehyde, 44 45 nickel, 46 47 phthalates, 42 43, 43t residual pesticides, 42 in textile industry, 47 49 Manufacturing restricted substances list (MRSL), 3 4, 101, 109, 124 documents, 126 structure of, 127 129 terms and definitions used in, 126 implementation of, 125 and restricted substances list, 125 role of, to ensure RSL compliance of a finished product, 126 scope of, 125 textile mill, practical challenges in, 132 Material safety data sheet (MSDS), 39, 50, 102 103, 107 108 Mercerization, 83 Mercury, 24 26 Metal pollution, 25 Methemoglobinemia, 34 Methodical approach, 100

212

Methyl mercury, 31 32 Microencapsulation, 185 Microplastics, 170 171 Microwave irradiation technique, 93 94 Miscibility of solvents, 93 94 Mistra Future Fashion methodology, 165 169 Model performance evaluation, 35 Modularized tool, 10 Monochloro triazine groups, 92 Mosquito repellency finish, 186 187 Motor Vehicle Act 1988, 151 MSDS. See Material safety data sheet (MSDS) Mutagenicity, 70 N “Name and shame” approach, 4 Nanofibers, for textile finishing, 193 195 Nanoparticles, for textile finishing, 193 195 Naphthol color (azoic), 83 Nasopharyngeal region, 28 Native crystalline cellulose, 82 Natural antibacterial compounds, 193 194 Natural cellulosic fibers, 79 80 Natural dyeing process, 180 182 mordants used for, 180 181, 182t Natural fabrics, 20 Natural fibers, 80 82 Natural resources, 177 of aroma, 186t Neem-chitosan nanocomposite, 184 Nickel, 25 26, 46 47 Nitrogenous, 19 20 N-methylene morpholine oxide (NMMO), 80 NMMO. See N-methylene morpholine oxide (NMMO) Nomex, 192 Nongovernmental organizations, 157 158 Nonintentionally added chemicals, 59 60, 73 74 Nonpolymerizing gases, 190 Nonylphenol ethoxylates (NPEO), 9 11, 22 Nonylphenols (NPs), 9, 22 Not detected (ND), 116 NOVACRON LS dyes, 92 NPEO. See Nonylphenol ethoxylates (NPEO) Nucleophilic

Index

addition reaction, 86 substitution reaction, 85 86 Nutrient cycles, 141 O Occupational exposure, 67 69 Octylphenols, 22 Oeko-Tex Standard 100, 4, 8, 109, 140 Oral exposure, 63 64 Organic cotton, 181 Organic electrolyte, use of, 92 Organic peroxides, 105 Organic salts, 92 Organic solvents, 31 Organomercury compounds, 31 32 Organophosphorus compounds, 32 Organotin compounds, 23 Outdoor industry, 8 Oxygen depleting substances (ODS), 152 Oxygen plasma treatment, 191 Oxygen transport, 34 Ozone Depleting Substance (R&C) Rules, 2000, 152 P Pad-batch dyeing process, 93 94 Pad-batch method, 88 89 Parts per billion (ppb), 117 Parts per million (ppm), 117 PBDEs. See Polybrominated diphenyl ethers (PBDEs) PDCA. See Plan-do-check-act (PDCA) model PD CR 12471:2002 standard, 47 Pentachlorobenzene, 24 Pentachlorophenol (PCP), 43 44 Pentane-2,4-dione method, 44 Perfluorinated chemicals (PFCs), 23 24 Perfluorooctane sulfonate (PFOS), 23 24 Persistent organic pollutants (POP), 1 3, 23 24, 157 Personal protective equipment (PPE), 26, 103 105 Pesticides, 42, 113 in cotton cultivation, 19 20 PFAS. See Polyfluoroalkyl substances (PFAS) PFCs. See Perfluorinated chemicals (PFCs) PFOS. See Perfluorooctane sulfonate (PFOS)

Index

Phosphoric fertilizers, 19 20 Photosensitizers, 30 Photosynthesis, 82 Phthalates, 23, 42 43 Physical-chemical equilibrium processes, 20 Plan-do-check-act (PDCA) model, 100 101, 100f Plasma polymerization, 189, 191 192 technology, 178 in textile and fashion, 189 192, 189t, 195 196 Polyacrylic acid, 191 Polyacrylic polyamides, 47 Poly(ethylene glycol)-based reverse micelle system, 93 94 Polybrominated diphenyl ethers (PBDEs), 23 Polychlorinated biphenyls (PCBs), 148 Polyester acetates, 47 Polyester fibers, production of, 81f Polyfluoroalkyl substances (PFAS), 157 Polyfunctional reactive dyes, 92 Polymer surface modifications, 190 Polysaccharide, 82 Polyvenyle chloride (PVC), 61 62 POP. See Persistent organic pollutants (POP) Potential hazards, 99 PPE. See Personal protective equipment (PPE) Precise water, 95 Primary irritants, 30 Printing of textiles, 20, 119 Priority hazardous substance, 23 24 Procion, 84 Procurement system, of chemical, 101 Profound chemical management, 138 Pulmonary acinus, 28 29 Purchasing policy, 101 Q Quaternary ammonium compounds, 93, 183 184 R RAPEX, 149 150 REACH. See Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) Reactive dyes, cellulosic fibers, 22, 79, 83

213

application techniques of, 88 89 classification, 85, 85f common structure of, 84 continuous methods of, 89f current technologies for improvement, 92 93 bifunctional and polyfunctional, 92 low salt reactive dyes, 92 machineries development, 92 93 use of organic electrolyte, 92 ecological aspects of, 89 91 alkali, 90 91 electrolyte, 89 factors affecting, 86 88 reactivity, 86 87 substantivity, 87 88 fixation percentage of, 90 history of, 84 hydrolysis of, 86 mechanism, 85 86 nucleophilic addition reaction, 86 nucleophilic substitution reaction, 85 86 unconventional, 93 95 effluent management, development in, 94 95 Reactivity, 86 87 Recycling system, 64 65 Red Cibacron CR (Reactive Red 238), 22 Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), 56 57, 56f, 101, 129 130, 138 140, 145, 152 authorisation, 146 147 enforcement, 147 evaluation, 146 function, 146 147 legislation, 148, 156 157 registration, 146 database, 164 165 regulation, 147 148 consolidated version of, 147 EC No. 1907/2006, 145 initial text, 147 restriction, 147 Registration, of REACH, 146 Regulation and labeling schemes, 4

214

Regulation (EC) No 1907/2006, 145, 147, 147, 147 Regulatory norms, hazard control through, 41 42 Regulatory standards, 138 140 Relative ability, 26 Remazol reactive dye, 190 Reporting limit, 116 Reproductive toxicity of textile chemicals, 70 71, 73 74 Residual dye, 90 Residual pesticides, 42 Resins, textile finishing, 68 69 Respiratory allergy, 69 Respiratory tract, 28 29 Restricted substances list (RSL), 3 4, 11 12, 101, 109, 113 114 for Calvin Klein, 120 124 azo dyes, 120 banned substances and processes, 124 disperse dyes, 121 other, 121 124 in chemical management, 37 39, 40t methodology, 38 39 compliance of finished product, 114 115 criteria for substance in, 114 115 document basic terms in, 116 117 contents of, 115 116 importance of, 114 major risk areas for, 117 120 manufacturing restricted substances list and, 125 scope of, 125 practical challenges in, 132 Restriction, of REACH, 147 Retail workers, 64 Reverse osmosis (RO) process, 91 Right purchase practices, 127 128 Risk, defined, 55, 55f Routes of entry, 26, 34 RSL. See Restricted substances list (RSL) S SAAT. See Substitution and Alternatives Assessment Toolbox (SAAT) SAC. See Sustainable Apparel Coalition (SAC) Safe handling of chemicals, 107 108

Index

Safety data sheet (SDS), 49 50, 102 Safety Quality Mark Act, 131 SAICM. See Strategic Approach to International Chemicals Management (SAICM) Salt requirement, 89, 90f, 91 Salt-free reactive dyeing, 93 SCCPs. See Short-chain chlorinated paraffins (SCCPs) Secondary containment, 105 Selenium, 25 26 Self-Regulatory Safety Confirmation Act, 131 Sensitization in textile dyes, 20 22 Sensitization phase immune system, 66 67 Short-chain chlorinated paraffins (SCCPs), 24 Short-term effects, 27 28 Silver nanoparticles, 70 71, 192 194 Silver zinc zeolite, 61 62 Skin, 29 30. See also Dermal exposure irritants, 30 Sodium carbonate, 86, 90 Sodium chloride, 87, 92 Sodium hydrosulfite, 132 Sodium hydroxide, 86 Sodium nitrite, 34 Sodium sulfate, 92 Solvent-based dyeing process, 93 94 Standard model, for risk assessment, 57 58 Staphylococcus aureus bacteria, 184 State law, 130 Sterculia foetida fruit shell, 177 178, 180 Stockings dye allergy, 21 Storage of chemicals, 103 106 incompatible chemicals, 105 safety measures of, 103 105 Strategic Approach to International Chemicals Management (SAICM), 157 158 Substance of very high concern (SVHC), 3 4, 146 147 Substantivity, 87 88 Substitution and Alternatives Assessment Toolbox (SAAT), 8 Sulfatoethyl sulfone groups, 92 Supercritical carbon dioxide, 1 Supercritical fluid based dyeing process, 93 94

Index

Superhydrophobic finishing, 192, 196 Supplier dominated companies, 6 7 Supply chain, lack of knowledge in, 5 Surface oxidation of wool fiber, 190 Sustainability, principles of, 141 Sustainable Apparel Coalition (SAC), 8 Sustainable development, 79 SVHC. See Substance of very high concern (SVHC) Swedish Chemicals Agency (KEMI), 5, 137 hazardous chemicals based on, 137t Synthetic chemicals, in textile and fashion, 53 54 Synthetic fabrics, 20 Synthetic fibers, 47, 79 81 Synthetic textiles, 61 62, 67 68 Systemic effects, 27 28 T Tackling challenges, on chemical management system, 110 111 TCE. See Trichloroethane (TCE) TEP. See Toxic equivalency potential (TEP) Testing methods for mosquito repellent, 186 187 Tetrachlorophenol (TeCP), 43 Textile and fashion industries compliance monitoring, 150 compliance requirements, 142 144 Consumer Product Safety Law, 151 green chemistry in. See Green chemistry hazardous chemicals. See Hazardous textile chemicals life cycle of chemicals used in, 145 Textile chemicals. See also Textile products and clothing. See Clothing, chemicals used in effects on humans and environment, 156 157 fibers, 54, 64 65, 72 finishing resins, 68 69 hazardous. See Hazardous textile chemicals inflows and outflows, 161 162, 162f input recipe, 165 167 and large emissions, 155 156 life cycle assessment in challenges in, 160 164

215

environmental impacts in reality, 159 160 holistic perspective, 158 life cycle inventory and, 158 159 pollution of, 158 process flow chart, 54f substances in, 58 60 nature and effect of, 60 toxicity data availability for, 163 wet processing, 65 71, 66f Textile dermatitis, 66 68 Textile dyes, 68 Textile end-products, 72 73 Textile fibers, 180 Textile industry, 23, 50, 54, 69, 99 100, 135 136 cancer risk for workers in, 70, 73 74 chemicals used in, 136 137, 136t compliance of chemicals in, 142 hazard management in, 47 49 with laws and regulations, 39 occupational exposure in, 69 70 pollution, 158 Textile products hazardous chemical in, 65 71 probability of release, 72 relevance of, 72 Textile-relevant hazardous chemicals, 1 3 Textiles available tools, 7 8 chemical hazards in. See Chemical hazards in textiles chemical management system, 3. See also Chemical management system (CMS) coloration of, 194 global legislations on harmful chemicals in, 129 131 hazardous chemicals in, 137 knowledge and awareness, 5 7 machinery for cotton dyeing, 92 93 manufacturing restricted substance list, 3 4 materials, 41, 184 185 mill, RSL and MRSL in, 132 practical feasibilities and challenges, 5 regulation and labeling schemes, 4 restricted substance list, 3 4 substitution process, 9 10, 10f

216

Textiles (Continued) tool development, 9 14 Textile sector, 135 136 chemical compliance in, 135 136, 138 142 regulatory standards, 138 140 voluntary standards. See Voluntary standards Textile supply chain, 1 3, 114, 127, 155 chemical management system in, 8 9 chemicals use and possible issues in, 2f stages in, 9 10 Textile value chain, 1 and information exchange routes, 6f Textile wet processing, 178 179, 197f Titanium dioxide, 70 Total dissolved solids (TDS), 91, 94 Toxic equivalency potential (TEP), 35 Toxic insecticides, 19 20 Toxicity, 26, 45, 135 136 acute, 61 62 assessments of, 35 data availability, 163 modeling in life cycle assessment, 163 164 Toxic leachates, 61 62 Toxicological studies, 115 Toxic Substance Control Act (TSCA), 1 3, 148 Trace residues (TR), 116 Tracheobronchial region, 28 Transformation products, 162, 167 168 Transportation of chemicals, 106 107 Tribolium castanum, 187 Tributyltin (TBT), 23 Trichloroethane (TCE), 24 Trichloroethylene, 157 Trichloro pyrimidine dyes, 86 Trims and accessories, 120 TSCA. See Toxic Substance Control Act (TSCA) U ULLR dyeing. See Ultralow liquor ratio (ULLR) dyeing Ultralow liquor ratio (ULLR) dyeing, 92 93 Ultrasonic energy, 93 94 Ultraviolet protection factor (UPF), 179 180

Index

in textile and fashion, 184 185 Unconventional reactive dyeing, 93 95 effluent management, development in, 94 95 Unintended ingestion of dust, 62 Urea, 90 USEtox model, 162 165 US Occupational Safety and Health Administration (OSHA), 102 V Vapor absorption method, 45 Vat dyes, 21 22 Ventilation system, 103 105 Vinyl sulfone dyes, 88 89 Vinyl sulfone system, 86 Violet Remazol 5R (Reactive Violet 5), 22 Volatile chemicals, 60, 64 Voluntary standards, 140 142 Bluesign, 141 Cradle-2-Cradle design, 141 142 EU ecolabels, 142 Global Organic Textile Standard, 140 141 label types of, 141 product categories, 141 Oeko-Tex STANDARD 100, 140 W Washington Children’s Safe Product Act (WCSPA), 130 Waste enforcement, 149 Waste reduction algorithm, 36 Water, 90 91 ecological problem due to, 91 requirement, 178 179, 179f, 189 Water solubility of dyes, 87 88 Water-soluble chemicals, 60, 63 64 Water-soluble direct dyeing, 21 WCSPA. See Washington Children’s Safe Product Act (WCSPA) Web-based learning tool, 9 Wet processing, textile, 65 71, 66f, 92 93, 178 179, 197f Woad (Isatis tinctoria), 181 Woolen fabrics, 181 Worsted fabrics, 181

Index

Z ZDHC. See Zero discharge of hazardous chemicals (ZDHC) Zero discharge of hazardous chemicals (ZDHC), 101, 109, 142 144 focus areas of, 144f input focus area, 143

217

Manufacturing Restriction Substance List, 142 144 output focus area, 143 process focus area, 143 Zero liquid discharge (ZLD), 91, 157 158 effluent treatment process, 94 95, 95t Zinc, 25 26 ZLD. See Zero liquid discharge (ZLD)