Modern Extraction Techniques 926 ACS SYMPOSIUM SERIES Modern Extraction Techniques Food and Agricultural Samples Charlotta Turner, Editor Uppsala University Sponsored by the ACS Division of Agricultural and Food Chemistry • American Chemical Society, Washington, DC Library ofCongressCataloging-in-PublicatioD Data Modem extraction techniques: food and agricultural samples/ CharlottaTurner, editor; sponsoredbythe ACS Division ofAgricultural and Food Chemistry. p. cm.-(ACS symposiumseries; 926) Includesbibliographicalreferences and index. ISBN-13: 978-0-8412-3940-1 (alk. paper) 1. Extraction (Chemistry}-Congresses. I. Turner, Charlotta, 1970-II. American ChemicalSociety. DivisionofAgricultural and FoodChemistry. III. Series. TP156.E8M63 2006 660'2842-dc22 2005053077 The paper used in this publication meets the minimum requirements of American National Standard for Information Sciences-Permanence ofPaper for Printed Library Materials, ANSI Z39.48-1984. 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ACS Books Department Preface This book is based on the symposium entitled "Modern Extraction Techniques for Food and Agricultural Samples," which was arranged by the Division of Agricultural and Food Chemistry during the American Chemical Society's 227th national meeting in Anaheim, California, held March 28-April2, 2004. One of the biggest challenges facing the chemical and pharmaceutical industry today is the need to replace current environmentally unsustainable and often polluting processes with cleaner ones. The transition to these new "green" processes will be easier ifthese technologies are more efficient and less costly than the current ones. In their book, Green Chemistry: Theory and Practice, Anastas and Warner (Oxford University Press, 1998) describe the 12 principles of green chemistry thus: 1. It is better to prevent waste than to treat or clean up waste after it has been created. 2. Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product. 3. Wherever practicable, synthetic methods should be designed to use and generate substances that possess little or no toxicity to human health and the environment. 4. Chemical products should be designed to effect their desired function while minimizing their toxicity. 5. The use ofauxiliary substances (e.g., solvents, separation agents, etc.) should be made unnecessary wherever possible and innocuous when used. 6. Energy requirements ofchemical processes should be recognized for their environmental and economic impacts and should be minimized. Ifpossible, synthetic methods should be conducted at ambient temperature and pressure. ix 7. A raw material or feedstock should be renewable rather than depleting whenever technically and economically practicable. 8. Unnecessary derivatization (use of blocking groups, protection/ deprotection, temporary modification of physical/chemical processes) should be minimized or avoided if possible, because such steps require additional reagents and can generate waste. 9. Catalytic reagents (as selective as possible) are superior to stoichiometric reagents. 10. Chemical products should be designed so that at the end oftheir function they break down into innocuous degradation products and do not persist in the environment. 11. Analytical methodologies need to be further developed to allow for real-time, in-process monitoring and control prior to the formation ofhazardous substances. 12. Substances and the form of a substance used in a chemical process should be chosen to minimize the potential for chemical accidents, including releases, explosions, and fires. Although these principles are mainly for chemical synthesis applications, they can also be applied to other processes, such as extraction. The extraction techniques described in this book fulfill many of Anastas and Warner's principles. For example, the use of supercritical carbon dioxide (SC-C0 as the sole extraction solvent results in a 2) nonpolluting process (prevention of waste and safer solvents and auxiliaries). Other beneficial properties of supercritical CO include fast 2 diffusivity and nearly zero surface tension, which lead to extremely efficient extractions. In Chapters 2-4, applications of SC-C0 as an 2 extraction solvent are described. Ethanol and water are also environmentally friendly solvents that can be used as extraction media in many applications (see Chapters 5-7). Pressurized hot water ("J100-200 °C) in particular is a safe and nonpolluting solvent that has a similar dielectric constant to polar organic solvents, such as ethanol or acetone. Hence, pressurized hot water is a viable green alternative to many current extraction processes that use toxic organic solvents. Similarly, pressurized hot ethanol is an excellent solvent for the extraction of most medium polar to nonpolar organic molecules. Some of the techniques, such as membrane-assisted solvent extraction, described in Chapter 10, use organic solvents but in much smaller amounts compared to classical extraction techniques. Other techniques, for instance solid-phase microextraction and stir-bar sorptive extraction, described in Chapter 11, use no solvents. x Chapters 2-5 and 7 describe an important aspect ofgreen chemistry: the use ofplants and biomass waste as feedstock for extraction ofvarious high-value compounds. Hence, instead of chemically synthesizing pharmaceutical drugs, food-grade antioxidants, or other high-value compounds of industrial and consumer interest, these compounds are extracted from renewable natural sources or from industrial wastes or byproducts using the green solvents and processes described in this book. This rather novel approach fulfills most of the green chemistry principles, including prevention ofwaste, atom economy, less hazardous chemical syntheses, use of renewable feedstocks, and inherently safer chemistry for accident prevention. More new extraction plants are being built around the world based on these ecologically sustainable processes. As the applications described in this book demonstrate, these modem extraction techniques are not only better for the environment but are also faster, easier to automate, more sensitive, more selective, and more robust than classical organic solvent-based extraction techniques. These qualities are demonstrated in Chapter 8, regarding online coupling of extraction and analysis techniques, and in Chapter 9, on extraction methodologies with integrated cleanup steps. The first chapter gives a short description ofeach ofthe techniques described in the book. This section is mainly intended for people who are new to the field. Those already familiar with the various extraction techniques can go straightto the second chapter. I would like to acknowledge all the contributing authors. They have put in a lot of time and effort, which has helped to make this book an excellent compilation ofdifferent areas ofexpertise. I am also grateful to the numerous reviewers, who also helped to improve the quality of the contributions. I would like to thank the American Chemical Society for publishing this book. I hope you will enjoy reading the book and that you will find the information useful for your own activities. Charlotta Turner Department ofAnalytical Chemistry Uppsala University P.O. Box 599 SE-751 24 Uppsala, Sweden xi Modern Extraction Techniques
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