Chemical Degradation Methods for Wastes and Pollutants Environmental and Industrial Applications edited by Matthew A. Tarr University of New Orleans New Orleans, Louisiana, U.S.A. . . . . . - - . MARCEL DEKKER, INC. DEKKER NEW YORK RASEL Although great care has been taken to provide accurate and current information, neither the author(s) nor the publisher, nor anyone else associated with this publica- tion, shall be liable for any loss, damage, or liability directly or indirectly caused or alleged to be caused by this book. The material contained herein is not intended to provide specific advice or recommendations for any specific situation. Trademark notice: Product or corporate names may be trademarks or registered trademarks and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress. ISBN: 0-8247-4307-5 This book is printed on acid-free paper. Headquarters Marcel Dekker, Inc., 270 Madison Avenue, New York, NY 10016, U.S.A. tel: 212-696-9000; fax: 212-685-4540 Distribution and Customer Service Marcel Dekker, Inc., Cimarron Road, Monticello, New York 12701, U.S.A. tel: 800-228-1160; fax: 845-796-1772 Eastern Hemisphere Distribution Marcel Dekker AG, Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-260-6300; fax: 41-61-260-6333 World Wide Web http://www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities. For more information, write to Special Sales/Professional Marketing at the headquarters address above. Copyright nnnn 2003 by Marcel Dekker, Inc. All Rights Reserved. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit): 10987654321 PRINTED IN THE UNITED STATES OF AMERICA TM Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved. Environmental Science and Pollution Control Series I. Toxic Metal Chemistry in Marine Environments, Muhammad Sadiq 2. Handbook of Polymer Degradation, edited by S. Halim Hamid, Mohamed B. Amin, and Ali G. Maadhah 3. Unit Processes in Drinking Water Treatment, Wily J. Masschelein 4. Groundwater Contamination and Analysis at Hazardous Waste Sites, edited by Suzanne Lesage and Richard E. Jackson 5. Plastics Waste Management: Disposal, Recycling, and Reuse, edited by Nabil Mustafa 6. Hazardous Waste Site Soil Remediation: Theory and Application of Innovative Technologies, edited by David J. Wilson and Ann N. Clarke 7. Process Engineering for Pollution Control and Waste Minimization, edited by Donald L. Wise and Debra J. Trantolo 8. Remediation of Hazardous Waste Contaminated Soils, edited by Donald L. Wise and Debra J. Trantolo 9. Water Contamination and Health: Integration of Exposure Assess- ment, Toxicology, and Risk Assessment, edited by fihoda G. M. Wang 10. Pollution Control in Fertilizer Production, edited by Charles A. Hodge and Neculai N. Popovici 1 1. Groundwater Contamination and Control, edited by Uri Zoller 12. Toxic Properties of Pesticides, Nicholas P. Cheremisinoff and John A. King 13. Combustion and Incineration Processes: Applications in Environ- mental Engineering, Second Edition, Revised and Expanded, Walter R. Niessen 14. Hazardous Chemicals in the Polymer Industry, Nicholas P. Chere- misinoff 15. Handbook of Highly Toxic Materials Handling and Management, edited by Stanley S. Grossel and Daniel A. Crowl 16. Separation Processes in Waste Minimization, Robert B. Long 17. Handbook of Pollution and Hazardous Materials Compliance: A Sourcebook for Environmental Managers, Nicholas P. Cheremisinoff and Madelyn Graffia 1 8. Biosolids Treatment and Management: Processes for Beneficial Use, edited by Mark J. Girovich TM Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved. 19. Biological Wastewater Treatment: Second Edition, Revised and Expanded, C. P. Leslie Grady, Jr., Glen T. Daigger, and Henry C:. Lim 20. Separation Methods for Waste and Environmental Applications,, Jack S. Watson 21. Handbook of Polymer Degradation: Second Edition, Revised and Expanded, S. Halim Hamid 22. Bioremediation of Contaminated Soils, edited by Donald L. Wise, Debra J. Trantolo, Edward J. Cichon, Hilary 1. Inyang, and Ulrich Stottmeister 23. Remediation Engineering of Contaminated Soils, edited by Donald L. Wise, Debra J. Trantolo, Edward J. Cichon, Hilary 1. Inyang, and Ulrich Stottmeister 24. Handbook of Pollution Prevention Practices, Nicholas P. Cheremisinoff 25. Combustion and Incineration Processes: Third Edition, Revised and Expanded, Walter R. Niessen 26. Chemical Degradation Methods for Wastes and Pollutants: Environmental and Industrial Applications, edited by Matthew A. ‘Tarr Addition a 1 Volumes in Preparation TM Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved. TM Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved. Preface Human activities have a large and important impact on the environment. Naturally occurring elements or compounds are often concentrated and redistributed in the environment through industrial processes, power pro- duction, and consumer activity. For example, lead, which is found in naturally occurring mineral deposits, has become a major pollutant through its use in batteries, paints, and gasoline additives. In addition, the production of non-natural or anthropogenic substances, such as halogenated solvents, can also result in the eventual release of often toxic and biorecalcitrant substances into the environment. Wide-scale redistribution of pollutants by humans dates at as far back as the ancient Greek and Roman civilizations (2000–2500 years ago), during which time extensive smelting activities resulted in significant atmospheric pollution by heavy metals such as lead. In fact, heavy-metal contamination of Arctic and Antarctic ice has revealed evidence of global pollution from smelting and other human activities since these ancient times. Most certainly the people of ancient Greek and Roman times were not aware of the extent of their pollution. In fact, only in the late twentieth century did widespread awareness and understanding of the degree of anthropogenic pollution begin to develop. Unfortunately, large releases of contaminants into the environment transpired without either knowledge of or concern for the consequences. Once contaminants have been introduced into the environ- ment, subsequent clean-up is extremely difficult, time consuming, and costly. Due to the existence of many contaminated sites, significant research and development efforts have been expended to develop effective means of remediating these sites. These methods must be both economically feasible and environmentally sound. For some sites, these chall enges have been successfully met, while other sites remain contaminated because of lack of acceptable (economically and/or environmentally) technologies or because the sites pose a low risk. TM Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved. While cleaning up previous contamination is a high priority, developing new technologies to prevent future contamination is equally important, if not more so. Without environmentally acceptable industrial processes, power production, and consumer activity, the Earth’s environment will continue to be threatened. Development of inherent ly clean technologies as well as implementation of effective wast e stream treatment are viable routes to preventing future environmental contamination. Chemical Degradation Methods for Wastes and Pollutants focuses on chemical methods of destroying pollutants. Chemical methods can be advan- tageous over biological methods because they are often faster, can treat highly contaminated systems, and may be less sensitive to ambient conditions. In contrast, bacteria can be killed by contaminants or solvents and lose viability outside relatively narrow pH and temperature ranges. However, chemical methods are often more costly and labor-intensive than biodegra dation technologies. Despite their limitations, both biological and chemical tech- nologies are valuable tools that can be used successfully under appropriate conditions. Furthermore, combinations of biological and chemical treatment methods can often provide advantages over the individual systems. The book covers several chemical technologies for remediation or waste stream treatment of predominantly organic contaminants. Although not every chemical technology has been included, ten common or potentially useful methods are covered. Each chapter presents the fundamentals behind each technology and covers selected applications and practical issues relevant to adaptation of the technique to real treatment systems. Continued research into both fundamentals and applications of chem- ical treatment technologies will hopefully provide solutions to many current pollution treatment problems, both for waste streams and for contaminated sites. Only through cooperation among scientists, engineers, industry, gov- ernment, and consumers can we maintain a healthy and productive environ- ment for the future. Finally, I would like to thank those who served as reviewers for each chapter. Matthew A. Tarr Prefaceiv TM Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved. Contents Preface Contributors 1. Ozone–UV Radiation–Hydrogen Peroxide Oxidation Technologies Fernando J. Beltra ´ n 2. Photocatalytic Degradation of Pollutants in Water and Air: Basic Concepts and Applications Pierre Pichat 3. Supercritical Water Oxidation Technology Indira Jayaweera 4. Fenton and Modified Fenton M ethods for Pollutant Degradation Matthew A. Tarr 5. Sonochemical Degradation of Pollutants Hugo Destaillats, Michael R. Hoffmann, and Henry C. Wallace 6. Electrochemical Methods for Degradation of Organic Pollutants in Aqueous Media Enric Brillas, Pere-Lluı ´ s Cabot, and Juan Casado 7. The Electron Beam Process for the Radiolytic Degradation of Pollutants Bruce J. Mincher and William J. Cooper TM Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved. 8. Solvated Electron Reduct ions: A Versatile Alternative for Waste Remediation Gerry D. Getman and Charles U. Pittman, Jr. 9. Permeable Reactive Barriers of Iron and Other Zero- Valent Metals Paul G. Tratnyek, Michelle M. Scherer, Timothy L. Johnson, and Leah J. Matheson 10. Enzymatic Treatment of Waters and Wastes James A. Nicell Contentsvi TM Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved. Contributors Fernando J. Beltra ´ n Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, Badajoz, Spain Enric Brillas Laboratori de Ciencia i Tecnologia Electroquimica de Materi- als, Departament de Quimica Fisica, Universitat de Barcelona, Barcelona, Spain Pere-Lluı ´ s Cabot Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Universitat de Barcelona, Barce- lona, Spa in Juan Casado Departamento de Investigacion, Carburos Meta ´ licos S.A., Barcelona, Spain William J. Cooper Department of Chemistry, University of North Caro- lina–Wilmington, Wilmington, North Carolina, U.S.A. Hugo Destaillats Department of Environmental Science and Engineering, California Institute of Technology, Pasadena, California, U.S.A. Gerry D. Getman Commodore Solution Techno logies, Inc., Marengo, Ohio, U.S.A. Michael R. Hoffmann Department of Environmental Science and Engineer- ing, California Institute of Technology, Pasadena, California, U.S.A. Indira Jayaweera SRI International, Menlo Park, California, U.S.A. Timothy L. Johnson AMEC Earth & Environmental, Inc., Portland, Ore- gon, U.S.A. TM Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved. Leah J. Matheson MSE Technology Applications, Inc., Butte, Montana, U.S.A. Bruce J. Mincher Radiation Physics Group, Idaho National Engineering & Environmental Laboratory, Idaho Falls, Idaho, U.S.A. James A. Nice ll Department of Civil Engineering and Applied Mathe- matics, McGill University, Mon treal, Quebec, Canada Pierre Pichat Laboratoire Photocatalyse, Catalyse et Environment, Ecole Centrale de Lyon, Ecully, France Charles U. Pittman, Jr. Department of Chemistry, Mississippi State Uni- versity, Mississippi State, Mississippi, U.S.A. Michelle M. Scherer Department of Civil and Environmental Engineering, University of Iowa, Iowa City, Iowa, U.S.A. Matthew A. Tarr Department of Chemistry, University of New Orleans, New Orleans, Louisiana, U.S.A. Paul G. Tratnyek Depart ment of Environmental and Biomolecular Sys- tems, Oregon Health and Science University, Beaverton, Oregon, U.S.A. Henry C. Walla ce Ultrasonic Energy Systems Co., Panama City, Florida, U.S.A. Contributorsviii TM Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved. [...]... Parathion a e, M 1 cm 1 (k, nm) 3300 (253.7) 18 .7 (253.7) 210 9900 (200) 516 ( 213 –400) 19 20 (272) 3760 (293) 17 50 (273) 3000 (292) 16 50 (278) 2400 (296) 5564 (254) 6643 (254) 16 654 (254) 40540 (254) 13 33 269 41 18.3 (254) 2486 (254) 2 512 3056 3 211 316 1 540 CEAT=2-chloro-4-ethylamine -1 , 3,5-s-triazine; CIAT=2-chloro-4-isopropylamine -1 , 3,5-s-triazine; c CAAT=2-chloro-4,6-diamine -1 , 3,5-s-triazine d In the... Einstein 1 (k, nm) 0.62 (253.7) 0.5d 0.5d 0.05 ( 213 –400) 0.03 (296) 0.30 (296) 0.09 (254 or 296) 0 .13 (254 or 296) 0.25 (254 or 296) 0.25 0.007 (254) 0.022 (254) 0.0075 (254) 0.0069 (254) 0.0052 0.004 0.06 ( 213 –400) 0.043 0.88 (254) 0.05 0.06 0.038 0.035 0. 018 0 .17 7 0.0076 (240–320)e 0.0 016 f Reference no 97 98,99 98,99 10 0 10 1 10 2 10 2 10 2 10 2 10 2 10 2 24 24 73 73 73 10 3 10 1 10 1 95 10 4 10 5 10 6 10 6 10 6 10 7... O3/UV/H2O2 Oxidation Technologies 15 Table 4 Rate Constants of the Reaction Between Ozone and Organic Compounds in Watera Organic compound Rate constant, M 1 s 1 pH Method Reference no 2 2.2 5.7 3000 2 413 13 00 2 10 6 1. 4 10 9 4.5 10 6 16 00 2.7 10 6 10 00 5 10 0 . NY 10 016 , U.S.A. tel: 21 2-6 9 6-9 000; fax: 21 2-6 8 5-4 540 Distribution and Customer Service Marcel Dekker, Inc., Cimarron Road, Monticello, New York 12 7 01, U.S.A. tel: 80 0-2 2 8 -1 160; fax: 84 5-7 9 6 -1 772 Eastern. Postfach 812 , CH-40 01 Basel, Switzerland tel: 4 1- 6 1- 2 6 0-6 300; fax: 4 1- 6 1- 2 6 0-6 333 World Wide Web http://www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities. For more. contamination. Chemical Degradation Methods for Wastes and Pollutants focuses on chemical methods of destroying pollutants. Chemical methods can be advan- tageous over biological methods because