Handbook of Detergents, Part B Environmental Impact (Surfactant Science Series Vol 121)(Marcel Dekker, 2004)

8/17/2019 Handbook of Detergents, Part B Environmental Impact (Surfactant Science Series Vol 121)(Marcel Dekker, 2004)

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HANDBOOK

of DETERGENTSPart B: Environmental Impact

Copyright © 2004 by Marcel Dekker


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1. Nonionic Surfactants, edited by Martin J. Schick (see also Volumes 19, 23,and 60)

2. Solvent Properties of Surfactant Solutions, edited by Kozo Shinoda (see Volume55)

3. Surfactant Biodegradation, R. D. Swisher (see Volume 18)4. Cationic Surfactants, edited by Eric Jungermann (see also Volumes 34, 37,

and 53)5. Detergency: Theory and Test Methods (in three parts), edited by W. G. Cutler

and R. C. Davis (see also Volume 20)6. Emulsions and Emulsion Technology (in three parts), edited by Kenneth J. Lissant 7. Anionic Surfactants (in two parts), edited by Warner M. Linfield (see Volume 56)8. Anionic Surfactants: Chemical Analysis, edited by John Cross 9. Stabilization of Colloidal Dispersions by Polymer Adsorption, Tatsuo Sato

and Richard Ruch

10. Anionic Surfactants: Biochemistry, Toxicology, Dermatology, edited byChristian Gloxhuber (see Volume 43)11. Anionic Surfactants: Physical Chemistry of Surfactant Action, edited by

E. H. Lucassen-Reynders12. Amphoteric Surfactants, edited by B. R. Bluestein and Clifford L. Hilton

(see Volume 59)13. Demulsification: Industrial Applications, Kenneth J. Lissant14. Surfactants in Textile Processing, Arved Datyner 15. Electrical Phenomena at Interfaces: Fundamentals, Measurements,

and Applications, edited by Ayao Kitahara and Akira Watanabe 16. Surfactants in Cosmetics, edited by Martin M. Rieger (see Volume 68)17. Interfacial Phenomena: Equilibrium and Dynamic Effects, Clarence A. Miller

and P. Neogi 18. Surfactant Biodegradation: Second Edition, Revised and Expanded,

R. D. Swisher 19. Nonionic Surfactants: Chemical Analysis, edited by John Cross 20. Detergency: Theory and Technology, edited by W. Gale Cutler and Erik Kissa 21. Interfacial Phenomena in Apolar Media, edited by Hans-Friedrich Eicke

and Geoffrey D. Parfitt 22. Surfactant Solutions: New Methods of Investigation, edited by Raoul Zana 23. Nonionic Surfactants: Physical Chemistry, edited by Martin J. Schick 24. Microemulsion Systems, edited by Henri L. Rosano and Marc Clausse 25. Biosurfactants and Biotechnology, edited by Naim Kosaric, W. L. Cairns,

and Neil C. C. Gray 26. Surfactants in Emerging Technologies, edited by Milton J. Rosen 27. Reagents in Mineral Technology, edited by P. Somasundaran

and Brij M. Moudgil 28. Surfactants in Chemical/Process Engineering, edited by Darsh T. Wasan,

Martin E. Ginn, and Dinesh O. Shah 29. Thin Liquid Films, edited by I. B. Ivanov 30. Microemulsions and Related Systems: Formulation, Solvency, and Physical

Properties, edited by Maurice Bourrel and Robert S. Schechter31. Crystallization and Polymorphism of Fats and Fatty Acids, edited by

Nissim Garti and Kiyotaka Sato 32. Interfacial Phenomena in Coal Technology, edited by Gregory D. Botsaris

and Yuli M. Glazman



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33. Surfactant-Based Separation Processes, edited by John F. Scamehornand Jeffrey H. Harwell

34. Cationic Surfactants: Organic Chemistry, edited by James M. Richmond 35. Alkylene Oxides and Their Polymers, F. E. Bailey, Jr., and Joseph V. Koleske 36. Interfacial Phenomena in Petroleum Recovery, edited by Norman R. Morrow 37. Cationic Surfactants: Physical Chemistry, edited by Donn N. Rubingh

and Paul M. Holland 38. Kinetics and Catalysis in Microheterogeneous Systems, edited by M. Grätzel

and K. Kalyanasundaram 39. Interfacial Phenomena in Biological Systems, edited by Max Bender 40. Analysis of Surfactants, Thomas M. Schmitt (see Volume 96)41. Light Scattering by Liquid Surfaces and Complementary Techniques, edited by

Dominique Langevin 42. Polymeric Surfactants, Irja Piirma

43. Anionic Surfactants: Biochemistry, Toxicology, Dermatology. Second Edition,Revised and Expanded, edited by Christian Gloxhuber and Klaus Künstler

44. Organized Solutions: Surfactants in Science and Technology, edited byStig E. Friberg and Björn Lindman

45. Defoaming: Theory and Industrial Applications, edited by P. R. Garrett 46. Mixed Surfactant Systems, edited by Keizo Ogino and Masahiko Abe 47. Coagulation and Flocculation: Theory and Applications, edited by

Bohuslav Dobiás 48. Biosurfactants: Production Properties Applications, edited by Naim Kosaric49. Wettability, edited by John C. Berg 50. Fluorinated Surfactants: Synthesis Properties Applications, Erik Kissa 51. Surface and Colloid Chemistry in Advanced Ceramics Processing, edited by

Robert J. Pugh and Lennart Bergström 52. Technological Applications of Dispersions, edited by Robert B. McKay 53. Cationic Surfactants: Analytical and Biological Evaluation, edited by John Cross

and Edward J. Singer 54. Surfactants in Agrochemicals, Tharwat F. Tadros 55. Solubilization in Surfactant Aggregates, edited by Sherril D. Christian

and John F. Scamehorn 56. Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache 57. Foams: Theory, Measurements, and Applications, edited by

Robert K. Prud’homme and Saad A. Khan 58. The Preparation of Dispersions in Liquids, H. N. Stein 59. Amphoteric Surfactants: Second Edition, edited by Eric G. Lomax 60. Nonionic Surfactants: Polyoxyalkylene Block Copolymers, edited by

Vaughn M. Nace 61. Emulsions and Emulsion Stability, edited by Johan Sjöblo m62. Vesicles, edited by Morton Rosoff 63. Applied Surface Thermodynamics, edited by A. W. Neumann and Jan K. Spelt 64. Surfactants in Solution, edited by Arun K. Chattopadhyay and K. L. Mittal 65. Detergents in the Environment, edited by Milan Johann Schwuger 66. Industrial Applications of Microemulsions, edited by Conxita Solans and

Hironobu Kunieda 67. Liquid Detergents, edited by Kuo-Yann Lai 68. Surfactants in Cosmetics: Second Edition, Revised and Expanded, edited by

Martin M. Rieger and Linda D. Rhein



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69. Enzymes in Detergency, edited by Jan H. van Ee, Onno Misset,and Erik J. Baas

70. Structure-Performance Relationships in Surfactants, edited by Kunio Esumiand Minoru Ueno

71. Powdered Detergents, edited by Michael S. Showell 72. Nonionic Surfactants: Organic Chemistry, edited by Nico M. van Os 73. Anionic Surfactants: Analytical Chemistry, Second Edition, Revised

and Expanded, edited by John Cross 74. Novel Surfactants: Preparation, Applications, and Biodegradability, edited by

Krister Holmberg 75. Biopolymers at Interfaces, edited by Martin Malmsten 76. Electrical Phenomena at Interfaces: Fundamentals, Measurements,

and Applications, Second Edition, Revised and Expanded, edited byHiroyuki Ohshima and Kunio Furusawa

77. Polymer-Surfactant Systems, edited by Jan C. T. Kwak 78. Surfaces of Nanoparticles and Porous Materials, edited by James A. Schwarzand Cristian I. Contescu

79. Surface Chemistry and Electrochemistry of Membranes, edited byTorben Smith Sørensen

80. Interfacial Phenomena in Chromatography, edited by Emile Pefferkorn 81. Solid–Liquid Dispersions, Bohuslav Dobiás, Xueping Qiu,

and Wolfgang von Rybinski 82. Handbook of Detergents, editor in chief: Uri Zoller

Part A: Properties, edited by Guy Broze 83. Modern Characterization Methods of Surfactant Systems, edited by

Bernard P. Binks 84. Dispersions: Characterization, Testing, and Measurement, Erik Kissa 85. Interfacial Forces and Fields: Theory and Applications, edited by Jyh-Ping Hsu 86. Silicone Surfactants, edited by Randal M. Hill 87. Surface Characterization Methods: Principles, Techniques, and Applications,

edited by Andrew J. Milling 88. Interfacial Dynamics, edited by Nikola Kallay 89. Computational Methods in Surface and Colloid Science, edited by

Malgorzata Borówko 90. Adsorption on Silica Surfaces, edited by Eugène Papirer 91. Nonionic Surfactants: Alkyl Polyglucosides, edited by Dieter Balzer

and Harald Lüders 92. Fine Particles: Synthesis, Characterization, and Mechanisms of Growth, edited

by Tadao Sugimoto 93. Thermal Behavior of Dispersed Systems, edited by Nissim Garti 94. Surface Characteristics of Fibers and Textiles, edited by Christopher M. Pastore

and Paul Kiekens

95. Liquid Interfaces in Chemical, Biological, and Pharmaceutical Applications,edited by Alexander G. Volkov

96. Analysis of Surfactants: Second Edition, Revised and Expanded,Thomas M. Schmitt

97. Fluorinated Surfactants and Repellents: Second Edition, Revisedand Expanded, Erik Kissa

98. Detergency of Specialty Surfactants, edited by Floyd E. Friedli 99. Physical Chemistry of Polyelectrolytes, edited by Tsetska Radeva



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100. Reactions and Synthesis in Surfactant Systems, edited by John Texter 101. Protein-Based Surfactants: Synthesis, Physicochemical Properties,

and Applications, edited by Ifendu A. Nnanna and Jiding Xia 102. Chemical Properties of Material Surfaces, Marek Kosmulski 103. Oxide Surfaces, edited by James A. Wingrave 104. Polymers in Particulate Systems: Properties and Applications, edited by

Vincent A. Hackley, P. Somasundaran, and Jennifer A. Lewis 105. Colloid and Surface Properties of Clays and Related Minerals,

Rossman F. Giese and Carel J. van Oss 106. Interfacial Electrokinetics and Electrophoresis, edited by Ángel V. Delgado 107. Adsorption: Theory, Modeling, and Analysis, edited by József Tóth 108. Interfacial Applications in Environmental Engineering, edited by

Mark A. Keane 109. Adsorption and Aggregation of Surfactants in Solution, edited by K. L. Mittal

and Dinesh O. Shah 110. Biopolymers at Interfaces: Second Edition, Revised and Expanded, edited byMartin Malmsten

111. Biomolecular Films: Design, Function, and Applications, edited by James F.Rusling

112. Structure–Performance Relationships in Surfactants: Second Edition, Revisedand Expanded, edited by Kunio Esumi and Minoru Ueno

113. Liquid Interfacial Systems: Oscillations and Instability, Rudolph V. Birikh,Vladimir A. Briskman, Manuel G. Velarde, and Jean-Claude Legros

114. Novel Surfactants: Preparation, Applications, and Biodegradability: Second

Edition, Revised and Expanded, edited by Krister Holmberg 115. Colloidal Polymers: Synthesis and Characterization, edited by

Abdelhamid Elaissari 116. Colloidal Biomolecules, Biomaterials, and Biomedical Applications, edited by

Abdelhamid Elaissari 117. Gemini Surfactants: Synthesis, Interfacial and Solution-Phase Behavior,

and Applications, edited by Raoul Zana and Jiding Xia 118. Colloidal Science of Flotation, Anh V. Nguyen and Hans Joachim Schulze 119. Surface and Interfacial Tension: Measurement, Theory, and Applications,

edited by Stanley Hartland 120. Microporous Media: Synthesis, Properties, and Modeling, Freddy Romm 121. Handbook of Detergents, editor in chief: Uri Zoller

Part B: Environmental Impact, edited by Uri Zoller 122. Luminous Chemical Vapor Deposition and Interface Engineering,

Hirotsugu Yasuda 123. Handbook of Detergents, editor in chief: Uri Zoller Part C: Analysis, edited by

Heinrich Waldhoff and Rüdiger Spilker 124. Mixed Surfactant Systems: Second Edition, Revised and Expanded, edited by

Masahiko Abe and John F. Scamehorn

ADDITIONAL VOLUMES IN PREPARATION



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Marcel Dekker New York

HANDBOOKof DETERGENTS

edited byUri Zoller

Haifa University–OranimKiryat Tivon, Israel

Editor-in-ChiefUri Zoller

Haifa University–OranimKiryat Tivon, Israel

Part B: Environmental Impact



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Cover gure : Typical (compared with a reference commercial product) homologic distribution

prole of APEOs (% of total concentration) in surface water.

Although great care has been taken to provide accurate and current information, neither theauthor(s) nor the publisher, nor anyone else associated with this publication, shall be liable forany 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 specic advice or recommendationsfor any specic situation.

Trademark notice: Product or corporate names may be trademarks or registered trademarksand are used only for identication and explanation without intent to infringe.

Library of Congress Cataloging-in-Publication DataA catalog record for this book is available from the Library of Congress.

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Handbook Introduction

The battle cry for sustainable development is persistent in all circles, gaining accept-ance, worldwide, as the guiding rationale for activities or processes in the science– technology–environment–economy–society interfaces targeting improvement andgrowth. Such activities are expected to result in higher standards of living, leadingeventually to a better quality of life for our increasingly technology-dependent modernsociety. Models of sustainable development and exemplary systems of sustainablemanagement are continually being developed and/or adapted and creatively applied,taking into consideration human needs versus wants on the one hand, and long-versus short-term benets and tradeoffs on the other.

‘‘Detergents’’ constitute a classic case study within this context: this is a multi-dimensional systemic enterprise, operating within complex sociopolitical/technoeco-nomical realities, locally and globally, reecting in its development and contemporary‘‘state-of-affairs’’ the changing dynamic equilibria and interrelationships betweendemands/needs, cost/benets, gains/tradeoffs, and social preferences. Interestingly, itis not surprising, despite the overall maturity of the consumer market, that detergentscontinue to advance more rapidly than population growth.

The soap and detergent industry has seen great change in recent years, respond-ing to the shifts in consumer preferences, environmental pressures, the availability andcost of raw materials and energy, demographic and social trends, and the overalleconomic and political situation worldwide. Currently, detergent product design isexamined against the unifying focus of delivering to the consumer performance andvalue, given the constraints of the economy, technological advancements, andenvironmental imperatives. The annual 2–3% growth of the detergent industry anda higher growth in personal care products reect impressive developments in for-mulation and application. The detergent industry is thus expected to continue steadygrowth in the near future.

For the detergent industry, the last decade of the twentieth century has been oneof transformation, evolution, and even some surprises (e.g., the increase of heavy-dutyliquid detergents at the expense of powder detergent products). On both the supplierand consumer market sides (both remain intensely competitive), the detergent industryhas undergone dramatic changes, with players expanding their offerings, restructuring

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divisions, or abandoning the markets altogether. This has resulted in the consolidationof the market, especially in the last several years, and this trend appears to be gainingmomentum. The key concepts have been and still are innovation, consumer prefer-ences, needs, multipurpose products, cost/benet, efficiency, emerging markets,partnership–cooperation–collaboration–merging (locally, regionally, and globally),and technological advancements. Although substantial gains and meaningful rapidchanges with respect to the preceding concepts have been experienced by thesurfactants/detergents markets, the same cannot be said for detergent/surfactanttechnology itself. The $9-billion-plus detergent ingredients market has manyentrenched workhorse products. This may suggest that the supply of ‘‘solutions’’ tomost cleaning ‘‘problems’’ confronted by consumers in view of the increasing globaldemand for a full range of synergistic, multifunctional detergent formulations havinghigh performance and relatively low cost, and the need for compliance with environ-mentally oriented (green) regulation, may be based on modications of existingtechnologies. What does all this mean for the future of the detergent enterprise?How will advances in research and development affect future development in detergentproduction, formulation, applications, marketing, consumption, and relevant humanbehavior as well as short- and long-term impacts on the quality of life and theenvironment? Since new ndings and emerging technologies are generating new issuesand questions, not everything that can be done should be done; that is, there should bemore response to real needs rather than wants .

Are all the questions discussed above reected in the available professional lit-erature for those who are directly involved or interested engineers, scientists, techni-cians, developers, producers, formulators, managers, marketing people, regulators,and policy makers? After a thorough examination of the literature in this and/orrelated areas, I came to the conclusion that a comprehensive series was needed thatfocuses on the practical aspects of the topic and provides the detergent industryperspective to all those involved and interested. The Handbook of Detergents is an up-to-date compilation of works written by experts each of whom is heavily engaged in hisor her area of expertise, emphasizing the practical and guided by a common systemicapproach.

The aim of this six-volume handbook (Properties, Environmental Impact,Analysis, Formulation, Applications, and Production) is to reect the above and toprovide readers who are interested in any aspect of detergents a state-of-the-artcomprehensive treatise, written by expert practitioners (mainly from industry) in theeld. Thus, various aspects involved—raw materials, production, economics, proper-ties, formulations, analysis and test methods, applications, marketing, environmentalconsiderations, and related research problems—are dealt with, emphasizing thepractical in a shift from the traditional or mostly theoretical focus of most of therelated literature currently available.

The philosophy and rationale of the Handbook of Detergents series are reectedin its title, its plan, and the order of volumes and ow of the chapters (within eachvolume). The various chapters are not intended to be and should not necessarily beconsidered mutually exclusive or conclusive. Some overlapping facilitates the pre-sentation of the same issue or topic from different perspectives, emphasizing differentpoints of view, thus enriching and complementing various perspectives and value judgments.

Handbook Introductioniv



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There are many whose help, capability, and dedication made this projectpossible. The volume editors, contributors, and reviewers are in the front line in thisrespect. Many others deserve special thanks, including Mr. Russell Dekker and Mr.Joseph Stubenrauch, of Marcel Dekker, Inc., as well as my colleagues and friends in(or associated with) the detergent industry, whose dedication and involvementfacilitated this work. My hope is that the nal result will complement the tremendouseffort invested by all those who contributed; you the reader, will be the ultimate judge.

Uri ZollerEditor-in-Chief

Handbook Introduction v



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vii

Preface

Regardless of the state-of-the-art and affairs in the detergent industry worldwide,with respect to scientic, technological, economic, safety, and regulatory aspects of detergent production, formulation, application, and consequently consumption,their environmental impact constitutes and will continue to be an issue of majorconcern. This is particularly so given the operating global free-market economy,which is supposed to, and is expected to, ensure sustainable development. Avoidanceof detrimental environmental impact primarily requires prevention rather thancorrection , which in turn should dictate what the detergent industry should do andwhat needs to be accomplished in the future to ensure environmentally-oriented

sustainable development, given contemporary shifts in consumer preferences, theavailability and cost of raw materials and energy, demographic and social trends,and the overall economical/political situation worldwide.

This second volume (Part B) of the six-volume series Handbook of Detergentsdeals with the potential environmental impact of detergents—surfactants, builders,and sequestering/chelating agents—as well as other components of detergent for-mulations as a result of their production, formulation, usage/consumption, andultimate disposal into the various compartments of the environment, particularlythe aquatic compartment. Since commercial detergent formulations comprise many

homologs, oligomers/polymers, and isomers, their identication, quantication,distribution, and persistence as well as specic and/or synergistic environmentalimpact (toxicity, estrogenicity, health risk, exotoxicity, and other factors) should beassessed, to be used as the solid and reliable scientic basis for action.

This volume is a comprehensive treatise on the multidimensional issuesinvolved, and represents an international industry–academia collaborative effort of over 50 experts and authorities worldwide.



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and Its Assessment’’ contains:

A historical review of detergents and the environment

A critical review and discussion of the distribution rate, effects, biodegradation,toxicology, and ecotoxicology of surfactants and other components of detergentformulationsRisk assessment, life-cycle assessment, biodegradability, toxicity, and structure– activity relationships of detergent components and their evaluationAn examination of the environmental impact of detergent packagingEnvironmental safety legislation on detergents

of Detergent Components,’’ include:

The fate, effects, safety, survival, distribution, biodegradability, biodegradation,ecology, and toxicology of anionic, cationic, and nonionic surfactantsEnvironmental impact ramications of inorganic detergent builders,chelating agents, bleaching activators, perborates, and other components of detergent formulationsToxicology and ecotoxicology of minor components in personal care detergentformulationsBiodegradation of surfactants in sewage treatment plants and in the natural

environmentScience versus politics in the environment-related regulatory process

All the above are accompanied and supported by extensive research-baseddata, occasionally accompanied by a specic ‘‘representative’’ case study, the derivedconclusions of which are transferable.

This resource contains more than 2300 cited works and is aimed to serve as apractical reference for environmental, surfactant, chemical/biochemical, toxicolog-ical/ecotoxicological scientists and engineers, regulators, and policy makers associ-ated with the detergent industry. I thank all the contributors who made therealization of this volume possible.

Uri Zoller

Prefaceviii


The topics addressed in Part II , ‘‘Environmental Behavior, Effects, and Impact

and

Part I , ‘‘The Multidimensionality of Detergent-Related Environmental Impact


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Contents

Handbook Introduction iii Preface vii

Contributors xiii

Part I The Multidimensionality of Detergent-Related EnvironmentalImpact and Its Assessment

1. Sustainable Relationships: Raw Materials–Surfactant/DetergentProduction/Formulation–Usage/Consumption–Environment:A Systemic Challenge for the New Millennium 1

2. Detergents and the Environment: Historical Review 11

3. Distribution, Behavior, Fate, and Effects of Surfactants and TheirDegradation Products in the Environment 77

4. Relevance of Biodegradation Assessments of Detergents/Surfactants 111

5. 129

6. Generation and Use of Data to Predict EnvironmentalConcentrations for Use in Detergent Risk Assessments 147

7. Life Cycle Assessment: A Novel Approach to the EnvironmentalProle of Detergent Consumer Products 195

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Uri Zoller

Marcel Friedman

Guang-Guo Ying

M. Rodriguez and D. Prats

Toxicology and Ecotoxicology of Detergent ChemicalsYutaka Takagi, Shinya Ebata, and Toshiharu Takei

M. S. Holt and K. K. Fox

Erwan Saouter, Gert van Hoof, and Peter White

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8. Biodegradability and Toxicity of Surfactants 211

9. The Biodegradability of Detergent Ingredients in an Environmental249

10. Environmental Risk Assessment of Surfactants: QuantitativeStructure–Activity Relationships for Aquatic Toxicity 271

11.of Plastic Bottles 299

12. 317

13. The Application of Environmental Risk Assessment to DetergentIngredients in Consumer Products 347

Environmental Behavior, Effects, and Impact of DetergentComponents

14. Surfactants in the Environment: Fate and Effects of LinearAlkylbenzene Sulfonates (LAS) and Alcohol-Based Surfactants 373

15. The Environmental Safety of Alkylphenol EthoxylatesDemonstrated by Risk Assessment and Guidelinesfor Their Safe Use 429

16. Estrogenic Effects of the Alkylphenol Ethoxylates and TheirBiodegradation Products 447

17. The Survival and Distribution of Alkylphenol EthoxylateSurfactants in Surface Water and Groundwater: The Case of

467

18. Ecology and Toxicology of Alkyl Polyglycosides 487

19.Perspective 523

20. Biodegradability of Amphoteric Surfactants 551

Contentsx


Torben Madsen

David W. Roberts

Susan E. Selke

Christina Cowan-Ellsberry, Scott Belanger, Donald Versteeg,

Part II

Geert Boeije, and Tom Feijtel

Luciano Cavalli

Carter G. Naylor

Karen L. Thorpe and Charles R. Tyler

Israel—Is There an Environmental Problem?Uri Zoller

Biodegradation of Cationic Surfactants: An Environmental

Andreas Willing, Horst Messinger, and Walter Aulmann

C. G. van Ginkel

Andreas Domsch and Klaus Jenni

Context: A Practical Approach

Environmental Impacts of Detergent Packaging: The Case

Luis BernaEuropean Environmental Safety Legislation on Detergents

John Solbe ´

Jose ´

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21. Environmental Impact of Inorganic Detergent Builders 573

22. Environmental Impact of Aminocarboxylate Chelating Agents 611

23. Environmental Impact of Bleaching Activators 629

24. Perborates: The Environmentally Problematic Bleaching Agents 645

25. Toxicology and Ecotoxicology of Minor Components in PersonalCare Products 663

26. The Environmental Impact of Surfactant Ingredients in PesticideFormulations—Special Focus on Alcohol Ethoxylates andAlkylamine Ethoxylates 691

27. Biodegradation of Surface-Active Detergent Components in SewageTreatment Plants 719

L

28. Surfactant Biodegradation: Sugar-Based Surfactants Comparedto Other Surfactants 739

29. Biotreatment of Wastewater with a High Concentrationof Surfactants 761

30. Science Versus Politics in the Environmental Regulatory Process 785

31. The Environmental Impact of Detergents: Which Way Is theWind Blowing? 803

Contents xi


Harald P. Bauer

Otto Grundler, Hans-Ulrich and Helmut Witteler

Vince Croud

J. Tarchitzky and Y. Chen

Louis Ho Tan Tai

Kristine A. Krogh, Bent Halling-Sørensen, Betty B. Mogensen,and Karl V. Vejrup

Zenon

I. J. A. Baker, C. J. Drummond, D. N. Furlong, and F. Grieser

Oded Vashitz and Ester Gorelik

John E. Heinze

Uri Zoller

ukaszewski

Ja ¨ ger,

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Contributors

Walter Aulmann Cognis Deutschland GmbH & Co. KG, Du s̈seldorf, Germany

I. J. A. Baker Kodak (Australasia) Pty Ltd., Coburg, Victoria, Australia

Harald P. Bauer Division of Pigments and Additives, Clariant GmbH, Hu r̈th,Germany

Scott Belanger Miami Valley Laboratories, The Procter & Gamble Company,Cincinnati, Ohio, U.S.A.

Jose ´ Luis Berna Research and Development, Petresa, Madrid, Spain

Geert Boeije European Technical Center, The Procter & Gamble Company,Brussels, Belgium

Luciano Cavalli * Sasol Italy, Milan, Italy

Y. Chen Department of Soil and Water Sciences, The Hebrew University of Jerusalem, Rehovot, Israel

Christina Cowan-Ellsberry Miami Valley Laboratories, The Procter & GambleCompany, Cincinnati, Ohio, U.S.A.

Vince Croud y Advanced Technologies Division, Warwick International Ltd.,Holywell, Flintshire, United Kingdom

Andreas Domsch Degussa Goldschmidt Personal Care, Essen, Germany

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*Current affiliation : UNICHIM, Milan, Italy.yCurrent affiliation : Antec International Ltd., Sudbury, Suffolk, United Kingdom.



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C. J. Drummond CSIRO Molecular Science, Clayton South, Victoria, Australia

Shinya Ebata Human Safety Evaluation Center, LION Corporation, Kanagawa,Japan

Tom Feijtel European Technical Center, The Procter & Gamble Company,Brussels, Belgium

K. K. Fox Department of Civil and Structural Engineering, University of Sheffield,Sheffield, United Kingdom

Marcel Friedman Research and Development, Neca-Agis Group, Petach-Tikva,

Israel

D. N. Furlong Applied Chemistry, RMIT University, Bundoora, Victoria,Australia

Ester Gorelik Zohar Dalia, Kibbutz Dalia, Israel

F. Grieser School of Chemistry, University of Melbourne, Melbourne, Victoria,Australia

Otto Grundler BASF Aktiengesellschaft, Ludwigshafen, Germany

Bent Halling-Sørensen Department of Analytical Chemistry, The Danish Uni-versity of Pharmaceutical Sciences, Copenhagen, Denmark

John E. Heinze Executive Director, Environmental Health Research Foundation,Manassas, Virginia, U.S.A.

Louis Ho Tan Tai Consultant, Lambersart, France

M. S. Holt European Center for Ecotoxicology and Toxicology of Chemicals,Brussels, Belgium

Hans-Ulrich Ja ¨ger BASF Aktiengesellschaft, Ludwigshafen, Germany

Klaus Jenni Degussa Goldschmidt Personal Care, Essen, Germany

Kristine A. Krogh Department of Analytical Chemistry, The Danish Universityof Pharmaceutical Sciences, Copenhagen, Denmark

Zenon I I I II ukaszewski Institute of Chemistry, Poznan University of Technology,Poznan, Poland

Torben Madsen Department of Ecotoxicology, DHI Water and Environment,Hørsholm, Denmark

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Horst Messinger Cognis Deutschland GmbH & Co. KG, Du s̈seldorf, Germany

Betty B. Mogensen Department of Atmospheric Chemistry, National Environ-mental Research Institute, Roskilde, Denmark

Carter G. Naylor * Consultant, Austin, Texas, U.S.A.

D. Prats Department of Chemical Engineering, University of Alicante, Alicante,Spain

David W. Roberts Safety and Environmental Assurance Center (SEAC), UnileverR&D, Sharnbrook, Bedford, United Kingdom

M. Rodriguez Department of Chemical Engineering, University of Alicante,Alicante, Spain

Erwan Saouter The Procter & Gamble Company, Petit Lancy, Switzerland

Susan E. Selke School of Packaging, Michigan State University, East Lansing,Michigan, U.S.A.

John Solbe ´ Consultant, Denbighshire, North Wales, United Kingdom

Yutaka Takagi Human Safety Evaluation Center, LION Corporation, Kana-gawa, Japan

Toshiharu Takei Human Safety Evaluation Center, LION Corporation, Kana-gawa, Japan

J. Tarchitzky Israeli Ministry of Agriculture, Bet-Dagan, Israel

Karen L. Thorpe y School of Biological Sciences, The Hatherley Laboratories,Exeter University, Exeter, Devon, United Kingdom

Charles R. Tyler School of Biological Sciences, The Hatherley Laboratories,Exeter University, Exeter, Devon, United Kingdom

C. G. van Ginkel Akzo Nobel Chemicals Research Arnhem, Arnhem, TheNetherlands

Gert van Hoof The Procter & Gamble Company, Strombeek-Bever, Belgium

Oded Vashitz Zohar Dalia, Kibbutz Dalia, Israel

*Retired from Huntsman Corporation, Austin, Texas, U.S.A.yCurrent affiliation : AstraZeneca UK Limited, Brixham, Devon, United Kingdom.

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Karl V. Vejrup Department of Atmospheric Chemistry, National EnvironmentalResearch Institute, Roskilde, Denmark

Donald Versteeg Miami Valley Laboratories, The Procter & Gamble Company,Cincinnati, Ohio, U.S.A.

Peter White The Procter & Gamble Company, Newcastle upon Tyne, UnitedKingdom

Andreas Willing Cognis Deutschland GmbH & Co. KG, Du s̈seldorf, Germany

Helmut Witteler BASF Aktiengesellschaft, Ludwigshafen, Germany

Guang-Guo Ying Adelaide Laboratory, CSIRO Land and Water, Glen Osmond,Australia

Uri Zoller Faculty of Science and Science Education-Chemistry, Haifa University– Oranim, Kiryat Tivon, Israel

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1Sustainable Relationships:Raw Materials^Surfactant //Detergent Production//Formulation^Usage//Consumption^Environment A Systemic Challenge for theNew MillenniumURI ZOLLER Haifa University–Oranim, Kiryat Tivon, Israel

I. SUSTAINABLE DEVELOPMENT: DETERGENTINDUSTRY–ENVIRONMENT RELATIONSHIPS

Sustainable development is a key demand in our world of nite resources andendangered ecosystems. Given the environmental imperatives, the potential ecotox-icological/health risks of anthropogenic chemicals/man-produced formulations, andthe limited economic feasibility of large-scale treatment and remediation technologies,the currently emerging corrective-to-preventive paradigm shift in the exploitation of raw materials, production/formulation, usage/consumption and disposal, as well as inthe conceptualization of future developments in these and related activities isunavoidable [1–3].

The role of science and technology in meeting the sustainable developmentchallenge is obvious and is recognized worldwide by all ‘‘stake holders.’’ In thiscontext, environmental sciences are emerging as a new multidimensional, cross-interdisciplinary scientic discipline and beyond. They draw on all the basic sciencesto explain the working of the entire complex and dynamic earth system—the environ-ment—which is constantly changing by natural causes and under human impact [4]. Atpresent, they are in a process of moving from a specialized, compartmentalized, (sub-)disciplinary, unidimensional enterprise into a multidimensional, cross-boundaryendeavor in the context of the science–technology–environment–society (STES)interfaces [5–7]. This poses new challenges with respect to both the intrinsic scienceand technology organization and performance and the way the relevant generated and

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acquired knowledge and accompanying processes will be put into action, guided by thesuperordinate idea(l)s of social responsibility and sustainability. Ultimately, thiswould require all involved to operate within an open-ended ideas-oriented culture [8].

In view of the fact that the public, many policymakers, some scientists andengineers, and even some environmental professionals believe that science andtechnology can solve most pollution problems, prevent future environmental impact,and (should) pave the way for sustainable development, it is of the utmost importanceto recognize the limits of environmental science and technology (alone) to meet thechallenge of sustainable development [9]. This is because science and technology areuseful in establishing what we can do. However, neither of them, or both, can tell uswhat we should do [1,6,7]. The latter requires the application of evaluative thinking[7,10] by socially responsible, reective, and active individual, group, and organiza-tional participants in the STES-economic-political decision-making process [1–2,6– 7,10], particularly in the context of the contemporary ‘‘stressed ecology’’ imperative.

The detergent industry is deliberate, steady, and mature, so its pattern of changeis evolutionary, avoiding drastic step changes. In spite of gloomy economic forecasts,detergent sales are expected to continue increasing, both in dollar and physicalvolume, in the rst decade of the new millennium, as new formulations providingbetter convenience for customers improve the value-added component of the prod-ucts. Anionic surfactants still dominate world output and consumption, accounting inthe United States for about two-thirds of the total, compared with about one-fourth of the nonionic detergents. The combined production of the United States, westernEurope, and Japan, which amounts to about 60% of that of the entire world, is sharedalmost equally ( f 30%) between the rst two, the rest being produced by Japan (about6%). Although some differences–as far as market share is concerned–are apparent, thegeneral pattern is quite similar worldwide. The laundry detergent segment dominatesthe market by far, comprising, together with the segment of dishwashing products,more than 75% of the market in the United States and western Europe and about two-thirds of the market in Japan. Not surprising, the annual growth in production/consumption in the last decade of the twentieth century ( f 2–3%) followed that of theGNP in these countries, and world production has been more or less stable in recentyears at a level of around 22 106 tons. These facts are very pertinent to the issue of sustainable development and relationships, since, one way or another, following theiruse all kinds of detergent formulations’ components and/or their degradation prod-ucts nd their way into man-made sewage systems and/or soils, natural surface water,and groundwater. Since (1) both world detergent production and consumption areexpected to grow in the years to come and (2) world population relies on both surfacewater and groundwater (primarily the latter) as its primary sources of drinking water,detergent/surfactant distribution, persistence, and survival as well as their potentialhealth risk in the environment constitute issues of major concern.

From the raw materials–natural resources perspective, detergent formulationsare based on surfactants derived from petrochemicals and/or fats and oils. Addition-ally, they contain builders: sequestrants such as carbonates, phosphates, silicates, aswell as oxidants and other ingredients.

Compared to other industries, the detergent industry recognized rather early theecological challenge. Its voluntary (for the most part) switch, in the 1960s from thenonbiodegradable (‘hard’) anionic, branched-chain dodecylbenzene sulfonate (DDBSor ABS: alkyl-benzene sulfonate) to the substituting biodegradable linear alkylben-

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zene sulfonate (LABS or LAS) is remarkable. The subsequent large-scale (preregula-tion) switch from polyphosphates to, mainly, zeolites in laundry and dishwashingformulations is no less impressive. Since then, the detergent industry worldwide hasbeen constantly confronted by one demand, the ‘‘minimization commandment’’: thatdetergent formulation be the very best that yields the desired effect with the leastamount. This demand is quite obvious in view of the fact that surfactants and othercomponents of detergent formulations constitute a signicant portion of municipalsewage water proles.

Ultimately, positive feedback–type relationships have been developed betweenenvironmental concerns and detergent formulation: The higher the public awarenessof the former, the higher the ‘‘environmental acceptability’’ of the latter. Indeed, thecurrent reformulation of detergent products reects the response of the detergentindustry to environmental regulatory as well as economic-technological and demo-graphic social factors in an attempt to cope with the increased awareness of environ-mental concerns, the upswing in action against phosphate builders and the unclearfuture of other builder systems, the tight sewage treatment requirements, the higherdemand for cost performance and added-value compositions associated with loweringof washing temperatures, the increasing share of washload held by synthetic textiles,the increasing demand for liquid formulations, ‘‘supereffective’’ or powdery ‘‘concen-trates,’’ and the pressure of the change in customer habits requiring efficient andconvenient multipurpose time-saving processes.

The appropriate response of the detergent industry to these pressures required(1) an overall increase of surfactants at the expense of builders in formulations, withthe nonionics gaining most of the increased share; (2) substitution of polyphosphatesmainly by zeolites as well as other effective sequestering agents; and (3) higherconcentrations of active components in multifunctional formulations effective inlow-temperature processes [14].

A major outcome of the foregoing was a three-fold development:

1. A dramatic switch from heavy-duty powder laundry formulations to heavy-dutyliquid (HDL) formulations, particularly in the United States, where the latter

accounts for more than 40% of heavy-duty laundry detergent sales2. A substantial reduction in the use of polyphosphates in detergent formulations,

with concomitant replacement, partially or totally, by zeolites3. The development and introduction, to the markets, of concentrated and/or

multifunctional heavy-duty, low-suds laundry formulations for use at lowtemperatures and having extra detergency.

Currently, concern about the environment is leading the detergent industry todevelop ‘‘environmentally friendly’’ products, which are increasingly being sold inrecycled packaging material to meet regulatory requirements and satisfy customerdemand. A case in point: the concentrated detergent formulations that are both morepowerful and require less packaging material.

Thus, in the nal analysis, the new products and modications made within thebasic formulations did make a difference as far as the environment is concerned. Whatis in store for us concerning the sustainable relationships—raw materials–surfactant/detergents production/formulation–usage/consumption environment—is contingenton the way that the relevant ‘‘guiding models’’ are conceptualized and ultimatelyimplemented.

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II. PARADIGM SHIFTS IN ENVIRONMENTAL SCIENCE,TECHNOLOGY RESEARCH, AND SUSTAINABILITY

Our so-called ‘‘global village/free global market/man-made world’’ requires a new

type of exible, contextually relevant, adaptive knowledge, followed by evaluative anddecision-making action, in accord, in order to sustainably cope with complexity andthe fragility of multidimensional socioeconomic technological/environmental sys-tems. This implies the importance of inter- and transdisciplinarity in environmentalresearch [5,15,16], appropriate research methodologies [16,17], as well as strategies fortechnology assessment in the context of sustainable action.

From the perspective of the environmental impact of human activity–sustain-able action/development relationships, selected paradigm shifts that are currentlytaking place in environmental science, technology, research, and consequent action

nation of these shifts reveals their pertinence and relevance to the systemic challenge of maintaining sustainable relationships as far as detergents and their environmentalimpact are concerned.

What are the implications with respect to sustainable detergent production andconsumption–environmental relationships? Given environmental concerns such asthe exploitation/use/consumption of natural resources and their environmentalimpact, particularly the potential health risk associated with persistent pollutantsand/or their metabolites [3,12,17], it appears that sustainable development as well as

maintaining a sustainable detergent–environmental relationship are imperative.Being led by the sustainable development imperative, Table 1 provides the

essence of the required shifts (some of them already implemented) in subjects,objectives, and methodologies of the environment-related scientic and technologicalresearch and development associated with detergent production, use/consumption,and disposal. Ensuring sustainable development requires, to begin with, a radicalchange in the environmental behavior (as well as ‘thinking Environment’) of individ-uals, institutions, industry, social organizations, politicians, and governments. This, inturn, requires reconceptualization of long-accepted relevant concepts and beliefs

[9,13,14,18]. Thus, for example, the shift from the acceptance of new technologies tofacilitating sustainable technologies in responding to society needs is substantiallydependent on the shift from people’s or customers’ ‘‘wants’’ to people’s needs. On theother hand, the technological feasibility of the economically and socially healthy shiftmay carry the seeds of contradiction with the shift from people’s ‘‘wants’’ to people’sneeds if economics is the governing criteria. Similarly, a shift from the conceptualiza-tion of environmental science and technology as omnipotent to a recognition of theirlimits in solving pollution problems, preventing future environmental impact, andpaving the way for sustainable development through appropriate design [9] has its

clear implications (and consequences) as far as detergents and their environmentalimpact are concerned.

If the foregoing imperative paradigm shifts are about to be realized, thendifferent quality criteria for research and practice in the sustainable development– environmental context become necessary. This is because not only do methodologicaldisciplinary aspects have to be rethought and reevaluated, but critical questions orissues arise, such as societal and practical relevance as well as external validity,particularly with respect to the risks and potentials of only partly controllable

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have been identied and are summarized in Table 1 [1]. In-depth systematic exami-


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variables and data of ‘‘in vivo’’ studies [1]. Further, different stakeholders, values, andperspectives will be involved and, consequently, integrated into the relevant science[13], technology, and development as well as the production/formulation/use anddisposal processes related to the environment [19]. Clearly, the application of the

identied paradigm shifts in the context of the environmental impact of detergentsrequires a corresponding paradigm shift in the related conceptualization.

III. RECONCEPTUALIZATION OF CONSENSUSLYACCEPTED CONCEPTS

Given (1) the environmental imperatives and (2) the limited economic feasibility of many of even the most innovative/advanced technologies, the switch from the

TABLE 1 Selected Paradigm Shifts in Environmental Science, Technology Research, andConsequent Action

From To

A. Sustainable development–environment interrelationship. Technological, economic, and social

growth at all costSustainable development

. Increase in the competitive gap betweencountries, nations, societies

Increase in collaboration/cooperationand decrease in polarization

. People’s ‘‘wants’’ People’s needs

. Passive consumption of ‘‘goods,’’culture, and education

Active participation/social actionin the decision-making process

. Selection from among available alternatives Generation of alternatives

. Selected environmental improvementon the local level at all costs

‘‘Globalization’’ in ecoeffective/efficient action

. Environmental ethics Environmental sustainability-oriented‘‘pragmatism’’

B. Scientic and technological research and development. Corrective Preventive. Reductionism, i.e., dealing with

in vitro isolated, highly controlled,decontextualized components

Uncontrolled, in vivo complex systems

.

Compartmentalization Comprehensiveness, ‘‘holism’’. Descriptive, as it is—‘‘here and now’’ (Attempted) Predictive models/modeling. Disciplinarity Problem-solving oriented, systemic,

inter-/cross-/transdisciplinarity. Technological feasibility Economic-social feasibility. Scientic inquiry (per se) Social accountability and responsible

and environmental soundness. Technological development per se Integrated technological development

and assessment. Convergent, self-centered Divergent, interactive/reective/

adaptive and related to differentframes of reference

Source : Ref. 1.




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currently dominant corrective paradigm to the emerging preventive practice inproduction–development–consumption–disposal is unavoidable. This requires arevolutionary change in the guiding philosophy, rationale, and models of thesurfactant/detergent industry concerning:

Customers wants or needs, at what cost?The more producing/selling the better?Raising the standard of living equals raising the quality of life?Responding to market trends or generating/leading them?Relying on disciplinary or transdisciplinary science research–based technology for

rational management of the environment and sustainable development.

A case in point, to serve as an example: ‘‘We are committed to meet ourcustomers’ needs’’ is a currently dominant central concept. A clear distinction betweencustomers’ ‘‘wants’’ and customers’ ‘‘needs’’ has to be made. The rst led tooverconsumption, which is not necessarily benecial to the consumer and, in fact, isperpetually and aggressively being promoted an industry motivated by ‘‘growth andprots at all cost,’’ with all the uncontrolled socioenvironmental consequencesinvolved. The latter, however, should be targeted and responded to by a responsible,environmentally concerned detergent industry. Only an orientation to people’s needshas the chance (albeit not guaranteed) to meaningfully contribute to sustainabledevelopment, not only in developing countries (‘‘emerging markets’’) but also inhighly developed Western countries. A ‘‘needs’’ orientation is, mainly, a promoter of quality of life, with a consumption-limiting potential. In contrast, a ‘‘wants’’orientation is a promoter of standard of living, which is not only inconsistent withthe existing trend of ever-increasing overconsumption, but in most cases furtheraccelerates the pace of this trend. The environmental consequences of over-consumption are apparent [1,14,18].

With respect to science and technology, virtually any discussion concerning thecurrent and future states of scientic and technological research and problem solving istypied by statements about the importance of enabling researchers and engineers towork seamlessly across disciplinary boundaries and by declarations that some of themost exciting problems, particularly the complex systemic environmental ones, spanthe disciplines. Moreover, transdisciplinary applied research evolves from real,complex problems in the interdisciplinary STES context, which are relevant tosocieties living in different environments. Such problems have no disciplinary algo-rithmic solutions or even resolutions. It is growing increasingly difficult to establish thetransdisciplinary basis necessary for addressing complex environmental problems[1,13,17]. Therefore, the challenge for this kind of target-oriented research andtechnology development is to develop problem-solving methodologies that not onlyintegrate different qualities and types of knowledge, but also envision researchers andengineers as an integral (nonobjective ‘‘insiders’’) part of the investigated, or to beremediated (‘‘corrected’’), system. Sustainable development via appropriate environ-mental management and industrial production, formulation, marketing, and businesspolicies is, thus, highly dependent on transdisciplinary research and development inthe STES context. This will facilitate transfer beyond the specic subject(s) ordiscipline(s) and, consequently (hopefully), a higher success in coping with previouslyunencountered complex problem situations [13,17].

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In view of the compartmentalized disciplinary orientation in science and technol-ogyresearchanddevelopment(R&D)andthecorrective approach in dealing with pointand diffuse pollution problems in the different parts of the environment, the failure tostrengthen the links between the social/behavioral sciences and advances in scienceand technology applied in different socioeconomic, cultural, and environmentalcontexts is of no surprise. However, the prevention approach to ensure environmentalquality and restoration of ecosystems requires, most of all, appropriate andresponsible environmental behavior and action on the part of both producers andcustomers, which, in turn, is contingent on an adequate environmental education [20].This implies an urgent need for strengthening the social and educational componentswithin the corrective-to-preventive paradigm shift process concerning the sustainablemanagement of, and maintaining system-sustainable relationships in, our environ-ment. Therefore, a major goal of sustainable development–promoting science andtechnology, research, education, and training at all levels should be the development of students’ higher-order cognitive skills (HOCS) in the context of both the speciccontent and processes of science and the processes/interrelationships related tointerdisciplinary societal, economic, scientic, technological, and environmentalissues. The expected resultant critical thinking and interdisciplinary transfercapabilities mean rational, logical, reective, and evaluative thinking in terms of what to accept (or reject) and what to believe in, followed by a decision—what to do(or not to do) about it and responsible action-taking. Thus, any meaningful responseto meet the challenge of sustainable development requires transdisciplinarity,essentially by denition, that is, the development and implementation of policiesand cross-disciplinary methodologies, which can lead to the changes in behavior–of individuals, industries, organizations, and governments–that will allow developmentand growth to take place within the limits set by ecological imperatives. Theeducational challenge is rather clear. It is a precondition for the requiredreconceptualization, which, in turn, will ensure sustainable development and growth.

The detergent industry is a representative case in point; e.g., the phosphates-euthrophication issue (transdisciplinarity prevention) and the recent growth of thepersonal care ethnic markets in the United States: ‘‘These ethnic consumers not onlycan afford to buy their share . . . of cosmetics . . . but they also want productsformulated to meet their needs’’ [21]. The sociobehavioral consumption economicsand environmental links are apparent.

Four recent pertinent publications, two more general and two more specic, dealwith the surfactants–environment–health relationship issue and can serve to illustratethe importance of reconceptualization in the context of the environmental system’schallenge that we are confronting.

1. It is claimed that since major environmental pollutants are coming under thecontrol of regulatory authorities, this part of ecotoxicology is more or lesscompleted, although there is still work, not expected to call for major scienticinnovation and discovery, remaining to be done. It is concluded that the mergerbetween ecotoxicology and ecology would give rise to a new science, stressecology , at the crossroads of ecology, genomics, and bioinformatrics [13].

2. Given that the public, many policymakers, and some environmental profes-sionals believe that science and technology can solve most pollution problems,




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prevent future (undesirable) environmental impacts, and pave the way forsustainable development, this paper makes the claim that since science andtechnology alone cannot meet the challenge of sustainable development, we allshould recognize the limits (reconceptualize the problem-solving capability) of environmental science and technology [9].

3. A recent publication by CLER (Council for LAB/LAS EnvironmentalResearch) and ECOSOL (European Council on Studies on LAB/LAS) [21]reports that their revised dossier and assessment report on LAS, which reviewsthe considerable data on LAS, showing that LAS is safe for human health andthe environment, was submitted to the U.S. EPA and recommends that nofurther testing is needed and that the EPA agreed that there is no need forfurther studies [21].

4. In contrast, following the completion of a comprehensive interdisciplinary,longitudinal EU-sponsored research program (COMPREHEND), on environ-mental hormones and endocrine disruptors, including APEOs, the investigatorsconclude that, although their studies did demonstrate impacts and endocrinedisruption in sh exposed to environmentally realistic levels of estrogenicsubstances, the question of deleterious impacts of estrogenic effluents on shpopulations is, as yet, one of the most important remaining to be answered [17].

Do the apparent different approaches to a similar (although, obviously, notidentical) environmental issue in the detergent–environment–sustainable relationships

context represent different (contradictory?) conceptualizations of the issue(s) at hand?This question and the response to it remain open.

IV. SUMMARY AND CONCLUSIONS: MEETING THECHALLENGE OF DETERGENT–ENVIRONMENT–SUSTAINABLE RELATIONSHIPS

Sustainability is an enormous challenge, particularly in the STES context. Mostproblems and issues boil down to: Who does what, for what, at what price, at theexpense of whom (or what), and in what order of priorities? The widely agreed-uponcall for sustainable development requires rational hard choices to be made betweeneither available or to-be-generated options [7]. This poses an even greater challenge toscience, technology, and education for sustainability, whatever that means. This is sobecause dealing effectively and responsively with complex interdisciplinary problemswithin complex systems in the context of STES interfaces requires evaluative thinkingand the application of value judgment by technologically, environmentally, andsociologically (i.e., STES-) literate, rational scientists, engineers, and citizens withina continuous process of critical thinking, problem solving, and decision making[6,10,22].

This implies an urgent need to strengthen the HOCS-promoting components of STES-oriented education within the corrective-to-preventive paradigm shift processconcerning the sustainable management of our environment [1,10,22].

The expected resultant critical thinking and interdisciplinary transfer capabil-ities mean a rational, logical, reective, and evaluative thinking in terms of what toaccept (or reject) and what to believe in, followed by a decision — what to do (or not todo) about it and taking responsible action accordingly. Thus, any meaningful response

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to the current leading challenge of sustainability requires transdisciplinarity inenvironmental science, technology, research, and action [1].

It follows, then, that what we are dealing with is not just a simple matter of economics that the free ‘‘market forces’’ (which, incidentally, are not God’s creationbut, rather, changeable, people-made, and people-controlled) will take care of.Rather, we are dealing with an array of very complicated problems within a complexsystem, the components of which are natural, man-made, and human environmentsand their related subsystems. Most of these problems have no ‘‘right’’ solutions(denitely not algorithmic), but rather resolutions that can be worked out via the useof appropriate methodologies, simultaneously guided by a sustainable development– oriented value system. The disciplinary/correction–transdisciplinary/preventionparadigm shift concerning environmental issues, the initial steps of which we arecurrently witnessing, is crucial for both sustainable development and our survival onplanet Earth. As far as the chemical and detergent industries are concerned, thisreconceptualization-based paradigm shift has to be translated into ‘‘sustainableaction,’’ in terms of raw materials to be used, ‘‘green’’ production in accord with needsrather than wants, economic feasibility/cost–benet–prot with respect to allinvolved, marketing (where, when, and to whom), given the local particular realitiesof constraints, risk assessment (methodologies and criteria applied), and environ-mental compatibility [14,18].

Can we meet the systemic challenge of sustainable detergents–environmentrelationships?

The evolutionary pattern of change in the deliberate and steady detergentindustry can serve as a test case for a reasonable response, by taking a historicalperspective: the switch from DDBS to LABS, the continuing use of the (potentiallyestrogenic?) branched-chain nonylphenol-based nonionic ethoxylates, the polyphos-phates-to-zeolites switch, the recent extensive use of enzymes, the development of theactivators/perborate bleach systems, the current switch (in the United States) fromhorizontal to vertical drums in washing (laundry) machines, the proliferation of personal-care products, and many other innovations. Whether or not each of these isconsonant with the new sustainable development–oriented criteria and in line with theparadigm shift in the STES context remains an open question. It is up to each of us,following our own a evaluative thinking, conceptualization, and assessment process,to respond. Can we meet the challenge? Are we getting it right? Then we should actaccordingly and take responsibility, each in her or his environmentally related milieu.

different perspectives, with the relevant issues involved.

REFERENCES

1. Zoller, U.; Scholz, R.W. Environ. Sci. Technol. 2003. submitted .2. Zoller, U. Environ. Sci. Pollut. Res. 2000, 7 , 63–65.3. Zoller, U.; Plaut, I.; Hushan, M. Wa. Sci. Technol. 2003 submitted .4. Glaze, W.H. Environ. Sci. Techno. 2002, 36 (23), 438A–439A.5. Gibbons, M.; Nowotny, H. In Transdisciplinarity : Joint Problem Solving Among Science,

Technology, and Society . An Effective way for Managing Complexity ; Klein, J.T., Gros-senbacher-Mansuy, W., Haberli, R., Bill, A., Scholz, R.W., Welti, M., Eds.; Birkha üser:Basel, 2001; 67–80.



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6. Zoller, U. Higher Educ. Europ. 1990, 15 (4), 195–197.7. Zoller, U. Environ. Sci. Pollut. Res. 2001, 8 (1), 1–4.8. Negroponte, N. Tech. Rev. 2003, 106 (1), 33–35.9. Huesemann, M.H. Environ. Sci. Technol. 2003, 37 (13), 259A–261A.

10. Zoller, U. J. Chem. Educ. 1993, 70 (3), 195–197.11. Glaze, W.H. Environ. Sci. Technol. 2002, 36 (17), 337A pp.12. Schnoor, J.L. Environ. Sci. Technol. 2003, 37 (7), 119A pp.13. Van Straalen, N.M. Environ. Sci. Technol. 2003, 37 (17), 324A–330A.14. Zoller, U. Chem. Educ. 1993, 70 (3), 195–197.15. Zoller, U. Environ. Sci. Pollut. Res. 1999, 7 (2), 63–65.16. Scholz, R.W., Marks, D., Klein, J.T., Grossenbacher-Mansuy, W., Ha b̈erli, R., Bill, A.,

Scholz, R.W., Welti, M., Eds.; Transdisciplinarity: Joint Problem Solving among Science,Technology and Society ; Birkjha üser: Basel, 2001; 236–252.

17. Pikering, A.S.; Sumpter, J.P. Environ. Sci. Technol. 2003, 37 (17), 331A–336A.18. Zoller, U. Proceedings of the 5th World Surfactants Congress, Cesio, Firenze, May 29–

June 2, 2000; 2, 15766–1571.19. Bill, A.; Oetliker, S.; Thompson-Klein, J. In Transdisciplinarity: Joint Problem Solving

among Science, Technology and Society. An Effective Way for Managing Complexity ;Thompson-Klein, J., Grossenbacher-Mansuy, W., Ha b̈erli, R., Bill, A., Scholz, R.W.,Welti, M., Eds.; Birkha üser: Basel, 2001; 25–34.

20. Keiny, S., Zoller, U., Eds.; Conceptual Issues in Environmental Education ; Peter Lang: NewYork, 1991.

21. Reisch, M.S. Chem. Eng. News, Apr 12; 19–24.22. Zoller, U. J. Coll. Sci. Teach. 1999, 26 (9), 409–414.

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2Detergents and the Environment Historical Review

MARCEL FRIEDMAN Neca-Agis Group, Petach-Tikva, Israel

I. INTRODUCTION

Soaps and detergents are essential products that safeguard our health. They belong tothat group of consumer products that are indispensable for the maintenance of cleanliness, health, and hygiene. It has been said that the amount of soap consumedin a country is a reliable measure of its civilization. The increase in per capitaconsumption of soap and detergents in various countries was found to correlate wellwith life span.

Cleanliness is essential to our well-being. A clean body, a clean home, and a cleanenvironment are the norm of today and a general concern shared by everyone.‘‘Cleanliness is next to godliness’’ was the ultimate historical religious praise of physical cleanliness leading to spiritual purity. Paraphrasing it, cleanliness was,throughout history, next to environment. For thousands of years soaps, and, in thelast century the synthetic detergents, followed by more complex washing and cleaningproducts, were the blessed way to get it. The use of soaps and detergents always led to asignicant contribution to the modern quality of life, the close environment alwaysbeing part of this. However, in the past 50 years a new dimension to this obviouspositive symbiosis has been imposed, and a long-unnished detergents–environmentdebate opened.

The detergent industry has faced dramatic changes since the early 1980s,developing into an interdisciplinary, multidimensional enterprise trying to cope withscientic/technological/ecological/toxicological/social/economic/political con-straints. At the outset of the new millenium, the detergent industry is focused oncoping with four challenges: economics, safety and environment, technology, andconsumer requirements. The products must not just meet consumer needs for qualityand efficacy, but must be dangerous neither to manufacture nor to use and must in noway have a detrimental impact on the user’s health. The products and their packagingshould not accumulate in the environment and shift or harm the ecological balance.

Not only the products but also washing habits are changing. In an age of growingenvironmental concern, a change of attitude toward the washing process has takenplace in many countries. Nowadays, the consumption of energy, water, and chemicals

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is faced not only from economic but also from ecological angles. As a consequence,new raw materials, washing processes, laundry practices, and cleaning technologieshave been developed, with the common challenge to use carefully the limited resourcesof the earth, to exploit the renewable ones, and to prevent environment pollution asmuch as possible.

The development of surfactants and detergents over the past decades has beenaffected tremendously by their environmental acceptability. The challenge for thefuture is to meet the most modern risk assessment approaches.

The aim of this chapter is to review this detergents–environment interrelateddevelopment frame throughout history.

II. DETERGENTS, WASTEWATER, ENVIRONMENTThe complex relationship between surfactants/detergents/cleaning products on onehand and wastewater, sewage treatment, surface water, and the environment on theother became the basis for most of the ecological issues, leading to a twofold approachtoward their solution.

First, surfactants and phosphates, as the main components of detergent for-mulations and cleaning products, have been the subject of longstanding and ongoingdetergent regulation and legislation. Second, efficient management has been imposedon sewage treatment, which is being updated continuously. A better understanding of this multidimensional input/output interaction is needed.

During the washing process, detergent components are released to the waste-water stream, to become a potentially undesirable troublemaker in sewage treatmentplants and in the environment. Wastewaters vary considerably in composition andconcentration and hence in their environmental impact. These differences are geo-graphically dependent and arise partly due to differences in laundry habits and soillevels and partly to the composition and amount of the detergent used. The environ-mental impact further depends on the specic ecological requirements and publicawareness in each particular geographical area. Also, household wastewater, gener-ated mainly from laundry and personal care products, differs from that from industrialand institutional outlets.

Typical sewage treatment systems in countries with developed environmentalprotection include intensive biochemical and physical degradation processes thatbring about the elimination of the pollutants. The extent of elimination depends onsludge levels, aeration efficacy, and residence time. In addition to bacterial metabolicreactions, physicochemical processes, such as adsorption on sewage sludge, contributeto the reduction of pollutant levels [1].

Variations in sludge loading and in peak loads of the wastewater are moderatedconsiderably by the predilution of household wastewater in the public sewage system.Wastewater from industrial sources is generally pretreated by pH adjustment andphysical separation in on-site sewage plant prior to discharge to municipal sewagetreatment plants. Sometimes a well-designed treatment plant on an industrial site maypermit direct discharge.

The sewage treatment effluents are discharged in the surface waters. Qualityrequirements for these effluents depend upon the intended use of the surface waters.The ultimate use, such as for drinking water, agriculture, or recreation, also governs

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the technical basis of the wastewater treatment as well as the intensity of the sewagetreatment process. Phosphorous and nitrogen elimination normally require additionaltreatment steps.

The sewage treatment effluent is diluted in surface waters. The dilution factorvaries according to the geographical place. Human waste and some remaining traces of surfactants in the surface waters are further biologically treated by a self-cleaningprocess [2].

The efficacy of a sewage treatment is evaluated by different parameters, such as

BOD (biochemical oxygen demand), which registers the biodegradable organicmatter present

COD (chemical oxygen demand) TOC (total organic carbon)

However, the most signicant parameter is the direct measurement of the pollutantlevels, mainly surfactant and phosphate concentrations.

Highly sensitive analytical test methods have been developed for the accuratedetermination of surfactant concentration [3,4]. Anionic surfactants are determined as‘‘methylene blue–active substances’’ (MBAS) by a method based on a modied Eptontwo-phase titration. Nonionic surfactants are determined as bismuth-active substan-ces (BiAS) after passage through cation and anion exchange columns.

Cationic surfactants are determined as ‘‘disulde blue–active substances’’(DSBAS).

Strict implementation of detergent regulations combined with effective sewagetreatment hes led to low surfactant concentrations in large rivers, such as those in theRhine, which currently are as follows [2]:

Anionic surfactants, about 0.05 mg/L MBAS (linear alkylbenzene sulfonates)Anionic surfactants, less than 0.01 mg/L LASNonionic surfactants, less than 0.01 mg/L BiASCationic surfactants, less than 0.01 mg/L DSBAS

The sewage treatment and surfactant levels just referred to represent, more orless, the present state of the art, which should come close to an appropriate resolutionto the ecological threat of surface contamination. It has taken some 40 years to reachthe present state from the time when rivers all over began to foam and gave rise to theFirst Detergent Law.

III. SURFACTANTS REGULATION (1950–1980)

A. First Surfactants’ Environmental Complication

As early as 1952, sewage treatment problems were observed in the UK. Foam on riverswas increasing, and tap water, drawn from wells located close to household dischargepoints, also tended to foam. In 1959, Germany encountered similar difficulties whenfoam formed on German rivers and stable foam layers developed downstream fromdams.

The sewage treatment of the time, based on physicochemical separations andsome biological treatment, was not able to cope with the surfactant load. The impacton sewage treatment was immediate and signicant. The efficacy of the sedimentation

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process was reduced, leaving a high dispersion of suspended solids in the treatmentplant. The few biological sewage treatment plants operating with an activated sludgeprocess collapsed, producing foam layers several meters high above the aeration tanks.

Increased surfactant concentrations were found not only in sewage waters andrivers, but also, as a result of soil inltration, in the groundwater. As a result, thedrinking water supply was contaminated. The anionic surfactant content of drinkingwater from the Ruhr River increased to as much as 1.73 mg/L, while the required limitwas nil [2]. During 1958–1960, increasing surfactant consumption in the United Statesled to similar ecological problems. The German market of 1960 consumed about80,000 tons/year of surfactants. DDBS accounted for more than 80%, while nonionicsand cationics added up to 15% and 5%, respectively, of market volume. Municipalsewage treatment plants could not cope with typical inuent concentrations of about20 mg/L MBAS on peak washing days. At a maximum reduction of 25% of theinuent, effluents were released into surface waters with concentrations as high as 16mg/L [2].

It was soon understood that these serious problems for water management weredue to the poor biodegradation prole of DDBS. The abnormal quantities of foamwere attributed to the presence of DDBS, which, in turn, was the result of incompletebiodegradation of propylene-based alkylbenzenesulfonates by the natural bacteriapresent in effluents. The branched-chain structure of alkylbenzene seemed to hinderattack by the bacteria. Supporting evidence for this judgment was provided by thefacile degradation of fatty alcohol sulfates and soap. Both are derived from straight-chain fatty acids, suggesting that a straight-chain, linear alkylbenzene might also bedegradable.

B. First Detergent Law on Surfactants in Detergentsand Cleaning Products (1961)

In 1960, Germany established the Main Committee on Detergents, which elaboratedin September 5, 1961, the rst piece of detergent legislation, known as First DetergentLaw [1,5]. This law imposed a strict requirement of a minimum of 80% biodegrad-ability for all the surfactants (anionic, nonionic, cationic, amphoteric). However, a1962 directive provided a dynamic test method according to a specied test protocolonly for control of anionic surfactants.

By this biodegradability test, the straight-chain, linear alkylbenzenesulfonates(LAS or LABS) were found to be readily biodegradable and, as a result of the strictlegislation, replaced totally the branched-chain dodecylbenzenesulfonates (ABS orDDBS):

DDBS (ABS): CH 3 [CH(CH 3 )CH 2 ]3 CH(CH 3 )4 C 6 H 4 SO 3 Na

LABS (LAS): CH 3 (CH 2 )11 C 6 H 4 SO 3 NaBeginning October 1, 1964, only those surfactants with a biodegradability of

over 80% were allowed to be incorporated into detergents. During the short timebetween mid-1964 and 1965, known as the ‘‘conversion period,’’ the foaming problemsin surface waters and sewage treatment were solved. The degradation/elimination ratein sewage treatment plants, which was 19–25% before the First Detergent Law,increased to 60%. The effects of the conversion to biodegradable surfactants were

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similar on surface waters and rivers, with a decrease in surfactant concentration of upto 77% having been measured [2].

The conversion from ‘‘hard’’ to ‘‘soft’’ surfactants was also legislated during1963–1964 in the United States, as amendments to the Federal Water PollutionControl Act, creating new water pollution control standards [6]. However, none of these measures was implemented. The problem was solved in 1966 by the detergentindustry, which agreed voluntarily to switch over from ABS to LAS. Similarregulations and voluntary agreements were put into place during the late 1960s andearly ’70s in several countries of Western Europe and in Brazil and Japan.

LABS was made commercially available in 1966. The manner in which theDDBS problem was solved is an excellent example of environmental improvementsachieved by cooperation of government, industry, and science. However, the detergentindustry faced advantages and disadvantages. The change to LABS offered betterdetergency in heavy-duty formulations and lower cloud points and viscosities in pastesand slurries. But, on the other hand, while a lower viscosity in slurries offered anadvantage for a spray-dry process, the liquid and paste LABS detergent of lowerviscosity looked less appealing to the consumer. Also, the LABS powders becamesticky and were less free owing [7].

It was found that the actual isomer distribution of the linear alkylate has an effecton the stickiness of the powder, identifying the 2-phenyl isomer as giving the greatesttendency to stickiness. The different phenyl isomers are obtained when, duringalkylation, the benzene molecules attach to the different carbons along the alkylchain. For instance, an attachment at the second carbon of the alkyl chain gives a 2-phenyl isomer. It was found that the phenyl isomer distribution depends on thecatalyst used during alkylation. Aluminum chloride (AlCl 3 ) alkylation gives a ‘‘high 2-phenyl’’ distribution (29%), while hydrouoric acid (HF) catalysis results in a ‘‘low 2-phenyl’’ distribution (19%) [8].

This catalytic versatility in LAB production, as well as additives furtherdeveloped, overcame most of the formulation problems.. However, in the case of solid laundry bars the lower viscosity and the less bulky molecular structure of LABSprovided a softer bar hardness and a stickier appearance. This disadvantage couldhardly be overcome for highly concentrated (above 30% active) bars.

C. Surfactant Biodegradation

Biodegradation is the process by which microorganisms in the environment convertcomplex materials into simpler compounds that are used as food for energy andgrowth. Biodegradation of the surfactants used in detergents is important because of the large volumes used worldwide and, of course, the detrimental toxic effects on theaqueous and soil environments.

Biodegradation is a multistep process that starts with the transformation of theparent compound into a rst degradation product (primary degradation) and leading,ultimately, to mineralization products (carbon dioxide, water) and bacterial biomass(ultimate or total degradation). A typical surfactant biodegradation is illustrated by

A good understating of past and present biodegradation i

Documents

Handbook of Detergents, Part B Environmental Impact (Surfactant Science Series Vol 121)(Marcel Dekker, 2004)