Fluorinated Surfactants and Repellents, Second Edition, (Surfactant Science)
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Anionic Surfactants in two parts , edited by Warner M. Linfield see Volume 56 8. Lucassen-Reynders Amphoteric Surfactants, edited by B. Bluestein and Clifford L. Hilton see Volume 59 Demulsification: Industrial Applications, Kenneth J. Lissant Surfactants in Textile Processing, Arved Datyner Surfactants in Cosmetics, edited by Martin M. Rieger see Volume 68 Miller and P. Neogi Swisher Detergency: Theory and Technology, edited by W.
Gale Cutler and Erik Kissa Parfitt Schick Microemulsion Systems, edited by Henri L. Rosano and Marc Clausse Biosurfactants and Biotechnology, edited by Naim Kosaric, W. Cairns, and Neil C. Gray Surfactants in Emerging Technologies, edited by Milton J. Rosen Reagents in Mineral Technology, edited by P. Somasundaran and Brij M. Moudgil Wasan, Martin E. Ginn, and Dinesh O. Shah Thin Liquid Films, edited by I.
Ivanov Schechter Botsaris and Yuli M. Scamehorn and Jeffrey H. Harwell Richmond Alkylene Oxides and Their Polymers, F. Bailey, Jr. Koleske Morrow Rubingh and Paul M. Holland Kinetics and Catalysis in Microheterogeneous Systems, edited by M. Grtzel and K. Kalyanasundaram Analysis of Surfactants, Thomas M. Schmitt see Volume 96 Polymeric Surfactants, Irja Piirma Anionic Surfactants: Biochemistry, Toxicology, Dermatology.
Friberg and Bjrn Lindman Defoaming: Theory and Industrial Applications, edited by P. Garrett Wettability, edited by John C. Berg Pugh and Lennart Bergstrm Technological Applications of Dispersions, edited by Robert B. McKay Singer Surfactants in Agrochemicals, Tharwat F. Tadros Solubilization in Surfactant Aggregates, edited by Sherril D. Christian and John F. Scamehorn Stache Prudhomme and Saad A. Khan The Preparation of Dispersions in Liquids, H.
Stein Lomax Nace Emulsions and Emulsion Stability, edited by Johan Sjblom Vesicles, edited by Morton Rosoff Applied Surface Thermodynamics, edited by A. Neumann and Jan K. Spelt Surfactants in Solution, edited by Arun K. Chattopadhyay and K. Mittal Detergents in the Environment, edited by Milan Johann Schwuger Liquid Detergents, edited by Kuo-Yann Lai Rieger and Linda D. Enzymes in Detergency, edited by Jan H. Baas Powdered Detergents, edited by Michael S.
Showell Biopolymers at Interfaces, edited by Martin Malmsten Polymer-Surfactant Systems, edited by Jan C. Kwak Schwarz and Cristian I. Contescu Interfacial Phenomena in Chromatography, edited by Emile Pefferkorn Binks Silicone Surfactants, edited by Randal M. Hill Milling Interfacial Dynamics, edited by Nikola Kallay Adsorption on Silica Surfaces, edited by Eugne Papirer Pastore and Paul Kiekens Volkov Schmitt Detergency of Specialty Surfactants, edited by Floyd E.
Friedli Physical Chemistry of Polyelectrolytes, edited by Tsetska Radeva. Nnanna and Jiding Xia Oxide Surfaces, edited by James A. Wingrave Hackley, P. Somasundaran, and Jennifer A. Lewis Giese and Carel J. Interfacial Electrokinetics and Electrophoresis, edited by ngel V. Delgado Keane Adsorption and Aggregation of Surfactants in Solution, edited by K. Mittal and Dinesh O. Rusling Birikh, Vladimir A. Briskman, Manuel G.
Velarde, and Jean-Claude Legros Colloidal Science of Flotation, Anh V. Nguyen and Hans Joachim Schulze 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 publication, 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 specic advice or recommendations for any specic situation. Trademark notice: Product or corporate names may be trademarks or registered trademarks and are used only for identication and explanation without intent to infringe. ISBN: This book is printed on acid-free paper.
Copyright n by Marcel Dekker. 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, microlming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. The battle cry for sustainable development is persistent in all circles, gaining acceptance, worldwide, as the guiding rationale for activities or processes in the science technologyenvironmenteconomysociety interfaces targeting improvement and growth. Such activities are expected to result in higher standards of living, leading eventually to a better quality of life for our increasingly technology-dependent modern society.
Interestingly, it is not surprising, despite the overall maturity of the consumer market, that detergents continue to advance more rapidly than population growth. The soap and detergent industry has seen great change in recent years, responding to the shifts in consumer preferences, environmental pressures, the availability and cost of raw materials and energy, demographic and social trends, and the overall economic and political situation worldwide.
Currently, detergent product design is examined against the unifying focus of delivering to the consumer performance and value, given the constraints of the economy, technological advancements, and environmental imperatives. The detergent industry is thus expected to continue steady growth in the near future. For the detergent industry, the last decade of the twentieth century has been one of transformation, evolution, and even some surprises e. On both the supplier and consumer market sides both remain intensely competitive , the detergent industry has undergone dramatic changes, with players expanding their oerings, restructuring iii Copyright by Marcel Dekker.
This has resulted in the consolidation of the market, especially in the last several years, and this trend appears to be gaining momentum. This may suggest that the supply of solutions to most cleaning problems confronted by consumers in view of the increasing global demand for a full range of synergistic, multifunctional detergent formulations having high performance and relatively low cost, and the need for compliance with environmentally oriented green regulation, may be based on modications of existing technologies.
What does all this mean for the future of the detergent enterprise? How will advances in research and development aect future development in detergent production, formulation, applications, marketing, consumption, and relevant human behavior as well as short- and long-term impacts on the quality of life and the environment? Since new ndings and emerging technologies are generating new issues and questions, not everything that can be done should be done; that is, there should be more response to real needs rather than wants.
Are all the questions discussed above reected in the available professional literature for those who are directly involved or interested engineers, scientists, technicians, developers, producers, formulators, managers, marketing people, regulators, and policy makers? The Handbook of Detergents is an upto-date compilation of works written by experts each of whom is heavily engaged in his or her area of expertise, emphasizing the practical and guided by a common systemic approach.
The aim of this six-volume handbook Properties, Environmental Impact, Analysis, Formulation, Applications, and Production is to reect the above and to provide readers who are interested in any aspect of detergents a state-of-the-art comprehensive treatise, written by expert practitioners mainly from industry in the eld.
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Thus, various aspects involvedraw materials, production, economics, properties, formulations, analysis and test methods, applications, marketing, environmental considerations, and related research problemsare dealt with, emphasizing the practical in a shift from the traditional or mostly theoretical focus of most of the related literature currently available. The philosophy and rationale of the Handbook of Detergents series are reected in its title, its plan, and the order of volumes and ow of the chapters within each volume.
The various chapters are not intended to be and should not necessarily be considered mutually exclusive or conclusive. Some overlapping facilitates the presentation of the same issue or topic from dierent perspectives, emphasizing dierent points of view, thus enriching and complementing various perspectives and value judgments. There are many whose help, capability, and dedication made this project possible.
The volume editors, contributors, and reviewers are in the front line in this respect. Many others deserve special thanks, including Mr. Russell Dekker and Mr. Joseph Stubenrauch, of Marcel Dekker, Inc. My hope is that the nal result will complement the tremendous eort invested by all those who contributed; you the reader, will be the ultimate judge.
Uri Zoller Editor-in-Chief. Regardless of the state-of-the-art and aairs 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 major concern. This is particularly so given the operating global free-market economy, which is supposed to, and is expected to, ensure sustainable development. This volume is a comprehensive treatise on the multidimensional issues involved, and represents an international industryacademia collaborative eort of over 50 experts and authorities worldwide.
The fate, eects, safety, survival, distribution, biodegradability, biodegradation, ecology, and toxicology of anionic, cationic, and nonionic surfactants Environmental impact and ramications of inorganic detergent builders, chelating agents, bleaching activators, perborates, and other components of detergent formulations Toxicology and ecotoxicology of minor components in personal care detergent formulations Biodegradation of surfactants in sewage treatment plants and in the natural environment Science versus politics in the environment-related regulatory process.
All the above are accompanied and supported by extensive research-based data, occasionally accompanied by a specic representative case study, the derived conclusions of which are transferable. I thank all the contributors who made the realization of this volume possible. Uri Zoller. Rodriguez and D. Holt and K. Thorpe and Charles R. Tarchitzky and Y. Mogensen, and Karl V. Baker, C. Drummond, D. Furlong, and F. Harald P. Jose Luis Berna. Furlong Australia Ester Gorelik F. Grieser Australia. Louis Ho Tan Tai.
Kristine A. Betty B. Rodriguez Alicante, Spain. Susan E. John Solbe. Karen L. Karl V. Peter White Kingdom. The role of science and technology in meeting the sustainable development challenge is obvious and is recognized worldwide by all stake holders. In this context, environmental sciences are emerging as a new multidimensional, crossinterdisciplinary scientic discipline and beyond.
They draw on all the basic sciences to explain the working of the entire complex and dynamic earth systemthe environmentwhich is constantly changing by natural causes and under human impact . At present, they are in a process of moving from a specialized, compartmentalized, sub- disciplinary, unidimensional enterprise into a multidimensional, cross-boundary endeavor in the context of the sciencetechnologyenvironmentsociety STES interfaces .
This poses new challenges with respect to both the intrinsic science and technology organization and performance and the way the relevant generated and 1 Copyright by Marcel Dekker. Ultimately, this would require all involved to operate within an open-ended ideas-oriented culture . In view of the fact that the public, many policymakers, some scientists and engineers, and even some environmental professionals believe that science and technology can solve most pollution problems, prevent future environmental impact, and should pave the way for sustainable development, it is of the utmost importance to recognize the limits of environmental science and technology alone to meet the challenge of sustainable development .
This is because science and technology are useful in establishing what we can do. However, neither of them, or both, can tell us what 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 organizational participants in the STES-economic-political decision-making process [12,6 7,10], particularly in the context of the contemporary stressed ecology imperative.
The detergent industry is deliberate, steady, and mature, so its pattern of change is evolutionary, avoiding drastic step changes.
In spite of gloomy economic forecasts, detergent sales are expected to continue increasing, both in dollar and physical volume, in the rst decade of the new millennium, as new formulations providing better convenience for customers improve the value-added component of the products. Anionic surfactants still dominate world output and consumption, accounting in the United States for about two-thirds of the total, compared with about one-fourth of the nonionic detergents. Although some dierencesas far as market share is concernedare apparent, the general pattern is quite similar worldwide.
Additionally, they contain builders: sequestrants such as carbonates, phosphates, silicates, as well as oxidants and other ingredients. Compared to other industries, the detergent industry recognized rather early the ecological challenge. Its voluntary for the most part switch, in the s from the nonbiodegradable hard anionic, branched-chain dodecylbenzene sulfonate DDBS or ABS: alkyl-benzene sulfonate to the substituting biodegradable linear alkylben-.
The subsequent large-scale preregulation switch from polyphosphates to, mainly, zeolites in laundry and dishwashing formulations is no less impressive.
Since then, the detergent industry worldwide has been constantly confronted by one demand, the minimization commandment: that detergent formulation be the very best that yields the desired eect with the least amount. This demand is quite obvious in view of the fact that surfactants and other components of detergent formulations constitute a signicant portion of municipal sewage water proles.
Ultimately, positive feedbacktype relationships have been developed between environmental concerns and detergent formulation: The higher the public awareness of the former, the higher the environmental acceptability of the latter. Indeed, the current reformulation of detergent products reects the response of the detergent industry to environmental regulatory as well as economic-technological and demographic social factors in an attempt to cope with the increased awareness of environmental concerns, the upswing in action against phosphate builders and the unclear future of other builder systems, the tight sewage treatment requirements, the higher demand for cost performance and added-value compositions associated with lowering of washing temperatures, the increasing share of washload held by synthetic textiles, the increasing demand for liquid formulations, supereective or powdery concentrates, and the pressure of the change in customer habits requiring ecient and convenient 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, with the nonionics gaining most of the increased share; 2 substitution of polyphosphates mainly by zeolites as well as other eective sequestering agents; and 3 higher concentrations of active components in multifunctional formulations eective in low-temperature processes . A major outcome of the foregoing was a three-fold development: 1.
A substantial reduction in the use of polyphosphates in detergent formulations, with concomitant replacement, partially or totally, by zeolites 3. Currently, concern about the environment is leading the detergent industry to develop environmentally friendly products, which are increasingly being sold in recycled packaging material to meet regulatory requirements and satisfy customer demand.
A case in point: the concentrated detergent formulations that are both more powerful and require less packaging material. Thus, in the nal analysis, the new products and modications made within the basic formulations did make a dierence as far as the environment is concerned. This implies the importance of inter- and transdisciplinarity in environmental research [5,15,16], appropriate research methodologies [16,17], as well as strategies for technology assessment in the context of sustainable action.
In-depth systematic examination of these shifts reveals their pertinence and relevance to the systemic challenge of maintaining sustainable relationships as far as detergents and their environmental impact are concerned. What are the implications with respect to sustainable detergent production and consumptionenvironmental relationships?
Ensuring sustainable development requires, to begin with, a radical change in the environmental behavior as well as thinking Environment of individuals, institutions, industry, social organizations, politicians, and governments. This, in turn, requires reconceptualization of long-accepted relevant concepts and beliefs [9,13,14,18]. Thus, for example, the shift from the acceptance of new technologies to facilitating sustainable technologies in responding to society needs is substantially dependent on the shift from peoples or customers wants to peoples needs.
On the other hand, the technological feasibility of the economically and socially healthy shift may carry the seeds of contradiction with the shift from peoples wants to peoples needs if economics is the governing criteria. Similarly, a shift from the conceptualization of environmental science and technology as omnipotent to a recognition of their limits in solving pollution problems, preventing future environmental impact, and paving the way for sustainable development through appropriate design  has its clear implications and consequences as far as detergents and their environmental impact are concerned.
If the foregoing imperative paradigm shifts are about to be realized, then dierent quality criteria for research and practice in the sustainable development environmental context become necessary. This is because not only do methodological disciplinary aspects have to be rethought and reevaluated, but critical questions or issues 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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Sustainable developmentenvironment interrelationship. Technological, economic, and social Sustainable development growth at all cost. Peoples wants Peoples needs. Selection from among available alternatives Generation of alternatives. Environmental ethics Environmental sustainability-oriented pragmatism B. Scientic and technological research and development. Corrective Preventive. Reductionism, i. Compartmentalization Comprehensiveness, holism.
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. Clearly, the application of the identied paradigm shifts in the context of the environmental impact of detergents requires a corresponding paradigm shift in the related conceptualization.
Raising the standard of living equals raising the quality of life? Relying on disciplinary or transdisciplinary science researchbased technology for rational management of the environment and sustainable development. A case in point, to serve as an example: We are committed to meet our customers needs is a currently dominant central concept. A clear distinction between customers wants and customers needs has to be made. The rst led to overconsumption, which is not necessarily benecial to the consumer and, in fact, is perpetually and aggressively being promoted an industry motivated by growth and prots at all cost, with all the uncontrolled socioenvironmental consequences involved.
The latter, however, should be targeted and responded to by a responsible, environmentally concerned detergent industry. Only an orientation to peoples needs has the chance albeit not guaranteed to meaningfully contribute to sustainable development, not only in developing countries emerging markets but also in highly 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 with the existing trend of ever-increasing overconsumption, but in most cases further accelerates the pace of this trend. The environmental consequences of overconsumption are apparent [1,14,18]. With respect to science and technology, virtually any discussion concerning the current and future states of scientic and technological research and problem solving is typied by statements about the importance of enabling researchers and engineers to work seamlessly across disciplinary boundaries and by declarations that some of the most exciting problems, particularly the complex systemic environmental ones, span the disciplines.
Moreover, transdisciplinary applied research evolves from real, complex problems in the interdisciplinary STES context, which are relevant to societies living in dierent environments. Such problems have no disciplinary algorithmic solutions or even resolutions. It is growing increasingly dicult to establish the transdisciplinary basis necessary for addressing complex environmental problems [1,13,17]. Therefore, the challenge for this kind of target-oriented research and technology development is to develop problem-solving methodologies that not only integrate dierent qualities and types of knowledge, but also envision researchers and engineers as an integral nonobjective insiders part of the investigated, or to be remediated corrected , system.
Sustainable development via appropriate environmental management and industrial production, formulation, marketing, and business policies is, thus, highly dependent on transdisciplinary research and development in the STES context. This will facilitate transfer beyond the specic subject s or discipline s and, consequently hopefully , a higher success in coping with previously unencountered complex problem situations [13,17].
However, the prevention approach to ensure environmental quality and restoration of ecosystems requires, most of all, appropriate and responsible environmental behavior and action on the part of both producers and customers, which, in turn, is contingent on an adequate environmental education . This implies an urgent need for strengthening the social and educational components within the corrective-to-preventive paradigm shift process concerning the sustainable management of, and maintaining system-sustainable relationships in, our environment.
The expected resultant critical thinking and interdisciplinary transfer capabilities mean rational, logical, reective, and evaluative thinking in terms of what to accept or reject and what to believe in, followed by a decisionwhat to do or not to do about it and responsible action-taking. Thus, any meaningful response to meet the challenge of sustainable development requires transdisciplinarity, essentially by denition, that is, the development and implementation of policies and cross-disciplinary methodologies, which can lead to the changes in behaviorof individuals, industries, organizations, and governmentsthat will allow development and growth to take place within the limits set by ecological imperatives.
The educational challenge is rather clear. It is a precondition for the required reconceptualization, which, in turn, will ensure sustainable development and growth. The detergent industry is a representative case in point; e. The sociobehavioral consumption economics and environmental links are apparent. Four recent pertinent publications, two more general and two more specic, deal with the surfactantsenvironmenthealth relationship issue and can serve to illustrate the importance of reconceptualization in the context of the environmental systems challenge that we are confronting.
It is claimed that since major environmental pollutants are coming under the control of regulatory authorities, this part of ecotoxicology is more or less completed, although there is still work, not expected to call for major scientic innovation and discovery, remaining to be done. It is concluded that the merger between ecotoxicology and ecology would give rise to a new science, stress ecology, at the crossroads of ecology, genomics, and bioinformatrics .
Given that the public, many policymakers, and some environmental professionals believe that science and technology can solve most pollution problems,. EPA and recommends that no further testing is needed and that the EPA agreed that there is no need for further studies . Do the apparent dierent approaches to a similar although, obviously, not identical environmental issue in the detergentenvironmentsustainable relationships context represent dierent contradictory?
This question and the response to it remain open. Most problems and issues boil down to: Who does what, for what, at what price, at the expense of whom or what , and in what order of priorities? The widely agreed-upon call for sustainable development requires rational hard choices to be made between either available or to-be-generated options .
This poses an even greater challenge to science, technology, and education for sustainability, whatever that means. This is so because dealing eectively and responsively with complex interdisciplinary problems within complex systems in the context of STES interfaces requires evaluative thinking and the application of value judgment by technologically, environmentally, and sociologically i.
This implies an urgent need to strengthen the HOCS-promoting components of STES-oriented education within the corrective-to-preventive paradigm shift process concerning the sustainable management of our environment [1,10,22]. The expected resultant critical thinking and interdisciplinary transfer capabilities mean a 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 taking responsible action accordingly.
Thus, any meaningful response. 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 Gods creation but, rather, changeable, people-made, and people-controlled will take care of. Rather, we are dealing with an array of very complicated problems within a complex system, the components of which are natural, man-made, and human environments and their related subsystems. Most of these problems have no right solutions denitely not algorithmic , but rather resolutions that can be worked out via the use of appropriate methodologies, simultaneously guided by a sustainable development oriented value system.
Can we meet the systemic challenge of sustainable detergentsenvironment relationships? The evolutionary pattern of change in the deliberate and steady detergent industry can serve as a test case for a reasonable response, by taking a historical perspective: the switch from DDBS to LABS, the continuing use of the potentially estrogenic? Whether or not each of these is consonant with the new sustainable developmentoriented criteria and in line with the paradigm 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 act accordingly and take responsibility, each in her or his environmentally related milieu. This Part B of the Handbook of Detergents: Environmental Impact deals, from dierent perspectives, with the relevant issues involved.
Zoller, U. Glaze, W. Gibbons, M. Higher Educ. Negroponte, N. Huesemann, M. Schnoor, J. Van Straalen, N. Scholz, R. Pikering, A. Bill, A. Keiny, S. Reisch, M. News, Apr 12; They belong to that group of consumer products that are indispensable for the maintenance of cleanliness, health, and hygiene.
It has been said that the amount of soap consumed in a country is a reliable measure of its civilization. The increase in per capita consumption of soap and detergents in various countries was found to correlate well with life span. Cleanliness is essential to our well-being. A clean body, a clean home, and a clean environment 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 the last century the synthetic detergents, followed by more complex washing and cleaning products, were the blessed way to get it.
The use of soaps and detergents always led to a signicant contribution to the modern quality of life, the close environment always being part of this. However, in the past 50 years a new dimension to this obvious positive symbiosis has been imposed, and a long-unnished detergentsenvironment debate opened.
At the outset of the new millenium, the detergent industry is focused on coping with four challenges: economics, safety and environment, technology, and consumer requirements. The products must not just meet consumer needs for quality and ecacy, but must be dangerous neither to manufacture nor to use and must in no way have a detrimental impact on the users health.
The products and their packaging should 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 growing environmental concern, a change of attitude toward the washing process has taken place in many countries.
Nowadays, the consumption of energy, water, and chemicals 11 Copyright by Marcel Dekker. As a consequence, new raw materials, washing processes, laundry practices, and cleaning technologies have been developed, with the common challenge to use carefully the limited resources of the earth, to exploit the renewable ones, and to prevent environment pollution as much as possible. The development of surfactants and detergents over the past decades has been aected tremendously by their environmental acceptability. The challenge for the future is to meet the most modern risk assessment approaches.
The aim of this chapter is to review this detergentsenvironment interrelated development frame throughout history. First, surfactants and phosphates, as the main components of detergent formulations and cleaning products, have been the subject of longstanding and ongoing detergent regulation and legislation. Second, ecient management has been imposed on sewage treatment, which is being updated continuously. During the washing process, detergent components are released to the wastewater stream, to become a potentially undesirable troublemaker in sewage treatment plants and in the environment.
Wastewaters vary considerably in composition and concentration and hence in their environmental impact. These dierences are geographically dependent and arise partly due to dierences in laundry habits and soil levels and partly to the composition and amount of the detergent used. The environmental impact further depends on the specic ecological requirements and public awareness in each particular geographical area.
Also, household wastewater, generated mainly from laundry and personal care products, diers from that from industrial and institutional outlets. Typical sewage treatment systems in countries with developed environmental protection include intensive biochemical and physical degradation processes that bring about the elimination of the pollutants.
The extent of elimination depends on sludge levels, aeration ecacy, and residence time. In addition to bacterial metabolic reactions, physicochemical processes, such as adsorption on sewage sludge, contribute to the reduction of pollutant levels . Variations in sludge loading and in peak loads of the wastewater are moderated considerably by the predilution of household wastewater in the public sewage system. Wastewater from industrial sources is generally pretreated by pH adjustment and physical separation in on-site sewage plant prior to discharge to municipal sewage treatment plants.
Sometimes a well-designed treatment plant on an industrial site may permit direct discharge. The sewage treatment euents are discharged in the surface waters. Quality requirements for these euents depend upon the intended use of the surface waters. The ultimate use, such as for drinking water, agriculture, or recreation, also governs. Phosphorous and nitrogen elimination normally require additional treatment steps. The sewage treatment euent is diluted in surface waters.
The dilution factor varies according to the geographical place. Human waste and some remaining traces of surfactants in the surface waters are further biologically treated by a self-cleaning process . However, the most signicant parameter is the direct measurement of the pollutant levels, mainly surfactant and phosphate concentrations. Highly sensitive analytical test methods have been developed for the accurate determination of surfactant concentration [3,4].
Anionic surfactants are determined as methylene blueactive substances MBAS by a method based on a modied Epton two-phase titration. Nonionic surfactants are determined as bismuth-active substances BiAS after passage through cation and anion exchange columns. Strict implementation of detergent regulations combined with eective sewage treatment hes led to low surfactant concentrations in large rivers, such as those in the Rhine, which currently are as follows : Anionic surfactants, about 0.
It has taken some 40 years to reach the present state from the time when rivers all over began to foam and gave rise to the First Detergent Law. Foam on rivers was increasing, and tap water, drawn from wells located close to household discharge points, also tended to foam. In , Germany encountered similar diculties when foam formed on German rivers and stable foam layers developed downstream from dams.
The sewage treatment of the time, based on physicochemical separations and some biological treatment, was not able to cope with the surfactant load. The impact on sewage treatment was immediate and signicant. The ecacy of the sedimentation. The few biological sewage treatment plants operating with an activated sludge process collapsed, producing foam layers several meters high above the aeration tanks.
Increased surfactant concentrations were found not only in sewage waters and rivers, but also, as a result of soil inltration, in the groundwater. As a result, the drinking water supply was contaminated. The anionic surfactant content of drinking water from the Ruhr River increased to as much as 1. During , increasing surfactant consumption in the United States led to similar ecological problems. It was soon understood that these serious problems for water management were due to the poor biodegradation prole of DDBS.
The abnormal quantities of foam were attributed to the presence of DDBS, which, in turn, was the result of incomplete biodegradation of propylene-based alkylbenzenesulfonates by the natural bacteria present in euents. The branched-chain structure of alkylbenzene seemed to hinder attack by the bacteria. Supporting evidence for this judgment was provided by the facile degradation of fatty alcohol sulfates and soap. Both are derived from straightchain fatty acids, suggesting that a straight-chain, linear alkylbenzene might also be degradable. However, a directive provided a dynamic test method according to a specied test protocol only for control of anionic surfactants.
During the short time between mid and , known as the conversion period, the foaming problems in surface waters and sewage treatment were solved. The eects of the conversion to biodegradable surfactants were. The conversion from hard to soft surfactants was also legislated during in the United States, as amendments to the Federal Water Pollution Control Act, creating new water pollution control standards . However, none of these measures was implemented. Similar regulations and voluntary agreements were put into place during the late s and early 70s in several countries of Western Europe and in Brazil and Japan.
LABS was made commercially available in The manner in which the DDBS problem was solved is an excellent example of environmental improvements achieved by cooperation of government, industry, and science. However, the detergent industry faced advantages and disadvantages. The change to LABS oered better detergency in heavy-duty formulations and lower cloud points and viscosities in pastes and slurries. But, on the other hand, while a lower viscosity in slurries oered an advantage for a spray-dry process, the liquid and paste LABS detergent of lower viscosity looked less appealing to the consumer.
Also, the LABS powders became sticky and were less free owing . It was found that the actual isomer distribution of the linear alkylate has an eect on the stickiness of the powder, identifying the 2-phenyl isomer as giving the greatest tendency to stickiness. The dierent phenyl isomers are obtained when, during alkylation, the benzene molecules attach to the dierent carbons along the alkyl chain. For instance, an attachment at the second carbon of the alkyl chain gives a 2phenyl isomer.
It was found that the phenyl isomer distribution depends on the catalyst used during alkylation. This catalytic versatility in LAB production, as well as additives further developed, overcame most of the formulation problems.. However, in the case of solid laundry bars the lower viscosity and the less bulky molecular structure of LABS provided a softer bar hardness and a stickier appearance. Surfactant Biodegradation Biodegradation is the process by which microorganisms in the environment convert complex materials into simpler compounds that are used as food for energy and growth.
Biodegradation of the surfactants used in detergents is important because of the large volumes used worldwide and, of course, the detrimental toxic eects on the aqueous and soil environments. Biodegradation is a multistep process that starts with the transformation of the parent 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 the linear alkylbenzenesulfonate LAS biodegradation path in Figure 1 . A good understating of past and present biodegradation issues requires precise denitions of biodegradability terms [5,10,11]. Primary biodegradability is the change in the chemical structure of an organic substance, resulting from a biological action that causes the loss of the specic chemical and physical properties of the substance. When this stage of biodegradation is reached, the remaining material is no longer a surfactant; it no longer has any surface-active properties, including the ability to foam.
Ultimate biodegradability in the presence of oxygen aerobic conditions represents the total level of degradation by which a test substance is consumed by microorganisms to produce carbon dioxide, water, mineral salts, and constituents of microbe cells biomass. Ready biodegradability is an arbitrary classication for chemical compounds that satisfy immediate biodegradability tests. The severity of the tests biodegradation and acclimation time ensures that such compounds will degrade quickly and completely in an aquatic environment under aerobic conditions.
Anaerobic biodegradability: Most biodegradation processes take place in the presence of oxygen aerobic conditions.
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However, biodegradation also proceeds in the absence of oxygen in anaerobic environments, albeit at slower rate. Anaerobic media are known as either anoxic in which the rate of oxygen consumption exceeds the rate of oxygen diusion or strictly anaerobic in which the oxygen is totally absent. Because of concerns about the presence of detergent ingredients in all parts of the environment, anaerobic biodegradability has been proposed as the criterion for several Eco-label requirements. Experimentally, LAS was found to pose no risk to anaerobic environments .
Separation of anionics and nonionics from a detergent com-. The disappearance of the specic analytical species corresponds to the loss of signcant ecological surface activity. Concurrently with the legal biodegradability requirements, specic test methods for measurement of biodegradability of synthetic anionic and nonionic surfactants in laundry detergents and cleaners were elaborated and approved. They are based mainly on the quantity of consumed oxygen and the disappearance of dissolved organic carbon DOC.
In , two biological tests were approved and mandated by the OECD Organization for Economic Cooperation and Development for establishing biodegradability [13,14]: 1. If the level of biodegradability is lower or if the results are in about, a subsequent Conrmatory Test is required.
The results of this are decisive and denitive. The revised edition of this directive was ocially implemented in . The OECD screening test is based on a static shake ask method and corresponds to surface water conditions. The measurements are made at xed intervals up to 19 days. The OECD Conrmatory Test, known also as simulation test, is a continuous procedure run under more realistic environmental conditions, simulating activated sludge plants, as shown in Figure 2 . The Conrmatory Test can simulate several types of environment, such as lake, sea, and land, and can be run under aerobic or anaerobic conditions conditions .
After inoculation of the test system and growth of the activated sludge, an acclimation period is run, following a predetermined procedure. After a minimum 14 days, the degradation rate reaches a plateau for readily biodegradable surfactants, while an irregular curve, with ups and downs of low biodegradation rate, is shown by hard surfactants. This initial period is followed by a day evaluation period in which the high-biodegradation-rate plateau is maintained by the readily biodegradable substance. From Ref. In this test two units are run in parallel. Typical results are presented in Table 1 .
Effect of Surfactant Regulation on Sewage and Surface Water Load The implementation of the surfactant regulation solved most of the signicant ecological problems in Europe, the United States, and Japan with respect to residual concentration of surfactants in sewage euents and surface waters. The order of magnitude of the contribution of laundry detergents and other cleansing agents to the sewage surfactant load in Germany in has been documented comprehensively [1,18,19].
This estimate was based on a liter daily water consumption per capita and took into account the detergent production in Germany as , tons. These gures translate into a Based on production volumes of , tons of anionic, 91, tons of nonionic, and 26, tons of cationic surfactants, the daily per capita consumption of each group has been calculated as 6. These gures lead to a calculated average concentration of The surfactant concentration in municipal sewage has been checked analytically and found to correspond on average to the theoretical calculated values.
Comprehensive and well-documented data based on extensive investigation of measuring points for anionic surfactants and 20 measuring points for nonionic surfactants were summarized in the late s for the main German rivers. The average concentrations were as follows : Anionic surfactants: V0. The Rhine Water Quality Report of took note of these remarkable improvements and clearly positioned them as an interim results in the Environmental Protection Program of the German Federal Government. The pragmatic decision of the early s on the manner of solving the surfactant issue served as the model for this interdisciplinary Environmental Protection Program, which was announced in and fully achieved its dened waters goals in the late s .
Several other reports measured water concentrations of LAS during the two decades, nding them in good agreement with model predictions [6,20]. Extensive references and documented reviews have been published on biodegradation of surfactant in dierent water media. A few selected examples are noted next. For Members. For Librarians. RSS Feeds. Chemistry World. Education in Chemistry.
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