Introduction to Green Chemistry PDF

ISBN: 0-8247-0411-8 This book is printed on acid-free paper. Headquarters Marcel Dekker, Inc. 270 Madison Avenue, New York, NY 10016 tel: 212-696-9000; fax: 212-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-261-8482; fa...

ISBN: 0-8247-0411-8 This book is printed on acid-free paper. Headquarters Marcel Dekker, Inc. 270 Madison Avenue, New York, NY 10016 tel: 212-696-9000; fax: 212-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-261-8482; fax: 41-61-261-8896 World Wide Web http://www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities. For more information, write to Special Sales/Professional Marketing at the headquarters address above. Copyright © 2001 by Marcel Dekker, Inc. All Rights Reserved. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit): 10 9 8 7 6 5 4 3 2 1 PRINTED IN THE UNITED STATES OF AMERICA Preface This book is intended for chemists, chemical engineers, and others who want to see a better world through chemistry and a transition from its present unsustainable course1 to a sustainable future.2 (A sustainable future is one that allows future gen- erations as many options as we have today.) It is meant to serve as an introduction to the emerging field of green chemistry— of pollution prevention. It is based on a one-semester three-credit course3 given at the senior–graduate level interface at the University of Delaware each year from 1995 to 1998. Books and courses in environmental chemistry usually deal with contaminants that enter air, water, and soil as a result of human activities: how to analyze for them and what to add to the smokestack or tailpipe to eliminate them. They are also concerned with how to get the contaminants out of the soil once they are there. Because texts such as those by Andrews et al.,4 Baird,5 Crosby,6 Gupta,7 Macalady,8 Manahan,9 and Spiro and Stigliani10 cover this area adequately, such material need not be repeated here. Green chemistry11 avoids pollution by utilizing processes that are “benign by design.” (The industrial ecology12 being studied by engineers and green chemistry are both parts of one approach to a sustainable future.) Ideally, these processes use nontoxic chemicals13 and produce no waste, while saving energy and helping our society achieve a transition to a sustain- able economy. It had its origins in programs such as 3M’s “Pollution Prevention Pays.” It was formalized in the United States by the Pollution Prevention Act of 1990. Since then, the U.S. Environmental Protection Agency and the National Science Foundation have been making small grants for research in the area. Some of the results have been summarized in symposia organized by these agencies.14 This book cuts across traditional disciplinary lines in an effort to achieve a holistic view. The material is drawn from in- organic chemistry, biochemistry, organic chemistry, chemical engineering, materials science, polymer chemistry, conserva- tion, etc. While the book is concerned primarily with chemistry, it is necessary to indicate how this fits into the larger soci- etal problems. For example, in the discussion of the chemistry of low-emissivity windows and photovoltaic cells, it is also pointed out that enormous energy savings would result from incorporating passive solar heating and cooling in building de- sign. Living close enough to walk or bike to work or to use public transportation instead of driving alone will save much more energy than would better windows. (Two common criticisms of scientists is that their training is too narrow and that they do not consider the social impacts of their work.) This book begins with a chapter on the need for green chemistry, including the toxicity of chemicals and the need for min- imization of waste. The next three chapters deal with the methods that are being studied to replace some especially noxious materials. Chapters 5–8 cover various ways to improve separations and to reduce waste. Chapter 9 continues this theme and switches to combinations of biology and chemistry. Chapter 10 discusses many optical resolutions done by enzymes or whole cells. Chapter 11, on agrochemicals, continues the biological theme. Chapters 12 through 15 cover various aspects of sustainability, such as where energy and materials will come from if not from petroleum, natural gas, or coal; how to pro- mote sustainability by making things last longer; and the role of recycling in reducing demands on the natural resource base. The last three chapters try to answer the question that arises at nearly every meeting on green chemistry: Why is it taking so long for society to implement new knowledge of how to be green? The topics within these chapters are not confined to specific areas. For example, cyclodextrins are discussed not only un- der supported reagents, but also under separations by inclusion compounds or under chemistry in water. Surfactants have iii iv Preface been placed under doing chemistry in water. They are also mentioned as alternatives for cleaning with organic solvents and in the discussion on materials from renewable sources. An effort has been made to cross-reference such items. But for the reader who has any doubt about where to find an item, a comprehensive index is included. The industrial chemistry on which much green chemistry is based may be foreign to many in academia, but many good references are available.15 There is much more emphasis in industrial chemistry on catalysis and the organometallic mech- anisms that often go with them. Improved catalysts are often the key to improved productivity, using less energy and gener- ating less waste.16 Again, many good sources of information are available.17 In addition, there are two books on the chem- istry and biology of water, air, and soil.18 Each chapter in Introduction to Green Chemistry lists recommended reading, consisting primarily of review papers and portions of books and encyclopedias. This allows detailed study of a subject. The introductions to current journal articles often contain valuable references on the status of a field and trends in research. However, the traditional grain of salt should be applied to some news items from trade journals, which may be little more than camouflaged advertisements. The examples in the book are drawn from throughout the world. In the student exercises that accompany each chapter, readers are often asked to obtain data on their specific location. In the United States, one need look no further than the local newspaper for the results of the toxic substances release inventory. This data can also be found on websites of the U.S. En- vironmental Protection Agency (http://www.epa.gov/opptintr/tri) and state environmental agencies,19 as well as on compa- rable websites of other countries (e.g., http:// www.unweltbundesamt.de for the German environmental agency). Non- governmental organizations also post some of this data (e.g., the Environmental Defense “Chemical Scorecard,” www.scorecard.org, and the Committee for the National Institute for the Environment, www.cnie.org). The data available on the Internet is growing rapidly.20 The environmental compliance records of more than 600 U.S. companies can be found at http://es.epa.gov/oeca/sfi/index.html. A catalog of U.S. Environmental Protection Agency documents can be found at http://www.epa.gov/ ncepihom/catalog.html. Data on the toxic properties of chemicals can be found at toxnet.nlm.nih.gov and http:// www.chemquik.com. Some of the exercises sample student attitudes. Others call for student projects in the lab or in the community. Some of the questions are open-ended in the sense that society has yet to find a good answer for them, but they leave room for dis- cussion. Those using this volume as a textbook will find field trips helpful. These might include visits to a solar house, a farm us- ing sustainable agriculture, a tannery, a plant manufacturing solar cells, etc. Although the course at the University of Delaware had no laboratory, one would be useful to familiarize students with techniques of green chemistry that they might not encounter in the regular courses. These might include the synthesis, characterization, and evaluation of a zeolite, running a reaction in an extruder, using a catalytic membrane reactor, adding ultrasound or microwaves to a reaction, making a chem- ical by plant cell culture, doing biocatalysis, making a compound by organic electrosynthesis, running a reaction in super- critical carbon dioxide, and use of a heterogeneous catalyst in a hot tube. Ideally, students would run a known reaction first, then an unknown one of their own choice (with appropriate safety precautions). Such a lab would require the collaboration of several university departments. There is a myth that green chemistry will cost more. This might be true if something was to be added at the smokestack or outlet pipe. However, if the whole process is examined and rethought, being green can save money. For example, if a pro- cess uses solvent that escapes into the air, there may be an air pollution problem. If the solvent is captured and recycled to the process, the savings from not having to buy fresh solvent may be greater than the cost of the equipment that recycles it. If the process is converted to a water-based one, there may be additional savings. It is hoped that many schools will want to add green chemistry to their curricula. Sections of this book can be used in other courses or can be used by companies for in-house training. The large number of references makes the book a guide to the lit- erature for anyone interested in a sustainable future. Albert S. Matlack REFERENCES 1. J. Lubchenko, Science, 1998, 279, 491. 2. (a) R. Goodland and H. Daly. Ecol. Appl., 1996, 6, 1002. (b) A. Merkel, Science, 1998, 281: 336. 3. A.S. Matlack, Green Chem, 1999, 1(1): G17. 4. J.E. Andrews, P. Brimblecombe, T.D. Jickells, P.S. Liss, eds. Introduction to Environmental Chemistry. Blackwell Science, Cam- bridge, MA 1995. Preface v 5. C.L. Baird, Environmental Chemistry, W.H. Freeman, New York, 1995. 6. D.G. Crosby, Environmental Toxicology and Chemistry, Oxford University Press, New York, 1998. 7. R.S. Gupta, Environmental Engineering and Science: An Introduction, Government Institutes, Rockville, MD, 1997. 8. D.L. Macalady, Perspectives in Environmental Chemistry, Oxford University Press, Oxford, England, 1997. 9. S.E. Manahan, Environmental Chemistry, 6th ed., Lewis Publishers, Boca Raton, FL, 1994; Fundamentals of Environmental Chem- istry, Lewis Publishers, Boca Raton, FL, 1993. 10. T.C. Spiro, W.M. Stigliani, Chemistry of the Environment, Prentice Hall, Upper Saddle River, NJ, 1996. 11. J. Clark, Chem Br, 1998, 34(10): 43. 12. (a) B. Hileman, Chem Eng News, July 20, 1998, 41; (b) J. Darmstadter, Chem Eng News, August 10, 1998, 6; (c) N.E. Gallopou- los, Chem Eng News, August 10, 1988, 7; (d) T.E. Graedel, B.R. Allenby, Industrial Ecology, 1995; Design for Environment, 1996; Industrial Ecology and the Automobile, 1996, all from Prentice Hall, Paramus, NJ. (e) B.R. Allenby, Industrial Ecology: Policy Framework and Implementation, Prentice Hall, Paramus, NJ, 1998. 13. A.W. Gessner, Chem. Eng. Prog., 1998, 94(12), 59. 14. (a) Anon., Preprints ACS Div. Environ Chem, 1994, 34(2), pp. 175–431. (b) P.T. Anastas, C.A. Farris, eds. Benign by Design: Al- ternative Synthetic Design for Pollution Prevention, ACS Symp. 577, Washington, D.C., 1994; (c) P.T. Anastas, T.C. Williamson, eds. Green Chemistry: Designing Chemistry for the Environment, ACS Symp 626, Washington, D.C., 1996; (d) S.C. DeVito, R.L. Garrett, eds. Designing Safer Chemicals: Green Chemistry for Pollution Prevention, ACS Symp. 640, Washington, D.C., 1996; Chemtech, 1996, 26(11):34. (e) J.J. Breen, M.J. Dellarco, eds. Pollution Prevention in Industrial Processes: The Role of Process An- alytical Chemistry, ACS Symp. 508, Washington, D.C., 1994. (f) P.T. Anastas, T.C. Williamson, eds. Green Chemistry: Frontiers in Benign Chemical Syntheses and Processes, Oxford University Press, Oxford, England, 1998. 15. (a) W. Buchner, R. Schliebs, G. Winter, K.H. Buchel, Industrial Inorganic Chemisty, VCH, Weinheim, 1989; (b) K. Weissermel, H.-J. Arpe, Industrial Organic Chemistry, 3rd ed., VCH, Weinheim, 1997. (c) P.J. Chenier, Survey of Industrial Chemistry, 2nd ed., VCH, Weinheim, 1992; (d) H. Wittcoff, B. Reuben, Industrial Organic Chemicals, 2nd ed., John Wiley, New York, 1996; (e) J.I. Kroschwitz, ed. Kirk-Othmer Encyclo Chem Technol, 4th ed., John Wiley, 1991; (f) J.I. Kroschwitz, ed. Encyclo Polymer Sci and Eng, 2nd ed., John Wiley, New York, 1985–1989; (g) W. Gerhartz, ed., Ullmann’s Encyclo Ind Chem, 5th ed., VCH, Weinheim, 1985. 16. J. Haber, Pure Appl Chem, 1994, 66: 1597 17. (a) J.N. Armor, Environmental Catalysis, A.C.S. Symp. 552, Washington, D.C., 1993; (b) G.W. Parshall, S.D. Ittel, Homogeneous Catalysis, 2nd ed. John Wiley, New York, 1992; (c) B.C. Gates, Kirk-Othmer Encyclo Chem Technol, 4th ed., 1993, 5, 320; (d) W.R. Moser, D.W. Slocum, eds., Homogeneous Transition Metal-Catalyzed Reactions, Adv Chem 230, American Chemical Society, Washington, D.C., 1992; (e) J. P. Collman, L. S. Hegedus, Principles and Applications of Organotransition Chemistry, University Science Books, Mill Valley, CA, 1980; (f) C. Elschenbroich, A. Salzer, Organometallics—A Concise Introduction, VCH, Weinheim, 1992; (g) G. Braca, Oxygenates by Homologation or CO Hydrogenation with Metal Complexes, Kluwer Academic Publishers, Dor- drect, The Netherlands, 1994; (h) F.P. Pruchnik, Organometallic Chemistry of the Transition Elements, Plenum, NY, 1993. 18. (a) J. Tolgyessy, ed., Chemistry and Biology of Water, Air, Soil—Environmental Aspects, Elsevier, Amsterdam, 1993; (b) B. Evan- gelou, Environmental Soil and Water Chemistry, Wiley, NY, 1998. 19. A. Kumar, R. Desai, R. Kumar, Environ. Prog., 1998, 17(2), S11. (gives a directory of World Wide Web sites) 20. (a) S.M. Bachrach, ed., The Internet: A Guide for Chemists, American Chemical Society, Washington, D.C., 1996; (b) T. Murphy, C. Briggs-Erickson, Environmental Guide to the Internet, Government Institutes, Rockville, MD, 1998; (c) K. O’Donnell, L. Winger, The Internet for Scientists, Harwood, Amsterdam, 1997; (d) L.E.J. Lee, P. Chin, D.D. Mosser, Biotechnol. Adv., 1998, 16: 949; (e) B.J. Thomas, The World Wide Web for Scientists and Engineers, SAE International, Warrendale, PA, 1998; (f) S. Lawrence, C.L. Giles, Science, 1998, 280: 98; (g) R.E. Maizell, How To Find Chemical Information: A Guide for Practicing Chemists, Edu- cators and Students, Wiley, NY, 1998. Contents Preface iii 1. INTRODUCTION 1 I. General Background 1 II. Toxicity of Chemicals in the Environment 2 III. Accidents with Chemicals 6 IV. Waste and Minimization 13 V. Conclusions 18 VI. Summary of Some Important Points 19 References 20 Recommended Reading 25 Exercises 25 2. DOING WITHOUT PHOSGENE 27 I. Introduction 27 II. Preparation of Isocyanates 28 III. Polycarbonates 39 IV. Summary and Conclusions 39 References 42 Recommended Reading 45 Exercises 45 3. THE CHLORINE CONTROVERSY 47 I. The Problem 47 II. Toxicity of Chlorine Compounds 50 III. Estrogen Mimics 51 IV. Bleaching Paper 52 V. Disinfecting Water 53 VI. Chlorofluorocarbons and Ozone Depletion 54 VII. Chlorinated Solvents 57 VIII. Syntheses Where the Chlorine Is Not in the Final Product 58 vii viii Contents IX. Summary and Conclusions 60 References 61 Recommended Reading 66 Exercises 66 4. TOXIC HEAVY METAL IONS 67 I. The Problem 67 II. End-of-the-Pipe Treatments 70 III. Biocides 72 IV. Catalysts for Reactions Other than Oxidation 74 V. Dyes and Pigments 75 VI. Electrical Uses 76 VII. Leather 77 VIII. Metal Finishing 77 IX. Oxidation 78 X. Miscellaneous 94 References 94 Recommended Reading 101 Exercises 101 5. SOLID CATALYST AND REAGENTS FOR EASE OF WORKUP 101 I. Introduction 103 II. The Use of Inorganic Supports 105 III. Ion-Exchange Resins 114 IV. Combinatorial Chemistry 118 V. Other Uses of Supported Reagents 120 VI. Cyclodextrins 126 References 128 Recommended Reading 135 Exercises 135 6. SOLID ACIDS AND BASES 137 I. Introduction 137 II. Polymeric Sulfonic Acids 138 III. Polymer-Supported Lewis Acids 139 IV. Sulfated Zirconia 140 V. Supported Metal Oxides 141 VI. Rare Earth Triflates 141 VII. Solid Bases 144 VIII. Zeolites and Related Materials 145 IX. Clays 155 X. Heteropolyacids 159 References 163 Recommended Reading 173 Exercises 173 7. CHEMICAL SEPARATIONS 175 I. The General Picture 175 II. Inclusion Compounds 178 Contents ix III. Separation of Ions 182 IV. Membrane Separations 185 References 192 Recommended Reading 200 Exercises 200 8. WORKING WITHOUT ORGANIC SOLVENTS 201 I. Advantages and Disadvantages of Solvents 201 II. Working Without Solvents 203 III. Reactions in Extruders 207 IV. Carbon Dioxide as a Solvent 210 V. Water as a Reaction Medium 214 VI. Surfactants and Cleaning 220 VII. Coatings 223 References 228 Recommended Reading 229 Exercises 229 9. BIOCATALYSIS AND BIODIVERSITY 241 I. Biocatalysis 241 II. Biodiversity 267 References 275 Recommended Reading 288 Exercises 288 10. STEREOCHEMISTRY 291 I. The Importance of Optical Isomers 291 II. The Chiral Pool 292 III. Resolution of Racemic Mixtures 295 IV. Asymmetric Synthesis 301 References 314 Recommended Reading 318 Exercises 318 11. AGROCHEMICALS 319 I. The Nature and Use of Agrochemicals 319 II. Problems with Agrochemicals 322 III. Alternative Agriculture 326 IV. Lawns 345 V. Genetic Engineering 346 VI. Integrated Pest Management 347 References 348 Recommended Reading 358 Exercises 358 x Contents 12. MATERIALS FOR A SUSTAINABLE ECONOMY 361 I. Introduction 361 II. Commodity Chemicals from Renewable Raw Materials 361 III. Use of Natural Polymers 372 IV. Polymers from Renewable Raw Materials 374 V. Conclusions and Recommendations 379 References 379 Recommended Reading 385 Exercises 385 13. CHEMISTRY OF LONGER WEAR 387 I. Why Things Wear Out 387 II. Stabilizers for Polymers 389 III. Lubrication, Wear, and Related Subjects 395 IV. Inhibition of Corrosion 397 V. Mending 400 VI. Miscellaneous 400 VII. The Future 401 References 401 Recommended Reading 405 Exercises 405 14. CHEMISTRY OF RECYCLING 407 I. Waste 407 II. Recycling 408 III. Methods and Incentives for Source Reduction 424 IV. The Overall Picture 431 References 432 Recommended Reading 440 Exercises 440 15. ENERGY AND THE ENVIRONMENT 441 I. Energy-Related Problems 441 II. Heating, Cooling, and Lighting Buildings 449 III. Renewable Energy for Electricity and Transport 454 IV. Use of Less Common Forms of Energy for Chemical Reactions 462 References 466 Recommended Reading 478 Exercises 479 16. POPULATION AND THE ENVIRONMENT 481 I. The Problems 481 II. Chemistry of Human Reproduction 483 III. The Chemistry of Family Planning 485 IV. Summary of the Problem 491 Contents xi References 492 Recommended Reading 495 Exercises 495 17. ENVIRONMENTAL ECONOMICS 497 I. Introduction 497 II. Nature’s Services 497 III. Environmental Accounting 499 IV. Corporations 503 V. Environmental Economics of Individuals 505 VI. Government Actions Affecting Environmental Economics 507 References 511 Recommended Reading 515 Exercises 515 18. GREENING 517 I. Introduction 517 II. Individuals 517 III. Nongovernmental Organizations 519 IV. Government 521 V. Corporations 523 References 529 Recommended Reading 534 Exercises 534 Index 535 1 Introduction This chapter will consider what is toxic, what is waste, why brown pelican. Rachel Carson was one of the first to call at- accidents occur, and how to reduce all of these. tention to this problem.2 Now that these insecticides have been banned in the United States, the species are recover- I. GENERAL BACKGROUND ing. Some are still made and used in other countries, but may return to the United States by long range aerial transport In the glorious days of the 1950s and 1960s chemists envi- (e.g., from Mexico). (Compounds applied to plants, build- sioned chemistry as the solution to a host of society’s ing surfaces, and such, may evaporate and enter the atmo- needs. Indeed, they created many of the things we use to- sphere where they may remain until returned to the ground day and take for granted. The discovery of Ziegler–Natta at distant points by rain or by cooling of the air.3) DDT is catalysis of stereospecific polymerization alone resulted in still made in Mexico, China, India, and Russia. A global major new polymers. The chemical industry grew by leaps treaty to ban these persistent pollutants is being sought.4 and bounds until today it employs about 1,027,000 workers It was also not appreciated that these compounds and in the United States.1 Some may remember the duPont slo- other persistent highly chlorinated compounds, such as gan, “Better things for better living through chemistry.” In polychlorinated biphenyls (PCBs), can act as estrogen the Sputnik era the scientist was a hero. At the same time, mimics. Some surfactants such as those made from doctors aided by new chemistry and antibiotics, felt that in- alkylphenols and ethylene oxide are also thought to do this, fectious diseases had been conquered. although perhaps to a lesser extent. The effects are now Unfortunately, amid the numerous success stories were showing up in populations of native animals, raising ques- some adverse outcomes that chemists had not foreseen. It tions about possible effects in humans.5 A program is being was not realized that highly chlorinated insecticides such as set up to screen 86,000 commercial pesticides and chemi- DDT [1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane] cals for this property.6 (1.1), also known as dichlorodiphenyltrichloroethane Thalidomine (1.2) was used to treat nausea in pregnant (made by the reaction of chloral with chlorobenzene) would women from the late 1950s to 1962. It was withdrawn from bioaccumulate in birds. This caused eggshell thinning and the market after 8000 children in 46 countries were born nesting failures, resulting in dramatic population declines in with birth defects.7 species such as peregrine falcon, bald eagle, osprey, and 1.1 1.2 1 2 Chapter 1 The compound has other uses as a drug as long as care is people think that chemicals are bad and “all natural” is bet- taken not to give it to pregnant women. In Brazil it is used ter, even though a lot of them do not know what a chemical to treat leprosy. Unfortunately, some doctors there have not is. There is a feeling that scientists should be more respon- taken the warning seriously enough and several dozen de- sible for the influence of their work on society. Liability formed births have occurred.8 The U. S. Food and Drug Ad- suits have proliferated in the United States. This has caused ministration (FDA) has approved its use for treating painful at least three companies to declare bankruptcy: Johns inflammation of leprosy.9 It also inhibits human immunod- Manville for asbestos in 1982, A. H. Robins for its “Dalkon eficiency virus (HIV) and can prevent the weight loss that Shield” contraceptive device in 1985, and Dow Corning for often accompanies the acquired immunodeficiency syn- silicone breast implants in 1995.14 Doctors used to be the re- drome (AIDS). Celgene is using it as a lead compound for spected pillars of their communities. Today they are the sub- an anti-inflammatory drug and is looking for analogues with jects of malpractice suits, some of which only serve to in- reduced side effects.10 The analogue below (1.3) is 400–500 crease the cost of health care. Medical implant research is times as active as thalidomide. threatened by the unwillingness of companies such as Chlorofluorocarbons were developed as safer alterna- duPont and Dow Corning to sell plastics for the devices to tives to sulfur dioxide and ammonia as refrigerants. Their the implant companies.15 The chemical companies fear lia- role in the destruction of the ozone layer was not antici- bility suits. Not long ago drug companies became so con- pated. Tetraethyllead was used as an antiknock agent in cerned about law suits on childhood vaccines that many gasoline until it was learned that it was causing lead poi- were no longer willing to make them. Now that the U. S. soning and lowering the IQ in children. We still have not Congress has passed legislation limiting the liability, vac- decided what to do with the waste from nuclear power cine research is again moving forward. The law suits had not plants that will remain radioactive for longer than the stimulated research into vaccines with fewer side effects, United States has been in existence. Critics still question but instead had caused companies to leave the market. the advisability of using the Yucca Mountain, Nevada, site. They say that the finding of 36Cl from atomic bomb tests in II. TOXICITY OF CHEMICALS IN THE the 1940s at the depth of the repository indicates that sur- ENVIRONMENT face water can get into this site.11 Doctors did not anticipate the development of drug-re- The public’s perception of toxicity and risk often differs sistant malaria and tuberculosis. The emergence of Legion- from that found by scientific testing.16 The idea that “natu- naire’s disease, Lyme disease, AIDS, Hantavirus, and ral”17 is better than “chemical” is overly simplistic. Many Ebola virus was not anticipated. Most drug companies are chemicals found in nature are extremely potent biologi- still unwilling to tackle tropical diseases because they fear cally. Mycotoxins are among these.18 Aflatoxins (1.4) were that the poor people afflicted with the diseases will not be discovered when turkeys fed moldy ground nut (peanut) able to pay for the drugs.12 meal became ill and died. They are among the most potent Today, there is often a public suspicion of scientists. carcinogens known. Some picture the mad chemist with his stinks and smells. Vikings went berserk after eating derivatives of lysergic There is a notion of some people “that science is boring, acid (1.5) made by the ergot fungus growing on rye. conservative, close-minded, devoid of mystery, and a neg- Some Amanita mushrooms are notorious for the poisons ative force in society.”13 Chemophobia has increased. Many that they contain. A Japanese fish delicacy of globe fish or 1.3 1.4 Introduction 3 1.7 prohibition with a special law that permits the use of this ar- tificial sweetener. It is now thought to be a carcinogen for rodents, but not for humans. Almost every tube of tooth- 1.5 paste in the United States contains it. An advisory panel of the U. S. National Toxicology Program recommends that it be classed as an “anticipated” human carcinogen.21 other fishes may contain potent poisons (such as Some Americans feel that food additives are an impor- tetrodotoxin; 1.6) if improperly prepared.19 Tainted fish tant source of cancer, and that the Delaney clause should be cause death in 6–24 h in 60% of those who consume it. retained. Bruce Ames, the father of the Ames test for mu- They die from paralysis of the lungs. Oysters may also con- tagens, disagrees.22 He feels that the very high doses of tain poisons acquired from their diet. The extract of the chemicals that are fed to rats to speed up the tumor-form- roots of the sassafras tree (Sassafras albidum) (1.7) used to ing process may bear little relation to reality. He feels that flavor the soft drink, “root beer,” contains the carcinogen this protocol alone may cause some of the tumors. Analyt- safrole, which must be removed before use. ical chemists are able to detect much smaller amounts of The natural insecticide Sabadilla, which is popular with contaminants in foods today than in 1958. A new technique organic farmers, contains 30 alkaloids present at a level of of accelerator mass spectrometry with 14C-labeled com- 3–6% in the seeds of Schoenocaulon officinale.235 It can af- pounds offers promise in testing at much closer to the real fect the cardiovascular system, respiration, nerve fibers, levels consumed.23 Is there a level below which a carcino- and skeletal muscles of humans. Gastrointestinal symp- gen affords no risk? A single mutation can lead to cancer. toms and hypotension may also result from its ingestion. However, Abelson has pointed out that mutations occur all The U. S. Congress added the Delaney clause to the the time and are eliminated by the normal DNA repair Food, Drug, and Cosmetic Act in 1958.20 The clause reads mechanisms.24 He feels that these cover both natural and “No additive shall be deemed to be safe if it is found to in- synthetic compounds. Thus, the usual type of dose–re- duce cancer when ingested by man or animal, or if it is sponse curve should apply here as well. Ames, Abelson, found, after tests which are appropriate for the evaluation of and others felt that the zero risk called for by the Delaney the safety of food additives, to induce cancer in man or an- clause had outlived its usefulness and should be replaced imal.” It does not cover natural carcinogens in foods or en- by a negligible risk standard.25 The Delaney clause was re- vironmental carcinogens, such as chlorinated dioxins and pealed on August 3, 1996.26 polychlorinated biphenyls. The Delaney clause was used to Ames feels that, instead of worrying so much about the ban saccharin in 1973, but the U. S. Congress overrode this last traces of contaminants in foods, we should focus our at- tention on the real killers. Annual Preventable Deaths in the United States27 Active smoking 430.700 Alcoholic beverages 100,000 Passive smoking 53,000 Auto accidents 43,300 AIDS 37,500 Homicides 24,926 Fires 3,200 Cocaine 4,202 Heroin and morphine 4,175 Radon, to nonsmokers 2,500 1.6 4 Chapter 1 The World Health Organization (WHO) estimates the Antioxidants have also reduced athersclerotic heart dis- number of smoking deaths worldwide to be about 3 ease.40 Thus, foods contain many protective substances, as million/y.28 Cigarette use is increasing among American well as some antinutrients, such as enzyme inhibitors and college students, despite these statistics.29 Indoor radon natural toxins.41 contributes to about 12% of the lung cancer deaths in the A U. S. National Research Council report concludes that United States each year.30 Infectious diseases cause 37% of natural and synthetic carcinogens are present in human all deaths worldwide.31 Many of these could be prevented foods at such low levels that they pose little threat.42 It by improved sanitation. There are 3 million pesticide poi- points out that consuming too many calories as fat, protein, sonings, including 220,000 fatalities and 750,000 chronic carbohydrates, or ethanol is far more likely to cause cancer illnesses, in the world each year. Smoke from cooking with than consuming the synthetic or natural chemicals in the wood fires kills 4 million children in the world each year. diet. However, it also mentions several natural substances It is estimated that perhaps 80% of cancers are environ- linked to increased cancer risk: heterocyclic amines formed mental in origin and related to lifestyle. (There are genetic in the overcooking of meat; nitrosoamines, aflatoxins, and factors, now being studied by the techniques of molecular other mycotoxins.43 Typical of the heterocyclic amine mu- biology, that predispose some groups to heightened risk, tagens are compounds 1.9 and 1.10, the first from fried beef e.g., breast cancer in women.32) In addition to cancers and the second from broiled fish:44 caused by tobacco and ethanol, there are those caused by a Two reviews cover the incidence of cancer and its pre- high fat diet,33 too much sun, smoked foods, foods pre- vention by diet and other means.45 Cancer treatments have served with a lot of salt, and viruses (for cancers of the liver had little effect on the death rates, so that prevention is the and cervix). Consumption of the blue–green alga, Micro- key.46 cystis, has increased liver cancer in China. Perhaps the Being sedentary is a risk factor for diseases such as heart biggest killer is sodium chloride, a compound necessary for attack and late-onset diabetes. One-third of adult Ameri- life, that plays a role in the regulation of body fluids and cans are obese, perhaps as much the result of cheap gaso- blood pressure.34 It raises the blood pressure of many of the line as the plentiful supply of food.47 Obesity-related com- 50 million Americans with hypertension, increasing the plications result in 300,000 premature deaths in the United risk of osteoporosis, heart attack, and stroke.35 The U. S. States each year. This is less of a problem in most other National Academy of Sciences suggests limiting consump- countries. For example, the incidence of obesity in the tion of sodium chloride to 6 g/day (2.4 g of sodium). This United Kingdom is 15–16.5%. means cutting back on processed foods (source of 80% of Prevention of disease is under-used.48 Needle ex- the total), such as soups, frozen dinners, salted snacks, change programs could prevent 17,000 AIDS infections in ham, soy sauce (18% salt), ready-to-eat breakfast cereals, the United States each year. Vaccines are not used and others. However, this may not be the whole story. If there is an adequate intake of calcium, magnesium, and potassium, together with fruits and vegetables in a low-fat diet, the sodium may not need to be reduced, as shown in a 1997 study.36 In the United States, snacks and soft drinks have tended to supplant nutrient-rich foods, such as fruits, vegetables, and milk. Not eating fruits and vegetables poses a greater cancer risk than the traces of pesticides in foods.37 Fruits and vegetables often contain natural antiox- idants,38 such as the resveratrol (1.8) found in grapes. It in- hibits tumor initiation, promotion and progression.39 1.9 1.8 1.10 Introduction 5 enough. For example, only 61% of the people in Mas- sachusetts are fully vaccinated. Only 15–30% of the el- derly, immunocompromised persons, and those with pul- monary or cardiac conditions have been vaccinated against pneumonia. A 1998 study, in New Jersey and Quebec, of patients older than 65 who had been pre- scribed cholesterol-lowering drugs found that on the aver- 1.11 age the prescription went unfilled 40% of the year. Good drug compliance lowered cholesterol level 39%, whereas medicine. These were all tested carefully for safety and ef- the poor compliance lowered it only 11%.49 ficacy, and provided in consistent standardized amounts, Many persons take unnecessary risks by using alterna- before acceptance by conventional medicine. The National tive, rather than conventional, medicine. Although some of Institues of Health Office of Dietary Supplements in the it works (e.g., a Chinese herbal medicine for irritable bowel United States has an international database at http://di- syndrome), much of it is ineffective.50 The use of herbal etary/supplements.info.nih.gov. See also www.amfounda- extracts and dietary supplements may help some people, tion.org/herbmed.htm. but many such materials are ineffective and may be dan- An additional note of caution must be added to this gerous.51 One lot of “Plantago” contained digitalis that sent discussion. Tryptophan, (1.11) an essential amino acid for two people to hospital emergency rooms with heart block- humans, was sold in health food stores as a sleeping pill.54 age. Cases of central nervous system depression and heavy It was taken off the market in 1989 after a lot made by a metal poisoning have also been reported. One child died new microorganism at Showa Denko caused an outbreak of while being treated by herbal extracts in a case where con- a rare blood disease that killed 39 people.55 Although the ventional medicine might have saved her life. Of 260 Asian material was 99% pure, it contained over 60 trace patent medicines bought in California stores, 83 contained contaminants. undeclared pharmaceuticals or heavy metals, and 23 con- The deadly contaminants compounds 1.12 and 1.13 tained more than one adulterant. Tests of ten brands of St. were present at about 0.01%. The moral is to test products John’s Wort, a popular herbal antidepressant, found that from new processes on animals first. Some samples of two had 20% of the potency listed on the label, six had over-the-counter 5-hydroxy-L-tryptophan contained impu- 50–90%, and two had 30–40% more than that listed.52 The rities that caused eosinophila–myalgia syndrome.56 problem is that the U. S. Dietary Supplement Health and Another sad saga resulted from the sale, by itinerant Education Act of 1994, said to have been passed by strong salesmen in Spain, of aniline-denatured rapeseed oil for industry lobbying, does not allow the Food and Drug Ad- cooking.57 The toxic oil syndrome affected 20,000 people ministration to regulate these materials. Herbal extracts are killing 839. The toxic compound is thought to have been also used in many other countries.53 The most research on compound 1.14. them has been done in Germany, where the Bundesinstitut Research on the long-term effects of low-level pollution fur Arzneimittel und Medizinproduckte regulates them continues. Air pollution by ozone, sulfur dioxide, and par- more effectively than is done in the United States. Many of ticulates in Britain kills 24,000 people annually.58 It is es- the drugs used by conventional medicine originated in folk timated that exposure to diesel exhaust over a 70-year life- time will cause 450 cases of cancer per million people in California.59 Epidemiologists continue to investigate clus- ters of diseases such as the two to four times higher inci- dence of neural tube and certain heart defects in children born within 1⁄4 mile of Superfund sites in California,60 the lower birth weight and prematurity of infants born to 1.12 1.13 6 Chapter 1 Ethanol 10.6 g/kg for young rats; 7.6g/kg for old rats Malathion 1.0 g/kg for female rats; 1.375 g/kg for male rats Glyphosate 4.873 g/kg for rats; 1.568 g/kg for mice HCN Average fatal dose for a human; 50–60 mg Aflatoxin 18.2 mg/50 g body weight day-old 1.14 duckling Acetone 10.7 ml/kg orally for rats This test probably would not pick up long-term effects women living next to the Lipari landfill in New Jersey,61 caused by bioaccumulation. Populations of animals can the brain cancers in researchers at the Amoco laboratory in also be decimated by chemical effects that do not kill the Napierville, Illinois and at the University of Maine,62 and a animals (e.g., the egg shell thinning of birds at the top of the cancer cluster near a Superfund site at Toms River, New food chain, feminization of males, and behavioral changes, Jersey. A U. S. General Accounting Office report suggests such as not feeding or protecting the young, or losing the that the list of the Superfund sites may have to be doubled ability to avoid predators). because of ground and drinking water contamination.63 Many chemists alive today have worked with com- Some persons may have multiple chemical sensitivities to pounds later found to be carcinogens, neurotoxins, and so low levels of pollutants.64 on. All chemicals need to be treated with due respect.74 Children are more sensitive to chemicals than adults.65 Childhood cancer and asthma are both rising. Pregnant women who smoke tend to have more low birth weight ba- III. ACCIDENTS WITH CHEMICALS bies and those who drink alcoholic beverages risk fetal al- cohol syndrome. Environmental standards are often set us- Chemists take pride in their ability to tame dangerous ing a statistical approach.66 The U. S. Environmental chemicals to make the things society needs. In fact, some Protection Agency sets pesticide limits at 1% of the level companies seek business by advertising their ability to do found to have no effects in animals. A 1996 law to protect custom syntheses with such chemicals. Aerojet Fine Chem- children may lower this level another tenfold. Some pesti- icals offers syntheses with azides and vigorous oxida- cide makers have gone to tests of pesticides on adult hu- tions.75 Carbolabs offers custom syntheses with phosgene, mans in the United Kingdom, presumably in an effort to fluorinating agents, and nitration. Custom syntheses with obtain higher limits.67 Some people consider this unethical. phosgene are also offered by PPG Industries, Hatco, Chemical safety is an international challenge.68 Complete Rhone-Poulenc, and SPNE (see Chap 2). A hazardous health effects data are available for only about 7% of the reagent may be attractive for fine chemical syntheses if it chemicals produced in more than 1 million lb annually.69 gives a cleaner product with less waste or saves two or The U. S. Environmental Protection Agency and the Amer- three steps. It may also be used because it is the traditional ican Chemistry Council (formerly the Chemical Manufac- way of doing the job. turers Association) have reached an agreement to test 3000 Chemistry is a relatively safe occupation. (Underground chemicals in an effort to speed up the work being done by coal mining is one of the most dangerous in the United the OECD in Europe. At first the Synthetic Organic Chem- States. A total of 47 coal miners lost their lives in 1995 ical Manufacturers Association did not agree with the way from surface and underground mining.76) In the United that this testing will be done,70 but agreed to it later. Ani- States in 1996, the nonfatal injury and illness rate for chem- mal rights activists have objected to the tests because ani- ical manufacturing was 4.8:100 full-time workers, com- mals will be used in at least some of the testing.71 pared with 10.6 for all of manufacturing. There were 34 Green chemistry chooses less toxic materials over more deaths in the chemical industry, about 5% of those for all toxic ones and tries to minimize the use of flammable, explo- manufacturing.77 The injury rate of the chemical industry sive, or highly reactive materials.72 It is not always easy to fig- in the United Kingdom fell to an all time low in 1997, 0.37 ure out which is least toxic. Toxicities can vary with the accidents per 100,000 h. This was in the middle of those for species as well as with the age and sex of the animal. The man- manufacturing industries, worse than the textile industry, ner of application may also vary. This is illustrated in the fol- but better than the food, beverage, and tobacco industries.78 lowing by some LD50 (50% of the animals die) data on chem- However, despite countless safety meetings and inspec- icals that are not very toxic and some that are very toxic.73 tions and safety prizes, accidents still happen.79 In chem- Introduction 7 istry, just as in airline safety, some of the accidents can be At the time of the accident, a refrigeration system, a tem- quite dramatic. There were 23,000 accidents with toxic perature indicator, and a flare tower were not functioning.87 chemicals in the United States in 1993–1995 (i.e., 7670/yr Curiously, the Maharashtra Development Council (in the compared with 6900/yr in 1988–1992. The accidents in state next to the one in which Bhopal is located) advertised 1993–1995 included 60 deaths and the evacuation of in 1998 41,000 people. Statistics for the United States compiled by the Chemical Safety and Hazard Investigation Board reveal... The strengthening of the green movement and an average of 1380 chemical accidents resulting in death, the growing protests against environmental pollution injury, or evacuation each year for the 10 years before in many Western countries provide an opportunity 1999.80 Each year, these accidents caused an average of for India to emerge as a major player in the global 226 deaths and 2000 injuries. About 60,000 chemical acci- dye market. Given the global tendency to take full dents are reported annually in the United States. The Amer- advantage of lower labor costs and less stringent ican Chemistry Council in the United States reported 793 effluent legislation, India has a competitive fires, explosions, and chemical releases in 1995.81 advantage.88 There is usually an investigation to determine the cause of an accident. Knowing the cause should help eliminate There have been 17 chemical releases that have ex- similar accidents in the future. Then engineering steps may ceeded Bhopal in volume and toxicity. Fortunately, their be taken to produce a fail-safe system. These may involve locations and weather conditions prevented disasters such additional alarms, interlocks (such as turning off the mi- as Bhopal. In 1994, failure of a storage tank at Occidental crowaves before the oven door can be opened), automatic Chemical allowed as much as 500 lb of chlorine to escape shut-offs if any leaks occur, and secondary vessels that through a hole the size of a filing cabinet.89 Fortunately, air would contain a spill. A special sump contained a leak of currents did not carry the cloud of chlorine over Delaware nerve gas when an O-ring failed at an incinerator at Tooele, City, about a mile away, or New Castle, Delaware, a few Utah.82 Underground storage tanks (made of noncorroding miles to the north. (Chlorine was used as a war gas in materials) may be fitted with a catchment basin around the World War I.) fill pipe, automatic shut-off devices to prevent overfilling, The explosion of the nuclear reactor at Chernobyl and a double wall complete with an interstitial monitor.83 (spelling changed recently to Chornobyl) in the Ukraine on Clearly, such methods can work, but they have not reduced April 26, 1986 sent radioactive material as far away as the overall incidence of accidents, as shown in the forego- Sweden.90 The current death toll is 45. There has been a ing data. The best solution will be to satisfy society’s needs huge increase in childhood thyroid cancer, with cases as far with a minimum of hazardous chemicals.84 A few of the as 500 km away.91 (U. S. bomb tests have also increased many accidents will be discussed in the following to show the incidence of thyroid cancers in the western United how and why they occurred, together with some green ap- States.92) There is a 30-km exclusion zone around the plant where no one is allowed to live. This was created by the proaches that could eliminate them. evacuation of 135,000 people.93 The accident is said to The chemical industry received a wake-up call for im- have happened “because of combination of the physical proved safety when 40 tons of methyl isocyanate escaped characteristics of the reactor, the design of the control rods, from a pesticide plant into a densely populated area of human error and management shortcomings in the design, Bhopal, India on Dec. 3, 1984. This resulted in 3500 deaths and implementation of the safety experiment.” and 150,000 injuries.85 According to one reviewer86 the The world’s worst radioactive contamination (twice that accident of Chernobyl) is at Mayak in Russia. This has resulted from explosion of a radioactive waste storage unit on September... was the ultimate outcome of faulty technolog- 29, 1957 and deliberate dumping of liquid waste into the ical design, years of poor management of an unprof- Techa River in 1949–1956.94 itable and highly dangerous facility, years of ignor- Although no nuclear plants in the United States have ex- ing an outrageously bad safety record on the part of ploded, there have been some scary incidents. The near both the parent company and the Indian government, melt-down at Three Mile Island, near Harrisburg, Pennsyl- inadequate education and training of the work force, vania, involved a faulty valve. At the Salem, New Jersey, uncontrolled growth of an industrial population cen- nuclear plants there have been “repetitive equipment prob- ter, a nonexistent emergency response system and the lems and personnel errors,” the latter including manually community’s ignorance about the dangers in its overriding safety alarms.95 The Nuclear Regulatory Com- midst. mission shut down all three units at the site in 1995 for “re- 8 Chapter 1 peated failures in their preventive maintenance programs” tional Safety and Health Administration (OSHA) fined according to an ex-employee.96 Fines of more than 700,000 the company 4 million dollars. Accidents of this type can dollars have been imposed on the utility.97 The corporate happen anywhere in the world where the petrochemical culture was said to be “production, production, produc- industry is located. There have been explosions in an tion.” A company official said, “We had a lackadaisical, ethylene plant at Beijing, China,111 at a Shell air separa- casual approach.”98 They were restarted after 2 years, pre- tions plant in Malaysia,112 a Shell ethylene and propylene sumably after the problems had been corrected. Since then, plant in Deer Park, Texas,113 a Shell propylene plant in there have been outages due a leak when an operator ex- Norco, Louisiana,114 at a BASF plant in Ludwigshafen, ceeded the design pressure for a coolant system and prob- Germany, that used pentane to blow polystyrene,115 and at lems with a water intake system.99 In the last two decades a Texaco refinery at Milford Haven, England.116 The these power plants have operated only 52% of the time, problems at the BASF plant might have been avoided by putting them among the 10 worst of the 110 nuclear plants blowing the polystyrene with nitrogen or carbon dioxide, in the United States. The U. S. General Accounting Office instead of pentane. Two weeks before this incident at the has questioned the effectiveness of the Nuclear Regulatory BASF plant, four people were injured by a fire from a Commission in regulating such plants.100 This is the second leak of benzene.117 BASF had two other accidents in Oc- largest commercial generating station in the United States. tober 1995, a polypropylene fire in Wilton, England, and At the Peach Bottom nuclear plant in southeastern Penn- spraying of a heat transfer fluid over the plant and adja- sylvania, an operator was found fast asleep. Federal labo- cent town in Ludwigshafen, Germany.118 There was an ratories in the United States have also had problems: ex- explosion in the hydrogenation area of the company’s 1,4- plosion of a solution of hydroxylamine nitrate in dilute butanediol plant in Geismar, Louisiana, on April 15, nitric acid at the Hanford plant in Richland, Washington 1997.119 It resulted from internal corrosion of a hydrogen (nearly identical with earlier ones at other federal facili- line. This corrosion might have been detected by periodic ties)101; a series of safety problems, including an explosion, nondestructive testing with ultrasound. The explosion and at Los Alamos, New Mexico102; and a series of seven inci- fires at the Texaco refinery have been attributed to mak- dents, including equipment problems, leading up to the clo- ing modifications in the plant, but not training people on sure of the High Flux Isotope Reactor Facility at Oak how to use them, having too many alarms (2040 in the Ridge, Tennessee.103 The Oak Ridge problems included, plant), insufficient inspection of the corrosion of the “Communication among all parties is inadequate and inef- equipment, not learning from past experience, and re- fective”; “inattention to detail”; a “significant lack of trust duced operator staffing.120 Investigation of an explosion and respect”; “high levels of frustration”; and too much pa- and fire at Shell Chemical’s Belpre, Ohio, thermoplastic perwork. New nuclear plants104 are no longer being built in elastomer plant revealed that the United States, but large numbers are being planned for [A]t the time of the accident, roughly seven times East Asia.105 France generates 75% of its electricity from the normal amount of butadiene had inadvertently nuclear energy. There has been an increase in the incidence been added to the reactor. Alarms indicated that the of leukemia within a 35-km radius of a nuclear waste-re- reactor had been overcharged, but interlocks were processing plant at La Hague on the Normandy coast.106 manually overridden to initiate the transfer of raw Electricity need not be generated by nuclear power. materials into the reactor vessel, contrary to estab- Generating it from fossil fuels contributes to global warm- lished procedures.121 ing. Producing it from renewable sources, such as wind, wave power, hydropower, geothermal, and solar energy The federal government fined the company 3 million does not (see Chap. 15). Sweden has voted to phase out nu- dollars for the various citations in relation to the acci- clear energy. The German government has agreed to phase dent.122 Hoechst is another company that has had repeated out the country’s 19 nuclear reactors.107 It has been esti- problems: “a serious pollution problem” at Griesheim, Ger- mated that offshore wind power sources could produce many in 1993, as well as “seven major incidents, mostly in electricity 40% more cheaply than the nuclear power sta- Europe, between January 1995 and June 1996,” including tions planned for Japan.108 Energy conservation can help a leaks of acrylic acid and a fire and explosion in an acetic great deal in reducing the amount of energy needed. acid plant at Clear Lake, Texas; a fire in a 2-ethylhexanol The flammable gases used by the petrochemical indus- plant in Oberhausen, Germany; and problems with the try have been involved in many accidents.109 A fire and methanol plant in Edmonton, Alberta, Canada.123 explosion following a leak of ethylene and isobutane from The difference between a minor incident and a major ac- a pipeline at a Phillips plant in Pasadena, Texas, in 1989, cident with fatalities may depend on the amount of wind at killed 23 people and injured 130.110 The U. S. Occupa- the time and whether or not a spark or a welding torch, Introduction 9 which can ignite the mixture, is nearby. A switch from a A leak in the hydrogen cyanide unit at a Rohm & Haas, base of petroleum and natural gas to renewable resources Deer Park, Texas plant, sent 32 workers to the hospital.132 would eliminate many of these types of accidents. The use Presumably, the hydrogen cyanide was being used to react of more paper and fewer plastics will help (e.g., paper bags with acetone in the synthesis of methyl methacrylate. An at supermarkets). Plastics made by biocatalysis [e.g., alternative route that does not use hydrogen cyanide is poly(lactic acid) and poly(3-hydroxybutyrate)] can be used available.133 Isobutylene is oxidized catalytically to instead of polypropylene. Plastics made from proteins from methacrolein, then to methacrylic acid, which is esterified corn, milk, or soybeans may be able to replace many of with methanol to give methyl methacrylate. The those derived from petrochemicals. Acetic acid can be pro- methacrolein can also be made by the hydroformylation of duced by fermentation, rather than by the reaction of propyne, although this does involve the use of toxic carbon methanol with carbon monoxide (a toxic gas).124 It may be monoxide and flammable hydrogen.134 These processes a nuisance to have to mop up a leak or spill in a fermenta- also eliminate the ammonium bisulfate waste from the pro- tion plant, but it is unlikely that there will be any fire or ex- cess using hydrogen cyanide. A leak of hydrogen fluoride plosion (see Chaps. 9 and 12). at a Marathon Petroleum plant in Texas City, Texas, sent Investigation of the causes of accidents should help pre- 140 people to the hospital for observation and treatment of vent recurrence of the same types, but this does not seem to inflamed eyes and lungs and caused the evacuation of 3000 work in some cases. An explosion killed 4 employees and more.135 Replacement of the hydrogen fluoride with a non- injured 18 others at a Terra Industries, Port Neal, Iowa, fer- volatile solid acid would eliminate such problems (see tilizer plant.125 The Iowa fire marshall blamed an over- Chap. 6). Many companies in the United Kingdom do not heated pump, which recirculated ammonium nitrate solu- store hazardous materials correctly, which has resulted in tion, that was left running during a shutdown of the unit. It some fires and explosions.136 caused water to evaporate, allowing the ammonium nitrate Stern government warnings are not enough to prevent to crystallize.126 The Environmental Protection Agency such releases. ICI spilled 704 lb of ethylene dichloride, in (EPA) investigation concluded that the explosion resulted July 1996, and 331,000 lb of chloroform, in April 1996, at from a lack of written, safe operation procedures. “In the its Runcorn plant near Liverpool, England. Other leaks at days and weeks just prior to the explosion equipment fail- the plant involved mercury, trichloroethylene, and hex- ures and maintenance problems were chronic.”127 Ammo- achlorobenzene.137 The company promised the British En- nium nitrate has been involved in other major catastro- vironment Agency that it would prevent spills in the future. phes.128 An explosion at Oppau, Germany, in September Then, on June 4, 1997, a leak of titanium tetrachloride 1921 killed 1000 people. The shock was felt 145 miles caused the closure of a nearby road for 2 h, and on June 5, away. A “terrific explosion” of two freighters loading am- 1997, an oil spill occurred at another site. The Environment monium nitrate containing 1% mineral oil killed 512 peo- Agency shut down the titanium dioxide plant saying, “It is ple, including many in chemical plants adjacent to the outrageous that, within weeks of ICI being called to a meet- dock.129 Ammonium nitrate is used primarily as a fertilizer. ing with the Agency, where it promised to clean up its act, It can be replaced by crop rotations involving nitrogen-fix- its plants have been involved in two further leaks.”138 ing legumes, spreading animal manure on fields, and fewer Abnormal events (i.e., the unforseen) can lead to acci- lawns (see Chap. 11). dents. The Napp Industries Lodi, New Jersey plant was de- An explosion at a Sierra Chemical explosives plant in stroyed by an explosion and fire on April 21, 1995, while Nevada on January 7, 1998, killed four workers and in- doing toll manufacturing. Five workers were killed, dozens juried three others. The explosion occurred when an oper- injured, and 400 nearby residents evacuated.139 A line ator turned on a mixing pot motor causing detonation of ex- feeding benzaldehyde into a mixture of aluminum powder plosives that had solidified on standing overnight. and sodium hydrosulfite plugged. In trying to clear the Investigation by the newly activated Chemical Safety and blockage workers inadvertently introduced some water. Hazard Investigation Board130 found that the training of They went home at 7:30 PM. No more was done until 6:00 workers had been conducted “primarily in an ineffective, AM when the morning shift arrived. Although they blan- informal manner that overrelied on the the use of on-the- keted the reaction with nitrogen, continuing build-up of job training.... Management believed that, short of using heat led to the explosion at 8:00 AM. The U. S. Occupa- a blasting cap, it was almost impossible to detonate the ex- tional Safety and Health Administration fined the company plosive materials they used or produced.”131 127,000 dollars for 18 alleged safety and health violations These examples show that even though companies have that involved “multiple mistakes and mismanagement.”140 a great deal of experience in handling hazardous materials, An abnormal event in a biocatalysis plant would not cause accidents can still occur. This includes toxic gases as well. such problems (see Chap. 9). 10 Chapter 1 Human error is a factor in many accidents. A 5:00 AM, lease of sulfur trioxide from General Chemical’s Augusta, fire at a poly(vinyl chloride) pipe plant in Samson, Al- Georgia, plant on November 17, 1998, sent 90 people to abama, resulted in evacuation of 2500 residents within a 2- the hospital with eye, nose, and lung irritation. This ex- mile radius.141 It was caused by a 40-gal mixing vat over- ceeded a worse-case scenario that had been prepared for heating when the heater was left on overnight by mistake. the plant.150 These reagents are often used to make deter- This accident might have been avoided by putting the gents. The use of alkyl polyglycoside detergents, which heater on a timer. A better solution would be to blow the are made from sugars and fats, would reduce or eliminate polymer with an inert gas, such as nitrogen or carbon the need for these reagents. dioxide. An October 23, 1992, release of 2.5 tons of unburned Add to these accidents the oil spills from ships, such as hydrocarbons, mainly butadiene, from an extinguished the Exxon Valdez in 1989, that lost 11 million gal of heavy flare at an Oxy Chem plant in Corpus Christi, Texas, re- crude oil into Prince William Sound in Alaska.142 Major sulted in an out-of-court settlement of a class action lawsuit spills have also occurred off of Ireland, France, Japan, for 65.7 million dollars by nearby residents with health Scotland, and Spain. In February 1996, a spill of 65,000 complaints.151 A jury in New Orleans, Louisiana, awarded tons occurred off of Wales.143 This, plus plant accidents at damages of 3.4 billion dollars for a fire that resulted when Hoechst in the same month and the problem of disposing of a tank car carrying butadiene caught fire in September an obsolete oil platform, have resulted in a proposed set of 1987. The fire caused the evacuation of more than 1000 Integrated Pollution Prevention Control rules in Europe. nearby residents.152 A fire occurred at the University of Opinions differ on how long it takes these marine ecosys- Texas on October 19, 1996, destroying a laboratory.153 It tems to recover. Duck, murre, and sea otter populations in was caused by pouring a solvent into which sodium had Alaska may take years to recover.144 Measures suggested been cut, down the drain, the reaction of remaining traces by the U. S. Oil Pollution Act of 1990 to minimize future of sodium with water igniting the mixture. The six-alarm spills include double-hulled ships, tug escort zones for tight fire was the tenth incident in the building which involved passages, and tanker-free zones for critical areas. To these the Austin Fire Department since February 1992. Under might be added minimum training requirements for the pressure from the Fire Department, the university will crews. Exxon now employs the following preventive mea- spend 30.2 million dollars to bring the building up to cur- sures in Prince William Sound.145 rent fire safety standards. Tugs escort tankers. More than 44 million Americans live or work near The U. S. Coast Guard follows traffic with radar. places that pose risks from the storage or use of dangerous Reduced speeds are used. industrial chemicals.154 The cost of accidents may be more Traffic restrictions are tighter in bad weather. than just a monetary one to the company. A fire and ex- Better equipment and training have made it safer to miss plosion occurred on July 4, 1993, in a Sumitomo Chemi- icebergs. cal plant in Niihama, Japan, that made over half of all the A harbor pilot assists navigation. epoxy-encapsulation resin for semiconductor chips used in The use of alcohol and drugs is prohibited and random the entire world. Cutting off the supply would have been a testing is done. serious inconvenience to the customers. The company took In 1991, 235 oil spills were reported in the Port of the unusual step of letting other companies use its tech- Philadelphia, Pennsylvania.146 Canada has 12 spills a day nology until it could rebuild its own plant, so that a supply of which 9 are due to oil.147 A crewman’s mistake on a crisis never developed. The company still supplied 50% of tanker released 18,000 gall of tetrachloroethylene into the the world’s requirements for that resin in 1999.155 shrimp-fishing grounds near Port O’Connor, Texas, in Why do these accidents continue to happen? One critic 1996.148 says, Accidents can be very expensive, not just in plant re- placement costs, but also compensation to victims (as Hourly workers struggle to maintain production in well as lost profits from lost sales). When operators at the face of disabled or ignored alarms, undocu- General Chemical’s Richmond, California, plant over- mented and often uncontrollable bypasses of estab- heated a railroad tank car, a safety relief valve sent fum- lished components, operating levels that exceed de- ing sulfuric acid over the area. More than 20,000 people sign limits, postponed and severely reduced sought medical treatment. Five freeways and several turnaround maintenance and increasing maintenance rapid-transit stations closed. A fund of 92.8 million dol- on ‘hot’ units by untrained, temporary non-union lars has been set up to compensate the victims.149 A re- contract workers.156 Introduction 11 Another source mentions “institutional realities that under- is setting up a Risk Management Program that will require cut corporate safety goals, such as incentives that promote users of hazardous chemicals “to publish emergency re- safety violations in the interest of short-term profitability, lease plans, worst-case scenarios and five year accident shielding upper management from ‘bad news’ and turnover histories,” by June 1999.165 Hazardous materials emergen- of management staff.”157 A third says that “Many chemical cies are covered in a book edited by Cashman.166 plant disasters have been precipitated by an unplanned New Jersey adopted a Toxic Catastrophe Prevention Act change in process, a change in equipment or a change in in 1986, which requires risk assessment by companies.167 personnel.”158 The Kanawha Valley Hazardous Assessment Project in It has been estimated that the U. S. petrochemical in- West Virginia developed worst-case scenarios for 12 dustry could save up to 10 billion dollars/yr by avoiding ab- chemical plants in the area.168 The chemicals studied in- normal situations or learning how to better deal with cluded acrylonitrile, vinylidene chloride, butyl isocyanate, them.159 A team studying abnormal situations management methylene chloride, chlorine, phosphorus trichloride, hy- identified eight key issues: drogen sulfide, methyl isocyanate, phosgene, ethylene ox- ide, sulfur trioxide, and others Lack of management leadership In addition to the amounts of chemicals released to the The significant role of human errors environment through accidents, the U. S. Toxic Release In- Inadequate design of the work environment ventory shows the release of 2.43 billion lb into air, land, or Absence of procedures for dealing with abnormal oper- water in 1996,169 down from 3.21 billion lb in 1992.170,171 ations (as opposed to emergencies) (The data is available on a number of Internet sites, includ- Loss of valuable information from earlier minor ing www.epa.gov/opptintr/tri.) The total decline since the incidents law became effective in 1987 has been 46%. This right-to- The potential economic return know law was enacted in the aftermath of the Bhopal acci- Transferability of good abnormal situations perfor- dent. It now covers nearly 650 chemicals out of about mance to other plants 72,000 in commerce. (It is credited with causing industries The importance of teamwork and job design. to reduce emissions more than the usual command-and- control regulations that can lead to cumbersome, adversar- The paper mentions 550 major accidents at U. S. petro- ial legal proceedings.172) Facilities are not required to re- chemical plants (each with more than 500,000 dollars lost) port releases unless they manufacture or process more than in the last 5 years, with 12.9 billion dollars total equipment 25,000 lb or handle more than 10,000 lb of the chemicals damage. Learning from case histories is helpful, but is evi- annually.173 The U. S. Environmental Protection Agency dently not enough.160 has proposed lower reporting amounts for some, especially It is easy to blame accidents on human error, but good toxic chemicals (e.g., 10 lb of chlordane [a persistent chlo- design can often minimize this.161 Avoid poor lighting or rinated insecticide], polychlorinated biphenyls, or mer- contrast. Provide a checklist so that the operator will find it cury; and 0.1 g dioxins). Some compounds have also been easy to recall all of the necessary information. Most valves removed from the list. Acetone (129 million lb, released in have right-handed threads. Do not mix in any that have left- 1993) and nonaerosol forms of sulfuric acid (106 million lb handed threads. Mount them so that they are easy to access, injected underground of 130 million lb, released in 1993) and the labels are easy to see. have been removed from the list recently because they are The state of Delaware has an Extremely Hazardous not likely to cause adverse effects to the environment or to Substances Risk Management Act enforced by a two-man human health under conditions of normal use.174 However, Industrial Disaster Management Group. It does not dis- the amount of production-related waste has remained rela- courage the use of hazardous substances, but it does require tively constant at about 37 billion lb since 1991, when data companies to have good equipment maintenance programs, collection began.175 About 250 million metric tons of haz- written instructions on how to operate the equipment, plus ardous waste is generated each year in the United States. operator training. The companies must also study how This is about 1 ton/person.176 The number of Superfund equipment can fail, how operators can make mistakes, the sites, where toxic waste was deposited in the past and that probability of human error, and what areas might be af- now need to be cleaned up, is expected to reach 2000, with fected if an accident occurs.162 The state also has an emer- an estimated cost to clean up each site of 26 million gency response team that is always on call.163 Delaware dollars.177 also proposes to monitor how much toxic pollution state The numbers in the Toxic Release Inventory must not be residents receive at home, at work, and in the air.164 On the taken out of context. Large reductions in the numbers for national scale, the U. S. Environmental Protection Agency hydrogen chloride and sulfuric acid between 1987 and 12 Chapter 1 1996 resulted from narrowing the reporting requirements ane from the extraction of oil from soybeans. Extraction to cover only airborne releases.178 About half of the major with supercritical carbon dioxide would eliminate the need reductions in the waste generated by an 80-company sam- for hexane (see Chap. 8). Other releases in the state in- ple resulted from redefining on-site recycling activies as in- cluded the carcinogens acrylonitrile, benzene, process recovery, which does not have to be reported.179 A dichloromethane, and ethylene oxide. For comparison, the change in the production level of a plant can also change state of Delaware estimates that cars and trucks contribute the numbers. 138,040 lb/day of volatile organic compounds into the air. The Toxic Release Inventory for Delaware for This means that local traffic puts out in 2.5 days what the 1993–1996 will illustrate how the system works Star Enterprise refinery (now Motiva Enterprises) releases (Table 1.1). in a year. The poultry industry, in the same county as the The large releases from the first two companies were nylon plant, probably releases more nitrates to streams than largely solvents used in painting cars. These might be re- the nylon plant (by putting excess manure on fields). The duced to near zero by use of powder coating for finishing total emissions in Delaware are less than what some single cars, and cleaning parts with aqueous detergents (see Chap. companies release in other parts of the nation (e.g., East- 8). Part of the reduction by Chrysler may have involved man Chemical, 29 million lb).180 substitution of a nonreportable solvent for a reportable one One interesting approach to the loss of volatile liquids is (as suggested by a GM employee.) The big reductions for the use of an evaporation suppressant for the styrene used both companies stem from major shutdowns to retool for to cure unsaturated polyester resins.181 The suppressant, new models. During this period, Chrysler reduced its use made from a bisphenol A epoxy resin, stearic acid, per unit of production by 6%, whereas GM increased its use colophony, triethanolamine, glycerol monostearate, cal- per unit of production by 19%. Included in the Sun Oil re- cium stearate, and sorbitan monostearate, may coat the sur- leases was 150,000 lb of ethylene oxide. The nylon plant face to retard evaporation. losses were mainly hydrochloric acid from traces of chlo- Chemicals in lakes and streams caused 46 states to issue ride in the coal burned to power the plant. The increased re- public health warnings to avoid or curtail the eating of fish. leases in 1995–1996 reflect a new requirement to report ni- Mercury was the cause in 60% of the cases, polychlori- trate released by the wastewater treatment plant. A nated biphenyls 22%, chlordane (a banned chlorinated in- scrubber could be used to remove the hydrogen chlorine secticide) 7%, DDT 2%, the remainder being spread over from the stack gases. The metals company lost primarily 25 chemicals.182 Fish advisories went up 26% from 1995 to trichloroethylene used in cleaning metal parts. Cleaning 1996 to the point where 15% of the lakes and 5% of the with aqueous detergent could reduce the amount lost to rivers in the United States are now covered.183 In fairness zero (see Chap. 8). (Elsewhere in Delaware, the town of to industry, it should be pointed out that a study by the Smyrna has to treat its water supply to remove Lindsay Museum, in Walnut Creek, California, found that trichloroethylene before distributing the water to its cus- 70% of the chemicals in San Francisco Bay came from the tomers.) The releases from Formosa Plastics included daily activities of ordinary people (e.g., oil from leaky cars, 111,000 lb of the carcinogen, vinyl chloride. The substitu- copper dust from brake pads, garden fertilizers, and pesti- tion of polyolefins, including those made with new metal- cides).184 Nearly 50% of the oil in the world’s waters locene catalysts, for polyvinyl chloride might eliminate the comes from people carelessly discarding used oil on the need to make vinyl chloride. Townsends’ losses were hex- ground or down drains.185 Sixty-six percent of Delaware Table 1.1 Toxic Release Inventory for Delaware (Partial) Pounds released by year Company 1993 1994 1995 1996 Chrysler 987,440 652,146 399,918 105,655 General Motors 826,311 1,285,570 995,747 581,039 Sun Oil refinery 463,010 120,280 147,200 92,500 duPont Seaford nylon plant 455,900 502,687 774,488 654,970 Star Enterprise refinery 344,549 292,758 195,007 162,642 Camdel Metals 240,005 92,000 10,740 7,020 Formosa Plastics 146,621 151,499 149,211 132,862 Townsends 532,278 500,154 Introduction 13 rivers and streams do not meet minimum standards for waste metal salts can be put into fertilizer as trace elements swimming, and 29% do not support normal aquatic life.186 essential for plant growth. However, this practice has been Occupational illness and injury187 cost 30–40 billion abused in some cases by putting in toxic waste (e.g., some dollars/yr in the United States.188 In 1994 there were 6.8 that contain dioxins and heavy metals).195 Even a waste as million injuries and illnesses in private industry, amounting cheap as sodium chloride can be converted back to the to 8.4 cases per 100 workers. Nearly two-thirds were dis- sodium hydroxide and hydrochloric acid that it may have orders associated with repeated trauma, such as carpal tun- come from, by electrodialysis using bipolar membranes.196 nel syndrome.189 The Occupational Safety and Health Act (Membrane separations are covered in Chap. 7). Waste of 1970 set up the National Institute Safety and Health acid can be recovered by vacuum distillation in equipment (NIOSH) to study the problem and the Occupational Safety made of fluoropolymers.197 and Health Administration (OSHA) to deal with it through Mixed solvents can be difficult to recover. If they are inspections and regulations. Both have received so much kept separate, they can be reclaimed by distillation on site. criticism of their effectiveness that they are struggling to The capital investment required is paid back by the reduced find more effective ways to deal with the problem.190 need to buy new solvent. In Germany “completely en- NIOSH is searching for practical ways to protect workers, closed vapor cleaners” give 99% reduction in solvent emis- especially those in small businesses from methylene chlo- sions.198 After cleaning and draining, the air-tight chamber ride, tetrachloroethylene, diesel exhaust in coal mines, iso- is evacuated, the solvent vapors are captured by chilling cyanates, 2-methoxyethanol, and others. OSHA is about to and adsorption on carbon. When a sensor shows that the expand a plan that worked well in Maine, a state that used solvent is down to 1 g/m3 the vacuum is released so that the to have one of the worst accident and illness records in the lid can be opened. United States.191 The 200 firms with the worst records In some cases the amount of waste may be considered were asked to look for deficiencies and to correct them. too small to justify the research needed to find a use for it They were also inspected. These measures cut injuries and or to improve the process to eliminate it. The staff may also illnesses over a 2-year period. be so busy with potentially profitable new ventures that it hesitates to take time to d