Green Chemistry: An Inclusive Approach

Green Chemistry

An Inclusive Approach

Editors

Béla Török

Timothy Dransfield

University of Massachusetts Boston, Boston, MA, United States

Table of Contents

Cover image

Title page

Copyright

List of Contributors

Preface

Part 1. Introduction

Chapter 1.1. Green Chemistry: Historical Perspectives and Basic Concepts

1.1.1. Emergence of Green Chemistry

1.1.2. Sustainable Production of Commodities: Principles and Basic Concepts

1.1.3. Green Chemistry and the Environment

1.1.4. Regulatory Agencies

1.1.5. Closing Thoughts

Problems

Part 2. Chemical Issues of Modern Society

Chapter 2.1. Environmental Chemistry, Renewable Energy, and Global Policy

2.1.1. Introduction

2.1.2. Environmental Challenges

2.1.3. Topics in Environmental Chemistry

2.1.4. Conclusions

Problems

Chapter 2.2. Sustainable Synthesis

2.2.1. Catalysis

2.2.2. Solvents

2.2.3. Activation and Energy Efficiency of Chemical Processes

2.2.4. Conclusions

Problems

Chapter 2.3. Integrating the Principles of Toxicology Into a Chemistry Curriculum

2.3.1. An Introduction to the Principles of Toxicology

2.3.2. Current Status of Toxicology in Green Chemistry

2.3.3. Current Status of Toxicology in the Chemistry Curriculum

2.3.4. Toxicology as a Core Component of a Complete Chemist's Education

2.3.5. Toxicology, Hazard, and Risk Assessment

2.3.6. Examples of Connecting Chemistry and Toxicology Principles

2.3.7. Toxicology and Molecular Design

2.3.8. Conclusions

Problems

Chapter 2.4. Effects of Environmental Factors on DNA: Damage and Mutations

2.4.1. DNA Mutations

2.4.2. Mutagenic Agents That May Affect DNA Sequence or Epigenetics

2.4.3. Transgenerational Inheritance

2.4.4. Bisphenol A (4,4′-Isopropylidenediphenol)

2.4.5. Repair of DNA Damage

Problems

Part 3. Green Chemistry in Practice

Chapter 3.1. The Natural Atmosphere

3.1.1. Introduction to the Atmosphere

3.1.2. Layers of the Atmosphere

3.1.3. Energy in the Atmosphere

3.1.4. Gases in the Atmosphere

3.1.5. Particulate Matter

3.1.6. Clouds

3.1.7. Research in Atmospheric Chemistry

Chapter 3.2. Air Pollution and Air Quality

3.2.1. Introduction

3.2.2. Long-Range Transport

3.2.3. Ozone

3.2.4. Fine Particulate Matter

3.2.5. Conclusion

Chapter 3.3. Stratospheric Ozone Depletion and Recovery

3.3.1. Stratospheric Ozone

3.3.2. Ozone-Depleting Substances

3.3.3. Halogen Chemistry in the Stratosphere

3.3.4. Polar Ozone Loss

3.3.5. Midlatitude Ozone Loss

3.3.6. Future of Stratospheric Ozone

3.3.7. Success of the Montreal Protocol

Chapter 3.4. The Greenhouse Effect, Aerosols, and Climate Change

3.4.1. Fundamentals

3.4.2. Sources and Sinks of Greenhouse Gases

3.4.3. Aerosols and Climate

3.4.4. Physics of Climate

3.4.5. Technology to Reduce Greenhouse Gas Emissions

Chapter 3.5. Chemistry of Natural Waters

3.5.1. Introduction

3.5.2. Fundamental Chemistry of Water

3.5.3. Acid-Base Interactions

3.5.4. Solubility and Saturation

3.5.5. Complexation

3.5.6. Ionization

3.5.7. Redox Reactions

3.5.8. Persistence

3.5.9. Final Remarks

Chapter 3.6. Water Contamination and Pollution

3.6.1. Introduction

3.6.2. Water Quality and Sustainability

3.6.3. Types of Contaminants

3.6.4. Case Study of Lead (Pb) in Drinking Water—Flint, MI

3.6.5. Case Study—The St. Clair River and Chemical Valley Sarnia

Chapter 3.7. Contaminants of Emerging Concern, With an Emphasis on Nanomaterials and Pharmaceuticals

3.7.1. Introduction

3.7.2. The Toxicology of Contaminants of Emerging Concerns

3.7.3. Two Contaminants of Emerging Concern Case Studies

3.7.4. Conclusions

Chapter 3.8. Pollution in the Coastal Zone: A Case Study of Wastewater on Cape Cod, MA

3.8.1. Cape Cod: An Imperiled Natural Treasure

3.8.2. Regulatory Framework for Addressing Coastal Pollution

3.8.3. New Challenges: Contaminants of Emerging Concern

3.8.4. Addressing Coastal Water Pollution on Cape Cod

Glossary of Key Terms

Chapter 3.9. The Composition of Soils and Sediments

3.9.1. Introduction

3.9.2. Origin of Soils and Sediments

3.9.3. Factors Affecting Composition of Soils and Sediments

3.9.4. Properties of Soils

3.9.5. Properties of Sediments

3.9.6. Importance of Soils and Sediments

3.9.7. Conclusions

Chapter 3.10. Heavy Metal Pollution and Remediation

3.10.1. Introduction

3.10.2. Remediation of Heavy Metals

3.10.3. Conclusions

Chapter 3.11. Application of Green Chemistry in Homogeneous Catalysis

3.11.1. Introduction

3.11.2. Metal-Based Catalysis

3.11.3. Organocatalysis

3.11.4. Conclusion

Chapter 3.12. Heterogeneous Catalysis: A Fundamental Pillar of Sustainable Synthesis

3.12.1. Introductory Remarks

3.12.2. Preparation of Catalysts and Their Use in Various Chemical Reactions

3.12.3. Catalytic Conversion of the Biomass

3.12.4. Selected Recent Reviews Concerning the Advances in Performing Reaction Types in a Green Way and Transforming the Biomass

3.12.5. Conclusions and Outlook

Chapter 3.13. Phase Transfer Catalysis: A Tool for Environmentally Benign Synthesis

3.13.1. Asymmetric Phase Transfer Catalysis

3.13.2. Polymer-Anchored and Multisite Phase Transfer Catalysts

3.13.3. Nanoparticle-Supported Phase Transfer Catalysts

3.13.4. Conclusions and Outlook

Chapter 3.14. Biocatalysis: Nature's Chemical Toolbox

3.14.1. Introduction

3.14.2. Benefits and Drawbacks of Biocatalyst Development

3.14.3. Case Studies of Biocatalysts

3.14.4. Case Study 1: Terpenes

3.14.5. Case Study 2: Polyketide and Nonribosomal Peptide Natural Products

3.14.6. Case Study 3: Ribozymes as Biocatalysts

3.14.7. Benefits and Drawbacks of RNA Catalysts

3.14.8. Conclusions

Chapter 3.15. Organic Solvents in Sustainable Synthesis and Engineering

3.15.1. The Role of Organic Solvents in Chemistry and Chemical Engineering

3.15.2. Rationale for Solvent Selection

3.15.3. Carbon Footprint of Organic Solvents

3.15.4. Solvents for Sustainable Chemistry

3.15.5. Solvent Recovery and Recycling

3.15.6. Adverse Impact of Organic Solvents

Chapter 3.16. Ionic Liquids as Novel Media and Catalysts for Electrophilic/Onium Ion Chemistry and Metal-Mediated Reactions

3.16.1. Introduction

3.16.2. Electrophilic Alkylation and Acylation Reactions

3.16.3. Generation of Tamed Propargylic and Allylic Cations in Ionic Liquids for Facile Propargylation and Allylation

3.16.4. Electrophilic Nitration in Ionic Liquids

3.16.5. Halofunctionalization of Arenes in Ionic Liquids

3.16.6. Synthesis of High-Value Small Molecules via Dediazoniative Functionalization in Ionic Liquids

3.16.7. Ionic Liquids as Solvent and Catalyst for the Synthesis of Heterocycles

3.16.8. Ritter Reaction

3.16.9. Schmidt Reaction

3.16.10. Metal-Mediated Cross-Coupling and Cyclization Reactions in Ionic Liquids

3.16.11. Diels-Alder Reaction in Ionic Liquids

3.16.12. Wittig Reaction in Ionic Liquids

3.16.13. Concluding Remarks

Chapter 3.17. Solvent-Free Synthesis of Nanoparticles

3.17.1. Introduction

3.17.2. Mechanochemistry

3.17.3. Solvent-Free Synthesis of Nanoparticles Through Thermal Treatment

3.17.4. Conclusions

Chapter 3.18. Application of Microwaves in Sustainable Organic Synthesis

3.18.1. Introduction

3.18.2. Multicomponent Reactions

3.18.3. Cyclization/Cycloaddition Reactions

3.18.4. Radical Cyclizations

3.18.5. Reactions by Solid Catalysts

3.18.6. Metathesis

3.18.7. Solid-Phase Synthesis on Polymer Supports

3.18.8. Combination of Ionic Liquids and Microwave Irradiation

3.18.9. Microwave Heating Effect

3.18.10. Conclusions and Future Outlook

Chapter 3.19. Application of Sonochemical Activation in Green Synthesis

3.19.1. Organic Synthesis

3.19.2. Synthesis of Nanoparticles and Nanostructures

3.19.3. Conclusion

Chapter 3.20. Principles of Electrocatalysis

3.20.1. Fundamentals of Cyclic Voltammetry

3.20.2. Electrocatalysis

3.20.3. A Case Study in Homogeneous Electrocatalytic CO2 Reduction

3.20.4. Highlights in Homogeneous Electrocatalytic CO2 Reduction by First-Row Transition Metals

3.20.5. Conclusions

Chapter 3.21. Principles of Photochemical Activation Toward Artificial Photosynthesis and Organic Transformations

3.21.1. Introduction

3.21.2. Solar Energy Distribution

3.21.3. The Jablonski Diagram

3.21.4. Principles of Photochemical Activation

3.21.5. Evaluating the Efficiency of a Photocatalytic System

3.21.6. Examples of Photocatalytic Systems

Chapter 3.22. Biopolymers: Biodegradable Alternatives to Traditional Plastics

3.22.1. Introduction

3.22.2. Protein: A Ubiquitous Biopolymer

3.22.3. Polysaccharides

3.22.4. Polyhydroxyalkanoate—A Natural and Diverse Polyester

3.22.5. Conclusion and Outlook

Chapter 3.23. Modern Applications of Green Chemistry: Renewable Energy

3.23.1. The Static Concentration of Energy in Chemical Bonds and the Physical Double Layer: Modern Methods of Energy Storage

3.23.2. The Movement of Electrons in Batteries, Fuel Cells, and Supercapacitors: Methods of Energy Delivery

3.23.3. Applications of Renewable Energy From Green Chemistry: Electric Vehicles, Smart Grids, Smart Roadways, and Smart Buildings/Homes

3.23.4. Innovations and Future Opportunities for Renewable Energy From Green Chemistry

Chapter 3.24. From Ethanol to Biodiesel: A Survey of Green Fuels

3.24.1. Introduction

3.24.2. Bioethanol Production

3.24.3. Higher Alcohols

3.24.4. Biodiesel: Lipid-Derived Biofuel

3.24.5. Conclusion and Future Prospects

Chapter 3.25. Solar Energy Conversion

3.25.1. Solar Energy and Dye-Sensitized Solar Cells

3.25.2. Dye-Sensitized Solar Cell Design, Mechanism, and Thermodynamic Considerations

3.25.3. Optimization of Dye-Sensitized Solar Cell Design

3.25.4. Dye Sensitizers and Anchoring Groups

3.25.5. Perovskites: Emerging Solar Cell Photosensitizers

Chapter 3.26. Toward a Sustainable Carbon Cycle: The Methanol Economy

3.26.1. Introduction

3.26.2. Why Methanol?

3.26.3. Methanol Production From Fossil Fuels With Reduced or No CO2 Emission

3.26.4. Sustainable Production of Methanol

3.26.5. Where Should the CO2 Come From?

3.26.6. The Path Toward an Anthropogenic Carbon Cycle

Chapter 3.27. Natural and Nature-Inspired Synthetic Small Molecule Antioxidants in the Context of Green Chemistry

3.27.1. Introduction

3.27.2. Identification, Isolation, and Structural Characterization

3.27.3. Limitations of Therapeutic Applications

3.27.4. Chemical Modifications and Formulations to Improve Druglike Properties and Therapeutic Potential

3.27.5. Conclusions

Chapter 3.28. The Value-Adding Connections Between the Management of Ecoinnovation and the Principles of Green Chemistry and Green Engineering

3.28.1. Introduction

3.28.2. Discussion

3.28.3. Conclusions and Summary

Chapter 3.29. The International Chemicals Regime: Protecting Health and the Environment

3.29.1. The International Regime for Regulation of Chemicals and Hazardous Waste

3.29.2. Implementing the Basel and Stockholm Conventions

3.29.3. International Chemicals and Waste Regulation at the National Level: Country Case Studies

3.29.4. Sustainable Development Goals: Future for Chemicals and Waste Regulation?

Index

Copyright

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List of Contributors

Steven Ackerman,     University of Massachusetts Boston, Boston, MA, United States

Karelle Aiken,     Georgia Southern University, Statesboro, GA, United States

Nicholas D. Anastas,     United State Environmental Protection Agency, Cincinnati, OH, United States

Paul T. Anastas,     Yale University, New Haven, CT, United States

Gopalakrishnan Aridoss,     LG Life Sciences Ltd, Daejeon, South Korea

Johannes Bader,     Beuth University of Applied Sciences, Berlin, Germany

Nadine Borduas,     ETH Zurich, Zurich, Switzerland

Christopher Brigham,     University of Massachusetts Dartmouth, North Dartmouth, MA, United States

Gabriela Bueno,     University of Massachusetts Boston, Boston, MA, United States

Timothy P. Canty,     University of Maryland, College Park, MD, United States

Philip Coish,     Yale University, New Haven, CT, United States

Kathryn E. Cole,     Christopher Newport University, Newport News, VA, United States

John Collins,     IBM Thomas J Watson Research Center, Yorktown Heights, NY, United States

Amy Costa,     Center for Coastal Studies, Provincetown, MA, United States

Levente Cseri,     The University of Manchester, Manchester, United Kingdom

Rupali Datta,     Michigan Technological University, Houghton, MI, United States

Neil M. Donahue,     Carnegie Mellon University, Pittsburgh, PA, United States

Daniel P. Dowling,     University of Massachusetts Boston, Boston, MA, United States

Timothy Dransfield,     University of Massachusetts Boston, Boston, MA, United States

Clifford J. Ellstrom,     University of Massachusetts Boston, Boston, MA, United States

Natalia Escobar-Pemberthy,     University of Massachusetts Boston, Boston, MA, United States

Daniel M. Genest,     University of Massachusetts Boston, Boston, MA, United States

Debanjana Ghosh,     Georgia Southern University, Statesboro, GA, United States

Gerald E. Gilligan,     University of Massachusetts Boston, Boston, MA, United States

Alain Goeppert,     University of Southern California, Los Angeles, CA, United States

Gerald Gourdin,     Georgia Institute of Technology, Atlanta, GA, United States

Robyn E. Hannigan,     University of Massachusetts Boston, Boston, MA, United States

Julie A. Himmelberger,     DeSales University, Center Valley, PA, United States

William Horton,     University of Massachusetts Boston, Boston, MA, United States

Patricia Hughes,     Center for Coastal Studies, Provincetown, MA, United States

Maria Ivanova,     University of Massachusetts Boston, Boston, MA, United States

Stefan D. Kalev,     Gulf Coast Research and Education Center, University of Florida, Wimauma, FL, United States

Daniel Kirk-Davidoff,     University of Maryland, College Park, MD, United States

Anne Kokel,     University of Massachusetts Boston, Boston, MA, United States

Kenneth K. Laali,     University of North Florida, Jacksonville, FL, United States

Shainaz Landge,     Georgia Southern University, Statesboro, GA, United States

Nicholas A. Lee,     University of Massachusetts Boston, Boston, MA, United States

Alexandra Maertens,     Johns Hopkins Bloomberg School of Public Health, Baltimore, MD, United States

Enda McGovern,     Sacred Heart University, Fairfield, CT, United States

Meaghan McKinnon,     University of Massachusetts Boston, Boston, MA, United States

Manisha Mishra,     University of Massachusetts Boston, Boston, MA, United States

Ken T. Ngo,     University of Massachusetts Boston, Boston, MA, United States

James Noblet,     California State University San Bernardino, San Bernardino, CA, United States

George A. Olah,     University of Southern California, Los Angeles, CA, United States

István Pálinkó,     University of Szeged, Szeged, Hungary

Peter Pogany,     Gedeon Richter Plc., Budapest, Hungary

Helen C. Poynton,     University of Massachusetts Boston, Boston, MA, United States

Deyang Qu,     University of Wisconsin Milwaukee, Milwaukee, WI, United States

Mayamin Razali,     The University of Manchester, Manchester, United Kingdom

William E. Robinson,     University of Massachusetts Boston, Boston, MA, United States

Jonathan Rochford,     University of Massachusetts Boston, Boston, MA, United States

Abhishek RoyChowdhury,     Stevens Institute of Technology, Hoboken, NJ, United States

Heather A. Rypkema,     Heritage Strategies, INTL, Washington, DC, United States

Ross J. Salawitch,     University of Maryland, College Park, MD, United States

Dibyendu Sarkar,     Stevens Institute of Technology, Hoboken, NJ, United States

Christian Schäfer,     University of Massachusetts Boston, Boston, MA, United States

Laurel Schaider,     Silent Spring Institute, Newton, MA, United States

Linda Schweitzer,     Oakland University, Rochester, MI, United States

Abid Shaikh,     Georgia Southern University, Statesboro, GA, United States

G.K. Surya Prakash,     University of Southern California, Los Angeles, CA, United States

Gyorgy Szekely,     The University of Manchester, Manchester, United Kingdom

Gurpal S. Toor,     University of Maryland, College Park, MD, United States

Béla Török,     University of Massachusetts Boston, Boston, MA, United States

Marianna Török,     University of Massachusetts Boston, Boston, MA, United States

David M. Wilmouth,     Harvard University, Cambridge, MA, United States

Julie B. Zimmerman,     Yale University, New Haven, CT, United States

Preface

The concept of this book was born in 2005 when we (along with Deyang Qu, who wrote Chapter 3.23) taught Introduction to Green Chemistry at UMass Boston. We team-taught the course because none of us individually had expertise in everything we wanted to cover. We were lucky to have faculty whose specialties included air pollution, novel battery technologies, and green synthesis, but even with our combined backgrounds, we felt unprepared to show the true breadth of the field of Green Chemistry. We searched for a textbook to help us fill in the gaps, but we could not find one. We successfully ran the course using an environmental chemistry textbook and a lot of primary literature, but from the outset, we realized that the course deserved a textbook designed around it.

This, then, is the textbook we wish had been available to us. It is intended for a broad audience, including industry and academia. It is aimed to be a contemporary and inclusive Green Chemistry text that can be used in undergraduate and graduate education and as a resource for researchers. The main goal of the work was to be as broad as possible, including many aspects of Green Chemistry. The book includes three main parts. The first two parts are intended for those who teach Green Chemistry: it covers the basic definitions, environmental chemistry, renewable energy, sustainable synthesis, fundamental chemical toxicology, and the effect of environmental factors on our genetic information. These chapters follow a textbook style, providing examples, recommended reading, and problem sets. The third part of the work is designed for researchers, as it contains in-depth reviews on selected topics. Our intention is that educators, after covering the fundamentals laid down in the first part, may select some of the specialized research chapters as case studies to further illustrate the state-of-the-art practice of Green Chemistry. Although the book includes more topics than could be covered in a typical undergraduate or even graduate class, the variety of topics will provide opportunity for the faculty instructors to select topics they are comfortable covering and can fit into their schedules.

The centerpiece of the third part of the book is Green Chemistry in practice. The topics included in this part focus on special areas of the field. Every chapter in this part provides an up-to-date reference section, together comprising thousands of original papers and review articles. We believe that by including experts in many of the fields discussed, the book provides the readers with insider information: the aspects or challenges of a given field that the specialists consider the most important and urgent. This way, we hope that the book will serve as a primary resource for those who are new to Green Chemistry or those who intend to branch out and discover other topics that are related to their own research fields.

We would like to thank our distinguished colleagues and authors, experts in their fields, for contributing to this unique endeavor. We also thank Kathryn Morrissey and Laura Kelleher, who helped us through the proposal phase of the book, and Anitha Sivaraj, who handled the galley proofs. We are indebted to Emily Thomson, our Editorial Project Manager, for her enormous help and continuous encouragements throughout the process.

Béla Török, and Timothy Dransfield

Boston, May 1, 2017

Part 1

Introduction

Outline

Chapter 1.1. Green Chemistry: Historical Perspectives and Basic Concepts

Chapter 1.1

Green Chemistry

Historical Perspectives and Basic Concepts

Béla Török, and Timothy Dransfield     University of Massachusetts Boston, Boston, MA, United States

Abstract

This chapter provides an introduction to the roots and progress of green chemistry as an overarching philosophy that guides sustainable development. The basic principles of green chemistry and engineering as well as several metrics that guide the design of processes are described along with a brief overview of the impacts of human society on the environment. The chapter concludes with a concise description of the major regulatory and enforcement agencies of selected major economies.

Keywords

Anthropocene; Environmental protection; Environmental regulations; Green chemistry; Principles; Sustainable production

Chemists and chemistry, in general, have made an enormous contribution to the history of humankind. Beginning with the early alchemists, these contributions include several developments that changed the course of history for the better or, in some cases, for the worse. Many of them may seem to be simple by today's standards, but at the time, they were groundbreaking discoveries and inventions. The fabrication of simple soaps made the formation of large cities possible by improving the personal hygiene. The production of dyes and paints contributed significantly to fashion and art over the centuries. As the usefulness of chemistry became clear, more people decided to pursue such endeavors, which brought exponential growth in this field. As Dalton, Avogadro, and Lavoisier made their famous discoveries, chemistry became viewed more and more as science than as black magic. With significant developments in chemical theory came the increased pace of new applications that inspired yet further progress. However, not every step along the way was problem free. Several inventions that were made with the best intentions backfired and caused health or environmental issues. The use of freons as inflammable carrier gases in all sorts of sprays in the 1960s–70s seemed to be perfect, until Rowland and Molina published their findings on the terrible effect of these chemicals on the ozone layer that protects the earth from harmful ultraviolet radiation. Antibiotics were hot commodities after World War II, until it was found that bacteria can develop resistance toward these compounds making them more difficult to fight against. Plastics seemed like a blessing until it was found that their degradation takes over a thousand years. Dichlorodiphenyltrichloroethane (DDT) appeared to be an effective agent to fight malaria-spreading mosquitos, until it was found in fish around Antarctica, proving that it lingers for a long time. Contemporary pesticides can leach into natural waters and cause gender change in frogs. Many drugs have unintended harmful side effects. The list is long. What is common in all these cases is that a product was developed for a certain purpose without a careful analysis of its broader impact on the ecosystem. All these disasters initiated a different chemical thinking that now we call green chemistry.

1.1.1. Emergence of Green Chemistry

Early in the evolution of the chemical industry, scientists were already, although unconsciously, applying some of the much later formulated principles of green chemistry. For instance, the development of heterogeneous catalytic petrochemical processes dates back to the 1930s. The more conscious development of such thinking began after several major environmental disasters and industrial accidents occurred. The aforementioned problems are just a few examples to demonstrate the potentially harmful nature of chemicals if applied and introduced to the biosphere without sufficiently careful forward thinking. Rachel Carson's book, Silent Spring (1962), which described the destruction of local ecosystems by toxic chemicals, likely was a wake-up call for the society to address the issues or face grave consequences. As the first important step to address these issues the US Congress passed the National Environmental Policy Act in 1969. The US Environmental Protection Agency (US EPA) was established by President Nixon in 1970. Since the 1970s several environmental legislations have been implemented, such as the Clean Air Act of 1970 and the Safe Drinking Water Act of 1974, that signaled the government's intention to solve the problems via regulations. The US Toxic Substances Control Act was passed in 1976, and now it has over 80,000 chemicals in its listings. Later the more comprehensive Clean Air Act and the Pollution Prevention Act were enacted, ​both in 1990. The term Green Chemistry was coined by the EPA Office of Pollution Prevention and Toxins in the early 1990s. In 1995, the US EPA established an annual awards program called the Presidential Green Chemistry Awards to recognize the leaders of innovation from both industry and academia. In 1997, the first PhD in Green Chemistry program was established at the University of Massachusetts Boston. In the same year the Green Chemistry Institute was founded, which later became the American Chemical Society Green Chemistry Institute. Starting with the 1990s, several scientific journals devoted to green chemistry research began publishing original research and review articles in the field. Today, all major publishers have at least one journal devoted to green or sustainable chemistry research with several books and textbooks published to aid research and education.

1.1.2. Sustainable Production of Commodities: Principles and Basic Concepts

Several tools and methods that are now considered as part of sustainable synthesis (e.g., catalysis) were developed much earlier than the formal green chemistry movement began. It took concerted and conscious efforts to envision and design a framework that included the earlier developments and initiated further progress in this field. The basic principle, benign by design, emphasized that both the product and the process used to produce it should conform to the basic rules of sustainability. In their seminal book in 1998, Anastas and Warner established the major principles of green chemistry. Although since then several new principles have been added to the list, the original list is still applicable.

1.1.2.1. Principles of Green Chemistry

1. Prevention: It is better to prevent waste than to treat or clean up waste after it has been created.

2. Atom economy: Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product.

3. Less hazardous chemical syntheses: Wherever practicable, synthetic methods should be designed to use and generate substances that possess little or no toxicity to human health and the environment.

4. Designing safer chemicals: Chemical products should be designed to affect their desired function while minimizing their toxicity.

5. Safer solvents and auxiliaries: The use of auxiliary substances (e.g., solvents, separation agents, etc.) should be made unnecessary wherever possible and innocuous when used.

6. Design for energy efficiency: Energy requirements of chemical processes should be recognized for their environmental and economic impacts and should be minimized. If possible, synthetic methods should be conducted at ambient temperature and pressure.

7. Use of renewable feedstocks: A raw material or feedstock should be renewable rather than depleting whenever technically and economically practicable.

8. Reduce derivatives: Unnecessary derivatization (use of blocking groups, protection/deprotection, temporary modification of physical/chemical processes) should be minimized or avoided if possible, because such steps require additional reagents and can generate waste.

9. Catalysis: Catalytic reagents (as selective as possible) are superior to stoichiometric reagents

10. Design for degradation: Chemical products should be designed so that at the end of their function they break down into innocuous degradation products and do not persist in the environment.

11. Real-time analysis for pollution prevention: Analytical methodologies need to be further developed to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances.

12. Inherently safer chemistry for accident prevention: Substances and the form of a substance used in a chemical process should be chosen to minimize the potential for chemical accidents, including releases, explosions, and fires.

Since products that involve any chemistry during their preparation are all manufactured by industry, the aforementioned list had to be amended to include specific issues that chemical engineers face while transitioning a laboratory process to the industrial setting. Hence, Anastas and Zimmerman developed a similar set of principles for engineering.

1.1.2.2. Principles of Green Engineering

1. Inherent rather than circumstantial: Designers need to strive to ensure that all materials and energy inputs and outputs are as inherently nonhazardous as possible.

2. Prevention instead of treatment: It is better to prevent waste than to treat or clean up waste after it is formed.

3. Design for separation: Separation and purification operations should be designed to minimize energy consumption and materials use.

4. Maximize efficiency: Products, processes, and systems should be designed to maximize mass, energy, space, and time efficiency.

5. Output pulled versus input pushed: Products, processes, and systems should be output pulled rather than input pushed through the use of energy and materials.

6. Conserve complexity: Embedded entropy and complexity must be viewed as an investment when making design choices on recycle, reuse, or beneficial disposition.

7. Durability rather than immortality: Targeted durability, not immortality, should be a design goal.

8. Meet need, minimize excess: Design for unnecessary capacity or capability (e.g., one size fits all) solutions should be considered a design flaw.

9. Minimize material diversity: Material diversity in multicomponent products should be minimized to promote disassembly and value retention.

10. Integrate material and energy flows: Design of products, processes, and systems must include integration and interconnectivity with available energy and materials flows.

11. Design for commercial afterlife: Products, processes, and systems should be designed for performance in a commercial afterlife.

12. Renewable rather than depleting: Material and energy inputs should be renewable rather than depleting.

Several other sets of principles have been developed by different groups, for example, Poliakoff's mnemonic PRODUCTIVELY, that similarly summarizes the basic concepts (Prevent waste, Renewable materials, Omit derivatization, Degradable products, Use of safe methods, Catalysis, Temperature, pressure ambient, In-process monitoring, Very few auxiliaries, E-factor, Low toxicity, Yes, it is safe). Certainly, the aforementioned principles were not developed overnight. Several research groups have contributed to the development of the major concepts that guided the growth of green chemistry. Here, we list these basic concepts and definitions that will be used in the later chapters of this book.

E-factor: The E (environmental)-factor, developed by Roger Sheldon, is one of the most practical descriptors of the efficiency; it is the mass ratio of waste to the target product. For instance, E=20 means that 20kg waste is produced to every kilogram of product. Obviously, the smaller the number, the better; in the best possible circumstances (0kg waste is generated with the product), E=0. The E-factor is a commonly accepted and applied measure to describe the efficiency of processes in the chemical and pharmaceutical industry for the assessment of the overall environmental impact.

Atom economy (AE): Atom economy (atom efficiency is also used), first described in 1991 by Trost, is defined by the ratio of the molecular weight of the product and the sum of the molecular weights of all substances consumed in the stoichiometric equation of a reaction. Commonly it is expressed as a percentage. It is important to highlight that AE is based on the theoretical reaction (i.e., no unexpected by-products are factored in) and 100% theoretical yield. Therefore the AE is the best possible scenario and can be used to assess a reaction at the theoretical level. For example, if a reaction scheme does not involve the formation of any expected by-product, the AE is 100% (Scheme 1.1.1).

However, it is worth noting that it cannot be used exclusively to describe the environmental impact of a reaction: it may be that a reaction with 100% AE yields unexpected by-products (e.g., stereo- or regioisomers) that would decrease the actual AE. Thus a highly selective reaction with 80% theoretical AE and no unexpected by-products may have less environmental impact than a 100% AE reaction that is accompanied by extensive unexpected by-product formation.

Scheme 1.1.1  Hydration of cyclohexene to cyclohexanol; a 100% atom economic process.

Although these are the two most important measures to describe the efficiency of a chemical process, several alternative metrics have been proposed, such as the reaction mass efficiency (RME) defined as the mass ratio of the obtained product to the total mass of the reactants, thus incorporating the actual percent yield into traditional AE calculations. Carbon efficiency is similar to RME, but only considers carbon as a part of the product or starting materials and reagents. Mass efficiency (total mass of the materials used divided by the mass of product obtained given as a percentage) and effective mass yield (the ratio of the mass of the desired product and the total mass of nonbenign reactants) are other available ways to describe the environmental impact of processes. There is a general agreement in the literature that the AE and E-factor are the most applicable and widely used measures in many industries.

Although the aforementioned metrics are able to estimate the impact of a process, there are other considerations to discuss, such as the chemical characteristics of the waste. Obviously, the ultimate process occurs with 100% AE and 0 E-factor; however, practical processes are different and mostly produce either expected or unexpected by-products that are considered waste. The nature of that waste is highly important. It is easy to realize that if the waste is water (e.g., dehydration reactions) or sodium chloride (nucleophilic substitutions) that are considered harmless, the process is quite different from, to choose one example from many, the Jones oxidation of alcohols to ketones that generates a significant amount of chromium salt waste (Scheme 1.1.2).

To consider this highly important aspect, Sheldon introduced the environmental quotient (EQ), which is calculated by multiplying the E-factor by an arbitrarily assigned environmental unfriendliness quotient, Q. As an example, one can assign 1 to benign chemicals (such as water or NaCl) and a large number (e.g., 100 or 1000) to chromium sulfate. Although as of yet a clear definition or individual assignment of Q values to chemicals is not available, theoretically it is possible to quantify the environmental impact of chemical waste based on its amount and toxicity. It is, however, a difficult task as compounds exhibit all sorts of harmful biological activities, and although it is possible to rank them in terms of one effect (e.g., carcinogenicity or mutagenicity), the ranking (and the Q value) could be significantly different if another type of toxicity is considered. In addition, when a process is generating a compound that is not yet known, its biological effect only can be estimated, e.g., by quantitative structure-activity relationship models.

An even more extended approach that embraces the holistic evaluation of a process or product is the life cycle assessment (LCA). The LCA considers a broad range of issues that can be quantified by environmental friendliness metrics. These indicators include energy consumption, carbon footprint and emission of other greenhouse gases, potential contributions to ozone depletion or smog formation, amount of waste generation, and toxicity of the waste generated. The application of EQ or LCA, however, requires extended analysis before a process can be implemented, and this often contributes to the cost of a product. Nonetheless, as highlighted by the original 12 principles, it is always better (and likely less expensive) to prevent problems by a thorough analysis than to clean up after an environmental disaster.

Scheme 1.1.2  Examples of chemical reactions producing toxic (red) and non-toxic (green) waste.

1.1.3. Green Chemistry and the Environment

It is not within the scope of this text to provide a comprehensive examination of environmental chemistry. Indeed, many fine textbooks exist on that subject, and our goal is not to reduplicate such works. Rather, the goal of the various environmental chemistry chapters in this text is to put into context the impact of human society on the natural world. While the precise placement of the dividing line between green chemistry and environmental chemistry can be debated, it is clear that the entire purpose of green chemistry is to minimize that impact. This is most evident in principles 1 and 10: waste prevention and the design of chemicals such that they degrade harmlessly in the environment. Obviously, then, the practice of green chemistry requires an understanding of those degradation pathways and an understanding of what happens to the waste and by-products when they are emitted. Although various textbooks exist that provide greener pathways for industrial synthesis, for example, there is an alarming shortage of texts that train green chemists to think about the chemistry of their products in the wild. With this work, we hope to begin to bridge that gap.

It may come as a surprise to some readers that society has long been aware of the impacts of science and industry on the environment. The Mishnah laws of first- and second-century Israel specified that threshing floors, leather tanneries, and lime kilns be removed 50  cubits from the city to reduce exposure to airborne pollutants, and that flax stems be soaked at least 4–5  m from any vegetable fields to prevent water pollution from affecting the neighbor's food crops. The impetus for the construction of the Roman aqueducts was to transport clean drinking water, as the Tiber had become so fouled with human waste. English laws attempted to curb pollution from the burning of coal as early as 1273, but the wave of the Industrial Revolution overwhelmed those early efforts.

Even if we as a species were unaware of our effect on the environment, there has been pollution as long as there has been civilization. There is evidence in ice core data that the expansion of agriculture by the Romans and the cultivation of rice by the Han dynasty in China, both in 1st century BCE, led to measurable increases in global methane concentrations. Looking even further into the past, there is clear evidence of heavy metal pollution of soil and water arising from metallurgy as long ago as 1500 BCE and continuing for nearly 2000  years. Indeed, significant levels of these pollutants measured in modern lakes may in fact be sourced to ancient industry rather than to more modern endeavors.

Ancient impacts aside, it is clear that since the Industrial Revolution the scale and the character of the pollution has fundamentally changed. Perhaps we can date this to 17th century England, when John Evelyn wrote of the damage caused by London's coal smoke in his pamphlet, Fumifugium, although even this document refers to the history of England's problems with coal dating back to the middle ages. Perhaps it dates to the cholera outbreaks around the world in the 19th century, caused by contaminated drinking water in the growing cities; or perhaps the burning of the Cuyahoga River, most notably in 1952, a result of the accumulation of oil slicks on its surface; or the smog incidents of the mid-20th century in London, and Pennsylvania and Belgium, in which thousands of people died; or the widespread use of DDT after World War II, now found in animal tissue samples from the most remote locations on Earth; or the tragedy of Love Canal, where people living in houses built on a landfill were exposed to toxic waste as the containers leeched into the soil; or the 1984 Union Carbide disaster in Bhopal, India, where 4000 people died from exposure to methyl isocyanate; or the photochemical smog in Los Angeles during the 1980s, or that of Mexico City, Delhi, and Beijing today; or Three Mile Island, Chernobyl, and Fukushima, reminding us that the wonders of the nuclear age bring with them new dangers. It is true that human science and technology have combined to produce a society that is awe inspiring. However, it is also true that this society has wreaked havoc on our natural environment.

According to most geology textbooks, the most recent geological epoch began nearly 12,000  years ago with the dawn of the Holocene. However, the conversation in recent years has recognized the shift in mankind's ability to harm our planet on a global scale. In 2000, Nobel laureate Paul Crutzen argued for the use of the term Anthropocene, referencing that our current period is defined by our species more than by any other characteristic. Crutzen did not coin the phrase—it had been used by Soviet scientists as early as the 1960s, and perhaps even predates them. However, the dawn of the 21st century was also the dawn of widespread acceptance of the harsh realities of global warming and its associated climate changes. Already the pH of the oceans is dropping, leading to the distinct possibility of mass extinction of life in the sea. The ongoing Holocene extinction is removing up to 140,000 species from our planet each year, a rate that rivals that of the extinction that took the dinosaurs. Left unchecked, the modern tail of the Industrial Revolution threatens all life on the planet. Often doomsayers will claim that we are on the verge of destroying the planet itself. This is presumably hyperbole—the planet has seen mass extinction before, and will again. However, the same cannot be said of the human race.

To be clear, the authors do not believe that we are witnessing the end of human civilization. Because one way or another, our destruction of the environment will be checked. At some point, the financial arguments against change will fall by the wayside as the need for change becomes more urgent. Whether driven by government intervention or an industrial recognition of the bottom line, at some point the solutions to these problems will become financially competitive with the cost of doing nothing. It falls to practitioners of green chemistry to provide the solutions at a cost that obtains that result as soon as possible.

1.1.4. Regulatory Agencies

Environmental regulatory agencies are part of life in most countries. They provide guidance for new developments and oversight for existing industrial technologies as well as common aspects of life, from the disposal of restaurant waste to application of cosmetics. Since the detailed discussion of environmental law and regulatory agencies is far beyond the scope of this introductory chapter, here we describe several of most visible regulatory agencies that are charged with managing the environmental issues in the largest economies.

1.1.4.1. International: The United Nations

The United Nations (UN) took a leadership role in facilitating discussions, organizing international conferences where the member nations could develop strategies to combat environmental issues. Per the suggestion of Sweden, the UN organized the United Nations Conference on Human Environment in Stockholm in 1972. The assembly agreed upon the Stockholm Declaration, which put forth 26 principles to guide environmental protection and development. The World Commission for Environment and Development, first chaired by Gro Harlem Brundtland (former Prime Minister of Norway), was established in 1983. It was tasked with generating a report on the environment and with making recommendations for a worldwide sustainable and environmentally benign economic development to 2000 and beyond. The assessment and recommendations of the commission were published in a book entitled Our Common Future (Oxford University Press) in 1987. Since then, the UN has spearheaded efforts on various environmental issues.

One enormously successful early agreement was the Montreal Protocol (1987) to combat the depletion of ozone over the poles in spring, commonly referred to as the ozone hole. The global ban on chlorofluorocarbons and related compounds succeeded in stopping the deterioration, and the atmosphere continues to recover slowly but surely. The success of the Montreal Protocol was remarkable; former UN Secretary-General Kofi Annan hailed it as perhaps the single most successful international agreement to date. This is in marked contrast to the international community's much slower and more contested response to global warming. The most important and well-known treaties to combat climate change are the Kyoto Protocol (1997) and the Paris Agreement (2015). The Kyoto Protocol described the commitment of the participating countries to reduce the emission of greenhouse gases. The Paris Agreement, the result of the UN Framework Convention on Climate Change, while aiming for a similar goal, made recommendations on how much to limit the annual temperature increase of the planet. As of today, 131 (out of 197) parties have ratified the Paris Agreement.

This leads us to mention the weaknesses of some of the UN-facilitated agreements. Given the nature of the UN, these treaties are negotiated by the governments of the participating countries. However, once the agreement is signed, the law-making bodies of the nations have to ratify it; thus the countries essentially commit themselves by their own laws to uphold the agreement. That has been so far the Achilles' heel of many such agreements: several countries ratified it, whereas many others did not. The reasons for not ratifying vary from country to country and depend on economic development, energy/fuel production and use, and many other socioeconomic factors. Unfortunately, many of these agreements are purely political and do not include the development of actual technologies as a response to global warming.

1.1.4.2. International: International Organization for Standardization

The International Organization for Standardization (ISO) is a nongovernmental international organization with 161 members that are commonly the similar standards bodies of the member countries. In 1946, 25 countries decided to establish the ISO to provide unified industrial standards. It is a forum to share knowledge and develop consensus-based international standards that help innovation and offer solutions to global problems. Although the ISO is not specifically an environmental organization, many of its approximately 21,000 international standards are related to environmental and safety issues. The most relevant of these are ISO1400-Environmental Management, ISO45001-Occupational Health and Safety, ISO50001-Energy Management, ISO22000-Food Safety Management, and ISO31000-Risk Management. However, it is important to note that similar to the above UN recommendations the ISO standards are applied voluntarily by the individual organizations (e.g., corporations) of the member countries.

1.1.4.3. United States

We have already introduced the US EPA earlier in this chapter, which takes the lead on many issues from toxic waste cleanup to mitigation of global warming. The EPA fulfills the roles of a regulatory agency and recommends changes and additions to current environmental laws that Congress considers. The EPA, however, is not just an agency that regulates and enforces regulations. It has a broad network of research facilities, institutes in which far-reaching scientific research is conducted in several areas of environment-related sciences, from sustainable synthesis to atmospheric chemistry. In addition, all US states have their own EPA-like agencies, sometimes just one umbrellalike agency; however, in many states, there are separate entities to deal with separate issues (water, agriculture, etc.).

The National Oceanic and Atmospheric Administration (NOAA) (part of the Department of Commerce) also concerns itself with environmental issues. It grew out of some of the oldest government branches dedicated to the environment, including the United States Coast and Geodetic Survey, which was first established in 1807 by Thomas Jefferson. In 1970, President Nixon created NOAA from several other agencies, including the Weather Bureau (1870) and the Bureau of Commercial Fisheries (1871). Its current substructure includes the National Weather Service, the National Ocean Service, and the Environmental Satellite, Data and Information Service, among others. Through these divisions it contributes by observing and communicating data related to global warming and atmospheric and water pollution. Similar to the EPA, the NOAA has facilities that conduct active research on the environment.

1.1.4.4. Canada

The Environment and Climate Change Canada is the major government agency that regulates and enforces environmental protection in Canada. It was established in 1971 by the Department of Environment Act to assess, monitor, and protect the environment, including providing basic weather and meteorological services to the citizens of Canada. The agency's responsibilities are those of a typical environmental agency: making environmental decisions/regulations based on available evidence, especially with regard to pollution prevention and the like. In addition to its support to policy making, the agency is a supporter of a broad variety of environment-related research through many funding initiatives. Just as in the United States, the Canadian Provinces have their own environmental agencies.

1.1.4.5. European Union

The European Union established its main environmental agency, the European Environment Agency (EEA), in 1990, which became operational in 1994. The agency has 33 member states (28 EU members and Norway, Iceland, Lichtenstein, Switzerland, and Turkey). Six additional countries from the Balkans work with the Agency as cooperating countries. Given the nature of the European Union, most member countries had established their own environmental agencies long before the EEA, such as the Federal Environmental Agency (and others) in Germany (1974), the Environment Agency in the United Kingdom (1995), the Ministry of Ecology, Sustainable Development and Energy in France (since 1974 under various names), just to name a few. Thus the EEA's role is mainly to provide independent information on the environment. They are the major EU information source for policy makers as well as the general public, integrating the principals of sustainability into political and economic decisions.

1.1.4.6. Russia

The Ministry of Natural Resources and the Environment (MNRE) is the main policy-making and enforcing body in Russia. Russia has had some sort of natural resources governmental unit since the 18th century. The MNRE was created in 2008 by merging the former Ministry of Environment and Ministry of Natural Resources (both founded in 1996, after the collapse of the Soviet Union). It has several agencies such as the Federal Service for the Supervision of Natural Resources, the Service for Hydrometeorology and Environmental Monitoring, and separate agencies for subsoil, water, and forestry management.

1.1.4.7. China

Immediately after the Stockholm Declaration, China created its Environmental Protection Leadership Group (1974) and environmental protection became a state policy in 1983 with the Environmental Protection Commission. After several upgrades and name changes, the current Ministry of Environmental Protection (MEP) was established in 2008. China, the most populous country in the world, has seen an unprecedented industrial growth and urbanization since the 1980s, which has brought with it significant environmental problems, including water and air pollution. The major mandates of the MEP include the design, organization, and implementation of national policies, programs, and plans for environmental protection, policy making, and regulations and leading the response to major environmental problems. In addition, it carries out environmental protection science and technological activities including the organization of projects on engineering, and facilitates the development of environmental technology management systems as well as conducts and organizes environmental education.

1.1.4.8. India

India, as the second most populous country in the world, with rapidly growing industrial activity has its fair share of environmental problems. In addition to industrial accidents, water shortages, soil problems (e.g., exhaustion, erosion), deforestation, and, especially in the major metropolitan areas, air and water pollution affect many areas in the country. To address these problems, the Central Pollution Control Board (founded in 1974) created the National Air Quality Monitoring Program. Due to the inspirational power of the Stockholm Declaration, in 1972, the National Council for Environmental Policy and Planning within the Department of Science and Technology was established to protect the environment. This council later became the Ministry of Environment and Forest, which is India's most important governmental agency for environmental protection. The Environment Protection Act of 1986 is one of the major early milestones in its actions. The current legislative framework includes climate change, deforestation management, coastal regulations zones, and pollution control, among many other tasks.

1.1.4.9. Japan

Many countries started seriously considering environmental protection only after the Stockholm Declaration (1972), whereas Japan was among the first countries to enact environmental regulations after four major pollution outbreaks occurred in the country in the 1950s–60s. In 1958, a water quality conservation law was passed, which was followed in 1962 by a smoke and soot emission control law. In 1971, the first Environmental Agency was established in Japan. Currently, the Ministry of the Environment is the branch of the Government of Japan that is responsible for activities related to the environment. This agency has broad responsibilities, as it is involved in policy making concerning waste management and recycling, pollution control, nature conservation, wildlife protection, air quality and transportation, as well as health and chemicals, and is also charged with the care of Japan's national parks.

1.1.4.10. Australia

The Department of Environment and Energy (DEE) is the major government agency in Australia in charge of environmental protection. It designs and implements government policies and programs to protect and conserve the environment, water, and heritage, and promotes climate action. DEE deals with a broad array of activities, such as far-reaching environmental protection of Australian air, land, and water; managing the national parks; conducting research on environmental problems; as well as acting as a funding agency for environmental research. Similar to the United States and Canada, the Australian states also have their own individual environmental agencies.

1.1.5. Closing Thoughts

The nature and scope of the field of chemistry has changed dramatically since the days of the alchemists. Chemistry impacts nearly every aspect of modern life. The progression has not always been smooth, and there have been significant missteps along the way. However, the harnessing of chemistry in the interest of society has brought us to a modern age unimaginable by our ancestors. Toward the end of the 20th century, the field of green chemistry was born from a recognition of those missteps and a desire to minimize the impact of human society, and especially of human industry, on our natural environment. The core philosophy can be expressed in various ways, with lists of principles and metrics. The goal is always the same: benign by design.

Societal impact on the environment presents us with multiple pressing problems, which can be addressed by various means. All things considered, it would be preferable if chemical solutions could be found before political solutions are required. This could entail, for example, a reimagining of an existing technology (e.g., the electric car, biodegradable plastics), a means to reduce the environmental impact (e.g., solvent-free synthesis, exhaust plume scrubbers), or a technology to remove existing pollutants (e.g., CO2 sequestration, bioreactor landfills). By finding a way for companies to profit from the mitigation of pollution, green chemists can encourage society to adopt these changes much more quickly and completely than would a reluctant culture enforced by governmental policies. This is not to minimize the importance of effective policies to control pollution; as we have seen, these efforts are critical to solving national- and global-scale problems. However, one of the goals of green chemistry must be to better facilitate widespread adoption of these new technologies and new methodologies by making them acceptable for everyone.

Problems

1. Calculate the atom economy and E-factor of the following processes:

2. Reactions A and B are two different methods producing the same product P. Reaction A has a theoretical atom economy of 100% with an actual yield of 65% for the product. Reaction B only possesses 85% atom economy, with 95% actual yield for the product. Which reaction is greener, that is, generates less waste considering 100% conversion of A and B?

3. Research the similarities and differences between environmental quotient and life cycle assessment.

4. Select any chemical product and design a green pathway for it considering the complete process (all details from finding/manufacturing starting materials, other components, minimizing environmental impact, etc.). Show your work in a flowchart from the beginning of the manufacturing phase to the likely fate of the product/postproduct in the environment.

5. Solar panels are a popular product marketed widely to offer consumers the opportunity to harness the energy of the sun. Research the manufacturing process of solar panels and prepare an in-depth analysis on the cost and environmental impact of their production. Compare the environmental impact of generating energy using solar panels through the complete lifetime of these panels with that of the same amount energy generated by a coal-based power plant.

6. Several times in this chapter, the smoke from coal burning was mentioned as being especially damaging to the environment and to human health. Research what compounds in coal smoke are primarily responsible for these effects.

7. John Evelyn's Fumifugium detailed the health impacts of coal burning in 17th century London and was written to request intervention by the Parliament and the King. Investigate the alarming health statistics that led to his appeal.

8. How does an increase in pastoral agriculture result in an increase in methane emissions? What about rice cultivation?

9. The history of environmental pollution is often the history of unanticipated consequences. Two excellent examples of this are the stories of DDT and CFCs.

a. In 1948, the Nobel Prize in medicine was awarded for the invention of DDT to combat disease in the aftermath of World War II. Why was DDT so effective in this role? What is it about DDT that made its widespread use so problematic?

b. CFCs were one of the miracle inventions of the 20th century, replacing toxic and/or flammable gases in a variety of applications. What were some of these applications and what were the gases that they replaced?

10. A staggering variety of organic pollutants were found in the soil, water, and air samples taken from Love Canal in 1977. One of the highest concentrations was of benzene. Research the toxicity of benzene, including its mode of action and its mandated concentration limits in the environment.

11. Analyze the 1997 Kyoto Protocol and 2015 Paris Agreement and describe the major points in both. By comparing the two, summarize the development that occurred during the nearly 20years that passed between the two agreements.

Recommended Reading

1. Anastas P.T, Warner J.C. Green chemistry: theory and practice. New York: Oxford University Press; 1998.

2. Lancaster M. Green chemistry – an introductory text. 3rd ed. Cambridge: RSC; 2016.

3. Matlack A.S. Introduction to green chemistry. 2nd ed. New York: CRC Press, Taylor & Francis; 2010.

4. Kovacs L, Csupor D, Lente G, Gunda T. 100 chemical myths: misconceptions, misunderstandings, explanations. Heidelberg, New York, Dordrecht, London: Springer Cham; 2014.

5. Li C.-J, Anastas P.T. Green chemistry: present and future. Chem Soc Rev. 2012;41(4):1413–1414.

6. vanLoon G.W, Duffy S.J. Environmental chemistry: a global perspective. 3rd ed. Oxford: Oxford University Press; 2010.

7. Spiro T.G, Purvis-Roberts K.L, Stigliani W.M. Chemistry of the environment. 3rd ed. California: University Science Books; 2012.

8. Baird C, Cann M. Environmental chemistry. 5th ed. New York: WH Freeman; 2012.

Part 2

Chemical Issues of Modern Society

Outline

Chapter 2.1. Environmental Chemistry, Renewable Energy, and Global Policy

Chapter 2.2. Sustainable Synthesis

Chapter 2.3. Integrating the Principles of Toxicology Into a Chemistry Curriculum

Chapter 2.4. Effects of Environmental Factors on DNA: Damage and Mutations

Chapter 2.1

Environmental Chemistry, Renewable Energy, and Global Policy

Heather A. Rypkema     Heritage Strategies, INTL, Washington, DC, United States

Abstract

This chapter provides a synopsis of the environmental challenges faced by scientists who seek to mitigate damage inflicted by human technological activities. Specific historical examples of chemical contamination are provided. A brief overview of alternative energy sources is also presented along with a discussion of global policy with reference to potentially planet-threatening environmental dangers.

Keywords

Air pollution; Green chemistry; Environmental chemistry; Environmental policy; Renewable energy; Soil pollution; Water pollution

2.1.1. Introduction

The future welfare of our planet depends on a thorough understanding of our current technology and its effects on the environment. Earlier manifestations of mankind, in which the height of environmental impact consisted of the occasional slaughtering of a large mammal, had little or no impact on the world that surrounded it. Today, however, almost every aspect of our lifestyle has a profound effect on the macrocosm of Earth's ecosystems. Most daily activities contribute to this impact in varied, and often unexpected, ways.

Most people realize that the mundane act of driving a car contributes to one's carbon footprint, thereby pouring carbon dioxide into the atmosphere, which contributes to global warming, more currently enveloped into the phenomenon of climate change. But what impact does this really have? What is the implicit environmental effect of trading in a traditional vehicle for a hybrid—does the increased fuel economy and reduced carbon footprint counterbalance the addition of an otherwise usable vehicle to the exploding mass of metal-contaminated landfill? And, more generally, what is the difference between global warming and climate change?

There are national movements to reduce the consumption of bottled water, but why? Most obviously, there is the economic element of paying $1 or more for a bottle of water, when the equivalent amount of tap water costs 0.1 cents. Additionally, there is the environmental waste impact of the plastic container. What are the long-term environmental impacts of the plastic bottle? In 2015, 11.7  billion gallons of bottled water were consumed in the United States, a volume that equates to more than 75  billion individual 20-oz bottles, more than 60% of which ultimately end up in landfills. Furthermore, how much energy is expended just to produce this packaging? The annual energy cost of producing plastic bottles to contain commercial water is enough to fuel 1.3  million cars for a year. It is easy to muster outrage at a cartoon image of a glowing, gelatinous goop being dumped into a pristine river full of happy, jumping fish, but too few people realize that even the most innocent and cleanest of man-made products can carry a hidden environmental threat.

The ambiguous phrase, pollution, has been used for decades to excoriate emissions from industry and other sources, but it is rarely explained in detail through mainstream media coverage because to truly understand the threat of pollution, one must first understand the chemistry of the pollutants being expelled. Yes, pollutants are bad, but what precisely are the climatological, ecological, and economic impacts of their presence? How and why are they so detrimental to ecosystems and human life? Without understanding these concepts, one is poorly armed to argue against them. And without well-researched dissent, there can be no change to the status quo of environmental pollution.

Today's technology offers myriad pathways for improving the life of any human being with access to it, but these advancements come with a cost. Almost any piece of technology you use on a daily basis has a hidden price of environmental degradation. Cars, as previously mentioned, contribute to your carbon footprint and add dangerous radicals to the atmosphere. Smartphones are now ubiquitous in the developed world and beyond, but the disposal of faulty or unwanted phones provides a new challenge toward chemical remediation in landfills. Nearly every industry associated with natural resources, mining, agriculture, drilling, etc., has a deleterious environmental impact that must ultimately be eliminated if we are to cooperatively maintain the health of our planet.

The fundamental purposes of green chemistry are to:

1. Identify environmental threats.

2. Understand the chemical processes leading to environmental threats.

3. Analyze how and why these threats are occurring.

4. Devise a way to alter current technology to avoid these problems.

5. Determine how to remediate damage already inflicted.

Each of these points is equally important, and the solution to any one of them will require a wide variety of chemical and other scientific expertise. Nevertheless, a thorough understanding of green chemistry can allow a scientist to initiate the process of resolution for any given step.

2.1.2. Environmental Challenges

2.1.2.1. Challenges by Air

Air pollution is one of the most immediate and visible forms of environmental harm enacted by human technological advances and the source of many of the early environmental disasters in human history. While far from being the earliest incident, the London killer fog is one of the most notorious. In the winter of 1952, an unexpected cold snap hit London, causing