Environmental Chemistry, (O'Neill, Peter)

Nov 11, 1996 - O'Neill has written an environmental handbook of the elements with chemical principles integrated into the topics, which, he states, is...
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Chemical Education Today

Reviews Environmental Chemistry, Second Edition Peter O’Neill. Chapman and Hall: New York, 1993. x + 268 pp. Figs. and tables. 13.8 × 21.5 cm. $33.95 PB. O’Neill has written an environmental handbook of the elements with chemical principles integrated into the topics, which, he states, is appropriate for first-year British college students. His presumed competence in virtually all aspects of chemistry will challenge most U.S. students at this level despite the informative asides. O’Neill uses cycle diagrams for elements and their compounds in nearly every chapter, which clearly summarize their chemical relationships with the environment. He includes a 10-page glossary—generous in such a small book—and an appendix on chemical bond formation that is a model of brevity and conciseness. The body of the book is divided into four parts: The Oxygen Rich Planet, Major Elements Found in Living Matter, Major Elements in the Earth’s Crust, and Minor Elements and Environmental Problems. Within these sections O’Neill includes discussions of atmospheric chemistry, biochemistry, electrochemistry, electromagnetic radiation, geochemistry, geology, mineralogy, nuclear chemistry, and toxicology. Environmental concerns addressed include expected topics like the greenhouse effect and ozone depletion and unexpected topics like the effect of hard water on heart disease and aluminum uptake by Alzheimer’s patients. His discussion of iron solution chemistry includes several Pourbaix (“Eh-pH”) diagrams rarely seen in elementary texts but excellent for summarizing a profusion of data succinctly. On the down side, there are no problems or exercises, few source references, and no use of photos or color. This book will probably find the greatest use in the U.S. as the text for a one-semester, special topics course in environmental chemistry at the sophomore or junior level. For such a course it is pretty much perfect. With access to its built-in reference materials, students will have to leave the text only for instructor-supplied problem sets.

Robert F. Drake Bronx Community College, Bronx, NY 10453-3102

Environmental Chemistry Colin Baird. W. H. Freeman: New York, 1995, xix + 484 pp. Figs. and tables. 18.8 × 24 cm. Written for students with an introductory chemistry background, Colin Baird’s new text does a superb job in covering environmental chemistry while also building on chemical principles developed in earlier course work. This book is truly written from a chemist’s perspective. Baird defines environmental chemistry as “being con-

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cerned with the chemical aspects of problems that human beings have created in the natural environment”. The text focuses on four major areas: atmospheric chemistry (three chapters on stratospheric chemistry, tropospheric chemistry, and global warming), toxic organic substances (an organic chemistry overview and a 71-page chapter on toxic organic chemicals), water chemistry and concerns (three chapters on contamination and purification, acid-base chemistry of the carbonate system, and heavy metals/soil chemistry), and energy (one chapter on energy production and its environmental consequences). Indicative of the thoroughness of the text is the first chapter (after the introduction) on stratospheric chemistry. The author covers photochemistry, ozone production, noncatalytic and catalytic ozone destruction, Lewis structure of free radicals, heterogeneous-driven Antarctic ozone depletion, CFCs, CFC replacements, and international agreements. It ends with a summary of principles that govern stratospheric processes. Students found this effective, since it condensed the many reactions into the coherent framework of principles that tied the subject together. Baird incorporates inset boxed sections to focus on related areas. The stratospheric chemistry chapter examines Lewis structures of free radicals, rates of free radical reactions, formulas and codes for carbon compounds (including CFCs), supersonic aircraft and ozone depletion, and recent research on ozone destruction. The kinetics discussion links reaction rates to enthalpy changes. Endothermic reactions necessarily have activation energies at least as large as their endothermicity and thus occur slowly (since a characteristic of these reactions is that activation energy exceeds the endothermicity by a small amount). Correspondingly, exothermic reactions have large rate constants. The chapter summary identifies relative bond strengths for stratospheric species containing loosely bound oxygen atoms. Students thus have the tools to predict enthalpy changes and relative rate constants for many important stratospheric reactions. At times, Baird devotes the first half of a chapter to a discipline overview, followed by more detailed discussions. For example, the tropospheric chemistry chapter introduces acid rain, photochemical smog, particulates, indoor air pollution, and outdoor air pollution. The last half spirals back to examine reactivity principles, methane oxidation mechanisms, photochemical smog formation mechanisms, and acid rain formation (both homogeneous gas phase and aqueous phase oxidation of sulfur dioxide) mechanisms. Students found this approach effective in better understanding the context in which specific mechanisms have importance. Baird does not assume students have completed organic chemistry; he devotes one chapter to organic fundamentals. This is directly followed by an extensive chapter on toxic organic chemicals. This section alone is well worth the price of the book. Topics include pesticides, organochlorine insecticides (DDT and analogs, toxaphenes, chlorinated cyclopentadienes), organophosphate

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Chemical Education Today

and carbamate insecticides, natural insecticides, herbicides (triazines, paraquat, phenoxy), dioxin contamination of herbicides and preservatives, dioxin sources, PCBs (structure, properties, uses) furan contamination, toxicology of PCBs dioxins, and furans, and finally PAHs. Baird traces the evolution of pesticide structure as well as the specific physiological effects. This historical and biochemical perspective provides the necessary background to readily understand environmental research involving anthropogenic organics in the environment. Baird addresses quantitative concepts in a chapter on the acid–base chemistry of the carbonate system. The carbon dioxide/water and carbonate/bicarbonate equilibria are examined separately and then together. The final system involves Henry’s law, weak acid equilibria, weak base equilibria, and solubility equilibria. Combined equilibria calculations are surprisingly close (in spite of not using activities) to the calcium and bicarbonate concentrations commonly observed in calcareous regions. This chapter provides an exceptional opportunity for students to integrate many of the concepts covered in the latter half of general chemistry. The results provide insights into the underlying chemical basis for the main ionic constituents of natural waters. For a first edition, the text has few errors—Baird and the reviewers have done meticulous work. Each chapter has quantitative exercises for students within sections. End-of-chapter problems are nonquantitative and can be answered by referring back to the appropriate paragraph. It would be nice to see more quantitative problems in each chapter’s problem set (including several that involve spreadsheets). The book is extremely readable—its clarity received the highest student ratings I have ever seen. This provided time in class to examine related issues, since there is less need to explain what is already discussed so well. One distraction was the author’s use of the Beer-Lambert equation in a form different from the convention used in analytical courses. Overall the selection of topics is exceptional. After covering the entire text in a semester, student feedback indicated that all topics covered were relevant and important. I found that all lessons involved issues I had routinely encountered in the environmental field. While toxocology is indirectly discussed a number of times; there is, unfortunately, no separate section on toxicology to discuss principles such as dose–response curves, toxicological testing, routes of entry, epidemiology, and determination of health limits. If ever a case could be made for requiring majors to complete environmental chemistry, Baird’s selection of environmental topics represents a compelling argument. The fundamentals so eloquently discussed are ideas that all graduates should well understand. This is a book hitting on all cylinders. Every so often, you find a text ideally organized and artistically put together to fit a discipline particularly well—I believe the two that best match this description are Dan Harris’s Quantitative Analysis, and Colin Baird’s Environmental Chemistry. The latter is certainly a winner that I

highly recommend, particularly for those developing a new course in environmental chemistry.

Patrick M. Owens Winthrop University, Rock Hill, SC 29733

Aquatic Chemistry: Chemical Equilibria and Rates in Natural Waters Third Edition. Werner Stumm and James J. Morgan. A Wiley-Interscience publication in Environmental Science and Technology (Series Editors, Jerald L. Schnoor and Alexander Zehnder), John Wiley & Sons: New York, 1996. xvi + 1022 pp. Figs. and tables. 15.8 × 23.6 cm. $79.95 (hard cover) ISBN 0-471-51184-6. $59.95. (paperback) ISBN 0-471-51185-4. Aquatic chemistry deals with chemical reactions and processes affecting the distribution and circulation of chemical species in natural waters. This textbook/monograph focuses on physicochemical principles as they pertain to the identification of pertinent variables that determine the composition of natural aquatic systems. The student will discover that such basic processes as dissolution and precipitation, oxidations and reductions, and acid–base and complexation interactions in natural systems are very similar to those experienced in a chemical laboratory. Following the 2nd edition published over twelve years ago, this text Aquatic Chemistry continues to emphasize the pedagogical approach from two fronts: (i) basic chemical principles in the quantitative treatment of the composition of natural waters, and (ii) the use of concepts of chemical equilibrium, rates of processes, and chemical reactions, to lay down the foundation for modeling natural systems. By comparison, this third edition is a greatly improved version due mostly to significant advances made during the last decade in the understanding of natural systems. In its teaching approach it employs general concepts and methods of problem solving so that the student may apply them to other aquatic systems. Every chapter has a bibliography of suggested readings and a list of relevant problems and answers. In addition, a hefty list of references (40 pages) is given at the end of the book along with various appendices of relevant tabulated thermodynamic data. Several novel features are worth noting in this third edition. A new chapter (Chapter 5) has been added that treats interactions between the atmosphere and water; it also shows the interconnection between land, water, and air environments. For even though water is a minor component in the atmosphere, it nevertheless plays a significant role in chemical reactions in clouds, fog, and rain. In the treatment of solid/water interfaces, the authors have brought several major revisions. Surface chemistry is emphasized in the quantitative treatment of rate laws in geochemical processes (Chapter 13),

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Reviews whereas Chapter 14 shows how essential surface chemistry is for a proper interpretation of the behavior of colloidal systems in particle–particle interactions. The significant progress in concepts and experimental approaches made during the last few years is summarized in Chapter 9. For example, adsorption interactions of solutes with solid surfaces are characterized by (i) formation of surface complexes (chemisorption) and (ii) hydrophobic adsorption of nonpolar solutes to the solid surface. These two notions form the backbone for an understanding of the various processes in natural systems. In Chapter 6, treatment of metal ions and aqueous coordination chemistry have been updated to provide a greater understanding of metal ion speciation and complexation kinetics. Chapter 10 pays particular attention to the cycling and the biological role of trace metals in nutrition and in the toxicity of aquatic systems. Important advances in the understanding of mechanisms of redox processes are presented in Chapter 8, while novel interpretations of rates of electron transfer processes are considered in Chapter 11, and Chapter 12 presents photochemical principles and analyzes several important light-induced and photocatalyzed processes. Pedagogically, this text is divided into two parts. The first part comprising chapters 2 through 9 represents a core of topics for an introductory course for advanced undergraduates and first-year graduates in environmental science and engineering, earth sciences, and oceanography, and would definitely be a relevant and rewarding elective course for chemistry majors. The second part comprising chapters 10 through 15 treats more advanced and detailed topics: (a) trace metals, (b) kinetics of redox processes, (c) photochemical processes, (d) kinetics at the solid/water interfaces, (e) particle–particle interactions, and (f) regulation of the chemical composition of natural waters. It is relevant to examine the core chapters briefly. Subsequent to an introductory chapter (Chapter 1) on terminology and various fundamental constants, chapter 2 on Chemical Thermodynamics and Kinetics describes the principles and applications of two alternative models to treat natural waters: thermodynamic models and kinetic models. It is succeeded by a chapter on Acids and Bases, which depicts how interactions between acids and bases influence the composition of natural waters: it’s been said that an ocean is the result of a gigantic acid–base titration. The distribution of CO2, H2CO3, HCO3} and CO32} in natural waters is considered in Chapter 4 (Dissolved Carbon Dioxide) together with an examination of CO2 exchange between the atmosphere and the waters, with an evaluation of the buffering mechanisms of fresh waters and seawater, and with a definition of their capacities for acid and base neutralization. In Chapter 5, some important reactions at the gas/water interface are described and the partitioning of molecules between the gas phase and the aqueous phase (Henry’s law) is discussed extensively. The chapter also treats processes that affect wet and dry deposition and the composition of atmospheric water droplets (clouds, fog, rain, snow, dew) and illustrates how pollutants released into the atmosphere are transferred back to the soil. Chapter 6 entertains several aspects of

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coordination chemistry and metal ions in aqueous solutions, while Chapter 7 (Precipitation and Dissolution) sets forth principles that concern reactions between solids and water utilizing equilibrium relations. Chapter 8 on redox equilibria and microbial mediation stresses the stability relations of pertinent redox components in natural water systems. Chapter 9, the last chapter in the core program, deals with solid/solution interfaces. It emphasizes the action of water on minerals that produce very high surface areas and reactive and with catalytic materials in surface environments. This book on Aquatic Chemistry is highly recommended for course adoption for a 1- to 2-semester course in fields dealing with natural water environments. Students and seasoned workers interested in natural aquatic environments and, by extrapolation, in the detoxification of environmental pollution will find this text/monograph an excellent companion to an earlier one, Environmental Organic Chemistry (WileyInterscience; 1993; ISBN 0-47-83941-8), and a good addition to one’s personal library.

Nick Serpone Concordia University, Montreal, PQ H3G 1M8

Introduction to Environmental Chemistry Nigel Bunce. Wuerz: Winnipeg, MB, Canada, 1993. xiv + 559 pp. Figs., tables, photos and color plates. 17.4 × 24.7 cm. $48 PB. Bunce’s book is almost a general chemistry text with integrated environmental applications and examples. I use the word “almost” because even the author admits in the preface that bonding and other topics have been left out to accommodate the applied environmental topics. (A comprehensive supplemental chapter on atomic theory and bonding by Bunce is available from the publisher to adopters.) Actually, many basic chemistry topics are included, but some of them are not particularly complete. Polar molecules are not mentioned until page 248, in a chapter on water. Until then, compounds are either ionic and soluble or covalent and not. In an early discussion of acids he avoids mentioning the partial ionization of weak acids. In fact he avoids the use of the equilibrium arrow until page 127, in a discussion of equilibrium vapor pressure. Equilibrium is not defined, however, until Chapter 8 (page 187), in a discussion of gasphase equilibria. complete solution equilibria discussions appear even later (Chapters 11 and 12). There are a number of small errors which will, no doubt, be corrected upon revision. An osmotic pressure apparatus diagram has the higher level on the wrong side. Line-art figures in some chapters are not numbered and not referenced. Terms are sometimes used before they are defined, and no glossary is provided as a secondary reference. Hydrate and aggregate “dots” are rendered, idiosyncratically, as decimal points throughout.

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On the positive side, Bunce writes with a clear style, setting off definitions and rules from the text with globe icon markers. His environmental topics are well-selected and interesting, and the problems associated with them are challenging, although the discussion of the environmental chemistry of iron would have benefitted from the use of Pourbaix (“Eh-pH”) diagrams. Chapters on topics not usually found in a general chemistry text are strategically placed through it, including Industrial Processes, Photochemical Smog and Ground Level Ozone, Stratospheric Ozone Depletion, and Metals and Mining. In addition there are unusually complete chapters on Water and Acid Rain. Illustrative exercises are set off from the body of the text with a gray shading, and the many chapter problems are grouped according to chapter section. This text should appeal to those favoring an applied approach to teaching general chemistry at a level well beyond that of liberal arts “consumer chemistry” texts. It may have limited appeal to many potential adopters because of its “engineering flavor”. This is unfortunate because an applied approach to chemistry was very well received by students in Australia, at the high school level. A text as this might be exactly what is needed to engage reluctant students.

Robert F. Drake

Books for Review Notice to Publishers: Books that are intended for review in the Journal should be sent to the editor. Please do not send books directly to prospective reviewers, as the editor and the book-review editor (to be named in the December 1996 issue) will be assigning books to reviewers. The Journal’s address is: Journal of Chemical Education University of Wisconsin–Madison Department of Chemistry 209 North Brooks Street Madison, WI 53715-1116 Phone: 608/262-7146 or 1-800-991-5534 FAX: 608/262-7145 email: [email protected] http://jchemed.chem.wisc.edu/

Bronx Community College, Bronx, NY 10453-3102

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