Water and Wastewater Analysis 399

CHAPTER 9 Introduction 401

9.1 Importance of Quantitative Measurements 401

9.2 Character of Environmental Engineering and Science Problems 402

9.3 Standard Methods of Analysis 402

9.4 Scope of a Course in Analysis of Environmental Samples 402

9.5 Expression of Results 403

9.6 Other Items 408 Problems 408


Statistical Analysis of Analytical Data 410

10.1 Introduction 410

10.2 Rounding Numerical Data 411

10.3 Definitions 412

10.4 Distribution of Experimental Data 416

10.5 Errors 419

10.6 Hypothesis Testing 426

10.7 Detection Limits 430

10.8 Lognormal Distribution 433

10.9 Regression Analysis 437

10.10 Quality Assurance and Quality Control 446

Problems 446 References 451

chapter 11

Basic Concepts from

Quantitative Chemistry 452

11.1 General Operations 452

11.2 The Analytical Balance 455

11.3 Gravimetric Analysis 457

11.4 Volumetric Analysis 458

11.5 Colorimetry 466

11.6 Physical Methods of Analysis 472

11.7 Precision, Accuracy, and Statistical Treatment of Data 474 Problems 474 References 475


Instrumental Methods of

Analysis 477

12.1 Introduction 477

12.2 Optical Methods of Analysis 478

12.3 Electrical Methods of Analysis 490

12.4 Chromatographic Methods of Analysis 503

12.5 Other Instrumental Methods 512 Problems 516

References 517


Turbidity 518

13.1 General Considerations 518

13.2 Environmental Significance 519

13.3 Standard Unit of Turbidity 520

13.4 Method of Determination 520

13.5 Application of Turbidity Data 521 Problems 522 Reference 522

CHAPTER 14 Color 523

14.1 General Considerations 523

14.2 Public Health Significance 524

14.3 Methods of Determination 524

14.4 Interpretation and Application of Color Data 526

Problems 527 Reference 527


Standard Solutions 528

15.1 General Considerations 528

15.2 Preparation of 1.00 N and 0.020 NH2S04. Solutions 530

15.3 Preparation of 1.00 N and 0.020 NNaOH Solutions 532 Problems 534 Reference 535


pH 536

16.1 General Considerations 536

16.2 Theoretical Considerations 536

16.3 Measurement of pH 538

16.4 Interpretation of pH Data 540 Problems 540 References 541


Acidity 542

17.1 General Considerations 542

17.2 Sources and Nature of Acidity 542

17.3 Significance of Carbon Dioxide and Mineral Acidity 544

17.4 Methods of Measurement 544

17.5 Application of Acidity Data 547 Problems 547

Reference 548

CHAPTER 18 Alkalinity 549

18.1 General Considerations 549

18.2 Public Health Significance 550

18.3 Method of Determining Alkalinity 550

18.4 Methods of Expressing Alkalinity 551

18.5 Carbon Dioxide, Alkalinity, and pH Relationships in Natural Waters 557

18.6 Application of Alkalinity Data 558

18.7 Other Considerations 559 Problems 560 Reference 562

CHAPTER 19 Hardness 563

19.1 General Considerations 563

19.2 Cause and Source of Hardness 564

19.3 Public Health Significance 566

19.4 Methods of Determination 566

19.5 Types of Hardness. 568

19.6 Application of Hardness Data 569 Problems 569

Reference 570


Residual Chlorine and Chlorine Demand 571

20.1 General Considerations 571

20.2 Chemistry of Chlorination 574

20.3 Public Health Significance of Disinfection Residuals 578 ■

20.4 Methods of Chlorine Residual Determination 580

20.5 Measurement of Chlorine Demand 583

20.6 Disinfection with Chlorine Dioxide 583

20.7 Disinfection with Ozone 584

20.8 Application of Disinfectant Demand and Disinfectant Residual Data 585 Problems 585

Reference 586

CHAPTER 21 Chloride 5S7

21.1 General Considerations 587

21.2 Significance of Chloride 588

21.3 Methods of Determination 588

21.4 Application of Chloride Data 590 Problems 591

References 592

CHAPTER 22 Dissolved Oxygen 593

22.1 General Considerations 593

22.2 Environmental Significance of Dissolved Oxygen 595

22.3 Collection of Samples for Determination of Dissolved Oxygen 596

22.4 Standard Reagent for Measuring Dissolved Oxygen 597

22.5 Methods of Determining Dissolved Oxygen 599

22.6 Dissolved-Oxygen Membrane Probes 601

22.7 Application of Dissolved-Oxygen Data 602

Problems 602 References 603

Biochemical Oxygen Demand 604

23.1 General Considerations 604

23.2 The Nature of the BOD Reaction 605

23.3 Method of Measuring BOD 610

23.4 Rate of Biochemical Oxidations 616

23.5 Discrepancy between L0 Values and Theoretical Oxygen Demand Values 620

23.6 Discrepancy between Observed Rates and First-Order Rates 621

23.7 Application of BOD Data 621 Problems 622

Reference 624

chapter 24

Chemical Oxygen Demand 625

24.1 General Considerations 625

24.2 History of the COD Test 626

24.3 Chemical Oxygen Demand by Dichromate 626

24.4 Inorganic Interferences 629

24.5 Application of COD Data 629 Problems 630 References 630

chapter 25 Nitrogen 631

25.1 General Considerations 631

25.2 Environmental Significance of Nitrogen Species 635

25.3 Methods of Analysis 640

25.4 Application of Nitrogen Data 646 Problems 647

References 648

chapter 26 Solids 649

26.1 General Considerations 649

26.2 Environmental Significance of Solids Determinations 651

26.3 Determination of Solids in Water Supplies 652

26.4 Determinations Applicable to Polluted Waters and Domestic Wastewaters 653

26.5 Determinations Applicable to Industrial Wastewaters 655

26.6 Determination of Solids in Sludges 656

26.7 Applications of Solids Data in Environmental Engineering Practice 657

Problems 657 Reference 658

Iron and Manganese 659

27.1 General Considerations 659

27.2 Environmental Significance of Iron and Manganese 661

27.3 Methods of Determining Iron 661 '

27.4 Methods of Determining Manganese 662

27.5 Applications of Iron and Manganese Data 663

Problems 664

chapter 28 Fluoride 665

28.1 General Considerations 665

28.2 Chemistry of Fluorine and Its Compounds 667

28.3 Methods of Determining Fluoride 668

28.4 Application of Fluoride Data 669 Problems 669

29.1 General Considerations 670

29.2 Methods of Analysis 674

29.3 Applications of Sulfate Data 675 Problems 676

Reference 676


Phosphorus and Phosphate 677

30.1 General Considerations 677

30.2 Phosphorus Compounds of Importance 679

30.3 Methods of Determining Phosphorus or Phosphate 679

30.4 Applications of Phosphorus Data 681 Problems 681

Reference 682

CHAPTER 31 Oil and Grease 683

31.1 General Considerations 683

31.2 Oil and Grease and Their Measurement 684

31.3 Methods of Analysis 685

31.4 Applications of Oil and Grease Data 687 Problems 688 Reference 688

c H A P T E R 32 Volatile Acids 689

32.1 General Considerations 689

32.2 Theoretical Considerations 691

32.3 Methods of Determining Volatile Acids 694

32.4 Applications of Volatile-Acids Data 697 Problems 698

Reference 698

CHAPTER 33 Gas Analysis 699

33.1 General Considerations 699

33.2 Methods of Analysis 700

33.3 Volumetric Analysis 701

33.4 Gas Chromatographic Analysis 705

33.5 Hydrogen Sulfide 706

33.6 Applications of Gas-Analysis Data 707 Problems 708

Reference 708

chapter 34

Trace Contaminants 709

34.1 General Considerations 709

34.2 The Safe Drinking Water Act 713

34.3 Drinking Water Standards 714

34.4 Trace Organic Contaminants 716

34.5 Trace Inorganic Contaminants 718

34.6 Secondary Standards and Guidelines 723

34.7 Trace Chemical Analyses 724 Problems 727 References 728

appendix A

Thermodynamic Properties at 25 °C 729 appendix B

Acronyms, Roman Symbols, and Greek Symbols 736

Index 742


ducation in environmental engineering and science has historically been conducted at the graduate level, and up to the present time has drawn mainly on students with a civil engineering background. In general, education in civil engineering does not prepare a student well in chemistry and biology. Since a knowledge of these sciences is vital to the environmental engineer, the graduate program must be designed to correct this deficiency. In recent years, students from other engineering disciplines and from the natural sciences have been attracted to this field. Some have a deficiency in chemistry and biology similar to that of the civil engineer and need exposure to general concepts of importance.

A current trend in the United States is the introduction of an undergraduate environmental engineering option or degree program within civil engineering departments. These students also require an introduction to important concepts in chemistry and biology.

This book is written to serve as a textbook for a first course in chemistry for environmental engineering and science students with one year of college-level chemistry. Environmental professionals need a wide background in chemistry, and in recognition of this need, Chemistry for Environmental Engineering and Science summarizes important aspects from various areas of chemistry. This treatment should help orient the students, aid them in choosing areas for advanced study, and help them develop a better "feel" for what they should expect to gain from further study.

The purpose of this book is twofold: It (1) brings into focus those aspects of chemistry that are particularly valuable for solving environmental problems, and (2) it lays a groundwork of understanding in the area of specialized quantitative analysis, commonly referred to as water and wastewater analysis, that will serve the student as a basis in all the common phases of environmental engineering practice and research.

Substantial changes continue to occur in the emphasis of courses for environmental engineers and scientists. The trend is toward a more fundamental understanding of the chemical phenomena causing changes in the quality of surface and groundwaters, of waters and wastewaters undergoing treatment, and of air. This fundamental understanding of chemistry is absolutely critical as environmental professionals attempt to solve complex problems such as hazardous waste pollution, air pollution from emission of toxic compounds, radioactive waste disposal, ozone depletion, and global climate change.

Chemistry for Environmental Engineering and Science is organized into two parts. Part One is concerned solely with fundamentals of chemistry needed by environmental engineers and scientists. It includes chapters on general chemistry, physical chemistry, equilibrium chemistry, organic chemistry, biochemistry, colloid chemistry, and nuclear chemistry. Each emphasizes environmental applications. In this new edition, the chapters on general and physical chemistry have been updated, and new homework problems have been added. The chapter on equilibrium chemistry has been revised, with many new example and homework problems. The chapter on organic chemistry includes an added emphasis on organic compounds of environmental significance (e.g., chlorinated solvents). Sections are included on the behavior (fate) of organic compounds in the environment and in engineered systems and on the use of structure-activity relationships. The chapter on biochemistry has been updated. We feel that these revisions make the text even more suitable for lecture courses on environmental chemistry principles.

Part Two is concerned with analytical measurements. A new chapter has been added on statistical analysis of analytical data. All analytical procedures are subject to errors. There is a critical need for students to leam how to evaluate the uncertainties such errors present. This chapter discusses basic methods for evaluating and reporting uncertainties in measurements that are essential for analytical chemists, regulatory agencies, and environmental professionals who use analytical data to make important decisions.

The next several chapters contain general information on quantitative, qualitative, and instrumental methods of analysis, useful as background materia! for die subsequent chapters concerned with water and wastewater analyses of particular interest to environmental engineers and scientists. These chapters are written to stress the basic chemistry of each analysis and show their environmental significance. They should be particularly useful when used with "Standard Methods for the Examination of Water and Wastewater," published jointly by the American Public Health Association, American Water Works Association, and Water Environment Federation, and giving the details for carrying out each analytical determination. The final chapter stresses trace contaminants, many of which are determined analytically with instrumental procedures discussed in earlier chapters. A listing of U.S. Environmental Protection Agency drinking water standards and World Health Organization drinking water quality guidelines for various trace contaminants are also contained in this chapter. Part Two is considered to be most useful as lecture material to accompany a laboratory course in environmental chemistry. Revisions have been made in other chapters to reflect the many changes in "Standard Methods" that have occurred since the last edition of this text.

Problems are included at the end of most chapters to stress fundamentals and increase the usefulness of this book as a classroom text. Example problems throughout the text help increase the students' understanding of the principles outlined. In Part One of the book, where the emphasis is on chemical fundamentals, answers are included after many homework problems, allowing students to evaluate independently their understanding of the principles emphasized.

To meet textbook requirements, brevity has been an important consideration throughout. For those who believe that we have been too brief, we can only beg their indulgence and recommend that they seek further information in standard references on the subject. Important references are listed at the end of each chapter.

Preface xv

It is inevitable that we have made errors in producing this textbook. For this we apologize. Hopefully they are not so numerous that they impede the student's ability to learn the material. Fortunately, for this new edition, McGraw-Hill is providing a website where we can list errata that can be readily downloaded with no charge to students and faculty. A solution manual for text problems can also be obtained at this website, but by faculty members only. We hope also to use this website to post more example problems and their solutions. There was a request for such by reviewers, and this is one way that we can provide additional material without expanding the number of pages and costs for the text The website for this textbook can be found at http://www.mhhe.com/sawyer. We would appreciate hearing from students and faculty when eixors are found so that we can enter them in a timely manner on the website. Our e-mail addresses are included in the errata section of the website.

Special thanks are due colleagues at the University of Iowa—Michelle Scherer for specific suggestions to improve the text and generous help with new homework problems, and Pedro Alvarez, Keri Hornbuckle, Craig Just, Jerry Schnoor, and Richard Valentine for helpful discussions. Thanks also to Mark Benjamin of the University of Washington for e-mail discussions of activity corrections and other weighty matters. Finally, we wish to express our gratitude to William Burgos, Pennsylvania State University; Cindy Lee, Clemson University; Howard Liljestrand, University of Texas, Austin; John Pardue, Louisiana State University; and Andrew Randall, University of Central Florida, as well as the anonymous reviewers, all of whom were selected by the publisher to provide comments about the textbook and to provide recommendations for change. We appreciate the many thoughtful and detailed comments that were offered and used them extensively in preparing this revision. We hope that the reviewers and other faculty find the changes to be beneficial to them and to their students.

Perry L. McCarty Gene F. Parkin

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