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Surface Water-Quality Modeling

Steven C. Chapra
Tufts University

WAVELAND

PRESS, INC.
Long Grove, Illinois

CONTENTS
Preface

xvi i
1

PART 1

Completely Mixed Systems

LECTURE 1 Introduction

1.1 Engineers and Water Quality 1.2 Fundamental Quantities 1.3 Mathematical Models 1.4 Historical Development of Water-Quality Models 1.5 Overview of This Book Problems
LECTURE 2 Reaction Kinetics

3 4 6 10 14 19 20 24 24 29 38 40 42
47

2.1 Reaction Fundamentals 2.2 Analysis of Rate Data 2.3 Stoichiometry 2.4 Temperature Effects Problems
LECTURE 3 Mass Balance, Steady-State Solution, and Response Time

3.1 Mass Balance for a Well-Mixed Lake 3.2 Steady-State Solutions 3.3 Temporal Aspects of Pollutant Reduction Problems
LECTURE 4 Particular Solutions

47 52 57 62 65 66 68 70 71 73 76 80 83 86 86 91 vii

4.1 Impulse Loading (Spill) 4.2 Step Loading (New Continuous Source) 4.3 Linear ("Ramp") Loading 4.4 Exponential Loading 4.5 Sinusoidal Loading 4.6 The Total Solution: Linearity and Time Shifts 4.7 Fourier Series (Advanced Topic) Problems
LECTURE 5 Feedforward Systems of Reactors

5.1 Mass Balance and Steady-State 5.2 Time Variable

viii CONTENTS 5.3 Feedforward Reactions Problems 95


99
101

LECTURE 6 Feedback Systems of Reactors

6.1 Steady-State for Two Reactors 6.2 Solving Large Systems of Reactors 6.3 Steady-State System Response Matrix 6.4 Time-Variable Response for Two Reactors 6.5 Reactions with Feedback Problems
LECTURE 7 Computer Methods: Well-Mixed Reactors

101 103 107 111 113 117


120

7.1 Euler's Method

7.2 Heun's Method 7.3 Runge-Kutta Methods 7.4 Systems of Equations Problems PART II Incompletely Mixed Systems

121 124 126 128 131

135

LECTURE 8 Diffusion

8.1 Advection and Diffusion 8.2 Experiment 8.3 Fick's First Law 8.4 Embayment Model 8.5 Additional Transport Mechanisms Problems
LECTURE 9 Distributed Systems (Steady - State)

137 137 138 141 143 149 153


156

9.1 Ideal Reactors

9.2 Application of the PFR Model to Streams 9.3 Application of the MFR Model to Estuaries Problems
LECTURE 10 Distributed Systems (Time - Variable)

156 164 168 171


173

10.1 Plug Flow 10.2 Random (or "Drunkard's") Walk 10.3 Spill Models

173 177 180

CONTENTS ix 10.4 10.5 Tracer Studies Estuary Number Problems 186 189 190
192

LECTURE 11

Control-Volume Approach: Steady-State Solutions 11.1

11.2 11.3 11.4 11.5 11.6 11.7 11.8

Control-Volume Approach Boundary Conditions Steady-State Solution System Response Matrix Centered-Difference Approach Numerical Dispersion, Positivity, and Segment Size Segmentation Around Point Sources Two- and Three-Dimensional Systems Problems

192 194 195 197 198 201 207 208 209


212

LECTURE 12

Simple Time-Variable Solutions

12.1 12.2 12.3 12.4

An Explicit Algorithm Stability The Control-Volume Approach Numerical Dispersion Problems

212 214 215 216 221


223

LECTURE 13

Advanced Time-Variable Solutions

13.1 13.2 13.3

Irnplicit Approaches The MacCormack Method Summary Problems

223 229 230 232


233

PART 111

Water-Quality Environments

LECTURE 14

Rivers and Streams

235

14.1 14.2 14.3 14.4 14.5 14.6

River Types Stream Hydrogeometry Low-Flow Analysis Dispersion and Mixing Flow, Depth, and Velocity Routing and Water Quality (Advanced Topic) Problems

235 238 243 245 247 250 257

x CONTENTS LECTURE 15 Estuaries


260

15.1 Estuary Transport 15.2 Net Estuarine Flow 15.3 Estuary Dispersion Coefficient 15.4 Vertical Stratification Problems
LECTURE 16 Lakes and lmpoundments

260 262 263 270 272


276

16.1 Standing Waters 16.2 Lake Morphometry 16.3 Water Balance 16.4 Near-Shore Models (Advanced Topic) Problems
LECTURE17 Sediments

276 278 282 287 293


295

17.1 Sediment Transport Overview 17.2 Suspended Solids 17.3 The Bottom Sediments 17.4 Simple Solids Budgets 17.5 Bottom Sediments as a Distributed System 17.6 Resuspension (Advanced Topic) Problems
LECTURE 18 The "Modeling" Environment

295 297 302 304 307 312 315


317

18.1 The Water-Quality-Modeling Process 18.2 Model Sensitivity 18.3 Assessing Model Performance 18.4 Segmentation and Model Resolution Problems

317 327 335 339 341

PART IV Dissolved Oxygen and Pathogens

345

LECTURE 19 BOD and Oxygen Saturation

347

19.1 The Organic Production/Decomposition Cycle 19.2 The Dissolved Oxygen Sag 19.3 Experiment 19.4 Biochemical Oxygen Demand 19.5 BOD Model for a Stream

347 348 351 353 355

CONTENTS xi 19.6 BOD Loadings, Concentrations, and Rates 19.7 Henry's Law and the Ideal Gas Law 19.8 Dissolved Oxygen Saturation Problems
LECTURE20 Gas Transfer and Oxygen Reaeration

357 360 361 365


367

20.1 Gas Transfer Theories 20.2 Oxygen Reaeration 20.3 Reaeration Formulas 20.4 Measurement of Reaeration with Tracers Problems
LECTURE 21 Streeter-Phelps: Point Sources

369 376 377 384 386


389

21.1 Experiment 21.2 Point-Source Streeter-Phelps Equation 21.3 Deficit Balance at the Discharge Point 21.4 Multiple Point Sources 21.5 Analysis of the Streeter-Phelps Model 21.6 Calibration 21.7 Anaerobic Condition 21.8 Estuary Streeter-Phelps Problems
LECTURE 22 Streeter-Phelps: Distributed Sources

389 391 391 393 396 398 399 401 403


405

22.1 Parameterization of Distributed Sources 22.2 No-Flow Sources 22.3 Diffuse Sources with Flow Problems
LECTURE 23 Nitrogen

405 407 410 417


419

23.1 Nitrogen and Water Quality 23.2 Nitrification 23.3 Nitrogenous BOD Model 23.4 Modeling Nitrification 23.5 Nitrification and Organic Decomposition 23.6 Nitrate and Ammonia Toxicity Problems
LECTURE 24 Photosynthesis/Respiration

419 421 424 426 428 430 432


433

24.1 Fundamentals

433

xii CONTENTS 24.2 Measurement Methods Problems


LECTURE 25 Sediment Oxygen Demand

437 448
450

25.1 Observations 25.2 A "Naive" Streeter-Phelps SOD Model 25.3 Aerobic and Anaerobic Sediment Diagenesis 25.4 SOD Modeling (Analytical) 25.5 Numerical SOD Model 25.6 Other SOD Modeling Issues (Advanced Topic) Problems
LECTURE 26 Computer Methods

451 455 457 459 470 474 480


482

26.1 Steady-State System Response Matrix 26.2 The QUAL2E Model Problems
LECTURE 27 Pathogens

482 486 500 503 503 504 506 510 512 516

27.1 Pathogens 27.2 Indicator Organisms 27.3 Bacterial Loss Rate 27.4 Sediment-Water Interactions 27.5 Protozoans: Giardia and Cryptosporidium Problems PART V Eutrophication and Temperature

519

LECTURE 28 The Eutrophication Problem and Nutrients

521

28.1 The Eutrophication Problem 28.2 Nutrients 28.3 Plant Stoichiometry 28.4 Nitrogen and Phosphorus Problems
LECTURE 29 Phosphorus Loading Concept

522 522 527 530 533 534 534 536 539

29.1 Vollenweider Loading Plots 29.2 Budget Models 29.3 Trophic-State Correlations

CONTENTS xiii 29.4 29.5 Sediment-Water Interactions Simplest Seasonal Approach Problems 545 551 558 560 561 563 565 571 575 577 577 580 585 588
590

LECTURE 30

Heat Budgets

30.1 Heat and Temperature 30.2 Simple Heat Balance 30.3 Surface Heat Exchange 30.4 Temperature Modeling Problems
LECTURE 31
Thermal Stratification

31.1 31.2 31.3

Thermal Regimes in Temperate Lakes Estimation of Vertical Transport Multilayer Heat Balances (Advanced Topic) Problems

LECTURE 32

Microbe/Substrate Modeling

32.1 32.2 32.3 32.4 32.5

Bacterial Growth Substrate Limitation of Growth Microbial Kinetics in a Batch Reactor Microbial Kinetics in a CSTR Algal Growth an a Limiting Nutrient Problems

590 592 596 598 600 602 603 603 605 607 609 612 613 615 621 622 622 626 629

LECTURE 33

Plant Growth and Nonpredatory Losses

33.1 33.2 33.3 33.4 33.5 33.6 33.7

Limits to Phytoplankton Growth Temperature Nutrients Light The Growth-Rate Model Nonpredatory Losses Variable Chlorophyll Models (Advanced Topic) Problems

LECTURE 34

Predator - Prey and Nutrient/Food-Chain Interactions

34.1 34.2 34.3

Lotka-Volterra Equations Phytoplankton-Zooplankton Interactions Zooplankton Parameters

xiv CONTENTS 34.4 Nutrient/Food-Chain Interactions Problems


LECTURE 35 Nutrient/Food-Chain Modeling

629 631
633

35.1 Spatial Segmentation and Physics 35.2 Kinetic Segmentation 35.3 Simulation of the Seasonal Cycle 35.4 Future Directions Problems
LECTURE 36 Eutrophication in Flowing Waters

633 634 637 641 642


644

36.1 Stream Phytoplankton/Nutrient Interactions 36.2 Modeling Eutrophication with QUAL2E 36.3 Fixed Plants in Streams Problems

644 649 658 663

PART VI Chemistry

665

LECTURE 37 Equilibrium Chemistry

667

37.1 Chemical Units and Conversions 37.2 Chemical Equilibria and the Law of Mass Action 37.3 Ionic Strength, Conductivity, and Activity 37.4 pH and the Ionization of Water 37.5 Equilibrium Calculations Problems
LECTURE 38 Coupling Equilibrium Chemistry and Mass Balance

667 669 670 672 673 676


677

38.1 Local Equilibrium 38.2 Local Equilibria and Chemical Reactions Problems
LECTURE 39 pH Modeling

677 680 682


683

39.1 Fast Reactions: Inorganic Carbon Chemistry 39.2 Slow Reactions: Gas Transfer and Plants 39.3 Modeling pH in Natural Waters Problems

683 686 689 691

CONTENTS xv
PART VII Toxics

693

LECTURE 40 Introduction to Toxic-Substance Modeling

695

40.1 The Toxics Problem 40.2 Solid-Liquid Partitioning 40.3 Toxics Model for a CSTR 40.4 Toxics Model for a CSTR with Sediments 40.5 Summary Problems
LECTURE 41

695 697 700 705 713 713


715

Mass-Transfer Mechanisms: Sorption and Volatilization

41.1 Sorption 41.2 Volatilization 41.3 Toxicant-Loading Concept Problems


LECTURE 42

715 727 732 737

Reaction Mechanisms: Photolysis, Hydrolysis, and Biodegradation

42.1 Photolysis 42.2 Second-Order Relationships 42.3 Biotransformation 42.4 Hydrolysis 42.5 Other Processes Problems
LECTURE 43 Radionuclides and Metals

739 739 751 751 753 755 756 757 757 758 761 768

43.1 Inorganic Toxicants 43.2 Radionuclides 43.3 Metals Problems

LECTURE 44 Toxicant Modeling in Flowing Waters

44.1 Analytical Solutions 44.2 Numerical Solutions 44.3 Nonpoint Sources Problems

769 769 778 779 782

xvi CONTENTS LECTURE 45 Toxicant/Food-Chain Interactions

45.1 Direct Uptake (Bioconcentration) 45.2 Food-Chain Model (Bioaccumulation) 45.3 Parameter Estimation 45.4 Integration with Mass Balance 45.5 Sediments and Food Webs (Advanced Topic) Problems
Appendixes A Conversion Factors B Oxygen Solubility C Water Properties D Chemical Elements E Numerical Methods Primer F Bessel Functions G Error Function and Complement References Acknowledgments Index

784 785 788 790 794 795 797 798


798 801 802 803 805 817 820
821

834 835