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WATER elt eRe Vernon L. Snoeyink David Jenkins WATER CHEMISTRY VERNON L, SNOEYINK University of Illinois, Urbana DAVID JENKINS University of California, Berkeley JOHN WILEY & SONS, New York + Chichester + Brisbane « Toronto « Singapore Copyright @ 1980. by John Wiley & Sons, Tne. Allzighis reserved, Published simvltanogusly a Gonads, Roproduction er iramelation of exy prt of this work beyond that permitted by Sections 107 end 108 of the L876 United States Copyright Act without the permission of the copyeight . over is unkewiul, Requests for pertnlssion for further inlormation should be addressed to tho Permissions Departipent, John Wiley & Sons Ubrary of Congress Cataloging tn Publication Dates Snowyink, Veunox L. Water Chemistry Includes bibliographies end index. L. Woter chemistey. 1 Janna, David, 1835. Jott cuther. Tl Tile QDIsa.waseS —S4ezz-UzasA 78.2108 ISBN 0471-08169 Printed in # 30 29 26 27 26 25 24 United States of America Printed and bound by Quinn - Woodbine, Inc.. ‘To Joannie, Todd, and Craig Joan, Daniel, and Sarah PREFACE This book is a first-level text of water chemistry that places special emphasis on the chomisity of natural and polluted waters and on the applied chemistry of water and wastewater treatment. It provides a comprehensive coverage of the dilute aqueous solution chemistry of acid- base roactions, complox formation, procipitation and dissolution roae- tions, and oxidation-reduction reactions, Although it is written primarily for students and those individuals who are currently working in environ- mental or sanitery engineering, much of its contents should also prove to be of value to chemists, biologists, ecologists, and geochemists, Wo assume that the roadere will havo a good background in gonorcl chom- istry; additional knowledge in the fields of analytical and physical chemisiry is useful but not essential. The material in the text has been eatistactorily taught to advanced undergraduates and first-level graduate students in environmental enginocring with one year of olemontary chemistry as a background. This book provides an integrated coverage of chemical kinetic and equilibrium principles and applies them to water chemistry in its broadest sense, that is, to natural and polluted water and to water and wastewater treatment processes. Special attention is paid to tho offects of temperature and ionic strength on reactions. In the first introductory chapter, the characteristics of the various types of water of concern ate presented long with a discussion of the concentration units unique to water chomisiry. Chapters 2 and 3 provide the background in chomica! kinetics end thermodynamics necessary for tho subsequont coverage of water chemisiry. If the text is to be used for teaching students with background in physical chemistry, Chapters 2 and 9 may be reud for review purposes only, Chapters 4 to 6, and 7 deal, respectively, with acid-base, complox- ation, precipitation disselution, and oxidation.reduction chemistry, In each of these chapters we first present the necessary principles for understanding the systems io be encountered and then the necessary tools to solve problems; following this, we present one or more gpplications of the topic in the water or wastewater areas. Tho graphical solution of equilibrium problems is stressed throughout the book. The acid-base chemistry chapter conchides with a detailed discussion of the carbonate system. The complexation chapter deals at length with the organic and inorganic complexes of metal ions found in natural waters. Phosphate chemistry and heterogenous calcium carbonate equilibria and kinetics are presented as applications of the principles of precipitation-dissolution, presented in Chapter 6. In Chapter 7, the topics of corrosion, iron chemisiry, chlorine chemistry, biologically important redox reactions, and principles of clectrechomical measuromonte are procented to illus- vl Preface trate the importance and practical application of the principles of oxi- dation-reduction reactions, Numerous example problems are presented throughout the discussion gs aids to the understanding of the subject matter, Many problems are presented at the end of the chapters. The answers to these problems are given in an appendix so that readers cum test their knowledge. References to more detailed treatments of selected topics are given at the end of each chapter. ‘The Water Chemistry Laboratory Manual by D. Jonkins, V. L. Snosyink, J. F. Ferguson, and J. 0. Leckie, Or ed., John Wiley & Sons, Inc., New York, 1980, initially published by the Association of Environmental Engineering Professors, contains many experiments that are based on the principles presented in this book. The laboratory manual is written for use in the same type of course for which this text is written. The nomenclature and format of these two texts are designed to make them companion volumes for an integrated lecture-laboratory course. ‘Our thanks are duc to tho otudonts ond many other porsons who aided in the preparation of this book: to J. F. Fitzpatrick, R. A. Minear, and R. R, Trussell, who were selected by the publishers to raview the-text; to the University of California at Berkeley and the University of Ilincis at Urbana-Champaign for their generous leave policies that enabled us to devote our time to writing this book: and to Miss Cathy Cassolls, Mrs. Ruth Wormer, Mrs. Flora Orsi, and especially to Mrs. Virginia Ragie for their typing services in the preparation of the manuscript. Yernoa L. Snosyink Usbana, [linois David Jenkins Borkeloy, Californic CONTENTS CHAPTER ONE - INTRODUCTION LL 12. 1a. 1a, Properties of Water Composition of Several Types of Water Methods of Expressing Concentration Adgitional Reading CHAPTER TWO - CHEMICAL KINETICS 21. 2.2, 2.8, 24. 2.5. 2.8, 20. 2.8. 2.8, 2.10, Introduction Collisions of Redeting Spocios Orientation of Reactants The Rate Law Reaction Mechanism Effect of Temperature on Reaction Rate Catalysis Empirical Rate Laws Probleme Additional Reading CHAPTER THREE - CHEMICAL EQUILIBRIUM. suis 3.2. 3.8. 8.4, 3.5. 9.8. 37. Introduction ‘The Dynamic Nature of Chemical Equilibrium The Thermodynamic Basis of Chemical Equilibrium Enthalpy and the Temperature Dependence of the Equilibrium Constant Nonideal Behavior of Jons and Molecules in Solution Problems Additional Reading 4 25 2 38 40 8 7 58 58 n 4. 82 85 x Contents CHAPTER FOUR - ACID-BASE CHEMISTRY 4.1, 4.2. 43, ag, ac. 4.1. anh. 411.2, 412, 412. 412.2, 4.13. 4.13.1. 4.18.2. Introduction Definition of Terms Rate of Reaction Equilibrium Caleulations—A General Approach Mase Balances Equilibrium Relationships ‘The Proton Condition The Cheage Balance or Electroneutrality Equation Strong Acid-Strang Base Cateulations Weak Acid-Weak Base Calculations Graphical Procedure for Equilibrium Caleutations—pC, pH Diagrams Dotormination of Tomperature and Ionic Strongth Effects on Equilibria Using pC-pH Diagrams Multiprotic Acid-Conjugate Base Equilibrium Calculations Ionization Fractions and Distribution Diagrams Mixtures of Acide ond Bases—pH Calculation Strong Acid Strong Base Mixtures Weak Acid-Strong Base and Strong Acid-Weak Base Mixtures pH Buffers and Buffer Intensity Buffer pH Buffer Intensity The Carbonate System The Carbonate Spocies and Thoir Acid-Bas0 Equilibria Calculation of Carbonate Species Concentrations in Open and Closed Systems Alkalinity and Acidity Alkalinity and Acidity Endpoints Analytical Definition of Alkalinity and Acidity 86 86 86 93 95. 95 96 7 98 102 108 14 122 125 134 196 186 189 Me M7 149 156 186 162 178 190 199 44 4.15, Problems Additional Reading (CHAPTER FIVE - COORDINATION CHEMISTRY 5.1, 5.2. 5.3. 5.4, 55. 58. 589. S21. 592. 5.7.8. 5.8, 58. Introduction Nomonelature and Definition of Torms Heaction Rate Complex Stability and Equilibrium Caleulations Metal Ion Hydrolysis HO and OH as Ligands: Complexes with Other Inorganic Ligands Complexes with Organic Ligands The Nature of Copper in Water and Wastewater Complexation by NTA Metal lon Association with Humic Substances Problems Additional Reading CHAPTER SIX - PRECIPITATION AND DISSOLUTION él. 6.2. 6.2.1. 6.2.2, Introduction Precipitation and Dissolution Kinotics Nucleation Crystal Growth Agglomeration omd Ripening Dissolution Equilibrium Calculations The Solubility Product Effect of Temperature on Solubility ‘The Common Ion Effect Conditional Solubility Product Leg Concentration Diagrame Solubility of Salts of Weck Acids and Bases xi 192 195 1s7 197 197 200 201 209 a7 223 228 228 23 2a 24a 243 RE BERRESES xii Contents 85. 8.6. 6.6.1 82.2 67. B71. 6.7.2. 68. 6.8.1. 6.8.2, 6.8.8. 63. 6.10. Effect of Complexation on Solubility ” Competitive Effects of Several Ligands Procipitation of Fe(OH) ond FeCO.—pC-pH and, Predominance Area Diagrams Aluminum Phosphate Precipitation Calcium Carbonate Solubility and Water Stability Calcium Carbonate Solubility in Opon and Closed Systems The Effect of Complex Formation on the Solubility of CaCO, Phosphate Chomistry Reactions of Phosphates Magnesium Ammonium Phosphate Precipitation Tron Phosphate Precipitation from Wastewater Problems Additional Reading CHAPTER SEVEN - OXIDATION - REDUCTION REACTIONS TL. 72. 73. 73.1 7.3.2. 7.3.3. 7.8.4. 7.8.5. 7.3.6 7.4. 75. 75.1. 7.5.2. Introduction Redox Stoichiometry Redox Equilibria Direction of Reaction Free Enorgy and Potential of Halt-Reactions ‘Combination of Half-Reactions ‘The Nemst Equation Formal Potentials ‘The Electron Balance and Equilibrium Celeulations Electron Activity and pe Graphica! Roprosontation of Redox Equilibria ‘The pepC Diagrams ‘The pepHl Predominance Area Diegrams 262 270 an 278 282 282 295 298 298 308 310 313 315 316 316 316 322 322 324 330 981 996 338 338 aa 344 348 7.5.8, 7.5.4 78. 78.1 7.8.2, 76.3. 764. 76.5. 77. 79h 192, 78. 78.1. 78.2, 78.8 78.4. 73. 73.1, 7.9.2, 79.3. 7.10. 710.1. 7.10.2, 7A 712, Contents Other Predominance Area Diagrams ‘The pe-pHt Diagrams Incorporating Solide Conosion ‘The Corrosion Col! ‘The Galvanic (or Electromotive) Series Corrosion Reactions Concentration Cells Corrosion Control Tron Chemistry Iron in Groundwaters Acid Mine Dreinage Chlorine Chemistry Forms of Rquecus Chlorine Chlorine Equilibria Chlorine Reactions with Inorganic Species Chlorine Reactions with Organic Substances Biologically Important Redox Reactions ‘The Nitrogen Cycle Electron Acceptors in Microbial Systems Microbial Yields Electrochemical Macsurements Potentiometric Measurements Amporomstric Polarographic} Measurements, Problems Additional Reading Appendix 1. Ionization Fractions Appendix 2, Answers to Problems Appendix 3. Usoful Data Indox 354 358 963 963 366 968 a7 374 978 378 982 386 987 988 398 404 405 407 ae aid 44 422 426 490 431 435 442 453 WATER CHEMISTRY : HAs INTRODUCTION 1.1, PROPERTIES OF WATER Although the title of this book is Water Chemistry, the contents deal only lightly with the chemistry of HO. With a few exceptions it is only in this introductory chapter that we feel compelled to even talk about tho properties of H,O. In common with the usage adopted by the sanitary/ environmental engineering profession and other branches of the scientific community, we use the word water to mean the dilute aqueous solution! suspension of inorganic and organic compounds that constitutes various types of aquatic systems. This hook is about the interactions between these compounds. The American Heritage Dictionary of the English Language’ concisely draws the distinction we want to make in its first three definitions of the word water. "Water (wo'tar, wot’ar) n, 1. A clear colorless, nearly odorless and tasteless liquid, H,O, ossontial for most plant and animal life and the most widely used of all solvents. Melting point °C (62°F), balling point 100°C {212°F), spacilic gravity (4°C) 1.0000, weight por gallon (15°C) €.337 pounds, 2, Any of various forms of water such as rain. 3. Any bedy of water such as a sea, lake, river, or atceam." This book is largely directed toward a consideration of the types of waters exemplified by definitions 2 and 3. However, it would be remiss if we did not consider the important properties of water that make it such dominant aspect of our environment. Most water molecules have a molecular weight of 18. However, since hydrogen and oxygen each have 3 isotopes, thoro exist 18 possible molecular weights for water. In the water molecule both hydrogen atoms are located on the same side of the oxygen atom; their bonds with the ‘oxygen atom are 105° apart, The hydrogen atoms curry a positive charge while the oxygen atom is negatively charged, Because of this distribution of chargo, H,0 is a strongly dipolar molecule, The wator molecule dipotos The American Heritage Dictionary of the English Language, William Mortis, ed. American Heritage and Houghton. 1968, p. 1447. 2 Introduction aitraet each other and form aggregates trough bonds that are known os “hydrogen bonds” It is thought that these aggregates in water at room tomperature can reach sizes of up to cbout 100 H,O molecules? ‘The hydrogen bonding in water is responsible for many of the unusual properties possessed by this substance. Water is the dihydride of oxygen. It we compato it with the dihydrides of the elements in the same family of the periodic table as oxygen, that is, hydrogen sulfide, HS: hydrogen selenide, H,Se; and hydrogen telluride, HeTe, we find that many of its physical properties are cnomalous. At atmospheric pressure and room tomporature (25°C) the heavior molecules, H,S (molecular weight 94), H.Se (molecular weight 81), and H,Te (molecular weight 130), are all gases. Water is ai liquid that becomes c gos only when the temperature is increased to 100°C and above, It is far denser than its related species at ony given temporature; the maximum density is at 4°C. Its surface tension and dieleciric constant are much higher than would be predicted from the properties of the other dihytrides. Its freezing point is lower than would be expected, and tt freezes toform ice, an open-structured substance that is less dense than the liquid water from which it forms. All of these properties (and many mote) are caused by the hydrogen bonding between H,O moloculos, Tho last proporty—that in which H,O forms a lass dense solid than the liquid from which it forms—has far-reaching ramifications, Ii solid 3,0 were denser than liguid HO, ice would form at the bottom of natural bodies of water rather than at the top, Lakes would freeze from the bottom upward and, consequontly, life in its prosont form in aquatic systems would not exist because natural bodies of water would freeze solid whenever the temperature fell below the freezing point of water ‘The polarity of water is an important factor in determining its solvent properties. The minerais that make up the earth's crust are largely inorganic solids in which positively charged and negatively charged ions exist in c lattice structure, attracted to each other by electrostatic bonds. Water, with its dipolar character, has the power to surround a positively charged ion with the negatively charged part of its molecule (or conversely surround tho negatively charged erystal ion with tho positively charged Part of ite molecule}, thereby isolating the ion from its surrounding ions *G, Nomethy ond G, H. Scheraga, “Structure of Water and Hydrophobic Bonding in Proteins, 1, A Model for.the Thermodynamic Properties of Liquid Water,” J. Phys. Cham, 36: 9382 (1962), Composition of Several Types of Water 3 and neutralising tho forces of attraction that maintain the integrity of the crystal structure, The ion, surrounded (or hydrated) by water molecules, can then leava the crystal lattice and move out into solution—it becomes a dissolved ion. In the lost cmalysis the solvent properties of water make necessary the several dictionary definitions of the word water. Water dissolves some (small or large} amount of viriually every sold or gas with which It comes in contact. In the global cycle of water on the earth (the hydrologic cycle! water contacts the gases in the atmosphere (including air pollutants an: volcanic omissions) and the minerals in the top few kilometers of the earth's crust. On a smaller scale water cfrculates in man-made systems (conduits and pipes made from synthetic minerals, such as concrete, and refined metals such as iron and copper), The sclvent powers of water axe oxorted in those systems loading to such gonoral phonomonc ae corrosion cond sealing, 12. COMPOSITION OF SEVERAL TYPES OF WATER ‘The general composition of the various types of water in the hydrosphero can best be discussed within the framework of the hydrologic cycle. Of the totel amount of water on the earth the oceans account for the vast majority: 97.18 percent, The polar ice caps and glaciers contain 2,24 percent; croundwater cccounts for 0.61 percent; and the rivers, lakes, and streams contain only 0.02 percent of tho total. ‘The ocean is an approximately 1.1 M solution of anions plus cations; its average composition is given in Table 1-1. In this table the category TABLE I.1 Mojor Constituents of Seawater gla (ppm) Sodium (Na*) 10,500 Magnesium (Mg?) 1,280 Caiclum Ca) 400 Potassium (+) 380 Chloride (Cl) 18,000 Sulfate (SOF) 2,700 Bicarbonate (HCO,") 142 Bromide (Br-) 85 Other solide 4 Total dissolved solids 34,500 Weter (balances) 985,517 Source: E. D. Goldberg, "Chemistry The Oceans ‘as a Chermical Systerr” in H. M. Hill, Compesitton ‘of Sea Water, Comparative and Descriptive Ocoan- ‘ocropay, Vel. 2 of The Soa. Wiley-Interscience, New York, 1953, pp. 3-25. Reprinted hy permission of John Wiley & Soas, Inc. 4 Introduction of “other solids” Incorporates a wide variety of species that includes just about every element present in the earth's crust, In this category average concentrations range from moderate (Sr (8 mg/liter), SiO; (6.4 mg/liter), B (46 mgilitor), and F (1.8 mgflitor)) to small (N (0.5 mg/liter), Li (0.17 mg/ Iiten), P (0.07 mg/liter), ema I (0.06 mg/liter) to minuto (Cd (0.0001 mg/liter), Cz (0.00005 mgiliter), and Hg (0.00006 mgfiter)) to miniscule (Pa (2 x 10-* mafliterand Ra (L x 10~® mgfliter)). The dissolved salt content of sea water (total dissolved solide of approximately 34,500 mgiliter) is sufliciont to raise its specific gravity at 20°C to a valuo of 1.0243 glee, which is significantly greater than pure water. From the oceans, water evaporates and then is transported over land manees, whore it con be deposited as one or another form of precipitation rain, snow, hail, etc.). During its passage from the ocean to the land surface, water passes throught the earth's lower atmosphere. Because of this, the water has a chance to equilibrate with the gases in the atmosphere. The mean composition of the lower cimosphere is shown in ‘Table 1-2, It should bo realizod thet the mean composition of the earth's atmosphere is subject to considerable variation, especially in the levels of some of the minor constituents such as CO,, CO, 80s, NO,, and so ‘Mean Composition of the Atmosphere Partial Pressure Gas __ Percentage by Volume (atm) N 78.1 0.781 o 208 0.203 Ar 0.93 0.0083 KO 0128 0.028 co, 0.03 o.0003 Ne 19x 10% 18 x 107* He 52 « 10" 52x 104 cH 15 x 10+ LS x 10 i Lx 10" Lax i co (0.06-2) x 10-4 (0.8-1) x 10 80, 1x lot 1x 10° NO 5x 10% 5x 107 H, 5x 109 $x 107 a 0.11.0) x 10 (0.1-1.0) x 107 Xe ar x lo 87 x 108 No, (0.05-2) x 19-* (0.05-21 x 10°* Ra 6x 10" 6x 107 Source: B. A. Mistoy, "Gaseous composition of the atmos- phere ond its analysis.” Akad. Wauk. SSSR. Inst. Priel Gootie Moskva {translated by the lace! Program for Sei entific Translations, published in Washington, U.S. Dept. of Commerce, Oifice of Technical Services, 1961, 209 pp.). Composition of Several Types of Water 5 forth, which are products of combustion processes and are associated with the air pollution that accompanies urban-industrial communities. The major atmospheric constituents, No and Oz, are both sparingly soluble in water (17.5 and $9.3 mg/kg, respectively, at 25°C) but some of the minor constituents, for example, CO, and $O,, are very soluble (1450 and $4,100 mg/kg, respectively, at 25°C). The composition of precipitation is quite voricble ond greatly influenced by atmospheric contaminants. Precipitation noar the oceans contains more SO¥", Cl, Net, and Mg** than precipitation that falls in tho interior of a groct land mass. Rein and snow that are generated from an atmosphere containing high concentra- tions of combustion-generated SO, can be very acidic. Even so, the figures in Table 1-9 show that rainwater is indeed an extremely dilute solution TABLE 1-8 Composition of Rain and Snow (in mg/liter) Constituent 2 3 SiO, a0 1208 Alam) » 0.0L Cast O09 6085 kk 8 Mg 02 Of 07 12 Ome Not 06 oss 00k x 06. ol 8600 oe NH 00 0.42 co, 3 2 4 00 soe 16 2B? 7H or 02 os 08 20 No;- 0.02 00 p02 Noy 01 0222 Total dissolved solids, 48 62 38 PH 56 e488 1. Snow, Spooner Summit, U.S. Highway $0, Nevada (east of Lake Tahoo) altitude ‘700 ft, Nov. 20, 1888. J. H. Feth, S. M. Rogers, and C. E, Roberson, Chornical Composition of Snow in the Northera Sierra Nevada and Other Arcos, U.S. Geological Survay Water Supply Paper 1835}, 1964, 39 pp. 2. Average composition of rain from August 1962 to July 1969 at 27 pointe in North Cenaling and Viginic, A. W. Gambell and D. W. Fisher, Chemical Composition of Rainfall, Fasten N. Carolina and Southecstem Virginia: U.S. Geological ‘Survoy Wator Supply Paper 535K, 1964, 41 pp. Sand4, Rain, Menlo Park, Calif, 7:09 P.M. Jan. $to 8:00 A.M. Jan. 10, 1958, White- head, and J. H, Feth, Chemical Composition of Rain, Dry Fallout, and Bulk Precipitation at Monlo Park, Calll., 1857-1858, }. Geophys. Fes., 68/3318 3335 (1964). 5, Sletion §26U, Belgium, European Aimoapheric Chomistry Network. Averase ‘of 180 samples. £. Granat, On the Relation Betwoon pH and the Chemical Composition in Atmospheric Precipitation, Tellus, 24, $50-8S6 (1972). * The solubility of gas is expressed as the weight of cas (mag) dissolved in 1 kg of water at « total pressure (partial pressure of the indicated gos plus the vapor Pressure of water ai 25°C) of 760 mm Hg (760 torr or 1 ctm). 8 Intieduction of dissolved salts, indicating the remarkable efficiency of the distillation process thai resulis in the production of "fresh water” from seawater. Noto that the pH of “unpolluted” precipitation (5.6 to 6.5) is significantly lowor than that of the seawater from which it was genorcted. This is c reflection of the equilibration that has taken place with atmospheric CO, Rainwater is poorly buffered so that it camot maintain its neutral pH in the presence of oven these smal] amounts of acid-producing gases. Jn procipitation, water falls onto the land surface and comes in contact with rocks, sediments, and soils and the animal and plant inhabitants of the land surface. Chemical reactions take place that further modify the composition of the water. The reactions can be viewed in general terms as a giant global acid-base titration in which the acids of the rainwater (CO,, SO, and NO, titrate the bases of the rocks, Since the composition of the Iond surface and the extent and nature of biological activity (including man's activity) vary from one place to another, we can expect that waters of a variety of compositions will result from these reactions, ‘Tho time and intimacy of contact betwoon water and rocks cleo influences the composition of the solution. Surface waters that originate in basins where the major rocks are Granite contain very small amounts of dissolved minerals, not more than approximately 30 mg/liter. Thess are an important group of waters: for example, the water supplies of New York City (irom the Catskill Moun- tains), San Francisco and Oakland (Irom the Sterrc Nevada Mountains) Seattle (from the Cascade Mountains), and many rivers and lakes in New England are of this type, They cre illustrated by Type A, in Table 1-4, ‘TABLE 1.4 Typical Analyses of Surface and Ground- waters in the United States Constituent, mg/tter B c SiO, as La 10 Felli oor oo = 0.08 Catt . 40 6 a Mgt LL al 4 Nat 28 85 82 KI 08 12 1a HOO 1219 see soe 16 2 Dt or 20 13 98 NO. ot OL 13 Total dissolved solids 34 185 434 Total herdness as CaCO, 146128 363 A Pavdoe Reservoir, Hest Bay Municipal Utility District, Oakland, Calif. Average data for 1876, B. Niagewa River, Niagara Falls, N.Y. ‘C. Well Water, Dayton, Ohio. ‘Composition of Several Typos of Water 7 which is the yearly average composition of tho outlet of Pardos Resorvoir of the East Bay Municipal Utility District, the water supply for much of the East Bay Arecr of the San Francisco Bay region. ‘Tho second general type of surface water (Table 1-4, Type B) originates from basing othor than tho granite basins doscribed above, This water, typified by that of the Great Lakes (except Lake Superior) is of intermediate hardness (calcium plus magnesium), alkalinity (HCO,"), and total mineral content, This type of water is widely used as public water supplies for cities ouch as Chicago, Cleveland, Buitalo, Niagara Falls, Detroit, Mil- waukee, and many smaller places along the lakes and rivers of the St. Lawrence River Basin, Groundwaters generally have higher dissolved mineral concentictions than surface waters. This is because of the intimate contact between the CO,-bearing water and rocks and soils in the ground and ihe length of time for dissolution. Additionally, CO, may be added to the water in the soil by the activities of soil microorganisms. Example C in Table 1-4 is a groundwater from 80 to 60-ft-deep wells used for the public water supply of Dayton, Ohio, Waters such as this are widoly distributed throughout the heartland of the United States. They usually require softening to make thom acceptable for general domestic use and most industrial uses. Jn an earth unpopulated by living things the natural waters formed by water-cir-catth interactions would now flow back to the ocean carrying thoir various dissolved constituents and suspended clay and silt particlos, For the moment let us assume that we have cr sterile earth, On the land surface the acids of the atinosphere have attacked the bases of the rocks to produce a water containing dissolved minerals. The dissolution of these minerals from the rocks causes thom to degrade and eventually to fom clay minerals. Cations such as K*, Nat, Ca®*, and Mg* are leached out of the rocks along with silica [SiO,) leaving behind a clay mineral, for example, montmorillonite, illite, or kaolinite, that is less rich in silica than the parent rock. Those particles of clay minerals can be washed dovm the rivers along with the dissolved salts into the ocean. It has been proposed by Mackenzie and Garrels that in the oceans the reverse of the reaction that weathered the rocks takes place. Cations, bicarbonate ion, and dissolved silica and clay minerals react to generate new rocks, which aro laid down at the bottom of the ocoan, Although tho detailed arguments in support of this view aro beyond the scope of this book, it is believed that the constancy of the concentrations of SiOz, K*, and HCO. in the ocean is attributable to this reaction. It is thought that this reaction controls the pH of the ocean at about pH €.0, The reaction aleo helps to rogulate the CO, content of the earth's atmosphere, Siever has summarized this global chemical scheme in the form of « series of chemical enginsering processes (Fig, 1-1). “F., Mackenzie and RM. Garcels, "Chemica! Mass Balance Between Rivers ‘and Oceans,” Am. J. Sci, 264: S07-525 (1986).

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