Appendix: Some Fundamental Principles and Calculations

Introduction

This appendix provides some very basic principles of chemistry and some informa- tion on calculating concentration of substances in solution. Much more detailed information is available in a general inorganic chemistry textbook.

Elements, Atoms, Molecules, and Compounds

Elements are the basic substances of which more complex substances are composed. Anything that has mass (or weight) and occupies space is matter made up of chemical elements such as silicon, aluminum, iron, oxygen, sulfur, copper, etc. Substances more complex than atoms of a single element consist of molecules. A molecule is the smallest entity of a substance that has all the properties of that substance. Elements are classified broadly as metals, nonmetals, or metalloids. Metals have a metallic luster, are malleable (but often hard), and can conduct electricity and heat. Some examples are iron, zinc, copper, silver, and gold. Nonmetals lack metallic luster, they are not malleable (but tend to be brittle), some are gases, and they do conduct heat and electricity. Metalloids have one or more properties of both metals and nonmetals. Because metalloids can both insulate and conduct heat and electric- ity, they are known as semiconductors. The best examples of metalloids are boron and silicon, but there are several others. There also are less inclusive groupings of elements than metals, nonmetals, and metalloids. Alkali metals such as sodium and potassium are highly reactive and have an ionic valence of +1. Alkaline earth metals include calcium, magnesium, and other elements that are moderately reactive and have an ionic valence of +2. Halogens illustrated by chlorine and iodine are highly reactive nonmetals, and they have an ionic valence of À1. This group is unique in that its members can exist in solid, liquid, and gaseous form at temperatures and pressures found on the earth’s surface. Because of their toxicity, halogens often are used as disinfectants. Noble gases such as helium, argon, and neon are unreactive except under very special conditions. In all there are 18 groups and subgroups of elements. Most elements are included in the

# Springer Nature Switzerland AG 2020 411 C. E. Boyd, Water Quality, https://doi.org/10.1007/978-3-030-23335-8 412 Appendix: Some Fundamental Principles and Calculations groups referred to as alkali metals, alkaline earth metals, transitional metals, halogens, noble gases, and chalcogens (oxygen family). The elements are grouped based on similar properties and reactions. However, in reality, each element has one or more unique properties and reactions. The most fundamental entity in chemistry and the smallest unit of an element is the atom. An atom consists of a nucleus surrounded by at least one electron. Electrons revolve around the nucleus in one or more orbitals or shells (Fig. A.1). The nucleus is made up of one or more protons, and with the sole exception of hydrogen, one or more neutrons. The protons and neutrons do not necessarily occur in the nucleus in equal numbers. For example, the oxygen nucleus has eight protons and neutrons, sodium has 11 protons and 12 neutrons, potassium has 19 protons and 20 neutrons, copper has 29 electrons and 34 neutrons, and silver has 47 electrons and 61 neutrons. Protons are positively charged and assigned a charge value of +1 each, electrons possess a negative charge and are assigned a charge value of À1 each, and neutrons are charge neutral. In their normal state, atoms have equal numbers of protons and electrons resulting in them being charge neutral. Atoms are classified according to the numbers of protons. All atoms with the same number of protons are considered to be the same element. For example, oxygen atoms always have eight protons while chlorine atoms always have 17 protons. The atomic number of an element is the same as the number of protons, e.g., the atomic number of oxygen is 8 while that of chlorine is 17. There are over 100 elements each with an atomic number assigned to it according to the number of protons in its nucleus. Some atoms of the same element may have one to several neutrons more than do other atoms of the particular element, e.g., carbon atoms may have 6, 7, or 8 neutrons but only 6 protons. These different varieties of the same element are known as isotopes. Moreover, all atoms of the same element may not have the same number of electrons. When uncharged atoms come close together, one or more electrons may be lost from one atom and gained by the other. This phenomenon results in an imbalance

Fig. A.1 The structure of oxygen, hydrogen, and sodium atoms. Appendix: Some Fundamental Principles and Calculations 413 between electrons and protons in each of the two interacting atoms that imposes a negative charge on the one that gained the electron(s) and a positive charge on the one that lost the electron(s). The charge on the atom is equal to the number of electrons gained or lost (À1 or + 1 charge per electron). Charged atoms are called ions, but the normal atom is uncharged. In the periodic table of chemical elements, an element is assumed uncharged and to have equal numbers of protons and electrons. The mass of atoms results almost entirely from their neutrons and protons. The masses of the two entities are almost identical; 1.6726 Â 10À24 g for one proton and 1.6749 Â 10À24 g for one neutron. Thus, their atomic masses usually are considered unity in determining relative atomic masses of elements. An electron has a mass of 9.1 Â 10À28 g—nearly 2000 times less than the masses of protons and neutrons. The mass of electrons is omitted in atomic mass calculations for elements. The atomic mass of elements increases as the atomic number increases, because the number of protons and neutrons in the nucleus increases with greater atomic number. The atomic mass of a given element differs among its isotopes because some isotopes have more neutrons than others, while all isotopes of an element have the same number of protons. The loss or gain of electrons by atoms forming ions is not considered to affect atomic mass. Because of the different natural isotopes of atoms of a particular element, the atomic mass typically listed in the periodic table for elements does not equal to the sum of the masses of the protons and neutrons contained in atoms of these elements. This results because the atomic masses typically reported for elements represent the average atomic masses of their isotopes. For example, copper typically has 29 protons and 34 neutrons, and the atomic mass of the most common isotope would be 63 based on addition of neutrons and protons. However, the atomic mass reported in the periodic table of copper is 63.546. The additional mass results from the effects of averaging the atomic masses of the copper isotopes. Atomic masses of some common elements are provided (Table A.1). The atomic mass is very important in stoichiometric relationships in reactions of atoms and molecules. The relative molecular mass (or weight) of a molecule is the sum of the atomic masses of the atoms contained in the molecule. Thus, when sodium atoms (relative atomic mass of 22.99) react with chlorine atoms (relative atomic mass of 35.45) to form sodium chloride, the reaction will always be in the proportion of 22.99 sodium to 35.45 chlorine, and the molecular mass of sodium will be the sum of the atomic masses of sodium and chloride or 58.44. Atomic and molecular masses may be reported in any unit of mass (or weight), but the most common is the gram. The mass or weight of atoms (Table A.1) often is referred to as the gram atomic mass (or weight) and the molecular mass of molecules usually is referred to as the gram molecular weight. Each element is assigned a symbol, e.g., H for hydrogen, O for oxygen, N for nitrogen, S for sulfur, C for carbon, and Ca for calcium. But, because of the large number of elements, it was not possible to have symbols suggestive of the English name for all elements. For example, sodium is Na, tin is Sn, iron is Fe, and gold is Au. The symbols must be memorized or found in reference material. The periodic 414 Appendix: Some Fundamental Principles and Calculations

Table A.1 Selected atomic weights Element Symbol Atomic weight Element Symbol Atomic weight Aluminum Al 26.9815 Magnesium Mg 24.305 Antimony Sb 121.76 Manganese Mn 54.905 Arsenic As 74.9216 Mercury Hg 200.59 Barium Ba 137.327 Molybdenum Mo 95.94 Beryllium Be 9.0122 Nickel Ni 58.6934 Bismuth Bi 208.9804 Nitrogen N 14.0067 Boron B 10.811 Oxygen O 15.9994 Bromine Br 79.904 Phosphorus P 30.9738 Cadmium Cd 112.411 Platinum Pt 195.078 Calcium Ca 40.078 Potassium K 39.0983 Carbon C 12.0107 Selenium Se 78.96 Chlorine Cl 35.453 Silicon Si 28.0855 Chromium Cr 51.996 Silver Ag 107.8682 Cobalt Co 58.9332 Sodium Na 22.9897 Copper Cu 63.546 Strontium Sr 87.62 Fluorine F 18.9984 Sulfur S 32.065 Gold Au 196.9665 Thallium Tl 204.3833 Helium He 4.0026 Tin Sn 118.71 Hydrogen H 1.0079 Tungsten W 183.84 Iodine I 126.9045 Uranium U 238.0289 Iron Fe 55.845 Vanadium V 50.9415 Lead Pb 207.19 Zinc Zn 65.39 Lithium Li 6.941 table of the elements is a convenient listing of the elements in a way that elements with similar chemical properties are grouped together. The periodic table is presented in various formats, but most presentations include, at minimum, each element’s symbol, atomic number, and relative atomic mass and indicate the group of elements to which it belongs. The maximum number of electrons that can occur in a shell of an atom usually is 2n2 where n is the number of the shell starting at the shell nearest the nucleus, i.e., two electrons in the first shell, eight in the second shell, etc. Elements with a large atomic number have several shells and some shells may not contain the maximum number of electrons. Chemical reactions among atoms involve only the electrons in the outermost shell of atoms. The laws of thermodynamics dictate that substances spontaneously change towards their most stable states possible under existing conditions. To be stable, an atom needs two electrons in the inner shell, and at least eight electrons in its outermost shell. Chemical combinations (reactions) occur so that atoms gain or lose electrons to attain stable outer shells. Nonmetals tend to have outer shells nearly full of electrons. For example, chlorine has seven electrons in its outer shell. If it gains one electron, it will have a stable Appendix: Some Fundamental Principles and Calculations 415 outer shell, but the acquisition of this electron will give the chlorine atom a charge of À1. Gaining the electron causes a loss of energy and the chlorine ion is more stable than the free atom. Nonmetals tend to capture electrons. The source of electrons for nonmetals is metals which tend to have only a few electrons in their outer shells. Sodium is a metal with one electron in its outer shell. It can lose the single electron and attain a charge of +1and lose energy to become more stable. If sodium and chlorine are brought together, each sodium atom will give up an electron to each chlorine atom (Fig. A.2). The chlorine atoms will now have fewer protons than electrons and acquire a negative charge while the opposite will be true of sodium atoms. Because opposite charges attract, sodium ions and chlorine ions will combine because of the attraction of unlike charges forming sodium chloride or common salt (Fig. A.2). Bonds between sodium and chlorine in sodium chloride are called ionic bonds. The number of electrons lost or gained by an atom or the charge it acquires when it becomes an ion is the valence. Some elements like carbon are unable to gain or lose electrons to attain stable outer shells. These elements may share electrons with other atoms. For example, carbon atoms have four electrons in their outer shells and can share electrons with four hydrogen atoms as shown in Fig. A.3. This provides stable outer shells for both

Fig. A.2 Transfer of electron from a sodium atom to a chlorine atom to form an ionic bond in sodium chloride 416 Appendix: Some Fundamental Principles and Calculations

Fig. A.3 Covalent bonding of hydrogen and carbon atoms to form methane

the carbon and hydrogen atoms. The resulting compound (CH4) is methane. The chemical bond that connects each hydrogen to carbon in methane is known as a covalent bond. When two or more elementary substances bond together, the resulting substance is called a compound. A compound has a characteristic composition and unique properties that set it aside from all other compounds. The Law of Definite Proportions holds that all samples of a given compound substance contain the same elements in the same proportions by weight. The smallest part of a substance with all of the properties of that substance is a molecule. A molecule may be composed of a single element as in the case of an elemental substance such as oxygen, sulfur, or iron or it may be composed of two or more elements as in acetic acid (CH3COOH) which contains carbon, hydrogen, and oxygen. The gram molec- ular weight or gram atomic mass of a substance contains as many molecules as there are oxygen atoms in 15.9994 g of oxygen. This quantity is Avogadro’s number of molecules (6.02 Â 1023), and it is known as a mole. Elements are represented by symbols, but to represent molecules, the elemental symbols are given numerical subscripts to represent their proportions. Such a notation is called a formula. For example, molecular oxygen and nitrogen have the formulas O2 and N2, respectively. Sodium chloride is NaCl and sodium carbonate is Na2CO3. The molecular weights of molecules can be determined by summing the atomic weights of all of the constituent elements. If an element has a subscript, its atomic weight must be summed the number of times indicated by the subscript. One molecular weight of a substance in grams is a gram molecular weight or a mole as illustrated in Ex. A.1. The percentage of an element in a compound is determined by dividing the weight of the element by the formula weight of the compound and multiplying by 100 (Ex. A.2). Appendix: Some Fundamental Principles and Calculations 417

Ex. A.1 The molecular weights of O2 and CaCO3 will be calculated from their formulas. Solution:

O2: The atomic weight of O is 15.9994 (Table A.1), but it usually is rounded to 16, thus 16 Â 2 ¼ 32 g/mole. CaCO3: The atomic weights of Ca, C, and O are 40.08, 12.01, and 16, respectively (Table A.1), thus 40.08 + 12.01 + 3(16) ¼ 100.09 g/mole.

The percentage composition of substances can be estimated from their formulas because of the Law of Definite Proportions.

Ex. A.2 The percentage Cu in CuSO4Á5H2O will be calculated. Solution: From Table A.1, the atomic weights of Cu, S, O, and H are 63.55, 32.06, 16.00 and 1.01, respectively. Thus, the molecular weight of CuSO4Á5H2Ois 63.55 + 32.06 + 9(16) + 10(1.01) ¼ 249.7 g. The percentage Cu is Cu 63:55  100 or  100 ¼ 25:4%: CuSO4 Á 5H2O 249:71

Some compounds dissociate into ions in water, e.g. sodium nitrate (NaNO3) + À dissociates into Na and NO3 . The ionic weight of a complex ion such as nitrate is calculated in the same manner as for the molecular weight of a compound. Of course, the weight of Na+ is the same as the atomic weight of sodium.

Definition of a Solution

A solution consists of a solvent and a solute. A solvent is defined as the medium in which another substance—the solute—dissolves. In an aqueous sodium chlorine solution, water is the solvent and sodium chloride is the solute. Miscibility refers to a solute and solvent mixing in all proportions to form a homogenous mixture or solution. A true solution is by definition a homogenous mixture of two or more components that cannot be separated into their individual ionic or molecular components. Most solutes are only partially miscible in water. If a soluble compound such as sodium chloride is mixed with water in progressively increasing amounts, the concentration of the solute will reach a constant level. Such a solution is said to be saturated, and the amount of the sodium chloride held in solution is the solubility of sodium chloride in water at the particular temperature. Any more sodium chloride added to the saturated solution will settle to the bottom without dissolving. Solubilities of chemical compounds often are reported as grams of solute in 100 mL of solution. Chemists generally consider substances that will dissolve to 418 Appendix: Some Fundamental Principles and Calculations the extent of 0.1 g/100 mL in water as soluble. A general list of classes of soluble compounds follows:

• nitrates • bromides, chlorides, and iodides—except those of lead, silver, and mercury • sulfates—except those of calcium, strontium, lead, and barium • carbonates and phosphates of sodium, potassium, and ammonium • sulfides of alkali and alkaline earth metals and ammonium.

Much of this book is devoted to a discussion of factors controlling concentrations of dissolved matter in natural waters. This dissolved matter in water includes inorganic ions and compounds, organic compounds, and atmospheric gases, and much of water quality depends upon the concentrations of solutes in water.

Methods of Expressing Solute Strength

The solubility of a solute in a saturated solution or its concentration in an unsaturated solution may be expressed in several ways—the most common of which will be described.

Molarity

In a molar solution, the solute strength is expressed in moles of solute per liter, e.g., a 1 molar (1 M) solution contains 1 mole of solute in 1 L of solution. In other words, a 1 M solution of NaCl consists of 1 mole (58.44 g NaCl) in 1 liter. Note: this is not the same as putting 1 mole of NaCl in 1 L of solvent. It is 1 mole of NaCl contained in 1 L of solution. The NaCl is dissolved in the solvent and the solution diluted to 1 l with additional solvent. Calculations for a molar solution are shown in Ex. A.3.

Ex. A.3 How much Na2CO3 must be dissolved and diluted to 1 L to give a 0.25 M solution? Solution:

The molecular weight of Na2CO3 is. 2Na¼ 22.99 g/mol  2 ¼ 45.98 g 1C¼ 12.01 g/mol  1 ¼ 12.01 g 48:0g 3O ¼ 16 g/mol  3 ¼ 105:99g 105:99 g=mole  0:25 mol=L ¼ 26:5 g=L:

Thus, 26.5 g Na2CO3 diluted to 1 L in distilled water gives 0.25 M Na2CO3. Appendix: Some Fundamental Principles and Calculations 419

Molality

Not to be confused with a 1 molar solution, a 1 molal solution contains 1 molecular weight of a solute in 1 kg of solvent. The unit of molality is moles of solute per kilogram of solvent, and it is abbreviated as m or m.

Ex. A.4 The preparation of a 0.3 m KCl solution is illustrated. Solution: The molecular weight of KCl is. K ¼ 39.1 g/mol Cl ¼ 35.45 g/mol KCl ¼ 74.55 g/mol 74:55 g=mol  0:3 mol=kg ¼ 22:36 g KCl=kg solvent:

Thus, to make the 0.3 m KCl solution weigh 22.36 kg KCl and dissolve it in 1 kg of distilled water (or other solvent).

Formality

There also is a formal concentration which is calculated as the number of moles of a substance in a liter of solution. The formal solution is denoted by the symbol F and represents the formula weights of solute per liter of solution. The formal solution is seldom used in water quality.

Normality

Because reactions occur on an equivalent weight basis, it is often more convenient to express concentration in equivalents per liter instead of moles per liter. A solution containing 1 gram equivalent weight of solute per liter is a 1 normal (1 N) solution. In cases where the equivalent weight and formula weight of a compound are equal, a 1 M solution and a 1 N solution have identical concentrations of solute. This is the case with HCl and NaCl, but with H2SO4 or Na2SO4, a 1 M solution would be a 2 N solution. The following rules may be used to compute equivalent weights of most reactants: (1) the equivalent weight of acids and bases equal their molecular (for- mula) weights divided by their number of reactive hydrogen or hydroxyl ions; (2) the equivalent weights of salts equal their molecular weights divided by the product of the number and valence of either cation component (positively charged ion) or anion component (negatively charged ion); (3) the equivalent weights of oxidizing and reducing agents may be determined by dividing their molecular weights by the number of electrons transferred per molecular weight in oxidation-reduction reactions. 420 Appendix: Some Fundamental Principles and Calculations

Oxidation-reduction reactions usually are more troublesome to students than other types of reactions. An example of an oxidation reduction reaction is provided below in which manganese sulfate reacts with molecular oxygen:

2MnSO4 þ 4NaOH þ O2 ! 2MnO2 þ 2Na2SO4 þ 2H2O ðA:1Þ

Manganese in MnSO4 has a valence of +2 and sulfate has a valence of À2. In manganese dioxide the valance of manganese is +4 (notice each of the two oxygens have a valence of À2 making a total valence of À4 for oxygen). Manganese was oxidized, because its valence increased. Molecular oxygen with valence of 0 was reduced to a valence of À2 in manganese dioxide. Each molecule of manganese sulfate (the reducing agent) lost two electrons which were gained by oxygen (the oxidizing agent). The equivalent weight of magnesium sulfate in this reaction is its formula weight divided by two. Additional examples illustrating calculations of equivalent weights and normalities of acids, bases, and salts are provided in Exs. A.5, A.6, and A.7.

Ex. A.5 What is the equivalent weight of sodium carbonate when it reacts with hydrochloric acid? Solution:

The reaction is: Na2CO3 + 2HCl ¼ 2NaCl + CO2 +H2O. One sodium carbonate molecule reacts with two hydrochloric acid molecules. Thus, the equivalent weight of sodium carbonate is Na CO 106 2 3 ¼ ¼ 53 g: 2 2

Ex. A.6 What are the equivalent weights of sulfuric acid (H2SO4), nitric acid (HNO3), and aluminum hydroxide [Al(OH)3]? Solution:

(i) Sulfuric acid has two available hydrogen ions

! þ þ 2À: H2SO4 2H SO4 Thus, the equivalent weight is H SO 98 2 4 ¼ ¼ 49 g: 2 2

(ii) Nitric acid has one available hydrogen ion

! þ þ À: HNO3 H NO3 The equivalent weight is Appendix: Some Fundamental Principles and Calculations 421

HNO 63 3 ¼ ¼ 63 g: 1 1

(iii) Aluminum hydroxide has three available hydroxide ions

ðÞ¼ 3þ þ À: Al OH 3 Al 3OH The equivalent weight is AlðÞ OH 77:98 3 ¼ ¼ 25:99 g: 3 3

Ex. A.7 How much Na2CO3 must be dissolved and diluted to 1 L to give a 0.05 N solution? Solution:

! þ þ 2À: Na2CO3 2Na CO3 þ ¼ 2À The formula weight must be divided by 2 because 2Na 2, or because CO3 ¼À : + ¼ 2À ¼ 2 The sign difference (2Na +2 and CO3 -2) with respect to valence) does not matter in calculating equivalent weight. 106 gNa CO =mole 2 3 ¼ 53 g=equiv: 2

53 g=equiv: Â 0:05 equiv:=L ¼ 2:65 g=L:

In expressing solute strength for dilute solutions, it is convenient to use milligrams instead of grams. Thus, we have millimoles (mmol), millimolar (mM), millimoles/L (mmol/L that is the same as mM), milliequivalents (meq), and milliequivalents/liter (meq/L). A 0.001 M solution is a 1 mM solution.

Weight per Unit Volume

In water quality, concentrations often are expressed in weight of a substance per liter. The usual procedure is to report milligrams of a substance per liter (Ex. A.8).

Ex. A.8 What is the concentration of K in a solution that is 0.1 N with respect to KNO3? Solution:

KNO3 ¼ 101:1 g=equiv: 422 Appendix: Some Fundamental Principles and Calculations

101:1 g=equiv: Â 0:1 equiv:=L ¼ 10:11g=L:

The amount of K in 10.11 g of KNO3 is 39:1 Â 10:11 g=L ¼ 3:9 g=L: 101:1

3:9 g=L Â 1; 000 mg=g ¼ 3; 900 mg=L:

The unit, milligrams per liter, is equivalent to the unit, parts per million (ppm) as shown in Ex. A.9; it is common in water quality to use parts per million (ppm) interchangeably with milligrams per liter.

Ex. A.9 It will be demonstrated that 1 mg/L ¼ 1 ppm for aqueous solutions. Solution:

1 mg 1 mg 1 mg 1 mg ¼ ¼ ¼ ¼ 1 ppm: 1 L 1 kg 1; 000 g 1; 000; 000 mg

It also is common in water quality to express concentration of minor constituents in micrograms per liter (μg/L); and, of course, 1 μg/L ¼ 0.001 mg/L. To convert milligrams per liter to micrograms per liter, simply move the decimal place to the right three places, e.g., 0.05 mg/L ¼ 50 μg/L, and vice versa. Sometimes micrograms per liter will be expressed as parts per billion (ppb). The rationale for this is easily seen if the calculation in Ex. A.9 is begun with 1 μg/L and we get 1 μg/ 1,000,000,000 μg. It also is convenient to express the strength of more concentrated solutions in parts per thousand or ppt (Ex. A.10). One part per thousand is equal to 1 g/L because there are 1000 g in 1 L. It also is equal to 1000 mg/L. An alternative way of indicating concentration in parts per thousand is the symbol ‰.

Ex. A.10 Express the concentration of sodium chloride in a 0.1 M solution as parts per thousand and milligrams per liter. Solution:

0:1 M Â 58:45 g NaCl=mole ¼ 5:845 g=L:

The salinity is 5.845 ppt that is equal to 5845 mg/L.

It is easy to convert water quality data in milligrams per liter to molar or normal concentrations (Ex. A.11). Appendix: Some Fundamental Principles and Calculations 423

Ex. A.11 Molarity and normality of 100 mg/L calcium will be calculated. Solution:

100 mg=L (i) ¼ 2:495 mmol=Lor0:0025 M: 40:08 mg Ca=mmol (ii) Calcium is divalent, so

100 mg=L ¼ 4:99 meq=Lor0:005 N: 20:04 mg=meq

Concentrations of solutions often are in milligrams per liter with no regard for molarity of normality as shown in Ex. A.12.

Ex. A.12 How much magnesium sulfate (MgSO4Á7H2O) must be dissolved and made to 1000 mL final volume and to provide a magnesium concentration of 100 mg/L? Solution:

x 100 mg=L ∙ ¼ MgSO4 7H2O Mg mw ¼ 246:31 gmw¼ 24:31 g rearranging, 24; 631 x ¼ ¼ 1; 013:2 mg=L of MgSO Á 7H O: 24:31 4 2

Weight Relationships in Reactions

Stoichiometry is the area of chemistry that considers weight relationships among reactants and products in chemical reactions. The equations for reactions allow weights of reactants and products to be calculated. The reaction of sodium hydroxide to neutralize hydrochloric acid is NaOH + HCl ¼ NaCl + H2O. Each mole of HCl requires 1 mol of NaOH for neutralization. Thus 40.00 g NaOH reacts with 36.46 g of HCl to yield 58.44 g NaCl and 18.02 g H2O. The weight on each side of the equation remains the same before and after a reaction that goes to completion (there were 76.46 g of reactants and 76.46 g of products in this instance). Calculations usually are more complex than for hydrochloric acid and sodium hydroxide as illustrated in Ex. A.13. 424 Appendix: Some Fundamental Principles and Calculations

Ex. A.13 The amount of calcium carbonate necessary to neutralize the acidity for 100 kg of aluminum chloride will be calculated. Solution: 3+ Al(Cl)3 dissolves releasing Al ðÞ¼ 3þ þ À Al Cl 3 Al 3Cl Al3+ hydrolyzes producing hydrogen ion (H+) which is a source of acidity: 3þ þ ¼ ðÞ#þ þ: Al 3H2O Al OH 3 3H

Hydrogen ion is neutralized by calcium carbonate (CaCO3):

þ 2þ 3H þ 1:5 CaCO3 ¼ 1:5 Ca þ 1:5 CO2 þ 1:5 H2O:

Weight of Al in 100 kg of AlCl3 is 100 kg X 3þ À AlCl3 ¼ Al þ 3Cl 133:34 g=mol 26:98 g=at:wt:

Al3+ ¼ 20.23 kg Al3+. Weight of CaCO3 needed to neutralize the acidity is. 3+ + 3+ Al ¼ 3H ; therefore, Al ¼ 1.5 CaCO3. 20:23 kg X 3þ Al ¼ 1:5 CaCO3 26:98 g=at:wt: 150 g

X ¼ 112.5 kg CaCO3.

Two more examples will be provided.

Ex. A.14 The amount of carbon dioxide required to produce 100 kg organic matter in photosynthesis will be determined. Solution: The photosynthesis equation is

6CO2 þ 6H2O ¼ C6H12O6 þ 6O2:

The relationship of CO2 to carbon in organic matter is CO2 ¼ CH2O. and X 100 kg CO2 ¼ CH2O 44 g=mol 30 g=mol

CO2 ¼ 146.7 kg. Appendix: Some Fundamental Principles and Calculations 425

Ex. A.15 The amount of molecular oxygen necessary to oxidize 5 kg of elemental sulfur to sulfuric acid will be computed. Solution: The reaction is:

S þ 1:5O2 þ H2O ¼ H2SO4:

The relationship of elemental sulfur to molecular oxygen is S ¼ 1.5 O2: 5 kg X S ¼ 1:5O2 32 48

O2 ¼ 7.5 kg. Note: In this particular instance, the amount of oxygen required is 1.5 times the amount of sulfur oxidized. This was the result of the coincidence that the molecular weight of O2 is the same as the atomic weight of S.

Some Shortcuts

Some important water quality variables are radicals such as nitrate, nitrite, ammonia, ammonium, phosphate, sulfate, etc. Sometimes, the concentration will be given as the concentration of the radical, and other times, it will be given as the concentration of the element of interest that is contained in the radical. For example, the concen- tration of ammonia may be given as 1 mg NH3/L or it may be given as 1 mg NH3-N/ L. It is possible to convert back and forth between the two methods of presenting concentration. In the case of NH3-N, use of the factor N/NH3 (14/17 or 0.824): 1 mg NH3/L Â 14/17 ¼ 0.82 mg NH3-N/L. It follows that 1 mg NH3-N/L Ä 14/17 ¼ 1.21 mg NH3/L. Similar reasoning may be used to convert between

Table A.2 Factor to Conversion Factor multiply by concentration NH to NH -N 0.824 of an ionic radical and CO 3 3 2 + + to obtain the elemental NH4 to NH4 -N 0.778 À À equivalent NO3 to NO3 -N 0.226 À À NO2 to NO2 -N 0.304 3À 3À PO4 to PO4 -P 0.326 2À 2À HPO4 to HPO4 -P 0.323 À À H2PO4 to H2PO4 -P 0.320 2À 2À SO4 to SO4 -S 0.333

H2StoH2S-S 0.941

CO2 to CO2-C 0.273 The concentrations in elemental form can be converted to the ion À concentration by dividing by the factor, e.g., 0.226 mg/L NO3 N Ä À 0.226 ¼ 1 mg/L NO3 . 426 Appendix: Some Fundamental Principles and Calculations

À À À 2À 2À NO3 and NO3-N, NO2 and NO2 -N, SO4 and SO4 -S, etc. Some conversion factors are given in Table A.2. It also is useful to note that the dimensions for molarity and normality are moles per liter and equivalents per liter, respectively. Thus, multiplying molarity or normality by volume in liters gives moles and equivalents, respectively. The same logic applies for multiplying millimoles or milliequivalents per milliliter by volume in milliliters. In some calculations, the quantity of a dissolved substance in a particular volume may be sought. It is helpful to remember that 1 mg/L is the same as 1 g/m3, because there are 1000 L in a cubic meter. Likewise, 1 μg/L is the same as 1 mg/m3 for the same reason. Index

A Adenosine triphosphate (ATP), 237, 292 Abeliovich, A., 255 Aerobic respiration Absolute salinity, 87 acetyl CoA, 238 Absorption coefficient, 31 ATP synthesis, 238 Absorption spectrum, 31 carbohydrate metabolism, 237 Accornero, M., 364 glycolysis and citric acid cycle, 238 Acidic deposition oxygen stoichiometry, 239–240 aragonite and calcite, 225 RQ, 239 fossil fuels, 225 Air temperature, 34 hydrogen sulfide and sulfur dioxide, 224 Alabama Stream Classification System, 401 smoke and haze, 225 Albedo, 16, 17 sulfur and nitrogen gases, 224 Alexander, L.T., 221 Acidification, 382 Alkalinity, 178 Acidity, 270, 280, 281, 289 carbon dioxide, 201, 202 acid-sulfate soil and sediment, 220–224 description, 202 concept pH, 199–201 fulvic acid, 217, 218 Alum (aluminum sulfate), 131 hydrogen ion concentration and pH, 216 Aluminum (Al), 361–364 mineral acids, 217 Aluminum and iron phosphate, 296, 299 tannic acid, 219 Aluminum hydroxide, 346 titratable acids, 216 Aluminum sulfate, 320 deposition, 224–225 American Society of Testing Materials effects, 227–228 (ASTM), 113, 114 measurement, 226–227 Ammonia, 269–276, 279, 281, 284, 286, 287 mitigation, 228–229 Ammonia-ammonium equilibrium, 282 Acid mine drainage, 223 283, 285 Acid rain, 227, 324, 332 Ammonia diffusion, 285, 286 Acid sulfate soil Ammonia hydrolysis, 282 acid drainage, 223 Ammonia toxicity, 287, 288 anaerobic microbial respiration, 220 Ammonium, 269, 272–274, 279, 282, 283 Desulfovibrio, 223 Amphoteric substance, 339, 363 jarosite, 222 Amphoterism, 345 metal and iron sulfides, 220 Anaerobic respiration pyrite oxidation, 222 ethanol production, 241 Thiobacillus, 223 fermentation, 241 Activity coefficient, 77, 79, 80 glucose to lactic acid, 241 Adams, F., 81 lactic acid production, 241 Adams, G., 285 methane production, 242 Adenosine diphosphate (ADP), 292 nitrate, 242

# Springer Nature Switzerland AG 2020 427 C. E. Boyd, Water Quality, https://doi.org/10.1007/978-3-030-23335-8 428 Index

Anderson, R.A., 356 Biological oxygen demand (BOD), 318 Anion-cation balance, 95, 96 Biological pollution, 389 Antimony (Sb), 364 Biotic ligand model (BLM), 371 Application factor, 397 Bismuth (Bi), 366 Aquaculture, ix Blue-green algae, 248 Aquatic ecosystems, 38, 380 Boehmite, 361 Aquatic macrophytes, 293 Bohr model, 22 Aquifers, 45, 54, 55 Boiler scale, 209, 210 Arnon, D.I., 357 Bollenbach, W.M. Jr., 390 Arrhenius, S., 37 Borda, M.J., 221 Arsenic (As), 360, 361 Boron (B), 358 Atmospheric circulation, 49–51 Bottled water, 115, 116 Atmospheric fixation, 272 Boyd, C.E., 49, 81, 219, 228, 229, 253, 255, Atmospheric gases, 136–138 261, 263, 302, 332, 341, 358, 389 Atmospheric motion, 50 Bromine (Br), 366 Atmospheric nitrogen fixation, 270, 271, 273 Brønsted theory, 344 Atmospheric pressure, 5–7, 11, 13, 14, 136–138 Brownian movement, 123 Avogadro’s number, 125, 416 Buffering, 194, 196–199 Bunsen coefficients, 141, 142 Butcher, R.W., 318 B Bacteria abundance, 244 C aerobic respiration (see Aerobic respiration) Cadmium (Cd), 355 anaerobic respiration (see Anaerobic Calcite, 189 respiration) Calcium carbonate, 184 growth, 235–239 Calcium carbonate saturation growth effects, 243, 244 Langelier Saturation Index, 212, 213 physiology, 235 precipitation/scaling, 212 Bagarinao, T., 332 Calcium fluoride (CaF2), 358 Baralkiewicz, D., 356 Calcium hardness Barium (Ba), 365 eriochrome black T, 209 Barometric pressure (BP), 136, 138, 139, 145 murexide indicator, 209 Beckett, R., 218 Calcium phosphate, 291–293, 300, 307 Beer-Lambert law, 31 Caldeira, K., 225 Beryllium (Be), 365 Calomel electrode, 172, 174 Besser, J.M., 355, 364 Capillary action, 9–11 Best management practices (BMPs), 400, 405 Capillary fringe, 11 Bicarbonate alkalinity, 187 Carbon and oxygen cycle, 261–263 Bioaccumulation, 391 Carbon availability, 202 Biochemical oxygen demand (BOD), 386, 387 Carbon dioxide (CO2), 181–183 ammonia nitrogen, 387 Carbonic acid, 181, 182 natural waters, 387 Carbonic anhydrase, 193 nitrification, 387, 389 Cation-anion balance, 94–96 organic matter, 385 Celsius scale, 22, 23 photosynthetic oxygen production, 385 Chalcopyrite, 352 phytoplankton respiration, 386 Chalker, J.M., 368 stream reaeration, 387 Chandra, A.P., 221 wastewater, 385 Chelated metal, 347 Bioconcentration, 391 Chelating agents, 347 Biocriteria, 404 Chemical equilibrium Biodiversity, 315 hydrochloric acid, 69 Biological fixation, 273 K values, 69 Index 429

molar activities, 69 Cowardin, L.M., 397 pH buffering, 69 Cowling, E.B., 227 principles, 65 Criterion continuous concentration (CCC), reaction quotient, 69 371, 395 saturated solution, 68 Criterion maximum concentration (CMC), thermodynamics 371, 395 endergonic, 71 Crout, D.H.G., 219 endothermic reaction, 70 Cultural eutrophication, 312 enthalpy, 69, 70 Cyanide (CN), 366, 367 entropy, 70 Cyanobacteria, 248 exergonic, 71 exothermic reaction, 69 K value, 72, 73 D non-equilibrium conditions, 72, 73 Dahl, T.E., 398 reactants, 69 Dalton’s Law of Partial Pressures, 139 standard Gibbs free energy, 70 Debye-Hückel equation, 77–80 Chemical weathering, 66 Deforestation, 384 Chlorination Deionizer, 113 chlorine residuals, 264 Delta P (ΔP), 150, 151 chlorine species, 264 de Melo, B.A., 228 coliform organisms, 263 Denitrification, 280–282, 286, 289 fecal coliforms, 263 Density, 8, 9, 12, 13, 18 human pathogens, 263 Deoxyribonucleic acid (DNA), 292 hypochlorous acid, 265 Deposition, 6 infections, 263 Desalination, 115, 117 trihalomethanes, 265 Desulfovibrio, 328 Chowdhury, U.K., 361 Deverel, S.J., 336 Chromium (Cr), 356, 357 Dielectric constant, 14, 15 Clay, J., 389 Diffuse reflection, 17 Clean Water Act, 399, 400, 406 Dihydrogen monoxide, 1 C/N ratio, 276, 277 Dihydrogen oxide, 1 Cobalt (Co), 356 Discharge permits, 399 Cogley, J.G., 17 Dissolutions, 65–67, 74 Coldwater species, 38 Dissolved organic matter, 105–107 Coliform organisms, 263 Dissolved oxygen Colligative properties, 108 aerobic organisms, 135 Colony-forming units (CFU), 244 aerobic respiration, 136 Colt, J., 137, 141, 142 atmospheric gases and pressure, Common ion effect, 67, 76 136–138 Common salinity, 87 biologic and geologic factors, 136 Compensation depth, 259 concentrations, 156 Compressibility of water, 12 gases, 136 Concentration limits, 403, 405 partial pressure, 138, 140 Conductivity, 16 warmwater fish, 161 Confined aquifers, 54, 55 Dodds, W.K., 318 Conley, D.J., 320 Dolomite, 189 Copper (Cu), 352–354 Drainage network, 56 Copper sulfate, 320 Drinking water, viii Coriolis force, 50 Drinking water standards, 391 Corrosion, 117, 175, 176 Durum, W.H., 357, 365, 369 Ćosović, B., 356 Dynamic viscosity, 12 Coulomb’s law, 15 Dystrophic water body, 219, 229 Covalent bond, 2, 416 Dystrophy, 311 430 Index

E gully, 383 Earth’s water land surface disruption, 384 freshwater, 42 raindrop, 383 hydrosphere, 42 sedimentation, 384 precipitation, 43 sheet, 383 runoff, 43 soil, 383 water cycling, 42 turbidity, 384 water footprint, 43 USLE, 383 water shortages, 44 Esdaile, J.L., 368 Eaton, A.D., 186, 207, 209, 216, 226, Essumang, D.K., 356 385, 393 Estuaries, 36, 62 Economic development, 402 Ethylenediaminetetraacetic acid (EDTA), Effluent standards, 400, 404 207, 208 Einstein’s equation, 25 Etowah River, 99 Eisely, L., 2 Eutrophication, 291, 293 Electrical conductivity (EC), 90, 91 anthropogenic activities, 313 Electrical neutrality, 94 aquatic ecosystems, 315 Electricity, 89 biological communities, 314 Electromagnetic radiation, 25 climate change, 318, 319 Electromagnetic spectrum, 27, 30 control, 319–321 Electron shell, 2 definition, 312 Electrostatic interactions, 77–80 diversity, 315 Elements ecologically-sensitive species, 313 alkaline earth metals, 411 ecological system, 316 atomic mass, 413 lakes, 316–318 atoms, 412 nitrogen and phosphorus, 313, 315, 321 classification, 411 physical and chemical environment, 313 formula, 416 phytoplankton species diversity, 314 ions, 413 runoff, 312 isotopes, 413 sedimentation, 312 metalloids, 411 stream, 318 molecules, 411 unpolluted water bodies, 315 noble gases, 411 variables, 313 nonmetals, 411, 414 water bodies, 312 nucleus, 412 water pollution, 321 protons, 412 water usage, 319 sodium and chlorine, 415 Eutrophy, 311, 313 symbol, 413 Evaporation, 48, 60 Elser, J.J., 252 dissolved salt concentrations, 47 Endothermic reactions, 37 energy, 44, 46 Energy, 22, 25, 46 measurement, 47–49 Enthalpy, 6, 69, 70 molecules, 46 Entropy, 23, 24, 70 phytoplankton, 47 Epilimnion, 35, 36 relative humidity, 46, 47 Equilibria, 192–194 saturation vapor pressure, 47 Equilibrium constant, 68, 69, 72–74, 81, VPD, 46 82, 164 wind velocity, 47 Equilibrium Law, 68 Evaporation pan, 48, 49 Equivalent conductances (λ), 91, 92 Evapotranspiration, 43, 45 Equivalent ionic conductance, 91 Everall, N.C., 227 Eriochrome black T, 207, 209 Exothermic reactions, 37 Erosion, 129 Extinction coefficient, 126 factors, 383 Index 431

F Gibbs free energy, 70, 71, 164, 168, 336 Fanning, D.S., 221 Gibbsite, 298, 361, 363 Faraday constant, 168 Gibbs, J.W., 70 Feely, R.A., 225 Gibbs standard-state free energy, 70 Fermentation, 241, 242 Gilbert, J.A., 358 Ferredoxins, 324 Global atmospheric circulation, 50 Feuchtmayr, H., 318 Global energy budget, 28 Filella, M., 366 Global warming, 30, 318 Firth, J., 361 Goldberg, E.D., 341 Flegal, A.R., 369 Goldman, C.R., 336 Fleming, J.F., 221 Goldmining, 368 Flocculation, 131 Gopakumar, G., 332 Fluoride (F), 358, 359 Gosselink, J.G., 397 Food web, 292, 316, 317 Gram atomic mass, 413 Formality, 419 Gram molecular weight, 413 Formazin attenuation units (FAU), 127 Gray, J.S., 332 Frattini, P., 369 Green and purple sulfur bacteria, 328 Frear, C.L., 190 Greenhouse effect, 30 Free energy of reaction, 70, 72 Greenhouse gases, 30 Freshwater, 42 Gross, A., 281, 285 Freshwater aquatic ecosystems, 407 Groundwater, 45, 54, 55, 97 Fries, L., 357 Groundwater pollution, 389, 390 Fulvic acids, 218, 219 Gully erosion, 383 Guo, T., 340 Gypsum, 66, 325 G Gaillardet, J., 336 Gallagher, L.M., 406 H Gary, J.E., 368 Haber-Bosch process, 273 Gas bubble trauma, 151, 270, 289 Haffty, J., 357, 365, 369 Gas solubility Haines, T.A., 224, 227 Bunsen’s absorption coefficients, 141 Halogens, 411 Henry’s law, 140 Hamilton, S.J., 360 STP, 142 Han, Y., 229 temperatures and salinities, 142 Hardness and biological productivity, 210 Gas solubility tables Hardness categories BP, 145, 146 calcium and magnesium hardness, 209 dissolved oxygen concentrations, 147 carbonate and noncarbonate hardness, 209 hydrostatic pressure, 146 Hargreaves, J.A., 287 universal gas law equation, 147 Hasler, A.D., 228 Gas transfer Hasselbalch, K.A., 196 air-water interface, 152, 153 Hayes, D., 324 dissolved oxygen concentrations, 152, 153 Heat, 23 gas-liquid contact system, 153 Hem, J.D., 200, 324, 336, 351, 356, 359, molecular diameters, 153 360, 362, 369 oxygen deficit/surplus, 152 Hemoglobin, 159, 160, 350 SOTR, 154, 155 Henderson-Hasselbalch equation, 196, 198, 199 WRR, 155 Henry’s law, 140 Gebbie, P., 212, 213 Hoekstra, A.Y., 43 Geissman, T.A., 219 Holland, A., 227 Gensemer, R.W., 364 Hoorman, J.J., 276 George, C., 264 Howarth, R.S., 371 Gerson, A.R., 221 Howe, P., 369 432 Index

Humankind, 43 Ion pairs, 80, 81, 341, 342, 344, 348 Human population, 380 Iron (Fe), 350–352 Humic acids, 218, 219 Iron pyrite, 331 Humic substances, 106, 125, 181 Islam, R., 276 fulvic acid, 217 Isotopes, 412 humic acid, 219 Izbicki, J.A., 357 mineral acids, 227 organic polymers, 218 toxic effect, 227 J toxicity, 228 Jackson turbidimeter unit (JTU), 126 Hutchinson, G.E., 84 Jaszczak, E., 367 Hydrogen (H2), 164 Jenkins, D., 185, 264 Hydrogen bonds, 4–6, 9, 10, 22 Jimenez, M.C.S., 265 Hydrogen sulfide (H2S), 329, 330 Johnson, D.S., 228 Hydrologic cycle, 41, 44, 45, 62 Johnston, J., 190 Hydrologic equation, 60 Jones, D.A., 366 Hydrolysis, 345, 346 Jones, J.B. Jr., 349 Hydrolysis of carbonate, 193, 194 Jumpertz, R., 240 Hydrometers, 87, 88 + Hydronium ion (H3O ), 178 Hydrosphere, 42 K Hydrostatic pressure (HP), 146, 150–152 Karbowska, B., 369 Hydroxide alkalinity, 187 Kaushal, S.S., 319 Hydroxyapatite, 300 Kautz, R.S., 318 Hyenstrand, P., 336, 350 Kellerman, K.F., 353 Hygroscopic coefficient, 53 Kelvin scale, 23 Hypolimnion, 35, 36, 173 Khan, T., 357 King, D.J., 253 Kirchhoff’s law, 30 I Klavins, M., 220 Ice, 6, 8 Knudsen equation, 87 Ice cover, 36 Knudsen, M., 86 Ideal gas law, 147, 169 Kochkodan, V., 358 Imhoff cone, 128, 129 Kociolek, J.P., 311 Immobilization of nitrogen, 276 Kopp, J.F., 354, 355, 358, 361, 365, 367 Industrial fixation, 273 Korečková-Sysalová, J., 365 Industrial revolution, 380 Krebs cycle, 237 Inorganic phosphorus, 293, 294, 296, 302 Kristensen, E., 243 Intergovernmental Oceanographic Kroner, R.C., 354, 355, 357, 358, 365, 367 Commission (IOC), 87 Kucuk, S., 287 International Desalination Association, 115 Kutler, B., 354 International Society of Soil Science (ISSS), 121 Kuttyamma, V.J., 332 International Standards Organization (ISO), 113, 114 International System of Units (SI units), 5, 90 L International Union of Pure and Applied Lakes, 58 Chemistry (IUPAC), 1 Lane, T.W., 355 Iodine (I2), 359 Langelier Saturation Index, 212 Ion activities Langelier, W.F., 212, 213 divalent, 79 Lantin-Olaguer, I., 332 monovalent, 79 Latent cancer fatalities (LCF), 392 Ion hydration, 15 Latent heat, 6, 7 Ionic strength, 77–79, 81 Law of Definite Proportions, 416, 417 Index 433

Law of mass action, 68, 164 Mercury (Hg), 367, 368 Lawrence, J., 219 Mesotrophy, 311 Laws of thermodynamics, 2, 22, 23, 69, 70, 414 Metalimnion, 35 LC50 tests, 288, 289 Metalloids, 411 Lead (Pb), 367 Methane production, 242 Le Chatelier’s principle, 68, 74 Methyl mercury, 368 Lee, J.G., 355 Microbial decomposition, 292 Lees, D.R., 227 Microbial growth efficiency (MGE), 276 Leib, K.J., 355, 364 Micronutrients, 336 Lethal concentration 50 (LC50), 393, arsenic, 360, 361 394, 396, 397 boron, 358 Lewis acid and base theory, 344 cadmium, 355 Lewis acid-base reaction, 344 chromium, 356, 357 Liebig’s law, 251 cobalt, 356 Ligands, 347 copper, 352–354 Light and dark reactions, 249 fluoride, 358, 359 Light-dark bottle technique, 257 iodine, 359 Light penetration in water, 30–32, 124 iron, 350–352 Lignins, 124 manganese, 352 Lignosulfonic acid, 219 molybdenum, 356 Li, M., 228 nickel, 357 Lime-soda ash process, 210, 211 selenium, 360 Lindemann, M.D., 356 and trace elements, 343 Livingstone, D.A., 98, 200, 357, 358, 367, 370 vanadium, 357 Load limits, 403, 405 zinc, 354, 355 Longwave radiation, 29 Microorganisms Lowest observed effect concentration bacteria (see Bacteria) (LOEC), 394 phytoplankton (see Phytoplankton) Luther III, G.W., 221 Miller, L.A., 406 Luxury consumption, 304 Miller, W.E., 252 Lysimeters, 49 Mineralization of nitrogen, 276, 277 Miscibility, 417 Mitsch, W.J., 397 M Molality, 419 Macrophytes, 303, 305 Molarity, 418, 426 Magazinovic, R.S., 366 Molecular oxygen, 136, 162 Magnesium hardness, 209 Molybdenum (Mo), 356 Manganese (Mn), 352 Monocalcium phosphate, 299, 300 Martell, A.E., 347, 362 Moore, G.T., 353 Massaut, L., 398 Morel, F.M.M., 355 Mass balance, 61 Moser River, 99 Masuda, K., 302 Moyle, J.B., 210 Maunder Minimum in astronomy, 27 Muller, S., 318 Maximum allowable toxicant concentrations Murexide indicator, 209 (MATC), 372, 394, 397 Mu, Y., 371 Maxwell, J., 46 Maxwell’s demon concept, 46 McBride, M.B., 336, 341 N McCarty, P.L., 210 Nadis, S., 336, 350 McNevin, A.A., 263, 332, 341 Nassar, L.J., 228 Mean sea level (MSL), 136 National Pollutant Discharge Elimination Mekonnen, M.M., 43 System (NPDES), 399 Meniscus, 9, 10 Natural ecosystems, 380 434 Index

Natural softening of groundwater, 104 No observed effect concentration (NOEC), 394 Natural waters, 65, 81 Normality, 419, 420, 426 coastal and ocean water, 104, 105 Novak, J.T., 253 dissolved organic matter, 105–107 Nutrient pollution, 381 inland waters Nutrients aquifers, 103 alkalinity and phytoplankton carbon dioxide, 97 productivity, 253 geological and climatic zones, 98 growth and metabolism, 235 groundwater, 97, 103 inorganic, 243 hydrogen ion concentration, 99 multiple limiting, 251 ionic constituents, 98, 99 phytoplankton growth, 252 limestone, 98, 99 single limiting, 251 mineral precipitation, 102 turbidity and discoloration, 248 minerals, 97 physiographic regions, 103 pond waters, 102 O runoff, 97 Ocean currents, 50 silica concentration, 98 Oceans, 42, 62 streams, 97 Ocean water, 104 rainwater, 96, 97 Ohm’s law, 89 Nephelometer, 127 Oligotrophy, 311, 313 Nephelometer turbidity units (NTU), 127 Organic phosphorus, 301–303 Nephelometry, 127 Orr, J.C., 225 Nernst equation, 169, 170, 180 Orthophosphoric acid, 294 Nesbitt, H.W., 221 Osmoregulation, 112 Nickel (Ni), 357 Osmotic pressure, 110–112 Ning, L., 354, 355, 357, 361, 367, 368 Oxidation-reduction (redox) potential Nitrate reduction in plants, 274 aquatic ecology, 176 Nitrification, 270, 278–280, 382 cell voltage and free-energy change, Nitrite toxicity, 288 168–171 Nitrobacter, 279 corrosion, 175, 176 Nitrogen, 270, 286, 287 electron transfer, 163 Nitrogen compounds, 289 half-cell reactions, 165 Nitrogen cycle, 271 hydrogen, 164 Nitrogen dioxide (NO2), 289 iodine, 164 Nitrogen fixation, 271, 273, 286 measurable electrical current, 164 Nitrosomonas, 279 measurement, 172–174 Nonessential trace elements oxidizing agent, 164 aluminum, 361–364 standard hydrogen electrode, 165–168 antimony, 364 Oxygen consumption, 160 barium, 365 Oxygen potential, 173, 174 beryllium, 365 Oxygen solubilities, 145 bismuth, 366 Oxygen tension, 149, 150, 152, 159 bromine, 366 Oxyhemoglobin, 159 cyanide, 366, 367 Oysters, viii lead, 367 mercury, 367, 368 silver, 368, 369 P strontium, 369 Pagenkopf, G.K., 347 thallium, 369 Pais, I., 349 tin, 369 Palmer, C.A., 358 uranium, 370 Partial pressure, 139, 140, 149, 152 Non-photosynthetic microorganisms, 21 Pecos River, 99 Index 435

Penman equation, 49 Pinsino, A., 352 Percentage saturation, 149, 150 Polarization, 15 pH Pollutants, 381 acidity/basicity, 177 Pollution, viii, ix alkalinity, 178 Pollution control averaging, 180 effluent discharge permits, 399 calculations, 179, 180 effluent limitations, 400 concept, 178, 179 water bodies, 400, 402 natural waters, 181 Polyphosphate, 296 on fish, 201 Ponds, 58 rainwater, 182, 183 Pore water, 294, 299, 301, 305, 306 Phenolphthalein alkalinity (PA), 187 Potential acid-sulfate (PAS), 221 Phosphate fertilizers, 293, 307 Potential evapotranspiration (PET), 49 Phosphorus Practical salinity, 87 analysis issues, 302 Practical salinity units (psu), 87 brain food, 292 Precipitation, 45, 49 concentrations in water, 302, 303 adiabatic lapse rate, 51 ecosystems, 308 air rising, 51 environment, 293, 294 hail, 52 fertilized fish ponds, 307 hygroscopic particles, 52 natural and agricultural ecosystems, 291 measurement, 52 nitrogen, 308 rules, 52 organic, 301 water droplets/ice particles, 52 organic matter, 292 Probable no effect concentrations (PNEC), 372 orthophosphate, 308 Proton-proton chain, 24, 25 orthophosphoric acid, 294–296 Puntoriero, M.L., 359 pH, 295, 301 Pure water, ix phospholipids, 292 phytic acid, 292 plant uptake, 303, 304 Q protein synthesis, 292 Q10 equation, 38 qualitative model, 294 sediment reactions, 296, 298–301 valence states, 292 R water and sediment, 304, 305, 307 Raindrop erosion, 383 Phosphorus removal, 320, 321 Rainfall, 42, 45, 52, 55, 56, 58, 60 Photic zone, 124 Rain gauges, 48, 53 Photosynthesis, 249, 250 Rainwater, ix, 41, 96, 97 Photosynthesis and respiration rates, Raoult, F., 108 measurement, 257–259 Raoult’s law, 108 Photosynthetically active radiation (PAR), 125 Rathbun, R.E., 228 Photosynthetic photon flux (PPF), 125 Redfield, A.C., 252, 308 Phytic acid, 292 Redfield ratio, 252, 308 Phytoplankton Reference salinity, 87 abundance Reflectivity, 17 chlorophyll a determination, 254 Refractive index, 18, 19, 87 Secchi disk visibility, 254 Refractometer, 87, 88 biochemical assimilation, 250 Relative humidity (RH), 46, 47 biology, 247–248 Republican River, 99 harmful algae, 260, 261 Reservoirs, 58 photosynthesis, 249 Resistivity, 90 Phytoplankton die-offs, 255, 256 Respiration Piezometric levels, 55 absorption, 157 436 Index

Respiration (cont.) Shiraishi, K., 370 air movement, 158 Shortwave radiation, 29 aquatic ecosystems, 162 Siepak, J., 356 aquatic environments, 157 Silicate, 97 aquatic organisms, 159 Silicate clays, 300 carbon dioxide, 160, 161 Silicic acid, 99 chemoautotrophic microorganisms, 160 Sillén, J.G., 347, 362 metalloproteins, 159 Silver (Ag), 368, 369 oxygen, 160 Six, J., 276 terrestrial ecosystems, 158 Sling psychrometer, 46 warmwater fish, 161 Smith, D.D., 383 weight/volume concentration, 158 Smith, D.J., 228 Respiratory quotient (RQ), 239 Smith, S.J., 225, 325 Ribonucleic acid (RNA), 292 Snell’s law, 18 Rickard, D., 221 Snoeyink, V.L., 185, 264 Roberson, C.E., 362 Sodium adsorption ratio (SAR), 111, 113 Runoff, 43, 44, 49, 56, 60 Sodium stearate, 208 Ryan, D., 341 Soil erosion, 383 Soil loss, 384 Soil water, 53, 54 S Soil-water system, 349 Salinity, 9, 10, 13, 86–88, 112 Solar constant, 26–28 Salinometers, 88 Solar radiation, 32, 39, 47 Salt effect, 67 deuterium nucleus, 24 Saturometer, 151 electromagnetic waves, 25 Saunders, G.W., 194 nuclear fusion, 24 Sawyer, C.N., 210 photons, 25 Schindler, D.W., 320 proton-proton chain, 25 Schippers, A., 221 shortwave and longwave, 27 Schmidt, R., 10 sunspots, 27 Schneider, B., 10 wavelength, 26 Schroeder, E.D., 264, 402 Solubility Schroeder, G.L., 155 endothermic reactions, 67 Seawater, 84, 104 exothermic reactions, 67 Secchi disk, 126, 129 inorganic/organic compounds, 66 Sedimentation, 122, 384 ion effect, 67 Sediment phosphorus, 293, 302, 303, 305, 308 low redox potential, 68 Sediment redox, 172, 173 pH, 67 Sediment respiration products, 74, 75 aerobic respiration, 245 rules, 67 aquatic ecosystems, 245 soluble compounds, 418 decomposition, 246 substances, 67 oxidation, 245 temperature, 67 zonation, 246, 247 Solubility product (Ksp), 336 Seepage, 60 Soluble reactive phosphorus, 302, 303 Seker, S., 354 Solutes, 65 Selenium (Se), 360 Solvent, 65, 417 Semiconductors, 411 Sorensen, D.L., 221 Sheet erosion, 383 Sørensen, S.P.L., 179 Shelford’s law, 251 Spears, J.W., 357 Shellfish poisoning, 261, 267 Specular reflection, 16, 17 Shilo, M., 255 Spotte, S., 285 Shinozuka, T., 218 Sprague, J.B., 371 Index 437

Standard electrode potential, 166, 167, T 172, 175 Tannic acid, 219, 220 Standard oxygen transfer rate (SOTR), 154 Tannins, 124 Standard temperature and pressure (STP), 136 Taras, M.J., 186 Steelink, C., 217 Tchobanoglous, G., 264, 402 Stefan-Boltzmann law, 26 Temperature, 21, 23, 38 Stoermer, E.F., 311 Terminal settling velocity, 121, 122, 129 Stoichiometry, 423 Thallium (Tl), 369 Stoke’s law equation, 121, 123 Thermal destratification, 8 Stream re-aeration, 156 Thermal stratification, 8, 34–36, 313 Streams Thermal stress, 21 channel precipitation, 56 Thermocline, 35 classification system, 400 Thièbaut, G., 318 dendritic pattern, 56 Thiobacillus, 327 discharge, 56 Thoenen, T., 370 ephemeral, 56 Thompson, W., 24 first-order, 56 Thornthwaite equation, 49 hydrograph, 56, 57 Tin (Sn), 369 intermittent, 56 Total alkalinity (TA), 94, 187, 195 order, 56 bicarbonate and carbonate, 184, 185 perennial, 56 carbon dioxide, 184 second-order, 56 definition, 184 sediment deposition, 57 expression, 185 subsurface storm drainage, 56 measurement, 185–187 watershed characteristics, 57 pH, 199, 200 Stream temperature, 34 sources Strontium (Sr), 369 calcite, 191 Sublimation, 6 calcium and bicarbonate, 190 Sulfate, 324 calcium carbonate, 188, 191 Sulfide oxidation, 324 calcium silicate, 192 Sulfur, 221–224 carbon dioxide, 190, 191 amino acids, 324 limestone, 187, 188, 191 concentrations, 331 mass action, 189 cycle, 325, 326 organic matter, 191 effects, 332 weathering of feldspars, 192 fuels and volcanic eruptions, 324 Total ammonia nitrogen (TAN), 389 geochemistry, 323 Total body burden (TBB), 391 oxidation states, 324 Total dissolved fixed solids (TDFS), 106 transformations Total dissolved solids (TDS) oxidations, 327, 328 alkalinity and hardness, 94 plant uptake and mineralization, analysis, 86 326, 327 aquatic ecosystems, 116 reductions, 328, 329 atmosphere, 84 valence states, 326 bottled water, 115, 116 Sulfur dioxide, 224, 225 degree of mineralization, 84 Sunspots, 27 desalination, 115 Surface tension, 9, 10 end of pipe discharges, 116 Suspended particles estuaries, 116 colloids, 123 evaporation, 85 color, 124 freezing and boiling points, 108, 109 settling characteristics, 121–123 freshwaters, 84 sources, 120 geological formations, 84 Suspended solids, 119 inorganic particles, 84 438 Index

Total dissolved solids (TDS) (cont.) carbon dioxide, 340 ion exchange, 113, 115 complex ions, 344, 345 laxative effect, 117 copper sulfate, 341 organic compounds, 85 description, 336 osmotic pressure, 110–112 drinking water, 374 salinity, 86–88 ferric hydroxide, 340 seawater, 84 freshwater systems, 341 specific conductance health effects, 371 EC, 90, 91 ion pairs, 341, 342, 344, 348 electricity, 89 ion principle, 336 electrostatic interactions, 92 metal ion hydrolysis, 345, 346 ions, 91 metals, 339 resistivities, 90 mineral nutrients, 349 salinity, 93 organic complexes/chelates, 347 SI units, 90 pH, 338 surface waters, 92 redox potential, 340 vapor pressure, 108 seawater, 342 Total dissolved volatile solids (TDVS), 106 solubility, 336 Total fixed suspended solids (TFSS), 128 temperatures, 338 Total gas pressure (TGP), 139, 150 toxicity, 371 Total hardness Trace metals, 341, 342, 345, 355, 371 biological productivity, 210 Trace nutrients, 336 boiler scale, 209, 210 Transparency, 16–18 calcium carbonate saturation, 212–213 Transpiration, 47 calcium hardness, 209 Tranvik, L.J., 336, 350 concentrations, 208 Trenberth, K.E., 29 definition, 206 Triethanolamine (HTEA), 347 EDTA, 207, 208 Triple point, 7 eriochrome black T, 209 Trisodium phosphate, 293 limestone/calcium silicate, 206 Trophosphere, 28 magnesium carbonate, 213 Tropic status of lakes, 266 magnesium hardness, 209 Tropical species, 38 permanent/noncarbonate hardness, 210 Troposphere, 136 problems, 208, 209 Tucker, C.S., 253, 261, 332 soap precipitation, 205 Turbidity, 120 soap-wasting property, 213 chemical coagulant, 131, 132 sodium stearate, 208 color, 132 sources, 206 measurement, 126, 127 temporary/carbonate hardness, 210 Secchi disk, 129 water softening, 210–211 settleable solids, 128 Total maximum daily loads (TMDLs), 404 settling basin, 129–131 Total suspended solids (TSS), 127, 128 suspended solids, 127, 128 Total volatile suspended solids (TVSS), suspended solids removal, 129 127, 128 Turekian, K.K., 341 Toxic algae, 261 2-Chloro-6-(trichloromethyl) pyridine Toxicity tests, 391, 393, 394, 397, 404 (TCMP), 387 aquatic organisms, 392 Tyndall effect, 123 aquatic toxicology, 392 Tyndall, J., 123 LC50, 393, 397 MATC, 394, 397 threshold concentrations, 392 U Trace elements Ultraeutrophy, 313 anaerobic bacteria, 340 Ultraoligotrophy, 313 Index 439

Ultra trace elements, 336 Water cycle, 45 Unit annual risk (UAR), 392 Water distillation unit, 114 Unit lifetime risk (ULR), 392 Water footprint, 43 United Nations Educational, Scientific Water measurements and Cultural Organization mass balance, 61 (UNESCO), 87 runoff, 58 United States Department of Agriculture seepage, 60 (USDA), 121 volumes of standing water bodies, 59 United States Pharmacopeia (USP), 113, 114 water budgets, 60 Universal gas law, 147, 148, 169 Water molecule Universal soil loss equation (USLE), 383 adhesive forces, 9 Uranium (U), 370 capillary action, 9–11 U. S. Environmental Protection Agency cohesive forces, 9, 10 (USEPA), 395, 399 compressibility, 12 US National Oceanographic and Atmospheric conductivity, 16 Administration, 263 density, 8, 9 Uthus, E.O., 360 dielectric constant, 14, 15 dissolved ions, 16 elasticity, 12 V electric field, 15 Vanadium (V), 357 meniscus, 10 van der Graaf, A.A., 279 pressure, 13, 14 van der Waals interactions, 3, 4 refraction of light, 19 van der Waals, J., 3 refractive index, 18, 19 van Hoff’s law, 243 SI unit, 10 van Niekerk, H., 92 structure van’t Hoff equation, 37 covalent bonds, 2 van’t Hoff factor, 109 electrons, 2 van’t Hoff, J., 37 electrostatic charges, 3 Vapor pressure, 7 hydrogen and oxygen atoms, 2, 3 Vapor pressure deficit (VPD), 46 hydrogen bonding, 4 Vesilind, P.A., 387, 398 laws of thermodynamics, 2 Viscosity, 11, 12 repulsions and attractions, 3 Visible light, 125 surface tension, 10 Vrede, T., 336, 350 surfactants, 10 temperature, 5–10, 12 thermal characteristics and phases, 5–7 W thermal properties, 6 Walley, W.W., 358 transparency, 16, 18 Warmwater species, 38 vapor pressure, 7 Water viscosity, 11, 12 agricultural crops, vii Water pollution, 44 availability, viii acidification, 382 bacteria, vii bioconcentration, 381 biochemical reactions, vii biological, 389 dissolution, erosion and deposition, vii BOD (see Biological oxygen demand early human settlements, vii (BOD)) microorganisms, vii erosion, 383, 384 organisms, vii fossil fuels, 381 transportation, viii groundwater, 389, 390 Water bodies, viii, 400 heated effluents, 382 Waterborne diseases, ix, 389 nonpoint sources, 381 Water budgets, 49, 60 nutrient pollution, 381 440 Index

Water pollution (cont.) riparian doctrine, 399 organic wastes, 381 Water softening pharmaceuticals, 382 lime-soda ash process and zeolite point sources, 381, 383 process, 210, 211 runoff, 381 magnesium hydroxide, 211 salinization, 382 Water supply sediment, 381 groundwater, 43 toxic chemicals/substances, 382 infrastructure, 44 toxicity, 381 weather rainfall patterns, 43 toxins and human risk assessment, 390–392 Water surface, 14 turbidity, 381 Water table, 54 Water pressure, 11, 13, 14, 54 Water temperature, 34, 39 Water quality heat content, 32 acidic and saline waters, ix ice cover, 36 aquatic ecosystems, ix statification, 36 contaminants, ix temperate zone change, 33 ecological services, x thermal stratification, 34–36 ecological systems, viii water quality, 36–38 guidelines, 402 Water vapor, 4, 6, 7 minerals, viii Watts, P., 369 pathogens and chlorination, 263–265 Wavelength, 25, 26, 29–31 phytoplankton Weight per unit volume, 421, 422 Anabaena variabilis, 255 Weight relationships, 423 die-offs, 255, 256 Weiler, R.R., 285 nutrients, 256 Wein’s law, 26 oxygen concentration, 256, 257 Welch, H.E., 155 photosynthesis, 254 Wentz, D.A., 368 thermal destratification or overturns, 256 Wessel, G., 357 phytotoxic substances, viii Wetland destruction, 397, 398 principles, x Wetlands, 58 salty water, viii Wetzel, R.G., 266 sensory perception and observations, viii Wheatstone bridge circuit, 89, 90 Water quality standards, viii, ix Whitening of water bodies, 194 biological, 404 Wickett, M.E., 225 concentration based standards, 402 Wind re-aeration rate (WRR), 155 delta based standards, 403 Wischeier, W.H., 383 discharge permits, 406 Wisniak, J., 366 drinking water, 406 Withlacoochee River, 99 guidelines, 408 World Health Organization (WHO), 359, 371 local based standards, 403 World Meteorological Organization, 47 TMDLs, 404 toxic chemical, 404 waste treatment and BMPs, 405 Z Water quantity Zeolite process, 210, 211 human affairs, 398 Zinc (Zn), 354, 355 prescriptive rights, 399 Zingg, A.W., 383