Chapter 4 Water Treatment Introduction In 2005 every 15 seconds a child under the age of 5 died from a water related

d illness. 17 % of the earths population (1.2 billion people) do not have a reliable water and 40% of the population do not have access to adequate sanitation.

Suspended Suspended solids are large enough to settle out of solution or be removed by filtration In envi engg., suspended solids are defined as those solids that can be filtered by a glass fiber disc and are properly called filterable solids. Suspended solids can be removed from water by physical methods such as sedimentation, filtration and centrifugation

Basic Definitions Pathogen = An organism which causes disease Potable = Safe to drink Palatable = Pleasing to drink Why make water palatable?=we have learned that we must provide a water that is both potable and palatable, for it is not palatable people will turn to untreated water that may not be potable.

Colloidal particles are in the size range between the dissolved substances and suspended particles. They are in a solid state and can be removed from the liquid by physical means such as very high force centrifugation or filtration through membranes with very small pore spaces.

Concentration of Solutions

Water Chemistry Physical Properties of Water (mass density, specific weight, specific gravity) State of Solution Impurities (suspended, colloidal, or dissolved) Chemical units (weight percent and milligram per liter, molarity and normality)

The concentration of a chemical solution refers to the amount of solute that is dissolved in a solvent. We normally think of a solute as a solid that is added to a solvent (e.g., adding table salt to water), but the solute could just as easily exist in another phase. For example, if we add a small amount of ethanol to water, then the ethanol is the solute and the water is the solvent. If we add a smaller amount of water to a larger amount of ethanol, then the water could be the solute!

State of Solution Impurities Dissolved A dissolved substance is one which is truly in solution The substance is homogeneously dispersed in liquid Dissolved substances are in the liquid, that is, there is only one phase present The substance cannot be removed from the liquid without accomplishing a phase change such as distillation, precipitation, adsorption, extraction or passage through ionic pore sized membranes

Chemical Units: Units of Concentration Once you have identified the solute and solvent in a solution, you are ready to determine its concentration. Concentration may be expressed several different ways, using percent composition by mass, mole fraction, molarity, molality, or normality.

Percent Composition by Mass (%) This is the mass of the solute divided by the mass of the solution (mass of solute plus mass of solvent), multiplied by 100.

Example: Determine the percent composition by mass of a 100 g salt solution which contains 20 g salt. Solution: 20 g NaCl / 100 g solution x 100 = 20% NaCl solution

Because the density of water at 25C is about 1 kilogram per liter, molality is approximately equal to molarity for dilute aqueous solutions at this temperature. This is a useful approximation, but remember that it is only an approximation and doesn't apply when the solution is at a different temperature, isn't dilute, or uses a solvent other than water.

Mole Fraction (X) This is the number of moles of a compound divided by the total number of moles of all chemical species in the solution. Keep in mind, the sum of all mole fractions in a solution always equals 1. Example: What are the mole fractions of the components of the solution formed when 92 g glycerol is mixed with 90 g water? (molecular weight water = 18; molecular weight of glycerol = 92) Example: What is the molality of a solution of 10 g NaOH in 500 g water? Solution: 10 g NaOH / (4 g NaOH / 1 mol NaOH) = 0.25 mol NaOH 500 g water x 1 kg / 1000 g = 0.50 kg water molality = 0.25 mol / 0.50 kg molality = 0.05 M / kg Solution: 90 g water = 90 g x 1 mol / 18 g = 5 mol water 92 g glycerol = 92 g x 1 mol / 92 g = 1 mol glycerol total mol = 5 + 1 = 6 mol xwater = 5 mol / 6 mol = 0.833 x glycerol = 1 mol / 6 mol = 0.167 It's a good idea to check your math by making sure the mole fractions add up to 1: xwater + xglycerol = .833 + 0.167 = 1.000 Molarity (M) Molarity is probably the most commonly used unit of concentration. It is the number of moles of solute per liter of solution (not necessarily the same as the volume of solvent!). molality = 0.50 m

Normality (N) Normality is equal to the gram equivalent weight of a solute per liter of solution. A gram equivalent weight or equivalent is a measure of the reactive capacity of a given molecule. Normality is the only concentration unit that is reaction dependent. Example: 1 M sulfuric acid (H2SO4) is 2 N for acid-base reactions because each mole of sulfuric acid provides 2 moles of H+ ions. On the other hand, 1 M sulfuric acid is 1 N for sulfate precipitation, since 1 mole of sulfuric acid provides 1 mole of sulfate ions.

Example: What is the molarity of a solution made when water is added to 11 g CaCl2 to make 100 mL of solution? Solution: 11 g CaCl2 / (110 g CaCl2 / mol CaCl2) = 0.10 mol CaCl2 100 mL x 1 L / 1000 mL = 0.10 L molarity = 0.10 mol / 0.10 L molarity = 1.0 M

Equivalent Weight

Example 1 Calcium (Ca2+)

Molality (m) Molality is the number of moles of solute per kilogram of solvent.

Example 2 Sulfuric Acid (H2SO4) Example 3 Calcium Carbonate (CaCO3) Problem 4-1

Show that a density of 1g/mL is the same as a density of 1,000 kg/m3. (Hint: Some useful conversions are listed inside the back cover of this book).

Solution: Use conversion factor from inside back cover a. 0.0438 (3 significant figures) =(0.0438 m3/s)(22.8245) = 0.99971 or 1.00 MGD b. 0.05 (1 significant figure) =(0.05)(22.8245) = 1.14123 or 1. MGD c. 0.438 =(0.438)(22.8245) = 9.99713 or 10.0 MGD d. 0.5 =(0.5)(22.8245): = 11.41 or 10 MGD e. 4.38 =(4.38)(22.8245) = 99.9713 or 100. MGD f. 5 =(5)(22.8245) = 114.1225 or 100 MGD Problem 4-9 Calculate the molarity and normality of the following: a. 80 g/L HNO3

Problem 4-1 Show that 1 g/mL = 1000 kg/m3 Given: Conversion factors inside back cover Required: Conversion of mg/L to kg/m3 Solution: =(1g/mL) x (0.001kg/g) x (1000 mL/L) x (1000L/m3) =1000 kg/m3 Problem 4-3

What is the concentration of NH3 (in mg/L) of household ammonia that contains 3.00 percent by weight of NH3? Assume the density of water=1,000 kg/m3).

Problem 4-3 Concentration of NH3 in mg/L Given: Household ammonia at 3.00% by weight, H2O = 1000 kg/m3 Required: Mass and Concentration Solution:

a. b. c.

135g/L CaCO3 10g/L Cr(OH)3 1000g/L Ca(OH)2

a.

Calculate the mass/concentration of NH3

=(0.0300)(1000 kg/m3) = 30 kg/m3 b. Convert kg/m3 to mg/L =(30 kg/m3)(106 mg/kg)(10-3 m3/L) = 30,000 mg/L Problem 4-7

Problem 4-9 Molarity and Normality Given: concentrations in g/L Solution: a. HNO3 Converting micrograms to milligrams =(80g/L)x(1/1000g/mg)=0.08 mg/L Molarity=(0.08mg/L)/(1000mg/g)(63.015 g/mol) =1.3 x10-6 M Normality=(1.3 x 10-6 M)(1) = 1.3 x 10-6 N

In a now antiquated and we hope, soon forgotten system of measurements, it was common to consider water flows in terms of million of gallons per day (MGD). Determine the numbers of MGD equivalent to the following flows in m3/s: 0.0438; 0.05; 0.438; 0.5; 4.38; and 5. Record both your calculated answer and the answer rounded to include only significant figures.

Problem 4-7 Convert m3/s to MGD Given: Flows of 0.0438; 0.05; 0.438; 0.5; 4.38; 5; all in m3/s

b. CaCO3 Converting micrograms to milligrams =(135g/L)x(1/1000g/mg)=0.135 mg/L

Molarity=(0.135mg/L)/(1000mg/g)(100.09 g/mol) =1.3 x10 M

-6

=980.7 mg/L d. SO42=(0.02000 M)(96.054 g/mole)(1000 mg/g) =1,921 mg/L Chemical Reactions There are four principal types of reactions of importance in environmental engineering: Precipitation Acid/Base Ion association Oxidation/reduction

Normality = (1.3 x 10-6 M)(2) = 2.7 x 10-6 N c. Cr(OH)3 Converting micrograms to milligrams =(10g/L)x(1/1000g/mg)=0.01 mg/L Molarity=(0.01mg/L)/(1000mg/g)(103.02 g/mol) =1.0 x10-7 M

Normality = (1.0 x 10-7 M)(3) = 3 x 10-7 N d. Ca(OH)2 Converting micrograms to milligrams Precipitation =(1000g/L)x(1/1000g/mg)=1.0 mg/L Molarity=(1.0mg/L)/(1000mg/g)(74.096 g/mol) =1.35 x10-5 M Normality = (1.35 x 10-5 M)(2) = 2.7 x 10-5 N Problem 4 -11 Calculate the mg/L of the following: a. 0.01000 N Ca2+ b. 1.000 M HCO3c. 0.02000 N H2SO4 d. 0.02000 M SO42Problem 4-11 Converting to mg/L Given: Molarity and normality Required: Convert Normality to Molarity Solution:

Dissolved ions can react with each other and form a solid compound. This phase change reaction of dissolved to solid state is called a precipitation reaction.

Acid/Base Reaction Acid/Base reactions are a special type of ionization when a hydrogen ion is added to or removed from a solution. An acid can be added to water to produce a hydrogen ion (acids are those compounds that release protons) An hydrogen ion could be removed from the water, as the addition of a base. (bases are those compounds that accept protons)

Ion Association In some cases, ions may exist in water complexed with other ions. Formation of dissolved complexes are ion association reactions. In this case, the ions are tied together in the solution.

a.

Ca

2+

(n = 2 since charge is +2)

=(0.01000N)x(40.08/2)g/eqx(1000mg/g) =200.4 mg/L b. HCO3- (n = 1 since charge is 1) =(1.000 M)(61.016 g/mole)(1000 mg/g) = 61.020 mg/L c. H2SO4 (n = 2) =(0.02000N)x(98.07/2)g/eqx(1000mg/g)

Oxidation/Reduction Reactions Oxidation/reductions involve valence changes and the transfer of electrons. When iron metal corrodes, it releases electrons; if one element releases electrons, then another must be available to accept the electrons. In

iron pipes corrosion, hydrogen gas is often produced. Buffer Solution A solution which resists large changes in pH when an acid or base is added A solution containing a weak acid and its salts is an example of a buffer Atmospheric carbon dioxide (CO2) produces a natural buffer; this is perhaps the most important buffer system in water and wastewater treatment

ALKALINITY is defined as the sum of all titratable bases down to about pH 4.5. ALK = [HCO3] + 2[CO3] + [OH] - [H] The greater the alkalinity, the greater the buffering capacity. Alkaline water has a pH greater than 7, while a water with high alkalinity has a buffering capacity. An alkaline water may or may not have a high buffering capacity. Likewise, a water with a high alkalinity may or may not have a high pH.

mg/L as CaCO3 = mg/L as Species [E.W.CaCO3/E.W. Species] By convention, alkalinity is not expressed in molarity units, but rather in mg/L as CaCO3. Types of Standards Physical (appearance, color or turbidity, temperature, taste and odor) Chemical (comparative performance of hard and soft waters) Microbiological (in relation to public health) Radiological (contact with radioactive substances)

Physical Characteristics Turbidity: the presence of suspended materials such as clay, silt, finely divided organic materials and plankton, and other particulate material in water is known as turbidity. The unit of measure is a Turbidity Unit (TU) or Nephlometric Turbidity Unit (NTU): it is determined by reference to a chemical

mixture that produces a reproducible refraction of light. Color: Dissolved organic materials from decaying vegetation and certain inorganic matter cause color in water. Occasionally, excessive blooms of algae or the growth of aquatic microorganisms may impart color. Its presence is aesthetically objectionable and suggests that the water needs appropriate treatment.

brine or industrial or domestic wastes. Fluoride: In some areas, water sources contain natural fluoride. Where the concentrations approach optimum levels, beneficial health have been observed. Excessive fluoride in drinking water supplies may produce flurosis (mottling) of teeth, which increases as the optimum fluoride level exceeded.

Iron: Small amounts of iron frequently are present in water because of large amount of iron in the geologic materials. The presence of iron in water is considered objectionable because it imparts a brownish color to laundered goals and affects the taste of beverages such as tea and coffee.

Taste and Odor: Taste and odor in water can be caused by foreign matter such as organic compounds, inorganic salts, or dissolved gases. These materials may come from domestic, agricultural, or natural sources. Drinking water should be free from any objectionable taste or odor at point of use.

Lead: Exposure to the body to lead, however brief, can be seriously damaging to health. Prolonged exposure to relatively small quantities may result in serious illness or death.

Temperature: The most desirable drinking water are consistently cool and do not have a temperature fluctuations of more than a few degrees. Groundwater and surface water from mountainous areas generally meet this criteria. Most individuals find that water having a temperature between 10-15 is most palatable.

Manganese: Manganese imparts a brownish color to water and to cloth that is washed in it. It flavors coffee and tea with a medicinal tastes.

Sodium: The presence of sodium in water can affect persons suffering from heart, kidney or circulatory ailments. When a strict sodium free diet is recommended, any water should be regarded with suspicion.

Chemical Characteristics Chlorides: Most water contain some chlorides. The amount present can be caused by the leaching of marine sedimentary deposits or by pollution from sea water, Sulfate:

Waters containing high concentrations of sulfate, caused by the leaching of

natural deposits of magnesium sulfate or sodium sulfate, may be undesirable because of their laxative effects. Zinc: Zinc is found in some natural waters, particularly in areas where zinc ore deposits have been mined. Zinc is not considered detrimental to health, but it will impart an undesirable taste to drinking water.

These organisms include viruses, bacteria, protozoa, and helminthes (worms). Some organisms which cause disease in people originate with the fecal discharges of infected individuals, Others from the fecal discharge of animals. The most widely used test estimates the number of microorganisms of the coli form group.

Arsenic: Arsenic occurs naturally in the environment, and it is also widely used in timber treatment, agricultural chemicals, and manufacturing of gallium arsenide wafers, glass and alloys. Arsenic in drinking water is associated with lung and urinary bladder cancer.

Why Coli forms Were Selected As An indicator Organism Common inhabitants of intestinal tract Excreted in large quantities Can survive in water Are relatively easy to culture

Radiological Characteristics The effects of human exposure to radiation or radioactive materials are harmful, and any unnecessary exposure should be avoided. Humans have always been exposed to natural radiation from water, food and air. Water with high radioactivity is not normal and is confined in great degree to areas where nuclear industries are situated.

Toxic Inorganic Substances: Nitrates, Cyanides, and Heavy Metals constitute the major classes of inorganic substances of health concern Methemoglobinemia (infant cyanosis or blue baby syndrome) given water or fed formula high conc. Of nitrates Cyanide causes chronic effects on the thyroid and central nervous system.

Water Quality Standards EPA National Primary Drinking Water Regulations Establish maximum contaminant levels (MCLs) allowed in public water supply

Toxic Organic Substances There are over 120 toxic organic compounds listed on the US EPA Priority List. These includes pesticides, insecticides and solvents. Like the inorganic substances, their effect may be acute or chronic.

EPA National Secondary Drinking Water Regulations Establish advisable MCLs allowed in public water supply

Microbiological Characteristics Water for drinking and cooking purposes must be free from diseaseproducing organisms (pathogens).

American Water Works Association (AWWA)

Establish GOALS which are DESIRABLE for levels of contaminants Two important factors in coagulation are pH and dose. Types of Water Treatment 1. 2. Filtering Plant Softening Plant The optimum dose and pH must be determined from laboratory tests. The optimal pH range for alum is approximately 5.5 to 6.5 with adequate coagulation possible between pH 5 to pH 8 under some conditions.

Coagulation The object of coagulation (and subsequently flocculation) is to turn the small particles of color, turbidity, and bacteria into larger flocs, either as precipitates or suspended particles. Applies more loosely to removal of dissolved ions, which actually precipitation A method to alter the colloids so that they will be approach and adhere to each other to form larger floc particles

Coagulation When the alum is added to the water, it immediately disassociates, resulting in the release of an aluminum ion surrounded by water molecules. The aluminum ion immediately starts to reacting with the water, forming large Al.OH.H2O complexes. Regardless of the actual species produced, the complex is a very large precipitate that removes many colloids by enmeshmest as it falls through the water. This precipitate is referred to as a floc. Floc formation is one of the important properties of a coagulant for a efficient colloidal removal.

Coagulation = Charge reduction Flocculation = Contact of particles Colloidal Destabilization Colloids are stable because of their surface In order to destabilize the particles, we must neutralize this charge Such neutralization can take place by the addition of an ion of opposite charge to the colloid Since most colloids found in water are negatively charged, the addition of sodium ions (Na+) should reduce the charge.

Jar Test One of the most common methods to evaluate coagulation efficiency is to conduct jar test. Six beakers are filled with water and then each is mixed and flocculated uniformly by a gang stirrer. The jars are square in order to prevent swirling and are called gator jars. A test is often conducted by first dosing each jar with the same alum does and varying the pH in each jar. The test can be then be repeated in a second set of jars by holding the pH constant and varying the coagulant dose.

Alkalinity in Coagulation Needed to neutralize acid formed Coagulants Is the substance (chemical) that is added to the water to accomplish coagulations Properties (Trivalent cations, Nontoxic and insoluble in the neutral pH range) The two most commonly used coagulants are Aluminum (dry or liquid alum) and Ferric iron (sulfates salt)

Coagulant Aids Acid adjusters (acid-sulfuric acid; alkalies-lime or soda ash)

Activated silica (can unite with the positively charge aluminum or with iron flocs, resulting in a larger, denser floc that settles faster and highly colored, low turbidity) Clays (can act much like activated silica; most useful for colored, low turbidity waters) Polymers (can have a negative charge, anionic, positive and negative charge, polyamphotype, or no charge, nonionic

The objective is to precipitate the calcium as CaCO3 and the magnesium as Mg(OH)2 In order to precipitate CaCO3, the pH of the water must be raised to about 10.3 To precipitate magnesium, the pH must be raised to about 11. Magnesium is more expensive to remove than calcium, so we must leave as much Mg+ in the water as possible. It is more expensive to remove noncarbonate hardness than carbonate hardness because we must add another chemical to provide them CO32-

Hardness Is used to characterize a water that does not lather well, causes a scum in the bathtub, and leaves hard, white, crusty deposits (scale) on coffee pots, tea kettles, and hot water heaters Is defined as the sum of all polyvalent cations (in mg/L as CaCO3 or meq/L)

Alkalinity in Softening Needed to provide CO3 for CaCO3 Precipitation

Natural Process by which water is made hard

Mixing Mixing or rapid mixing, as it is called, is the process whereby the chemicals are quickly and uniformly dispersed in water Ideally, the chemicals would be instantaneously dispersed throughout the water During coagulation and softening the chemical reactions that take place in rapid mixing form precipitates.

As rain water enters the top soil, the respiration of microorganisms increases the CO2 content in water. CO2 reacts with the water to form H2CO3. Limestone, which is made up of solid CaCO3 and MgCO3 reacts with the carbonic acid to form calcium bicarbonate and magnesium bicarbonate. While CaCO3 & MgCO3 are both insoluble in water, the bicarbonates are quite soluble. Gypsum (CaSO4) and MgSO4 may also go into solution to contribute to the hardness.

Rapid Mix Is probably the most important physical operation affecting coagulant dose efficiency The chemical reaction in coagulation is completed in less than 0.1 s Rapid mixing can be accomplished within the tank utilizing a vertical shaft mixer, within a pipe using an in line blender, or in a pipe using a static mixer.

Total Hardness

Because Ca2+and Mg2+ predominate, it is often convenient in performing softening calculations to define the total hardness (TH) Total Hardness is often broken down into two components: Carbonate Hardness (temporary hardness-heating removes it) and Non carbonate Hardness (permanent hardness)

Flocculation The precipitates formed in these processes must be brought into contact with one another so that they can agglomerate and form larger particles, called flocs This contact process is called flocculation.

Lime-Soda Softening

Lets say v0 = 0.20 mm/s Sedimentation Particles that will settle within a reasonable period of time can be removed in a sedimentation basin Sedimentation basins are usually rectangular or circular with either a radial or upward water flow pattern Regardless of the type of basin, the design can be divided into four zones (inlet, settling, outlet and sludge storage) What % removal for particles with settling velocity = 0.15 mm/s? Filtration Water filtration is a process for separating suspended or colloidal impurities from water by passage through a porous medium, usually a bed of sand or other medium. Water fills the pores (open spaces) between the sand particles, and the impurities are left behind, either clogged in the open spaces or attached to the sand itself.

THEORETICAL DETENTION TIME (q) Sedimentation Concepts There are two important terms to understand in sedimentation zone designs. The first is the particle (floc) settling velocity (vs) The second is the velocity at which the tank is design to operate, called the overflow rate (vo).

There are several methods of classifying filters: One way is to classify them according to the type of medium used, such as sand, coal (called anthracite), dual media (coal plus sand) or mixed media (coal, sand and garnet). Another common way to classify the filters is by allowable loading rate (is the flow rate of water applied per unit area of the filter). Based on loading rate, the filters are described as being slow sand filters, rapid sand filters, or high rate sand filters.

OVERFLOW RATE (Vo)

Disinfection Settling in an upflow clarifier In this design, the particles fall downward and the water rises vertically. The rate at which the particle is settling downward is the particle settling velocity, and the velocity of the liquid rising is the overflow rate. If a particle is to be removed from the bottom of the clarifier and not go out in the settled water, then the particlesettling velocity must be greater than the liquid-rise velocity. Is used in water treatment to reduce pathogens to an acceptable level. Is not the same as sterilization (implies the destruction of all living organisms) Drinking water need not be sterile. Three categories of human enteric pathogens are normally of consequence: bacteria, viruses and amebic cysts. Purposeful disinfection must be capable of destroying all three.

Chlorine Reaction in Water Chlorine is the most common disinfecting chemical used. Chlorination is often used synonymously with disinfection. Chlorine may be used as the element (Cl2), as sodium hypochlorite (NaOCl) or as calcium hypochlorite [Ca(OCl)2].

When chlorine is added to water, a mixture of hypochlorous acid (HOCl) and hydrochloric acid (HCl)

involves the separation of the water from the solid constituents to the degree necessary for the selected disposal method. Figure 4-52 shows the most common sludge handling options available, listed by general categories of thickening, dewatering, and disposal.

Sludge Treatment The treatment of solid/liquid waste produced in water treatment process

Chapter 5 Water Quality Introduction The use we make of water in lakes, ponds and streams is greatly influenced by the quality of the water found in them. Activities such as fishing, swimming, boating, shipping and waste disposal have very different requirements for WATER QUALITY.

Domestic sewage consists of wastes from homes, schools, office buildings, and stores. The term municipal sewage is used to mean domestic sewage into which industrial wastes are also discharged. In general, point source pollution can be reduced or eliminated through waste minimization and proper wastewater treatment prior to discharge to a natural water body.

Non-Point Sources Urban and agricultural runoff are characterized by multiple charge points. These are called NON POINT SOURCES. Often the polluted water flows over the surface of the land or along natural drainage channels to the nearest water body. Non point pollution from urban storm water and in particular storm water collected in combined sewers that carry both storm water and municipal sewage may require major engineering work to correct. Run off agricultural land is a significant non point source. Fertilizer, whether in the form of manure and commercial fertilizer and pesticides, contributes nutrient.

Water Quality Management Is concerned with the control of pollution from human activity so that water is not degraded to the point that it is no longer suitable for intended use. To know how much waste can be tolerated (assimilated) by a water body, you must know the type of pollutants discharged and the manner in which they affect water quality.

Water Pollution Water pollution occurs when a body of water is adversely affected due to the addition of large amounts of materials to the water. When it is unfit for its intended use, water is considered polluted.

Water Pollutants Oxygen Demanding Material Nutrients Pathogens Suspended solids

Point Sources Domestic sewage and industrial wastes are called POINT SOURCES because they are generally collected by a network of pipes and channels and conveyed to a single point of discharge into a receiving water.

Oxygen Demanding Materials Anything that can be oxidized in the receiving water with the consumption of dissolved molecular oxygen is termed OXYGEN DEMANDING MATERIAL.

This material is usually biodegradable organic matter but also includes certain organic compounds.

384,000 cases of cholera and 16 million cases of typhoid per year. The widespread disease causing organism in the US are Giardia lambia and Cryptosporiduim parvum. These are protozoan pathogens from both human and animal sources.

Dissolved Oxygen Abbreviated DO Pronounced dee oh

Suspended Solids

Is dissolved molecular oxygen (O2) Consumption of DO, poses a threat to fish and other higher forms of aquatic life that must have oxygen to live.

Organic and inorganic particles that are carried by the wastewater into a receiving water are termed SUSPENDED SOLIDS (SS). When the speed of the water is reduced by flowing into a pool or a lake, many of these particles settle down to the bottom as sediment.

Importance of Dissolved Oxygen Higher forms of aquatic life must have DO to live Nutrients Nitrogen and phosphorus, two nutrients of primary concern, are considered pollutants because they are too much of a good thing. Problems arise when nutrient levels became excessive and the food web is grossly disturbed, which causes some organisms to proliferate at the expense of others. Excessive nutrients often lead to large growth of algae, which in turn become oxygen demanding material when they die and settle to the bottom. Some major sources of nutrients are phosphorus based detergents, fertilizers, and food processing wastes.

Salts Although most people associate salty water with oceans and salt lakes, all water contain some salt. These salts are often measured by evaporation of a filtered water sample. The salts and other things that dont evaporate are called TOTAL DISSOLVED SOLIDS (TDS). A problem arises when the salt concentration in normally fresh water increases to the point where the natural population of plants and animals is threatened or the water is no longer useful for public water supplies or irrigation.

Toxic Metals and Toxic Organic Compounds Agricultural runoff often contains pesticides and herbicides that have been used on crops. Urban runoff is a major source of zinc in many water bodies. The zinc comes from tire wear. Many industrial wastewaters contain either toxic metals or toxic organic substances. Many toxic compounds are concentrated in the food chain, making fish and shellfish unsafe for human consumption.

Pathogenic Organisms Microorganisms found in wastewater include bacteria, viruses and protozoa excreted by diseased persons or animals. When discharged into surface waters, they make the water unfit for drinking (that is, non potable). If concentration of pathogens is sufficiently high, the water may also be unsafe for swimming and fishing. Cholera and typhoid are endemic diseases in the world with over

 Endocrine Disrupting Chemicals The class of chemicals known an ENDOCRINE DISRUPTERS, or EDCs, alter the normal physiological function of the endocrine system and can affect the synthesis of hormones. EDCs can mimic estrogen, androgens, or thyroid hormones or their antagonists. They can interfere with the regulation of reproductive and developmental process in mammals, birds, reptiles, and fish.

The introduction of oxygen demanding material, either organic or inorganic, into a river causes depletion of the dissolved oxygen in the water. This poses a treat to fish and other higher forms of aquatic life if the concentration of oxygen falls below a critical point. Organic oxygen demanding materials are commonly measured by determining the amount of oxygen consumed during degradation in a manner approximating in natural waters.

Oxygen Demanding Material Biochemical Oxygen Demand (BOD) (pronounced bee oh dee) Chemical Oxygen Demand (COD) (pronounced as see oh dee)

Heat Water comes primarily from industry through use of cooling water. Waters released by many industrial processes are much hotter than the receiving waters. High temperatures also increase the rate of oxygen depletion in areas where oxygen demanding wastes are present.

Theoretical Oxygen Demand (ThOD) The amount of oxygen required to oxidize a substance to carbon dioxide and water may be calculated by stoichiometry if the chemical composition of the substance is known. This amount of oxygen is known as the Theoretical Oxygen Demand (ThOD).

Water Quality Management in Rivers The objective of water quality management is simple: to control the discharge of pollutants so that the water quality is not degraded to an unacceptable extent below the natural background level. We must be able to measure the pollutants, predict the impact of the pollutant on water quality, determine the background water quality which would be present without human intervention, and decide the levels acceptable for intended uses of the water.

DEFINITION OF COD Amount of dichromate consumed in the oxidation of inorganic and organic matter. In the COD Test, a strong chemical oxidizing agent (chromic acid) is mixed with a water sample and then boiled. The difference between the amount of oxidizing agent at the beginning of the test and that remaining at the end of the test is used to calculate the COD.

Major pollutants Affecting Rivers Biochemical Oxygen Demand (BOD) Ammonia (NH3)

DEFINITION OF BOD Amount of oxygen consumed by microorganisms as they consume biodegradable organic matter. If the oxidation of an organic compound is carried out by microorganisms using the organic matter as a food source, the oxygen

Effects of Oxygen Demanding Waste on Rivers

consumed is known as biochemical oxygen demand. The actual BOD is less than the ThOD due to the incorporation of some of the carbon into new bacterial cells.

- Where Lo is often considered to as the ULTIMATE BOD, that is, the maximum oxygen consumption possible when the waste has been completely degraded. RATE CONSTANT NOTATION k = BOD rate constant in base e

BOD Test Is an indirect measurement of organic matter because we actually measure only the change in dissolved oxygen concentration caused by the microorganisms as they degrade the organic matter. Is still the most widely used method of measuring organic matter because of the direct conceptual relationship between BOD and oxygen depletion in receiving waters.

K = BOD rate constant in base 10 k = 2.303 K

Factors Which Affect K Nature of Waste Ability of Organisms to use Waste Temperature

Temperature Correction KT = K20 ( ) Between

T-20

Biochemical Oxygen Demand When a water sample containing degradable organic matter is placed in a closed container and inoculated with bacteria, the oxygen consumption, the oxygen consumption typically follows the pattern shown in FIG. 5-2. During the first few days the rate of oxygen depletion is rapid because the high concentration of organic matter present. As the concentration of organic matter decreases, so does the rate of oxygen consumption. During the last part of the BOD Curve, oxygen consumption is mostly associated with the decay of the bacteria that grew during the early part of the test. It is generally assumed that the rate at which oxygen is consumed is directly proportional to the concentration of degradable organic matter remaining at any time.

4 and 20C 20 and 30C

= 1.35 = 1.056

Laboratory measurement of BOD 1. Prepare Dilution of Wastewater Sample- completely filled of water that has been appropriately diluted and inoculated with microorganisms (seed). Prepare a Blank-containing only the inoculated dilution water Incubate Sample and Blank 5 days (in the dark) @ 20 C Measure DO Remaining and Calculate BOD

2.

3.

4.

Dilution Sample Size (%) =V of Undiluted Sample /V of Diluted Samplex100 DILUTION FACTOR D.F. = 100 / Sample Size (%)

BOD RATE EQUATION BODt = Lo (1-10-Kt ) BODt = Lo (1- e-kt )

BOD CALCULATION

BODt = (DOb,t - DOs,t) (D.F.)

Additional Notes on Biochemical Oxygen Demand Although the 5-day BOD has been chosen as the standard value for most wastewater analysis and for regulatory purposes, ultimate BOD is actually a better indicator of total waste strength. For any one type of waste having a defined BOD rate constant, the ratio between ultimate BOD and BOD5 is constant so that BOD5 indicates relative waste strength. For different types of waste having the same BOD5, the ultimate BOD is the same only, if by chance BOD rate constants are the same. The 5-day BOD was chosen as the standard value for most purposes because the test was devised by environmental engineers in England, where rivers have travel times to the sea of less than 5 days, so that there was no need to consider oxygen demand at long times.

As the amount of waste increases, the self purification capacity is exceeded, causing detrimental changes in plant and animal life. The stream losses its ability to cleanse itself and the DO level decreases. When the DO drops below about 4 to 5 mg/L, most game fish will have been driven out. If the DO is completely removed, fish and other higher animals are killed or driven out and extreme noxious conditions result. The water becomes blackish and foul smelling as the sewage and dead animal life decompose under anaerobic conditions (that is without oxygen) One of the major tools of water quality management in rivers is the ability to assess the capability of a stream to absorb a waste load. This is done by determining the profile of the DO concentration downstream from a waste discharge. This profile is the DO SAG CURVE (see Fig 5-8) because the DO concentration dips as oxygen demanding materials are oxidized and then rises again further downstream as the oxygen is replenished from the atmosphere.

DO SAG CURVE The concentration of dissolved oxygen in a river is an indicator of the general health of the river. All rivers have some capacity for self purification. As long as the discharge of oxygen demanding wastes is well within the self purification capacity, the DO level will remain high and a diverse population of plants and animals, including game fish, can be found.

STREETER- PHELPS MODEL

DEOXYGENATION RATE CONSTANT at 20C (BASE e) REAERATION RATE CONSTANT at 20C (BASE e) DEOXYGENATION RATE CONSTANT at 20C (BASE 10) REAERATION RATE CONSTANT at 20C (BASE 10)

CONVERTING kr OR Kr TO STREAM TEMPERATURE Kt = K20 = 1.024

T-20

2.

When the algae die, they become an oxygen demanding organic material as bacteria seek to degrade them.

Limnology Types of Lakes TIME TO CRITICAL POINT (BASE 10) Oligotrophic Eutrophic Mesotrophic Senescent

Algal Growth Requirements Carbon Nitrogen Phosphorus Trace Elements

Effects of Nutrients on Water Quality of Rivers Although oxygen demanding materials are the most important river pollutants on the overall basis, nutrients can also contribute to deteriorating water quality in rivers by causing excessive plant growth. Nutrients are those elements required by plants for their growth. They include, in order of abundance in plant tissue: carbon, nitrogen, phosphorus, and a variety of trace elements.

The limiting Nutrient is P

Effects of Nitrogen

1. 2. 3.

In high concentrations, NH3-N is TOXIC to fish. NH3, in low concentrations, and NO3serves for excessive growth of algae. The conversion of NH4+ to NO3consumes large quantities of dissolved oxygen.

Effects of Phosphorus 1. The major deleterious effect of phosphorus is that it serves as a vital nutrient for the growth of algae.