CHAPTER 3

DRINKING WATER TREATMENT

Clean drinking water is the most important public health factor. But well over 2 billion people worldwide do not have adequate supplies of safe drinking water. Worldwide, between 15 to 20 million babies die every year from water-borne diarrheal diseases such as typhoid fever and cholera. Contaminated water supplies and poor sanitation cause 80% of the diseases that afflict people in the poorest countries. The development of municipal water purification in the last century has allowed cities in the developed countries to be essentially free of water-carried diseases.

In 1974, discovered that water disinfectants react with organic compounds form unintended disinfection byproducts (DBPs) causing health risks (Trihalomethane DBPs were regulated by the EPA in 1979) Since then, several DBPs (bromodichloromethane, bromoform, chloroform, dichloroacetic acid, and bromate) have been shown to be carcinogenic in laboratory animals at high doses.. EPA published guidelines for minimizing their formation and established standards in 1998 for drinking water concentrations of DBPs and disinfectant residuals. Goal of EPA disinfectant and disinfection byproduct regulations is to balance the health risks of pathogen contamination, normally controlled by water disinfection, against DPB formation.

WATER TREATMENT

Major changes are occurring in the water treatment field driven by increasingly tighter water quality standards, a steady increase in the number of regulated drinking water contaminants (from about 5 in 1940 to around 100 in 1999), and new regulations affecting disinfection and disinfection byproducts. Municipalities are constantly seeking to refine their water treatment and provide higher quality water by more economical means. A recent development in water treatment is the application of membrane filtration to drinking water treatment. Membrane filters have been refined to the point where, in certain cases, they are suitable as stand-alone treatment for small systems. More often, they are used in conjunction with other treatment methods to economically improve the overall quality of finished drinking water.
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BASIC DRINKING WATER TREATMENT

The purpose of water treatment: (1) to make water safe to drink by ensuring that it is free of pathogens and toxic substances, (2) to make it a desirable drink by removing offensive turbidity, tastes, colors, and odors. 4 steps in conventional drinking water treatment: 1) Primary settling 2) Aeration 3) Coagulation and filtration 4) Disinfection

PRIMARY SETTLING
Water, which has been coarsely screened to remove large particulate matter, is brought into a large holding basin to allow finer particulates to settle. Chemical coagulants are added to form floc. Lime is added at this point to help clarification if pH < 6.5. The floc settles by gravity, removing solids larger than about 25 microns.

AERATION

The clarified water is agitated with air to promote oxidation of any easily oxidizable substances If chlorine were added at this point and reducing agents were still in the water, they would reduce the chlorine and make it ineffective as a disinfectant. Fe2+ is a particularly troublesome reducing agent.

water passing through iron pyrite (FeS2) or iron carbonate (FeCO3) minerals. with dissolved oxygen present, Fe2+ is oxidized to Fe3+ (precipitates as Fe(OH)3, at any pH greater than 3.5). Fe(OH)3 gives a metallic taste to the water and causes the ugly red-brown stain commonly found in sinks and toilets in iron-rich regions. stain is easily removed with weak acid solutions, such as vinegar.

COAGULATION AND FILTRATION

The finest sediments (pollen, spores, bacteria, and colloidal minerals) dont settle out in the primary settling step. Hydrated aluminum sulfate (Al2(SO4)318 H2O) = alum or filter alum, applied with lime (Ca(OH)2): Al2(SO4)3 + Ca(OH)2 -> Al(OH)3(s) + CaSO4 At pH = 68, Al(OH)3(s) is near its minimum solubility and formed as a light, fluffy, gelatinous flocculant having an extremely large surface area that attracts and traps small suspended particles, carrying them to the bottom of the tank as the precipitate slowly settles. Additonal filtration with sand beds or membranes may be used in a final polishing step before disinfection.

DISINFECTION

Killing bacteria and viruses is the most important part of water treatment. Proper disinfection provides a residual disinfectant level that persists throughout the distribution system (not only kills organisms that pass through filtration and coagulation at the treatment plant, preventing reinfection during the time the water is in the distribution system. In a large city, water remain in the system for 5 days or more before it is used. Five days is plenty of time for any missed microorganisms to multiply. Leaks and breaks in water mains can permit recontamination, especially at the extremities of the system where the pressure is low. High pressure causes the flow at leaks to always be from the inside to the outside. At low pressure, bacteria can seep in.
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Concerns about DBPs, the EPA and the water treatment industry are placing more emphasis on the use of disinfectants other than chlorine, which at present is the most commonly used water disinfectant. Another approach to reducing the probability of DBP formation is by removing DBP precursors (naturally occurring organic matter) from water before disinfection. However, use of alternative disinfectants has also been found to produce DBPs. Current regulations try to balance the risks between microbial pathogens and DBPs

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DBPs

Halogenated organic compounds: trihalomethanes (THMs), haloacetic acids, haloketones, and other halogenated compounds (formed primarily when chlorine or ozone (in the presence of bromide ion) used for disinfection). Organic oxidation byproducts: aldehydes, ketones, assimilable organic carbon (AOC), and biodegradable organic carbon (BDOC). AOC and BDOC (large organic molecules) being oxidized to smaller molecules, which are more available to microbes, plant, and aquatic life as a nutrient source. Oxidized organics are formed when strong oxidizing agents (ozone, permanganate, chlorine dioxide, or hydroxyl radical) used. Inorganic compounds: chlorate, chlorite, and bromate ions are formed when chlorine dioxide and ozone disinfectants are used.

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DISINFECTION PROCEDURES

Most disinfectants are strong oxidizing agents that react with organic and inorganic oxidizable compounds in water. In some cases, the oxidant is produced as a reaction byproduct (hydroxyl radical) To destroy pathogens, disinfectants are also used for removing disagreeable tastes, odors, and colors. They also can assist in the oxidation of dissolved iron and manganese, prevention of algal growth, improvement of coagulation and filtration efficiency, and control of nuisance water organisms (Asiatic clams and zebra mussels). Chlorine is commonly used in water treatment disinfectant (first used in Belgium in the early 1900s) Other disinfectants sometimes used are ozone, chlorine dioxide, and ultraviolet radiation.
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DISINFECTION PROCEDURES

Only chlorine and chlorine dioxide have residual disinfectant capability. Adding a small excess of disinfectant maintains protection of the drinking water throughout the distribution system (residual chlorine or chlorine dioxide concentration of about 0.2 to 0.5 mg/L). Disinfectants (not provide residual protection) are normally followed by a low dose of chlorine to preserve a disinfection capability throughout the distribution system. Part of the disinfection procedure involves removing DBP precursors, mainly total organic carbon (TOC), by coagulation, water softening, or filtration. A high TOC concentration (greater than 2.0 mg/L) indicates a high potential for DBP formation.
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Required Percentage Removal of Total Organic Carbon by Enhanced Coagulation(a) for Conventional Water treatment Systems

Source Water TOC (mg/L)

Source Water Alkalinity (mg/L as CaCO3)

0 to 60

>60 to120

>120

>2.0 to 4.0 >4.0 to 8.0 >8.0

35.0% 45.0% 50.0%

25.0% 35.0% 40.0%

15.0% 25.0% 30.0%

(a)

Enhanced coagulation: the coagulant dose where an incremental addition of 10 mg/L of alum (or an equivalent amount of ferric salt) results in a TOC removal to below 0.3 mg/L.
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DISINFECTION BYPRODUCTS AND DISINFECTION RESIDUALS

Principal precursor of organic DBPs is naturally occurring organic matter (NOM). Halogenated organic byproducts: NOM reacts with free chlorine (Cl2) or free bromine (Br2). Nonhalogenated DBPs: Reactions of strong oxidants (nonchlorine oxidants: ozone and peroxone) with NOM.

Common nonhalogenated DBPs: aldehydes, ketones, organic acids, ammonia, and hydrogen peroxide.

Br is present, especially where geothermal waters impact surface and groundwaters, and in coastal areas (saltwater incursion is occurring). Ozone or free chlorine oxidizes Br to form brominated DBPs: bromate ion, bromoform, cyanogen bromide, bromopicrin, and brominated acetic acid.

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STRATEGIES FOR CONTROLLING DISINFECTION BYPRODUCTS

DBPs are difficult to remove from a water supply. DBP control focused on preventing their formation:
Lowering NOM concentrations in source water by coagulation, settling, filtering, and oxidation Using sorption on granulated activated carbon (GAC) to remove DOC Moving the disinfection step later in the treatment train, so that it comes after all processes that decrease NOM Limiting chlorine to providing residual disinfection, following primary disinfection with ozone, chlorine dioxide, chloramines, or ultraviolet radiation Protection of source water from bromide ion
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The EPA classifications for carcinogenic potential of chemicals (January 1999): A: Human carcinogen; sufficient evidence in epidemiologic studies to support causal association between exposure and cancer. B: Probable human carcinogen; limited evidence in epidemiologic studies (B1) and/or sufficient evidence from animal studies (B2). C: Possible human carcinogen; limited evidence from animal studies and inadequate or no data in humans. D: Not classifiable; inadequate or no animal and human evidence of carcinogenicity. E: No evidence of carcinogenicity for humans; no evidence of carcinogenicity in at least two adequate animal tests or in adequate epidemiologic and animal studies. Note: Not all of the EPA cancer classifications are found among the listed disinfectants and DBPs. The EPA is in the process of revising these cancer guidelines.

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CHLORINE DISINFECTION TREATMENT

At room temperature, chlorine is a corrosive and toxic yellowgreen gas with a strong, irritating odor, stored and shipped as a liquefied gas. Chlorine is the most widely used water treatment disinfectant because of its many attractive features: Effectively against a wide range of pathogens commonly found in water, particularly bacteria and viruses. Leave a residual that stabilizes water in distribution systems against reinfection. Be economical and easily measured and controlled. Used for a long time and represents a well-understood treatment technology. Maintain an excellent safety record despite the hazards of handling chlorine gas. Be available from sodium and calcium hypochlorite salts, as well as from chlorine gas. For small treatment system, hypochlorite solutions are more economical and convenient than chlorine gas.
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 Beside

disinfection, chlorination used for:

Taste and odor control, including destruction of hydrogen sulfide. Color bleaching. Controlling algal growth. Precipitation of soluble iron and manganese. Sterilizing and maintaining wells, water mains, distribution pipelines, and filter systems. Improving some coagulation processes.

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 Problems

with chlorine usage:

Not effective against Cryptosporidium and limited effectiveness against Giardia lamblia protozoa. Formation of undesirable DBPs when react with NOM Require special equipment and safety programs because of hazards of handling chlorine gas. Arise taste and odor problems in site conditions with high chlorine doses.

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Chlorine dissolves in water by the following equilibrium reactions: Cl2(g) Cl2(aq) Cl2(aq) + H2O H+(aq) + Cl(aq) + HOCl(aq) HOCl(aq) H+(aq) + OCl(aq)

- pH < 7.5, hypochlorous acid (HOCl) is the dominant. - pH > 7.5, chlorite anion (OCl) is dominant. - Cl2 exist only below about pH = 2 - Formation of H+ chlorination reduces total alkalinity

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Definitions Chlorine dose: the amount of chlorine originally used. Chlorine residual: the amount remaining at time of analysis. Chlorine demand: the amount used up in oxidizing organic substances and pathogens in the water, for example the difference between the chlorine dose and the chlorine residual. Free available chlorine: the total amount of HOCl and ClO in solution. (Cl2 is not present above pH = 2.)
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All these species are oxidizing agents, but chloride ion (Cl) is not. HOCl is about 100 times more effective as a disinfectant than OCl the amount of chlorine required for a given level of disinfection depends on the pH. Higher doses are needed at a higher pH. At pH 8.5, 7.6 times as much chlorine must be used as at pH 7.0, for the same amount of disinfection.

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Relations among chlorine dose, chlorine demand, and chlorine residual

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DRAWBACKS TO USE OF CHLORINE: DISINFECTION BYPRODUCTS (DBPS)

Trihalomethanes (THMs)

Greatest problem concerns with the use of chlorine is the formation of chlorination byproducts, particularly trihalomethanes (CHCl3, CHBrCl2, CHBr2Cl, CHBr3, CHCl2I, CHBrClI) and CCl4 as possible carcinogens. THMs were formed by chlorination of dissolved methane (reaction of HOCl with acetyl groups in NOM, chiefly humic acids). There is no evidence that chlorine itself is carcinogenic. Addition of ammonia with chlorination forms chloramines weaker oxidants than chlorine and are useful for providing a residual disinfectant capability with a lower potential for forming DBPs.

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Chlorinated Phenols Phenol and derivatives from industrial activities are in the water problem of taste and color. Phenols are easily chlorinated, forming compounds with very penetrating antiseptic odors. At the ppm level, chlorinated phenols can make water completely unfit for drinking or cooking. If phenol is present in the intake water, treatment choices are to employ additional nonchlorine oxidation for removing phenol, to remove phenol with activated charcoal, or to use a different disinfectant.
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CHLORAMINES Many utilities use chlorine for disinfection and chloramines for residual maintenance. Chloramines are formed in the reaction of ammonia with HOCl (inexpensive and easy to control). Reaction of chlorine with ammonia can be used for the purpose of destroying ammonia and also serves to generate chloramines (usefulness are more stable and longer lasting in a water distribution system than is free chlorine) Chloramines are effective for controlling bacterial regrowth in water systems although they are not very effective against viruses and protozoa.
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CHLORAMINES Chloramines are not useful for oxidizing iron and manganese. When chloramine disinfection is the goal, ammonia is added in the final chlorination step (Chloramines are always generated on site). Optimal chloramine disinfection occurs when weight ratio of chlorine:ammonia(N) around 4 before the chlorination breakpoint occurs. Monochloramine (NH2Cl) and dichloramine (NHCl2) are the main reaction products and the effective disinfectant species. The normal dose of chloramines is between 1 and 4 mg/L. Residual concentrations are usually maintained between 0.5 and 1 mg/L. The maximum residual disinfection level (MRDL) mandated 32 by the EPA is 4.0 mg/L.

CHLORINE DIOXIDE Chlorine dioxide (ClO2) is a gas at T > 12C with high water solubility. ClO2 was first used as a municipal water disinfectant in Niagara Falls, NY in 1944. In 1977, about 100 municipalities in the U.S. and thousands in Europe were using it. Unlike chlorine, it reacts quite slowly with water, remaining mostly dissolved as a neutral molecule. It is a very good disinfectant, about twice as effective as HOCl from Cl2 but also about twice as expensive. Main drawback to its use is that it is unstable and cannot be stored. It must be made and used on site, whereas chlorine can be delivered in tank cars.

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5 NaClO2 + 4 HCl 4 ClO2(g) + 5 NaCl + 2 H2O. 2 NaClO2 + Cl2(g) 2 ClO2(g) + NaCl. 2 NaClO2 + HOCl 2 ClO2(g) + NaCl + NaOH. Sodium chlorite is extremely reactive, especially in the dry form, and it must be handled with care to prevent potentially explosive conditions. If chlorine dioxide generator conditions are not carefully controlled (pH, feedstock ratios, low feedstock concentrations, etc.), the undesirable byproducts chlorite (ClO2) and chlorate (ClO3) may be formed.

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Insufficiently high vapor pressures with chlorine dioxide solutions < 10 g/L to create an explosive hazard under normal environmental conditions of temperature and pressure. For drinking water treatment, ClO2 solutions are generally less than 4 g/L and treatment levels generally are between 0.07 to 2.0 mg/L. ClO2 is an oxidizer but not a chlorinating agent trihalomethanes or chlorinated phenolsnot unformed no problem in taste or odor. Common applications for ClO2 are to control taste and odor problems associated with algae and decaying vegetation, to reduce the concentrations of phenolic compounds, and to oxidize iron and manganese to insoluble forms. Chlorine dioxide can maintain a residual disinfection concentration in distribution systems. The toxicity of ClO2 restricts the maximum dose. At 50 ppm, ClO2 can cause breakdown of red corpuscles with the release of hemoglobin (dose of ClO2 is limited to 1 ppm).
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OZONE DISINFECTION TREATMENT

Ozone use for water disinfection started in 1893 in the Netherlands and in 1901 in Germany. Significant use in the U.S. did not occur until the 1980s. Ozone is one of the most potent disinfectants used in water treatment today. Ozone (O3) is a colorless, highly corrosive gas at room temperature, with a pungent odor that is easily detectable at concentrations as low as 0.02 ppmv well below a hazardous level. Strongest chemical oxidizing agents available, second only to hydroxyl free radical (HO), among disinfectants commonly used in water treatment... Ozone disinfection is effective against bacteria, viruses, and protozoan cysts, including Cryptosporidium and Giardi lamblia.

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OZONE DISINFECTION TREATMENT

Ozone is unstable, it cannot be stored and shipped efficiently. must be generated at the point of application. Ozone gas is transferred to water through bubble diffusers, injectors, or turbine mixers. Once dissolved in water, ozone reacts with pathogens and oxidizable organic and inorganic compounds. Undissolved gas is released to the surroundings as off-gas and must be collected and destroyed by conversion back to oxygen before release to the atmosphere., Ozone is readily converted to oxygen by heating it to above 350C or by passing it through a catalyst held above 100C. OSHA currently requires released gases to contain no more than 0.1 ppmv of ozone for worker exposure. Typical dissolved ozone concentrations in water near an ozonator are around 1 mg/L.
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(dry, pressurized air) high voltage electric discharge (20,000 V)

3 O2(g) + energy 2 O3(g) Ozonator off-gas contains as much as 3000 ppmv of ozone

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Direct Oxidation Off gas ozone +M Mox Radical Oxidation (indirect Oxidation) +M

O3
+OH+ H2O2/HO2+UV

Applied Ozone

OH.

Scavangers KHCO3-, KCO3239

Cyclo addition (Criegee mechanism) Consequentially to is dipolar structure, an ozone molecule can undergo a 1-3 dipolar cyclo addition with saturized compounds (double or tripple bonds). This leads to the formation of a compound called ozonide (I):

disintegration of ozonide
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Electrophilic reactions

Electrophilic reactions occur in molecular solutions that have a high electronic density and mainly in solutions that contain a high level of aromatic compounds. Aromatic compounds that are substituted by electron donors (such as OH and NH2), have a high electronic density on the carbon compounds in ortho and para position. Consequentially, in these positions aromatic compounds react actively with ozone.

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Indirect reactions
- Contrary to those of ozone, OH-radical reactions are largely selective. - Indirect reactions in an ozone oxidation process can be very complex. 1. Initiation 2. Radical chain-reaction 3. Termination

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1. Initiation The first reaction that takes place is accelerated ozone decomposition by a type of initiator. This can be an OH-molecule: 1: O3 + OH- O2 - + HO2 This radical has an acid/ base equilibrium of pKa = 4,8. Above this value, this radical no longer splits, because it forms a superoxide radical: 2: HO2 O2- + H+ (pKa = 4,8)
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Radical chain-reaction Now, a radical chain-reaction takes place, during which OH-radicals are formed. The reaction mechanism is as follows:

3: O3 + O2- O3- + O2
4: O3- + H+ HO3 (PH < 8)

The OH-radicals that have formed react with ozone according to the following reaction mechanism:
5: OH + O3 HO4

6: HO4 O2 + HO2

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Initiator OHH2O2

Promotor Humic acid Aryl-R

Radical catcher (inhibitor) HCO3-/CO32PO34-

Fe2+

Primary and secondary alcohols

Humic acids
Aryl-R Tert-butyl alcohol (TBA)

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