MODULE 4

DISINFECTION AND OXIDATION

Microbiologically polluted water has been associated with the transmission of infectious diseases such as gastroenteritis, amoebiasis, giardiasis, salmonellosis, dysentry, cholera, typhoid fever and hepatitis A (Craun, 1986) for over a 100 years. Snow, in 1854, was the first to demonstrate the relationship between contaminated water and disease. Koch and Pasteur developed the theory of disease resulting from germs and Koch demonstrated that bacteria could be killed by chlorine in 1881. Frohlich (1886) disinfected water with ozone, but Schnbein may have experimented with ozonation in water treatment as early as 1840. The first water disinfection plants were built in Europe, in the late 19th century, some based on ozone, some on chlorine, no clear evidence to which came first. Infectious diseases occur as the result of interactions between pathogenic (disease-producing) microorganisms and the host (Pelczar et al., 1986). Several types of microorganisms are pathogenic. Typhoid, cholera and gastroenteritis are bacterial diseases, which are commonly waterborne. Similarly, viral diseases such as hepatitis, parasitic worms such as Schistasoma (bilharzia) and some tape worms, together with protozoan diseases such as amoebic dysentery, are waterborne. In the production of potable water, all water-borne organisms but especially water-borne pathogens are of concern. The majority of these pathogens affect the gastro-intestinal tract and can be bacteria, viruses, protozoa and sometimes fungi (Carlson, 1991). For a historical and present day etiology of some of these pathogens, the reader is referred to White (1992). Some of the most common waterborne diseases prevented by disinfection are shown in Table 4.1 (adapted from USAID, 1992). Table 4.1 : Some common water-borne diseases prevented by disinfection Bacterial Typhoid fever Para-typhoid Childhood bacterial diarrhoea Cholera Legionnaires disease Viral Hepatitis Rotavirus diarrhoea Parasitic Amoebiasis Giardiasis Cryptosporidiasis

Protozoa have lately been identified as the gravest concern in disinfection. They form cysts that are more resistant to disinfection than bacterial indicators (Rubin et at, 1983). Cryptosporidium and Giardia lamblia are the most common/problematic protozoa in drinking water. In the United States the inactivation of the protozoan Giardia (along with intestinal viruses) has been used as a yardstick for measuring the efficacy of disinfection (Teefy and Singer, 1990). The mechanism of inactivation of microorganisms has not been established conclusively, but indicators are that chemical changes effected in the enzyme reactions of the cell render the
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organism incapable of ingestion and reproduction. It has been suggested that ozone attacks cells directly by oxidation of the cell wall. Water supplies in the First World are usually disinfected. The widespread adoption of disinfection was a major factor in reducing waterborne diseases, and this has been interpreted as the major single factor in increasing average human life expectancy. Effluents can be disinfected prior to discharge from treatment plants to receiving waters, to reduce the concentration of pathogens. This practice is not universally adopted as disinfectant residuals may be environmentally detrimental and because of financial restrictions. This disinfectant demand of a water is usually governed by substances other than microorganisms themselves. Certain dissolved substances are easily oxidized by disinfectants and their oxidation competes with the disinfection reaction. Sufficient disinfectant has to be dosed to oxidize these substances and to inactivate pathogens completely. Modern thinking on water treatment sees oxidation as a separate unit process, independent from disinfection. Oxidation by-products play a significant role in subsequent treatment. Failure to provide for this can detrimentally affect water distribution, however, proper design of the whole process involving oxidation with ozone in particular, can actually benefit the quality of the product.

4.1 REQUIREMENTS OF A DISINFECTANT

Disinfection is the elimination or inactivation of harmful organisms. It should be distinguished from sterilization, which is the destruction of all life forms. Economic considerations preclude such drastic procedures. A disinfectant must be able to destroy particular pathogens at the concentrations likely to occur, and it should be effective in the normal range of environmental conditions. Disinfectants which require extremes of temperature or pH, or which are effective only for waters with a very low turbidity, are unsuitable for large-scale use. While the disinfectant should destroy pathogens, it must not be toxic to man or other higher animals, such as fish, in receiving water. Ideally, some residual disinfecting capability should be provided for a water supply to provide protection against re-infection while the water is in a distribution system. The residual, which passes to the consumer, should not be unpalatable or significantly alter the taste. A disinfectant should be safe and easy to handle, both during storage and during addition. The availability of simple or automatic analytical procedures ensures a reliable and consistent dosing system, which can be accurately controlled. The other major consideration is that of cost, which is particularly important for municipal plants where large volumes must be disinfected continuously. These factors severely restrict the number of reliable disinfectants. The requirements of effectiveness in destroying pathogens, safety of handling, and non-toxicity to man in normal use, present a major problem. For example, the addition of certain toxic metals can provide effective destruction of pathogens but the residual toxicity is harmful to humans. Chlorine, the most common disinfectant is a dangerous chemical and requires rigorous safety precautions. The other disinfectants that have found large-scale use are ozone and chlorine dioxide. Others, such as heat, ultraviolet irradiation, ultrasonic vibration, ultra-filtration, silver, bromide and iodine, only find limited application.
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Status of disinfection practices In a recent survey (Disinfection Committee, 1992) of the disinfection practices in the USA it was found that most water utilities were making concerted efforts towards reducing halogenated by-products in potable water. Chlorine reacts with organic compounds present in the water to form halogenated disinfection by-products (DBPs), most notably trihalomethanes (THM), which may adversely affect human health. The most significant change by utilities was to alter the point of application of chlorine, the dosage of chlorine used, and the addition of ammonia. It should be noted that although chloramines are recommended as a primary disinfectant (Longley and Roberts, 1982) and for controlling bacterial regrowth in distribution systems (Neden et al., 1992), these substances could affect kidney dialysis patients and aquarium fish (White, 1992). In a world-wide survey on disinfection practices (Hiisvirta, 1993) it was concluded that:
Water-borne epidemic outbreaks still occur today - even in developed countries. Outbreaks in developed countries were due to poor disinfection due to fear of chemical by-product formation. Chlorination is still the dominant disinfection method throughout the world, with the use of Chlorine dioxide as a substitute for chlorine decreasing rather than increasing.

Kinetics of Disinfection The ability of a reagent to destroy pathogens is related to the concentration of the disinfectant and the contact time between the pathogens and disinfectant. One general relationship is known as Chick's Law (Equation 4.1), which assumes that the inactivation of microorganisms is controlled by processes of diffusion, resulting in a first-order rate of decrease. This relationship applies for a given concentration of disinfectant. dN dt = -kN [4.1]

where N is the number of variable micro organisms of one type at time t, and k is a constant (dimension : t-1). Integrating for N loge N No Therefore N No = e-kt [4.3] = = No at t=0 gives -kt [4.2]

The rate of inactivation depends upon the number of microorganisms which were present originally. If the micro-organisms all possess the same resistance, the kills follow an exponential pattern (Equation 4.3). A complete kill is not feasible according to this model. The efficiency of disinfection reported in terms of the ratio of microorganisms inactivated to the original number of present, such as 99 % (2 logs) or 99.99 % (4 logs).
The definition of "life" is somewhat vague in microorganisms and "inactivation" is preferred to "kill".

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Chick's Law is not followed by all disinfectants for all micro-organisms. The rate of inactivation depends upon such factors as the penetration of the cell wall, the time to penetrate vital centers. Each species of microorganism therefore will have a different sensitivity to each disinfectant. This is accounted for by manipulating k or t in equation 4.3 to linearalize plots of N/No. The simplest form of such equations is Watsons Law, which enables us to quantify the effect of concentration for a given fraction of inactivation over which we have linearized: Cn t = constant [4.4]

where C is the concentration of disinfectant; t is the contact time between disinfectant and microorganism to achieve the desired inactivation; and the exponent, n is a constant for one system of disinfectant and microorganism at one inactivation rate. A value of n>1 implies greater dependence on disinfectant concentration, e.g. ozone. For n<1, the contact time is more important , e.g. chlorine. Since n is usually close to 1, the C.t value (note without exponents) has become an important concept . Table 4.1 lists Ct values as required by different organisms. Organisms differ greatly in their resistance to different disinfectants. Design should be for the worst case: Table 4.1 is based on the requirements to inactivate enteric viruses by 4 logs and the protozoon, Giardia lamblia by 3 logs. As Ct can be 100 mgL-1min, it means that a retention time of 100 min at 1mg/L of free chlorine is required or that a concentration of 1.67 mg/L is required if the retention time is limited to 1 h.

Disinfectant Free chlorine , 2mg/L, pH 7 Free chlorine, 2 mg/L, pH 8 Ozone Chlorine dioxide Chloramines

C.t (mg.min/l) 83 122 0.95 19 1500

Table 4.1 Ct values at 15C for inactivation of 99.9% Giardia lamblia and 99.99% enteric viruses Monitoring of disinfection Criteria for effluent disposal usually reflect the use of the receiving water. For example, if it is used for non-contact recreational purposes, standards of a mean of less than 1000 fecal coliforms/100 mL may suffice, while, for body-contact recreational purposes, the mean would be less than 100 fecal coliforms/100 mL. Turbidity measurements can be used as an indirect assessment of pathogen numbers as microorganisms contribute to turbidity. A value of 1 turbidity unit, as used in drinking water, implies that the water will contain few pathogens.
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The wide range of pathogens and their extremely low number preclude routine testing for particular pathogens. Instead, the requirements for disinfection refer to indicator organisms, usually coliform bacteria or Escherichia coli (see Module 1). Coliform bacteria are the most common intestinal flora and if they have all been eliminated, the disinfection process is considered complete. The absence of fecal coliform bacteria, especially E. coli, in at least three samples of 100mL is acceptable as an indication that drinking water has been properly disinfected. It is not necessary to inactivate all bacteria and total plate counts of up to 100 bacteria per mL are acceptable for drinking water. Many pathogens are much more resistant to disinfectants than coliforms, leading to some doubt over suitable indicator organisms.

4.2 CHLORINE REACTIONS DURING WATER TREATMENT

Under normal conditions, chlorine is a yellow-green, corrosive gas with a density 2.5 times that of air. It can be liquefied under a relatively small pressure, 370 kPa. It is very soluble in water and is a potent disinfectant even at low concentrations. It is normally dosed into a small sidestream on large plants. It forms hypochlorous acid in water solution, which is the primary disinfectant. On smaller plants, compounds which release hypochlorous acid, are dosed. The reaction between chlorine and water The addition of chlorine gas (Cl2) to pure water gives rise to the following equilibrium state: Cl2 + H2O HOCl + H+ + Cl[4.5]

This equilibrium state may be represented in its mass action form by: {[HOCl] [H+] [Cl-] }/ [Cl2] = K1 [4.6]

The equilibrium constant (K1) has a value of 4.0 x 10-4 at 20C. The hypochlorous acid itself ionizes as below. HOCl H+ + OClThe equilibrium state may be represented in its mass action form by: {[H+] [OCl-]} / [HOCl] = K2 (3.3 x 10 -8 at 20C)

[4.7]

[4.8]

The distribution of the chlorine species according to Reaction 4.7 is shown in Figure 4.1. Below pH 2, chlorine is present in the dissolved molecular (Cl 2) form; at a pH of between 3 and 7.5, the main species are hypochlorous acid (HOCl) and the chloride ion (Cl -); and at a pH of > 7.5, the predominant species are the hypochlorous and chloride ions (OCl- and Cl-).

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Figure 4.1 Hypochlorous acid (HOCl) and hypochlorite ion (OCl-) species distribution as a function of pH (25C) The reaction between hypochlorous acid and ammonia Extensive laboratory investigations are largely responsible for the present knowledge on the chemistry of chlorine-ammonia systems in water. Several reactions between ammonia and hypochlorous acid or the hypochlorite ion may take place, usually simultaneously, the relative proportion of the products formed being governed by the pH of the water. The overall effect is the oxidation of ammonia to chloramines, and even further to nitrogen. The removal of ammonia through oxidation by chlorine is referred to as breakpoint chlorination. During optimum removal by breakpoint chlorination, the ammonia is oxidized to nitrogen gas as follows: Cl2 + H2O NH3 + HOCl HOCl + H+ + Cl NH2Cl + H2O [4.5] [4.9] [4.10]

2NH2Cl + HOCl N2 + 3H+ + H2O + 3Cl-

3Cl2 + 2NH3

N2 + 6H+ + 6Cl- (overall reaction)

[4.11]

The general reaction scheme can be represented as in Figure 4.2 in which the chlorine residual is plotted against the total chlorine dose.

Figure 4.2 Progress of the reaction between ammonia and chlorine in water For the region A-B, the chlorine added reacts rapidly with any reducing agents in the sample. This reduces the chlorine to chloride (Cl-), which is not a disinfectant. The residual chlorine is low and, for a small chlorine dose, there will be little or no disinfection. The addition of more chlorine is represented by region B-C. The chlorine has completely oxidized the reducing agents and has formed monochloramine with ammonia. Monochloramine and the minor by-product dichloramine are much less powerful disinfectants than is free chlorine. If they are present in high concentrations or if a long reaction time is permitted, these chloramines will inhibit pathogens. The chloramines are disinfectants and are detectable as a chlorine residual. Monochloramine and dichloramine are referred to as combined available chlorine. In the region (B-C) the addition of chlorine produces an approximately proportional increase of combined chlorine residual. The chloramines are oxidized to nitrogen in the region C-D. Stoichiometrically, the oxidation of ammonia through monochloramine to nitrogen gas corresponds with a chlorine to ammonia nitrogen mass ratio of 7.6 to 1. The presence of other substances exerting a chlorine demand will, however, necessitate higher chlorine dosages in order to achieve breakpoint chlorination. Undesirable side reactions, which are a function of pH may also occur as shown below. low pH: NH2Cl + HOCl low pH: NHCl2 + HOCl NHCl2 + H2O (dichloramine) [4.12]

NCl3 + H2O (trichloramine) [4.13] NO3- + 4Cl- + 2H+ [4.14]

high pH: NH2Cl + 3OCl-

Further addition of chlorine at a pH lower than about 6 produces di- and trichloramine (4.12 and 4.13), while nitrate and nitrous oxide are produced at a higher pH than 8. Nitrogen, nitrates and nitrous oxide do not disinfect and the concentration of chloramines is
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lowered during these oxidation reactions. Thus, in the region C-D, the addition of further chlorine reduces the available chlorine and, hence, the ability of the solution to disinfect. On further chlorine addition these reactions are complete (point D) and most of the ammonia will be removed. Any subsequent addition of chlorine will remain as free available chlorine (HOCl) and will act as a strong chlorine residual (DE). Point D is referred to as the breakpoint. Chlorination is commonly carried out beyond the breakpoint, requiring a dosage of 8 to 10 times the NH3-N concentration. The relative concentrations of free and combined chlorine residual can be monitored by simple calorimetric or instrumental means. The methods rely upon the greater reactivity of the free chlorine (HOCl) which rapidly gives a reading, while the combined residual (NH 2Cl) and NHCl2) reacts relatively slowly. For example, the reagent diethyl-p-phenylene-diamine sulphate (DPD) gives a red color by reaction with free chlorine. The addition of varying amounts of potassium iodide induces the production of color by monochloramine and dichloramine. A complexing agent is incorporated with DPD sulfate to prevent interference by trace metals. The reagent is available in tablet form; No 1 DPD will determine free available chlorine, No 2 DPD the free chlorine plus monochloramine, and No 3 DPD the total chlorine. Chlorination Terminology Free chlorine or available free chlorine Free chlorine may be present as elemental chlorine (Cl 2), hypochlorous acid (HOCl), the hypochlorous ion (OCl-), or as hypochlorous acid together with either of the other forms, depending on the pH of the solution. The free chlorine species distribution is shown in Figure 4.1. The (available) free chloride residual is the amount of free chlorine available for further disinfection after breakpoint has been achieved. Combined chlorine residual The combined (available) chlorine residual is the sum of all chlorinated nitrogenous products distinguishable as by analytical methods. The relevant species in water containing organic nitrogenous forms are monochloramine, dichloramine and trichloramine (more correctly: nitrogen trichloride). Total chlorine residual The total chlorine residual refers to the sum of the combined and free chlorine residuals. Chlorine demand The chlorine demand of a water is the difference between the amount of chlorine applied to a treated supply and the total chlorine residual. It can also be regarded as the excess chlorine introduced to produce a free chlorine residual. The chlorine demand of a water varies with the amount of chlorine applied, pH, time of contact and temperature. Any value given for chlorine demand is worthless unless all conditions are specified. The chlorine demand of water increases with higher concentrations of nitrogenous compounds. From the above it is clear that chlorine is still the most universally used disinfectant for the production of potable water. However, the designer should take note of the developments regarding the potential health hazard of disinfection by-products, and how to minimize or avoid it, as well as the advantages and disadvantages of alternative disinfectants.
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The Environmental Protection Agency (EPA) in the USA has developed the so-called "Surface Water Treatment Rules" (SWTR) for the disinfection of surface water (Teefy and Singer, 1990). The SWTR contains tables of disinfectant-Ct values that have been demonstrated to achieve the required degree of inactivation of viruses and Giardia cysts. The methods by which C and t values for a particular application are calculated are very important since factors like pH, temperature and flow pattern in the contact chamber, each plays a role (Rubin et at, 1983; Teefy and Singer, 1990; White, 1992). Note: When chlorine gas is used for breakpoint chlorination, alkalinity is consumed. Stoichiometrically, 14,3 mg/L of alkalinity, expressed as CaCO3, will be consumed for each 1,0 mg/l (NH3-N) that is oxidized in the chlorination process. Chloramination The efficiency of the various chlorine forms as disinfectants differs, and thus, the concentration of available chlorine is insufficient to characterize process performance. The inactivation potency of HOCl : OCl- : NH2Cl : NHCl2 is approximately 1 : 0,0125 : 0,005 : 0,0166 (Haas, 1990). Although the immediate disinfection efficacy of chloramines is less than that of chlorine, they have a relatively long half life (approximately 100 h in distilled water). Because of this property, chloramines are often used in a post-chlorination step to prevent secondary microbial growth in water distribution networks.

4.3 CHLORINATION DESIGN

Chlorination is in essence a chemical process and the laws that govern chemical processes are also applicable in the design of chlorination systems. According to the Chick-Watson law of disinfection, three major parameters govern chemical disinfection, namely the number of pathogens that must be inactivated, the disinfectant concentration, and the contact time. There are no established standards or codes of practice in the potable water industry for the design of chlorination systems in general and the contact tanks in particular. In most waterworks the main function of contact tanks is to give temporary storage to treated water, as a buffer between the steady output of the works and the fluctuating demand of the distribution system (Water Research Centre, 1989). The nearest approach to a general standard for disinfection is the WHO Guideline which recommends that the treated water should have a free chlorine residual of at least 0.2 to 0.5 mg/L after a contact time of 30 minutes (Water Research Centre, 1989). In the USA more attention has recently been given to the control of contact times since the adoption of the "Surface Water Treatment Rule", where Ct values were provided (Teefy and Singer, 1990; Disinfection Committee, 1992). With Ct values recommended of around 100 mgL -1min for free chlorine in the SWTR, the WHO Guideline would appear to be inadequate for the elimination of intestinal viruses and Giardia. Design considerations The primary purpose of disinfection of potable water is to reduce the potential health risk associated with pathogens for the user. Although health risks due to pathogen contaminated water is probably the most important, risks due to other water quality parameters (see Water Quality Criteria elsewhere) should be used as a guide to the degree of treatment required. The criteria shown in Table 3 for indicator organisms should be used as basis for determining
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the required Ct values. Since the time of the Ct factor is a function of the residence time distribution in the chlorine contact tank, reliable Ct factors may only be calculated once the flow pattern in the contact tank is known (see USEPA 1989). The two main additional parameters to be taken in account are: pH: HOCl is more effective than OCl- (see Figure 4.1). Temperature: disinfection rate is considerably influenced by temperature A chlorination system for disinfection of potable water consists of four separate subsystems: (i) (ii) (iii) (iv) chlorine storage and supply; chlorine solution mixing; provision of contact time, and chlorine dosing control.

Chlorine storage and supply Some important design and safety considerations of chlorine storage and supply are given by Qasim (1985): Chlorine storage and chlorinator equipment must be housed in a separate building. If not, it should be accessible from an outside door. Adequate exhaust ventilation at floor level should be provided because chlorine gas is heavier than air. Fan control and gas masks should be located at room entrance. The temperature in the chlorine supply area should not be allowed to drop below 10 oC. Dry chlorine liquid and gas can be handled in wrought-iron, SM steel, Hasteloy, Monel alloys and appropriate stainless steel (AISI 318-322); wet chlorine gas in glass, silver, hard rubber (Masschelein, 1992) and plastic. Valves and pipe fittings should be specially designed for chlorine use. Chlorine cylinders in use should be set on platform scales set flush with the floor, and loss of weight should be used for record keeping of chlorine dosages. Storage should be provided for at least a 30-day supply. Chlorine solution mixing One of the most neglected aspects in disinfection with chlorine is the initial mixing of the relatively small, high chlorine concentration stream with the bulk of the clarified water. The effective initial mixing of the chlorine solution can be accomplished in a number of ways (White, 1992; Harnby et al., 1992): (a) Diffusers; (b) Mechanical mixers; (c) Hydraulic mixers including static mixers, and hydraulic jumps. Mixing intensities, measured as the velocity gradient, G, should be > 500 s-1 (White, 1992). Contact tanks The chlorine contact tank must be designed to provide the optimum distribution of residence time for contact between the disinfectant and the pathogens. The distribution of residence time may differ appreciably in tanks of different geometrical configuration, although tanks volumes and flow rates are identical. For disinfection the ideal contact tank should have a configuration that encourage 'plug-flow' characteristics. The flow characteristics of a contact tank can be determined by tracer tests which have become necessary in the USA where the Ct
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standard has become mandatory (Teefy and Singer, 1990). With the proper use of tracer information it is possible to rationalize (Trussel and Chao, 1977) and optimize (Tikhe, 1976) the design of chlorination systems. For some design details of chlorine contact tanks the reader is referred to White (1992). Chlorine dosing equipment Chlorine is supplied as a liquefied gas under high pressure in containers varying in size from 150 to 2000 lbs. Chlorine can be abstracted directly from the gas phase of the pressurized container with a chlorinator. The most widely used chlorinators are those using vacuum-feed devices. In each of these systems, the chlorine injector is the basic component. The injector is used to create the vacuum that is used to draw the chlorine gas from the storage supply through the chlorine regulator, which serves as a metering device, and into the injector. At the injector, the chlorine dissolves in the injector water to form hypochlorous acid. From the injector the hypochlorous acid solution flows to the point where it is to be injected into the clarified water. At liquid chlorine temperatures of 10 oC, about 10 kg chlorine/h can be evaporated per 2000 lb container (Degrmont, 1991). If higher rates are required, more containers can be used in parallel, or special heated evaporators installed. A chlorine concentration of 2,5 g chlorine/L (or higher) at the injector can be obtained in this way. For a complete discussion on equipment available, design calculations and physical layout the reader is referred to White (1992). Properties of chlorine In its normal state chlorine is a greenish-yellow gas with the following physical constants (Degrmont, 1991):
Density relative to air : 2,491; Relative atomic mass: Cl = 35,45; Specific mass : 3.214 kg/m 3 at 0 C, 101 kPa;
At 15 C, 101kPa, 1 kg of chlorine converts to 314 L of chlorine gas and 1L of liquid chlorine corresponds to 456 L of gas.

Chlorine liquefies on cooling and compression at a pressure varying with temperature:

1000 kPa at 40 C or 500 kPa at 18 C Liquefaction point (at 100 kPa) -34,1C Freezing point -102 C Critical temperature 144 C Critical pressure 77,1 bars Heat capacity of gas 0,518 kJ/kg from 15 to 100 C at 100kPa Heat capacity of liquid 0,92 kJ/kg

Solubility in water varies with temperature:

Temperature (oC) Solubility (g/l) 0 14,8 5 11,8 10 9,6 20 6,7 25 5,4 30 4,5

Latent heat of evaporation varies with temperature:

Temperature (C) kJ/kg 0 249,1 10 242,0 20 234,1 30 226,1

At liquid chlorine temperatures of 10 C, about 10 kg chlorine/h can be evaporated from a 2000 lb container. 11

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Conventional chlorinators A conventional chlorinator consists of the following units: an inlet-pressure-reducing valve, a rotameter, a metering control orifice, and a vacuum-differential regulating valve. A simple schematic is shown in Figure 4.5. The driving force for the system comes from the vacuum created by the chlorine injector. The chlorine gas comes to the chlorinator and is converted to a constant pressure (usually a mild vacuum) by the influent-pressure-reducing valve. The chlorine then passes through the rotameter, where the flow rate is measured under conditions of constant pressure (and consequently constant density), then through a metering or control orifice. A vacuum differential regulator is mounted across the control orifice so that a constant pressure differential (vacuum differential) is maintained to stabilize the flow for a particular setting on the control orifice. The flow through the control orifice can be adjusted by changing the opening on the orifice. The control orifice has a typical range of 20 to 1, while the vacuum-differential regulator has a range of about 10 to1. Thus the overall range of devices combined is about 200 to 1. On the other hand, a typical rotameter has a range of about 20 to 1. Thus, the chlorinator should be selected based on design capacities, and the rotameter installed at any particular time should be appropriate for current demands. Chlorination equipment Simple and conventional chlorination equipment is shown in Figures 4.3, 4.4 and 4.5. Mixing and Contact Time Rapid mixing of chlorine at the point of application is important. Some of the chlorine should be added with a large amount of dilution water through a full channel or pipe diameter diffuser submerged to the maximum depth available. Chlorine applied prior to a weir will be stripped by the aeration effect of the hydraulic jump. Chlorine added before a suction pump or the upstream side of a valve can cause severe corrosion problems to brass unless applied at a sufficient distance upstream to obtain full dissolution. Chloramine disinfection The avoidance of THMs has led to renewed interest in selecting chloramine as a disinfectant, because chloramine impedes the formation of THMs. In a survey conducted in 1984 in the United States, none of the utilities using chloramine reported any adverse effects on bacteriological quality (Staff, 1985a). A recent survey on the occurrence of disinfection byproducts indicated that the occurrence of almost all of the by-products was significantly reduced in the systems using chloramine as opposed to chlorine (Bryant et al.., 1992). The advantages and disadvantages of using chloramine as a disinfectant are listed in Table 4.2.

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Figure 4.3 Floating bowl chlorinator

Figure 4.4 Plastic can chlorinator

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Figure 4.5 Flow diagram for conventional chlorinator

Advantages

Disadvantages

Insignificant formation of trihalomethanes ((THMs) and other disinfection by-products. Eliminates certain taste and odor conditions associated with chlorine. More stable residual in water distribution system. Introduction of chloramine is simple and similar to that of chlorine. More stable than chlorine (Kreft et al.., 1985).

Not as effective as chlorine in deactivating bacteria, viruses, and Giardia. May produce chlorinated phenols, which gives taste to water. May produce gas poisoning hazards similar to that of chlorine. Uncontrolled dosage of ammonia could lead to nitrification problems. Takes a much longer time than chlorine for effective disinfection.

Table 4.2 Relative Merits of Chloramine as a Disinfectant (Adapted from Vigneswaran et al., 1987) For pHs above 8 the OCl- ion is comparable to monochloramine in its disinfecting power. Many of the plants that currently use the chloramine process add chlorine first and maintain a free chlorine residual for some time.

4.4 DISINFECTION BY-PRODUCTS

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Chlorination may have saved millions of lives, but it is being challenged more and more because it is now known that chlorine reacts with aquatic organic material present in natural water to form trace levels (between 0.01 and 1.0 mg/L) of the trihalomethanes (THMs), a group of lightweight chlorinated hydrocarbons which are suspected carcinogens. Other chlorinated organic compounds may also form and their toxicity is being evaluated. Many water utilities may not be able to adequately disinfect their water supply using chlorine without exceeding limits or future lower limits imposed by various authorities. A number of options are available for controlling formation of trihalomethanes and other chlorination byproducts, and these are widely discussed in the literature. This module will be limited to a discussion of chlorination and the use of alternative disinfectants. Since the turn of this century, chlorination was (and still is) the universal disinfectant used for the disinfection of potable water (White, 1992). The dominant role of chlorination has seriously been challenged since the discovery of the presence of organo-halogenated compounds in chlorinated drinking water (Rook, 1974; Bellar et al., 1974). The best known of these products are the trihalomethanes (THMs) of which chloroform (CHCl 3) has been found to be an animal carcinogen (Pieterse, 1988). This has lead to the abandonment of the use of chlorine in some industrialized countries (like the Netherlands) with a corresponding increase in the use of alternative disinfection methods and chemicals (Wondergem and Van Dijk-Looijaard, 1991; Kruithof et al., 1992). In the Netherlands, microbiological regrowth in the reticulation systems is being controlled by the elimination of growth-promoting substances in the water. According to Van der Kooij (1992) a low AOC (assimilable organic carbon) content can be obtained, resulting in the chances for regrowth being low. None of these alternative methods are, however, entirely devoid of problems. Many studies have shown that potential hazardous chemical by-products are formed with virtually every type of disinfectant method or chemical used (Jacangelo et al., 1989; Lykins et al., 1990; Lykins et al., 1992). After a comprehensive review on the potential health risks of THMs, Pieterse (1988) concluded that the removal of microbiological contamination remains the most important consideration in ensuring the safety of potable water. Chlorination should not be phased out in preference to other methods until the potential dangers of alternative disinfectants are fully evaluated. A large amount of research has been done on the possible formation, types, and prevention of disinfection by-products (Stevens et al., 1976; Jolley et al., 1977; Krasner et al., 1989; Duke et al., 1980): _ Formation: Disinfection by-products are formed due to the action of the disinfection chemical on naturally occurring organic matter, such as fulvates and humates that constitute natural organic color in surface waters. _ Types: The most common disinfection by-products include: trihalo-methanes, haloacetonitriles, haloketones, haloacetic acids, chlorophenols, aldehydes (and many more). The latest scare is bromate formation when ozone is used (Kruithof and Meijers, 1994). This view has now been superseded by the realization that chlorination also results in the formation of bromate. _ Prevention: There are generally four approaches in minimizing or preventing the formation of especially THMs:

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(i)
(ii) (iii) (iv) (v)

Remove the THM formation potential (THMFP) by improving organic removal. In some cases it may be justified to lower the pH for better coagulation of organics. Pre-ozonation can usually lower the THMFP, but there are exceptions. Control the concentration and contact time of free chlorine. This may be achieved by altering the point of chlorine application - usually to after clarification. In the case of pre-chlorination, the action of free chlorine can be ended by ammonification. The use of alternative disinfectants such as chloramines, chlorine dioxide and ozone which do not form or form little THM's, and Removal of THMFP as well as THMs by activated carbon. From the various methods investigated this method was the least cost effective. Bromate formation can be averted at lower pH values (<7) and in the presence of free ammonia. The latter is important when ozonating as ozone will not react with ammonia.

Alternative disinfectants Although chlorination is by far the most common disinfectant in water treatment, certainly in Australia, it has many disadvantages in its by-products and in its shortcomings as a disinfectant. It does not come as a surprise that chlorination is rapidly being supplanted, or at least supplemented by other disinfectants. Before considering each of the other in detail, it is worth comparing chlorine with alternatives. The principle alternatives are ozonation, chlorine dioxide, and combined chlorine residuals. Others, which may be occasionally employed, are ultraviolet irradiation, iodine, bromine, bromine chloride and gamma radiation. Table 4.3 displays certain physical constants for the three most common disinfecting agents, i.e. chlorine, ozone and chlorine dioxide. It should be noted that all three normally exist as gases. Chlorine is available as a compressed liquid, but ozone and chlorine dioxide must be manufactured on site because they decompose, and are dangerous to store in a concentrated, compressed form.
Solubility in water at 1 atm and 25C, g/L 7.29 0.012* 8.0^

Name Symbol Chlorine Ozone Chlorine dioxide

* ^

Molecular mass 70.91 48.00 67.45

Boiling point, C -34.5 -112.0 10.9

Melting point, C -101 -192 -59

Heat of vaporization cal/g 68.7 54.0 96.6

Cl2 O3 ClO2

2% O3 by mass in air. Assumes equilibrium with 10% ClO 2 gas phase.

Table 4.3 Physical constants for Common Disinfecting Agents Table 4.4 shows the specific lethality coefficients for the disinfectants discussed here with respect to four general classes or organisms. These values should be taken as an approximation of these agents because so many variables affect the results of disinfection experiments that it is hard to compare one set of results with the next. This is particularly true for chlorine dioxide.
Disinfectant O3 16 Enteric bacteria 500 Viruses 5 Spores 2 Amoebic cysts 0.5

ClO2 10 HOCl 20 OCl0.2 NH2Cl 0.1 *(mg/L).min, assuming that n is equal to 1

1.5 1.0+ 0.02 0.005

0.6 0.05 0.0005 0.001

0.1 0.01 0.0005 0.02

Table 4.4 Specific Lethality* of Alternative Disinfectants

4.5 CHLORINE DIOXIDE

Chlorine dioxide is a useful alternative among disinfectants. Chlorine dioxide is effective in destroying phenols, yet it does not form trihalomethanes in significant amounts. Chlorine dioxide's disinfectant properties are not adversely affected by a higher pH, as those of free chlorine residue are. Consequently, chlorine dioxide is a useful disinfectant at higher pHs. In western Europe, use of chlorine dioxide is popular, particularly in Belgium, Germany, France and Switzerland in regions where potable water is produced from polluted rivers. In these locations, chlorine dioxide is used for disinfection, often as an adjunct to ozonation.
Chlorine dioxide can be reduced by two alternative pathways in aqueous solution, as shown below.
C lO 2+e-

C lO 2

+5e2C l- + 2O

The redox potential of chlorine dioxide in being reduced to ClO 2- is 1.15 V. Reduced to Cl-, its potential is 1.9 V. By comparison, the redox potential of Cl when reduced to Cl - is 1.4 V. At the pHs normally encountered in water utility practice, chlorine dioxide is most often reduced to the chlorite ion (ClO2-); hence, both of its redox potential and the redox equivalents are lower for chlorine dioxide than for chlorine. On the other hand, chlorine dioxide is a good disinfectant, and because it is selective, it does not participate in a number of undesirable side reactions as chlorine does. For example, chlorine dioxide does not react with organic compounds to form trihalomethanes, nor does it react with ammonia to form chloramines. As a result, chlorine dioxide residuals are sometimes purported to last longer than free chlorine residuals under the same circumstances. One of chlorine dioxide's principal advantages as an oxidant is that it effectively removes phenols, a continuing odor problem in certain water supplies. Chlorine dioxide does not dissociate or disproportionate as chlorine does at normal drinking water pHs. Like chlorine, chlorine dioxide exerts a demand when it is first added to a water supply, which must be overcome if a persistent residual is to be maintained. Again like chlorine, chlorine dioxide is photosensitive (light sensitive). The principal reason for the increasing interest in chlorine dioxide in the United States is the fact that it does not form trihalomethanes. On the other hand, the organic by-products of chlorine dioxide are not yet well understood; it may have other undesirable reaction products. Information presently available indicates that the reaction products would include aldehydes, carboxylic acids, and ketones. Few chlorinated by-products are known, although some are likely. The principal inorganic by-products of chlorine dioxide reactions within water
17

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treatment are chlorite (ClO2), chloride (Cl-), and chlorate (ClO3-), in the order listed. Both chlorate and chlorite, particularly the chlorite ion, have been implicated in the formation of methaemoglobin. Consequently, most European countries limit the level of chlorine dioxide which can be used, and the EPA has considered doing so in the United States as well. The current EPA recommendation is that the sum of chlorine dioxide, chlorite, and chlorate in the distribution system be less than 1.0 mg/L. Generation of chlorine dioxide All chlorine dioxide for drinking water treatment is generated from sodium chlorite. Most generation techniques use the oxidative process, in which chlorine (either as a gas or in solution) is mixed with a sodium chlorite solution. The stoichiometry of this reaction is (written for molecular chlorine): 2NaClO2 + Cl2 2ClO2 + 2NaCl (4.15)

In addition to the desired formation of chlorine dioxide, chlorate ion may be formed in the generation system as an undesired by-product in a competing reaction: NaClO2 + Cl2 + OH NaClO3 + HCl + Cl(4.16)

The goal in generating chlorine dioxide from chlorine and sodium chlorite is to maximize the chlorine dioxide yield, defined as the molar ratio of chlorine dioxide produced to the theoretical maximum. The term 'conversion' is also used when referring to chlorine dioxide generation reactions; this is the molar ratio of the amount of chlorine dioxide formed to the amount of sodium chlorite fed to the system. For Reaction 4.15, yield and conversion will have the same value. For other reactions that produce chlorine dioxide, such as the hydrochloric acid-sodium chlorite reaction, yield and conversion will have different values: 5NaCl2 + 4HCl 4ClO2 + 5NaCl + 2H2O (4.17)

For Reaction 4.17, maximum yield is 100 percent; maximum conversion, 80 percent. Studies of the mechanism and kinetics of the chlorine-sodium chlorite reactions have shown that conditions favoring the formation of chloride dioxide are those in which the reactants are present in high concentrations and the chloride is present as hypochlorous acid or molecular chlorine (Cl2). Two methods for the generation of chlorine dioxide from chlorine and sodium chlorite are commercially available. They are the aqueous chlorine-sodium chlorite system and the gas chloride-sodium chlorite system.

Aqueous chlorine-sodium chlorite system The earliest systems produced chlorine dioxide by simply pumping a sodium solution into a chlorine solution, followed by a short reaction time. Acceptable yields were achieved by feeding 200 to 300 percent more chlorine than the stoichiometric requirement according to reaction 4.15. The chlorine dioxide solution from a generator of this type contains high levels of chlorine in addition to the chlorine dioxide. A side reaction that occurs in the chlorine dioxide solution under these conditions is:

18

2ClO2 + HOCl + H2O

2ClO3- + 2H+ + HCl

(4.18)

The discovery that potentially toxic chlorinated organic compounds are generated by the reaction of chlorine and naturally occurring humic substances in water supplies, plus the interest in chlorine dioxide as a replacement for some chlorination practices, led to a search for generation methods that would produce a chlorine free chlorine dioxide. One of the most common methods for chlorine dioxide generation currently in use, that strives to meet this requirement, is the pH adjusted method. The pH-adjusted system utilizes hydrochloric acid fed into the chlorine solution before the reaction with the sodium chlorite. The acid shifts the chlorine hydrolysis equilibrium to the left, favoring molecular chlorine formation: Cl2 + H2O HOCl + HCl (4.5)

The acid feed must be carefully controlled so that the pH of the chlorine dioxide solution can be maintained between 2 and 3. Higher pH values result in decreased yields. At a lower pH, however, Reaction 4.17 becomes significant, again reducing yield because of the maximum conversion of only 80 percent from this reaction. Yields of more than 90 percent have been reported from the pH-adjusted system, with approximately 7 percent excess (unreacted) chlorine remaining in the solution. Another modification that produces high yields of chlorine dioxide, with minimal amounts of chlorine remaining in the chlorine dioxide solution, requires that the chlorine solution used for generation have a chlorine concentration greater than 4g/L. Since this concentration of chlorine in solution is near the upper operating limit of commercial chlorine ejectors, and these ejectors operate at constant water flow rates, the yield of this method of generation is dependent on the production rate, with lower production rates resulting in lower yields. This type of generator is normally operated on an intermittent basis to maintain high yield when less-than-maximum production capacity is required. Chlorine dioxide solutions in the 6- to 10-g/L concentration range are prepared and immediately diluted to about 1g/L for storage and subsequent use as needed. A schematic of the aqueous chlorine-sodium chlorite system is shown in Figure 4.6.

Figure 4.6 Aqueous chlorine - sodium chlorite system with optional acid feed Gas-chlorine chlorite system
19

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The most recent development in chlorine dioxide generator technology is a patented system that reacts gas chlorine with a concentrated sodium chlorite solution under vacuum. The chlorine dioxide produced is removed form the reaction chamber by a gas ejector, which is very similar to the common chlorine gas vacuum feed system. This generation technique produces chlorine dioxide solutions with yields in excess of 95 percent. The chlorine dioxide solution concentration is 200 to 1000 mg/L and contains less than 5 percent excess chlorine, which is defined as the amount of unreacted chlorine remaining in the chlorine dioxide generator effluent. The system is operated on a continuous basis, and achieves a high yield over the entire production range (see Fig 4.7).

Figure 4.7 Gas chlorine-sodium, chlorite system schematic

4.6 OZONE DISINFECTION

The first use of ozone in the treatment of water coincided with the first use of chlorine for disinfection, until recently ozonation was a common practice in only a small number of countries, notably France and Switzerland. It has become much more popular recently and is now in use in about 3000 drinking water and waste water treatment plants all over the world. Ozone is a highly reactive gas formed from oxygen by electrical discharges. Its most distinguishing characteristic is a very pungent odor. In fact, the word "ozone" is derived from a Greek word which means "to smell". The use of this gas in water treatment requires an understanding of its physical and chemical behavior. The physical chemistry of ozone is important because a number of complex factors affect its solubility, reactivity, autodecomposition, and stability. Ozone is a strong oxidant and an excellent disinfectant. It finds wide application in water treatment and increasingly in wastewater treatment. Ozonation can play an important role in
20

improved water treatment and help to achieve a better, safer water quality. Ozone is usually used as more than just a disinfectant. Its excellent properties in aiding coagulation, promoting the removal of organic and inorganic contaminants and removal of taste and odors have made in a popular choice in modern water treatment practice. It is used as an early treatment procedure to enhance coagulation and to improve the biodegradability of organic constituents for subsequent removal during biological filtration. Whereas the older drinking water plants were using ozone towards the end of the process for disinfection, the move worldwide has been towards using ozonation as a pretreatment. With few exceptions, chlorination is used as a final disinfection stage. Ozone is an excellent disinfectant on its own in tertiary wastewater treatment. Caboolture Shire uses ozonation in a water reclamation plant of 10ML/d. Studies for the implementation of ozonation have been conducted for the Gold Coast City Council and the Armidale City Council. The author had involvement in all three and also with plants in Africa, ie the Windhoek Water Reclamation Plant, Western Transvaal Regional Water Company and a large pilot scale for disinfection of mine service water for GoldFields. This chapter describes the process of ozonation and its applications in some detail. The chemistry of ozone is described, the equipment required for ozonation and some of the applications are discussed. Ozone production in nature Ozone is formed by the interaction of energy with oxygen molecules to form oxygen radicals which then combine with oxygen molecules as shown in the following reactions; O2 + Energy O + O2 O3 O +O (4.16) (4.15)

These reactions occur naturally in the Earth's ozone layer under the influence of sunlight, and artificially using electrical discharge, ultraviolet light and electrolysis. Oxidation of inorganic compounds Ozone will oxidize most metals, such as Mn(II), Mn(IV), Fe(II), Co(II), cyanide to cyanate or to carbon dioxide and nitrogen, sulfides, sulfur dioxide, bromide and nitrite. At pH > 8, ozone will oxidize ammonia. Example: A simple oxidation reaction for ozone is: O3 + NO2 NO3- + O2

Oxidation of organic compounds In theory ozone can oxidize organic pollutants to carbon dioxide and water. In practice this does not happen, as it would take too long. The oxidation reactions usually attack C-C double bonds or aromatic groups in humic molecules, and aliphatic side chains or fatty acids by hydrogen atom abstraction. It will also oxidize complexed metal ions. Care needs to be taken when using ozone for reversible oxidations, for example the removal
21

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of color from dye waste. If the treated waste comes into contact with a reducing environment the molecule may convert to its previous form. This is not important for irreversible reactions. Oxidation capability Ozone, O3, is a triatomic allotrope of oxygen. It is a powerful oxidant with an E o value of 2.07 V. Ozone also produces hydroxyl radicals which have an E o value of 2.80 V. The oxidation potentials of various compounds is shown in Table 4.5, from which it can be seen that ozone and hydroxyl radicals are the most powerful oxidants. Table 4.5 Oxidation potentials of various commonly used aqueous oxidants
Compound F OH radical O3 H2O2 MnO4HOCl Cl2(aq) Cl2(g) Cr2O72HCrO4ClO2(g) Eo (V) 3.20 2.80 2.07 1.77 1.68 1.63 1.40 1.36 1.33 1.20 1.15

Corrosivity of ozone Being a strong oxidant, ozone can be aggressive to many metals and polymers, both as a gas and in solution. Mild steel is resistant only when ozone concentrations in water are below 0.2 mg/l and only under turbulent conditions. Ozone resistant paints are available but are not totally satisfactory. Stainless steels, concrete and ceramics (304 & 316) are totally resistant to oxidation by ozone. Seals need to be manufactured from Viton, Teflon or ozone resistant rubbers. The decomposition of ozone Ozone rapidly degrades to oxygen by a series of reactions involving a range of intermediate hydroxyl radicals which are utilized in some oxidation reactions. The overall reaction is: 2O3 3O2 (4.17) This reaction occurs very rapidly, and approximately follows first order kinetics. In "pure" water ozone typically has a half life of approximately 20 minutes. The half life is affected by the pH of the water, reductants and carbonate ion concentration and is typically between 10 seconds and 2 minutes in surface waters.
22

Transfer of ozone from the gas phase to the aqueous phase Ozone is normally produced in air or oxygen. In order to use ozone in the treatment of water it is necessary to dissolve it in water. The solubility of ozone in water depends on the gas phase concentration, water temperature, water pressure and diffusion. The quantity of ozone, which can be transferred into water, is limited by the equilibrium between the amount of ozone in the gas phase and the amount dissolved in water. Table 4.6 shows equilibrium concentrations of ozone dissolved in water for various gas phase concentrations. Table 4.6 Ozone solubility in water at equilibrium, mg/L
Temperature oC 15 25 30 0.001 % 0.006 0.004 0.003 0.1% 0.60 0.35 .027 Ozone concentration in gas phase 1% 1.5% 2% 6.04 3.53 2.70 9.05 5.29 4.04 12.06 7.05 5.39 3% 18.10 10.58 8.09

The values in Table 4.6 represent theoretical maximums at ambient pressure. The solubility of ozone follows a linear relationship with concentration and pressure according to Henrys Law, PiH = Ci, where Pi is the partial (fractional) pressure of ozone in the gas (air or oxygen) and Ci the concentration of ozone in the water. The value of H would normally be expressed as a liquid phase concentration per (partial) pressure of the ozone in the gas phase. It should be appreciated that during the transfer of ozone from the gas phase to water that the gas phase concentration decreases. If, for instance, 90% of the ozone has been transferred, the gas phase concentration has been decreased to 10% of its initial value. Consequently the equilibrium water phase concentration will be reduced by approximately 90%. Diffusion Values in Table 4.6 represent maximum concentrations of ozone reached at equilibrium after an indefinite period of time of contact. The transfer is, however, affected by various diffusion rate phenomena such as; the net area of contact between the gas and water, the degree of gas saturation of the water, boundary layer and mixing conditions. These characteristics are consequently influenced by the selection of the equipment used for ozone transfer. A general relationship for gas diffusion is Fick's Law, which can be expressed as:

N A = cA uo DAB

dcA db

(4.18)

NA is the diffusion flux, CA is the concentration of component A, uo is the velocity which components A and B travel past each other, D AB is is the diffusivity of component A in mixture with component B, dCA/db is the concentration gradient between component A and component B. From this equation the diffusion flux for ozone is increased as:
23

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the relative velocity between the two phases decreases, the concentration of ozone in the gas phase increases
Ozone concentration in water (mg/l)

Figure 4.8 shows the effect of diffusion phenomena on the transfer of ozone from gas to water
5 4.5 4 3.5 3 2.5 2 1.5 1 0.5 0 0 2.5 5 7.5 10 12.5 Time (min) 15 17.5 20 22.5 25 Decreasing: Bubble diameter Improved: Mixing

Figure 4.8 Typical relationship between time of contact and ozone concentration reached during batch ozonation Developing an ozone residual For disinfection a residual of ozone needs to be obtained. Due to its high oxidation potential, ozone reacts rapidly with a range of contaminants in water. The oxidation reactions are so fast that they are difficult to measure. These reactions consume ozone and are referred to as ozone demand. Until the ozone demand has been met, the residual of ozone will be consumed rapidly with consequently poor disinfection. It is impossible to predict the ozone demand of a particular water so experimental work must be done in order to determine the dose required to obtain a sufficient residual. This can be done in a laboratory or by pilot scale testing. Ozone demand is determined by applying ozonated air (or oxygen) to a sample of water. The ozone concentration of the ozonated air, the air leaving the water and the ozone concentration of the water are measured. The ozone dosage can be calculated from a mass balance of the ozone applied and the ozone in the exit gas. The ozone concentration measured in the water is the residual. The difference between ozone dosage and the residual measured in the water is the ozone demand of the water. These destinations of ozone are shown in Figure 4.9. Testing is essential to the design an ozonation system to ensure the applied dose is adequate to meet the ozone demand of the water and to avoid unnecessarily over-design. Many waters will have low ozone demands, whereas it possible that other waters have ozone demands so high as to make it uneconomic to use ozonation. Figure 4.10 shows a typical relationship between the amount of ozone applied to a water sample and the residual that becomes available for disinfection.

24

Ozone in Exit Gas

Measured

Water Ozone Residual Measured

Ozone Demand

Inferred:

Applied - Exhaust - Residual

Ozonated Air Applied

Measured

Figure 4.9 Ozone pathways in water treatment

0.8 0.7 OZONE RESIDUAL (mg/l) 0.6 0.5 0.4 0.3 0.2 0.1 0 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 OZONE DOSAGE (mg/l)

Figure 4.10 Typical relationship between ozone dosage and the residual in water

As a sample of water moves through an ozone contactor, the residual slowly builds up in the water sample. Once the water leaves an ozone contacting unit this residual breaks down according the half life decomposition discussed above. Figure 4.11 shows how a disinfection residual builds up and breaks down with time in a typical contacting system.
0.8 0.7 OZONE RESIDUAL (mg/l) Ozone dose A 0.6 0.5 0.4 0.3 Ozone dose B 0.2 0.1 0 0 1 2 3 4 5 TIME (min) 6 7 8 9 10

Figure 4.11. Typical build-up of ozone residual in a contacting chamber and the subsequent breakdown when leaving the chamber
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As mentioned, the ozone residual is short lived. Ozone cannot be used, therefore, for residual disinfection of water distribution systems. Disinfectants, which are typically used for establishing a residual, are chlorine, chloramines and chlorine dioxide. Ct Values Ct values are used by the United States Environmental Protection Agencies' (USEPA) Surface Water Treatment Rules (SWTR) to protect the public from contracting waterborne disease from drinking water. Instead of setting maximum contaminant levels, Ct values are used to emphasize water treatment techniques as the condition for compliance to regulation. Ct values can be calculated for disinfection methods, as well as other processes in potable water treatment such as coagulation and filtration. C is the concentration of the disinfectant residual and t is the time that the water is in contact with the disinfectant. The product of C and t is the Ct value. Ct can be calculated by the integration of a concentration-time curve like the one shown in Figure 4.11. The area under the dose B curve represents the Ct value for that specific dose. This means that for every type of water the Ct values for ozone need to be determined experimentally. This is different from chlorination where the chlorine product's stability ensures a relatively constant relationship between concentration and time. Ct values are useful for making estimates of the size requirements of a disinfection system, and for comparisons between disinfectants. Tables 4.7 and 4.8 show the Ct values recommended by the USEPA for 99.9% inactivation of Giardia lamblia and 99.99% inactivation of enteric viruses, for various disinfectants. From these tables it can be seen that ozone is much faster acting than other disinfectants.
Temperature Disinfectant free chlorine 2 mg/l ozone chlorine dioxide preformed chloraminesa pH 7 8 6-9 6-9 6-9 10o C 124 182 1.4 23 1850 15o C 83 122 0.95 19 1500 20o C 62 91 0.72 15 1100 25o C 41 61 0.48 11 750

Extracted from: Von Huben, 1991

Table 4.7. Ct values for inactivation by 99.9% of Giardia lamblia and 99.99% of enteric viruses with various disinfectants
Temperature % inactivation 90 % 99 % 99.9 % pH 6-9 6-9 6-9 10o C 0.48 0.95 1.4 15o C 0.32 0.63 0.95 20o C 0.24 0.48 0.72 25o C 0.16 0.32 0.48

Extracted from: Von Huben, 1991

Table 4.8 Ct values for different levels of inactivation of Giardia lamblia with O3

26

4.7 DISINFECTION BYPRODUCTS (DBPs)

Ozone forms fewer DBPs than other disinfectants, except chlorine dioxide. This is one of the major considerations leading to the use of ozone as a disinfectant. Concern about THMs has been one of the major reasons for increasing use of ozone in disinfection. All disinfectants can leave by-products in water, some of which are shown in Table 4.9.
Disinfectant Byproduct Chloroform (THM) Bromodichloromethane (THM) Chlorodibromomethane (THM) Bromoform (THM) Dichloroacetic acid Trichloroacetic acid 2,4,6-Trichlorophenol Formaldehyde Other aldehydes & Ketones Bromate Cyanogen chloride Chlorite/chlorate X X X X X X X X (X) X X X (X) (X) (X) (X) (X) (X) (X) (X) X X X X HOCl NH2Cl ClO2 O3

Table 4.9 Some significant disinfection by-products of the common disinfectants

# Chloramine by-products depend on the method of chloramination. When chlorine is added prior to ammonia, chloramines will have the same by-products as chlorine. When chlorine and ammonia are mixed prior to dosing, chloramine has very few by-products, mainly cyanogen chloride which only forms when conditions are suitable.

Environmental toxicity of disinfectants Ozone has very limited residual toxicity for distribution systems or the environment. Due to rapid decomposition most ozone will have left the system within an hour, having no further impact on the environment or humans. Hypochlorite, chlorine dioxide and chloramine, the most commonly used disinfectants and oxidizing agents, all maintain a residual in water. Free chlorine and monochloramine are lethal to insects and crustaceans at levels of as low as 0.03 mg/L. They are lethal to some fish at levels of 0.014 mg/l. Sub-lethal effects such as avoidance behavior and reproductive failure occur at 0.002 - 0.005 mg/L in fish. Bromoform Ozone will form bromoform, bromoacetones and bromoacetonitriles. This has been of major concern with ozonation. Reactions are as shown below: O3 + Br TOBr O2 + OBr H+ + OBr(4.21) (4.19) (4.20)

HOBr HOBr + DOC

Where DOC is dissolved organic carbon and TOBr total brominated organic compounds.
27

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Chlorination will also oxidize bromide to hypobromous acid leading to the same result as shown below. HOCl + BrBromate Bromate formation has recently been perceived as a major problem with ozonation. Bromate will also form during chlorination. The formation of bromate is described in the following reactions: For ozone: O3 + Br2O3 + OBrFor chlorine: HOCl + Br2OBrOBr-+ BrO2 HOBr + ClBrO2- + BrBrO3- + Br(4.25) (4.26) (4.27) HOBr + Cl(4.22)

O2 + OBr2O2 + BrO3-

(4.23) (4.24)

Bromate formation can be avoided by adjusting conditions, in several ways: Below a pH of 6.5 all hypobromous (OBr -) species are present as hypobromous acid (HOBr), which cannot be oxidized. Bromate cannot form, therefore. Below a pH of 6 bromide and bromate will rapidly react with each other to form hypobromous acid, reducing the amount of bromate present in water. In the presence of ammonia, monobromamine will form which is rapidly oxidized by ozone: OBr- + NH3 2NH2Br + O3 OH- + NH2Br 2Br- + N2 + O2 + H2O + 2H+ (4.28) (4.29)

Reaction 4.28 is favored over reaction 4.24 resulting in a cycling of brominated products in Reactions 4.28, 4.29 and 4.23 causing bromine to become unavailable for the formation of bromate.

4.8 OZONATION EQUIPMENT

The preceding discussion shows several important characteristics of ozone. Ozone has two main applications in water and wastewater treatment: oxidation and disinfection. For both oxidation and disinfection:
1. Ozone must be generated on-site due to its instability 28

2. Ozone contact with water must be carefully designed to overcome poor solubility and to provide the conditions for diffusion from the gas phase into the liquid phase

For disinfection:
3. Applying enough ozone to satisfy the ozone demand and leave an adequate residual concentration to provide a driving force for disinfection.

A final important consideration is that ozone at ground level is a lung irritant and an important greenhouse gas and in general should not be released to the atmosphere. Figure 4.12 is a flow chart showing the elements typically required for a practical ozonation system when considering the reactions and chemistry of ozone.
INFLUENT

OZONE GENERATOR OZONE CONTACT CHAMBER OZONE DESTRUCTOR

AIR/OXYGEN PREPARATION

AIR

VENT

OTHER OXYGEN APPLICATIONS EFFLUENT Alternative paths for enriched oxygen recycle

Figure 4.12 Typical layout of an ozone system Selecting an ozone generation system Ozone can be generated in air or oxygen. The concentrations achievable with oxygen are higher than in air. Making a choice between using air or oxygen for the production of ozone requires a full cost benefit analysis. Table 4.10 shows the approximate concentrations of ozone produced in air and oxygen with technology currently on the market.
Ozone generation Air UV irradiation Corona discharge 0.001 to 1.0% 2 to 4% Gas utilized Oxygen Not typically used 6 to 12%

Table 4.10 Concentrations of ozone produced in air or oxygen using current technology Oxygen is not typically used as a source of gas for UV systems due to the expense of oxygen preparation equipment and the small concentration of ozone produced. Generating Ozone There are three systems used to generate ozone: corona discharge, UV and electrolysis. Corona discharge

29

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A corona discharge is created when a high voltage is applied across two electrodes separated by a dielectric and a discharge gap. Electrons flowing thought the discharge gap are used to bombard oxygen atoms in the feed gas, causing some of the oxygen molecules to break into atoms which then combine with molecular oxygen to form ozone. The electrodes are usually arranged as two concentric reaction cylinders around each other with the discharge gap between them. The outer electrode is usually jacketed in cooling water. The dielectric is usually made of glass or ceramic and together with a metallic coating this makes the inner electrode. The outer electrode is usually stainless steel. Up to 20kV is required to ensure an adequate corona discharge rate. Frequencies exceeding 50 Hz improve the efficiency. Most ozone generators are equipped with solid state medium frequency converters to produce frequencies around 500 Hz ensuring higher ozone concentrations, higher production and to reduce power consumption. Gas preparation for corona discharge Adequate air preparation is essential in a corona discharge system. Comparatively wet gas entering the discharge system can cause substantial problems. It must not be assumed that a high purity oxygen preparation system will provide an adequately low dew point for ozone generation. The gas used must have a dew point of approximately -60 oC, and should be relatively free of hydrocarbons. Water can cause several problems in a corona unit. Ozone production in a gas with dew point of -20oC is almost half that produced at a dew point of -60oC. A more significant problem arises when nitrogen gas enters the corona discharge unit with moist air. Oxides of nitrogen are produced by reaction with ozone, which will then react with water vapor to produce nitric acid. This will damage components of the generator and downstream equipment. In large systems cooling followed by desiccation is used to lower the dew point. Desiccants are usually either alumina or silica, which are thermally regenerated. Regeneration is usually done on a daily basis to allow the desiccant to cool following regeneration. In smaller systems air can be compressed and passed over activated alumina where the higher pressure favors the adsorption of water. The alumina is regenerated by releasing the pressure and purging it with low pressure air. Two columns of alumina can be used with constant switching between pressurized feed air and purge air for regeneration of the alumina on a continuous basis every few minutes. Generation of ozone with UV Ozone can be produced using ultra violet irradiation. This is a much less expensive system than corona discharge, although lower concentrations of ozone are formed. Air is passed through a quartz sleeve with UV light shone through the quartz into the air. Quartz is used as it is transparent to UV whereas glass and plastic absorb UV. Production of ozone with UV has the advantage of not requiring air to be dried. UV units are also easy to control as the rate of ozone production is linearly related to the power applied to the lamp. Low production of ozone limits this application to small systems It is however a far cheaper system as it requires no air preparation and the UV equipment is less expensive than
30

corona discharge. Low production of ozone in UV is due to the wavelengths of light generated by low pressure mercury lamps which are used as the UV light source. They produce light at wavelengths of 187 nm and 254 nm. 187 nm light causes reactions which lead to the production of ozone and the 254 nm light causes photo-dissociation of ozone as shown in equation 4.30 below. The net result is that only a small amount of ozone is produced. O3 + h O2 + O (h = 254 nm) Future developments in UV lamps may lead to improved efficiency. Electrolysis The electrolysis process consists of electrodes placed in water dosed with an acidic electrolyte. Ozone is produced at the anode by the oxidation of water and oxygen is reduced at the cathode to produce water. To date practical problems related to power consumption have limited this technology. It is possible in the near future that this process will develop to the stage of being economically feasible. Ozone Transfer into Solution Several technologies are available for dissolving ozone in water. As mentioned earlier, ozone is not very soluble and has a very short half-life in water, so particular attention should be paid to selecting a contacting system that will obtain the most cost-effective results. Ozone can be contacted with water in bubble columns, spray columns, deep U-tube, packed columns, mechanical mixers and venturi tubes. Table 4.11 shows the efficiency of three of these technologies
Efficiency 55m deep U-tube Bubble column Static mixer > 95% ~ 85% < 75%

(4.30)

Table 4.11 A comparison of the efficiency of three types of ozone contacting devices
(Van Leeuwen and van der Westhuizen, 1992)

Bubble columns Bubble columns are the most commonly used ozone contact unit (Figure 4.13). The ozonated air or oxygen is introduced at the bottom of a cylindrical column or baffled chamber, which is usually 5 to 8 m deep. The ozone is diffused through a porous diffuser. Water is introduced at the top at rates of up to 120 m/h to create a countercurrent flow against the bubbles, which rise at a rate of around 180 m/hr. Coalescence of bubbles limit the amount of gas that can be introduced and irregularities in water flow patterns are often the cause of under-performance of this type of equipment. Packed columns Packed columns are similar to bubble columns except that they are packed with ceramic
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beads. These beads increase the turbulence and surface area of the water, improving the diffusion of ozone into water. Little or no back mixing of the water is possible, but gas phase short-circuiting can occur.

Spray columns In spray columns water is introduced as a spray through nozzles at the top of a reactor and ozonated feed gas is introduced at the bottom of the reactor. In these units short residence times limit the dosage and ozone transfer efficiency.

Figure 4.13 A typical bubble column for use in small systems

(Van Leeuwen and van der Westhuizen, 1992)

Mechanical mixing devices Mechanical mixing devices are best used for the re-contacting of spent gases from a previous ozonation step as they have an ozone transfer efficiency of less than 75%. Two types are mainly used; surface aerators, which require totally enclosed chambers, and self-aspirating submerged aerators. Deep U-Tube A deep U-Tube is shown in Figure 4.14. Ozonated feed gas and water are mixed and passed co-currently down a tube at 360 m/hr which is fast enough to prevent the rise of air bubbles, which rise at approx. 180 m/hr. The mixture is taken to depths greater than 15m, so that the
32

pressure rises to several hundred kPa increasing the solubility of ozone in water. The mixture then rises to the surface again through the annulus of the concentrically arranged outer tube. A 55m deep U-tube has an ozone transfer efficiency of greater than 95%. Exhaust air is separated from the water stream by a small unit on top of the U-tube. The only pumping effort required for this system is that necessary to overcome normal pipe friction losses, making this an economical method of obtaining high ozone transfer efficiencies provided that reaction rates are high.

Figure 4.14 A typical deep U-tube Venturi systems

(Van Leeuwen and van der Westhuizen, 1992)

Venturi systems consist of a constricted pipe, which has an air inlet perpendicular to the direction of flow of the water. The ozonated air is drawn into the water by the pressure differential created in the pipe constriction, the turbulence of the water is then relied upon to create an intimate contact between the water and the gas phase. It may also have a static mixer such as vanes and flow dividers downstream of the inlet to improve the ozone transfer. Venturi systems are not very efficient because they rely on a single stage completely mixed system where the exhaust gas concentration will be in equilibrium with the residual ozone concentration in the water. They are however, cheap and small and can be quite effective in water with a high demand as a pretreatment. Off-gas Treatment
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Ozone should generally be destroyed before exhaust gases are released to the atmosphere. In some cases away from populated areas where the off-gas can be adequately diluted no treatment may be necessary. It should be realized that ground level ozone is a greenhouse gas, but that it also decomposes rapidly into oxygen. Ozone can also cause minor lung and mucous irritation if it does not dissipate rapidly. In most cases catalytic or thermal destruction of ozone is required. Off-gas can also be reutilized for other applications, which will reduce the volume of ozone requiring destruction. One method of this is to send the spent gas to a water pretreatment stage for mechanical mixing before the water is treated in the main ozone contact system. Instrumentation and Control Requirements for instrumentation and control can vary from almost zero for simple applications such as UV generated ozone for use in home spas to totally automatic control in large plants where adequately trained personnel is not available. Measurements can be done in batch or continuous samples, control can be fully automated with a range of automatic overrides and shutdowns. Selection of instrumentation and control systems is by necessity a decision, which is individual to each plant. Instrumentation and control systems can increase the cost of a plant by between approximately 50 and 100% over the cost of the basic equipment. Storage of Ozone Due to its instability ozone cannot be effectively stored or bottled. This is a particular disadvantage in shock dosing situations where the ozone generator has to have sufficient capacity for the highest dose. This leaves huge idle capacity during lower dosing periods. The only prospect that exists for the storage of ozone is a Japanese patent for liquefaction. Ozone is a liquid at -50oC though it is unstable and explosive in this state.

4.9 POTABLE WATER TREATMENT APPLICATIONS

In potable water treatment ozone is primarily used as an oxidant to improve the removal of undesirable products. Ozone is also used as a disinfectant but usually another disinfectant is subsequently required to establish a stable residual for distribution systems. Chlorine, chloramine or chlorine dioxide, are typically used. Pre-ozonation Pre-ozonation, that is ozonation ahead of the whole treatment procedure, has been shown to have a range of benefits when is used in drinking water treatment, including:
34 Control of algae Removal of cyanobacterial toxins Removal of taste, odors and color Oxidation of iron and manganese Microflocculation Partial oxidation and volatilization of organics

 Longer filter and activated carbon run lengths Reduction of DBPs, particularly THM To enhance biological activated carbon performance

The benefits of using ozone in disinfection are:

Less residual disinfectant is required Reduced formation of DBPs, particularly THM Short residence times for ozone contact compared with chlorine High levels of viral and bacterial inactivation.

Figure 4.15 shows the locations in potable water treatment at which ozone is typically applied.

Pre-ozonation

Ozone Disinfection

Raw Water

Screening

Clarification

Filtration

G A C

Distribution

Residual Disinfection
Figure 4.15 Typical locations of ozone application in modern potable water treatment Residual disinfection would be chlorine, chloramines or chlorine dioxide. The philosophy about this in some countries, particularly the Netherlands and Germany, is to have no residual disinfectant. It is argued that with proper pretreatment, particularly ozonation followed by a biological treatment step on granular activated carbon and/or deepbed filtration, the biodegradable material has been removed to such an extent that there is little opportunity for bacterial regrowth during distribution. Benefits of pre-ozonation Reduction of THM formation potential Trihalomethane (THM) and other halogenated organic formation has become a major problem as consumers demand a safer water supply. The precursors of THM are organic molecules present in all water supplies. When the organic molecules are oxidized in the presence of chlorine halogenated organics and THMs form. Ozone oxidizes these precursors, reducing the potential for the formation of THMs and other halogenated organics. This has become a very important reason for the use of ozone in potable water supply.
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Iron(II) and manganese(II) removal Iron and manganese can impart undesirable color to water, causing aesthetic problems for water suppliers. Iron and manganese form in impoundments when anoxic conditions occur. During seasonal turnover these cations become mixed into throughout the reservoir, and eventually to the consumers taps. Ozone acts to oxidize these contaminants to less soluble oxides as shown in the reactions below. 2Fe2+ + O3 + 2H+ Fe3+ + 3OHoverall reaction: 2Fe2+ + O3 + 2H+ + 6OH- Mn2+ + 2O3 2Fe(OH)3 + O2 + H2O MnO2(s) + 2O2 2Fe3+ + O2 + H2O Fe(OH)3(s)

There can be difficulty with overdosing of ozone leading to the formation of permanganate resulting in "pink water" as shown below. MnO2 + 2O3 MnO4- + 2O2

Removal of taste and odor Geosmin and 2-methylisoborneol (2-MIB) which are produced by microbial activity in eutrophic waters are responsible for many of the earthy, musty odors found in some drinking water supplies. They can have a detrimental effect on the aesthetics of water at threshold concentrations of 4 ng/l for geosmin and 8.5 ng/l for 2-MIB. Ozone on its own or followed by GAC treatment can be very effective in the removal of tastes and odors caused by these organisms. Ozone probably acts by causing the formation of hydroxyl radicals, which then oxidize these substances. Control of algae Ozone is effective in the destruction of algae in water treatment systems. The algae are a nuisance organism in water treatment plants, tending to impair the efficiency of treatment. Removal of cyanobacterial toxins Toxic cyanobacteria in regions, which have had blooms of these organisms in their water supply, pose a significant health risk. Break-point chlorination is typically used as a pre-oxidant in water treatment for the destruction of algal toxins. The use of chlorine in a pre-oxidation step has the disadvantage
36

of causing high THM and other chlorinated byproducts. Ozone has been found to be particularly effective in destroying the peptide hepatotoxin Mycrocystin-LR which is produced by Microcystis cyanobacteria which frequent eutrophic waters. It also apparently destroys cylindrospermopsin, a toxin from Cylindrospermopsis. Color removal Color removal is achieved by oxidation of the responsible organic molecules. The color is mainly caused by light absorption on conjugated bonds. These bonds are easily oxidized by ozone resulting in the disappearance of color. Microflocculation Pre-ozonation has a micro-flocculant effect at levels of approximately 0.5 to 2 mg/L. It assists in the removal of particles in the 1 to 60 m size range. The microflocculation is caused by particle destabilization and is dependant on the carbonate content of the water and the organic content. Improved filter run lengths, and reduced coagulation demand are the benefits of microflocculation. Reduction in the required doses of coagulant and flocculant has been observed in Queensland coastal waters. A further subsequent benefit of microflocculation is a reduced production of sludge, reducing the load on clarifiers and potentially opening the door to direct filtration. Improved biodegradability The oxidation of organics in water by ozone will convert many non-biodegradable organic molecules into a more biodegradable form. If followed by some type of biological process this will result in a decrease in the total organic carbon (TOC) of the water. Care must be taken to remove the now biodegradable organics. Ozone biodegradation will result in an increase in BOD without having changed the TOC of the water. If provision for biodegradation (e.g. biological activated carbon, or biofiltration), ozonation is a benefit to the removal of organics. Without this provision ozonation can be a liability with respect to promoting biological regrowth within the distribution system.

4.10 OTHER APPLICATIONS OF OZONATION IN THE WATER FIELD The most important applications of ozone in wastewater treatment are disinfection and sludge bulking control. Tertiary treatment of wastewater is closely related and similar to potable water treatment. Other uses of ozone include cooling water treatment, swimming pool disinfection, advanced oxidation, biological growth enhancement and industrial applications. Wastewater disinfection Wastewater discharges in many countries including Australia have a maximum discharge standard for fecal coliform or heterotrophic plate count bacteria (HPC). In disinfection of wastewater where discharge is direct to surface water residual disinfectants should be viewed as contaminants due to their environmental toxicity. Ozone forms no residual, making it ideal for wastewater disinfection particularly where the water is to be released to the environment. Systems for wastewater disinfection are similar to those for potable water disinfection. Care should be exercised when using ozone in wastewater treatment as BOD 5 can be increased. This can create problems with achieving discharge requirements unless taken into
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account during the design of wastewater treatment systems. Sludge bulking control Filamentous bacteria cause foaming and sludge bulking which occur in most activated sludge plants around the world, severely affecting solids separation. Ozone is used to destroy the exposed ends of filamentous bacteria in flocs which assists in settlement. The advantage of ozone over disinfectants with a residual is that the ozone will destroy filamentous bacteria projecting from the floc without penetrating which would destroy all bacteria within the floc. High doses of residual disinfectants such as chlorine can penetrate the floc destroying bacteria inside the floc. There are three locations at which ozone can be applied to reduce bulking problems. The most effective location is within the activated sludge reactor itself as close to the effluent exit point as possible. Ozone can also be applied between the reactor and the settler or in the sludge return lines, though this is the least effective application point. Figure 4.16 shows an ozonation system that incorporates sludge bulking control. The Daspoort Sewage Treatment plant, in the heart of the capital Pretoria, employs three parallel nutrient removal activated sludge plants, each of 13ML/d capacity. An ozonation system, capable of dosing 2kg/h of ozone into one of the plants, was tested in an effort to ameliorate sludge bulking. Ozone was introduced through a number of porous diffusors directly into the final aerobic stage. Although bulking was reduced to some extent, it did not make a huge difference as compared with chlorine, which was also trialed. It did effectively combat foaming and it did not interfere with the sensitive nitrifiers and phosphate removal as chlorine did (Saayman, Schutte and van Leeuwen, 1996).
Ozone recycle for bulking control

Waste Water

Activated sludge

Ozone Disinfection

Discharge

Ozone Sludge recycle

Sludge disposal

Figure 4.16 Ozone use for sludge bulking control

Water Reclamation The aim of water reclamation is to reuse water from treated sewage effluent for another purpose. Some applications such as irrigation or industrial reuse require a single disinfectant to ensure that human contact with the water is safe from pathogenic contamination, whereas
38

uses such as garden watering and drinking water require multiple barriers to infection. The benefit of ozone in multiple barrier water reuse systems is that ozone works to disinfect water by a considerably different route to chlorine disinfectants. Changing conditions that make one of the disinfectants less effective will often not affect the efficiency of the other. Different disinfectants have slightly different effectiveness on particular organisms. Thus an organism that is resistant to chlorine disinfection is often susceptible to ozone disinfection. Finally if one system breaks the other is able to continue to form a barrier to pathogens. The first use of ozone in the treatment of water coincided with the first use of chlorine for disinfection, until recently ozonation was a common practice in only a small number of countries, notably France and Switzerland. It has become much more popular recently and is now in use in about 3000 drinking water and waste water treatment plants all over the world. The first Australian plant to use ozone in drinking water: a military plant at Jervis Bay of 4 ML/d. Armidale City Council is investigating the use of ozone together with biological activated carbon and UNE students under my supervision ozonation with slow sand filtration. Plants using ozonation have been designed for one of the Great Barrier Reef island resorts and for a Townsville supply. Caboolture Shire has a 10 ML/d advanced wastewater treatment plant involving ozonation. The US is rapidly developing more ozone installations in both drinking water and advanced wastewater treatment. Biological Activated Carbon This process is used in swimming pool water treatment, potable water purification and in wastewater treatment. Ozone is applied to water after which enough time is allowed for the decomposition of the ozone before passing the water through a column of granular activated carbon (GAC). The use of ozone prior to GAC increases the removal of dissolved organic carbon (DOC) under due to the increase in the biodegradability of organic matter caused by oxidation. Microorganisms that have colonized the GAC bed are able to utilize the biodegradable organics as a carbon source. Oxidation of organics also causes a reduction of the adsorbability of organics on GAC due to the increased polarity of the oxidized substances. The overall effect of pre-ozonation on removal of organics on GAC is to increase the efficiency of removal and to increase GAC run lengths. Cooling Water Treatment Ozone is used as an effective disinfectant for high recirculation cooling water systems such as air conditioning. If the time taken to recirculate water through the entire cooling system is greater than about 10 minutes, the ozone residual will decay too much to continue disinfecting properly and some bacterial mass may form in regions distant from the point of ozone generation. In most instances it will not cause corrosion problems, however it can be aggressive to elastomers, metal and wood. Corrosion is normally driven by water chemistry particularly carbonate saturation level which far overrides any concern about ozone. An ozone demand will be exerted by reducing agents present in the water.

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High water temperatures can quickly deactivate ozone and temperatures below 30 C are recommended. Cooling towers can strip ozone from the water during atmospheric exposure. Swimming Pool and Spa Water Treatment Swimming pool disinfection by ozone has become a very important application of ozone. The objectives of swimming pool disinfection are primarily to remove pathogenic organisms, secondarily to reduce odors, color and irritation of swimmers. The tertiary aim is to the aggressivity and corrosivity of the water. These objectives relate to all activities where the body comes in contract with the water such as spas and water slides. There are several problems with the use of chlorine. The dose required for disinfection can be quite high to overcome contaminants from the human body and the environment. This results in tastes, odors, irritation, chlorinated byproducts and corrosivity. Ozone can be used to overcome this problem either by using it in conjunction with chlorine or as a sole treatment. When ozone is used prior to chlorination many of the impurities are partially oxidized which reduces the chlorine demand. Chlorine is then only required for the residual disinfection which considerably reduces the problems with chlorination. Ozone should only be used as the sole disinfectant when the pool hydraulics are very good having no dead spots and excellent circulation. The ozone residual must be low enough that the amount of ozone in the air above the pool is minimized. Ozonated Ice One very interesting application of ozone that has recently been suggested is the use of ozonated ice for the preservation of fish. The ozone in the frozen water appears to be unusually stable. As the ice freezes the ozone acts to disinfect the fish maintaining a high quality of the caught product for the pelagic fishing industry. Industrial Applications Ozone is being used in a small number of pulp and paper plants around the world as a means of reducing the requirement for chlorine bleaching, and hence the toxicity of effluents. Caution should be exercised as too high an application can result in the weakening of the final product. There are a number of other applications of ozone in industry other than waste treatment. Some of the largest ozone installations in the world are for chemical production purposes, mainly chemical production in which ozonolysis plays an important role. Ozone could also be used to oxidize cyanides and thiocyanates, both occurring in high concentrations in coke oven wastewaters. These substances are more economically removed by biological treatment, but at concentrations of hundreds mg/L these substances become toxic to the biological process. Ozone is a good candidate for removing these substances.

Mining Service Water Treatment

40

A pilot plant investigation into mine service water treatment with ozonation was carried out on 4 ML/d scale at Kloof Gold Mine. Although this was not a potable treatment situation, the aim was still to achieve disinfection as underground workers drink the water. It was found that ozonation was highly suitable and economical in a situation where high nitrite and ammonia levels were encountered due to the use of explosives (Jooste and van Leeuwen, 1994). Tests were also performed to compare the efficiency of deep well (55m), bubble column and injector with static mixer systems. The transfer efficiencies for each system were 96%, 80-90% and 73-80% at dosages of about 7 mg/L, respectively (Van Leeuwen and van der Westhuizen, 1992). The expense of the units range from most to least expensive and choice would be dictated by that and the expense Advanced oxidation Advanced oxidation refers to systems of oxidation whose purpose is to produce the maximum number of hydroxyl radicals. There are several advanced oxidation systems that use ozone, shown in Table 4.12. Advanced oxidation has been found very effective at destroying a range of organic contaminants in water including petrochemicals and pesticides.
Advanced oxidation systems Ozonated water with ultra violet irradiation Ozone with hydrogen peroxide (PEROXONE) Ozone at a pH greater than 8.5 Ozonation in the presence of titanium dioxide * Ozonated water plus ultrasound. * Or any other suitable catalyst O3 + h O3 + H2O2 O3 @ pH>8.5 O3 + TiO2 O3 + ultrasound

Table 4.12 Advanced oxidation systems utilizing ozone

Hazardous Waste Treatment Ozonation and/or advanced oxidation have a wide range of applications in the treatment of wastewater, particularly those containing hazardous organic compounds. It will destroy phenol, cyanide and some organic lead compounds and degrades many herbicides. Two examples of ozone use in hazardous waste treatment are cyanide treatment and phenol ring rupture.

Cyanide treatment The method used for cyanide oxidation by chlorine shown in the following reactions;

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NaCN + Cl2 at alkaline pH CNCl + 2NaOH 2NaCNO + 4NaOH + 3Cl2

CNCl + NaCl NaCNO + NaCl + H2O 6 NaCl + 2CO2 + N2 + 2H2O

pH control is very important in this system as if the pH drops the deadly gas CNOCl is formed. By contrast the ozone system for cyanide oxidation is very simple with no risk of the production of CNOCl; O3 + CN CNO- + O2

or if additional ozone is applied O3 + CN CO2 + N2 + O2

Thiocyanate is also amenable to ozone oxidation. This was established in 1999 by Badriyha and van Leeuwen results yet to be published.

4.11 ISSUES IN EQUIPMENT SELECTION AND DESIGN

No system should ever be designed without bench scale and/or pilot plant testing. Air preparation * Noisy components of the system such as compressors and blowers should be housed separately to other components of the system in order to improve operator comfort. * Gas should be filtered prior to entering a corona discharge unit whether it comes from an ambient air or high purity oxygen feed. Plants with carbon steel carrying high purity oxygen to the generator have often had to install 3 micron filters in the supply line to prevent oxidized metal particles being carried into the corona discharge units. * Continuous dew point monitoring with automatic plant shutdown should be incorporated. Ozone generation * Cooling of corona discharge units can be problematic particularly with air cooled units. With dual cooled (water and oil or freon) very high quality cooling water is needed for the heat exchangers which can cause operational difficulty. Cooling systems should be conservatively designed to avoid unforeseen cooling problems, particularly at annual periods of high temperature and humidity. * Accurate determination of design capacity to avoid prolonged operation of the generators at their maximum design capacity. * There are a range of corona discharge systems available on the market at present. International experience suggests that horizontal, water cooled, low to medium frequency (60-900 Hz) units are the most reliable. Gas treatment
42

* Fine bubble diffusers submerged 5m with 2 or more countercurrent stages should be used for gas contacting. * Off gas demisters and foam control systems should be conservatively designed with a backup unit, view ports, flow indicators, and alarms for continuous monitoring. In wastewater treatment plants foam suppression may be necessary in the contacting chambers prior to off-gas treatment. Foam carryover can cause oxygen fires or catalyst overheating in the off-gas treatment. * Catalytic ozone destruction equipment should have a backup system, inspection ports, and drains. Other Considerations * Gas piping should be stainless steel with welded connections and appropriate pressure rating. Some plants have replaced unplasticized polyvinyl chloride (UPVC) pipe with stainless steel to convey ozonated gas to contacting units after problems with pipe failure. * All meters, valves and other control systems including seating, facing and gaskets should be selected on the basis of proven performance with ozone. * Ozone dosing system should be based on easily measured parameters. Closed loop control based on contactor off-gas ozone concentration has proven reliable.

4.12 CAPITAL COSTS OF OZONE TREATMENT

The cost of an ozone treatment plant is difficult to estimate. Cost will depend on;
1. The amount of ozone which needs to be applied: UV is much cheaper than Corona discharge Air as a feed gas is much cheaper than oxygen, though to achieve a given ozone dose larger generators are required for the for air than oxygen. The type of contact system selected: Static mixing is extremely cheap and deep U-tubes expensive Whether the ozone needs to be destroyed after contacting The need for additional pumps for pre-ozonation Instrumentation requirements. Instrumentation can typically add between 50 and 100% to the cost of a treatment plant.

2. 3. 4. 5.

The prices in Table 4.13 were kindly provided in 1995 by several Australian firms which sell ozonation equipment. The prices used here were the cheapest possible to provide the required plant size without considering instrumentation requirements.
kgO3/hr 0.03 O2 Preparation $ 3,000 - 9,600 (6,000) Air preparation $ 2,000 - 5,000 (3,500) O3 Generation $ 15,000 - 56,000 (27,000) Contacting $ 2,000 - 5,000 (3,500)

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0.3

16,500 - 60,000 (38,000) 42,500 - 210,000 (126,000) up to 1,200,000 up to 7,200,000

10,000 - 15,000 (12,500) approx 28,000

65,000 - 100,000 (88,000) 300,000 - 425,000 (360,000) approx 1,600,000 approx 12,600,000

5,000 - 8,000 (6,500) approx 36,000

30 300

N/A N/A

approx 160,000 approx 1,250,000

Table 4.13 The cost of ozonation equipment A list of suppliers of ozone equipment is beyond the scope of this course, but could be obtained from the International Ozone Association, Australian Chapter, in Sydney. Water Reclamation The pioneer investigator on ozonation in water reclamation has been Schutte (1969), who investigated disinfection, but mainly its usefulness in removing organic compounds, with or without activated carbon, typified as COD, ABS and color. Ozonation has also been studied on the Stander Water Reclamation Plant in Pretoria, where its main usefulness was found to be enhancing biological removal of residual organic material on granular activated carbon, leading to a greatly extended life of the activated carbon (Van Leeuwen,1979). This work has finally found application in the extension of the Gammams Water Reclamation Plant in Windhoek, where ozonation will play an important role in the new 21ML/d plant supplying the capital of Namibia with part of its water requirements (Burmeister et al., 1992). Ozonation adds yet another safety barrier towards achieving disinfection and detoxification. A further application of this research was the 10ML/d South Caboolture Water Reclamation Plant north of Brisbane, Queensland, Australia.

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Fair, G.M. J C Geyer & D A Okun (1968). Water and Wastewater Engineering, Volume 2: Water purification and wastewater treatment and disposal. John Wiley & Sons, Inc., New York, USA. Glaze, W.H. (1987) Drinking Water Treatment With Ozone. Environmental Science & Technology, 21(3), 224. Grasso, D. (1987) Ozonation of Drinking Water: A Design Methodology I. Background and Design Rationale. Ozone Science and Engineering, 9, pp 109-124. Haas, C N (1990). Disinfection. In : Water Quality and Treatment . Pontius F W (Edit). American Water Works Association. 4th Edit. McGraw-Hill. Hart, F L (1979). Improved hydraulic performance of chlorine contact chambers. Journal WPCF, Vol 51, No 12, pp 2868-2875. Haung, J Y C, R Warriner & N S N Ni (1985). Pilot tests of chlorination facility for disinfecting secondary effluent. Journal WPCF, Vol 57, No 7, pp 777-784. Harnby, N, M F Edwards & A W Nienow (1992). Mixing in the Process Industry. Butterworth/Heinemann. Hiisvirta, L O (1993). Disinfection and disinfection by-products. International Report. 19th International Water Supply Congress and Exhibition. Budapest, Hungary 2-8 October. Jacangelo, J G, N L Patania, K M Reagan, E M Aieta, S W Krasner & M J McGuire (1989). Ozonation: Assessing its role in the formation and control of disinfection by-products. Journal AWWA. August, Vol 81 No 8 pp 74-84. Jolley, R L, H Gorchev & D H Hamilton. (Edit) (1977). Water chlorination - Environmental impact and health effects. Vol 2. Proc 2nd Conf on the Environmental impact of water chlorination, Gatlinburg, Tennessee, Oct 31 - Nov 4. Jooste, S H J and van Leeuwen, J (1994) Oxidation of Nitrites in Mine Waters, Ozone Sci & Engng 16(3) 261 Krasner, S W, M J McGuire, J Jacangelo, N L Patania, K M Reagan & E M Aieta (1989). The occurrence of disinfection by-products in U S drinking water. Journal AWWA, Vol 81 No 8 pp 41-53. Kruithof, J C, R C van der Leer & W A M Hijnen (1992). Practical experience with U V disinfection in the Netherlands. J. Water SRT - Aqua, Vol 41, No 2, pp 88-94. Kruithof, J C & R T Meijers (1993). Bromate formation by ozonation and advanced oxidation and potential treatment options in drinking water treatment. Disinfection of potable water. International Specialized Conference IWSA. Kruger National Park, South Africa 13-18 March 1994. Longley, K E & B Roberts (1982). Drinking water disinfectant. Water engineering and management Reference handbook No 31, pp 26, 28-30. Louie, D S & M S Fohrman (1968). Hydraulic model studies of chlorine mixing and contact chambers. Journal WPCF, Vol 40, No 2, Part 1, pp 174-184. Lykins, B W, J A Goodrich & J C Hoff (1990). Concerns with using chlorine-dioxide disinfection in the U S A. J Water SRT - Aqua. Vol 39, No 6, pp 376-386. Lykins, B W, K M Schenk, W E Koffskey & M H Griese (1992). Chemical, micro-biological, and mutagenic effects of using alternative disinfectants for drinking water treatment. 42nd Environmental Engineering Conference. Risk Reduction Engineering Laboratory, Office of Research and Development, U S Environmental Protection Agency, Cincinnati, OHIO 45268. Marske, D M & J D Boyle (1973). Chlorine contact chamber design - a field evaluation. Water & Sewage Works. January, pp 70-77. Masschelein, W J (1992). Unit Processes in Drinking Water Treatment. Marcel Dekker, New York. Metcalf & Eddy (1979). Wastewater engineering : Treatment, disposal, re-use. McGraw-Hill. Neden, D G, R J Jones, J R Smith, G J Kirmeyer, & F W Foust (1992). Comparing chlorination and chlorimination for controlling bacterial regrowth. Journal AWWA, Vol 84, No 7, pp 80-88. National Health and Medical Research Council (1994). Australian Drinking Water Guidelines - Draft. Pelczar, M J, E C S Chan & N R Krieg (1986). Microbiology. (5th Edit) McGraw-Hill. Pieterse, M J (1988). The potential health risk of trihalomethanes in drinking water: a perspective. South African Journal of Science. Vol 84, pp 166-170. Pieterse, M J (1989). Drinking-water quality criteria with special reference to the South African experience. Water SA, Vol 15, No 3, pp 169-178. Potapchenko, N G & O S Savluk (1991). Use of ultraviolet radiation in the practice of disinfection of water. Soviet Journal of Water Chemistry and Technology, Vol 13, No 12, pp 78-93. Quasim, S R (1985). Wastewater Treatment Plants : Planning, design and operation. Holt, Rineholt and Winston. Rice, R.G. & Netzer, A. (1982) Handbook of Ozone Technology and Applications. Butterworths ltd.

Robson, C.M., & Rice, R.G. (1990) Wastewater Ozonation in the U.S.A. - History and Current Status. Ozone Science and Engineering, vol 12, no 6, pp23-40.
Rogers, S E & W C Lauer (1986). Disinfection for potable re-use. Journal WPCF, Vol 58, No 3, pp 193-198 . Rook, J J (1974). Formation of haloforms during chlorination of natural waters. J. Wat. Treat. Exam, Vol 23, pp 234-243. Rubin, A J, J P Engel, & O J Sproul (1983). Disinfection of amoebic cysts in water with free chlorine. Journal 45

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WPCF, Vol 55, No 9, pp 1174-1182. Saayman,G B, Schutte C F and van Leeuwen (1996) Full-scale bulking control with ozonation. Proc Ozone Down Under (February) IOA and submitted to Ozone Science and Engineering. Schulz, C R & D A Okun (1984). Surface Water Treatment for Communities in Developing Countries . John Wiley & Sons, New York. Schutte, CF (1969) Studie van osonering teenoor chlorering in die gevorderde suiwering van rioolwater vir hergebruik. Msc (Ind. Chem.) thesis, University of Potchefstroom. Sepp, E (1981). Optimization of chlorine disinfection effiency. Journal of the environmental engineering division ASCE, Vol 107, No 1, pp 139-153. Severin, B F, M T Suidan & R S Engelbrecht (1984). Series-event kinetic model for chemical disinfection. Journal of environmental engineering division, (ASCE) Vol 110, No 2, p430-. Stevens, A A, C J Slocum, D R Seeger & G G Robeck (1976). Chlorination of organics in drinking water. Journal AWWA, Vol 68, No 11, pp 615-620. Teefy, S M & P C Singer (1990). Performance and analysis of tracer tests to determine compliance of a disinfection scheme with the SWTR. Journal AWWA, Vol 82, No 12, p88-98. Tetlow, J A & C R Hayes (1988). Chlorination and drinking water quality - an operational overview. J IWEM, Vol 2, No 4, pp 411-416. Tikhe, M L (1976). Optimal design of chlorination systems. Journal of the environmental engineering division ASCE, Vol 102, No 5, pp 1019-1028. Trussell, R R & J L Chao (1977). Rational design of chlorine contact facilities. Journal WPCF, Vol 49, No 4, pp 659-667. USAID (1992). Disinfection for rural community water supply systems in developing countries. U S Agency for International Development. 1611 Kent Street, Room 1001, Arlington, Virginia 22209-2111, USA. USEPA (1989). Guidance manual for compliance with the filtration and disinfection requirements for public water systems using surface water sources . (March 31). Van der Kooij, D (1992). Assimilable organic carbon as an indication of bacterial regrowth. Journal AWWA. Vol 84, No 2, pp 57-65. Van Leeuwen, J (1979). The design and application of a packed column ozone absorber in water reclamation. Ozone Sci & Engng, Vol 2, No 3, pp283-298. Van Leeuwen, J and van der Westhuizen (1992). Ozonation for reuse of gold mine service water. Water Sci. & Tech Vol 26, No 7/8, pp 1465-1474. Van Leeuwen, H. (1993) Ozonation: A Perspective on its Merits in Water and Wastewater Treatment. Disinfection '93, symposium proceedings, Griffith University, Queensland, sept 28-29. pp59-72. Von Huben, H (1991) Surface Water Treatment: The New Rules, American Water Works Association. Water Research Centre (1989). Disinfection of Rural and Small-community Water Supplies . A manual for design and operation. WRC, Medmenham, Buckinghamshire, England. White, G C (1992). The Handbook of Chlorination and Alternative Disinfectants. Third Edit. Van Nostrand Reinhold, New York. Wondergem, E & A M van Dijk-Looijaard (1991). Chlorine dioxide as a post-disinfectant for Dutch drinking water. The Science of the Total Environment , Vol 102, pp 101-112.

Attachment
Cryptosporidium What is it?
Cryptosporidium is from the protozoan genera in the phylum Apicomplexa. It is found in the stools of infected warm-blooded animals and sometimes in humans. Figure 1 shows Cryptosporidium oocysts in the human intestine. An oocyst is a dormant form of the organism about two to six microns in diameter.

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Figure 1. Cryptosporidium oocysts in the human intestine

Cryptosporidium is commonly found in rivers, lakes and streams contaminated with animal faeces or which receive wastewater from sewage treatment plants. Cattle, especially calves, seem to be a major source of Cryptosporidium. These rivers, lakes and streams often drain into a municipals water supply. The treatment plant then has the hard task of removing these oocysts from the drinking water. 1955 1971 1976 1982 1982 1993 Cryptosporidium meleagridis was discovered and it was found to be associated with illness and death in young turkeys. Cryptosporidium was found to be associated with bovine diarrhoea (Panciera et. al. 1971). Cryptosporidiosis was first identified in humans. Twenty one males from six large cities in the U.S. had sever diarrhoea caused by Cryptosporidium in association with Acquired Immune Deficiency Syndrome (AIDS The above outbreak increased the worldwide interest in Cryptosporidium. A massive waterborne outbreak occurred in Milwaukee. This outbreak involved approximately 403,000 persons and killed over 100 people. These fatalities further prompted an increase in research into the protozoan including the development of methods for recovery, detection, prevention and treatment. 1994 Forty three people were infected and killed in Las Vegas, Nevada. Continued outbreaks across the world. 1994 onwards

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