STATE-OF-THE-ART REVIEW

Ozonation of Municipal Wastewater Efuents

Panagiota Paraskeva, Nigel J. D. Graham

ABSTRACT: The increasing use of ozone in the treatment of municipal wastewater efuents has been stimulated by the need to achieve higher efuent quality and greater compliance with physicochemical and microbiological quality standards before discharge. These standards are applied when the efuent may pose a risk to the public through direct contact and where the efuent is used for agricultural purposes or water reclamation. Although various alternative technologies exist for upgrading wastewater efuents, ozone treatment may be the most appropriate approach in particular cases. This review summarizes the current status of the use of ozone for treating municipal efuents with respect to disinfection efciency, its effect on the treatability of the efuent and on aggregate efuent parameters, the potential for the formation of ozonation byproducts, and its effect on the toxicity and mutagenicity of the efuent. The importance of treatment conditions (e.g., contact time) is also reviewed. Water Environ. Res., 74, 569 (2002). KEYWORDS: wastewater, efuent, municipal, treatment, disinfection, ozone, oxidation, byproducts, toxicity.

Introduction Ozone (O3) is a highly reactive chemical with a high oxidation reduction potential (EH , 1998). Its use in 0 ) of 2.07 V (Hoigne aqueous conditions usually leads to the simultaneous production of secondary oxidants, such as radical species (OH), whose oxidation power is much greater than molecular ozone (Hoigne and Bader, 1985). This factor, taken with the absence of any halogen constituent, has made ozone a valuable chemical in water and wastewater treatment. The primary eld of ozone application is the water industry, although ozone is increasingly being applied to solving gaseous and liquid problems in other industries (e.g., textiles, paper and pulp, and cooling waters), and in medical therapy. In water treatment, ozone can be used in various steps of the treatment process to enhance biological processes and microocculation, iron and manganese removal, degradation of pesticides and other micropollutants, and taste and odor removal. Ozone is particularly benecial for the disinfection of potable water because it is effective against both bacteria and viruses and can also remove cysts and eggs (Anderson, 1997; Langlais et al., 1991; Rice and Netzer, 1984); currently, there is considerable interest in its effectiveness against the Cryptosporidium parvum cyst, in particular. Camel and Bermond (1998) recently completed an extensive review of the use of ozone in drinking water.
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In the context of wastewater treatment, the high reactivity of ozone makes it appropriate for achieving certain objectives when applied either alone or in combination with other processes (e.g., ltration). These objectives relate to either the need to achieve higher quality standards prior to nal discharge or to meeting standards for efuent recycling. Specically, the objectives may include color removal, disinfection, the degradation of organic micropollutants, the conversion of hard chemical oxygen demand (COD), and efuent oxygenation. The heterogenous nature of municipal wastewaters and the economic limitation of ozone application make it unlikely that organic substrates can be completely degraded (to carbon dioxide and water) by ozone treatment. This has led to concern over the presence of intermediate byproduct compounds that may be of toxicological signicance. Many studies have been conducted concerning the reactivity of ozone and its secondary oxidants with a wide range of inorganic and organic substances. Details of these studies, including rate constants, can be found in recent reviews in the literature (Hoigne , 1998). Similarly, the reactivity of ozone with humic substances has received considerable attention in recent years because such substances are found in all kinds of natural and polluted waters and are known to inuence ozone decomposition and the presence of secondary radicals. Ozone causes substantial structural changes to humic substances such as a strong and rapid decrease in color and UV-absorbance resulting from a loss of aromaticity and depolymerization; a small reduction in total organic carbon (TOC) (e.g., 10% at 1 mg O3/mg C); a slight decrease in the high apparent molecular weight fractions and a slight increase in the smaller fractions; a signicant increase of the carboxylic functions; and the formation of ozonation byproducts. These byproducts are mainly aldehydes (formaldehyde, acetaldehyde, glyoxal, and methylglyoxal) and carboxylic acids (formic, acetic, glyoxylic, pyruvic, and ketomalonic acids) (Camel and Bermond, 1998). In addition, the results available to date indicate that the ozonation of humic substances tends to increase their biodegradability, although directly quantifying the extent of this increase is difcult because of the variety of methods used to measure biodegradability. Some of these studies have been described by Langlais et al. (1991) and others. This review summarizes the current status of the use of ozone
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Table 1Microbiological standards for designated bathing areas in the European Union (CEC, 1976).
Guideline value (G) (80th percentile) Mandatory value (I) (95th percentile)

Microorganism Total coliforms (count/100 mL) Fecal coliforms (count/100 mL) Fecal streptococci (count/100 mL) Salmonella (count/L) Enteroviruses (plaque forming units/10 L)

500 100 100

10 000 2000 0 0

for treating municipal efuents with respect to disinfection efciency, its effect on the treatability of the efuent and on aggregate efuent parameters, the potential for the formation of ozonation byproducts, the effect of ozone on the toxicity and mutagenicity of the efuent, and the inuence of the ozone-contacting conditions on performance. Disinfection of Municipal Efuents In municipal wastewater treatment, ozone has been used primarily for efuent disinfection. Generally, the need for efuent disinfection has arisen through the enactment of legislation that has dened specic microbiological standards for efuent discharge quality. These standards not only vary with the specic country or region of application, but they also depend on whether the efuent is to be discharged to a sensitive waterbody or used for agricultural or reuse purposes. Within countries of the European Union (EU), current legislation concerning efuent discharge to receiving waters involves the EU bathing waters directive (CEC, 1976), which sets microbiological and physicochemical standards for inland and coastal waters designated as bathing areas (Table 1). Individual efuent limits are, therefore, set by local regulatory bodies to comply with these standards. In the United States, the California requirements for total coliforms are 1000/100 mL (80th percentile) for coastal bathing waters (equivalent to a median of 230/100 mL), 70/100 mL (median) for shellsh growing areas, and 23/100 mL (median) for conned waters used for bathing or recreation (White, 1999). A common efuent discharge standard in the United States is 200 fecal coliforms/100 mL (Rice, 1997). For efuent reuse, the World Health Organization (WHO) guidelines on efuent quality (WHO, 1989) dene a maximum value of 1000 fecal coliforms/100 mL of efuent (on a geometric mean basis)

and less than 1 viable intestinal nematode egg/L (on an arithmetic mean basis) for unrestricted agricultural reuse. In the United States, specic criteria for efuent quality for wastewater reclamation and reuse are set by individual states. However, the California Title 22 regulations (State of California, 1978) are recognized as being particularly comprehensive and, as such, have been adopted by some European countries (Liberti and Nortanicola, 1999). The California regulations require physicochemical treatment and disinfection to achieve a limit of 2.2 total coliforms/100 mL (median) and a 5-log removal of virus. Although ozone is approved for short-term eld trials only in the United Kingdom, in other countries ozone has been applied to wastewater efuents primarily for disinfection. Ozonation has also been used for COD polishing (i.e., lowering of residual concentrations) and enrichment of efuent with oxygen. In the United States, the rst ozonation plant for the disinfection of municipal efuent was built in 1975. Since then, at least 45 ozone plants have been built. However, in recent years the number of plants has declined because legislation has changed and, in most cases, disinfection is no longer required (Robson and Rice, 1991). There are two operational ozone plants in Canada (Larocque, 1999) and several in Korea. There are approximately 200 ozonation units in Japan treating wastewater efuent and approximately 400 units treating night soil wastewater efuent (Matsumoto and Watanabe, 1999). In Europe, there are two major ozone plants in France and 134 plants in Germany treating municipal wastewater efuent and exhaust air. The use of ozonation for the disinfection of efuents before agricultural use is also increasing in southern Europe (Bo hme, 1999; Le Pauloue and Langlais, 1999; Liberti et al., 1999). In the United Kingdom, there is currently one wastewater treatment plant treating its secondary efuent with ozone for color removal (Churchley and Upton, 1997). Ozone has been found to be very effective at inactivating a wide range of microorganisms. The mechanism of bacterial inactivation by ozone is thought to occur by general inactivation of the whole cell. Thus, ozone causes damage to the cell membrane, to the nucleic acids, and to certain enzymes. Ozone is particularly effective against viruses, where its use can achieve the highest standards (Tyrrell et al., 1995). The mechanism of viral inactivation involves coagulation of the protein and oxidation of the nucleobases forming the nucleic acid. Protozoan cysts, specically Giardia and Cryptosporidium, and bacterial spores are more resistant to ozone than bacteria and viruses, although moderate degrees of inactivation (Table 2) have been demonstrated under realistic ozonation conditions (Owens et al., 2000). It has been reported that microorganism reactivation after ozonation is unlikely to occur (CES, 1988; U.S. EPA, 1986), and Lazarova et al. (1998) did not observe any measurable regrowth of Escherichia coli in seawater after

Table 2Inactivation of microorganisms by pilot-scale ozonation (Owens et al., 2000).

Microorganism Bacillus subtilis endospores Cryptosporidium parvum oocysts Cryptosporidium muris oocysts Giardia muris oocysts Poliovirus 1
a

Temperature (C) 22.7 1.0 24.5 1.6 23.6 1.6 25.2 1.1 25.0 1.0

pH 7.93 0.32 8.24 0.20 8.40 0.11 7.57 0.29 8.05 0.17

CTa (mgmin/L) 0.7018.35 2.557.15 0.9810.7 0.281.04 0.192.49

Log inactivation range 02.17 0.572.67 0.362.56 1.522.70 1.433.85

Concentration time (CT) product, based on integrated dissolved ozone concentration values (C) and theoretical residence time (t). Water Environment Research, Volume 74, Number 6

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Figure 1Reduction of fecal coliforms with transferred ozone dose for different treated efuents (and contact times): Evry, Francesecondary; Washington, U.K.secondary; Indianapolis, Indianatertiary (Janex et al., 1999).

ozonation. A more complete summary of the specic mechanisms of microbial inactivation can be found in Langlais et al. (1991). As a disinfection method for wastewater efuents, ozone is applied mainly to secondary-or tertiary-treated efuents because the ozone demand of primary or raw efuents is so large that it makes the use of ozone not cost- and energy-effective. The effectiveness of disinfection depends on the ozone dose, the quality of the efuent, the ozone demand, and the transfer efciency of the ozone system. An example of the dependence of disinfection on ozone dose and the nature of the efuent is shown in Figure 1. The disinfection dose (i.e., the dose of ozone that achieves certain microbiological standards in a municipal efuent) is expressed as the transferred (or absorbed) mass of ozone per liter of efuent in milligrams per liter. Another form of characterization for disinfection conditions is the C t product, where C is the concentration of dissolved (residual) ozone measured at the outlet of the contact chamber (in milligrams per liter) and t is the contact time between the residual of ozone and water (in minutes). However, this characterization may not be appropriate for efuent disinfection because signicant bacterial inactivation can be achieved (e.g., 2 or 3 logs) prior to an ozone residual appearing (Absi et al., 1993; Janex et al., 2000; Paraskeva and Graham, 1999). The physicochemical quality of the efuent is particularly inuential in determining the effectiveness of disinfection and the ozone dose required to achieve a specied performance. The organic content of the efuent, as expressed by COD and total suspended solids (TSS), is commonly used as an indicator of the ozone dose required for disinfection of secondary efuents (unltered) and the likely overall performance (Table 3). Attempts have been made to establish empirical relationships or formulas to predict the total or
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fecal coliform inactivation by ozonation in terms of the organic and inorganic species, such as COD, TSS, and nitrite-nitrogen (NO2-N). Absi et al. (1993) found a close linear relationship (correlation coefcient 0.95) between the logarithm of fecal coliform survival (counts remaining/initial counts) and the inuent COD for a chemically assisted primary wastewater, although this was for a very narrow ozone dose range (8 to 10 mg/L). White (1999) summarized mathematical expressions developed by Venosa et al. (1979), the following of which are those for unltered secondary efuent: Total coliforms: log10 TC 0.96 log10 TCI 0.89 0.012 TCOD 0.60 NO2-N 0.013 TSS 4.024 log10 T 0.57R1/2 (1)

Table 3Transferred ozone doses for secondary efuents corresponding to a 2-log reduction in fecal coliforms (Janex et al., 2000).
Efuent location Evry, France COD (mg O2/L) TSS (mg/L) Transferred O3 dose (mg/L) 40 15 47 68 Washington, U.K. 80 15 1035 812 Buenos Aires, Argentina 140 30 4060 817

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Table 4 Previous ozone-disinfection studies involving indicator bacteria.

Type of efuent Secondary Disinfection O3 dose (mg/L) 714 Contact time (min) 5 Residual ozone (mg/L) 0.05 Type of microorganisma FC FS TC TC Initial concentration (CFU/100 mL) 5.2 1038.5 105 0.7 1035.0 103 4.0 1059.0 106 2.4 1059.3 106 2.43.7 106 0.24.0 105 n/a n/a 0.11.0 107 Final concentration (CFU/100 mL) 0.32 1028.0 102 0 1.3 102 0.1 2.6 103 9.3 1021.5 104 0.11.0 104 3.67.0 102 n/a n/a 0.11.0 103 Log reduction

Source Nebel et al., 1973 Legeron and Girardin, 1981 Joret et al., 1982 Langlais, 1983 FressonnetChambarlhac et al., 1983 Rakness et al., 1984 Legube et al., 1987 Finch and Smith, 1989 Greene and Stenstrom, 1994 Rice, 1997 Rice, 1997 Liberti and Notarnicola, 1999 Liberti and Notarnicola, 1999 Paraskeva and Graham, 1999 Janex et al., 1999

Secondary

814

21

0.20.4

Raw Secondary Tertiary (sand ltration) Secondary nitried Secondary Secondary Storm drain water Secondary Filtered nitried Secondary claried Filtered claried Secondary

24 615 69

20 1025 1030 30 min 15 n/a n/a

0.10.4 0.30.4 0.20.8

EC FS FC FS TC

34 23 4

1.5 612 310 1020

n/ab 0.10.5 n/a 0.11 200 200 1.1 103 0.9 102 FC FS EC 1.0 1031.0 108 1 102.51.0 106 n/a n/a n/a n/a 4 3 1.34.5

1215 35 15

n/a n/a 10

n/a n/a n/a

FC FC TC

n/a n/a 1.4 106 0.8 106 3.0 1034.2 105 3.0 1042.5 105 1 104.31 106.5 1 103.6 104.5 1 102.71 104.5

n/a n/a

n/a

TC

46

110

0.20.8

EC TC

4.0 65.0 8.01.5 103 1.0 103 1.0 103 1.0 103

Secondary Secondary Tertiary

15 4 2

2 2 2

n/a n/a n/a

FC FC EC

a b

FC fecal coliforms, FS fecal streptococci, TC total coliforms, and EC E. coli. n/a not available.

Fecal coliforms: log10 FC 4.06 0.020 TCOD 0.37 NO2-N 0.012 TSS 3.94 log10 T 0.59R1/2 (2) Where TC TCI FC T TCOD NO2-N R total coliforms (count/100 mL); initial TC concentration (count/100 mL); fecal coliforms (count/100 mL); absorbed ozone dose (mg/L); total chemical oxygen demand (mg/L); and TSS are in mg/L; and ozone residual (mg/L).

The signicance of suspended solids, or particles, was demonstrated in the study by Janex et al. (1999), which showed that the ltration of particles greater than 10 m increased the removal by one order of magnitude for the same ozone dose.
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Both pilot-plant studies and reports from operating plants have shown that ozone effectively removes fecal and total coliforms as well as enteric viruses from secondary efuents. Typical disinfection doses, contact times, and residual ozone concentrations required for the reduction of indicator organisms from pilot-plant studies and operating plants are presented in Table 4. With higher ozone doses, greater removals of up to 6 logs have been reported by Boucher et al. (1968) and Greene and Stenstrom (1994). A previous study of a more heavily polluted raw wastewater (Joret et al., 1982) found a 2-log reduction of E. coli and Fecal streptoccocci and a 1-log reduction of viruses. Lazarova et al. (1998) reported that ozone is effective against viruses by demonstrating that a 5-mg/L dose and 5-minute contact time were sufcient to achieve a 5-log removal of the highly resistant MS2 bacteriophage. Other studies have shown that, compared with chlorine and UV irradiation, ozone required a shorter contact time to achieve the same inactivation level and achieved a 10-fold greater removal of
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Table 5Treatment of selected pathogens by ozone (15-mg O3/L dose, 10 minutes) in tertiary municipal efuents (Liberti et al., 2000).
Feed CLa Pathogen Pseudomonas aeruginosa (CFU/100 mL) Giardia lamblia cysts (count/L) Cryptosporidium parvum oocysts (count/L)
a

Feed Fa Treated 28 92 8 Inuent 800 33 2 Treated 8 10 2

Inuent 1800 213 10

CL claried and F claried and ltered.

viruses than chlorine (CES, 1988; Tyrrell et al., 1995). The performance of ozone with other microoganisms and parasites (e.g., protozoan cysts and nematodes) in wastewater efuents is presently unclear because of the lack of sufcient studies. Liberti et al. (2000) reported that in tests with tertiary-treated municipal efuents, ozone was very effective toward Pseudomonas aeruginosa, moderately effective toward Giardia lamblia, and substantially ineffective toward Cryptosporidium parvum, although it was acknowledged that the low numbers of C. parvum in the untreated efuent made the results uncertain (Table 5). Generally, ozone treatment of secondary efuents has been found to be capable of achieving an efuent quality equivalent to the EU bathing waters and WHO agricultural standards as well as other comparable standards. However, for more stringent standards such as the California Title 22 regulations, a tertiary-treatment step (e.g., ltration) may be necessary before ozonation (Janex et al., 1999). The Effect of Ozone on Efuent Constituents Because of its high oxidation potential, ozone reacts with a wide range of organic and inorganic compounds in water. As previously described, chemical oxidation by ozone occurs via two distinct reaction mechanisms, namely a molecular ozone reaction pathway and a hydroxyl radical (OH) reaction mechanism. The molecular reaction mechanism is more selective than the radical reaction pathway, but the latter mechanism results in much greater reaction rates. The predominant mechanism, or relative contribution of each mechanism, in an ozonation process depends on various water quality parameters such as pH, alkalinity, and organic content because these determine the presence and inuence of species that act as radical initiators, promoters, and scavengers. Many

previous ozonation studies established that ozone attacks aromatic and unsaturated compounds, thereby affecting the chemical composition and the overall quality of the water (Hoigne , 1998). Following the ozonation of four municipal secondary efuents, Gardiner and Montgomery (1968) observed a reduction in COD, an initial increase followed by a decrease in 5-day biochemical oxygen demand (BOD5), and a reduction of TOC and of suspended solids concentration. Ozone also removed 50 to 90% of anionic and nonanionic detergents. Four different types of pesticides and ve types of phenols spiked into the wastewater efuent samples were also substantially removed after ozonation. In a pilot-plant study using ozone for the disinfection of secondary municipal efuent, Nebel et al. (1973) observed the removal of turbidity and color after ozonation, and a 30% average reduction of COD. The TOC remained primarily unaffected whereas the BOD5 decreased, although there were cases where increases in BOD5 were observed. The work of Legube et al. (1987) indicated a 25 and 50% reduction of COD and BOD5, respectively. Langlais et al. (1992) also found a complete or partial elimination of aromatic compounds, a reduction of unsaturated fatty acids, and a 50% reduction of anionic detergents. In the same study, the concentration of combined amino acids and polysaccharides decreased after ozonation. Sasai et al. (1997) reported a 12% reduction of TOC and a 33% reduction of COD after ozonation of a secondary efuent. Paraskeva et al. (1997, 1998) observed a 30% reduction in COD, a decrease in BOD in the range of 10 to 60%, a reduction in color between 25 and 55%, and a 254-nm reduction in UV absorbance between 15 and 40%, whereas parameters such as TOC and pH remained unaffected. In terms of color reduction, ozone is known to be particularly

Table 6 Summary of COD reduction by ozone treatment of secondary efuents.

Source Gardiner and Montgomery, 1968 Nebel et al., 1973 Fressonnet-Chambarlhac et al., 1983 Legube et al., 1987 Absi et al., 1993 Toffani and Richard, 1995 Sasai et al., 1997 Paraskeva et al., 1998 Ozone dose (mg/L) 541 1216 69 612 14 20 15 2.55 510 1030 Initial COD (mg/L) 2656 2040 2035 3375 40170 120200 20 2249 Final COD (mg/L) Reduction of approximately 50% ozone dose n/a 1530 n/a n/a n/a 13 Reduction (%) n/aa 23 n/a 25 5 3050 33 350 2040 3075

n/a not available. 573

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Table 7Summary of BOD5 changes after ozone treatment of secondary efuents.

Source Gardiner and Montgomery, 1968 Nebel et al., 1973 Legube et al., 1987 Absi et al., 1993 Paraskeva et al., 1998
a

Ozone dose (mg/L) 621 80 1216 612 18 510

Initial BOD5 (mg/L) 4 12 1025 523 2648 530

Final BOD5 (mg/L) 56 5 n/a n/a n/a

Reduction (%) n/aa n/a 15 50 4 1667

n/a not available.

effective. Studies from two large municipal wastewater treatment plants in Japan that receive strong inuents from dyeing factories (Hiromi and Tsujimoto, 1997; Sasai et al., 1997) showed that ozonation achieved almost full decolorization of the efuents. In the United Kingdom, the only ozonation plant treating secondary efuent is operating principally for color reduction because of the presence of dye waste in the raw wastewater. The plant is operating successfully with a color reduction of 30 to 80% in absorbance wavelengths from 400 to 600 nm (Churchley, 1998). A summary of values for COD, BOD, and color removal from several studies are presented in Tables 6, 7, and 8, respectively. A small amount of information concerning the effect of ozone on other efuent quality parameters has been reported in the literature. Graham and Paraskeva (2001) observed that for a wellnitried secondary efuent, ammonia-nitrogen was further reduced by 20% and the nitrate-nitrogen concentration correspondingly increased slightly; however, the absolute magnitude of the changes were small (1 to 2 mg/L). Absi et al. (1993) reported that ozone had no effect on the ammonia-nitrogen concentration for a chemically assisted primary treatment efuent where the ammonianitrogen concentrations ranged from 9 to 14 mg/L. Instead, they

suggested that the presence of organic materials may have protected the ammonia from oxidation. In the same study, iron concentrations (residual coagulant) were slightly reduced, and measurable concentrations of hydrogen sulde in the efuent (0.8 mg/L) were reduced to zero by ozone. In general, the physicochemical quality of municipal wastewaters increases systematically with ozone dose. Thus, both Paraskeva et al. (1998) and Sasai et al. (1997) have reported increased COD reductions at higher ozone doses (Figure 2). The average reduction for an ozone dose less than 5 mg/L was small. For doses in the typical disinfection range (i.e., 4 to 10 mg O3/L), the average COD reduction was 20 to 30% while, for higher ozone doses (e.g., 20 mg/L), the average reduction was 30 to 50%. Biochemical oxygen demand removal has also been found to increase with ozone dose, although, as mentioned earlier, an increase in BOD has been noted after a low ozone dose (Gardiner and Montgomery, 1968). Reductions in efuent color and UV absorbance (at 254 nm) are strongly correlated with ozone dose (Paraskeva et al., 1998) (Table 8). Because ozone is generated and applied in a feed-gas ow of either air or oxygen (ozone concentration between 1.6 and 16% of

Table 8 Summary of color reduction by ozone treatment of secondary efuents.

Source Nebel et al., 1973 Fressonnet-Chambarlhac et al., 1983 Toffani and Richard, 1995 Ozone dose (mg/L) 1216 69 20 Color units Alpha units mg/L platinum cobalt standard UV absorbance (abs) at 420 nm (5 cm) Japan Industrial Standards Z7880 color difference UV abs/cm at: 400 nm 450 nm 500 nm 550 nm 600 nm 650 nm UV abs at 400 nm (4 cm) Initial color 20100 5 0.30.5 Final color n/aa 5 n/a Reduction (%) 79 n/a 6080

Sasai et al., 1997

15

1.4

0.2

Churchley and Upton, 1997

9.5

Paraskeva et al., 1998

2.55 510 1030

0.095 0.075 0.070 0.055 0.040 0.020 0.150.20

0.040 0.020 0.020 0.012 0.010 0.005 1530 2555 6070

n/a not available. Water Environment Research, Volume 74, Number 6

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Figure 2Variation of COD with transferred ozone dose for a secondary efuent (Paraskeva et al., 1998).

feed gas, by weight), and during reaction it decomposes to oxygen, the concentration of dissolved oxygen (DO) in the treated water therefore increases, almost to saturation levels (Paraskeva et al., 1997). Although the level of dissolved oxygen in rivers is regulated in many countries, the ozonation of efuents has the added benet of increasing the DO levels of the receiving waters. In one reported case, increased receiving water DO was one of the principal reasons ozone was chosen as the method of disinfection. This involved two disinfection plants in Indianapolis, Indiana, where the DO level of the White River dropped to zero after the wastewater treatment plants were initially installed but increased to 8 to 10 mg O2/L after ozonation became operational (Rice, 1997). Ozonation Byproducts The reactions of molecular ozone and free radicals to a wide range of organic and inorganic compounds present in natural and contaminated waters have been well-researched in the last 20 years and these have been reviewed elsewhere (see, for example, Hoigne , 1998). In general, ozone is capable of reacting with a wide range of such compounds, leading to the formation of reaction intermediates and stable byproducts. Thus, the ozonation of secondary wastewater efuents leads to a change in the nature of the organic matter as observed by a shift in the molecular size distribution from large to smaller fractions (Paraskeva, 1998; Sasai et al., 1997). Previous studies of the ozonation of surface waters indicated that the most common ozonation byproducts are shortchain aldehydes comprising up to nine carbon atoms (Glaze et al., 1989; Schechter and Singer, 1995). Based on samples of a secondary efuent after ozone disinfection, Legube et al. (1987) reported increases in the presence of short-chain fatty acids, carboxylic acids, alcohols, alkanes, ketones, and free amino acids. Langlais et al. (1992) also reported an increase in the concentration
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of aldehydes, especially heptanal and nonanal, and an increase in short-chain saturated fatty acids (6 to 9 carbon atoms) after ozonation of a secondary municipal efuent. Most recently, Liberti et al. (2000) reported that in tests with two different tertiary-treated municipal efuents (i.e., coagulationsedimentation and coagulationsedimentationltration) that had similar organic contents (7 mg/L dissolved organic carbon), a numerically similar increase in total aldehydes was found (from 0.1 mg/L to 0.35 mg/L, as fomaldehyde), with an ozone dose of 15 mg/L. A signicant concern associated with ozone in drinking water treatment is the potential formation of halogenated substances such as bromate, a possible carcinogen, and brominated organics arising from the reaction of ozone and bromide. The proposed reaction involves the intermediate formation of hypobromous acid, which then reacts with more ozone to create bromate or reacts directly with organic precursors to form bromoform and other brominated species. Numerous studies have been published in the last 10 years (e.g., Von Gunten and Hoigne , 1994) regarding factors affecting the formation of these compounds and how to avoid or minimize bromate formation. In contrast, the potential formation of brominated compounds in the eld of wastewater treatment has received comparatively little research attention. Among the few studies conducted, the study by Liberti et al. (1999) did not observe any appreciable bromate or bromoform formation after ozonation of a secondary efuent. Although the efuent contained a signicant concentration of bromide (3 mg/L), the lack of any measurable formation of bromate and bromoform was explained by the presence of ammonia (22 to 23 mg/L), which reacts rapidly with hypobromous acid to produce monobromamine; the reaction rate of hypobromous acid with ammonia is several orders of magnitude greater than the bromate or bromoform reactions (Von Gunten and Hoigne , 1994).
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Figure 3Variation of efuent AOX (g/L as Cl) with transferred ozone dose (Paraskeva et al., 1998).

The scarcity of information concerning the formation of ozonation byproducts in wastewater efuents clearly indicates that further investigations are necessary on this subject. The scarcity is partly explained by the obvious practical difculties in identifying and quantifying individual compounds at low concentrations in a complex efuent matrix. An alternative, indirect approach has been to determine an overall measure of change within the pool of organic substances. Therefore, Paraskeva et al. (1998) used the parameter adsorbable organic carbon concentration (AOX) as an indicator of the presence (and change) of organo-halogen compounds. In ozonation experiments with a secondary efuent, an increase in AOX concentration was observed, especially at low ozone doses. No apparent relationship was observed between the increase of AOX and the initial AOX concentration. Higher ozone doses resulted in a gradual decrease of the AOX concentration, with a value at the highest ozone dose (20 mg/L) similar to or less than the initial AOX concentration of the efuent (Figure 3). Toxicity and Mutagenicity Effects The presence of residual ozone concentrations following ozonation can be toxic to many forms of aquatic life. Although the tolerance to ozone varies with the type of organism, its age, the residual ozone concentration, and period of exposure (Asbury and Coler, 1980), even very small residual ozone concentrations can cause mortality to sh and larvae. In the context of wastewater disinfection, however, residual ozone concentrations are believed to be short-lived and to have decayed before the nal discharge of the efuent to the receiving water system (CES, 1992). Paraskeva et al. (1998) reported that, for relatively low residual ozone doses arising from typical disinfection conditions (i.e., 0.2 to 1.0 mg O3/L), the time taken for ozone to decay to below-measurable concentrations was between 20 seconds and 2 minutes.
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Regarding the overall effect of the treatment process on the toxicity of the wastewater efuent, the reported effects of ozonation are variable and depend on the nature of the toxicity test. Fauris et al. (1985) examined the effect of ozonation on surface water using a toxicity method based on the inhibition of RNA synthesis of cultured human cells and found that ozone was capable of both destroying existing toxic substances and creating new ones. An increase in toxicity was observed at a low ozone dose and over a short contact time (1 mg/L and 10 minutes). A higher ozone dose (5 mg/L) over a longer contact time (30 minutes) resulted in a reduction of toxicity. A study by Blatchley et al. (1997) measured chronic toxicity responses in disinfected and undisinfected samples from seven municipal efuents using the survival and reproduction of a selected organism (Ceriodaphnia dubia). The results indicated that the toxicity responses were site-specic and seasonal, but conrmed that ozone had the ability to change the toxicity of the efuent, either by increasing or reducing it. However, a previous study using the same organism had found no toxicity arising from ozonation (Rein et al., 1992). A recent investigation of the inuence of different disinfectants on wastewater toxicity also found that ozone can both increase and decrease toxicity (Monarca et al., 2000). In this study, the authors used a bacteria bioluminescence assay (using a LUMIStox system, Dr. Bruno Lange GmbH & Co., Berlin, Germany) and found that, with summer samples of secondary efuent, ozone increased the efuent toxicity while, with winter samples, ozone reduced efuent toxicity (Table 9). Langlais et al. (1992), using sh and crustaceans as test organisms, did not observe any changes in the toxicity of a secondary efuent after ozonation. Similar results are reported by Absi et al. (1993) using Daphnia and the Microtox (AZUR Environmental/
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Table 9 Bioluminescence toxicity of urban wastewater samples (Monarca et al., 2000).

ECF50a Treatment Treated wastewaterb Ozone (3 mg/L summer, 2.5 mg/L winter)
a

Summer 63.0 (60.865.2) 16.5 (14.618.6)

Winter 85.7 (82.888.8) 205.7 (192.8219.5)

ECF50 Effective concentration factor that inhibits 50% of the light emitted by bacteria after 15 minutes of exposure (low values indicate high toxicity). b Wastewater treated with activated sludge.

dose is applied in a given contact time. The highly variable nature of wastewater ows has led to design owrates for ozone-disinfection systems that are typically 2 to 3 times the average daily owrate; additionally, the ozone-generation capacity is that required to achieve a specied applied ozone dose at the peak design owrate (U.S. EPA, 1986). In traditional disinfection practice (e.g., in chlorination and the use of ozone in drinking water disinfection), the concept of the C t product is normally applied, where C is the concentration of dissolved (residual) ozone measured at the outlet of the contact chamber (in mg/L), and t is the contact time between the residual of ozone and water (in minutes). This is a conservative approach that is based on the well-known ChickWatson model ln Nt /N0 kC nt (3)

Strategic Diagnostics, Inc., Newark, Delaware) bioluminescence test methods. Paraskeva et al. (1998) used the Microtox test and reported that both unozonated and ozonated efuents were not toxic and that a value for the 50% effective concentration factor could not be established. In contrast, the study by Nebel et al. (1973) found that a variety of sh exposed to ozonated secondary efuent survived the duration of the pilot study, whereas many sh did not survive exposure to the undisinfected efuent. Similarly, Collivignarelli et al. (2000) showed that ozone treatment increased the survival of test sh (Salmo gairdnerii) in diluted secondary efuent (100% survival compared with 90% for untreated efuent). A much earlier study by Venosa and Ward (1978) reported that ozonation reduced the toxicity of an initially toxic secondary efuent. Biological monitoring downstream of the discharge of the Leek Wastewater Treatment Plant (Straffordshire, England) to the River Churnet in the United Kingdom showed that ozonation did not induce toxicity but improved the biological health of the river, as indicated by an increase in the biotic score (Churchley and Upton, 1997). Changes in efuent mutagenicity were found to be site-specic according to Jolley et al. (1982). Results from the ozonation of nine different efuents showed that mutagenicity could both decrease and increase. Greene and Stenstrom (1994) concluded that ozonation did not change the mutagenicity of physicochemically treated municipal efuent. Although a 7 to 24% reduction of mutagenicity was recorded, this result was not considered statistically signicant. In contrast, studies by Nakamuro et al. (1989) and Ono et al. (1992) showed signicant reductions of mutagenicity following the ozonation of municipal river water and of an activated-sludge municipal efuent. Similar results are reported by Ono et al. (1995), after the ozonation of night soil efuent, and Sasai et al. (1997), for a wastewater secondary efuent (14 mg O3/L). Paraskeva et al. (1999) also reported that ozone did not induce any mutagenicity in a secondary municipal efuent, and there was an indication that ozone could reduce the mutagenicity of the efuent. In contrast, Collivignarelli et al. (2000) observed that, using the Ames method, ozone at low doses (2.5 to 3 mg O3/L) produced a low level of mutagenicity in samples of secondary efuent taken in both summer and winter; no mutagenicity was recorded in untreated efuent samples. However, the results of a second genotoxicity test, the onion (Allium cepa) roots test, did not show any adverse effect. Ozone-Contacting Conditions The ozonation of wastewater efuents is typically via an ozone gasliquid contacting system in which a nominal ozone
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where Nt and N0 are the number of microorganisms surviving at time t (t 0); C is the residual disinfectant; and k and n are empirically derived constants. Normally, the value of n is assumed to be unity, and values for the C t product corresponding to different degrees of microorganism inactivation have been established from well-controlled laboratory and pilot-plant tests (e.g., Table 2). In applying eq 3 to wastewater disinfection there are difculties in that the C t approach assumes that an aqueous ozone concentration is available throughout the contact time, t. However, a characteristic of the high-redox potential of ozone (EH 0 2.07 V) is that, when it is applied to water, there is an instantaneous ozone demand (occurring in the initial 20 seconds) (Roustan et al., 1997) arising from very rapid reactions with a range of inorganic and organic species. The magnitude of this ozone demand varies with the nature of the water. For wastewaters, Janex et al. (1999) reported immediate ozone demands of 3.1 to 4.2 mg/L and 7.4 to 9.6 mg/L for two secondary efuents and 2.5 to 5.3 mg/L for a tertiary efuent. Associated with this immediate ozone demand is a signicant reduction in microbiological counts (e.g., 2-log reduction in fecal coliforms) (Janex et al., 2000). However, there seems to be no correlation between the extent of inactivation and the immediate ozone demand (Janex et al., 1999). Once the immediate ozone demand is satised, further applied ozone will produce a measurable residual that is available for further microbial disinfection. The appearance of a residual ozone concentration (CR) has been modeled for the case of a bubble-column reactor as a simple equation in terms of the overall transferred (or absorbed) ozone dose (TOD), the immediate ozone demand (X), the hydraulic residence time of ow in the reactor (), and a kinetic constant, k, (Roustan et al., 1997) as follows: C R TOD X/1 k (4)

In theory, the utility of this model is that, provided representative values for X and k can be obtained for a given wastewater, the total consumption of ozone can be determined corresponding to a set ozone residual at the reactor outlet (CR); hence, the ozone gas ow rate can be determined for a given ozone gas concentration. The principal factor that determines the disinfection performance has been found to be the overall transferred, or absorbed, ozone dose (in milligrams per liter). This is simply dened as the difference in the ozone applied in the feed gas and the ozone lost in the exhaust gas per unit volume of wastewater. Previous studies have shown an empirical relationship between the logarithm of
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Figure 4 Reduction of E. coli and total coliforms with transferred ozone dose (Paraskeva and Graham, 1999).

bacterial survival (log10 Nt/N0) and either the TOD or the logarithm of TOD. In the case of the latter, the U.S. EPA has suggested the following relationship of the form (U.S. EPA, 1986): log N/N0 n log TOD/q (5)

where n is the slope of the doseresponse curve and q is the x-axis intercept of the doseresponse curve (which is the amount of ozone transferred before a measurable kill is observed). An example of this relationship is shown in Figure 4, which has been plotted from the data of laboratory ozonation tests with a U.K. nitried, secondary efuent (Paraskeva and Graham, 1999). These results gave values for n and q of 3.65 and 0.77, respectively, for E. coli and 3.04 and 0.61, respectively, for total coliforms. These values are typically of a similar magnitude to those obtained from eld-scale trials of nitried secondary efuents at two plants in the United States, where n and q were in the range of 2.51 to 3.14 and 0.50 to 1.05, respectively, for total coliforms, and 3.15 and 0.79, respectively, for fecal coliforms (U.S. EPA, 1986). However, in all of these studies, the data were highly variable (Figure 4) and the correlation coefcients (R2) are typically poor. Contact time is an important parameter in ozone treatment because it affects the size of the contact tanks, the treatment rate, and the associated equipment and facilities of an ozonation plant. Although most U.S. plants operate with a contact time of 10 to 15 minutes, there are studies indicating that efcient disinfection can be achieved regardless of the contact time. Nebel et al. (1973) reported that disinfection occurred after only a few seconds but, for practical reasons, suggested a 5-minute contact time. Finch and Smith (1989) observed no changes in the doseresponse curve of E. coli for contact times from 1 to 22 minutes, and, most recently, Janex et al. (1999) reported that for a given TOD, a 2-minute contact time achieved the same fecal coliform inactivation as 10 minutes. More studies are necessary to conrm whether this behavior generally applies to all types of microorganisms of interest because such microorganisms have a range of tolerances to ozone.
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The need to reduce the comparatively high costs of ozone technology in the last 10 years has resulted in the production of more efcient ozone corona discharge generators capable of producing ozone at concentrations of up to 6% w/w in air and up to 20% w/w in oxygen. These generators are able to reduce energy costs by producing more ozone at approximately the same energy consumption level as traditional generators, to economize oxygen consumption, increase the mass-transfer rate of ozone with the appropriate contact chamber, and reduce the treatment rate (DyerSmith, 1997). Such generators not only provide a faster treatment but also signicantly reduce the size of contact chambers. In the study by Paraskeva et al. (1998), three gaseous ozone concentrations (1.5, 4.5, and 13.5% w/w in oxygen) were studied with respect to their effect on the treatability of the secondary efuent. It was found that neither the ozone concentration nor the contact time were important factors as far as the overall treatment (in terms of the principal quality parameters COD, BOD, TOC, color, etc.) was concerned. The single factor governing the extent of treatment was found to be the TOD, as shown in Figure 5. However, higher gaseous inlet ozone concentrations resulted in a faster treatment (Figure 6). In view of these results, the optimal design of the ozone-contacting system should be based on maximizing the ozone transfer rate, corresponding to an overall TOD that achieves the required degree of efuent treatment. Conclusions The use of ozone for wastewater disinfection has received a considerable amount of attention in the last 20 years. Interest in this application of ozone is likely to increase in the future, particularly where wastewater efuents are to be reused and a high degree of treatment is required. Given its high reactivity with a wide range of substances and relative cost of application, ozone is likely to be most appropriate for achieving specic treatment goals with efuents that have received some degree of pretreatment, such as secondary efuents. Thus, ozone treatment of secondary efuents has been found to be able to meet bacteriological stanWater Environment Research, Volume 74, Number 6

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Figure 5Variation of efuent of COD with transferred ozone dose at different gaseous ozone concentrations (4.5 and 13.5 % in oxygen, w/w; constant ozonation rate) (Paraskeva et al., 1998). dards typically required for discharge to recreational waters, and a high degree of virus removal has been reported. Limited data are currently available on the inactivation of specic pathogenic organisms (e.g., protozoa cysts) in wastewater efuents or their regrowth potential following ozonation. Given the highly variable nature of efuent quality, the performance of ozone treatment is likely to be equally variable, and thus considerable attention will need to be given to plant design and operation of the ozone system. Attempts to model bacterial removal during ozone treatment have been frustrated by the inherent complexity of the process, although some empirical performance relationships exist for the principal indicator bacteria. The TOD has been found to be a signicant parameter that determines microbiological performance. Clearly, a part of the TOD is represented by the immediate ozone demand and a signicant degree of microbial inactivation occurs by satisfying this immediate demand. Further studies would be useful to develop a process model that can represent the simultaneous consumption of ozone by microbial inactivation and the efuent

Figure 6 Effect of gaseous inlet ozone concentration (20 and 60 mg/L) on E. coli inactivation (Paraskeva and Graham, 1999).
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organic matrix for both the immediate ozone demand and the residual ozone decay phases. In addition to providing disinfection, ozone application can improve the general physicochemical quality of efuents. This has been a key factor in the selection of ozone in some cases. Thus, efuent COD, BOD5, color, and UV absorbance are typically reduced by ozone treatment and DO levels are increased. Although quantitative information on the formation of ozone byproducts during efuent treatment is presently scarce, ozone is likely to produce low-molecular-weight organic intermediate compounds of the kind found in drinking water treatment. Similarly, the overall effect of ozone on efuent toxicity has received little attention to date, and results of studies that have considered this aspect have found the effects to be variable. In this respect, ozone treatment can both decrease or increase efuent toxicity, although overall the effects are generally minor in nature. In light of the importance given by regulatory bodies to the environmental effect of chemical treatment technologies (in terms of approving the use of such technologies), considerable research is still needed on the formation of ozone-byproduct species and the effect of ozone on efuent toxicity. Acknowledgments Authors. Nigel Graham is a professor of environmental engineering in the Department of Civil and Environmental Engineering, Imperial College of Science, Technology and Medicine, London, United Kingdom. Panagiota Paraskeva was a postdoctoral research associate in the Department of Civil and Environmental Engineering, Imperial College, when this review was undertaken. Correspondence should be addressed to Nigel Graham, Department of Civil and Environmental Engineering, Imperial College of Science, Technology and Medicine, Imperial College Road, London SW7 2AZ, U.K.; e-mail: n.graham@ic.ac.uk. Submitted for publication November 20, 2001; accepted for publication June 14, 2002. The deadline to submit Discussions of this paper is March 15, 2003. References
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