Ozonation of drinking water: part I. Oxidation kinetics and product formation

The oxidation of organic and inorganic compounds during ozonation can occur via ozone or OH radicals or a combination thereof. The oxidation pathway is determined by the ratio of ozone and OH radical concentrations and the corresponding kinetics. A huge database with several hundred rate constants for ozone and a few thousand rate constants for OH radicals is available. Ozone is an electrophile with a high selectivity. The second-order rate constants for oxidation by ozone vary over 10 orders of magnitude, between < 0.1 M(-1)s(-1) and about 7 x 10(9) M(-1)s(-1). The reactions of ozone with drinking-water relevant inorganic compounds are typically fast and occur by an oxygen atom transfer reaction. Organic micropollutants are oxidized with ozone selectively. Ozone reacts mainly with double bonds, activated aromatic systems and non-protonated amines. In general, electron-donating groups enhance the oxidation by ozone whereas electron-withdrawing groups reduce the reaction rates. Furthermore, the kinetics of direct ozone reactions depend strongly on the speciation (acid-base, metal complexation). The reaction of OH radicals with the majority of inorganic and organic compounds is nearly diffusion-controlled. The degree of oxidation by ozone and OH radicals is given by the corresponding kinetics. Product formation from the ozonation of organic micropollutants in aqueous systems has only been established for a few compounds. It is discussed for olefines, amines and aromatic compounds.     

Disinfection by-product formation following chlorination of drinking water: Artificial neural network models and changes in speciation with treatment

Artificial neural network (ANN) models were developed to predict disinfection by-product (DBP) formation during municipal drinking water treatment using the Information Collection Rule Treatment Studies database complied by the United States Environmental Protection Agency. The formation of trihalomethanes (THMs), haloacetic acids (HAAs), and total organic halide (TOX) upon chlorination of untreated water, and after conventional treatment, granular activated carbon treatment, and nanofiltration were quantified using ANNs. Highly accurate predictions of DBP concentrations were possible using physically meaningful water quality parameters as ANN inputs including dissolved organic carbon (DOC) concentration, ultraviolet absorbance at 254 nm and one cm path length (UV₂₅₄), bromide ion concentration (Br⁻), chlorine dose, chlorination pH, contact time, and reaction temperature. This highlights the ability of ANNs to closely capture the highly complex and non-linear relationships underlying DBP formation. Accurate simulations suggest the potential use of ANNs for process control and optimization, comparison of treatment alternatives for DBP control prior to piloting, and even to reduce the number of experiments to evaluate water quality variations when operating conditions are changed. Changes in THM and HAA speciation and bromine substitution patterns following treatment are also discussed.     

Comparison of the disinfection by-product formation potential of treated waters exposed to chlorine and monochloramine

The formation of disinfection by-products (DBPs) from chlorination and monochloramination of treated drinking waters was determined. Samples were collected after treatment at 11 water treatment works but before exposure to chlorine or monochloramine. Formation potential tests were carried out to determine the DBPs formed by chlorination and monochloramination. DBPs measured were trihalomethanes (THMs), haloacetic acids (HAAs), halonitromethanes (HNMs), haloacetonitriles (HANs), haloaldehydes (HAs), haloketones (HKs) and iodo-THMs (i-THMs). All waters had the potential to form significant levels of all the DBPs measured. Compared to chlorine, monochloramination generally resulted in lower concentrations of DBPs with the exception of 1,1-dichloropropanone. The concentrations of THMs correlated well with the HAAs formed. The impact of bromine on the speciation of the DBPs was determined. The literature findings that higher bromide levels lead to higher concentrations of brominated DBPS were confirmed.     

Disinfection by-products formation and precursors transformation during chlorination and chloramination of highly-polluted source water: Significance of ammonia

Many studies have demonstrated the different trends of disinfection by-products (DBPs) formation between chlorination and chloramination. However, the reactions between precursors and disinfectants are widely assumed to be “black box” and the reasons for abovementioned difference are not well illustrated. This study focused on source water with high levels of natural organic matter (NOM) and bromide, and compared the transformation of NOM specific characteristics and the ratios of specific DBPs as an equivalent of chlorine to total organic halogen (TOX) among three disinfection scenarios of chlorination, chloramination and chlorine–chloramine sequential treatment (Cl₂–NH₂Cl process). A three-reaction-phrases model was proposed thereafter to illustrate the major reactions involved in, i.e., stage-I: rapid consumption of fast reactive sites (DOC₁), which transformed to slow reactive sites (DOC₂) and measured DBPs, i.e., trihalomethanes, haloacetic acids, etc; stage-II: oxidation and/or halogenation of DOC₂ into unknown TOX (UTOX) intermediates; stage-III: oxidation of UTOX intermediates into measured DBPs. The effect of ammonia was also quantified. Ammonia is observed to inhibit the formation of measured DBPs by 68–92%, 94–99%, and 92–95% of that in chlorination in Stage-I, II, and III, respectively, and the formation of UTOX is reduced by 2–80%, 60–94%, and 82–93% accordingly. These effects lead to the steady accumulation of DBPs intermediates such as UTOX, and to the elevated UTOX/TOX during chloramination and Cl₂–NH₂Cl process thereafter. The results illustrate the mechanism of ammonia participating in DBPs formation, and are valuable to fill in the gap between the transformation of precursors and the formation of different DBPs.     

Disinfection and formation of disinfection by-products in a photoelectrocatalytic system

In this study, disinfection and formation of disinfection by-products (DBPs) were studied in a photoelectrocatalytic (PEC) treatment system. Disinfection performance of titanium dioxide (TiO₂) in the PEC system was determined through Escherichia coli (E. coli) inactivation. Humic acid (HA) was used as a model organic compound and its removal was monitored by total organic carbon (TOC) measurements using 410 nm (color) and 254 nm (UV₂₅₄) wavelengths. Trihalomethanes (THMs) were measured for the evaluation of DBPs formation during PEC treatment of chloride and HA mixture. It was found that unlike photocatalytic treatment, THMs might form in the PEC system. To investigate the effects of anions on the PEC treatment, chloride (Cl⁻), sulfate (SO₄²⁻), phosphoric acid (H₂PO₄⁻)/hydrogen phosphate (HPO₄²⁻) and bicarbonate (HCO₃⁻) ions were added separately to the HA and bacterial suspensions. Presence of H₂PO₄⁻/HPO₄²⁻ and HCO₃⁻ ions resulted in inhibitory effects on both HA degradation and E. coli inactivation, which were also examined in the photoanode. It was observed that the presence of HA had a strong inhibitory effect on the disinfection of E. coli.     

Disinfection of swine wastewater using chlorine, ultraviolet light and ozone

Veterinary antibiotics are widely used at concentrated animal feeding operations (CAFOs) to prevent disease and promote growth of livestock. However, the majority of antibiotics are excreted from animals in urine, feces, and manure. Consequently, the lagoons used to store these wastes can act as reservoirs of antibiotics and antibiotic-resistant bacteria. There is currently no regulation or control of these systems to prevent the spread of these bacteria and their genes for antibiotic resistance into other environments. This study was conducted to determine the disinfection potential of chlorine, ultraviolet light and ozone against swine lagoon bacteria. Results indicate that a chlorine dose of 30 mg/L could achieve a 2.2-3.4 log bacteria reduction in lagoon samples. However, increasing the dose of chlorine did not significantly enhance the disinfection activity due to the presence of chlorine-resistant bacteria. The chlorine resistant bacteria were identified to be closely related to Bacillus subtilis and Bacillus licheniformis. A significant percentage of lagoon bacteria were not susceptible to the four selected antibiotics: chlortetracycline, lincomycin, sulfamethazine and tetracycline (TET). However, the presence of both chlorine and TET could inactivate all bacteria in one lagoon sample. The disinfection potential of UV irradiation and ozone was also examined. Ultraviolet light was an effective bacterial disinfectant, but was unlikely to be economically viable due to its high energy requirements. At an ozone dose of 100 mg/L, the bacteria inactivation efficiency could reach 3.3-3.9 log.     

Oxidative elimination of cyanotoxins: comparison of ozone, chlorine, chlorine dioxide and permanganate

As the World Health Organization (WHO) progresses with provisional Drinking Water Guidelines of 1 microg/L for microcystin-LR and a proposed Guideline of 1 microg/L for cylindrospermopsin, efficient treatment strategies are needed to prevent cyanotoxins such as these from reaching consumers. A kinetic database has been compiled for the oxidative treatment of three cyanotoxins: microcystin-LR (MC-LR), cylindrospermopsin (CYN), and anatoxin-a (ANTX) with ozone, chlorine, chlorine dioxide and permanganate. This kinetic database contains rate constants not previously reported and determined in the present work (e.g. for permanganate oxidation of ANTX and chlorine dioxide oxidation of CYN and ANTX), together with previously published rate constants for the remaining oxidation processes. Second-order rate constants measured in pure aqueous solutions of these toxins could be used in a kinetic model to predict the toxin oxidation efficiency of ozone, chlorine, chlorine dioxide and permanganate when applied to natural waters. Oxidants were applied to water from a eutrophic Swiss lake (Lake Greifensee) in static-dose testing and dynamic time-resolved experiments to confirm predictions from the kinetic database, and to investigate the effects of a natural matrix on toxin oxidation and by-product formation. Overall, permanganate can effectively oxidize ANTX and MC-LR, while chlorine will oxidize CYN and MC-LR and ozone is capable of oxidizing all three toxins with the highest rate. The formation of trihalomethanes (THMs) in the treated water may be a restriction to the application of sufficiently high-chlorine doses.     

Implications of sequential use of UV and ozone for drinking water quality

The formation of bromate levels exceeding the drinking water standard of 10 microg L-1 may impose the reduction of ozone doses used in the treatment of drinking water. This paper illustrates the procedure of evaluating the use of reduced ozone doses while implementing an additional UV disinfection step for an actual drinking water treatment plant. Ozonation was performed at low ozone doses in bench-scale experiments with a pretreated river water from the Paris area (France). At the low ozone dose of 0.5 mg L-1, bromate formation could be kept below 0.4 microg L-1, while inactivation of vegetative bacteria and UV-resistant viruses was calculated to exceed 5 log units, and a substantial decoloration (31% of the absorption at lambda=254 nm) was achieved. Based on the measured transient ozone and OH radical concentrations, the oxidation of micropollutants was calculated. Fast reacting micropollutants containing phenol, amine or double bond moieties, such as sulfamethoxazole, diclofenac and 17-alpha-ethinylestradiol, were completely oxidized. Slow-reacting synthetic micropollutants, e.g., atrazine, iopromide and methyl tertiary butyl ether (MTBE), were oxidized by only 20%, 20% and 10%, respectively, and the taste and odor compounds 2-methylisoborneol (MIB) and geosmin by 40% and 50%, respectively. The addition of an UV treatment step to the existing treatment train, which should guarantee disinfection of ozone-resistant pathogenic microorganisms, including Cryptosporidium parvum oocysts, has negligible effects on water matrix components but may induce significant transformation of micropollutants. Overall, the combination of ozonation at reduced doses and UV treatment leads to an improved water quality with regard to disinfection, oxidation of micropollutants and minimization of bromate.     

Impact of H2O2 and (bi)carbonate alkalinity on ammonia's inhibition of bromate formation

Ammonia can be used to minimize bromate concentrations by blocking two of three potential bromate formation pathways. It was theorized that (bi)carbonate alkalinity in the presence of ammonia would inhibit bromate formation since the pathway that ammonia does not block requires hydroxyl radicals (OH()), and (bi)carbonate alkalinity is an OH() scavenger. Experiments where (bi)carbonate alkalinity was increased from 50 to 119 mg/L (as CaCO(3)) in the presence of excess ammonia resulted in up to 50% reduction in bromate formation, providing evidence in support of the theory. While OH() is scavenged by (bi)carbonate alkalinity, it is promoted by hydrogen peroxide (H(2)O(2)). When ozone reacts with natural organic matter the H(2)O(2) that is formed may therefore render ammonia less effective. Experiments conducted in this study demonstrated this principle.     

UV/H2O2 treatment of drinking water increases post-chlorination DBP formation

Ultraviolet (UV) irradiation has become popular as a primary disinfectant because it is very effective against Cryptosporidium and does not directly form regulated disinfection by-products. Higher UV doses and UV advanced oxidation (UV/H₂O₂) processes are under consideration for the treatment of trace organic pollutants (e.g. pharmaceuticals, personal care products). Despite the disinfection effectiveness of UV light, a secondary disinfectant capable of maintaining a distribution system residual is required to meet current U.S. regulation. This study investigated changes in disinfection by-product (DBP) formation attributed to UV or UV/H₂O₂ followed by application of free chlorine to quench hydrogen peroxide and provide residual disinfectant. At a UV dose of 1000 mJ/cm², trihalomethane (THM) yield increased by up to 4 μg/mg-C and 13 μg/mg-C when treated with low and medium pressure UV, respectively. With the addition of hydrogen peroxide, THM yield increased by up to 25 μg/mg-C (5 mg-H₂O₂/L) and 37 μg/mg-C (10 mg-H₂O₂/L). Although no changes in DBPs are expected during UV disinfection, application of UV advanced oxidation followed by chlorine addition was assessed with regard to impacts on DBP formation.     

Spatial and temporal evaluations of disinfection by-products in drinking water distribution systems in Beijing, China

Disinfection by-products were determined in 15 water treatment plants in Beijing City. The effects of different water sources (surface water source, mixture water source and ground water source), seasonal variation and spatial variation were examined. Trihalomethanes and haloacetic acids were the major disinfection by-products found in all treated water samples, which accounted for 42.6% and 38.1% of all disinfection by-products respectively. Other disinfection by-products including haloacetonitriles, chloral hydrate, haloketones and chloropicrin were usually detected in treated water samples but at lower concentrations. The levels of disinfection by-products in drinking water varied with different water sources and followed the order: surface water source > mixture water source > ground water source. High spatial and seasonal variation of disinfection by-products in the drinking water of Beijing was shown as a result.     

2. Comparison of the disinfection by-product formation potentials between a wastewater effluent and surface waters

In this study, the chemical reactivity with chlorine as measured by disinfection by-product formation potential (DBPFP) is compared among samples of a wastewater effluent and surface waters. Water samples that had higher anthropogenic impacts were found to have higher overall DBPFP due primarily to higher dissolve organic carbon (DOC) concentrations. Effluent-derived organic matter (EfOM), however, was found to be less reactive with chlorine on a per DOC concentration basis. Yet, EfOM had higher proportions of brominated DBP, which may be associated with greater health risks. In this research, pyrolysis-GC/MS was used to establish relationship between structural features of DOC and DBPFP. We show that there is a critical set of pyrolysis fragments that separates the waters based on the degree of anthropogenic influence. Even though no single chemical marker was found to be indicative of the formation potentials of different classes of DBP, combinations of chemical fragments were found to be associated with the formation potentials of total trihalomethane (THM), brominated THM, total haloacetic acid (HAA), and brominated HAA for this set of samples. In contrast to previous work, the phenolic signature of these samples was negatively correlated to DBPFP, whereas strong relationships were found between DBPFP and the organic nitrogen and halogenated signatures.     

Kinetic assessment and modeling of an ozonation step for full-scale municipal wastewater treatment: Micropollutant oxidation, by-product formation and disinfection

The kinetics of oxidation and disinfection processes during ozonation in a full-scale reactor treating secondary wastewater effluent were investigated for seven ozone doses ranging from 0.21 to 1.24 g O₃ g⁻¹ dissolved organic carbon (DOC). Substances reacting fast with ozone, such as diclofenac or carbamazepine (kP,O₃ > 10⁴ M⁻¹ s⁻¹), were eliminated within the gas bubble column, except for the lowest ozone dose of 0.21 g O₃ g⁻¹ DOC. For this low dose, this could be attributed to short-circuiting within the reactor. Substances with lower ozone reactivity (kP,O₃ < 10⁴ M⁻¹ s⁻¹) were only fully eliminated for higher ozone doses.The predictions of micropollutant oxidation based on coupling reactor hydraulics with ozone chemistry and reaction kinetics were up to a factor of 2.5 higher than full-scale measurements. Monte Carlo simulations showed that the observed differences were higher than model uncertainties. The overestimation of micropollutant oxidation was attributed to a protection of micropollutants from ozone attack by the interaction with aquatic colloids. Laboratory-scale batch experiments using wastewater from the same full-scale treatment plant could predict the oxidation of slowly-reacting micropollutants on the full-scale level within a factor of 1.5. The Rct value, the experimentally determined ratio of the concentrations of hydroxyl radicals and ozone, was identified as a major contribution to this difference.An increase in the formation of bromate, a potential human carcinogen, was observed with increasing ozone doses. The final concentration for the highest ozone dose of 1.24 g O₃ g⁻¹ DOC was 7.5 μg L⁻¹, which is below the drinking water standard of 10 μg L⁻¹. N-Nitrosodimethylamine (NDMA) formation of up to 15 ng L⁻¹ was observed in the first compartment of the reactor, followed by a slight elimination during sand filtration. Assimilable organic carbon (AOC) increased up to 740 μg AOC L⁻¹, with no clear trend when correlated to the ozone dose, and decreased by up to 50% during post-sand filtration. The disinfection capacity of the ozone reactor was assessed to be 1-4.5 log units in terms of total cell counts (TCC) and 0.5 to 2.5 log units for Escherichia coli (E. coli). Regrowth of up to 2.5 log units during sand filtration was observed for TCC while no regrowth occurred for E. coli. E. coli inactivation could not be accurately predicted by the model approach, most likely due to shielding of E. coli by flocs.     

Occurrence of bromate, chlorite and chlorate in drinking waters disinfected with hypochlorite reagents. Tracing their origins

Bromate was first reported as a disinfection by-product from ozonated waters, but more recently it has been reported also as a result of treatment using hypochlorite solutions worldwide. The aim of this study was to study the scope of this phenomenon in the drinking waters (n = 509) of Castilla y León, Spain, and in the hypochlorite disinfectant reagents. Two thirds of the treated waters monitored were found to have bromate concentrations higher than 1 µg/l, and of them a median value of 8 µg/l and a maximum of 49 µg/l. These concentrations are higher than those reported so far, however, a great variability can be found. Median values for chlorite were of 5 µg/l, and of 119 µg/l for chlorate. Only 7 out of 40 hypochlorite feedstock solutions were negative for bromate, the rest showing a median of 1022 mg/l; and 4 out of 14 calcium hypochlorite pellets were also negative, the rest with a median of 240 mg/kg. Although bromate is cited as potentially added to water from calcium hypochlorite pellets, no reference is found in scientific literature regarding its real content. Chlorite (median 2646 mg/l) and chlorate (median 20,462 mg/l) and chlorite (median 695 mg/kg) and chlorate (median 9516 mg/kg) were also monitored, respectively, in sodium hypochlorite solutions and calcium hypochlorite pellets. The levels of chlorite and chlorate in water are considered satisfactory, but not those of bromate, undoubtedly owing to the high content of bromide in the raw brines employed by the chlor-alkali manufacturers. Depending on the manufacturer, the bromate concentrations in the treated waters may be very heterogeneous owing to the lack of specification for this contaminant in the disinfectant reagents —the European Norms EN 900 and 901 do not mention it.     

Controversies about the occurrence of chloral hydrate in drinking water

Besides trihalomethanes (THMs) and haloacetic acids (HAAs), chloral hydrate (CH) is the next most prevalent disinfection by-product (DBP) in drinking water, formed as a result of the reaction between chlorine and natural organic matter (NOM). Chloral hydrate (trichloroacetaldehyde) should be limited in drinking water because of its adverse health effect. The controversies concerning the appearance of CH in disinfected water found in literature are discussed in the present paper. According to some authors the CH yield during chlorination of water depends only on TOC. However, there are other data available that do not confirm this relationship. Another fact requiring clarification is the dependence of CH formation on pH. In the present study, CH formation is analysed in different types of water disinfected with different doses of chlorine. Formation of CH is correlated with the dose of Cl₂ and the contact time. The formation of chloral hydrate takes place as long as chlorine is available in the water. Total organic carbon (TOC) is not considered the main factor influencing the production of chloral hydrate in water treated with Cl₂ as the production depends also on the nature of NOM. Higher levels of CH are observed at alkaline conditions (pH > 7). A significant correlation (R² > 0.9) between the concentrations of chloral hydrate and chloroform has been observed. The preozonation increases significantly the chloral hydrate formation potential in the water treated. Biofiltration process does not remove all of CH precursors and its efficiency depends strongly on the contact time. Chloral hydrate was analyzed by gas chromatography with electron capture detector with the detection limit 0.1 μg L⁻¹.     

Disinfection by-product formation after biologically assisted GAC treatment of water supplies with different bromide and DOC content

Chlorination of drinking water in the presence of bromide and dissolved organic carbon (DOC) leads to the formation of brominated and chlorinated disinfection by-products (DBP). The concentration of bromide ions in the raw water is a significant factor in the speciation of DBP formed, and causes shifts in trihalomethane (THM) formation from chlorinated to brominated species. Drinking water treatment techniques that remove organic contaminants without affecting bromide ion concentrations cause increases in the brominated THM. For the present study, three water supplies containing different DOC and ambient bromide concentrations were filtered through biologically assisted granular activated carbon (BGAC). Similar to adsorption and coagulation treatment, this treatment does not remove bromide from drinking water; also, THMFP (trihalomethane formation potential) analysis indicated that the chlorinated effluent contained higher concentrations of brominated THM in comparison to the influent. Although BGAC may increase the brominated THM, which may be more toxic than the chlorinated THM, the overall reduction of THMFP by DOC removal far exceeds this negative change, thereby producing a much less toxic finished drinking water. This work is part of a study to make high DOC surface waters on the Canadian prairie safe and palatable for small volume users (individuals or small communities).     

Impact of a magnetic ion exchange resin on ozone demand and bromate formation during drinking water treatment

The objective of this research was to examine the impact of a magnetic ion exchange resin (MIEX) on ozone demand and bromate formation in two different ozonated waters at bench scale. The first raw water had a high bromide ion concentration, a high ozone demand, and was highly colored. Based on experimental findings from the first water, the second water was selected as a model water in which more controlled experiments were performed. The waters were treated with the MIEX resin using jar test procedures to find the optimal MIEX dosage based upon the removal of ultraviolet (UV)-absorbing substances, dissolved organic carbon (DOC), and bromide. The optimal resin dosage was chosen for bulk MIEX treatment and subsequent ozonation in a semi-batch reactor. The ozone demand and formation of bromate were analyzed as a function of ozone dosage and dissolved ozone concentration for the MIEX pre-treated water, and compared to the results obtained by ozonating the water without MIEX pre-treatment. The results indicate that pre-treatment of the water with the MIEX resin significantly reduces total organic carbon, DOC, UV absorbance, color, and to some extent, bromide. MIEX pre-treatment of the water prior to ozonation substantially lowered the ozone demand and formation of bromate during subsequent ozonation.     

Ozonation of water containing chlorine or chloramines. Reaction products and kinetics

Ozone reacts with free aqueous chlorine when present as hypochlorite ion (OCl⁻) with a second order rate constant of 120 ± 15 M⁻¹ s⁻¹ at 20°C. About 77% of the chlorine reacts to produce Cl⁻ and 23% is oxidized to ClO⁻₃. No ClO⁻₄ is formed. Conversion of chlorine to monochloramine reduces the ozone reaction rate to 26 ± 4 M⁻¹ s⁻¹, independent of pH, NH₂Cl is transformed quantitatively to NO⁻₃ and Cl⁻ by O₃. Rate data for other chloramines are also presented. The direct reaction of ozone with chlorine accounts for a significant amount of the chlorine and ozone demand found when the two oxidants are used in combination under water works conditions.     

Disinfectant efficacy of chlorite and chlorine dioxide in drinking water biofilms

The drinking water industry is closely examining options to maintain disinfection in distribution systems. In particular this research compared the relative efficiency of the chlorite ion (ClO2-) to chlorine dioxide (ClO2) for biofilm control. Chlorite levels were selected for monitoring since they are typically observed in the distribution system as a by-product whenever chlorine dioxide is applied for primary or secondary disinfection. Previous research has reported the chlorite ion to be effective in mitigating nitrification in distribution systems. Annular reactors (ARs) containing polycarbonate and cast iron coupons were used to simulate water quality conditions in a distribution system. Following a 4 week acclimation period, individual ARs operated in parallel were dosed with high (0.25mg/l) and low (0.1mg/l) chlorite concentrations and with high (0.5 mg/l) and low (0.25mg/l) chlorine dioxide concentrations, as measured in the effluent of the AR. Another set of ARs that contained cast iron and polycarbonate coupons served as controls and did not receive any disinfection. The data presented herein show that the presence of chlorite at low concentration levels was not effective at reducing heterotrophic bacteria. Log reductions of attached heterotrophic bacteria for low and high chlorite ranged between 0.20 and 0.34. Chlorine dioxide had greater log reductions for attached heterotrophic bacteria ranging from 0.52 to 1.36 at the higher dose. The greatest log reduction in suspended heterotrophic bacteria was for high dose of ClO2 on either cast iron or polycarbonate coupons (1.77 and 1.55). These data indicate that it would be necessary to maintain a chlorine dioxide residual concentration in distribution systems for control of microbiological regrowth.     

Modeling Cryptosporidium parvum oocyst inactivation and bromate in a flow-through ozone contactor treating natural water

A reactive transport model was developed to simultaneously predict Cryptosporidium parvum oocyst inactivation and bromate formation during ozonation of natural water. A mechanistic model previously established to predict bromate formation in organic-free synthetic waters was coupled with an empirical ozone decay model and a one-dimensional axial dispersion reactor (ADR) model to represent the performance of a lab-scale flow-through ozone bubble-diffuser contactor. Dissolved ozone concentration, bromate concentration (in flow-through experiments only), hydroxyl radical exposure and C. parvum oocyst survival were measured in batch and flow-through experiments performed with filtered Ohio River water. The model successfully represented ozone concentration and C. parvum oocyst survival ratio in the flow-through reactor using parameters independently determined from batch and semi-batch experiments. Discrepancies between model prediction and experimental data for hydroxyl radical concentration and bromate formation were attributed to unaccounted for reactions, particularly those involving natural organic matter, hydrogen peroxide and carbonate radicals. Model simulations including some of these reactions resulted in closer agreement between predictions and experimental observations for bromate formation.