Some problems in the determination of total residual “chlorine” in chlorinated sea-water

In the determination of residual chlorine in sea-water by the amperometric titrimetric method, potassium iodide must be added to the sample before the addition of the pH 4 buffer, and the addition of these two reagents should not be more than one minute apart. Serious analytical error may arise if the order of the addition of the reagents is reversed. There is no evidence suggesting the formation of iodate by the reaction between hypobromite and iodide. For concentrations of residual chlorine below one mg 1⁻¹, iodate, which occurs naturally in sea-water, may cause serious analytical uncertainties. In sea-water, the preferred concentration unit of residual chlorine is μM. The unit, mg 1⁻¹, must be used with care and clear definition. The unit, ppm, should be avoided.     

Inactivation of Bacillus subtilis spores and formation of bromate during ozonation

Inactivation of B. subtilis spores with ozone was investigated to assess the effect of pH and temperature, to compare the kinetics to those for the inactivation of C. parvum oocysts, to investigate bromate formation under 2-log inactivation conditions, and to assess the need for bromate control strategies. The rate of B. subtilis inactivation with ozone was independent of pH, decreased with temperature (activation energy of 42,100 Jmol(-1)), and was consistent with the CT concept. B. subtilis was found to be a good indicator for C. parvum at 20-30 degrees C, but at lower temperatures B. subtilis was inactivated more readily than C. parvum. Bromate formation increased as both pH and temperature increased. For water with an initial bromide concentration of 33 microgl(-1), achieving 2-logs of inactivation, without exceeding the 100 microg l(-1) bromate standard, was most difficult at 30 degrees C for B. subtilis and at midrange temperatures (10-20 degrees C) for C. partum. pH depression and ammonia addition were found to reduce bromate formation without affecting B. subtilis inactivation, and may be necessary for waters containing more than 50 microgl(-1) bromide.     

Adsorptive ozonation of 2-methylisoborneol in natural water with preventing bromate formation

This paper presents an application of our newly developed adsorptive ozonation process using a high silica zeolite adsorbent (USY) for drinking water treatment. First, the adsorption of 2-methylisoborneol (2-MIB) on USY in a river water/pure water mixture was clarified by a batch-type adsorption experiment. The results showed that 2-MIB was adsorbed on USY; however, almost all of the adsorbed 2-MIB was desorbed over time. The desorption rate was increased with the ratio of river water to pure water, indicating that compounds dissolved in the river water, such as natural organic matter (NOM), prevent the adsorption of 2-MIB on USY. Second, the ability of the river water to consume ozone was confirmed in an experiment using a USY-packed column reactor. The ozone consumption was obviously increased by the presence of USY, indicating that USY-adsorbing compounds dissolved in the river water (probably small size NOM) consumed the ozone. However, the rapid ozone consumption was occurred by 6-8 s in the retention times when 3.14-4.38 mgL(-1) of water dissolved ozone was fed, this rapid ozone consumption lasted no more than these times. This result revealed that the rapid consumption of ozone by the adsorptive compounds in our process could be avoided within a certain retention time (6-8 s; especially for the river water used in this study) when enough concentration of ozone (3.14 mgL(-1) or more; same above) was supplied. We therefore performed a trial in which 2-MIB dissolved in river water was continuously decomposed using a USY-packed column with various ozone concentrations. In the process, the adsorptive compound dissolved in the river water adsorbed and reacted with ozone in the parts of the apparatus upstream of the column, while the adsorption and decomposition of 2-MIB took place in the parts of the apparatus downstream of the column. This resulted in a sufficient 2-MIB decomposition with minimizing bromate ion formation.     

Biofiltration for removal of BOM and residual ammonia following control of bromate formation

Nitrification was developed within a biological filter to simultaneously remove biodegradable organic matter (BOM) and residual ammonia added to control bromate formation during the ozonation of drinking water. Testing was performed at pilot-scale using three filters containing sand and anthracite filter media. BOM formed during ozonation (e.g., assimilable organic carbon (396-572 microg/L), formaldehyde (11-20 microg/L), and oxalate (83-145 microg/L)) was up to 70% removed through biofiltration. Dechlorinated backwash water was required to develop the nitrifying bacteria needed to convert the residual ammonia (0.1-0.5 mg/L NH(3)-N) to nitrite and then to nitrate. Chlorinated backwash water resulted in biofiltration without nitrification. Deep-bed filtration (empty-bed contact time (EBCT) = 8.3 min) did not enhance the development of nitrification when compared with shallow-bed filtration (EBCT = 3.2 min). Variable filtration rates between 4.8 and 14.6 m/h (2 and 6 gpm/sf) had minimal impact on BOM removal. However, conversion of ammonia to nitrite was reduced by 60% when increasing the filtration rate from 4.8 to 14.6 m/h. The results provide drinking water utilities practicing ozonation with a cost-effective alternative to remove the residual ammonia added for bromate control.     

Modeling of bromate formation by ozonation of surface waters in drinking water treatment

The main objective of this paper is to try to develop statistically and chemically rational models for bromate formation by ozonation of clarified surface waters. The results presented here show that bromate formation by ozonation of natural waters in drinking water treatment is directly proportional to the "Ct" value ("Ctau" in this study). Moreover, this proportionality strongly depends on many parameters: increasing of pH, temperature and bromide level leading to an increase of bromate formation; ammonia and dissolved organic carbon concentrations causing a reverse effect. Taking into account limitation of theoretical modeling, we proposed to predict bromate formation by stochastic simulations (multi-linear regression and artificial neural networks methods) from 40 experiments (BrO(3)(-) vs. "Ctau") carried out with three sand filtered waters sampled on three different waterworks. With seven selected variables we used a simple architecture of neural networks, optimized by "neural connection" of SPSS Inc./Recognition Inc. The bromate modeling by artificial neural networks gives better result than multi-linear regression. The artificial neural networks model allowed us classifying variables by decreasing order of influence (for the studied cases in our variables scale): "Ctau", [N-NH(4)(+)], [Br(-)], pH, temperature, DOC, alkalinity.     

Occurrence and determination of dinitrotoluene isomers in sea-water

The occurrence and determination of three dinitrotoluene isomers. 2.6-, 2.4- and 2.3-dinitrotoluene in the sea-water of Dokai bay in Japan, and their behaviour in surrounding sea environment were investigated. 206-0.890 μgl⁻¹ of 2.4-dinitrotoluene. 14.8-0.072 μgl⁻¹ of 2.6-dinitrotoluene and 0.412-0.081 μgl⁻¹ of 2.3-dinitrotoluene were detected in sea-water heavily polluted by industrial waste. After the industrial waste containing three dinitrotoluene isomers was discharged into the bay, a distance of 1.5 km had to be traversed by the water before the concentration of 2.4-dinitrotoluene was reduced by the action of tidal current to one half of its initial concentration in the bay. Three dinitrotoluene isomers were extracted with benzene and identified by a gas-chromatography-mass spectrometry-computer technique and gas-chromatography with an electron capture detector.     

Sources and behaviour of dinitrotoluene isomers in sea-water

The sources and behaviour of dinitrotoluene (DNT) isomers in the sea-water of Dokai Bay in Japan were investigated. DNT isomers such as 2,6-, 2,5-, 2,4-, 2,3- and 3,4-DNT were identified in an industrial effluent. One drain, the main source, discharged about 150 kg of DNT isomers as the maximum value in a day. This value roughly agrees with that obtained from seven months of monitoring of DNT isomers in sea-water. The monitoring revealed that about 76 kg of DNT isomers was discharged into the bay daily. 2,6-, 2,4- and 2,3-DNT were detected in the sea-water at the levels of 14,8-ND μg l⁻¹ (n = 82), 206-ND μg l⁻¹ (n = 82) and 0.412-ND μg l⁻¹ (n = 82), respectively. The relationship between the concentration of 2,4-DNT (Y) and the distance (X) is statistically expressed by the equation of Y = (6.38 ± 4.02)e^{−(0.269 ± 0.044)X}, and the relationship between the 2,6-DNT/2,4-DNT ratio (y) and the distance (X) is expressed as y = −(0.795 ± 0.131) X + (9.35 ± 4.1). These relationships reveal that the decrease of DNT isomers in the sea-water is caused by factors more complex than mechanical dilution by tidal action.     

Low-temperature formation and degradation of chlorinated benzenes, PCDD and PCDF in dust from steel production

Dust from thermal processes may catalytically enhance the formation of chlorinated aromatic compounds under oxygen-rich conditions. The activities of two dust samples from electric arc furnaces and one from iron ore-based steelmaking (oxygen converter) were investigated in a laboratory experiment. The dust samples were heated at 300 degrees C for 2 h in an air atmosphere. The concentrations of chlorinated benzenes did not change greatly upon heating, while the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans decreased. The addition of copper in parallel runs resulted in a substantial increase in the concentration of chlorinated benzenes, thus indicating that the experimental setup was suitable for the evaluation of low-temperature catalysis. The outcome of the experiment seems to suggest that results cannot easily be extrapolated between different thermal and metallurgical processes. Some measures to reduce emissions, such as inhibition of catalytic activity and rapid cooling, could possibly be counterproductive when applied to off-gases from the steelmaking processes investigated here.     

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.     

Disinfectant decay and disinfection by-products formation model development: chlorination and ozonation by-products

Comprehensive disinfectant decay and disinfection by-product formation (D/DBP) models in chlorination and ozonation were developed to apply to various types of raw and treated waters. Comparison of several types of models, such as empirical power function models and empirical kinetic models, was provided in order to choose more robust and accurate models for the D/DBP simulations. An empirical power function model based on dissolved organic carbon and other parameters (Empirically based models for predicting chlorination and ozonation by-products: haloacetic acids, chloral hydrate, and bromate, EPA Report CX 819579, 1998) showed a strong correlation between measured and predicted trihalomethane (THM) and haloacetic acid (HAA) formation for raw waters. Internal evaluation of kinetic-based models showed good predictions for chlorine decay and THM/HAA formation, but no significant improvements were observed compared to the empirical power function model simulations. In addition, several empirical models for predicting ozone decay and bromate (ozonation disinfection by-product) formation were also evaluated and/or developed. Several attempts to develop kinetic-based and alternative models were made: (i) a two-stage model (two separate decay models) was adapted to ozone decay and (ii) an ozone demand model was developed for bromate formation. Generally, internal evaluation of kinetic-based models for ozone decay showed significant improvements, but no significant improvements for the simulation of bromate formation were observed compared to the empirical power function model simulations. Additional efforts were performed to reduce the gaps between specific models and their actual application. For instance, temperature effects and configuration of ozone contactors were considered in actual application.     

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.     

Catalysis of copper corrosion products on chlorine decay and HAA formation in simulated distribution systems

This study investigated the effect of copper corrosion products, including Cu(II), Cu₂O, CuO and Cu₂(OH)₂CO₃, on chlorine degradation, HAA formation, and HAA speciation under controlled experimental conditions. Chlorine decay and HAA formation were significantly enhanced in the presence of copper with the extent of copper catalysis being affected by the solution pH and the concentration of copper corrosion products. Accelerated chlorine decay and increased HAA formation were observed at pH 8.6 in the presence of 1.0 mg/L Cu(II) compared with that observed at pH 6.6 and pH 7.6. Further investigation of chlorine decay in the presence of both Suwannee River NOM and Cu(II) indicated that an increased reactivity of NOM with dissolved and/or solid surface-associated Cu(II), rather than chlorine auto-decomposition, was a primary reason for the observed rapid chlorine decay. Copper corrosion solids [Cu₂O, CuO, Cu₂(OH)₂CO₃] exhibited catalytic effects on both chlorine decay and HAA formation. Contrary to the results observed when in the absence of copper corrosion products, DCAA formation was consistently predominant over other HAA species in the presence of copper corrosion products, especially at neutral and high pH. This study improves the understanding for water utilities and households regarding chlorine residuals and HAA concentrations in distribution systems, in particular once the water reaches domestic plumbing where copper is widely used.     

A reactive species model for chlorine decay and THM formation under rechlorination conditions

Chlorine is typically used within drinking water distribution systems to maintain a disinfectant residual and minimize biological regrowth. Typical distribution system models describe the loss of disinfectant due to reactions within the water matrix as first order with respect to chlorine concentration, with the reactants in excess. Recent work, however, has investigated relatively simple dynamic models that include a second, hypothetical reactive species. This work extends these latter models to account for discontinuities associated with rechlorination events, such as those caused by booster chlorination and by mixing at distribution system junction nodes. Mathematical arguments show that the reactive species model will always represent chlorine decay better than, or as well as, a first-order model, under single dose or rechlorination conditions; this result is confirmed by experiments on five different natural waters, and is further shown that the reactive species model can be significantly better under some rechlorination conditions. Trihalomethane (THM) formation was also monitored, and results show that a linear relationship between total THM (TTHM) formation and chlorine demand is appropriate under both single dose and rechlorination conditions. This linear relationship was estimated using the modeled chlorine demand from a calibrated reactive species model, and using the measured chlorine demand, both of which adequately represented the TTHM formation.     

Ozone decomposition of 2-methylisoborneol (MIB) in adsorption phase on high silica zeolites with preventing bromate formation

This work elucidates the applicability of our newly developed adsorptive ozonation process for the decomposition of 2-methylisoborneol (MIB), a typical taste and odor chemical, without the formation of possibly carcinogenic bromate ions. First, zeolite adsorbents were screened for their ability to adsorb MIB with a batch-type adsorption experimental apparatus and a flow-type decomposition experimental apparatus included an adsorbent-packed column. The USY zeolite with the highest silica to alumina ratio (SiO(2)/Al(2)O(3) molar ratio=70) showed the best performance as an adsorbent. Using this adsorbent, an ozonation experiment on an MIB solution including bromide ions was performed under various retention times using the flow-type apparatus. As a result, sufficient decomposition of MIB was achieved with preventing bromate formation.     

Differential absorbance study of effects of temperature on chlorine consumption and formation of disinfection by-products in chlorinated water

Effects of chlorine dose, reaction time and temperature on the formation of disinfection by-products (DBPs) and corresponding changes in the absorbance of natural organic matter (NOM) in chlorinated water were examined in this study. Although variations of chlorination parameters, notably those of temperature that was varied from 3 to 35 degrees C, influenced the kinetics of chlorine consumption and DBP release, correlations between chlorine consumption, concentrations of trihalomethanes (THMs), haloacetonitriles (HANs), other DBP species and, on the other hand, intensity of differential absorbance at 272nm remained unaffected. THM and HAN speciation was correlated with the differential absorbance, indicating preferential incorporation of bromine at the initial phases of halogenation that correspond to low DeltaA(272) values. Because the DeltaA(272) parameter is a strong indicator of the formation of DBP species and chlorine decay, optimization of chlorination operations and DBPs control based on this parameter can be beneficial for many water utilities, especially those with pronounced variability of water temperature and residence times.     

Determination of nutrients limiting biofilm formation and the subsequent impact on disinfectant decay.

Understanding the contribution of both organic and inorganic nutrients to biofilm development and the subsequent impact of developed biofilms on disinfectant decay are important requirements for distribution system management strategies. Nutrient limitation may be one way to control biofilm development without increasing disinfectant dosing. Little is known, however, of the nutrient requirements of biofilms in distribution systems. Indeed, the effects on biofilm development due to the addition of nutrients to distribution systems and what impact biofilm development may have on disinfectant decay is still poorly understood. This study used annular reactors to determine the nutrients limiting for biofilm development in drinking water from two different Sydney sources and the subsequent effects of biofilm development on disinfectant decay. It was found that biofilm development in Sydney water was limited by organic carbon and that biofilm development promoted chloramine decay. Moreover, biofilm development occurred in the presence of chloramine. The ability of biofilms to respond to increases in disinfectant concentrations was dependent on the biomass of the biofilms. In a comparative study using chlorinated drinking water containing very low levels of organic carbon, biofilm development was not detected. Removal of organic carbon resulted in greater persistence of chlorine, which led to greater biofilm control. It was also shown that biofilms could contribute cells to the aqueous phase. The results of the study indicate that treatment and system management strategies should incorporate organic carbon removal to limit biofilm development through a combination of retarding bacterial growth and enhancing disinfectant persistence.     

Microbially available organic carbon, phosphorus, and microbial growth in ozonated drinking water

Ozonation is a disinfection technique commonly used in the treatment of drinking water. It destroys harmful microbes, but it also degrades organic matter in water, increasing the bioavailability of organic matter. Recently, it was found that not only organic carbon but also phosphorus can limit the microbial growth in drinking water, which contains high amount of organic matter. We used a bioassay to analyze whether ozone could also increase the microbially available phosphorus (MAP) in drinking water, and whether MAP in ozone-treated water was associated with the growth of heterotrophic microbes. We found that both assimilable organic carbon and MAP concentrations were increased by ozone treatment. In ozonated water, microbial growth was mainly limited by phosphorus, and even minor changes in MAP concentration dramatically increased the growth potential of heterotrophic microbes. In this study, ozonation increased the MAP by 0.08-0.73 microgram P/l, resulting in an increase of 80,000-730,000 CFU/ml in water samples. In contrast to MAP, the content of assimilable organic carbon (AOCpotential) did not correlate with microbial growth. The results show that in water treatment not only AOCpotential but also MAP should be considered as an important factor that can limit microbial growth in drinking water.     

The impact of bromide on the formation of neutral and acidic disinfection by-products (DBPs) in Mediterranean chlorinated drinking water

By using the Grob closed loop stripping analysis technique a wide variety of disinfection by-products (DBPs) was determined, in finished drinking water of 15 important cities of Greece distributed in the southern, northern, west continental land and in the islands of Aegean and Ionian Seas. Trihalomethanes, haloacetonitriles, haloacetic acids, chloropicrin, halogenated ketons and chloral hydrate were the main DBPs determined. In chlorinated drinking water of coastal cities brominated DBPs were most abundant than their chlorinated homologues due to the higher bromide concentration in raw waters of these areas. Factor analysis with principal component extraction of the results demonstrated a clear differentiation between the examined drinking waters on the basis of their DBPs content and vicinity to the sea.