Predicting the Formation of Chlorinated and Brominated By-Products

Although disinfection was one of the major public health advances in the last century and continues to be so in the twenty-first century, the disinfectants themselves may react with naturally occurring materials in treated water to form unintended by-products, which may themselves pose risks. This is of particular concern with regard to the use of chlorine. Generation of disinfection by-products (DBPs) has been shown to be a function of various factors including total organic carbon concentration, type of organic precursor, chlorination level, pH, temperature, reaction time, and UV-254 absorbance. Another factor affecting DBP formation is the presence and concentration of the bromide ion in the raw or finished water. Bromine substitutes for chlorine to produce bromine-containing homologues of the more familiar chlorine species. The current list of by-products targeted for regulation contains brominated and mixed bromine-chlorine species of total trihalomethanes and haloacetic acids. These are known to form in bromide-containing waters when chlorinated. To control chlorination DBPs therefore requires an understanding of the factors that influence their formation. This paper presents a model that can be used to predict the formation of chlorinated, brominated, and mixed species compounds based on initial chlorine concentration, chlorine consumption, bromide ion concentration, and pH. The model clearly shows that higher levels of bromide in the water favor the formation of brominated compounds. Brominated compounds also form faster than chlorinated compounds.     

Disinfection By-Product Formation during Long-Term Water Storage in Alaska

In many areas of Northern and Western Alaska, small streams and shallow lakes serve as community raw water supplies. These water supplies freeze completely during winter. In order to supply drinking water during the 6–9 month winter, communities store water that was treated during summer. A chlorine residual is maintained in the stored water. Raw water sources derived from surface water may be heavily laden with dissolved organic matter. At utilities where organic matter escapes treatment, the potential for accumulation of disinfection by-products (DBPs) during storage is a significant health concern. The following study was performed to evaluate this potential threat. Water was collected from five operating utilities, four that normally store water for 6–9 months and one that produces drinking water year-round. Raw, filtered (i.e., unchlorinated) and “finished” (i.e., filtered and chlorinated) water samples were collected during the summer pumping season and stored in the laboratory for 8 months. In order to mimic practice in the field, the chlorine residual was maintained in the finished water for the full storage period. While the concentration of DBPs in the finished water varied over the study period, there was not a statistically significant trend from the third to the eighth month of storage. The observed DBP values were strongly a function of the type of treatment system used. Those systems passing more organic matter had higher DBP values throughout the storage period. The ultraviolet absorbance at 254 nanometers ?start(UV254)end? decreased continuously in the finished water coincident with chlorine consumption. ?startUV254end?, often used as a surrogate for DBPs, remained constant during the entire storage periodin raw and filtered water samples. Filtered water that was stored prior to chlorination accumulated fewer DBPs than finished water that was continuously chlorinated during the storage period. This result suggests that storing filtered water instead of finished water for long periods would limit DBP exposure to consumers. This conclusion was based on a comparison of DBP formation potentials (i.e., raw and filtered water) to DBPs (i.e., finished water). It is important to note that DBP formation potentials are based on a ?start24?hend?chlorine contact time. If long term storage were provided for filtered water, a smaller volume of secondary storage would still be needed to provide contact time for disinfection.     

Exposure estimates to disinfection by-products of chlorinated drinking water

Exposure to disinfection by-products (DBPs) of drinking water is multiroute and occurs in households serviced by municipal water treatment facilities that disinfect the water as a necessary step to halt the spread of waterborne infectious diseases. Biomarkers of the two most abundant groups of DBPs of chlorination, exhaled breath levels of trihalomethanes (THMs) and urinary levels of two haloacetic acids, were compared to exposure estimates calculated from in-home tap water concentrations and responses to a questionnaire related to water usage. Background THM breath concentrations were uniformly low. Strong relationships were identified between the THM breath concentrations collected after a shower and both the THM water concentration and the THM exposure from a shower, after adjusting for the postshower delay time in collecting the breath sample. Urinary haloacetic acid excretion rates were not correlated to water concentrations. Urinary trichloroacetic acid excretion rates were correlated with ingestion exposure, and that correlation was stronger in a subset of individuals who consumed beverages primarily within their home where the concentration measurements were made. No correlation was observed between an average 48-hr exposure estimate and the urinary dichloroacetic acid excretion rate, presumably because of its short biological half-life. Valid biomarkers were identified for DBP exposures, but the time between the exposure and sample collection should be considered to account for different metabolic rates among the DBPs. Further, using water concentration as an exposure estimate can introduce misclassification of exposure for DBPs whose primary route is ingestion due to the great variability in the amount of water ingested across a population.     

Predicting Chlorine Residuals and Formation of TTHMs in Drinking Water

Chlorination is the most widely practiced form of disinfection in the United States. It is highly effective against most microbiological contaminants. However, there is concern that the disinfection by-products (DBPs) formed by the use of chlorine might be carcinogenic. One class of DBPs that are formed and the only class of DBPs that currently are regulated are total trihalomethanes (TTHMs). Therefore, much effort is being expended in developing models that can be used to predict both TTHMs and chlorine residual levels in treated drinking water. This paper presents a model that predicts both TTHMs and chlorine residuals based on the consumption of chlorine and can be used to assist in evaluating the complex balance between microbial and DBP risks associated with disinfecting drinking water with chlorine. The parameters of the model have been found to be functions of total organic carbon, pH, temperature, and initial chlorine residual level. Bromide and the subsequent formation of brominated by-products were not considered in this paper.     

Effect of Bromide Ion on Haloacetic Acid Formation during Chlorination of Biscayne Aquifer Water

Water drawn from the Biscayne Aquifer, an extensively used potable water supply source in Florida, was used to study the effect of the bromide ion on haloacetic acid (HAA) formation during chlorination. The source water contained an ambient bromide ion concentration (160 μg∕L) and a substantial concentration of natural organic matter (nonpurgeable organic carbon = 10.9 mg∕L). A systematic evaluation, encompassing a range of bromide ion concentration spikes, and reaction times at fixed pH, chlorine dose, and temperature conditions, was conducted. Two chlorinated HAAs (dichloroacetic acid and trichloroacetic acid), two brominated HAAs (dibromoacetic acid and tribromoacetic acid), and three mixed HAAs (bromochloroacetic acid, bromodichloroacetic acid, and dibromochloroacetic acid) were found. Monobromoacetic acid and monochloroacetic acid were below detection limits in all of the chlorinated samples. In contrast to the findings of previous studies, the molar yield of HAAs increased as the initial bromide ion concentration increased. Concentrations of total HAAs, brominated, and mixed HAAs increased substantially, while chlorinated HAAs decreased slightly, with the addition of the bromide ion.     

Incorporating Reservoir Transfer into Treatment Optimization Decisions

The Massachusetts Water Resources Authority (MWRA) supplies unfiltered water from two large surface water reservoirs to the metropolitan Boston area, as well as to three smaller communities in central Massachusetts [the Chicopee Valley Aqueduct (CVA) communities]. Quabbin Reservoir is larger than Wachusett Reservoir, and has traditionally been used to supplement the Wachusett during the summer period. Quabbin water is also of better quality, with lower reactive natural organic matter (NOM). The MWRA began to add chlorine at Wachusett in 1997, and a new facility for adding chlorine at Quabbin for the CVA was also started up in 2000 to meet primary disinfection regulations to meet pathogen inactivation. The reaction of chlorine with NOM produces undesirable disinfection by-products (DBPs). The absorption of ultraviolet light at a wavelength of 254 nm was identified in chlorine decay studies to be the most important raw water quality parameter for predicting chlorine decay and DBP formation. This technical note summarizes the chlorine decay model for Wachusett and Quabbin water. The model is extended to ozonation of Wachusett water for the future Walnut Hill treatment plant. The models allowed the development of a trigger using UV-254 to time the Quabbin transfer to optimize treatment results. It is believed that the model for disinfectant decay and the use of UV-254 as a trigger for water treatment decisions are generalized and applicable to other water utilities.     

Iron Oxide Enhanced Chlorine Decay and Disinfection By-Product Formation

This study investigates the interaction of natural organic matter with iron oxide (goethite) on chlorine decay, disinfection by-product (DBP) formation, and DBP compound speciation [total trihalomethanes (TTHM4) and haloacetic acids (HAA5)]. Batch experiments were conducted with goethite, multiple finished drinking waters, variable chlorine dose, and fixed pH 8. The overall objective was to assess natural organic matter (NOM) adsorption onto goethite and its effect on chlorine decay and DBP formation. Chlorine consumption always increased in the presence of goethite and is attributed to an increase in the reactivity and/or modification of adsorbed NOM. Adsorbed NOM also led to an overall increase in TTHM4, however, HAA5 formation was suppressed during the first 2?h. Chloroform was identified as the increasing species and dichloracetic acid was identified as the suppressed species. This study clearly shows that goethite, which is the predominant iron oxide of pipe deposits, alters both chlorine decay and DBP formation and should be considered when assessing water treatment plant operations and DBP monitoring site selection.     

Particulate and THM Precursor Removal with Ferric Chloride

Pilot-scale experiments were performed to investigate the effectiveness of enhanced coagulation in removing particles and trihalomethane (THM) precursors from two surface source waters: California State Project water and Colorado River water. The removal of suspended particles and natural organic matter at various ferric chloride doses and coagulation pHs was assessed through source water and filter effluent measurements of turbidity, particle count, UV254, TOC, and THM formation potential. Overall, it was found that optimal removal of particles and THM precursors by enhanced coagulation with ferric chloride is obtained at high coagulant doses (>16 mg∕L) and low pH conditions. Generally, turbidity removal is more efficient and head loss is more moderate at ambient pH compared with pH 5.5. Additionally, filter effluent particle counts were found to be consistent with residual turbidity data. The removal of THM precursors by enhanced coagulation is significantly enhanced at pH 5.5 compared with ambient pH. The reduction in THM formation potential is consistent with the trends observed for the THM precursor removal data (i.e., UV254 and TOC data). Furthermore, specific UV absorbance was used to estimate the proportion of humic substances in the raw waters. Enhanced coagulation was found to be less effective for the source water with the lower specific UV absorbance.     

Lime-Soda Softening Process Modifications for Enhanced NOM Removal

In this research, a number of process modifications to the lime-soda softening process were examined, including utilization of high Mg-content lime, addition of MgCl2, and the recycling of softening sludge, in order to improve the removal of natural organic matter (NOM) and reduce the formation of disinfection byproducts (DBPs). Jar test results showed that dissolved organic carbon (DOC) removal increased and trihalomethane (THM) formation was reduced as the magnesium in hydrated lime increased, and was directly correlated with the amount of magnesium removed from the system. However, a dolomitic quick lime hydrated under atmospheric conditions resulted in less effective DOC removal due to a lack of available Mg, and subsequently, less co-precipitation of Mg(OH)2-NOM complexes. The addition of MgCl2 to the raw water also increased DOC removal and reduced THM formation in both the presence and absence of softening sludge, with DOC removal increasing as softening sludge and magnesium dosages increased. As high as 43% removal of DOC was achieved at the stoichoimetric lime-soda ash dose in the presence of 457 mg/L sludge and 7.5 mg/L MgCl2, as compared to only 13% removal in the absence of sludge and MgCl2. The recycling of softening sludge had little or no effect on the hardness and the level of inorganic elements in treated water. The results presented here provide new approaches for improving DBP precursor removal during lime-soda softening without significantly increasing lime and soda ash dosage or the generation of waste sludge.     

Modeling the Transformation of Chromophoric Natural Organic Matter during UV/H2O2 Advanced Oxidation

This research developed a differential kinetic model to predict the partial degradation of natural organic matter (NOM) during ultraviolet plus hydrogen peroxide (UV/H2O2) advanced oxidation treatment. The absorbance of 254?nm UV, representing chromophoric NOM (CNOM) was used as a surrogate to track the degradation of NOM. To obtain reaction rate constants not available in the literature, i.e., reactions between the hydroxyl radical (?OH) and NOM, experiments were conducted with “synthetic” water, using isolated Suwannee River NOM, and parameter estimation was applied to obtain the unknown model parameters. The reaction rate constant for the reaction between ?OH and total organic carbon (TOC), k?OH,TOC, was estimated at 1.14(±0.10)×104??L?mg-1?s-1, and the reaction rate constant between ?OH and CNOM, k?OH,CNOM, was estimated at 3.04(±0.33)×104??L?mol-1?s-1. The model was evaluated on two natural waters to predict the degradation of CNOM and H2O2 during UV/H2O2 treatment. Model predictions of CNOM degradation agreed well with the experimental results for UV/H2O2 treatment of the natural waters, with errors up to 6%. For the natural water with additional alkalinity, the model also predicted well the slower degradation of CNOM during UV/H2O2 treatment, owing to scavenging of ?OH by carbonate species. The model, however, underpredicted the degradation of H2O2, suggesting that, when NOM is present, mechanisms besides the photolysis of H2O2 contribute appreciably to H2O2 degradation.     

Secondary Benefits of Aquifer Storage and Recovery: Disinfection By-Product Control

The potential of biological processes during aquifer storage to reduce disinfection by-products (DBP), and DBP precursors were examined under controlled conditions. Finished water treated by conventional water treatment practice was pumped into a sand media column for up to 34 days of residence time. Two experiments were conducted where the finished water was chlorinated or ozonated prior to injection. Chlorination of water withdrawn from simulated aquifer storage conditions resulted in reduced formation of trihalomethane (THM) concentrations for all three treated water types. Ozonation of finished water resulted in a 70% decrease in TTHM formation. Aquifer storage of finished water resulted in a 26–28% reduction in TTHM formation and the removal of preformed THM species was as high as 40%. Overall, aquifer storage of chlorinated finished water resulted in a 44% reduction in TTHM formation when additionally chlorinated after withdrawal. Bromate formed during ozonation was reduced by approximately 54%. This study indicates that the sequencing of chlorination or ozonation with respect to aquifer storage and recovery operations can impact DBP formation.     

Filariasis in northern Ghana: some cultural beliefs and practices and their implications for disease control

All four possible trihalomethanes (THMs) containing bromine and chlorine, as well as perchloroethylene (PCE), were evaluated for their ability to produce DNA strand breaks, alpha 2u-globulin rich renal deposits, and testosterone changes in male F-344 rats. Rats received daily equimolar doses (0.75 or 1.5 mmol/kg) of THMs or PCE (1000 mg/kg) in 4% Emulphor vehicle by oral gavage for 7 days. No significant DNA strand breaks were produced by any THM or PCE treatment. PCE treatment produced increased hyaline droplet formation in renal tubules. However, all THM treatments reduced or eliminated the appearance of renal hyaline droplets. All four THM treatments also produced a decrease in serum testosterone concentrations on day 7, which might account for decreased hyaline droplet formation. No significant increase in cell proliferation, measured by [3H]thymidine incorporation in vivo, appeared in this 1-week study.     

Treatment of Chlorophenols by UV-Based Processes: Correlation of Oxidation By-Products, Wastewater Parameters, and Toxicity

The aim of the study was to evaluate the toxicity and biodegradability of para-chlorophenol (p-CP) model wastewater when treated by UV and UV/H2O2 processes. We investigated the correlations between the toxicity and the concentration of p-CP and its oxidation by-products, as well as other parameters—summarizing characteristics which potentially indicate hazardous water components, e.g., AOX (adsorbable organic halides), TOC (total organic carbon), and COD and BOD5 (chemical and biochemical oxygen demand). Biodegradability is estimated by the BOD5/COD ratio. The toxic effects were investigated on luminescent bacteria Vibrio fischeri, determining the EC50 value. The correlation between each data pair was estimated using a statistical approach calculating the Spearman rank coefficients. The biodegradability of the p-CP model wastewater was improved by the UV/H2O2 process; the BOD5/COD ratio increased from 0.37 to 0.73 after a 1-h treatment (F = 1243??mJ?cm-2). According to the calculated Spearman rank coefficient, the highest correlation with toxicity data among all monitored parameters was obtained for hydroquinone and benzoquinone, as by-products of p-CP degradation, as well as for the BOD5/COD ratio.     

Temporal and Spatial Variations in Bulk Chlorine Decay within a Water Supply System

Modern water treatment must maintain an acceptable balance between the microbial safety of potable water supply, the costs of treatment, and the formation of potentially harmful disinfection by-products (DBPs). In order to achieve the optimum balance, it is essential to understand and predict both the formation of DBP and the decay of chlorine, in relation to source water, treatment processes, storage, and supply. Reported herein are new data which demonstrate the lack of durability, precision, and accuracy associated with earlier empirical chlorine decay rate equations. This work develops an improved methodology for the prediction of variation in chlorine decay rates in distribution systems enabling practical, cost-effective prediction of the effects of both seasonal variations and management interventions on chlorine levels at treatment works and in distribution systems.     

NOM Accumulation at NF Membrane Surface: Impact of Chemistry and Shear

The effects of solution chemistry, surface shear, and composition of natural organic matter (NOM) were investigated for their impact on accumulation of foulant material at the surface of charged polymeric nanofiltration membranes. The source of NOM was the Suwannee River. A bench-scale, batch recycle system was used with 20 hollow fiber, nanofiltration membranes. Membrane flux decline and foulant accumulation increased at low pH and high ionic strength as a result of neutralization of charge, electric double layer compression, and the apparent shift in conformation of charged NOM macromolecules. The rate of NOM accumulation decreased with operating time, suggestive of an eventual steady state between adsorption and desorption. The effect of NOM composition on membrane fouling could not be discerned by a standard technique to isolate hydrophobic and hydrophilic NOM fractions, quite possibly because of the fractionation methodology's failure to recover a small but important fouling fraction or because of NOM interactions that are lost when individual fractions are separately tested. However, a greater percentage of the hydrophilic than hydrophobic fraction permeated the membrane, in agreement with prior observations by others. Increasing the cross flow velocity from 85 to 255 cm∕s reduced the extent of flux decline, presumably due to hydrodynamic disruption of cake layer formation.     

Trihalomethane Species Forecast Using Optimization Methods: Genetic Algorithms and Simulated Annealing

Chlorination is an effective method for disinfection of drinking water. Yet chlorine is a strong oxidizing agent and easily reacts with both organic and inorganic materials. Trihalomethanes (THMs), formed as a by-product of chlorination, are carcinogenic to humans. Models can be derived from linear and nonlinear multiregression analyses to predict the THM species concentration of empirical reaction kinetic equations. The main objective of this study is to predict the concentrations of THM species by minimizing the nonlinear function, representing the errors between the measured and calculated THM concentrations, using the genetic algorithm (GA) and simulated annealing (SA). Additionally, two modifications of SA are employed. The solutions obtained from GA and SA are compared with the measured values and those obtained from a generalized reduced gradient method (GRG2). The results indicate that the proposed heuristic methods are capable of optimizing the nonlinear problem. The predicted concentrations may provide useful information for controlling the chlorination dosage necessary to assure the safety of water drinking.     

Staged Coagulation for Treatment of Refractory Organics

Seasonal periods of high rainfall have been shown to cause elevated natural organic matter (NOM) loadings at treatment works. These high levels lead to difficulties in removing sufficient NOM to meet trihalomethane standards, and hence better alternative treatments are required. Here the removal of NOM was investigated by conventional coagulation treatment using both bulk and fractionated NOM. Initial experiments showed that over 70% removal of the hydrophobic and hydrophilic acid fractions was achieved at the works, while only 16% of the hydrophilic nonacid fraction was being removed. Bench scale jar testing of the isolated NOM fractions demonstrated that high removals of the hydrophobic fractions were achieved and that optimized conditions increased removal of the hydrophilic fractions, indicating that staged coagulation could be of benefit in the removal of the recalcitrant fractions. Experiments using optimized staged coagulation indicated that a small increase in the removal of the total NOM of this water was possible when compared to conventional treatment.     

Extradural temporopolar approach for giant pituitary adenomas invading the cavernous sinus and parasellar regions]

Natural organic matter (NOM) was extracted from a raw water source (Forge Pond, Granby, Mass.) and fractionated into eight groups: fulvic acid, humic acid, hydrophilic acid, weak hydrophobic acids, hydrophilic neutrals, hydrophobic neutrals, hydrophilic bases, and hydrophobic bases. The extent of adsorption of these fractions on preformed aluminum hydroxide flocs was determined. Also, the adsorption affinities of various fractions were correlated to selected NOM properties, i.e., organic charge, molecular weight, and specific ultraviolet absorbance. The nature of the reactions leading to adsorption was discussed, along with the induced dissolution of aluminum from the floc surface and its resulting association with NOM in particulate or colloidal forms.     

Hydrophobicity and Molecular Size Distribution of Unknown TOX in Drinking Water

The analysis of total organic halogen (TOX) in drinking water indicates that a substantial amount of the halogenated compounds cannot be accounted for by known specific disinfection by-products (DBPs). The primary aim of this research was to characterize the hydrophobicity and molecular size distribution of the unknown halogenated DBPs using XAD resins and ultrafiltration membranes. The impact of membrane rejection on the size analysis of unknown TOX was also investigated using chlorinated fulvic acid. Six finished waters from different locations and treatment processes were collected and fractionated into various hydrophobicity and molecular size groups. The results showed that most unknown TOX was in the size range between 0.5?kDa and 10?kDa, but it could have a wide spectrum of hydrophobicities. Simple ultrafiltration was not always reliable as a characterization tool, as it was shown to reject a significant fraction of DBPs with molecular weight (MW) lower than the membrane cutoffs. Flushing with deionized water was effective in removing these low MW compounds from the ultrafiltration cell. A significant reduction in the apparent size of unknown TOX resulted when low MW DBPs were flushed out of the cell (comparing with classic parallel ultrafiltration). Coagulation of fulvic acid also significantly reduced the apparent size of unknown TOX formed by chlorine.     

Ozonation of Spent Reactive Dye-Baths: Effect of HCO3?/CO32? Alkalinity

The effect of carbonate and bicarbonate alkalinity (soda ash buffer as 5,180 mg/L HCO3? alkalinity at pH 7 and as 5,100 mg/L CO32? alkalinity at pH 12) on the ozonation of reactive vinylsulphone dyestuffs in a simulated spent dye-bath has been studied at varying pHs. Adsorbable organic halogen (AOX) formation due to the high chloride content of the effluent and detoxification, which was evaluated in terms of the relative toxicity index Itox determined from the ED50 values for the marine photobacteria Vibrio fischeri, were also evaluated. Highest total organic carbon (56%), chemical oxygen demand (44%), and UV254 (77%) removals were achieved at pH 7 in the presence of HCO3? alkalinity. The fastest decolorization was observed for the case pH 2, the first order decolorization rate constant found as k620 = 0.16?min?1, closely followed by the pH 12 case with soda ash (k620 = 0.12?min?1) case. No positive correlation was evident between AOX, whose maximum value (=1.3 mg/L) appeared after 40 min ozonation at pH 7 and decreased to 0.54 mg/L after 120 min treatment, and Itox, which decreased to 0.16 at t = 50?min and increased rapidly thereafter. The Itox values were more related to color abatement kinetics. The maximum relative toxicity index of Itox = 0.83 occurred after 120 min. It was also established that the presence of alkalinity in the spent reactive dye-bath had no negative impact on the oxidation rates. In contrast, its absence seriously inhibited treatment efficiency. It is speculated that, with added soda ash, the carbonate radicals HCO3? and CO3??, which are more stable and selective than OH?, were produced and promoted the oxidation process.