Effects of Bromide Ion and Natural Organic Matter Fractions on the Formation and Speciation of Chlorination By-Products

The impacts of bromide concentration and natural organic matter (NOM) characteristics on the formation and speciation of disinfection by-products (DBPs) in chlorinated NOM fractions were investigated. A total of 20 bulk water NOM fractions with a wide range of specific ultraviolet (UV) absorbance (SUVA254) values were obtained from a source water employing XAD-8 or XAD-4 resin adsorption in completely mixed batch reactors. SUVA was not a good predictor of DBP [trihalomethanes (THMs), haloacetic acids (HAAs), and adsorbable organic halogens (AOX)] formation and speciation. The destruction in the UV254 absorbance from chlorination did not correlate with DBP formation at any bromide level. NOM moieties which do not absorb UV light at 254?nm significantly contributed to DBP formation. Mass balance calculations on halogens using THMs, HAAs, and AOX data indicated that significant amounts of DBPs (>54% of AOX) other than THMs and HAAs were formed in NOM fractions with 60–110?μg/L bromide concentration. The relative occurrence of such other halogenated by-products decreased with increasing bromide concentrations up to 500?μg/L level. NOM in the studied water was more susceptible to the formation of brominated THM species as opposed to brominated HAAs. At constant dissolved organic carbon concentration, chlorine dose and pH, increasing bromide concentrations in NOM fractions increased the total concentrations of DBPs and resulted in a shift toward the formation of brominated species. Further, increasing bromide concentrations increased the spectrum of detected species (i.e., occurrence of all nine HAAs) and provided a competitive advantage to THM and HAA precursors in NOM over precursors of other DBPs.     

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.     

Modeling Formation of Natural Organic Matter Fouling Layers on Ultrafiltration Membranes

Three simple mathematical models to describe fouling of an ultrafiltration membrane by natural organic matter (NOM) are developed and compared. These models attribute the fouling to: (1) an increase of the effective pore length by an amount equal to the thickness of the NOM gel layer that forms on the membrane surface; (2) formation of a uniform, microporous NOM gel layer on the membrane surface, made of primary particles comprising tens to hundreds of NOM molecules; or (3) narrowing of the membrane pores by sorption of a monolayer of NOM molecules along the full length of each pore. The key parameters characterizing each model are identified and estimated based on data for flux and film growth gathered in the same system. In each case, the estimated parameter values are plausible in light of the known physical properties of the membrane and NOM molecules.     

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.     

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.     

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.     

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.     

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.     

Use of Dubinin–Astakhov Equation to Describe Preloading Effect of Natural Organic Matter

This note presents a simple model to quantify the preloading effect of naturally occurring organic matter (NOM) in water on the adsorption capacity of activated carbon for a trace synthetic organic chemical (SOC). The model was developed from the Dubinin–Astakhov (DA) equation based on the assumption that the NOM preloading irreversibly reduced the limiting adsorption pore volume for the target SOC. Given that the DA-n value equal to one, the model reduces to a form similar to the one obtained by modifying the Freundlich equation directly. By assuming that the reduction of the limiting adsorption pore volume was proportional to the volume of NOM adsorbed, the NOM preloading effect was correlated directly to the amount of total organic carbon preloaded on the carbon. The resulting model was then compared with the experimental data in the literature. This simple model may be useful for certain practical applications that require only the estimation of the NOM preloading effect on the adsorption capacity of a target SOC from natural water.     

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.     

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.     

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.     

Natural Organic Matter Removal by Adsorption onto Carbonaceous Nanoparticles and Coagulation

Nanoparticles have emerged as promising adsorbents for water purification. In this study, nanoscale carbon black was employed to remove natural organic matter (NOM) from water in the presence and absence of coagulation. Standard Suwannee River NOM was employed as the targeted pollutant. In the absence of coagulation, more than 60% NOM removal was achieved by carbon black adsorption. A higher hydrogen ion concentration (pH) (3–5) was favorable for NOM removal. More than 35% NOM was removed by carbon black adsorption in the first 20 min, and the adsorption of NOM onto carbon black occurred within about 2 h. Proper stirring was essential for the mixture of NOM and carbon black, while insufficient stirring or overstirring decreased NOM removal efficiency. When low dosages of coagulants were used in combination with carbon black at pH 6–7, the removal efficiency of NOM increased significantly. Depending on the coagulant, the sequencing of adsorption and coagulation can be important. Almost 90% NOM was removed in 15 min by carbon black adsorption and alum coagulation, which is a higher removal than for conventional treatment. This study indicated that carbon black might be an important adsorbent for NOM removal in water treatment in combination with low doses of alum.     

Characterization of the Flocculation Process from the Evolution of Particle Size Distributions

A flocculator-imaging system was developed to characterize the dynamics of particle size distribution (PSD) during flocculation. The system consisted of a flocculator coupled with an external flow-through cell for observation and photography, a microscopic charge-coupled device video recorder with backlighting, and an image analyzer. This nonintrusive side-stream setup was used to record the evolution of the PSD to determine the flocculation dynamics of three types of particle systems: Clean kaolin, kaolin coated with natural organic matter (NOM), and the kaolin/NOM system after ozonation. In addition to the PSD measurement, the ζ potential, NOM reduction, and turbidity removal after the jar test of flocculation and sedimentation were determined for the particle systems at various alum dosages. The results of the ζ-potential analysis and the PSD measurement indicated that flocculation takes place rapidly to form highly porous aggregates when the particle surface charge is fully neutralized. The adsorption of NOM on the particle surface stabilized the particles considerably, and thus hindered the flocculation process. Sweep flocculation using a much higher alum dosage was an effective means of process enhancement for the removal of particulates and associated organic matter. Ozonation of the kaolin/NOM solution, however, did not appear to have any positive effect on particle destabilization and flocculation. It is argued that ozonation produced more acidic functional groups in the NOM on kaolin, which increased the surface charge density and hence the stability of the particles in softer water.     

Trihalomethane and Haloacetic Acid Disinfection By-Products in Full-Scale Drinking Water Systems

Trihalomethane (THM), haloacetic acid (HAA5), and total organic carbon (TOC) data provided by the Missouri Dept. of Natural Resources for drinking water treatment systems in the State of Missouri was analyzed for the years 1997–2001. These data indicated that a significant portion of systems exceeded the current regulatory limits of 80 and 60?μg/L for THM and HAA5 in these years. The vast majority of the treatment plants exceeding the regulatory limits were small plants with service populations less than 10,000 people. No significant temporal trend in either THM or HAA5 was noted for the years 1997–2001. This work suggests that the proposed use of a locational running annual average may have a significant effect on compliance. The use of chloramines (combined chlorine) versus free chlorine (HOCl/OCl?) as a residual disinfectant was shown to significantly reduce both THM and HAA5 in systems that treat their own water (primary systems), but did not have a significant effect in systems which purchase their water from primary systems (secondary systems). Comparison of finished water at the treatment plant versus in the distribution system suggested that a majority of THM and HAA5 may be produced within the plant as opposed to the distribution system. Hence, reducing these chlorinated disinfection byproducts within the treatment plant itself should be a key focus for achieving compliance, and supports Environmental Protection Agency disinfection byproducts compliance guidelines using enhanced coagulation.     

Impact of Booster Chlorination on Chlorine Decay and THM Production: Simulated Analysis

The effect of conventional and booster chlorination on chlorine residuals and trihalomethane (THM) formation in drinking water distribution systems was modeled using the EPANET hydraulic modeling software. The model results suggest that booster chlorination may allow utilities to meet disinfection goals better by carrying chlorine residuals to remote points in the distribution system while lowering the total mass of chlorine applied to the system. The model results suggest that booster chlorination may provide the greatest advantages to points in the distribution system located near storage tanks by providing a more consistent chlorine residual and possibly reducing THM formation. A new version of the EPANET model, the EPANET Multispecies model, was also used to compare chlorine decay due to reactions in the bulk fluid and reactions occurring at the pipe wall. The results suggest that chlorine decay due to wall reactions can be very significant at remote points in the distribution system. Additionally, if THMs are assumed to form primarily through reactions in the bulk fluid, use of the new EPANET Multispecies software allows for calculation of THM formation based solely on chlorine reactions in the bulk fluid rather than on overall chlorine decay.     

Novel reagents for iron and sulphur control in medium temperature leaching of sulphide concentrates

Hydrometallurgical leaching of sulphide concentrates of copper and nickel at medium temperature (150°C) produces residues that contain sulphur and iron-bearing minerals and phases. During leaching, and depending on various process parameters, iron may be precipitated as hematite, goethite, jarosite or other oxyhydroxides, which may be more or less crystalline. Hematite is the favoured iron precipitate, because it is the most environmentally stable and does not ad/absorb as much copper, nickel or other solution constituents during precipitation. However, the low solubility of iron during the medium temperature processing of sulphide ores can favour the formation of poorly crystalline, nano-scale iron oxide/oxyhydroxide phases. In some cases, these phases have been positively identified as the metastable ferrihydrite, which transforms into iron oxides such as goethite, hematite and magnetite over time. A better understanding of what may help drive this transformation during leaching would ultimately result in lower valuable metal losses and more stable leach residues. Higher acid concentrations result in increased copper extractions and favour the formation of hematite during concentrate leaching, rather than other metastable phases. Furthermore, commercially available water displacement formula ‘WD40®’ and other novel reagent(s) affect Fe precipitation and sulphur chemistry, leading to very different process outcomes such as improved extractions and larger, more easily separated, sulphur particles.     

Predicting Minimum Carbon Usage for PAC Adsorption of Trace Organic Contaminants from Natural Water

Powdered activated carbon (PAC) is an excellent adsorbent for drinking water treatment of many trace organic contaminants. To evaluate and design a PAC adsorption process for a particular application, it is necessary to know the minimum (lowest economical) carbon (adsorbent) usage (MCU) defined thermodynamically. In this work, an explicit relationship is developed for predicting the MCU required for a desirable level of treatment of a target trace organic compound (TC). The adsorption processes considered are PAC slurry contactors idealized either as batch reactors, plug flow reactors, or continuous-flow stirred tank reactors. Comparing with the ones previously available in the literature, this newly developed relationship, as a predictive tool for practical uses as well, is more accurate because it does not need to assume that the MCU required for target TC removal can always reduce the competing background natural organic matter (NOM) to a level much less than the NOM initial/influent concentration. Applications of the relationship developed herein to PAC adsorption of typical trace organic contaminants in natural water are demonstrated with isotherm data from multiple literature sources.     

Zeta Potential, Dissolved Organic Carbon, and Removal of Cryptosporidium Oocysts by Coagulation and Sedimentation

This study evaluated the removal of viable Cryptosporidium parvum oocysts and changes in zeta potential during alum coagulation and sedimentation. Experiments were designed to evaluate oocyst removal and oocyst zeta potential at three initial dissolved organic carbon (DOC) concentrations and a wide range of alum doses and coagulation pH values. The study showed that changes in the initial DOC concentration affected the zeta potential of Cryptosporidium parvum oocysts and the removal of oocysts. Oocysts did not appear to be removed by a charge neutralization mechanism under the conditions used in this research. Sweep flocculation appeared to be the primary removal mechanism at the lowest DOC concentration tested in this study. For the highest DOC concentration tested, optimal coagulation conditions for oocyst removal coincided with optimal coagulation conditions for natural organic matter (NOM) removal, suggesting that NOM played a key role in the interaction between oocysts and the aluminum hydroxide precipitate.