Formation Of Haloacetic Acids Research Articles

Persistent free radicals in natural organic matter activated by iron particles enhanced disinfection byproduct formation

The widespread presence of iron (Fe) particles and natural organic matter (NOM) in drinking water distribution systems (DWDS) can significantly affect tap water quality, contributing to aesthetic issues and potentially generating harmful disinfection byproducts (DBPs). This study revealed that Fe particles, when combined with humic acid (HA), substantially increased DBP formation during chlorination. Fe particles (particularly preformed Fe particles) significantly increased haloacetic acid (HAA) formation by activating the persistent free radicals (PFRs) in the HA. Compared with the control system without Fe particles, greater than 2 times of HAA increase were observed for the system with Fe pariticles. PFRs accumulated on Fe particle surface could generate hydroxyl radicals, facilitating the decomposition of HA into smaller molecules, which were more reactive with chlorine disinfectants, thus elevated the DBP formation including both known and unknown N-DBPs and Cl-DBPs. The DBP promotion effect of in-situ formed Fe particles was much less than that of preformed Fe particles although both in-situ formed and preformed Fe particles could accumulate PFRs from HA. In-situ formed particles primarily accumulated carbon-centered PFRs, while preformed particles accumulated oxygen-centered PFRs. To mitigate the Fe particle induced water quality risks, it is crucial to control iron pipe corrosion and iron release in DWDS. In addtion, the optimization of treatment processes such as coagulation and filtration to more completely remove NOM and Fe particles could help minimize the DBP formation.

Optimizing the number, locations, and chlorine dosages of booster chlorination stations in water distribution networks

ABSTRACT Safe and reliable drinking water is essential for sustaining life. Chlorination is widely used for disinfection in water distribution networks (WDNs). A higher dose of chlorine is required in an overhead service reservoir to maintain minimum residual chlorine at the farthest end in WDNs. However, delivering high dosages of chlorine from storage tanks can pose public health issues, especially for the residents living near overhead service reservoirs due to the formation of trihalomethanes, haloacetic acids, and chlorophenols. In addition, a higher dosage will lead to increased chlorine consumption and will accelerate pipe corrosion. Booster chlorination (BC) stations with smaller dosages are a solution to this problem. However, identifying the optimal number, locations, and dosage of each BC station in a cost-effective manner is challenging. This study proposes a methodology for determining the optimal number, locations, and chlorine dosages of BC stations in WDNs using a mixed integer linear programming problem. The methodology is illustrated through a simplified WDN in Holeta town, Ethiopia. The results indicate that if one adds two BC stations beyond the three dosage stations at the source, it will lead to a 49% reduction in chlorine use and a 27% decrease in the life cycle cost.

Control of chlorination disinfection by-products in drinking water by combined nanofiltration process: A case study with trihalomethanes and haloacetic acids

Disinfection by-products (DBPs) are prevalent contaminants in drinking water and are primarily linked to issues regarding water quality. These contaminants have been associated with various adverse health effects. Among different treatment processes, nanofiltration (NF) has demonstrated superior performance in effectively reducing the levels of DBPs compared to conventional processes and ozone-biological activated carbon (O3-BAC) processes. In this experiment, we systematically investigated the performance of three advanced membrane filtration treatment schemes, namely "sand filter + nanofiltration" (SF + NF), "sand filter + ozone-biological activated carbon + nanofiltration" (SF + O3-BAC + NF), and "ultrafiltration + nanofiltration" (UF + NF), in terms of their ability to control disinfection by-product (DBP) formation in treated water, analyzed the source and fate of DBP precursors during chlorination, and elucidated the role of precursor molecular weight distribution during membrane filtration in relation to DBP formation potential (DBPFP). The results indicated that each treatment process reduced DBPFP, as measured by trihalomethane formation potential (THMFP) and haloacetic acid formation potential (HAAFP), with the SF + O3-BAC + NF process being the most effective (14.27 μg/L and 14.88 μg/L), followed by the SF + NF process (21.04 μg/L and 16.29 μg/L) and the UF + NF process (26.26 μg/L and 21.75 μg/L). Tyrosine, tryptophan, and soluble microbial products were identified as the major DBP precursors during chlorination, with their fluorescence intensity decreasing gradually as water treatment progressed. Additionally, while large molecular weight organics (60–100,000 KDa) played a minor role in DBPFP, small molecular weight organics (0.2–5 KDa) were highlighted as key contributors to DBPFP, and medium molecular weight organics (5–60 KDa) could adhere to the membrane surface and reduce DBPFP. Based on these findings, the combined NF process can be reasonably selected for controlling DBP formation, with potential long-term benefits for human health.

Comparison of Fe‐based and Al‐based coagulants in the removal of organic and disinfection by‐product precursors

AbstractSurface water is renowned for its natural organic matter, constituting approximately 45% of total dissolved organic carbon (DOC) which can be removed in water treatment plants. However, residual DOC in water can react with chlorine to form several carcinogenic disinfectant by‐products (DBPs). This study aimed to examine the molecular weight of organic fractions dissolved in three different water sources that act as precursors to the formation of DBPs species. The coagulants used were Al‐ and Fe‐based, frequently used in water treatment plants to remove organic fractions. Characterization of DOC in source water served as the first step in determining the performance of both coagulants in terms of organic properties. The results showed that the selected surface waters had similar DOC characteristics, including biopolymers, humic substances, building blocks, and a low molecular weight. These fractions contributed to the formation of trihalomethanes (THMs) and haloacetic acids (HAAs). The Fe‐based coagulant was more effective than the Al‐based coagulant in removing all organic fractions and reducing THMs compared to HAAs. Furthermore, one‐way ANOVA analysis showed a significant difference in the average removal of organic fractions and DBP species between the Fe‐based and Al‐based coagulants. The Fe‐based coagulant showed higher efficiency in removing biopolymers, dibromochloromethane, and chlorodibromoacetic acid than the Al‐based coagulant. In contrast, the Al‐based coagulant had better performance in reducing dibromo HAA and tribromo HAA. Both coagulants had no significant difference in extracting other organic fractions or DBPs species.

Modeling chloramine stability and disinfection byproduct formation in groundwater high in bromide

AbstractBromide can promote monochloramine decomposition and disinfection byproduct (DBP) formation. Monochloramine and total chlorine stability as well as total trihalomethane and haloacetic acid formation were examined in groundwater with high bromide levels (300–1700 μg/L) following chlorine or KMnO₄ preoxidation. An N,N‐Diethyl‐p‐phenylenediamine (DPD)‐based total chlorine method detected chloramines and brominated amines (e.g., NH2Br, NHBrCl). An indophenol‐based monochloramine method showed minimal interference from brominated amines. Differences between these methods' measurements likely indicated brominated amine concentrations. Substantial total chlorine demands (up to ~3.5 mg/L in 4 days) following chlorine preoxidation were observed due to the presence of brominated amines. Total chlorine measurements were more stable and DBP formation was limited following KMnO₄ preoxidation because ammonia was dosed before chlorine, which inhibited brominated amine formation. A kinetic model developed elsewhere for dissolved organic matter (DOM)‐free water generally tracked with experimental results but some deviations occurred possibly because DOM consumed bromochloramine or its reaction intermediates.

Comparative formation of chlorinated and brominated disinfection byproducts from chlorination and bromination of amino acids

Amino acids are the main components of dissolved organic nitrogen in algal- and wastewater-impacted waters, which can react with chlorine to form toxic halogenated disinfection by-products (DBPs) in the disinfection process. In the presence of bromide, the reaction between amino acids and secondarily formed hypobromous acid can lead to the formation of brominated DBPs that are more toxic than chlorinated analogues. This study compares the formation of regulated and unregulated DBPs during chlorination and bromination of representative amino acids (AAs) (e.g., aspartic acid, asparagine, tryptophan, tyrosine, and histidine). In general, concentrations of brominated DBPs (trihalomethanes, haloacetonitriles, and haloacetamides, 24.9–5835.0 nM) during bromination were higher than their chlorinated analogues (9.3–3235.3 nM) during chlorination. This indicates the greater efficacy of bromine as a halogenating agent. However, the formation of chlorinated haloacetic acids during chlorination was higher than the corresponding brominated DBPs from bromination. It is likely that an oxidation pathway is required for the formation of haloacetic acids and chlorine is a stronger oxidant than bromine. Moreover, chlorine forms higher levels of haloacetaldehydes (74.4–1077.8 nM) from amino acids than bromine (1.0–480.2 nM) owing to the instability of brominated species. The DBP formation yields depend on the types of functional groups in the side chain of AAs. Eight intermediates resulting from chlorination/bromination of tyrosine were identified by triple quadrupole mass spectrometer, including N-chlorinated/brominated tyrosine, 3-chloro/bromo-tyrosine, and 3,5-dichloro/dibromo-tyrosine. These findings provided new insights into the DBP formation during the chlorination of algal- and wastewater-impacted waters with elevated bromide.

Insight into the chemical transformation and organic release of polyurethane microplastics during chlorination

The ubiquitous occurrence of microplastics in water and wastewater is a growing concern. In this study, the chemical transformation and organic release of virgin and UV-aged thermoplastic polyurethane (TPU) polymers during chlorination were investigated. As compared to virgin TPU polymer, the UV-aged TPU polymer exhibited high chlorine reactivity with noticeable destruction on its surface functional groups after chlorination, which could be ascribed to the UV-induced activation of hard segment of TPU backbone and increased contact area. The concentrations of leached organics increased by 1.6-fold with obviously high abundances of low-molecular-weight components. Additives, monomers, compounds relating to TPU chain extension, and their chlorination byproducts contributed to the increased organic release. Meanwhile, the formation of chloroform, haloacetic acids, trichloroacetaldehyde, and dichloroacetonitrile increased by 3.8-, 1.7-, 4.9-, and 2.4-fold, respectively. Two additives and six chlorination byproducts in leachate from chlorinated UV-aged TPU were predicted as highly toxic, e.g., butyl octyl phthalate, palmitic acid, 2,6-di-tert-butyl-1,4-benzoquinone, and chlorinated aniline. Evaluated by human hepatocarcinoma cells, the 50% lethal concentration factor of organics released from chlorinated UV-aged TPU was approximately 10% of that from its virgin counterpart, indicating a substantially increased level of cytotoxicity. This study highlights that the release of additives and chlorination byproducts from the chemical transformation of UV-aged microplastics during chlorination may be of potentially toxic concern.

Nontargeted identification of disinfection by-product precursors from soluble microbial products in municipal secondary effluent

As soluble microbial products (SMPs) can serve as precursors for disinfection by-products (DBPs), the release of SMPs from municipal secondary effluent has the potential to increase the health hazards associated with reused water. Nontargeted identification of DBPs precursors from SMPs in municipal secondary effluent was explored in the present research. The hydrophobic (HPO) fraction that constituted the major portion of the SMPs was 48.0%, and the majority of organic SMPs were composed of low molecular weight (LMW) compounds. The results showed that the HPO fraction with MW < 1 kDa component has the highest disinfection by-product formation potentials (DBPFPs). X-ray photoelectron spectroscopy (XPS) results showed that the HPO fraction with MW < 1 kDa component was mainly composed of OC–OH (40.2%) and amide/peptide N (46.7%) functional groups. This finding was in line with the results showing the highest yields of DBPFPs in terms of HAAs (haloacetic acids) and trichloroacetamide (TCAcAm). Ultra-performance liquid chromatography coupled with tandem quadrupole-time-of-flight mass spectrometry (UPLC-Q-ToF-MS) data revealed that phospholipids, fatty acids, fatty acyls-fatty amides, phosphatidylcholine, glycosides, fatty acid esters, glycolipid, and steroids were the main chemical classes in SMPs. Among these chemical classes, phospholipids containing amino acids structures and fatty acids containing carboxyl functional groups with the maximum abundance could promote the formation of HAAs. This research offers a thorough characterization of SMPs derived from municipal secondary effluent. These results enable the implementation of targeted methods to decrease the formation of DBPs by identifying potential precursors of DBPs.

Biological Activated Carbon Filtration Controls Membrane Fouling and Reduces By-Products from Chemically Enhanced Backwashing during Ultrafiltration Treatment

Water purification by ultrafiltration (UF) requires regular membrane cleaning via backwashing. In the case of chemically enhanced backwashing (CEB), it can result in the formation of unwanted by-product precursors due to reactions with organic matters present in the backwashing water and accumulating on the membrane. After subsequent disinfection, these precursors are prone to generate trihalomethanes (THMs) and haloacetic acids (HAAs), posing potential risks to the chemical safety of drinking water. However, limited information was available regarding the removal of these disinfection by-products. In this study, biological activated carbon (BAC) pretreatment followed by UF with chemically enhanced backwashing (CEB) (BAC-UF-CEB) was investigated to mitigate membrane fouling and reduce by-product formation. It was tested in parallel with UF with CEB (UF-CEB) and UF with sole physical backwashing. Compared to UF-CEB, BAC pretreatment prior to UF-CEB reduced transmembrane pressure (TMP) by 49.0%. BAC achieved high removals of dissolved organic carbon (59.99%) and UV254 absorbance (80.82%) in the BAC-UF-CEB effluent. Moreover, BAC-UF-CEB substantially decreased trihalomethane and haloacetic acid formation potentials by 83.28% compared to UF-CEB. BAC alleviated irreversible membrane fouling by 78.7%. By removing disinfection by-product precursors, BAC-UF-CEB markedly improved treated water quality and chemical safety. This study demonstrates BAC pretreatment effectively mitigates membrane fouling and controls disinfection by-products during UF water treatment.

Magnetic ion exchange resin for reducing disinfection byproducts in drinking water: Pilot-scale study and organic matter characterization

Disinfection is an essential step in drinking water treatment to prevent waterborne illnesses. However, reaction of disinfectants with organic matter in the water can produce carcinogenic disinfection byproducts (DBPs), including trihalomethanes (THMs) and haloacetic acids (HAAs). Magnetic ion exchange (MIEX) resin has been used as a pretreatment to remove organics and reduce DBPs. In this study, a pilot-scale water treatment plant in Birmingham, AL (USA) that employed MIEX as a pretreatment to the conventional pilot treatment train was compared against an adjacent full-scale train that did not use MIEX. THM and HAA formation was tested via simulated distribution system (SDS) testing, and changes in organic character were assessed using fluorescence spectroscopy. MIEX treatment provided 20 % and 25 % removal of THMs and HAAs, respectively, compared to the full-scale treatment under typical SDS conditions. With higher residence times and incubation temperatures (15 days at 35 °C), MIEX treatment reduced HAAs by 36 %. Parallel factor (PARAFAC) analysis revealed that MIEX treatment reduced loadings for a terrestrial humic-like component. Additionally, MIEX treatment resulted in secondary benefits, including a reduction in the coagulant feed rate and a more stable pH and chlorine residual in the MIEX-treated water compared to full-scale treatment.

CuO Promotes the Formation of Halogenated Disinfection Byproducts during Chlorination via an Enhanced Oxidation Pathway.

Previous studies showed that cupric oxide (CuO) can enhance the formation of trihalomethanes (THMs), haloacetic acids, and bromate during chlorination of bromide-containing waters. In this study, the impact of CuO on the formation kinetics and mechanisms of halogenated disinfection byproducts (DBPs) during chlorination was investigated. CuO does not enhance the formation of DBPs (i.e., 1,1,1-trichloropropanone, chloroform, and trichloroacetaldehyde (TCAL) /dichloroacetonitrile) during chlorination of acetone, 3-oxopentanedioic acid (3-OPA), and aspartic acid, respectively. This indicates that the halogen substitution pathway cannot be enhanced by CuO. Instead, CuO (0.1 g L-1) accelerates the second-order rate constants for reactions of chlorine (HOCl) with TCAL, citric acid, and oxalic acid at pH 8.0 and 21 °C from <0.1 to 29.4, 7.2, and 15.8 M-1 s-1, respectively. Oxidation pathway predominates based on the quantification of oxidation products (e.g., a trichloroacetic acid yield of ∼100% from TCAL) and kinetic modeling. CuO can enhance the formation of DBPs (e.g., THMs, haloacetaldehydes, and haloacetonitriles) during chlorination of model compounds and dissolved organic matter, of which both halogen substitution and oxidation pathways are required. Reaction rate constants of rate-limiting steps (e.g., citric acid to 3-OPA, aromatic ring cleavage) could be enhanced by CuO via an oxidation pathway since CuO-HOCl complex is more oxidative toward a range of substrates than HOCl in water. These findings provide novel insights into the DBP formation pathway in copper-containing distribution systems.

Formation and speciation of hazardous trihalomethanes and haloacetic acids during chlorinated washing of brined kimchi cabbage in the presence of bromide

Brominated disinfection byproducts (Br-DBPs) may be generated in high concentrations during the chlorinated washing of brined kimchi cabbage (BKC) in kimchi manufacturing. However, the generation of these DBPs is not sufficiently understood. Therefore, in this study, we investigated the formation and speciation of the DBPs trihalomethanes (THMs) and haloacetic acids (HAAs) during the chlorinated washing process. The average bromide content in 22 salt products sourced from various regions of Korea was 1600 ± 468 mg/kg. Increasing bromide content shifted the speciation of DBPs from chlorinated to mixed bromochloro to brominated species, which would be more harmful than their chlorinated analogs. DBP formation during the washing of BKC at average bromide levels changed based on the brine salinity, salting temperature, and disinfectant type. Based on our findings, we recommend that low salinity and low temperature should be maintained during the salting of KC and that NaOCl should be used as the disinfectant rather than slightly acidic electrolyzed water during the chlorinated washing of KC to alleviate the formation of Br-DBPs. Moreover, we recommend the use of salts with low bromide levels for the salting of KC and the addition of a rinse step after chlorinated washing.

Degradation of natural organic matter and disinfection byproducts formation by solar photolysis of free available chlorine

Environment disinfection effectively curbs transmission of the Severe Acute Respiratory Syndrome Coronavirus-2 (SARS-CoV-2). However, elevated concentration of free available chlorine (FAC) in disinfectants can be discharged into surface water, generating toxic disinfection byproducts (DBPs). The impact of solar photolysis of FAC on natural organic matter (NOM) to form DBPs has not been well studied. In this work, solar photolysis of FAC was found to result in higher formation of DBPs, DBPs formation potential (DBPsFP), total organic chlorine (TOCl) and lower specific ultraviolet absorbance at 254 nm (SUVA254), compared to dark chlorination. In solar photolysis of FAC, formation of total DBPs was promoted by pH=8, but hindered by the addition of HCO3−, radical scavenger or deoxygenation, while addition of NO3−and NH4+both enhanced the formation of nitrogenous DBPs. Differences in the formation of DBPs in solar photolysis of FAC under various conditions were influenced by reactive species. The formation of trichloromethane (TCM) and haloacetic acids (HAAs) in solar photolysis of FAC positively correlated with the steady-state concentrations of ClO• and O3. The steady-state concentrations of •NO and •NH2 positively correlated with the formation of halonitromethanes (HNMs). HAAs and haloacetonitriles (HANs) mainly contributed to calculated cytotoxicity of DBPs. This study demonstrates that solar photolysis of FAC may significantly impact the formation of DBPs in surface water due to extensive use of disinfectants containing FAC during SARS-CoV-2 pandemic.

Removal of Haloacetic Acids via Adsorption and Biodegradation in a Bench-Scale Filtration System

Brominated disinfection byproducts (DBPs) are a concern to drinking water utilities due to their toxicity and increasing prevalence in water systems. Haloacetic acids (HAAs) are a class of DBPs that are partially regulated by the United States Environmental Protection Agency (USEPA), but regulations are likely to increase as evidenced by the brominated HAAs listed on the USEPA Fourth Unregulated Contaminant Monitoring Rule and Fifth Contaminant Candidate List. Utilities often use a pre-oxidant to assist in their treatment training, but this can lead to increased HAA formation during treatment. In this study, tap water was spiked with bromine (Br2) at varying concentrations to simulate bromine-to-chlorine ratios found in the natural environment and the DBPs that may be formed from those waters. The water was fed through a bench-scale biological filter (biofilter) with a small layer of fresh granular activated carbon (GAC) media followed by acclimated anthracite media. The HAA species studied were found to be removable by an average of 89.5% through combined GAC filtration and biofiltration. Biodegradation occurred predominantly in the first five minutes for the acclimated anthracite, with minimal additional removal observed at longer empty bed contact times (15 and 30 min EBCT). This study provides recommendations on biofilter parameters for utilities to reduce the formation of both regulated and unregulated HAAs during the drinking water treatment process.

Genotoxicity and endocrine disruption potential of haloacetic acids in human placental and lung cells

Chlorination of water results in the formation of haloacetic acids (HAAs) as major disinfection byproducts (DBPs). Previous studies have reported some HAAs species to act as cytotoxic, genotoxic, and carcinogenic. This work aimed at further exploring the toxicity potential of the most investigated HAAs (chloroacetic (CAA), bromoacetic (BAA), iodoacetic (IAA) acid) and HAAs species with high content of bromine (tribromoacetic acid (TBAA)), and iodine in their structures (chloroiodoacetic (CIAA) and diiodoacetic acid (DIAA)) to human cells. Novel knowledge was generated regarding cytotoxicity, oxidative stress, endocrine disrupting potential, and genotoxicity of these HAAs by using human placental and lung cells as in vitro models, not previously used for DBP assessment. IAA showed the highest cytotoxicity (EC50: 7.5 μM) and ability to generate ROS (up to 3-fold) in placental cells, followed by BAA (EC50: 20–25 μM and 2.1-fold). TBAA, CAA, DIAA, and CIAA showed no significant cytotoxicity (EC50 > 250 μM). All tested HAAs decreased the expression of the steroidogenic gene hsd17b1 up to 40 % in placental cells, and IAA and BAA (0.01–1 μM) slightly inhibited the aromatase activity. HAAs also induced the formation of micronuclei in A549 lung cells after 48 h of exposure. IAA and BAA showed a non-significant increase in micronuclei formation at low concentrations (1 μM), while BAA, CAA, CIAA and TBAA were genotoxic at exposure concentrations above 10 μM (100 μM in the case of DIAA). These results point to genotoxic and endocrine disruption effects associated with HAA exposure at low concentrations (0.01–1 μM), and the usefulness of the selected bioassays to provide fast and sensitive responses to HAA exposure, particularly in terms of genotoxicity and endocrine disruption effects. Further studies are needed to define thresholds that better protect public health.

Challenges of point-of-use devices in purifying tap water: The growth of biofilm on filters and the formation of disinfection byproducts

Currently, polypropylene (PP) and granular activated carbon (GAC) are widely used as the filters in point-of-use devices (POUs). However, the effect of biofilms formation in aged filters and subsequent formation/removal of disinfection byproducts (DBPs) during the use of POUs on purifying tap water remains unclear. In this study, the influence of filter replace event and filter usage time on the removal of DBPs by pristine or aged filters, such as trihalomethanes (THMs) and haloacetic acids (HAAs), was investigated. Additionally, the effect of biofilms-attached PP filters and GAC filters on DBPs concentration in treated water was explored. The results showed that POUs effectively removed over 60% of THMs and HAAs from tap water, while the removal efficiency decreased with the operation time. The increase in usage time of PP filters led to elevated levels of DBPs. Moreover, the pristine pre-GAC filters removed 12.31% of THMs and 6.62% of HAAs, respectively, while aged GAC filters enhanced the removal of HAAs. SEM and high-throughput sequencing analysis confirmed the attached growth of biofilms on aged PP and GAC filters. The biofilms growth on PP filters led to the formation of THMs and HAAs, and the formed DBPs increased with increasing influent chlorine concentration, lengthened filters usage time and stagnation time. Nevertheless, the DBPs in effluent of biofilms-attached GAC filters increased with increasing influent chlorine concentration and filter usage time while decreased with stagnation time. These results indicated that growth of biofilms commonly observed in filters of POUs leads to the formation of DBPs and increases the risk of DBPs exposure to users of POU devices.

Investigation of Chloramines, Disinfection Byproducts, and Nitrification in Chloraminated Drinking Water Distribution Systems.

Four chloraminated drinking water distribution systems (CDWDSs) required to maintain numeric versus "detectable" residuals were spatially and temporally sampled for water quality and associated trihalomethane (THM) and haloacetic acid (HAA) formation. Monochloramine decreased from entry point (EP) to maximum residence time (MRT) samples while THMs and HAAs initially increased and then stabilized or slightly decreased. Subsequently, EP and MRT samples were used in laboratory-held studies to further evaluate disinfectant residual stability, chloramine speciation, and nitrification occurrence. MRT water exhibited a faster monochloramine concentration decline compared to EP water, indicating a decreasing disinfectant residual stability from increasing water age through distribution. Using a simple technique based on published inorganic chloramine chemistry, samples were also investigated for nondisinfectant positive interference (NDPI) on total chlorine measurements. NDPI concentrations represented up to 100% of the total chlorine concentration when total chlorine concentrations decreased to 0.05 mg-Cl2/L, indicating little to no effective disinfectant residual remained.

Model for halo-acetic acids formation in bulk water of water supply systems.

With increased understanding of the differences in toxicity between species of haloacetic acids (HAAs) and the possibility of more stringent regulations, the ability to predict individual HAA species formation is important. Nine different haloacetic acids are regulated and their total concentration is referred to as HAA9. A mathematical model to predict concentrations of HAA species was proposed and tested using independent data sets. The amount of HAA9 formed per unit amount of chlorine consumed (μg-HAA9/mg-consumed chlorine) remained constant throughout the reaction times in each sample. Similarly, the fraction of a given HAA species largely remained constant during most of the reaction time. Thus, each HAA species was assumed to have its own yield with respect to consumed chlorine in a given water sample. The parallel second-order (2R) model describing chlorine decay kinetics was then extended to predict HAA species formation kinetics. The combined chlorine and HAA species model closely predicts all tested HAA species and its sum with standard error ≤ 5 μg/L. Within the tested waters having Cl2/N mass ratio ≥ 10.7 (g-Cl2/g-N), ammonia did not impact the mass yield. The mass yield of each HAA species can be calculated from three measurements (e.g. at 0, 4 and 24 h) of HAA species and chlorine. Once the yield is known, HAA species concentrations could be predicted for up to 120 h with only chlorine measurements. The model extends the previous work of predicting the trihalomethane species formation kinetics to HAA species formation kinetics. Further research is needed to understand how the yield varies with source water quality, treatment and in distribution systems.

Developing a UV dosing strategy for UV/chlorine process towards the trade-off between pharmaceuticals and personal care products degradation and disinfection by-products formation

In addition to UV wavelength and pH, UV irradiation intensity and fluence also play crucial roles in the UV/chlorine treatment of drinking water. This work aimed to develop a novel UV irradiation strategy to achieve a trade-off between pharmaceuticals and personal care products (PPCPs) degradation and disinfection by-products (DBPs) formation during UV/chlorine water treatment under a specific chlorine dose. Under high UV irradiation intensity at the same UV fluence, the faster chlorine photolysis produced higher steady-state concentrations of •Cl and •OH species but abated cumulative exposures of free available chlorine (CTFAC = ∫0t[Cl2]dt). As a result, the degradation rate of PPCPs was accelerated, but the removal percentage of some PPCPs decreased. Meanwhile, the degradation of the chromophores of dissolved organic matters (DOM) declined by 23.3%–24.8% under the higher UV irradiation intensity. Reducing CTFAC values (50.7%–57.6%) by high UV irradiation intensity could mitigate the formation of haloacetic acids, trihalomethanes and absorbable organic halogens (13.9%–14.9%), which addressed the key role of active chlorine in the formation of DBPs in the UV/chlorine process. DBPs were mainly generated from the interactions of DOM with reactive chlorine. The Vibrio fischeri data further indicated that increasing UV intensity reduced acute toxicity regardless of UV wavelength or water pH. For the same UV fluence dose, the high UV irradiation intensity can effectively control the trade-off between oxidation efficiency and DBPs formation during UV/chlorine treatment.

Changes in the structural characteristics of EfOM during coagulation by aluminum chloride and the effect on the formation of disinfection byproducts

The effects of coagulation on the removal efficiency of different fractions of effluent organic matter (EfOM) from wastewater treatment plants were investigated to identify changes in their structural characteristics and the influences on trihalomethane formation potential (THMFP) and haloacetic acid formation potential (HAAFP). The results indicated that coagulation performed better for the removal of hydrophobic base (HOB) and hydrophobic neutral (HON) fractions than hydrophilic (HI) and hydrophobic acid (HOA) fractions. The removal efficiency was higher under neutral than under acidic conditions for all fractions. As a result, lower levels of THMFP and HAAFP were detected at pH7. The excitation-emission matrix spectra indicated that the HI fraction contained humic acid-like substances that reacted with chlorine to form THMs. The HON fraction contained soluble microbial byproduct-like substances with a higher potential to create HAAs. The results of Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and high-pressure size exclusion chromatography (HP-SEC) of the raw and coagulated water indicated that a higher molecular weight, α-carbon, COOH, aromatic structures, and polysaccharides were associated with a higher production of disinfection byproducts (DBP). These results elucidate the coagulation efficiencies of EfOM fractions associated with different mechanisms and facilitate the prediction of DBP formation by each fraction based on specific structural characteristics.