Innovative method for prioritizing emerging disinfection by-products (DBPs) in drinking water on the basis of their potential impact on public health

Providing microbiologically safe drinking water is a major public health issue. However, chemical disinfection can produce unintended health hazards involving disinfection by-products (DBPs). In an attempt to clarify the potential public health concerns associated with emerging disinfection by-products (EDBPs), this study was intended to help to identify those suspected of posing potential related health effects. In view of the ever-growing list of EDBPs in drinking water and the lack of consensus about them, we have developed an innovative prioritization method that would allow us to address this issue. We first set up an exhaustive database including all the current published data relating to EDBPs in drinking water (toxicity, occurrence, epidemiology and international or local guidelines/regulations).We then developed a ranking method intended to prioritize the EDBPs. This method, which was based on a calculation matrix with different coefficients, was applied to the data regarding their potential contribution to the health risk assessment process. This procedure allowed us to identify and rank three different groups of EDBPs: Group I, consisting of the most critical EDBPs with regard to their potential health effects, has moderate occurrence but the highest toxicity. Group II has moderate to elevated occurrence and is associated with relevant toxicity, and Group III has very low occurrence and unknown or little toxicity. The EDBPs identified as posing the greatest potential risk using this method were as follows: NDMA and other nitrosamines, MX and other halofuranones, chlorate, formaldehyde and acetaldehyde, 2,4,6-trichlorophenol and pentachlorophenol, hydrazine, and two unregulated halomethanes, dichloromethane and tetrachloromethane. Our approach allowed us to define the EDBPs that it is most important to monitor in order to assess population exposure and related public health issues, and thus to improve drinking water treatment and distribution. It is also important to extend our knowledge about exposure to mixtures of emerging DBPs and possible related health effects.     

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

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

Removal of low-molecular weight DBPs and inorganic ions for characterization of high-molecular weight DBPs in drinking water

High-molecular weight (MW) halogenated disinfection byproducts (DBPs) may cause adverse health effects. In this work several issues related to the better separation and characterization of the high MW halogenated DBPs (MW>500Da) were studied. Ultra-filtration (UF) coupled with a nominal 500-Da membrane was employed to flush out low MW DBPs and inorganic ions. Two procedures, intermittent UF and continuous UF, were used and compared. The results demonstrate that haloacetic acids, chloride and sodium ions could be effectively flushed out, and most of phosphate ions could be flushed out for a given dilution number or sufficient Milli-Q water. The size exclusion chromatograms indicate that haloacetic acids and trihalomethanes were not bound to Suwannee River fulvic acid (SRFA); 2,4,6-trichlorophenol might form some binding with SRFA, but it appeared to be very weak and readily broken up when passing along the size exclusion column. The octanol-water partition coefficients of low MW DBPs and the properties of humic substances seem to play key roles in determining the formation of possible bindings between low MW DBPs and humic substances.     

Disinfection by-products and their precursors in a water treatment plant in North China: Seasonal changes and fraction analysis

A one-year-long monitoring project was conducted to assay the concentrations of THMs, HAAs and their formation potential along the conventional process in a water treatment plant in North China. Subsequent investigations of organic matter fractionation and the contribution of the algae to the precursor were also conducted to trace the source of the DBPs. The results showed that the concentration of DBPs and their formation potential varied with the seasons. The highest concentrations of THMs and the highest HAAs formation potential, each almost 500 microg/L, were detected in autumn and the lowest were in spring, no more than 100 microg/L. Both organic matter and algae were found to be important DBP precursors. The hydrophobic acid fraction in dissolved organic matter has the highest formation potential for both THM and HAA. Algae contribute about 20% to 50% of the total formation potential during an algal bloom. The efficiency of each unit process for DBPs and precursors was also assayed. Unfortunately, the conventional drinking water treatment process is limited in its efficiency for precursor removal. The pre-chlorination and filtration process had a negative effect on DBP or precursor removal.     

Modeling DBPs formation in drinking water in residential plumbing pipes and hot water tanks

Disinfection byproducts (DBPs) in municipal supply water are a concern because of their possible risks to human health. Risk assessment studies often use DBP data in water distribution systems (WDS). However, DBPs in tap water may be different because of stagnation of the water in plumbing pipes (PP) and heating in hot water tanks (HWT). This study investigated occurrences and developed predictive models for DBPs in the PP and the HWT of six houses from three municipal water systems in Quebec (Canada) in a year-round study. Trihalomethanes (THMs) in PP and HWT were observed to be 1.4-1.8 and 1.9-2.7 times the THMs in the WDS, respectively. Haloacetic acid (HAAs) in PP and HWT were observed to be variable (PP/WDS = 0.23-2.24; HWT/WDS = 0.53-2.61). Using DBPs occurrence data from these systems, three types of linear models (main factors; main factors, interactions and higher orders; logarithmic) and two types of nonlinear models (three parameters Logistic and four parameters Weibull) were investigated to predict DBPs in the PP and HWT. Significant factors affecting DBPs formation in the PP and HWT were identified through numerical and graphical techniques. The R² values of the models varied between 0.77 and 0.96, indicating excellent predictive ability for THMs and HAAs in the PP and the HWT. The models were found to be statistically significant. The models were validated using additional data. These models can be used to predict DBPs increase from WDS (water entry point of house) to the PP and HWT, and could thereby help gain a better understanding of human exposure to DBPs and their associated risks.     

Disinfection by-products in filter backwash water: Implications to water quality in recycle designs

The overall purpose of this research was to investigate disinfection by-product (DBP) concentrations and formation potential in filter backwash water (FBWW) and evaluate at bench-scale the potential impact of untreated FBWW recycle on water quality in conventional drinking water treatment. Two chlorinated organic compound groups of DBPs currently regulated in North America were evaluated, specifically trihalomethanes (THMs) and haloacetic acids (HAAs). FBWW samples were collected from four conventional filtration water treatment plants (WTP) in Nova Scotia, Canada, in three separate sampling and plant audit campaigns. THM and HAA formation potential tests demonstrated that the particulate organic material contained within FBWW is available for reaction with chlorine to form DBPs. The results of the study found higher concentrations of TTHMs and HAA9s in FBWW samples from two of the plants that target a higher free chlorine residual in the wash water used to clean the filters (e.g., clearwell) compared to the other two plants that target a lower clear well free chlorine residual concentration. Bench-scale experiments showed that FBWW storage time and conditions can impact TTHM concentrations in these waste streams, suggesting that optimization opportunities exist to reduce TTHM concentrations in FBWW recycle streams prior to blending with raw water. However, mass balance calculations demonstrated that FBWW recycle practice by blending 10% untreated FBWW with raw water prior to coagulation did not impact DBP concentrations introduced to the rapid mix stage of a plant’s treatment train.     

Disinfection by-products in ballast water treatment: An evaluation of regulatory data

To reduce the global spread of invasive aquatic species, international regulations will soon require reductions of the number of organisms in ballast water discharged by ships. For this purpose, ballast water treatment systems were developed and approved by an international procedure. These systems rely on established water treatment principles which, to different degrees, have been proven to generate disinfection by-products with hazardous properties but have only scarcely been investigated in marine environments. Our study evaluates the publicly available documentation about approved ballast water treatment systems with regard to by-product formation. The most commonly employed methods are chlorination, ozonation, and ultraviolet (UV) irradiation. Chlorination systems generate trihalomethanes, halogenated acetic acids, and bromate in substantially larger quantities than reported for other areas of application. Levels are highest in brackish water, and brominated species predominate, in particular bromoform and dibromoacetic acid. Ozonation, which is less frequently utilized, produces bromoform in lower concentrations but forms higher levels of bromate, both of which were effectively reduced by active carbon treatment. In systems based on UV radiation, medium pressure lamps are employed as well as UV-induced advanced oxidation. For all UV systems, by-product formation is reported only occasionally. The most notable observations were small increases in nitrite, hydrogen peroxide, halogenated methanes and acetic acids. The assessment of by-product formation during ballast water treatment is limited by the lacking completeness and quality of available information. This concerns the extent and statistical characterisation of chemical analysis as well as the documentation of the test water parameters.     

A new method for differentiating adducts of common drinking water DBPs from higher molecular weight DBPs in electrospray ionization-mass spectrometry analysis

With the presence of bromide in source waters, numerous brominated disinfection byproducts (DBPs) are formed during chlorination. Many of them are polar/highly polar DBPs and thus hard to be detected by gas chromatography mass spectrometry. Electrospray ionization triple quadrupole mass spectrometry (ESI-MS/MS) is reported to be an effective method in finding polar brominated DBPs by setting precursor ion scans of m/z 79 and 81. But as a soft ionization technique, ESI could form adducts of common DBPs, which may complicate ESI-MS/MS spectra and hinder the efforts in finding new brominated DBPs. In this paper, a new method was developed for differentiating adducts of common DBPs from higher molecular weight DBPs. This method was based on the ESI-MS/MS precursor ion scans of the fragments that correspond to the molecular ions of common DBPs. Adducts of common DBPs were selectively detected in the ESI-MS/MS spectra of a simulated drinking water sample. Moreover, the structures of several new brominated DBPs in the sample were tentatively proposed.     

Estimation of chlorination by-products presence in drinking water in epidemiological studies on adverse reproductive outcomes: A review

Chlorination of drinking water is essential to prevent waterborne disease. However, chlorine reacts with organic matter present in surface waters to form various by-products. In the last decade, several epidemiological studies have been conducted to determine the connection between exposure to these chlorination by-products (CBPs) and human health defects, such as adverse reproductive outcomes. However, the methodology used to assess exposure of pregnant women in these studies had serious limitations, particularly in relation to determining CBP presence in the subject's tap water. The purpose of this paper is to critically review of methods used to evaluate the CBP presence in a subject's tap water for exposure assessment purposes in epidemiological studies focused on adverse reproductive outcomes and CBPs in drinking water. Interest is directed more precisely at space-time features related to CBPs for an optimal estimation of their presence in a subject's tap water.     

Development of predictive models for geosmin-related taste and odor in Kansas, USA, drinking water reservoirs

The presence of taste and odor compounds can greatly reduce the quality of drinking water supplies. Because the monetary costs associated with the removal of these compounds can be high, it is impractical for most facilities to continuously treat their raw water. Instead, new tools are needed to help predict when taste and odor events may be most likely to occur. Water quality data were collected between June and October in 2006-2007 from five Kansas (USA) reservoirs in order to develop predictive models for geosmin, a major taste and odor compound; two of these reservoirs were also sampled during specific taste and odor events in December 2006 and January 2007. Lake trophic state alone was not a good predictor of geosmin concentrations as the highest average geosmin concentration was observed in the reservoir with the lowest nutrient and chlorophyll a concentrations. In addition, taste and odor events were not confined to summer months; elevated geosmin concentrations were observed in several reservoirs during the winter. Growth limitation by inorganic phosphorus appeared to be the primary determinant of geosmin production by algal cells in these reservoirs.     

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

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

Occurrence and control of nitrogenous disinfection by-products in drinking water--a review

The presence of nitrogenous disinfection by-products (N-DBPs), including nitrosamines, cyanogen halides, haloacetonitriles, haloacetamides and halonitromethanes, in drinking water is of concern due to their high genotoxicity and cytotoxicity compared with regulated DBPs. Occurrence of N-DBPs is likely to increase if water sources become impacted by wastewater and algae. Moreover, a shift from chlorination to chloramination, an option for water providers wanting to reduce regulated DBPs such as trihalomethanes (THMs) and haloacetic acids (HAAs), can also increase certain N-DBPs. This paper provides a critical review of the occurrence and control of N-DBPs. Data collated from surveys undertaken in the United States and Scotland were used to calculate that the sum of analysed halonitromethanes represented 3-4% of the mass of THMs on a median basis; with Pearson product moment correlation coefficients of 0.78 and 0.83 between formation of dihaloacetonitriles and that of THMs and HAAs respectively. The impact of water treatment processes on N-DBP formation is complex and variable. While coagulation and filtration are of moderate efficacy for the removal of N-DBP precursors, such as amino acids and amines, biofiltration, if used prior to disinfection, is particularly successful at removing cyanogen halide precursors. Oxidation before final disinfection can increase halonitromethane formation and decrease N-nitrosodimethylamine, and chloramination is likely to increase cyanogen halides and NDMA relative to chlorination.     

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

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

Speciation and distribution of vanadium in drinking water iron pipe corrosion by-products

Vanadium (V) when ingested from drinking water in high concentrations (> 15 μg L^− 1) is a potential health risk and is on track to becoming a regulated contaminant. High concentrations of V have been documented in lead corrosion by-products as Pb₅(V⁵⁺O₄)₃Cl (vanadinite) which, in natural deposits is associated with iron oxides/oxyhydroxides, phases common in iron pipe corrosion by-products. The extent of potential reservoirs of V in iron corrosion by-products, its speciation, and mechanism of inclusion however are unknown. The aim of this study is to assess these parameters in iron corrosion by-products, implementing synchrotron-based μ-XRF mapping and μ-XANES along with traditional physiochemical characterization. The morphologies, mineralogies, and chemistry of the samples studied are superficially similar to typical iron corrosion by-products. However, we found V present as discrete grains of Pb₅(V⁵⁺O₄)₃Cl likely embedded in the surface regions of the iron corrosion by-products. Concentrations of V observed in bulk XRF analysis ranged from 35 to 899 mg kg^− 1. We calculate that even in pipes with iron corrosion by-products with low V concentration, 100 mg kg^− 1, as little as 0.0027% of a 0.1-cm thick X 100-cm long section of that corrosion by-product needs to be disturbed to increase V concentrations in the drinking water at the tap to levels well above the 15 μg L^− 1 notification level set by the State of California and could adversely impact human health. In addition, it is likely that large reservoirs of V are associated with iron corrosion by-products in unlined cast iron mains and service branches in numerous drinking water distribution systems.     

Ozone in drinking water treatment: A review

The paper reviews the application of ozone for the treatment of potable water. The period covered by the review is 1937–1975. A complete bibliography is available from the authors upon request.     

Human health risk assessment of chlorinated disinfection by-products in drinking water using a probabilistic approach

The presence of chlorinated disinfection by-products (DBPs) in drinking water is a public health issue, due to their possible adverse health effects on humans. To gauge the risk of chlorinated DBPs on human health, a risk assessment of chloroform (trichloromethane (TCM)), bromodichloromethane (BDCM), dibromochloromethane (DBCM), bromoform (tribromomethane (TBM)), dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) in drinking water was carried out using probabilistic techniques. Literature data on exposure concentrations from more than 15 different countries and adverse health effects on test animals as well as human epidemiological studies were used. The risk assessment showed no overlap between the highest human exposure dose (EXP(D)) and the lowest human equivalent dose (HED) from animal test data, for TCM, BDCM, DBCM, TBM, DCAA and TCAA. All the HED values were approximately 10(4)-10(5) times higher than the 95th percentiles of EXP(D). However, from the human epidemiology data, there was a positive overlap between the highest EXP(D) and the lifetime average daily doses (LADD(H)) for TCM, BDCM, DCAA and TCAA. This suggests that there are possible adverse health risks such as a small increased incidence of cancers in males and developmental effects on infants. However, the epidemiological data comprised several risk factors and exposure classification levels which may affect the overall results.     

Neutral degradates of chloroacetamide herbicides: occurrence in drinking water and removal during conventional water treatment

Treated drinking water samples from 12 water utilities in the Midwestern United States were collected during Fall 2003 and Spring 2004 and were analyzed for selected neutral degradates of chloroacetamide herbicides, along with related compounds. Target analytes included 20 neutral chloroacetamide degradates, six ionic chloroacetamide degradates, four parent chloroacetamide herbicides, three triazine herbicides, and two neutral triazine degradates. In the fall samples, 17 of 20 neutral chloroacetamide degradates were detected in the finished drinking water, while 19 of 20 neutral chloroacetamide degradates were detected in the spring. Median concentrations for the neutral chloroacetamide degradates were ∼2-60 ng/L during both sampling periods. Concentrations measured in the fall samples of treated water were nearly the same as those measured in source waters, despite the variety of treatment trains employed. Significant removals (average of 40% for all compounds) were only found in the spring samples at those utilities that employed activated carbon.     

Disinfection byproduct formation in reverse-osmosis concentrated and lyophilized natural organic matter from a drinking water source

Drinking water treatment and disinfection byproduct (DBP) research can be complicated by natural organic matter (NOM) temporal variability. NOM preservation by lyophilization (freeze-drying) has been long practiced to address this issue; however, its applicability for drinking water research has been limited because the selected NOM sources are atypical of most drinking water sources. The purpose of this research was to demonstrate that reconstituted NOM from a lyophilized reverse-osmosis (RO) concentrate of a typical drinking water source closely represents DBP formation in the original NOM. A preliminary experiment assessed DBP formation kinetics and yields in concentrated NOM, which demonstrated that chlorine decays faster in concentrate, in some cases leading to altered DBP speciation. Potential changes in NOM reactivity caused by lyophilization were evaluated by chlorination of lyophilized and reconstituted NOM, its parent RO concentrate, and the source water. Bromide lost during RO concentration was replaced by adding potassium bromide prior to chlorination. Although total measured DBP formation tended to decrease slightly and unidentified halogenated organic formation tended to increase slightly as a result of RO concentration, the changes associated with lyophilization were minor. In lyophilized NOM reconstituted back to source water TOC levels and then chlorinated, the concentrations of 19 of 21 measured DBPs, constituting 96% of the total identified DBP mass, were statistically indistinguishable from those in the chlorinated source water. Furthermore, the concentrations of 16 of 21 DBPs in lyophilized NOM reconstituted back to the RO concentrate TOC levels, constituting 86% DBP mass, were statistically indistinguishable from those in the RO concentrate. This study suggests that lyophilization can be used to preserve concentrated NOM without substantially altering the precursors to DBP formation.     

A role for human reliability analysis (HRA) in preventing drinking water incidents and securing safe drinking water

The prevalence of water quality incidents and disease outbreaks suggests an imperative to analyse and understand the roles of operators and organisations in the water supply system. One means considered in this paper is through human reliability analysis (HRA). We classify the human errors contributing to 62 drinking water accidents occurring in affluent countries from 1974 to 2001; define the lifecycle of these incidents; and adapt Reason's ‘Swiss cheese’ model for drinking water safety. We discuss the role of HRA in human error reduction and drinking water safety and propose a future research agenda for human error reduction in the water sector.     

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

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