Non-regulated Disinfection By-products Research Articles

In vitro bioassays for monitoring drinking water quality of tap water, domestic filtration and bottled water

BackgroundLocation-specific patterns of regulated and non-regulated disinfection byproducts (DBPs) were detected in tap water samples of the Barcelona Metropolitan Area. However, it remains unclear if the detected DBPs together with undetected DPBs and organic micropollutants can lead to mixture effects in drinking water.ObjectiveTo evaluate the neurotoxicity, oxidative stress response and cytotoxicity of 42 tap water samples, 6 treated with activated carbon filters, 5 with reverse osmosis and 9 bottled waters. To compare the measured effects of the extracts with the mixture effects predicted from the detected concentrations and the relative effect potencies of the detected DBPs using the mixture model of concentration addition.MethodsMixtures of organic chemicals in water samples were enriched by solid phase extraction and tested for cytotoxicity and neurite outgrowth inhibition in the neuronal cell line SH-SY5Y and for cytotoxicity and oxidative stress response in the AREc32 assay.ResultsUnenriched water did not trigger neurotoxicity or cytotoxicity. After up to 500-fold enrichment, few extracts showed cytotoxicity. Disinfected water showed low neurotoxicity at 20- to 300-fold enrichment and oxidative stress response at 8- to 140-fold enrichment. Non-regulated non-volatile DBPs, particularly (brominated) haloacetonitriles dominated the predicted mixture effects of the detected chemicals and predicted effects agreed with the measured effects. By hierarchical clustering we identified strong geographical patterns in the types of DPBs and their association with effects. Activated carbon filters did not show a consistent reduction of effects but domestic reverse osmosis filters decreased the effect to that of bottled water.Impact statementBioassays are an important complement to chemical analysis of disinfection by-products (DBPs) in drinking water. Comparison of the measured oxidative stress response and mixture effects predicted from the detected chemicals and their relative effect potencies allowed the identification of the forcing agents for the mixture effects, which differed by location but were mainly non-regulated DBPs. This study demonstrates the relevance of non-regulated DBPs from a toxicological perspective. In vitro bioassays, in particular reporter gene assays for oxidative stress response that integrate different reactive toxicity pathways including genotoxicity, may therefore serve as sum parameters for drinking water quality assessment.

Insights to estimate exposure to regulated and non-regulated disinfection by-products in drinking water

BackgroundKnowledge about human exposure and health effects associated with non-routinely monitored disinfection by-products (DBPs) in drinking water is sparse.ObjectiveTo provide insights to estimate exposure to regulated and non-regulated DBPs in drinking water.MethodsWe collected tap water from homes (N = 42), bottled water (N = 10), filtered tap water with domestic activated carbon jars (N = 6) and reverse osmosis (N = 5), and urine (N = 39) samples of participants from Barcelona, Spain. We analyzed 11 haloacetic acids (HAAs), 4 trihalomethanes (THMs), 4 haloacetonitriles (HANs), 2 haloketones, chlorate, chlorite, and trichloronitromethane in water and HAAs in urine samples. Personal information on water intake and socio-demographics was ascertained in the study population (N = 39) through questionnaires. Statistical models were developed based on THMs as explanatory variables using multivariate linear regression and machine learning techniques to predict non-regulated DBPs.ResultsChlorate, THMs, HAAs, and HANs were quantified in 98–100% tap water samples with median concentration of 214, 42, 18, and 3.2 μg/L, respectively. Multivariate linear regression models had similar or higher goodness of fit (R2) compared to machine learning models. Multivariate linear models for dichloro-, trichloro-, and bromodichloroacetic acid, dichloroacetonitrile, bromochloroacetonitrile, dibromoacetonitrile, trichloropropnanone, and chlorite showed good predictive ability (R2 = 0.8–0.9) as 80–90% of total variance could be explained by THM concentrations. Activated carbon filters reduced DBP concentrations to a variable extent (27–80%), and reverse osmosis reduced DBP concentrations ≥98%. Only chlorate was detected in bottled water samples (N = 3), with median = 13.0 µg/L. Creatinine-adjusted trichloroacetic acid was the most frequently detected HAA in urine samples (69.2%), and moderately correlated with estimated drinking water intake (r = 0.48).SignificanceFindings provide valuable insights for DBP exposure assessment in epidemiological studies. Validation of predictive models in a larger number of samples and replication in different settings is warranted.Impact statementOur study focused on assessing and describing the occurrence of several classes of DBPs in drinking water and developing exposure models of good predictive ability for non-regulated DBPs.

Genotoxicity of disinfection byproducts and disinfected waters: A review of recent literature

The presence of water disinfection byproducts (DBPs) in tap water, resulting from disinfection processes involving chlorination or chloramination, increases the mutagenicity of the water and may pose adverse health effects. The topic was reviewed by DeMarini and coworkers in 2007. Here, we review research on the genotoxicity of DBPs published since that time. Studies, primarily using the Salmonella mutagenicity assay, have continued to show that chlorination or chloramination of source waters results in finished, tap, or swimming pool/spa water that is more mutagenic than the original source water. The genotoxic potencies of DBPs in both bacterial and mammalian cells generally rank as iodinated > brominated > chlorinated. Several DBPs are genotoxic in vivo in plants as well as in animals such as the worm Caenorhabditis elegans and the zebrafish Danio rerio. Studies primarily using the comet assay in mammalian cells have identified several non-regulated DBPs as genotoxic. However, the comet assay detects DNA damage that is generally repaired by the cells; thus, genotoxicity data more relevant to persistent mutations, such as chromosomal or gene mutations, are needed for these DBPs. Recent molecular epidemiology has indicated that activation of brominated trihalomethanes by the enzyme GSTT1 and the lack of metabolism of haloacetic acids by a variant of enzyme GSTZ1 are likely causative mechanisms for bladder cancer associated with exposure to chlorinated water. Further studies, especially in vivo, are needed to determine the ability of various DBPs, especially unregulated ones, to induce both gene as well as chromosomal mutations. Such investigations, along with additional molecular epidemiology studies, are required for a comprehensive understanding of the genotoxic and carcinogenic risks associated with DBP exposure.

Models for estimation of the presence of non-regulated disinfection by-products in small drinking water systems.

Among all the organic disinfection by-products (DBPs), only trihalomethanes (THMs) and haloacetic acids (HAAs) are regulated in drinking water, while most DBPs are not. Very little information exists on the occurrence of non-regulated DBPs, particularly in small water systems (SWS). Paradoxically, SWS are more vulnerable to DBPs because of a low capacity to implement adequate treatment technologies to remove DBP precursors. Since DBP analyses are expensive, usually SWS have difficulties to implement a rigorous characterization of these contaminants. The purpose of this study was to estimate non-regulated DBP levels in SWS from easy measurements of relevant parameters regularly monitored. Since no information on non-regulated DBPs in SWS was available, a sampling program was carried out in 25 SWS in two provinces of Canada. Five DBP families were investigated: THMs, HAAs, haloacetonitriles (HANs), halonitromethanes (HNMs), and haloketones (HKs). Multivariate linear mixed regression models were developed to estimate HAN, HK, and HNM levels from water quality characteristics in the water treatment plant, concentrations of regulated DBPs, and residual disinfectant levels. The models obtained have a good explanatory capacity since R 2 varies from 0.77 to 0.91 according to compounds and conditions for application (season and type of treatment). Model validation with an independent database suggested their ability for generalization in similar SWS in North America.

Behavior of non-regulated disinfection by-products in water following multiple chlorination points during treatment

In this study, the behavior of regulated (trihalomethanes–THMs, haloacetic acids–HAAs) and non-regulated (haloacetonitriles–HANs, haloketones–HKs, chloropicrin–CPK) disinfection by-products (DBPs) was investigated during treatment and distribution in a municipal drinking water system that adds chlorine at multiple points within the water treatment plant (WTP). Three to eight locations in the WTP and four locations in the distribution network were sampled weekly for DBP measurements during the warmest period of the year. The results show that most DBPs found in the study area are formed during treatment, not distribution. However, the DBP species studied behave differently during treatment and distribution. Moreover, the location where DBP concentration is the highest in the distribution network differs among species of the same family, especially HAAs and HKs, and between the sampling campaigns. As a result, the relevance of using the sum of the concentrations of the species of the same DBP family to select sampling sites for DBP monitoring is questionable. This study illustrates the difficulties that drinking water supply managers must face to control and monitor the presence of DBPs.

Seasonal evaluation of the presence of 46 disinfection by-products throughout a drinking water treatment plant

In this work, we studied a total of 46 regulated and non-regulated disinfection by-products (DBPs) including 10 trihalomethanes (THMs), 13 haloacetic acids (HAAs), 6 halonitromethanes (HNMs), 6 haloacetonitriles (HANs) and 11 aldehydes at different points in a drinking water treatment plant (DWTP) and its distribution network. Determining an increased number of compounds and using accurate, sensitive analytical methodologies for new DBPs can be useful to overcome some challenges encountered in the comprehensive assessment of the quality and safety of drinking water. This paper provides a detailed picture of the spatial and seasonal variability of DBP concentrations from raw water to distribution network. Samples were collected on a monthly basis at seven different points in the four seasons of a year to acquire robust data for DBPs and supplementary quality-related water parameters. Only 5 aldehydes and 2 HAAs were found in raw water. Chlorine dioxide caused the formation of 3 new aldehydes (benzaldehyde included), 5 HAAs and chloroform. The concentrations of DBPs present in raw water were up to 6 times higher in the warmer seasons (spring and summer). The sedimentation process further increased their concentrations and caused the formation of three new ones. Sand filtration substantially removed aldehydes and HAAs (15–50%), but increased the levels of THMs, HNMs and HANs by up to 70%. Chloramination raised the levels of 8 aldehydes and 7 HAAs; also, it caused the formation of monoiodoacetic acid, dibromochloromethane, dichloroiodomethane and bromochloroacetonitrile. Therefore, this treatment increases the levels of existing DBPs and leads to the formation of new ones to a greater extent than does chlorine dioxide. Except for 5 aldehydes, the 23 DBPs encountered at the DWTP exit were found at increased concentrations in the warmer seasons (HAAs by about 50% and THMs by 350%).

Disparity in disinfection byproducts concentration between hot and cold tap water

The quality of water entering a distribution system may differ substantially from the quality at the point of exposure to the consumer. This study investigated temporal variations in the levels of regulated and non-regulated disinfection byproducts (DBPs) in cold and hot tap water in a home on a medium-sized municipal water system. In addition, samples were collected directly from the water plant with some being held in accordance with a simulated distribution system (SDS) test protocol. The location for this work was a system in western Massachusetts, USA that uses free chlorine as a final disinfectant. Very little short term variability of DBPs at the point of entry (POE) was observed. The concentration of DBPs in the time-variable SDS test was similar to concentrations in the cold water tap. For most DBPs, the concentrations continued to increase as the cold water tap sample was held for the time-variable SDS incubation period. However, the impact of heating on DBP levels was compound specific. For example, the concentrations of trihalomethanes (THMs), dichloroacetic acid (DCAA) and chloropicrin (CP) were substantially higher in the hot water tap than in the cold water time-variable SDS samples. In contrast, the concentration of trichloroacetic acid (TCAA) was lower in the heated hot tap water, but about equal to that observed in the cold tap water. The situation was more pronounced for dichloroacetonitrile (DCAN), bromodichloroacetic acid (BDCAA), bromochloroacetic acid (BCAA) and 1,1,1-trichloropropanone (TCP), which all showed lower concentrations in the hot water then in either of the cold water samples (instantaneous or time-variable SDS). The latter was viewed as a clear indication of thermally-induced decomposition. The ratio of unknown total organic halide (UTOX) to TOX was substantially lower in the hot tap water as the THM to TOX ratio became correspondingly larger. The results of this study show that DBP exposure in the home is not well represented by concentrations measured in cold water taps where most compliance monitoring is done.

Occurrence of regulated and non-regulated disinfection by-products in small drinking water systems

The occurrence of regulated and non-regulated disinfection by-products (DBPs) was investigated in the drinking water of small systems in two provinces in Canada, Newfoundland and Labrador (NL) and Quebec (QC), through an intensive sampling program. Sixteen DBPs were studied: four trihalomethanes (THMs), five haloacetic acids (HAAs), four haloacetonitriles (HANs), one halonitromethane, chloropikrin (CPK) and two haloketones (HKs). Average measured concentrations of these compounds were much higher than those reported in the literature for medium and large systems. The measured average value for THMs was 75μgL−1 (Stdv=69μgL−1); HAAs, 77μgL−1 (Stdv=75μgL−1); HANs, 2.5μgL−1 (Stdv=1.8μgL−1); CPK, 0.4μgL−1 (Stdv=0.3μgL−1) and HKs, 6.0μgL−1 (Stdv=4.5μgL−1). The gap (some 10 times difference) between the average levels of regulated DBPs (THMs, HAAs) and non-regulated DBPs (HANs, CPK and HKs) is comparable to that observed in large systems where the occurrence of the same compounds has been reported. Generally, investigated DBPs followed a comparable seasonal evolution during the year: they decreased between the fall and winter and then increased to eventually reach a maximum in late summer. This trend was less observable in NL than in QC. However, observed seasonal fluctuations of DBPs were less considerable than those observed in medium and large systems located in similar temperate environments reported in the literature. Spatial variations from the plant to the extremities were high and comparable to those observed in large systems, which is surprising, considering the smaller size of distribution networks supplying small communities. Generally speaking, the results support the premise that problems associated with implementing treatment that removes DBP precursors in water submitted to chlorination can increase population exposure to these contaminants in small systems.

Spatio-temporal variability of non-regulated disinfection by-products within a drinking water distribution network

The non-regulated disinfection by-products (NrDBP) targeted in this study include four haloacetonitriles (trichloroacetonitrile (TCAN); dichloroacetonitrile (DCAN); bromochloroacetonitrile (BCAN) and dibromoacetonitrile (DBAN)); one halonitromethane (trichloronitromethane, better known under the name chloropicrin (CPK)); and two haloketones (1,1-dichloro-2-propanone (11DCPone) and 1,1,1-trichloro-2-propanone (111TCPone)). This study provides a detailed picture of the spatial and temporal variability of these NrDBP concentrations throughout a drinking water distribution system located in a region with major seasonal climate variations. The results obtained show that the concentrations of the investigated NrDBPs varied significantly according to time and location. The average concentrations of TCAN, DCAN, CKP and 111TCPone were significantly higher in summer. Surprisingly, the average concentrations of 11DCPone were significantly higher in winter. For BCAN and DBAN, the average concentrations observed in winter were higher, but not in a statistically significant way. On the other hand, the four HANs, CPK and 111TCPone generally had spatial profiles involving an increase of the concentrations along the network according to increasing water residence times, whereas 11DCPone overall had a profile where concentrations increased at the beginning of the network, followed by a drop in the concentrations towards the ends of the network. In spite of certain disparities in the individual spatio-temporal variation profiles, strong correlations were generally observed between NrDBPs, and trihalomethanes (THMs) and haloacetic acids (HAAs). Therefore, THMs and HAAs could be good statistical indicators of the presence of NrDBPs in the drinking water of the system under study.

Chlorination and chloramination of high-bromide natural water: DBPs species transformation

Many source waters in China are in high levels of natural organic matter (NOM) and bromide ion (Br−), and the control of the formation of regulated and non-regulated disinfection by-products (DBPs) is a great challenge. This study uses the natural water with substantial NOM and Br− from Weishan Lake to evaluate the formation and species transformation of DBPs in three disinfection scenarios of chlorination, chloramination, and chlorine–chloramine sequential treatment (Cl2–NH2Cl process), and the reaction pathways involved are also proposed. Compared with chlorination, the formation of trihalomethanes and haloacetic acids is reduced by 88% and 85% and by 68% and 65% in chloramination and Cl2–NH2Cl process, respectively. During chloramination, the proportion of brominated-DBPs (Br-DBPs) is lower initially, and then increases afterwards due to the continuous reaction between NOM slow reactive sites and N-bromo amines. Additionally, the ratios of dihalogenated acetic acids to total organic halogen increase continuously from 4.5% to 6.3% with pre-chlorination and from 4.3% to 9.8% without pre-chlorination. The halonitriles (HANs) formation during chlorination is the most significant in the initial 30min at the level of 6.5nM, and then decreases to 2.5nM after 72h. During chloramination, however, the formation of HANs increases steadily with prolonged contact time. After 72-h contact time, the level of HANs in Cl2–NH2Cl process is 3.9 and 2.5 times of that in chlorination and chloramination, respectively. In Cl2–NH2Cl process, HOCl rapidly oxidizes Br− to HOBr, and these two active species react with the fast reactive sites within NOM to form Br-DBPs and the intermediates for nitrogenous DBPs (N-DBPs). The subsequent introduction of ammonia inhibits the hydrolysis and oxidation of the formed N-DBPs and contributes to the most significant formation of N-DBPs.

Effect of UV treatment on DBP formation

This study—s objective was to investigate the effect of ultraviolet (UV) treatment on the subsequent formation of regulated and unregulated disinfection by‐products (DBPs). UV treatment of two sets of waters did not substantially change the waters— tendency to form trihalomethanes, haloacetic acids, or total organic halogen under the conditions of these tests. Evidence was found of small reductions in the formation of these DBPs, but the decreases did not exceed 10%. Formation of chloropicrin and 1,1,1‐trichloropropanone increased as a result of medium‐pressure UV treatment but remained at levels well below those of the regulated DBPs. Low‐pressure UV did not cause any detectable increase in chloropicrin formation. The authors propose that photonitration leads to the formation of new nitroorganics during UV treatment and these form halonitromethanes during subsequent chlorination. It is recommended that the effects of UV treatment on nonregulated DBPs be considered as new UV drinking water systems are brought on line.

Predicting disinfection by-product formation potential in water

Formation of regulated and non-regulated disinfection by-products (DBPs) is an issue at both potable water and wastewater treatment plants (W/WWTPs). Water samples from W/WWTPs across the USA were collected and DBP formation potentials (DBPFPs) in the presence of free chlorine and chloramine were obtained for trihalomethane (THM), haloacetic acid (HAA), haloacetonitrile (HAN), and N-nitrosodimethylamine (NDMA). With nearly 200 samples covering a range of dissolved organic carbon (0.6–23 mg/L), ultraviolet absorbance (0.01–0.48 cm −1 at 254 nm wavelength), and bromide (0–1.0 mg/L) levels, power function models were developed to predict the carbonaceous DBP (C-DBP) and nitrogenous DBP (N-DBP) precursors spanning 3 orders of magnitudes. The predicted THM and HAA formation potentials fitted well with the measured data (analytical variance of less than 22%). Inclusion of dissolved organic nitrogen (DON) into the HANFP model improved the predictions. NDMAFP was the most difficult one to predict based upon the selected water quality parameters, perhaps suggesting that bulk measurements such as DOC or UVA 254 were not appropriate for tracking NDMAFP. These are the first such DBPFP models for wastewater systems, and among the few models that consider both C-DBPs and N-DBPs formation potentials from the same water sources.

Degradation of trichloronitromethane by iron water main corrosion products

Halogenated disinfection byproducts (DBPs) may undergo reduction reactions at the corroded pipe wall in drinking water distribution systems consisting of cast or ductile iron pipe. Iron pipe corrosion products were obtained from several locations within two drinking water distribution systems. Crystalline-phase composition of freeze-dried corrosion solids was analyzed using X-ray diffraction, and ferrous and ferric iron contents were determined via multiple extraction methods. Batch experiments demonstrated that trichloronitromethane (TCNM), a non-regulated DBP, is rapidly reduced in the presence of pipe corrosion solids and that dissolved oxygen (DO) slows the reaction. The water-soluble iron content of the pipe solids is the best predictor of TCNM reaction rate constant. These results indicate that highly reactive DBPs that are able to compete with oxygen and residual disinfectant for ferrous iron may be attenuated via abiotic reduction in drinking water distribution systems.