Trihalomethanes Research Articles

Multivariate experimental design provides insights for the optimisation of rechloramination conditions and water age to control disinfectant decay and disinfection by-product formation in treated drinking water

The stability of drinking water disinfectant residuals is known to be influenced by multiple variables. To evaluate the effects of various influencing variables on disinfectant stability, a multivariate analysis of chloramine decay and associated disinfection by-products (DBPs) formation was investigated in a series of bench-scale experiments. Of nine water quality variables previously identified, monochloramine dose, pH, and bromide concentration were selected as key water quality variables based on previous investigations and modelling. Co-effects of these key variables on monochloramine decay and formation of 33 halogenated and nitrogen-containing DBPs were investigated using response surface experimental design.Rechloramination conditions, including monochloramine dose, pH and bromide concentration, were optimised via a 3-factorial multivariate analysis of monochloramine stability in post-treatment drinking water. Effects of influencing variables on disinfectant decay and DBP formation were assessed and graphically presented as response surfaces with minimal experiments using Doehlert matrix experimental design compared to other multivariate experimental designs. Concentrations of trihalomethanes (THMs), haloacetic acids (HAAs), and N-nitrosamines were found to increase with water age, whereas opposite phenomenon was observed in the net production of haloacetonitriles (HANs). Increasing pH was found to stabilise monochloramine but it could cause DBP speciation to shift. Furthermore, increasing bromide concentration elevated Br-DBP formation. In bromide-containing water, pH = 7.8–8.0 should be considered as higher pH increases Br-THMs formations and lower pH increases formations of Br-HAAs and Br-HANs. However, water age or pH has insignificant impacts on DBP formation after significant monochloramine decay or at low initial monochloramine dose.These findings indicate that effective combined control measures to maintain monochloramine stability should include the application of high monochloramine dose (>1.5 mg-Cl2.L−1) under conditions of moderate to high pH (pH = 7.8–8.0) and minimal bromide concentration. This study provides relevant insights to water utilities aiming to design effective disinfectant residual management strategies for controlling monochloramine decay and DBP formation.

Effects of seawater intrusion on the formation of disinfection byproducts in drinking water

Seawater contains high levels of halides, which can increase the concentrations of bromide and iodide ions in coastal groundwater and surface water sources. Intrusion of seawater alters the chemistry of fresh water leading to the formation of additional brominated and iodinated disinfection byproducts (DBPs), many of which are cyto- and genotoxic to the mammalian cells, and have cancer risks to humans. In this study, effects of seawater intrusion on the formation of trihalomethanes (THMs), and haloacetic acids (HAAs) were investigated by spiking groundwater using 0.0–2.0% seawater (by volume) and liquid chlorine as disinfectant. The concentrations of bromide and iodide ions in groundwater (0.0% seawater) were 42.5 and non-detected (ND) μg/L respectively, which were increased up to 1100 and 2.1 μg/L respectively, following mixing with 2.0% seawater. The regulated THMs (THM4) were increased from 30.4 to 106.3 μg/L while iodinated THMs (I-THMs) were increased from 0.13 to 1.6 μg/L respectively due possibly to molecular substitution and additional pathways of THMs formation. Bromoform was increased from 0.5 to 94.3 μg/L while iodoform was increased from ND to 1.02 μg/L. HAAs were increased from 27.9 to 72.9 μg/L where tribromoacetic acid was increased from 2.0 to 43.7 μg/L. In 0.0% seawater, bromine incorporation factor (BIF) for THM4 and HAAs were 0.077 and 0.050 respectively, which were increased to 0.942 and 0.38 at 2% seawater respectively. For dihalogenated HAAs (X2AA) and trihalogenated HAAs (X3AA), BIF in 0.0% seawater were 0.098 and 0.14 respectively, which were increased to 0.863 and 0.924 for 2.0% seawater respectively. Mixing of 2.0 seawater increased the toxicity of THM4, HAAs and I-THMs by 4.2, 5.9 and 201.8 folds, respectively indicating the importance of reducing seawater intrusion into the freshwater sources. Further, alteration of water sources and/or adaptation of advanced treatment can assist in lowering the risks.

Which pre-oxidation methods to choose? From perspective of DBPs formation and toxicities reduction

Pre-oxidation have been widely applied in drinking water treatment plants with micro-polluted water as water sources. In this study, the effects of three commonly used oxidants (ozone, chlorine, and potassium permanganate) on disinfection by-products (DBPs) formation from micro-polluted water during subsequent chlorination and chloramination were investigated. Moreover, the toxicities of treated water were also compared. In addition, principal component analysis was applied to clarify the main components that contributed to DBPs generation. The results demonstrated that all the selected oxidants could reduce DBPs to some extent, but the species and amounts were quite different. Pre-KMnO4 greatly reduced haloacetic acid (HAAs) formation in subsequent chloramination; the removal rate reached up to 45.2%. Pre-HClO could produce trihalomethane (THMs) and HAAs directly, and its effect on DBPs reduction during subsequent disinfection processes was limited. Pre-O3 performed best on N, N-dimethyl nitrosamine (NDMA) reduction during subsequent chloramination; the corresponding removal rates were 49.7%. In addition, pre-O3 significantly reduced UV254 and SUVA. Pre-KMnO4 transferred more organic matter to cationic components (24%), while the highest polar component augmentation was observed during pre-HClO (15%). Based on the analysis of total toxicity of formed DBPs, pre-O3 performed best on toxicity reduction no matter subsequent chlorination or chloramination, which decreased by 25.8% and 46.4%, respectively. The principal component analysis showed that DBPs has a weak correlation with regular water quality parameters, but related with specific organic fractions. The results of this paper had significant guidance for the selection of pre-oxidation methods in drinking water treatment plants for this kind of water sources.

Disinfection of Drinking Water and Trihalomethanes

Best known by-products of chlorination of drinking water are trihalomethanes (THMs) which can have negative effects on human health. The research goals in this paper were to emphasise the importance of THMs as by-products of disinfecting drinking water, to show the practice of controlling the THMs in drinking water on the example of three water supply systems in the Republic of Srpska and to propose measures for reducing formation of THMs in drinking water. The results have shown that values of THMs in drinking water in these three water supply systems were within the reference values, but the level of the proscribed control is significantly below the minimal requirements.

Evaluation of Trihalomethane Formation Risk Analysis in Swimming Pools in Eskisehir, Turkey

Swimming pools are popular entertainment and sport areas that people often use. For this reason, it is crucial to determine the physicochemical properties and Trihalomethanes (THMs) concentrations of swimming pools and the effect of THMs on swimmer health. This study focuses on the physicochemical parameters and THM concentrations of six swimming pools in Eskisehir and the impacts of THMs on human health. Within the study context, physicochemical parameters were examined and swimming pool water standards of various countries and organizations were evaluated. The alkalinity, pH, temperature, hardness, and free chlorine values of the swimming pools were determined to compare with the current standards. Concentrations of chloroform (TCM), bromodichloromethane (BDCM), and dibromochloromethane (DBCM) were also determined in the collected samples. Concentrations were found to be in the range of 11.6-100.1 µg/l for BDCM, 151.5-366.4 µg/l for TCM, ND-6.95 µg/l for DBCM, and 172.1-380.7 µg/l for TTHM. From the results, it was determined that TTHM concentrations were above the limit values defined by WHO, while chloroform (except P1 and P5 pools), BDCM (except P3 pool), and DBCM concentrations were significantly below the limit values. TTHMs and chloroform concentrations were high in tap water using sodium hypochlorite as a disinfectant. BDCM and DBCM concentrations were high in pools where groundwater was used. Health risks of THMs in pools through ingestion and dermal absorption were also estimated for both women and men. In the interpretation of the result, it was also found that high concentrations of TTHMs increased the risk, and women’s ingestion-based risk values are slightly higher than men’s ingestion-based risk values. Fingerprints of THM formation in pool water are precursor parameters and it is of great importance to constantly control and take precautions. It has been observed that the use of groundwater as a water source and NaCl as a disinfectant significantly reduces THM formation in swimming pools. However, in order to reduce the BDCM and DBCM concentrations in the use of groundwater, it is recommended to measure the precursor bromide and establish the relevant limit values. The use of hypochlorite disinfectants in pools where tap water is used as a water source increases THM formation. For this reason, it is necessary to determine the amount of organic carbon as a precursor for pools using tap water as a water source and add it to the limit values. In addition, the use of calcium hypochlorite disinfectant instead of sodium hypochlorite reduces THM formation. Highlight Physicochemical properties and THMs concentrations of swimming pools and effects of trihalomethanes (THMs) on the health of swimmers. Physicochemical parameters and THM concentrations of six swimming pools were determined, and the effects of THMs’ on human health. Physicochemical parameters (alkalinity, pH, temperature, and hardness), chloroform (TCM), bromodichloromethane (BDCM), and dibromochloromethane (DBCM) were studied. As a result of the study, total THMs and TCM concentrations were high in pools where tap water, and sodium hypochlorite were used. BDCM and DBCM concentrations were high in pools where groundwater was used. High THM concentrations increase the risk, and at the same time, women’s ingestion-based risk values are slightly higher than men’s ingestion-based risk values.

Flume and single-pass washing systems for fresh-cut produce processing: Disinfection by-products evaluation

Free chlorine is widely used in fresh-cut produce washing to minimize microbial cross-contamination, but its application can also lead to the formation of harmful disinfection byproducts (DBPs). This study compared DBPs in process water and washed produce during commercial operation. Samples of shredded lettuce and diced cabbages washed in chlorinated water in the traditional double-flume wash and novel immersion-free single-pass wash systems were collected at multiple time points and locations from the processing lines. A suite of 33 conventional and emerging DBPs, including 4 trihalomethanes (THMs), 9 haloacetic acids (HAAs), 9 nitrogenous DBPs (N-DBPs), and 11 carbonaceous DBPs (C-DBPs), were investigated. Overall, N-DBPs and HAAs dominated the concentration of detected DBPs. Wash water in the flumes contained 7–111 folds higher DBP levels compared to that in the single-pass system, with the abundance of DBPs following the order of N-DBPs > HAAs > C-DBPs > THMs. DBPs were detected on washed produce, presenting primarily in the forms of N-DBPs and HAAs followed by C-DBPs and THMs. While higher levels of DBPs were detected in flume-washed produce, the final potable water rinse significantly reduced the DBP concentration in these products. The concentrations of THMs and HAAs on these washed products were used to estimate potential exposure via consumption of fresh-cut produce and the levels were below the daily allowable exposure for drinking water standard established by the U.S. Environmental Protection Agency. The detected high concentration and potential toxicity of N-DBPs indicate the need for further research. The findings of this study advance the understanding of the formation and removal of DBPs during wash processes, and identify additional research opportunities for further reduction in DBPs and food safety improvement.

Chlorination by-products in drinking water and risk of bladder cancer – A population-based cohort study

Chlorination by-products have been consistently associated with risk of bladder cancer in case-control studies, but confirmation from large-scale cohort studies is lacking. We assessed the association of drinking water trihalomethanes (THM), a proxy for chlorination by-products, with risk of bladder cancer in 58,672 men and women. Data came from two population-based cohorts, parts of the Swedish Infrastructure for Medical Population-Based Life-Course and Environmental Research (SIMPLER). Individual exposure to THM was assessed by combining residential information with tap water monitoring data. Participants were categorized into non-exposed, low (<15 µg/L) or high (≥15 µg/L) THM exposure. Incident cases were ascertained from 1998 through 2019 via register linkage. During 16 years of follow-up (965,590 person-years), 831 bladder cancer cases were ascertained. We observed no overall association of THM with risk of bladder cancer, hazard ratio for the highest exposed compared to the non-exposed 0.90 (95% confidence interval: 0.73 – 1.11). The null association remained after restricting the analysis to long-term residents and across strata of smoking status and cancer stage. Our results indicate that chlorination by-product exposure at THM concentrations representative of chlorinated drinking waters in most European countries, is not associated with an increased risk of bladder cancer.

Advanced oxidation of Trihalomethane (THMs) precursors and season-wise multi-pathway human carcinogenic risk assessment in Indian drinking water supplies

Advanced oxidation processes (AOPs) in water treatment industries can simultaneously offer disinfection and eradicate organic contaminants. The present work examined the direct exposure impact of various oxidative (UV, O3, and H2O2) and their eclectic combinations (UV/O3, H2O2/O3, and UV/H2O2) for the abolition of Trihalomethane (THMs) precursors. The application of the Fenton process proved to be the most effective technique for reducing TOC (85.23%) and UV254 (91.11%) than other used AOPs. Higher removal of THMs precursors found in the Fenton process may be attributed to the higher degradation potential of hydroxyl radical generated from this process than other AOPs. The deformed ferrous iron salts (Fe2+) in the Fenton reagent catalyzed the hydrogen peroxide (H2O2) and produced highly reactive radicals. Seasonal probabilistic lifetime cancer and non-cancer risks of THMs in males and females were also investigated in the drinking water supplies of five major cities in India. Comparative risk analysis through different pathways revealed significant risk from oral ingestion (99%), followed by inhalation exposure (0.77%) and dermal absorption (0.002%), where females were found at higher risk of cancer. Sensitivity analysis using a radar plot was also performed to identify the most influential parameter affecting the total risk of cancer. The Risk value of chloroform (CF) was highest among the THMs compound in all the WTPs for both seasons. Seasonal risk assessment revealed a higher risk of cancer in the pre-monsoon season.

Potential risks and approaches to reduce the toxicity of disinfection by-product – A review

Water contamination through anthropogenic and industrial activities has led to the emergence and necessity of disinfection methods. Chlorine and bromine gases, often used to disinfect water, resulted in the by-product formation by reacting with organic matter. The Disinfectant by-products (DBP) led to the formation of Trihaloaceticacid (TAA), Trihalomethane (THM), and other minor components. The release of chemicals has also led to the outbreak of diseases like infertility, asthma, stillbirth, and types of cancer. There are new approaches that are found to be useful to compensate for the generation of toxic by-products and involve membrane technologies, namely reverse osmosis, ultrafiltration, and nanofiltration. This review mainly focuses on the toxicology effects of DBPs and various approaches to mitigate the same. The health hazards caused by different DBPs and the various treatment techniques available for the removal are discussed. In addition, a critical comparison of the different removal techniques was discussed.

Modeling the formation of trihalomethanes in rural and semi-urban drinking water distribution networks of Costa Rica

Chlorination is one of the most important stages in the treatment of drinking water due to its effectiveness in the inactivation of pathogenic organisms. However, the reaction between chlorine and natural organic matter (NOM) generates harmful disinfection by-products (DBPs), such as trihalomethanes (THMs). In this research, drinking water quality data was collected from the distribution networks of 19 rural and semi-urban systems that use water sources as springs, surfaces, and a mixture of both, in three provinces of Costa Rica from April 2018 to September 2019. Twelve models were developed from four data sets: all water sources, spring, surface, and a mixture of spring and surface waters. Linear, logarithmic, and exponential multivariate regression models were developed for each data set to predict the concentration of total trihalomethanes (TTHMs) in the distribution networks. Concentrations of TTHMs were found between < 0.20 and 91.31µg/L, with chloroform being the dominant species accounting for 62% of TTHMs on average. Turbidity, free residual chlorine, total organic carbon (TOC), dissolved organic carbon (DOC), and ultraviolet absorbance at 254nm (UV254) showed a significant correlation with TTHMs. In all the data sets the linear models presented the best goodness-of-fit and were moderately robust. Four models, the best of each data set, were validated with data from the same systems, and, according to the criteria of R2, standard error (SE), mean square error (MSE), and mean absolute error (MAE), spring water and mixed spring/surface water models showed a satisfactory level of explanation of the variability of the data. Moreover, the models seem to better predict TTHM concentrations below 30µg/L. These models were satisfactory and could be useful for decision-making in drinking water supply systems.

Changes in molecular dissolved organic matter and disinfection by-product formation during granular activated carbon filtration by unknown screening analysis with Orbitrap mass spectrometry

The minimization of disinfection by-product (DBP) formation by the removal of its precursors before water disinfection is a highly effective approach. Granular activated carbon (GAC) filtration is widely used for water treatment, but our understanding of molecular dissolved organic matter (DOM) remains insufficient. This research investigates the removal of DOM and the minimization of DBP formation by pilot-scale coal- and coconut-based granular activated carbon filtrations (coAC and ccAC, respectively) using unknown screening analysis with Orbitrap mass spectrometry. DOM adsorption rates by both GACs were fitted with pseudo-second order models with initial adsorption rates of 0.005 mg g−1 min−1 and 0.022 mg g−1 min−1 for ccAC and coAC, respectively. Based on observations, ccAC was more effective in the removal of dissolved organic carbon and prolonged adsorption longer than coAC, as the breakthrough of coAC was found on Day 10. ccAC removed compounds with carbon, hydrogen, and oxygen (CHO features) with a wide range of oxidation states, as indicated by the carbon oxidation state (Cos), and a wide range of unsaturation, as indicated by oxygen subtracted double bond equivalent per carbon ([DBE−O]/C), while coAC selectively removed only those CHO features with less oxidized characters. Less oxidized compounds (low Cos) were preferentially removed with less contact time, while more oxidized compounds needed more contact time to adsorb on the GACs. A biofilm was developed on Day 60, and many CHO features were found to have increased after GAC treatment on Day 60, indicating the formation of microbial products. Chlorination resulted in a decrease in many CHO and CHO with Cl atom (CHOCl) features and the formation of CHOCl DBPs more than CHO DBP features. ccAC was effective in the minimization of trihalomethane (THM) and CHOCl DBP feature formations on Day 10 and Day 60, while coAC was found to be much less effective.

Chlorine decay and disinfection by-products formation during chlorination of biofilms formed with simulated drinking water containing corrosion inhibitors

Corrosion inhibitors used to reduce pipe corrosion can alter the physical structure and biochemical components of the biofilm in premise plumbing systems. We studied the effects of corrosion inhibitors on chlorine decay and associated disinfection by-products (DBPs) formation by biofilms grown with simulated drinking water amended with silicate, phosphate, and the phosphate blends. Experiments were conducted with either intact biofilms or biofilm materials dispersed in solution during sonication (referred to as biomass). While there was no significant difference in chlorine decay among biomass from different biofilms, biomass from the phosphate blend biofilm showed the lowest trihalomethane (THMs) and haloacetic acids (HAAs) formation. The chlorine decay rate constants from the biofilm experiment were ranked as: phosphate blends > phosphate ≈ groundwater (GW) > silicate. The kinetics of chlorine decay and formation of DBPs were successfully described by pseudo-first-order kinetics. These fitting parameters were used to predict the DBPs formation in a realistic premise plumbing system. The results showed that biofilm-derived THMs and HAAs increased with increasing chlorine concentration, while THMs and HAAs first increased and then stabilized to a maximum with increasing biofilm total organic carbon (TOC) concentration. In general, the biofilms grown with phosphate-based corrosion inhibitors resulted in lower DBPs formation yield but higher bacterial release, which could potentially increase the risk of user exposure to opportunistic pathogens in drinking water. The silicate biofilms showed the largest yield coefficient of DBPs formation but had the least biomass and lower bacterial release.

Pyrogenic carbon-promoted haloacetic acid decarboxylation to trihalomethanes in drinking water

Drinking water disinfection by chlorination or chloramination can result in the formation of disinfection byproducts (DBPs) such as haloacetic acids (HAAs) and trihalomethanes (THMs). Pyrogenic carbonaceous matter (PCM), such as activated carbon (AC), is commonly used as an ostensibly inert adsorbent to remove HAAs from water. HAA degradation has been mainly attributed to biological factors. This study, for the first time, revealed that abiotic HAA degradation in the presence of PCM could be important under water treatment conditions. Specifically, we observed complete destruction of Br3AA, a model HAA, in the presence of powder AC at pH 7 within 30 min. To understand the role of PCM and the reaction mechanism, we performed a systematic study using a suite of HAAs and various PCM types. We found that PCM significantly accelerated the transformation of three HAAs (Br3AA, BrCl2AA, Br2ClAA) at pH 7. Product characterization indicated an approximately 1:1 HAA molar transformation into their respective THMs following a decarboxylation pathway with PCM. The Br3AA activation energy (Ea) was measured by kinetic experiments at 15–45 °C with and without a model PCM, wherein a significant decrease in Ea from 25.7 ± 3.2 to 13.6 ± 2.2 kcal•mol−1 was observed. We further demonstrated that oxygenated functional groups on PCM (e.g., -COOH) can accelerate HAA decarboxylation using synthesized polymers to resemble PCM. Density functional theory simulations were performed to determine the enthalpy of activation (ΔH‡) for Br3AA decarboxylation with H3O+ and formic acid (HCOOH). The presence of HCOOH significantly lowered the overall ΔH‡ value for Br3AA decarboxylation, supporting the hypothesis that -COOH catalyzes the C-C bond breaking in Br3AA. Overall, our study demonstrated the importance of a previously overlooked abiotic reaction pathway, where HAAs can be quickly converted to THMs with PCM under water treatment relevant conditions. These findings have substantial implications for DBP mitigation in water quality control, particularly for potable water reuse or pre-chlorinated water that allow direct contact between HAAs and AC during filtration as well as PAC fines traveling with finished water in water distribution systems. As such, the volatilization and relative low toxicity of volatile THMs may be considered as a detoxification process to mitigate adverse DBP effects in drinking water, thereby lowering potential health risks to consumers.

Feasibility of micropollutants removal by solar-activated persulfate: Reactive oxygen species formation and influence on DBPs

As a natural source of visible light and a type of renewable energy, solar energy is extensively used in the field of photochemistry. In this study, solar was employed to activate persulfate (PS) to degrade typical micropollutants. The removal kinetics of aspirin (ASA) and flunixin meglumine (FMME) in the solar/PS system were well fitted by pseudo-first-order models (R2 > 0.99). In the system containing 1.0 mM PS activated by solar irradiation at a fluence of 1.14 × 10−4 E·m−2·s−1, 72.6% and 97.5% of ASA and FMME were degraded, and the corresponding kinetic constants were 6.8–9.8 × 10−2 and 1.6–9.8 × 10−1 min−1, respectively. Qualitative and quantitative analyses of the reactive oxygen species (ROS) indicated that sulfate radical (SO4·−) played a major role in degradation, with the maximum contributions of 77.7% and 88.8% for the degradation of ASA and FMME, whereas the maximum contributions of hydroxyl radical (·OH) were only 11.6% and 6.5%, respectively. The contributions of singlet oxygen (1O2) were less than 15% at pH 5.5, but increased to 25.6% and 45.5% at pH 8.5, respectively. Solar/PS pre-oxidation increased disinfection byproducts (DBPs) (95.8% for trihalomethanes (THMs) and 47.9% for haloacetic acids (HAAs) at pH 7.0) after chlorination in deionized water, and an opposite trend was found in systems coexisting with natural organic matter (NOM). Residual PS after oxidation resulted in a high aquatic toxicity, with an inhibition rate of 18.70% to algae growth. Economic analysis showed that the electrical energy per order values of the system ranged from 23.5 to 86.5 kWh·m−3·order−1, indicating that the solar/PS system shows promise for practical applications.

Occurrence of Disinfection By-Products in Swimming Pools in the Area of Thessaloniki, Northern Greece. Assessment of Multi-Pathway Exposure and Risk.

This study investigated the occurrence of disinfection by-products (DBPs) (trihalomethanes (THMs), haloacetic acids (HAAs), halonitriles (HANs), halonitromethane (TCNM) and haloketones (HKs)) in different type of swimming pools in the area of Thessaloniki, northern Greece by employing the EPA methods 551.1 and 552.3. Moreover, general water quality parameters (pH, residual chlorine, dissolved organic carbon, UV254 absorption, total nitrogen, alkalinity and conductivity) were also measured. The concentrations of DBPs showed great variability among swimming pools as well as within the same pool between sampling campaigns. HAAs exhibited the highest concentrations followed by THMs, HANs, TCNM and HKs. Exposure doses for four age groups (3–<6 y, 6–<11 y, 11–<16 y and adults) were calculated. Route-specific exposures varied among DBPs groups. Inhalation was the dominant exposure route to THMs and TCNM (up to 92–95%). Ingestion and dermal absorption were the main exposure routes to HAAs (40–82% and 18–59%, respectively), depending on the age of swimmers. HANs contributed up to 75% to the calculated cytotoxicity of pool water. Hazard indices for different exposure routes were <1, suggesting non-carcinogenic risk. Inhalation posed the higher carcinogenic risk for THMs, whereas risk via oral and dermal routes was low. Ingestion and dermal contact posed the higher risk for HAAs. Risk management strategies that minimise DBPs exposure without compromising disinfection efficiency in swimming pools are necessary.

Effect of bromide on molecular transformation of dissolved effluent organic matter during ozonation, UV/H2O2, UV/persulfate, and UV/chlorine treatments

Ozonation and ultraviolet-based advanced oxidation processes (UV-AOPs) play important roles in advanced treatment of municipal wastewater for water reuse. Bromide is widely present in wastewater at different concentration levels (ranging from μg/L to mg/L). However, the effect of bromide on molecular transformation of dissolved effluent organic matter (dEfOM) in real wastewater during ozonation and UV-AOPs treatments still remains unclear. Herein, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was utilized to characterize the overall molecular transformation of dEfOM and the formation of unknown halogenated byproducts (X-BPs) in ozonation, UV/H2O2, UV/persulfate (UV/PS), and UV/chlorine (UV/Cl) processes in the presence of additional bromide. Compared with the same oxidation processes without additional bromide, the degree of dEfOM oxygenation had some extent decrement with the effect of bromide. A slightly increment of the number of unknown brominated byproducts (Br-BPs) was observed during ozonation, UV/H2O2, and UV/PS treatments in the presence of additional bromide, and the largest increment of these compounds was found in UV/Cl process. A total of 82 chlorinated byproducts (Cl-BPs) and 183 Br-BPs were detected in all oxidation processes with the effect of bromide, and the number of Br-BPs was significantly higher than that of Cl-BPs. Based on mass difference analysis, 69 pairs of possible precursors/Br-BPs were identified. In addition, the additional bromide did not remarkably increase the concentrations of trihalomethanes (THMs) and haloacetic acids (HAAs) in ozonation, UV/H2O2, and UV/PS treatments, while the production of THMs and HAAs significantly decreased by 68.06% and 54.55%, respectively, during UV/Cl treatment. The calculated cytotoxicity increased to some extent for each treatment, especially for UV/Cl treatment, and the compound with largest contribution to cytotoxicity was monobromoacetic acid. This study provides new insights into the formation and transformation of X-BPs during advanced treatment of real wastewater with the effect of bromide.

Chemical characterization of dissolved organic matter as disinfection byproduct precursors by UV/fluorescence and ESI FT-ICR MS after smoldering combustion of leaf needles and woody trunks of pine (Pinus jeffreyi)

Forested land plays an essential role in water supply across the United States (US). Smoldering commonly existing in wildfires contributes significantly to biomass consumption and gas emission, but its influence on source water quality has been rarely studied. Here, we investigated the impact of smoldering temperature (i.e., no burn, 250, 400, and 600 °C) on the nutrients, elements, and dissolved organic matter (DOM) of water extracts from the residues of the leaf needles and woody trunks of pine (Pinus jeffreyi) under the lab-simulated smoldering fire. Results showed the increase of pH and the yields of the dominated exchangeable cations of K+ and Mg2+, P, PO43−-P, and SO42− with increasing temperature increasing from 250 to 600 °C, whereas significant decreases in the fraction of dissolved organic C in residue C with increasing temperature and the yields of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) after burnings. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) presented consistent results with UV/fluorescence, suggesting that the unburned materials contained more biodegradable tyrosine/tryptophan/soluble microbial byproduct-like compounds with high molecular weight (MW), whereas the 600 °C-smoldering materials composed of more aromatic, humified, fulvic/humic acid-like, and oxidized compounds with a potentially high density of C=C bonds had less reactivity in forming trihalomethanes (THMs) and haloacetonitriles (HANs). Our study indicates the smoldering-dominated prescribed fire as a potential forest management strategy for reducing biomass fuel and disinfection byproducts (DBPs) precursors in source water from forested lands.

Exposure to widespread drinking water chemicals, blood inflammation markers, and colorectal cancer.

Trihalomethanes (THMs) and nitrate are widespread chemicals in drinking water associated with colorectal cancer risk but mechanisms are not well understood. We explored the association between exposure to THMs and nitrate in drinking water and inflammation markers, and the link with colorectal cancer risk. A subset of 198 colorectal cancer cases and 205 controls from the multicase-control study MCC-Spain were included. Average concentration of THMs (chloroform, bromodichloromethane, dibromochloromethane, bromoform) and nitrate in tap water at the residence was estimated from age 18 until 2years before the interview ("long term") and for a recent period (3years before diagnosis). Serum levels of EGF, eotaxin, G-CSF, IL-17E, IL-1rA, IL-8, IP-10, MDC, MPO, periostin, VEGF, and C-reactive protein (CRP) were measured. We estimated the linear association between inflammation markers and exposure among controls, and the odds ratio of colorectal cancer associated with THM and nitrate exposure, and inflammation markers. A mediation analysis was conducted to identify inflammation markers in the pathway between THM/nitrate exposure and colorectal cancer. Serum concentrations of EGF, IL-8, IL-17E and eotaxin increased with recent residential levels of brominated THMs, chloroforom and/or total THM. No associations were observed for nitrate and for long-term residential THM levels. All residential exposures except chloroform were positively associated with colorectal cancer. Serum concentrations of VEGF and periostin were positively associated with colorectal cancer, while EGF was inversely associated. One protein-exposure combination (periostin-recent ingested brominated THMs) slightly mediated the association with colorectal cancer risk. Results suggest that estimated THM exposure is involved in inflammation processes. However, the study design was limited to stablish etiologically relevant associations between the protein levels and colorectal cancer risk. The lack of association between nitrate exposure and inflammation markers suggests other biological mechanisms are involved in the link with colorectal cancer.

Trimester-specific associations of maternal exposure to disinfection by-products, oxidative stress, and neonatal neurobehavioral development.

Toxicological studies suggest that maternal exposure to disinfection by-products (DBPs) can impair fetal neurodevelopment. However, evidence from epidemiological studies is scarce and the underlying mechanisms remain unclear. To explore the trimester-specific associations between maternal blood trihalomethane (THM) and urinary haloacetic acid (HAA) concentrations and neonatal neurobehavioral development, and the potential mediating role of oxidative stress (OS). We included 438 pregnant Chinese women from the Xiaogan Disinfection By-Products (XGDBP) birth cohort. Biospecimens were repeatedly collected across trimesters and measured for blood THMs, urinary HAAs, and urinary OS biomarker concentrations. On the third day after birth, the Neonatal Behavioral Neurological Assessment (NBNA) test was administered to newborns. Associations of trimester-specific DBP measurements and OS biomarkers with neonatal NBNA scores were assessed using linear regression models with generalized estimating equations. The potential mediating role of maternal OS biomarkers was also investigated using mediation analyses. After adjusting for potential confounders, blood bromodichloromethane (BDCM) concentrations in the first trimester were inversely associated with NBNA scores [percent change comparing the extreme BDCM tertiles=-28.1% (95% CI: -55.2%, -0.88%); p for trend=0.043]. Besides, third-trimester urinary trichloroacetic acid (TCAA) concentrations were inversely associated with NBNA scores [percent change comparing the extreme TCAA tertiles=-32.9% (95% CI: -64.7%, -1.0%); p for trend=0.046]. These inverse associations differed across pregnancy trimesters (Type 3p-value=0.066 and 0.053, respectively) and were stronger in male infants and mothers aged≥25years. There was no evidence of mediating effect by 8-hydroxy-2-deoxyguanosine (8-OHdG), 4-hydroxy-2-nonenal-mercapturic acid (HNE-MA), or 8-iso-prostaglandin F2α (8-isoPGF2α). Higher prenatal BDCM and TCAA concentrations during specific pregnancy trimesters were associated with lower NBNA scores. However, additional research is required to investigate underlying mechanisms.

Integration of fluorescence quenching correction into trihalomethane formation prediction models.

Despite there being numerous models of trihalomethane (THM) formation, they are limited by high estimation errors, which can be close to the regulatory limits for THMs, due to the fluorescence quenching effect. In this research, the estimation error for THM formation was reduced by correcting the quenching effect. The trihalomethane formation potential (THMFP) test was conducted in the presence of chlorine and bromine, individually and in mixtures. The THM precursors used in this study were protein (bovine serum albumin; BSA), amino acids (tryptophan and tyrosine), chlorine, bromine, and Suwannee River natural organic matter (SWNOM). BSA tended to form bromodichloromethane (BDCM) rather than trichloromethane (TCM) during chlorination in the presence of bromide (Br-). In contrast, SWNOM tended to form chlorinated THMs (TCM) rather than brominated THMs (BDCM and dibromochloromethane; DBCM), and no TBMs were formed in these processes. BSA with SWNOM decreased the formation of TCM due to the decrease in the amount of TCM precursor in SWNOM through binding with BSA. The concentration of each THM species was predicted from the fluorescence intensity of peak C, corrected fluorescence intensity of peak T, and Br- concentration. The use of humic-like and corrected protein-like fluorescence in the excitation-emission matrix model for predicting THM species reduced the prediction error. In this research, correction of the fluorescence quenching decreased the mean percentage estimation error for TCM, BDCM, and DBCM from 47%, 35%, and > 100% in classical approaches to 6.6%, 26.9%, and 2.0%, respectively. This study is expected to make contributions in reporting the relationship between the concentration of natural organic matter compositions and the formation of THM species.