Effect of bromide on the formation of disinfection by-products during wastewater chlorination

The effect of bromide ion on the formation and speciation of trihalomethanes (THMs) and haloacetic acids (HAAs) during the chlorination of biologically treated wastewaters was investigated. The experimental results showed that the formation of total THMs and total HAAs during chlorine disinfection increased with increasing bromide levels in wastewater. The formation of CHBr₃ increased nearly linearly with increasing bromide ion levels, while CHCl₂Br and CHClBr₂ increased with increasing bromide concentration from 0 to 3.2 mg L⁻¹ and thereafter remained constant or slightly decreased. Increasing initial bromide levels up to 12.8 mg L⁻¹ resulted in sharp decrease of the concentration of CHCl₃ and chloro- HAAs. The mixed bromochloro- HAAs and bromo-only species replaced chloro- HAAs as the dominated species of HAA with increasing bromide levels. The distribution of monohalogenated, dihalogenated and trihalogenated species of HAAs in chlorinated wastewater at high concentration of bromide (>2 mg L⁻¹) is different from that of drinking/natural water. The values of the bromine incorporation factors, n (Br) and n′ (Br), increased with increasing bromide concentration and remained constant or slightly decreased with increasing contact time under the studied range of bromide ion concentrations during chlorination. Moreover, the bromine incorporation into THMs was higher than that of HAAs with bromide levels ranging from 1.0 to 12.8 mg L⁻¹, indicating the dissimilar formation mechanisms of THMs and HAAs involving bromide.     

Determination of attenuation rates of recycled water disinfection by‐products in a natural reservoir system using a laboratory‐based approach

A batch test approach was used to assess the in situ attenuation by natural reservoir systems of selected disinfection by‐products (DBPs). The aim was to determine which natural attenuation processes (volatilisation, photolysis and biodegradation) dominated for selected trihalomethanes (THMs) and N‐nitrosodimethylamine (NDMA), common DBPs present in reclaimed water which could be used to potentially augment drinking water supplies. Attenuation rates for THMs were found to be all very similar, with half‐lives ranging from 1.5–1.6 days for open batch tests. The dominant attenuation mechanisms for THMs were volatilisation with hydrolysis and biodegradation of potentially minor importance. NDMA had a half‐life of 3.5–4.3 days for vials exposed to light. The most important attenuation mechanism for NDMA was photolysis with volatilisation and biodegradation of minor importance. The results indicate that the selected DBPs could be effectively attenuated by a natural reservoir system such as a surface water reservoir.     

Trihalomethanes formation in water treated with chlorine dioxide

Formation of trihalomethanes (THMs) was investigated in water treated with chlorine dioxide (ClO₂) and/or chlorine (Cl₂) where humic acid (HA) was used as THMs precursors. When ClO₂ was used as the only disinfectant, no THMs were detected in bromide-free water; while only CHBr₃ was formed in water containing bromide ion because ClO₂ could oxide bromide to form hydrobromous acid which subsequently reacted with HA, and the yield CHBr₃ increased with bromide concentration and ClO₂ dosing. When water was treated with ClO₂ combined with Cl₂, only CHCl₃ was formed in the absence of bromide, however, all four species of THMs were formed in the presence of bromide; the THMs formation potential decreased gradually with an increase in the ratio of ClO₂ to Cl₂ because ClO₂ reacted with HA to render them unreactive or unavailable for THMs production. When water (with or without bromide ion) was irradiated by light, the yield of THMs was increased as a function of irradiation time to a maximum, and thereafter decreased markedly; the possible mechanism is that irradiation could activate the THMs precursors in HA, and at the same time destroy the reactivity of ClO₂ or Cl₂. The same results could be collected from natural water treated by ClO₂ with or without irradiation.     

Impact of source waters,disinfectants, seasons and treatment approaches on trihalomethanes in drinking water: a comparison based on the size of municipal systems

This study compares concentrations of trihalomethanes (THMs) in municipal water for 2001–2007 from the small and large systems in two provinces in Canada (Newfoundland and Quebec) based on source waters, disinfectants, seasons and treatment approaches. Approximately 71 and 94%, respectively, of the municipal systems in Quebec and Newfoundland are small systems (serving fewer than 3000 people). The small systems serve approximately 8.6% (0.57 million) and 44.1% (0.18 million) of the populations in Quebec and Newfoundland, respectively. Concentrations of THMs and its variability are much higher in the small systems (Quebec: 0–941 μg/L; Newfoundland: 0–875 μg/L) than in the systems with populations 10 000 or more (Quebec: 0–364 μg/L; Newfoundland: 2.3–205 μg/L). The study reveals that the differences in THMs between the small and medium/large systems are because of different types of source waters, treatments, disinfection strategies and seasons. The results emphasize that regulatory agencies must focus more on the occurrence of DBPs in small systems and identify strategies to reduce their levels in drinking water.     

Analysis of triclosan and 4n‐nonylphenol in Colombian reservoir water by gas chromatography‐mass spectrometry

In this work were determined triclosan and 4n‐nonylphenol in water from a reservoir that is used to provide water to a purification plant in an important city in Colombia. The analytical methodology was validated using solid‐phase extraction and analysis by gas chromatography‐mass spectrometry (GC‐MS). The analysis by GC‐MS showed good linearity in the range of 0.05–5 μg/L for both compounds. Recoveries from 79 to 109% and standard deviations of 2.5–7.7 for low concentrations and from 3.8 to 9.6 (n = 5) for high concentrations were obtained for both compounds. In Colombia, this is the first time that these compounds have been analysed in water supplying of a drinking water treatment plant. The validated method was applied to the analysis of 27 samples collected in August 2010 in 11 locations from the reservoir and in the influent and effluent of the drinking water treatment plant. In total, seven samples were found to contain triclosan.     

Distribution of halomethanes in potable waters of Kuwait

The distribution of bromine containing trihalomethanes in the water distribution system of Kuwait has been studied. Total halomethanes in the drinking water averaged 25.6 ± 9.1 μg l⁻¹ with a maximum of 50.5 μg l⁻¹. Average concentrations (μg l⁻¹) of individual compounds were: CHBr₃, 13.6 ± 4.6; CHBr₂Cl, 8.8 ± 3.7; CHCl₂Br, 3.3 ± 1.5. Water from roof top storage tanks contained significantly less halomethanes than that from underground reservoirs.     

An analytical method for the analysis of trihalomethanes in ambient air using solid‐phase microextraction gas chromatography‐mass spectrometry: An application to indoor swimming pool complexes

A simple method for the collection and analysis of the four brominated and chlorinated trihalomethanes (THMs) in air samples is described. Ambient air samples were collected in pre‐prepared glass vials, with THM analysis performed using solid‐phase microextraction gas chromatography‐mass spectrometry, where the need for chemical reagents is minimized. Analytical parameters, including oven temperature program, solvent volume, incubation time, vial agitation, extraction time and temperature, as well as desorption time and temperature, were evaluated to ensure optimal method performance. The developed method allows for point‐in‐time quantification (compared to an average concentration measured over extended periods of time), with detection limits between 0.7 to 2.6 µg/m³. Excellent linearity (r² > 0.99), repeatability (3% to 11% RSD), and reproducibility (3% to 16% RSD) were demonstrated over a concentration range from 2 to 5000 µg/m³. The method was validated for the analysis of THMs in indoor swimming pool air and was used to investigate the occurrence of THMs in the air above 15 indoor swimming pools. This is the first study to report the occurrence of THMs in swimming pool air in Australia, and concentrations higher than those previously reported in other countries were measured.     

Effects of UV/H2O2 advanced oxidation on chemical characteristics and chlorine reactivity of surface water natural organic matter

The advanced oxidation process utilizing ultraviolet and hydrogen peroxide (UV/H₂O₂) is currently applied in commercial drinking water applications for the removal of various organic pollutants. Natural organic matter (NOM) present in the source water can also be oxidized and undergo changes at the fluence and H₂O₂ concentrations applied in commercial drinking water UV/H₂O₂ applications (fluences less than 2000 mJ cm⁻², initial H₂O₂ concentrations less than 15 mg L⁻¹). In this study, the impact of UV/H₂O₂ on NOM’s aromaticity, hydrophobicity, and potential to form trihalomethanes (THMs) and haloacetic acids (HAAs) was investigated for raw surface water and the same water with the very hydrophobic acid (VHA) fraction of NOM removed. During UV/H₂O₂ treatments, NOM in the raw surface water was partially oxidized to less aromatic and hydrophobic characteristics, but was not mineralized, confirming findings from past research. Below fluences of 1500 mJ cm⁻² UV/H₂O₂ treatment of the raw water did not lead to reduction in the formation potential of THMs. The formation potential of HAAs was reduced at a fluence of 500 mJ cm⁻² with only small additional reductions as fluence further increased. For the water from which the VHA fraction was removed, UV/H₂O₂ treatment led to mineralization of NOM suggesting that, when coupled with a pre-treatment capable of removing the VHA fraction, UV/H₂O₂ could achieve further reductions in NOM. These subsequent reductions in NOM led to continuous reductions in the formation potentials of THMs and HAAs as fluence increased.     

Investigating effects of bromide ions on trihalomethanes and developing model for predicting bromodichloromethane in drinking water

Chlorination for drinking water can form brominated trihalomethanes (THMs) in the presence of bromide ions. Recent studies have reported that bromodichloromethane (BDCM) has a stronger association with stillbirths and neural tube defects than other THMs species. In this paper, the results of an experimental investigation into the factors forming THMs in the presence of bromide ions are presented. The experiments were conducted using synthetic water samples with different characteristics (e.g., pH, temperature, dissolve organic content). Different combinations of these characteristics were considered in the experimental program. The results showed that increased bromide ion concentrations led to increases in the formation of total THMs, with higher BDCM and dibromochloromethane (DBCM), and lower chloroform formation. By increasing the pH from 6 to 8.5, increased chloroform and decreased BDCM and DBCM formation were observed. Higher bromide ions to chlorine ratios increased BDCM and DBCM and decreased chloroform formation, while higher temperatures increased BDCM, DBCM and chloroform formation. In most cases, bromoform (CHBr₃) concentrations were found to be below the detection limit. Significant factors influencing BDCM formation were identified using a statistical analysis. A model for BDCM formation was estimated from 44 experiments and statistical adequacy was assessed using appropriate diagnostics, including residual plots and an R² of 0.97. The model was validated using external data from 17 water supply systems in Newfoundland, Canada. The predictive performance of the model was found to be excellent, and the resulting model could be used to predict BDCM formation in drinking water and to perform risk-cost balance analyses for best management practices.     

Trihalomethanes formation in point of use surface water disinfection with chlorine or chlorine dioxide tablets

In remote or underdeveloped areas, natural disaster emergencies and armed conflict zones, point‐of‐use surface water disinfection with chlorine tablets provides microbiologically safe water, but disinfection by‐products such as trihalomethanes (THMs) are formed. While the health risks from THMs are much less than the risks from consuming microbiologically unsafe water, it is nonetheless desirable to understand and minimise THM formation. We show that THM concentrations in surface water samples from the Northern British Isles disinfected with chlorine tablets increased with contact time, in some cases to significantly exceed EU, US EPA and WHO drinking water guidance values after more than an hour. More stagnant water from ponds and lochs had higher THM formation than river water. Doubling the chlorine tablet dose slightly enhanced THM formation, and passing water through coffee filter paper reduced it. Chlorine dioxide tablets produced minimal amounts of THMs.     

Inhalation exposure to THMs from drinking water in south Taiwan

Trihalomethanes (THMs) are important disinfection byproducts (DBPs) in drinking water. To understand the magnitude of exposure to THMs for the people in southern Taiwan, models are used to estimate the inhalation exposure associated with drinking water based on raw water quality. Two parts of models are used in this study, one for estimating THM concentration from raw water quality, and one for estimating inhalation exposure to people. Important raw water quality and operational parameters, including TOC, UV254, pH, temperature, chlorine dosage, and water residence time of a major water treatment plant in south Taiwan were collected. An empirical THM formation model was then employed to predict the THM concentration at consumers' dwellings based on the parameters collected. Differences between the predicted results and experimental data were found to be small, indicating that the model is appropriate. The predicted THM concentration distribution was served as input parameters for the exposure models. Three major scenarios associated with probable inhalation exposure of THMs, including shower, pre- and post-cooking activities, and cooking processes, were considered in the exposure models. The model results show that the mean inhalation exposure of THMs for shower, pre- and post-cooking activities, and cooking processes are 26.4, 1.56, 3.29 micrograms/day, respectively. The total inhalation exposure (summation of the three scenarios) was found to be comparable with that for direct ingestion, indicating that inhalation is an important pathway for THM exposure from drinking water.     

Biodegradation of chlorpyrifos and 3, 5, 6‐trichloro‐2‐pyridinol by a novel rhizobial strain Mesorhizobium sp. HN3

A chlorpyrifos (CP) and 3,5,6‐trichloro‐2‐pyridinol (TCP) degrading bacterial strain, Mesorhizobium sp. HN3, was isolated and characterized. Mesorhizobium sp. HN3 degraded CP efficiently up to 400 mg/L initial concentration at wide range of temperatures (30–40°C) and pH (6.0–8.0). However, optimal degradation of CP was achieved at 37°C and neutral pH (7.0) at an initial inoculum density 2 × 10⁷ colony forming unit/mL of culture medium. Kinetic parameters for CP degradation by Mesorhizobium sp. HN3 were estimated at different initial concentrations. Cultures exhibited significant variation (P ≤ 0.05) in the specific growth rate (μ), cell mass formation rate (Q_X) and the substrate uptake rate (Q_S) during degradation of CP. The values of kinetic parameters increased up to 100 mg/L CP and decreased at higher concentration. Investigation of degradation metabolites indicated that CP is converted to diethylthiophosphate and TCP that leads to the formation of 3,5,6‐trichloro‐2‐methoxypyridine.     

Low trihalomethane formation in Korean drinking water

Organics in water have the potential to generate harmful disinfection by-products (DBPs) such as trihalomethanes (THMs) during the chlorination process. To clarify the regulatory implications of Korean THMs levels which appear to be significantly lower than those in the US where the Stage 1 and 2 D/DBPs rule has been promulgated, the characteristics of THMs formation were investigated on five major river waters in Korea. Water samples were taken from 12 water treatment plants on five major rivers that serve as drinking water sources for more than 90% of the Korean population. Trihalomethane formation potential (THMFP), total organic halide formation potential (TOXFP) and ultraviolet absorbance at 254 nm (UV(254)) were determined and compared with those from US data. A survey of existing data [J Korean Soc Water Qual; 16(4) 2000b 431-443] provided evidence that THMs levels in treated drinking water in Korea were one-third of those reported in the US. The lower THMs levels were mainly attributable to the differences in the level and THMFP of dissolved organic carbon (DOC). The DOC levels and the THMFP normalized to DOC were approximately 60% of those in the US. Results which combined could quantitatively account for the lower THMs levels (i.e. 0.6 x 0.6 approximately 1/3) in Korea. The observed Korean THMs levels were over-predicted by the THMs model () developed in the US. The level of THMFP was found to be similar if normalized for aromaticity as measured by UV(254). These findings suggest that: (i) the case for more stringent THMs control is not likely to be a high priority among issues of drinking water quality in Korea; and (ii) significant variation of THMFP level may exist over different geographic regions; hence (iii) independent THMs models should be developed to make accurate predictions for different regions.     

Effect of THMs concentrations on the redesigning of Bani Suef water distribution system

Controlling trihalomethanes (THMs) formed in water distribution systems (WDS) is an important issue for producing safe drinking water in the last decades. The main objective of this study is to design WDS to minimize THMs formation. Implemented case of Bani Suef water distribution system (BSWDS), Egypt, was modeled and studied for operating scenarios 2020 and 2040 (case study) using WaterCAD software, alternative [1]. Drinking water samples were collected from fifteen points located on BSWDS according to monthly sampling program performed between February and September 2015. Laboratory analysis showed that the total growth rate coefficient was 1.157 day^?1, used in THMs prediction by WaterCAD. Three design alternatives [2, 3, 4] were prepared to reduce the formed THMs based on WaterCAD results. Alternative [2] represented new design of alternative [1] through using decreased pipes diameters to study the effect of reducing travel time on minimizing THMs. Alternative [3] was prepared by redesigning alternative [1] using extending new pipelines from dead ends. Alternative [4] was prepared by redesigning alternative [1] through replacing asbestos cement pipes with new UPVC ones. Predicted THMs from alternatives [2, 3, 4] are lower about 27.85, 21.82 and 11.4% than alternative [1], respectively, for 2020. While, for 2040, are lower about 26.41, 20.2 and 11.4%, respectively.     

Fatigue damage analysis of reinforced concrete column considering low‐cycle behavior of HRB400 steel

In this study, a damage model‐based fatigue behavior is proposed. To consider the fatigue behavior of steel in the damage model, the experimental research on reinforcing steel bar grades HRB400 was presented. The monotonic tension test and low‐cycle fatigue test were carried out. The plastic strain amplitude–fatigue cycle (ε_p–2N_f) curve and plastic strain amplitude–strength loss factor (ε_p–?_SR) curve were obtained. The fatigue parameters (C_f, C_d, and α) were proposed by nonlinear fitting. The specimens were simulated using the “Reinforcing Steel” material in “OpenSees” program. These fatigue parameters were proved to accurately describe the fatigue behavior of HRB400 rebar. Moreover, to verify the application of fatigue damage model in RC column, fiber‐based element models were established based on the quasi‐static cyclic test on RC columns. The calculated results agreed well with those of the tests. The damage degree of RC column was calculated by the recorded stress–strain curves of material. The proposed fatigue parameters could be referred in damage model based on material fatigue behavior.     

Preliminary laboratory investigation of disinfection by-product precursor removal using an advanced oxidation process

Natural organic matter (NOM) is ubiquitous in surface and ground waters throughout the world. During drinking water treatment, the NOM that remains in treated water can react with chlorine to form disinfection by‐products. It has been shown that titanium dioxide photocatalysis can achieve over 96% reduction in ultraviolet (UV)₂₅₄ absorbing species such as hydrophobic NOM and over 81% reduction in dissolved organic carbon (DOC). However, an additional filtration stage is required to recover the suspended catalyst before it is suitable for municipal drinking water application. To overcome this problem, we have used immobilised catalysts prepared using chemical sol–gels, and their performance has been assessed during bench‐scale experiments. An immobilised catalyst enables in situ regeneration using UV light and subsequent reuse of the catalyst. In this research, titanium dioxide sol–gels have been used to coat substrates at a laboratory scale. Results showed that the various coatings prepared had different removal efficiencies for both DOC and UV₂₅₄ absorbance. Maximum removals were 1.336 g/m² and 89%, respectively.     

Surface runoff estimation over heterogeneous foothills of Aravalli mountain using medium resolution remote sensing rainfall data with soil conservation system‐curve number method: A case of semi‐arid ungauged Manesar Nala watershed

Manesar Nala watershed, having an aerial extent of 71.53 km², was subjected to modelling of its hydrological behaviour for assessing its water resource potential. Modern tools and techniques of Remote Sensing (RS) and Geographic Information System (GIS) were used for assessment of runoff generating potential using the Hydrologic Soil Cover Complex (HSCC) Method [U.S. Department of Agriculture (USDA)‐Soil Conservation System‐Curve Number (SCS‐CN) approach]. RS and GIS were used in generation and integration of thematic maps [such as Land use/Land cover (using LISS‐III data) and Hydrologic Soil Group (HSG), (using soil map of study area) to derive the Curve Number (CN) for simulating Runoff (R_o)]. The daily rainfall (P) data for the study period 2002–2015 were acquired from NOAA Climate Prediction Center (NCPC). Corresponding R_o from the watershed for intense storm events for 14 years were calculated through RS and GIS. GIS and SCS‐CN model was employed for modelling the runoff production to study its hydrological behaviour. The study showed that the Manesar Nala watershed was having a composite Curve Number – II (CN_II) value of 82.5 for normal conditions. For dry and wet conditions these values were estimated at 66.44 (CN_I) and 91.56 (CN_III), respectively. This investigation showed that Manesar Nala watershed exhibited an annual average (of 14 years, 2002–2015) R_o volume of 4 542 514.37 m³ based on the average annual rainfall (P) of 0.72 m (720 mm). The average annual surface runoff (R_o) was predicted to be approximately 0.21 m with annual runoff coefficient (C_R) of 0.29. During the study, we also found a strong correlation ‘r’ between satellite driven P and R_o from NRCS‐CN method of the order of 0.94. The methodology so developed has the potential to be used in other similar ungauged watersheds in the same agro‐climatic conditions for the purpose of planning of watershed conservation measures and other developmental activities.     

Size‐resolved fluorescent biological aerosol particle concentrations and occupant emissions in a university classroom

This study is among the first to apply laser‐induced fluorescence to characterize bioaerosols at high time and size resolution in an occupied, common‐use indoor environment. Using an ultraviolet aerodynamic particle sizer, we characterized total and fluorescent biological aerosol particle (FBAP) levels (1–15 μm diameter) in a classroom, sampling with 5‐min resolution continuously during eighteen occupied and eight unoccupied days distributed throughout a one‐year period. A material‐balance model was applied to quantify per‐person FBAP emission rates as a function of particle size. Day‐to‐day and seasonal changes in FBAP number concentration (N_F) values in the classroom were small compared to the variability within a day that was attributable to variable levels of occupancy, occupant activities, and the operational state of the ventilation system. Occupancy conditions characteristic of lecture classes were associated with mean N_F source strengths of 2 × 10⁶ particles/h/person, and 9 × 10⁴ particles per metabolic g CO₂. During transitions between lectures, occupant activity was more vigorous, and estimated mean, per‐person N_F emissions were 0.8 × 10⁶ particles per transition. The observed classroom peak in FBAP size at 3–4 μm is similar to the peak in fluorescent and biological aerosols reported from several studies outdoors.