The current study determines the concentrations of trihalomethanes (THMs), and the cancer risk associated with them. The tap water sampling was done from the command area of nine water treatment plants (WTPs) of Delhi, India. THMs levels in the water samples from eighteen distribution points were investigated for one year. The cancer risk (CR) related to THMs by different exposure routes i.e., ingestion, dermal absorption, and inhalation, was assessed for males and females. The THM levels varied between 11.41 µg/L to 175.54 µg/L in the distribution system, having a mean level of 77.58 µg/L. The average concentrations of THMs exceeded the maximum permissible limit given by Indian Standards. The concentration of chloroform was maximum, followed by bromodichloromethane, dibromochloromethane, and bromoform. For males and females, the mean value of total CR was 5.09E-05 5.70E-05, respectively. As the THMs levels were high, the total CR value was also more than the negligible level of risk i.e., 1.0 x 10-6 through all exposure routes.

The present study aims at evaluating the risk of Mutagen X (MX) (3-chloro-4-(dichloromethyl)-5-hydroxy-2 (5H)-furanone) and adverse health effects, associated with direct ingestion of chlorinated drinking water in west of Tehran, supplied by chlorinated drinking water from surface and underground water sources. For one year, MX concentrations in tap water samples has been measured for consumers in four different zones in western Tehran. It has been found that average MX concentration in the whole study area is 24.16 ng/L, with the highest concentration being in Zone 1 with a value of 38 ng/L. Also, the role of water sources, seasonal changes, and effective factors such as Total Organic Carbon (TOC) have been evaluated on MX formation. The highest of excess lifetime cancer risk (ELCR), estimated as 0.0037E-05, belongs to Zone 1, which uses surface water to supply drinking water, while the lowest can be seen in Zone 4, being 0.0021E-05. This latter zone utilizes underground water as the water source. In all zones, the highest risk of excessive cancer is related to winter, ranging from 0.0045E-5 in Zone 1 to 0.0023E-5 in Zone 4. The estimated number of cancer cases for Zones 1 to 4 have been 0.012, 0.016, 0.016, and 0.004, respectively, based on their population. The estimated average risk and the number of ELCR, caused by exposure to MX, through direct ingestion of drinking water have been 0.0030E-5 and 0.047, respectively, in the entire studied area for the duration of one year.

Chlorinated and brominated polycyclic aromatic hydrocarbons (Cl/Br-PAHs) are persistent organic pollutants with potential carcinogenic toxicities that are even higher than those of their parent PAH congeners. Current knowledge of Cl/Br-PAH sources and emission characteristics is lacking. Electric arc furnace (EAF) steelmaking is a potential source for Cl/Br-PAHs, considering that preheating of raw materials before they enter the EAF could produce suitable conditions for Cl/Br-PAHs formation. In this field study, we identified EAFs as an important source of Cl/Br-PAHs and clarified their emission concentrations, fingerprints by gas chromatography coupled with high-resolution magnetic mass spectrometry. Potential formation mechanisms of Cl/Br-PAHs were also proposed. The mass concentration ranges for Σ₁₈Cl-PAHs and Σ₁₈Br-PAHs in stack gas were 25.85–4191 ng Nm⁻³ and 1.02–341 ng Nm⁻³, respectively. The variation of concentration indicated that the steel scrap composition greatly affected the production of Cl/Br-PAHs. The congener ratios including 6-chlorobenzo [a]pyrene/3-chlorofluoranthene and 1-chloroanthracene/1-chloropyrene could be used to estimate the influence of industrial sources on Cl-PAH occurrences in the air. Ring structure growth was the dominant formation pathway for Cl/Br-PAHs, distinctly different from dioxin formation mechanisms dominated by precursor dimerization and chlorination.

Silver nanoparticles (AgNPs) are used in many industries for multiple applications that inevitably release AgNPs into surface water sources. The formation kinetics of disinfection by-products (DBPs) in the presence of AgNPs was investigated during chlorination. Experiments were carried out with raw water from a canal in Songkhla, Thailand, which analyzed the formation potential (FP) of trihalomethanes FP (THMFP), iodo-trihalomethanes FP (I-THMFP), haloacetonitriles FP (HANFP), and trichloronitromethane FP. Increased AgNP concentrations by 10–20 mg/L led to a higher specific formation rate of chloroform which is described by zero- and first-order kinetics. The increase in the specific formation of chloroform as increasing chlorine contact time could enhance both the THMFP rates and the maximum THMFP concentrations in all tested AgNPs. The AgNP content did not have a significant influence on I-THMFP and HANFP concentrations or speciation. The I-THMFP and HANFP increased in a short-chlorination time as mostly complete formation <12 h, and then the rate decreased as the reaction proceeded. The levels of THMs and many emerging DBPs are related to the presence of AgNPs in chlorinated water and chlorine reaction time. THMFP had a higher impact on integrated toxic risk value (ITRV) than I-THMFP and HANFP because of the chlorination of water with AgNPs. The chlorine reaction time was more effective for increasing the ITRV of THMFP than the level of AgNPs. Water treatment plants should control the DBPs that cause possible health risks from water consumption by optimizing water distribution time.

Restoring woody vegetation to riparian zones helps to protect waterways from excessive sediment and nutrient inputs. However, the associated leaf litter can be a major source of dissolved organic matter (DOM) leached into surface waters. DOM can lead to the formation of disinfection by-products (DBPs) during drinking water treatment. This study investigated the DBPs formed during chlorination of DOM leached from leaf litter and assessed the potential toxicity of DBPs generated. We compared the leachate of two native Australian riparian trees, Casuarina cunninghamiana and Eucalyptus tereticornis, and a reservoir water source from a catchment dominated by Eucalyptus species. Leachates were diluted to dissolved organic carbon concentrations equivalent to the reservoir (~9 mg L⁻¹). E. tereticornis leachates produced more trihalomethanes (THMs), haloacetic acids (HAAs), and haloketones after chlorination, while C. cunninghamiana produced more chloral hydrate and haloacetonitriles. Leachate from both species produced less THMs and more HAAs per mole of carbon than reservoir water. This may be because reservoir water had more aromatic, humic characteristics while leaf leachates had relatively more protein-like components. Using in vitro bioassays to test the mixture effects of all chemicals, chlorinated E. tereticornis leachate induced oxidative stress in HepG2 liver cells and bacterial toxicity more frequently and at lower concentrations than C. cunninghamiana and reservoir water. Overall, this study has shown that the DOM leached from litter of these species has the potential to generate DBPs and each species has a unique DBP profile with differing bioassay responses. E. tereticornis may pose a relatively greater risk to drinking water than C. cunninghamiana as it showed greater toxicity in bioassays. This implies tree species should be considered when planning riparian zones to ensure the benefits of vegetation to waterways are not offset by unintended increased DBP production and associated toxicity following chlorination at downstream drinking water intakes.

Disinfection means the killing of pathogenic organisms (e.g. bacteria and its spores, viruses, protozoa and their cysts, worms, and larvae) present in water to make it potable for other domestic works. The substances used in the disinfection of water are known as disinfectants. At municipal level, chlorine (Cl₂), chloramines (NH₂Cl, NHCl₂), chlorine dioxide (ClO₂), ozone (O₃) and ultraviolet (UV) radiations, are the most commonly used disinfectants. Chlorination, because of its removal efficiency and cost effectiveness, has been widely used as method of disinfection of water. But, disinfection process may add several kinds of disinfection by-products (DBPs) (∼600–700 in numbers) in the treated water such as Trihalomethanes (THM), Haloacetic acids (HAA) etc. which are detrimental to the human beings in terms of cytotoxicity, mutagenicity, teratogenicity and carcinogenicity. In water, THMs and HAAs were observed in the range from 0.138 to 458 μg/L and 0.16–136 μg/L, respectively. Thus, several regulations have been specified by world authorities like WHO, USEPA and Bureau of Indian Standard to protect human health. Some techniques have also been developed to remove the DBPs as well as their precursors from the water. The popular techniques of DBPs removals are adsorption, advance oxidation process, coagulation, membrane based filtration, combined approaches etc. The efficiency of adsorption technique was found up to 90% for DBP removal from the water.

Polyhalogenated carbazoles (PHCs) are a class of emerging organic contaminants that have received increasing concern due to their widespread distribution and dioxin-like toxicity. Although previous studies have suggested possible natural sources of PHCs in the environment, the formation pathways are poorly understood. Here we explored the production of PHCs from halogenation of carbazole in the presence of Br⁻ and/or Cl⁻ under the catalysis of chloroperoxidase (CPO) isolated from the marine fungus Caldariomyces fumago. Overall, a total of 25 congeners including mono-to tetra-substituted chlorinated, brominated, and mixed halogenated carbazoles (with substitution patterns of –BrCl, –BrCl2, –BrCl3, –Br2Cl, –Br2Cl2, and –Br3Cl) were produced from the reactions under various conditions. The PHC product profiles were apparently dependent on the halide concentrations. In the CPO-mediated chlorination of carbazole, 3-mono- and 3,6-dichlorocarbazoles predominated in the formation products. In addition to the less abundant mixed halogenated carbazoles (-Br2Cl), 1,3,6-tri- and 1,3,6,8-tetrabromocarbazoles were the dominant products in reactions containing both Br⁻ and Cl⁻. The CPO-catalyzed halogenation of carbazole could take place in pH 3–7, but the formation products were pH dependent. Results of this study suggest that CPO-catalyzed halogenation of carbazole may play an important role in the natural formation of PHCs.

AgCl and Ag2S prevalently exist in the environment as minerals and/or the chlorination and sulfidation products of ionic silver and elemental silver nanoparticles (AgNPs). In this work, we investigated the chemical transformation of AgCl and Ag2S under simulated sunlight (in water) and incineration (in sludge and simulated municipal solid waste, SMSW). In the presence of natural organic matter, AgCl in river water was observed to be transformed into AgNPs under simulated sunlight, while photo-reduction of Ag2S could not take place under the same experimental conditions. During the course of incineration, pure Ag2S was transformed into elemental silver while AgCl remained stable; however, both Ag2S in sludge and AgCl in SMSW can be transformed to elemental silver under incineration, evident by the results of X-ray absorption spectroscopy and scanning electron microscopy measurements. Incineration temperature played an important role in the transformation of Ag2S and AgCl into elemental silver. These results suggest that chemical transformations of Ag2S and AgCl into elemental silver could be a possible source of naturally occurring or unintentionally produced AgNPs, affecting the fate, transport, bioavailability and toxicity of silver. Therefore, it is necessary to include the contributions of this transformation process when assessing the risk of ionic silver/AgNPs and the utilization and management of incineration residues.

Carbazole in source water is a potential precursor for toxic chlorocarbazoles in drinking water when chlorine is used as a disinfection agent in drinking water treatment plants. However, the reactivity of carbazole and the specific structures and predominant analogues of chlorocarbazoles produced during aqueous chlorination remain unknown. In this study, the aqueous chlorination of carbazole was performed to characterize its reactivity and the chlorinated products. Chlorocarbazoles generated from carbazole were identified by a comprehensive two-dimensional gas chromatography-mass spectrometry method, and their molecular structures were predicted by the Fukui index of electrophilic attack, f−1(r). As a result, the comprehensive chlorination pathway of carbazole was extrapolated with a total of nine chlorocarbazoles identified, including two monochlorocarbazoles (3-chlorocarbazole and 1-chlorocarbazole), four dichlorocarbazoles (3,6-dichlorocarbazole, 1,6-dichlorocarbazole, 1,3-dichlorocarbazole and 1,8-dichlorocarbazole), two trichlorocarbazoles (1,3,6-trichlorocarbazole and 1,3,8-trichlorocarbazole) and one tetrachlorocarbazole (1,3,6,8-tetrachlorocarbazole). The f−1(r) value indicates that the C1, C3, C6 and C8 atoms of carbazole were the favored positions for electrophilic attack, with the C3 and C6 atoms being the predominant sites for chlorine substitution. 3-Chlorocarbazole, 3,6-dichlorocarbazole, 1,3,6-trichlorocarbazole and 1,3,6,8-tetrachlorocarbazole were the major analogues of each chlorocarbazole group; however, the production of minor analogues such as 1-chlorocarbazole and 1,6-dichlorocarbazole should not be overlooked. The chlorination of carbazole was a pseudo first order reaction with a reaction rate of 0.1836 nmol/(L· h) and half-life of 3.77 h (pH = 6.4, Cl2 = 4.7 mg/L), and the chlorination rate of carbazole was approximately 5 times faster than that of an known chlorination precursor pyrene. These results showed that Fukui index was efficacious to predict the chlorination sites of aromatic compounds, and that carbazole is readily transformed into toxic chlorocarbazoles in drinking water treatment plants that use chlorine as a disinfection agent.

Concentrations of organochlorines (OCs), brominated flame retardants (BFRs) and mercury (Hg) were measured in eggs of six seabird species breeding in the Gulf of St. Lawrence, Canada. Stable nitrogen (δ15N) and carbon (δ13C) isotopes were used as ecological tracers to measure trophic level and connectivity with benthos, respectively. Concentrations, patterns as well as ecological tracers varied significantly between species. The sum of polychlorinated biphenyls (ΣPCBs) was the most important group measured in all seabird species based on concentration followed generally by the sum of chlorinated pesticides (ΣCPs), the sum of brominated flame retardants (ΣBFRs) and finally total Hg (THg). ΣPCBs, ΣCPs and ΣBFRs increased with trophic level, whereas THg did not. Only ΣBFRs increased with a higher connectivity with the benthos. Seabird species resident to the Great Lakes-St. Lawrence ecosystem showed higher Hg and BFR levels than migratory species. Molt patterns were used to explain variations of contaminant levels.