Reduction of Trihalomethanes Forming Potential by Adsorption of Natural Organic Matter on Ionic Exchange Resins

In a sanitation process of drinking water, carbon from the organic matter reacts with chlorine, forming by-products, among which are trihalomethanes (THM). These substances are carriers of mutagenic and can-cerogenic potential and hence should be removed in drinking water treatment. Since the natural organic mat-ters are precursors of THM formation, their removal from the water decreases the concentration of THMs. The THM forming potential is the most reliable indicator in evaluation of organic matter removal during drinking water treatment processes. The results have shown that the reaction producing THMs follows sec-ond order kinetics. The second order rate constant ranged from 0.024 M-1s-1 to 0.065 M-1s-1 at 22 °C and pH = 8.2 for 96 hours. The removal of 78.4% of natural organic matter, by adsorption on anionic exchange res-ins, resulted in the THM forming potential reduction by 63.1%. Various fractions of natural organic matter differ in their reactivity with chlorine, which is important when it comes to selection of the adsorption me-dium in the drinking water treatment processes.

Trihalomethanes adsorption on activated carbon fiber

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The Effect of Trihalomethanes in Contaminating the Major Watersheds of Middle Tennessee

We have analyzed the contamination of the three major watersheds in Middle Tennessee (Middle Cumberland River Watershed, Stones River Watershed, and Harpeth River Watershed) by trihalomethanes, such as chloroform, bromodichloromethane, dibromochloromethane, and bromoform. These chemicals play an important role in the develop-ment of cancer and adverse reproductive outcomes, and were found to be present above the threshold established by the Environmental Protection Agency. Certain portions of each watershed were found to be contaminated by the trihalomethanes, and deemed un-healthy. The household incomes in the major areas in the three watershed regions were also examined to determine a possible relationship with the level of water contamination. We concluded that income did not necessarily relate to water quality. Specific areas within each watershed that had lower average household incomes were found to have a higher concentration of the trihalomethanes in their drinking water, while other high-income areas were also affected by unhealthy water. However, these effects were random, and the level of contamination remained below the guidelines regulated by the State of Tennessee.

Trihalomethanes in Comerio Drinking Water and Their Reduction by Nanostructured Materials

The formation of disinfection by-products (DBPs) during chlorination of drinking water is an issue which has drawn significant scientific attention due to the possible adverse effects that these compounds have on human health and the formation of another DBPs. Factors that affect the formation of DBPs include: chlorine dose and residue, contact time, temperature, pH and natural organic matter (NOM). The most frequently detected DBPs in drinking water are trihalomethanes (THMs) and haloacetic acids (HAAs). The MCLs are standards established by the United States Environmental Protection Agency (USEPA) for drinking water quality established in Stage 1, Disinfectants and Disinfection Byproducts Rule (DBPR), and they limit the amount of potentially hazardous substances that are allowed in drinking water. The water quality data for THMs were evaluated in the Puerto Rico Aqueduct and Sewer Authority (PRASA). During this evaluation, the THMs exceeded the maximum contamination limit (MCLs) for the Comerio Water Treatment Plant (CWTP). USEPA classified the THMs as Group B2 carcinogens (shown to cause cancer in laboratory animals). This research evaluated the THMs concentrations in the following sampling sites: CWTP, Río Hondo and Pinas Abajo schools, Comerio Health Center (CDT), and the Vázquez Ortiz family, in the municipality of Comerio Puerto Rcio. The results show that the factors affecting the formation of THMs occur in different concentrations across the distribution line. There are not specific ranges to determine the formation of THMs in drinking water when the chemical and physical parameters were evaluated. Three different nanostructured materials (graphene, mordenite (MOR) and multiwalled carbon nanotubes (MWCNTs)) were used in this research, to reduce the THMs formation by adsorption in specific contact times. The results showed that graphene is the best nanomaterial to reduce THMs in drinking water. Graphene can reduce 80 parts per billion (ppb) of THMs in about 2 hours. In addition mordenite can reduce approximately 80 ppb of THMs and MWCNTs adsorbs 71 ppb of THMs in the same period of time respectively. In order to complement the adsorption results previously obtained, total organic carbon (TOC) analyses were measured, after different contact times with the nanomaterials. During the first 30 minutes, graphene C/Co was reduced to c.a. 0.9, in presence of each THMs solution. MWCNTs and MOR show similar adsorptions trends in comparison with graphene.

Formation of Trihalomethanes during Seawater Chlorination

The use of seawater for industrial cooling is a vital technology that poses some of the most profound environmental impact on the water quality in the Arabian Gulf. Biocide (chlorine) is added to the seawater to control biofouling of the cooling system. This added chlorine reacts with bromide and other chemicals naturally exist in the water to form a wide range of oxidants. Regrettably, reactions between the residual oxidants and natural organic matter in the water lead to formation of toxic halogenated organic compounds that have detrimental effects on the environment when they are discharged into the Gulf. This paper describes the formation of trihalomethanes (THMs) in seawater cooling systems. Results of kinetic experiments have shown that concentrations of THMs increased rapidly with time during the first half hour. Chlorination of seawater has shown significant increase in total THMs (TTHMs) and in bromoform concentrations. Rapid decrease of UV absorbance at 254 nm was also observed during seawater chlorination which is indicative of natural organic matter degradation into small organic molecules including THMs and other by-products. The increase in chlorine dose was accompanied with an increase in TTHMs and bromoform concentrations. Linear relationships between total chlorine concentration and both final TTHMs and bromoform concentrations were established. First order exponential decay and exponential associate functions were developed to correlate chlorine dose with formed THMs.

Effects of typical nitrogenous compounds on trihalomethanes formation and chlorine demand during drinking water chlorination

Glycine(Gly),cysteine(Cys),aspartic acid(Asp),leucine(Leu),lysine(Lys),and methyl amine(MA) were chosen as typical nitrogenous compounds,and the effects of them on trihalomethanes (THMs) formation and chlorine demand were performed on filtrated water. Results show that the nitrogenous compounds enhance THMs formation,and the increased levels are controlled by characteristics and the concentration of nitrogenous compounds. The increase in THMs formation follows the order of Asp(126 μg/L)>Cys(119 μg/L)>MA(106 μg/L)>Lys(97 μg/L)≈Gly(96 μg/L)>Leu(80 μg/L)(while nitrogenous compounds=1.0 mg/L,and background THMs=60 μg/L). The increase in chlorine demand is approximately proportionate to the content of nitrogenous compounds,which illustrates that the increase is mainly caused by the reaction of nitrogenous compounds with chlorine. And the increase in chlorine demand follows the order of Cys(27.8 mg/L)>Asp(22.6 mg/L)=Gly(22.6 mg/L)>Lys(21.6 mg/L)>MA(14.1 mg/L)>Leu(11.8 mg/L) (while nitrogenous compounds=1.0 mg/L,and background chorine demand=1.8 mg/L). The mechanisms of nitrogenous compounds enhancing THMs formation are summ the increase of chlorine demand raising THMs formation in reaction of NOM with chlorine,and the THMs formation in chlorination of nitrogenous compounds themselves.

Factors affecting the formation of trihalomethanes in the presence of bromide during chloramination

The effects of the concentration of dissolved total organic carbon (TOC), the TOC/Br- ratio, bromide ion levels, the chlorine to ammonia-N ratio (Cl:N), the monochloramine dose and the chlorine dose on the formation of trihalomethanes (THMs) (including chloroform, bromodichloromethane, chlorodibromomethane, and bromoform) from chlorination were investigated using aqueous humic acid (HA) solutions. The profile of the chloramine decay was also studied under various bromide ion concentrations. Monochloramine decayed in the presence of organic material and bromide ions. The percentage of chloroform and brominated THMs varied according to the TOC/Br- ratio. Total THMs (TTHMs) formation increased from 112 to 190 μg/L with the increase concentrations of bromide ions from 0.67 to 6.72 mg/L, but the chlorine-substituted THMs were replaced by bromine-substituted THMs. A strong linear correlation was obtained between the monochloramine dose and the formation of THMs for Cl:N ratios of 3:1 and 5:1. These ratios had a distinct effect on the formation of chloroform but had little impact on the formation of bromodichloromethane or chlorodibromomethane. The presence of bromide ions increased the rate of monochloramine decay.

Formation control of bromate and trihalomethanes during ozonation of bromide-containing water with chemical addition: Hydrogen peroxide or ammonia?

To ensure the safety of drinking water,ozone (O3) has been extensively applied in drinking water treatment plants to further remove natural organic matter (NOM).However,the surface water and groundwater near the coastal areas often contain high concentrations of bromide ion (Br-).Considering the risk of bromate (Br O3-) formation in ozonation of the sand-filtered water,the inhibitory efficiencies of hydrogen peroxide (H2O2) and ammonia(NH3) on Br O3-formation during ozonation process were compared.The addition of H2O2effectively inhibited Br O3-formation at an initial Br-concentration amended to 350μg/L.The inhibition efficiencies reached 59.6 and 100%when the mass ratio of H2O2/O3was 0.25and>0.5,respectively.The UV254and total organic carbon (TOC) also decreased after adding H2O2,while the formation potential of trihalomethanes (THMs FP) increased especially in subsequent chlorination process at a low dose of H2O2.To control the formation of both Br O3-and THMs,a relatively large dose of O3and a high ratio of H2O2/O3were generally needed.NH3addition inhibited Br O3-formation when the background ammonia nitrogen(NH3–N) concentration was low.There was no significant correlation between Br O3-inhibition efficiency and NH3dose,and a small amount of NH3–N (0.2 mg/L) could obviously inhibit Br O3-formation.The oxidation of NOM seemed unaffected by NH3addition,and the structure of NOM reflected by synchronous fluorescence (SF) scanning remained almost unchanged before and after adding NH3.Considering the formation of Br O3-and THMs,the optimal dose of NH3was suggested to be 0.5 mg/L.

Simultaneous removal of trihalomethanes by bimetallic Ag/Zn:kinetics study

In the present work,bimetallic silver/zinc was applied into the degradation of trihalomethanes,THMs:CHCl_(3),CHBrCl_(2),CHBr_(2)Cl,and CHBr_(3).The kinetics reaction rates and removal efficiencies of the THM compound mixtures,in the aqueous solutions,were investigated.Batch experiments were conducted under mild conditions,ambient temperature,and pressure.The primary degradation reaction followed a pseudo-first-order kinetic law.The first-order rate constants and the degradation efficiencies followed the decreasing order of CHBr_(3)>CHBr_(2)Cl>CHBrCl_(2)>CHCl_(3).The bond dissociation energy and hydrophilic/hydrophobic characteristics of the THM compounds may become the most important parameters affecting the degradation kinetics and efficiency by bimetallic Ag/Zn.

臭氧氧化深度处理二级处理出水的研究

以某城市污水处理厂二级处理出水为原水,研究了臭氧氧化深度处理对水中残留有机物以及病原微生物的降解和去除效果.结果表明,臭氧投加量达到6mg/L时,DOC、UV254、色度的去除率分别为15.49%、36.36%、73.61%,环境激素类痕量有机物邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)的去除率分别为37.29%和14.6%,三维荧光光谱荧光峰的各区域有机物质平均去除率在80%以上,DBP出水浓度为2.64μg/L,DEHP出水浓度为1.4μg/L,满足《城市污水再生利用地下水回灌水质》(GB/T 19772-2005)的标准.臭氧投加量达到10mg/L时,出水中指示性微生物粪大肠菌群仍接近103CFU/L,5mg/L有效氯消毒后出水粪大肠菌群仍接近10CFU/L,6mg/L臭氧与5mg/L有效氯组合消毒出水的粪大肠菌群下降至3CFU/L,满足《城市污水再生利用景观环境用水水质》(GB/T 18921-2002)的标准.三卤甲烷(THMs)的生成量随着有效氯投加量的增加而增加,臭氧与氯组合消毒过程与氯单独消毒过程相比,THMs生成量减少了78.08%.

Disinfection of swimming pools with chlorine and derivatives: formation of organochlorinated and organobrominated compounds and exposure of pool personnel and swimmers

Chlorination of pool water leads to the forma-tion of many by-products, chloroform usually being the most abundant. The paper reports the results of a study evaluating exposure of bath-ers and pool employees to trihalomethanes (chloroform, bromodichloromethane, dibromo-chloromethane, bromoform) in four indoor swimming pools with chlorinated water. Chlo-roform concentrations in environmental air samples when the pool was in use (about 9 h), in the range 1-182 μg/m3, were greater near the pool than in the change rooms, passageways and offices. Chloroform concentrations in per-sonal air samples of pool employees were in the range 18-138 μg/m3. Urinary concentrations of chloroform averaged (geometric means) 0.123 and 0.165 μg/l and 0.404 and 0.342 μg/l prior and at the end of exposure during in water and out of water activities, respectively. The significant increase in urinary excretion of chloroform confirms that the source of the contaminant was pool water. Absorption of chloroform, estimated from airborne and water concentrations, was significantly correlated with delta chloroform (after/before exposure) and urinary concentra-tions of chloroform at the end of exposure. As chloroform is a toxic and possibly carcinogenic substance, these observations pose a problem principally for the general population of pool users.

Colorectal cancers and chlorinated water

Published reports have revealed increased risk of colorectal cancers in people exposed to chlorinated drinking water or chemical derivatives of chlorination. Oestrogen plays a dual positive functions for diminishing the possibilities of such risk by reducing the entrance, and increasing the excretion, of these chemicals. In addition, there are supplementary measures that could be employed in order to reduce this risk further, such as boiling the drinking water, revising the standard concentrations of calcium, magnesium and iron in the public drinking water and prescribing oestrogen in susceptible individuals. Hypo-methylation of genomic DNA could be used as a biological marker for screening for the potential development of colorectal cancers.

Small Water Distribution System Operations and Disinfection By Product Fate

The Stage-2 Disinfectant and Disinfection By-Product (D/DBP) regulations force water utilities to be more concerned with their finished and distributed water quality. Compliance requires changes to their current operational strategy, which affect the formation of DBPs over time. This study quantifies changes in DBP formation and chlorine decay kinetics under different operational conditions and pipe materials found at many small-scale water utilities. A physical model (Pipe Loop) of a distribution system was used to evaluate the change in water quality from conditions such as having a high chlorine dosage entering the distribution system, using a chlorine booster system in the distribution system, and operation of clearwells/storage tanks. The High Chlorine Run (HC) is least favorable option with approximately 64% and 30% higher TTHMs than Normal Run (NR) and Chlorine Booster Run (CB), respectively. High Chlorine conditions also minimize the wall effects. The location of Boosters should always be after the storage systems to avoid extra contact time that can produce approximately 23% - 78% higher TTHMs. The following trends are discovered from the data analysis: Chlorine residual HC > CB > NR and TTHM NR > CB > HC.

Influence of Cleaning Time in Household Reservoirs on Trihalomethane Formation in Treated Water

Chlorination is an efficient and low-cost technique in disinfecting water for public water supply. However, during the process, the formation of undesirable by-products called halogen compounds, such as trihalome-thanes (THMs), occurs. Some of these compounds are proven to be carcinogenic to laboratory animals. The goal of this study was to investigate the occurrence of THMs in household reservoirs and the influence of cleaning time of these reservoirs on the formation of THMs. A total of 103 households were investigated in the city of Maringá, State of Paraná, Brazil. The residences were classified according to the cleaning time of the reservoir into: up to one year, one to two years and more than two years. Samples were taken from the reservoirs and total trihalomethanes (THMt) were analyzed by gas chromatography (GC-MS), total organic carbon (TOC) by means of a Hach kit for low concentrations and free residual chlorine (CLres) by means of a kit for in loco determination. According to the results, the highest concentrations of THMt were observed in the reservoirs with cleaning time of more than 2 years. However, no amount has exceeded the maximum limit allowed by law. In general, the longer the time for cleaning the reservoir, the greater the degradation of water quality in THMt.

Total Trihalomethane Levels in Major Watersheds across the United States

Trihalomethanes, such as chloroform, bromoform, dibromo(chloro)methane, and bromo(dichloro)methane, are present in the major watersheds across the United States. These chemicals play an important role in the development of cancer, have adverse reproductive outcomes, and were found to be present above the threshold established by the Environmental Protection Agency. To understand the impact of socioeconomic background on the quality of water and possible disparities, we have analyzed the levels of total trihalomethanes in the metropolitan areas in the major watersheds across the United States, in 2018, as they correlated to average household incomes. Our study found that Arkansas, Nevada, and Rhode Island demonstrated higher than federally mandated levels of total trihalomethanes in their watersheds. The median annual household and per capita incomes of the three states (Arkansas, Nevada, and Rhode Island) were lower than the national average. In addition, Delaware, New Hampshire, and Wisconsin, which had higher median income levels, demonstrated the lowest total trihalomethane levels across the United States.

THMs Precursor Removal Efficiency from Different Wastewater Treatment Technologies Effluents

Treated wastewater is one of the critical practices of sustainable water management. In Palestinian authority region different wastewater technologies are used to produce variety of effluents that are potentially suitable for different purposes. In this study, these different treated wastewater effluents were characterized chemically, biologically, and physically. Results showed that some of these effluents neither comply with Palestinian nor with other global effluent discharge guidelines. Chemical reactivity of five different treated wastewater effluents with chlorine was measured by determining their chlorine demand and total trihalomethane formation potential (TTHMFP). Results showed that different wastewater effluents chemical reactivity with chlorine and TTHMFP is not only dependent on wastewater treatment technology but also is affected by original water source from which was the water emerged. In all cases, measured THMs superseded acceptable drinking water limits. This would indicate responsibility of high percentage of cancer, hepatic and renal diseases among the local people.

Increase in Organochlorine Contaminant Levels in Major Water Sources of the United States in Response to the Coronavirus Pandemic

Organochlorine contaminants, such as triclosan (TCS), are present in major water sources across the United States. These antimicrobial compounds are widely used as multipurpose ingredients in everyday consumer products. They can be ingested or absorbed through the skin and are found in human blood, breast milk, and urine samples. Studies have shown that the increased use of antimicrobial agents leads to their presence and persistence in the ecosystem, particularly in soil and watersheds. Many studies have highlighted emerging concerns associated with the overuse of TCS, including dermal irritations, a higher incidence of antibacterial-related allergies, microbial resistance, disruptions in the endocrine system, altered thyroid hormone activity, metabolism, and tumor metastasis and growth. Organochlorine contaminant exposures play a role in inflammatory responsiveness, and any unwarranted innate response could lead to adverse outcomes. The capacity of TCS and other organochlorine contaminants to induce inflammation, resulting in persistent and chronic inflammation, is linked to various pathologies, such as cardiovascular disease and several types of cancers. Chronic inflammation presents a severe consequence of exposure to these antimicrobial agents, as any changes could result in the loss of immune competence. Organochlorine contaminant levels were established by the United States Environmental Protection Agency (EPA) in 2019-2020 and have consistently increased in response to the novel coronavirus (nCoV) (COVID-19) pandemic. Our previous research examined the overuse of products containing triclosan (TCS), which led to an increase in total trihalomethane (TTHM) levels affecting the quality of our water supply. We also investigated the impact of the FDA ban that now requires pre-market approval. To comprehend the consequences of excessive antimicrobial use on water quality, we conducted an analysis of the levels of total trichloromethane (chloroform), a byproduct of free chlorine added to TCS, in primary water sources in metropolitan areas across the United States in 2019-2020. We repeated this analysis after the peak of the COVID-19 pandemic in 2021-2022 to examine its correlation with organochlorine exposure. Our study found that the COVID-19 pandemic, along with the increased use of antimicrobial products, has significantly raised the levels of total trihalomethanes compared to those reported in water quality reports from 2019-2020, in contrast to the reports from 2021-2022.

Comparison of UV-based advanced oxidation processes for the removal of different fractions of NOM from drinking water

This study examined the effectiveness for degradation of hydrophobic (HPO),transphilic(TPI) and hydrophilic (HPI) fractions of natural organic matter (NOM) during UV/H_(2)O_(2),UV/TiO_(2)and UV/K2S2O8(UV/PS) advanced oxidation processes (AOPs).The changing characteristics of NOM were evaluated by dissolved organic carbon (DOC),the specific UV absorbance (SUVA),trihalomethanes formation potential (THMFP),organic halogen adsorbable on activated carbon formation potential (AOXFP) and parallel factor analysis of excitation–emission matrices (PARAFAC-EEMs).In the three UV-based AOPs,HPI fraction with low molecular weight and aromaticity was more likely to degradate than HPO and TPI,and the removal efficiency of SUVA for HPO was much higher than TPI and HPI fraction.In terms of the specific THMFP of HPO,TPI and HPI,a reduction was achieved in the UV/H_(2)O_(2)process,and the higest removal rate even reached to 83%.UV/TiO_(2)and UV/PS processes can only decrease the specific THMFP of HPI.The specific AOXFP of HPO,TPI and HPI fractions were all able to be degraded by the three UV-based AOPs,and HPO content is more susceptible to decompose than TPI and HPI content.UV/H_(2)O_(2)was found to be the most effective treatment for the removal of THMFP and AOXFP under given conditions.C1 (microbial or marine derived humic-like substances),C_(2) (terrestrially derived humic-like substances)and C_(3) (tryptophan-like proteins) fluorescent components of HPO fraction were fairly labile across the UV-based AOPs treatment.C_(3) of each fraction of NOM was the most resistant to degrade upon the UV-based AOPs.Results from this study may provide the prediction about the consequence of UV-based AOPs for the degradation of different fractions of NOM with varied characteristics.

Formation of Iodinated Trihalomethane Disinfection By-products by Co-oxidation of Natural Organic Matter with Sodium Hypochlorite and Lead Dioxide

Iodinated trihalomethanes(I-THMs)in drinking water pipelines have attracted wide attention due to their high toxicity.The coexistence of widely present lead dioxide(PbO_(2))with commonly used disinfectant sodium hypochlorite(NaClO)in drinking water might change the formation characteristics of I-THMs due to the strongly oxidizing properties of PbO_(2).This study investigated the formation of I-THMs during the co-oxidation of natural organic matter including humic acid(HA),extracellular organic matter(EOM),and intracellular organic matter(IOM)of algogenic organic matter by PbO_(2) and NaClO.Triiodomethane(CHI_(3))is the dominant product in the single oxidation system of PbO_(2),whereas trichloromethane(CHCl_(3)),chlorodiiodomethane(CHClI_(2)),and dichloroiodomethane(CHCl2I)are the major products in the single NaClO system.In the co-oxidation system,the dominant I-THMs are similar to those in the single NaClO system.However,the CHCl_(3) content decreased to 56.4%whereas I-THMs concentrations remained unchanged with the increase of PbO_(2) concentration.The main reason is attributed to the reduced residual chlorine content due to the reaction of PbO_(2) with NaClO.IOM is more prone to forming I-THMs than HA and EOM due to the specified structures.This study suggested that PbO_(2) in the drinking water supply pipelines might change the risk of THMs.

Relationships between regulated DBPs and emerging DBPs of health concern in U.S. drinking water

A survey was conducted at eight U.S. drinking water plants, that spanned a wide range of water qualities and treatment/disinfection practices. Plants that treated heavily-wastewaterimpacted source waters had lower trihalomethane to dihaloacetonitrile ratios due to the presence of more organic nitrogen and HAN precursors. As the bromide to total organic carbon ratio increased, there was more bromine incorporation into DBPs. This has been shown in other studies for THMs and selected emerging DBPs(HANs), whereas this study examined bromine incorporation for a wider group of emerging DBPs(haloacetaldehydes, halonitromethanes). Moreover, bromine incorporation into the emerging DBPs was, in general, similar to that of the THMs. Epidemiology studies that show an association between adverse health effects and brominated THMs may be due to the formation of brominated emerging DBPs of heath concern. Plants with higher free chlorine contact times before ammonia addition to form chloramines had less iodinated DBP formation in chloraminated distribution systems, where there was more oxidation of the iodide to iodate(a sink for the iodide) by the chlorine. This has been shown in many bench-scale studies(primarily for iodinated THMs), but seldom in full-scale studies(where this study also showed the impact on total organic iodine. Collectively, the THMs, haloacetic acids, and emerging DBPs accounted for a significant portion of the TOCl, TOBr, and TOI;however, ~50% of the TOCl and TOBr is still unknown. The correlation of the sum of detected DBPs with the TOCl and TOBr suggests that they can be used as reliable surrogates.