Sunlight enhanced the formation of tribromomethane from benzotriazole degradation during the sunlight/free chlorine treatment in the presence of bromide.

The coexistence of free chlorine and bromide under sunlight irradiation (sunlight/FC with Br-) is unavoidable in outdoor seawater swimming pools, and the formation of brominated disinfection byproducts could act more harmful than chlorinated disinfection byproducts. In this study, benzotriazole was selected as a model compound to investigate the degradation rate and the subsequent formation of disinfection byproducts via sunlight/FC with Br- process. The rate constants for the degradation of benzotriazole under pseudo first order conditions in sunlight/FC with Br- and sunlight/FC are 2.3 ± 0.07 × 10-1 min-1 and 6.0 ± 0.7 × 10-2 min-1, respectively. The enhanced degradation of benzotriazole can be ascribed to the generation of HO•, bromine species, and reactive halogen species (RHS) during sunlight/FC with Br-. Despite the fact that sunlight/FC with Br- process enhanced benzotriazole degradation, the reaction results in increasing tribromomethane (TBM) formation. A high concentration (37.8 µg/L) of TBM was detected in the sunlight/FC with Br-, which was due to the reaction of RHS. The degradation of benzotriazole was notably influenced by the pH value (pH 4 - 11), the concentration of bromide (0 - 2 mM), and free chlorine (1 - 6 mg/L). Furthermore, the concentration of TBM increased when the free chlorine concentrations increased, implying the formation potential of harmful TBM in chlorinated seawater swimming pools.

Formation potential of disinfection byproducts during chlorination of petroleum hydrocarbon-contaminated drinking water.

Recent leaks of underground fuel storage tanks in the Pearl Harbor region have led to direct release of un-weathered petroleum hydrocarbons (PHCs) into drinking water sources, which then directly underwent chlorination disinfection treatment. Since the control of disinfection byproducts (DBPs) traditionally focuses natural organic matters (NOM) from source water and little is known about the interactions between free chlorine and un-weathered PHCs, laboratory chlorination experiments in batch reactors were conducted to determine the formation potential of DBPs during chlorination of PHC-contaminated drinking water. Quantitative analysis of regulated DBPs showed that significant quantities of THM4 (average 3,498 µg/L) and HAA5 (average 355.4 µg/L) compounds were formed as the result of chlorination of un-weathered PHCs. Amongst the regulated DBPs, THM4, which were comprised primarily of chloroform and bromodichloromethane, were more abundant than HAA5. Numerous unregulated DBPs and a large diversity of unidentified potentially halogenated organic compounds were also produced, with the most abundant being 1,1-dichloroacetone, 1,2-dibromo-3-chloropropane, chloropicrin, dichloroacetonitrile, and trichloracetonitrile. Together, the results demonstrated the DBP formation potential when PHC-contaminated water undergoes chlorination treatment. Further studies are needed to confirm the regulated DBP production and health risks under field relevant conditions.

Synergistic disinfection effects and reduction of disinfection by-products in water treatment using magnetic quaternized cyclodextrin polymer combined with chorine disinfection process.

Disinfection is vital in ensuring water safety. However, the traditional chlorine disinfection process is prone to producing toxic and harmful disinfection by-products (DBPs). The combination of quaternary ammonium polymer and the chlorine disinfection process can solve this shortcoming. Currently, research on the control of DBPs through the combined process is not systematic and the control effect between reducing the dosage of disinfectants and DBPs remains to be studied. Quaternized cyclodextrin polymers have attracted increasing attention due to their excellent adsorption and antibacterial properties, but their synergistic effect with chlorine disinfection is still unclear. In this study, a magnetic quaternized cyclodextrin polymer (MQCDP) is synthesized in an ionic liquid green system, and a combined process of MQCDP treatment and chlorine disinfection is established. The disinfection performance of the combined process on the actual water body along with its reducing effect on the amount of chlorine disinfectant as well as the trihalomethanes (THMs) and haloacetic acids (HAAs) DBPs are explored. MQCDP has a porous structure with a specific surface area of 825 m2 g-1 and is easily magnetically separated. MQCDP can remove most of the natural organic matter (UV254 absorbance decreased by 97 %) in the water at the dosage of 1 g L-1 and kill bacteria with a sterilization rate of 85 %. Compared with disinfection using chlorine alone, the combined process has higher disinfection efficiency and significantly reduces the amount of disinfectant used. A concentration of 5 mg/L of NaClO was needed to meet the standard by chlorine disinfectant alone, while only 2 mg/L of NaClO can meet the standard for the combined process, indicating 60 % of the chlorine demand was reduced. More importantly, the combined process can significantly reduce the generation potential of DBPs. When 10 mg/L of NaClO is added, the THMs and HAAs generated by the combined process decreased by 65 % and 34 %, respectively, compared with the levels produced by single chlorine disinfection. The combined process can reduce the dosage of chlorine disinfectant and MQCDP can adsorb humic acid DBP precursors in raw water, thus lowering the generation of DBPs during disinfection. In summary, MQCDP has excellent separation and antibacterial ability, and its synergistic effects combined with the chlorine disinfection process are of great significance for controlling the amount of disinfectant and the formation potential of DBPs, which has potential applications in actual water treatment.

Alkaline chlorination of drinking water: A trade-off between genotoxicity control and trihalomethane formation.

The pH of chlorination is an important factor affecting the formation of disinfection byproducts (DBPs). In this study, we discovered that the genotoxicity induced by chlorination can be effectively reduced under alkaline conditions. As the pH of chlorination increased from 6.5 to 8.5, the genotoxicity of investigated waters reduced by ∼30-90 %. By assessing the genotoxicity of the mixture of measured DBPs, it was found that the contribution of measured DBPs to the overall genotoxicity was lower than 5 %, and the significant reduction of genotoxicity was largely associated with unknown DBPs. The result of Pearson's correlation analysis indicated that humified organics and soluble microbial byproducts were likely responsible for the genotoxicity, and their derived genotoxic compounds (i.e., unknown DBPs) tended to decompose during alkaline chlorination. However, the control of genotoxicity by alkaline chlorination was achieved at the expense of promoting trihalomethane (THM) formation. The highest genotoxicity reduction (93 %) was observed for chlorinated granular activated carbon-treated waters, but the formation of THMs was promoted to a level approaching that in untreated waters. The inconsistent trend of overall genotoxicity and THM concentration during alkaline chlorination suggested the inadequacy of THMs as metric for DBP exposure, and considerations should also be given to the toxicity of bulk water in addition to regulated DBPs.

Formation characteristics and acute toxicity assessment of THMs and HAcAms from DOM and its different fractions in source water during chlorination and chloramination.

The formation characteristics of trihalomethanes (THMs) and haloacetamides (HAcAms) from dissolved organic matter and its fractions were investigated during chlorine-based disinfection processes. The relationships between water quality parameters, fluorescence parameters, and the formation levels of THMs and HAcAms were analyzed. The fractions contributing most to the acute toxicity were identified. The trichloromethane (TCM) generation level (72 h) generally followed the order of Cl2 > NH2Cl > NHCl2 process. The NHCl2 process was superior to the NH2Cl process in controlling TCM formation. Hydrophobic acidic substance (HOA), hydrophobic neutral substance (HON), and hydrophilic substance (HIS) were identified as primary precursors of 2,2-dichloroacetamide and trichloroacetamide during chlorination and chloramination. The formation of TCM mainly resulted from HOA, HON and HIS fractions relatively uniformly, while HOA and HIS fractions contributed more to the formation of bromodichloromethane and dibromomonochloromethane. UV254 could be used as an alternative indicator for the amount of ΣTHMs formed during chlorination and chloramination processes. Dissolved organic nitrogen was a potential precursor of 2,2-dichloroacetamide during chlorination process. The fractions with the highest potential acute toxicity after the chlorination were water-dependent.

Ipso Substitution of Aromatic Bromine in Chlorinated Waters: Impacts on Trihalomethane Formation.

Parabens and salicylates were examined as disinfection byproduct (DBP) precursors to explore the possible influence of ipso substitution (i.e., halogen exchange) on the yield and speciation of trihalomethanes (THMs) formed during water chlorination. Substoichiometric conversion of C-Br bonds into C-Cl bonds was confirmed for several parabens and salicylates. The co-occurrence of (mono)brominated and nonhalogenated precursors in the presence of free chlorine (but in the absence of added Br-) generated polybrominated THMs, implicating ipso substitution. The THM molar yield, bromine incorporation, and bromine recovery from brominated and nonhalogenated precursor mixtures were commensurate with those observed from equimolar additions of NaBr, indicating efficient displacement of aromatic bromine by free chlorine followed by reincorporation of liberated HOBr into DBP precursors. The THM molar yield from brominated precursors was enhanced by a factor of ≤20 relative to that from nonhalogenated precursors. Trends in THM molar yields and bromine incorporation differed between brominated parabens and brominated salicylates, suggesting that the influence of ipso substitution on THM formation varies with the structure of the organic precursor. Collectively, these results provide new evidence of the often-overlooked role ipso substitution can play in promoting halogen exchange and bromine enrichment among DBPs in chlorinated waters.

Removal effect of trihalomethanes (THMs) and halogenated acetic acids (HAAs) precursors in reclaimed water by polyaluminum chloride (PACl) coagulation.

This study analyzed the removal effect of various doses of polyaluminum chloride (PACI) on wastewater treatment plants at pH 7. The sewage plant's secondary effluent organic matter (EfOM) separates into four components: hydrophobic base (HOB), hydrophilic (HI), hydrophobic acid (HOA), and hydrophobic neutral (HON). The removal effect for various forms of organic waste is optimum at 16 mg/L and that halogenated acetic acids (HAAs) and trihalomethanes (THMs) are formed simultaneously. After PACI treatment, hydrophobic organic compounds were converted to humic acid (HA), fulvic acid (FA), soluble microbial products (SMPs), and other HI organic compounds, increasing the amount of HAAs produced by HI fractions. Removal rate of hydrophobic organic compounds, particularly HON, is 92.8% when using PAC. Moreover, after EfOM coagulation, most HAAs are trichloroacetic acid (TCAA), followed by bromochloroacetic acid (BCAA) and bromodichloroacetic acid (BDCAA). Only HOB can produce monochloroacetic acid (MCAA), whereas HA and SMPs with HOA are primary components of dichloroacetic acid (DCAA). The toughest removable byproduct of THMs is CHBr3, and after condensation of each THM component, only HOA and HON produce CHBr3, while HI produces only a minimal quantity of CHBrCl2 and CHCl3.This finding is critical for understanding how disinfection byproducts are produced after chlorinating EfOM.

NOM fractionation by HPSEC-DAD-OCD for predicting trihalomethane disinfection by-product formation potential in full-scale drinking water treatment plants.

Chlorination is a common method for water disinfection; however, it leads to the formation of disinfection by-products (DBPs), which are undesirable toxic pollutants. To prevent their formation, it is crucial to understand the reactivity of natural organic matter (NOM), which is considered a dominant precursor of DBPs. We propose a novel size exclusion chromatography (SEC) approach to evaluate NOM reactivity and the formation potential of total trihalomethanes-formation potentials (tTHMs-FP) and four regulated species (i.e. CHCl3, CHBrCl2, CHBr2Cl, and CHBr3). This method combines enhanced SEC separation with two analytical columns working in tandem and quantification of apparent molecular weight (AMW) NOM fractions using C content (organic carbon detector, OCD), 254-nm spectroscopic (diode-array detector, DAD) measurements, and spectral slopes at low (S206-240) and high (S350-380) wavelengths. Links between THMs-FP and NOM fractions from high performance size exclusion chromatography HPSEC-DAD-OCD were investigated using statistical modelling with multiple linear regressions for samples taken alongside conventional full-scale as well as full- and pilot-scale electrodialysis reversal and bench-scale ion exchange resins. The proposed models revealed promising correlations between the AMW NOM fractions and the THMs-FP. Methodological changes increased fractionated signal correlations relative to bulk regressions, especially in the proposed HPSEC-DAD-OCD method. Furthermore, spectroscopic models based on fractionated signals are presented, providing a promising approach to predict THMs-FP simultaneously considering the effect of the dominant THMs precursors, NOM and Br-.

Has the formation of disinfection by-products been overestimated? Membrane leakage from syringe filter heads serves as unexpected precursors.

Syringe filters are widely used for sample pretreatments in laboratories. This study found that, surprisingly, these filters can leak dissolved organic carbon (DOC) that can potentially serve as precursors of disinfection by-products (DBPs). Nine common types of syringe filters were assessed. The results showed that the DOC of ultrapure water increased after syringe filtration. The DOC shed from filter membranes was characterized, whose spectra showed that the main compounds exhibited a low apparent molecular weight. Five classes of DBPs were investigated including trihalomethanes, haloacetaldehydes, haloacetonitriles, haloacetamides and halonitromethanes, among which trichloromethane (TCM), dichloroacetaldehyde (DCAL), trichloroacetaldehyde (TCAL), dichloroacetonitrile (DCAN), and trichloronitromethane (TCNM) were principally detected. The DBP formation was affected by chlorination time and membrane types. In general, the use of the poly vinylidene fluoride membrane resulted in the highest formation of TCM and TCAL, whereas nylon and mixed cellulose esters membranes contributed significantly to the formation of DCAN and TCNM, respectively. The shedding DOC and the formation of TCM, DCAL and TCAL from filter membranes were mitigated effectively by pre-washing; however, the contribution of membrane leakage to DCAN and TCNM formation was still notable, even with a pre-wash volume of 50 mL. When unwashed syringe filters were used for a real water sample, the DBP formation increased by up to 73.2% compared to the pre-washed ones; particularly for TCNM it was always over 15%. Therefore, for better quality control in laboratories, more attention should be paid to the syringe filters during sample pre-treatments, particularly when DBP formation is being investigated.

The formation of disinfection by-products from the chlorination and chloramination of amides.

This study examined the potential of six aliphatic and aromatic amides, commonly found in natural waters or used as chemical aids in water treatment, to act as organic precursors for nine haloacetamides (HAcAms), five haloacetonitriles (HANs), regulated trihalomethanes (THMs) and haloacetic acids (HAAs) upon chlorination and chloramination. The impact of key experimental conditions, representative of drinking water, including pH (7 & 8), retention time (4 & 24 h) and bromide levels (0 & 100 µg/L), on the generation of the target DBPs was investigated. The highest aggregate DBP yields upon chlor(am)ination were reported for the aromatic and hydrophobic hydroxybenzamide; 2.7% ± 0.1% M/M (chlorination) and 1.7% M/M (chloramination). Increased reactivity was observed in aliphatic and hydrophilic compounds, acrylamide (2.5 ± 0.2% M/M) and acetamide (1.3 ± 0.2% M/M), in chlorination and chloramination, respectively. The addition of bromide increased average DBP yields by 50-70%. Relative to chlorination, the application of chloramines reduced DBP formation by 66.5% (without Br-) and by 46.4% (with Br-). However, bromine incorporation in HAAs and HAcAms was enhanced following chloramination, of concern due to the higher toxicological potency of brominated compounds.

Coupling changes of disinfectant and bacteria induced by the water stagnation and disinfection strategy.

This paper studied stagnation-induced changes of disinfectant and bacteria using an orthogonal test and kinetic analysis, and then proposed a disinfection strategy. Tap water from a drinking water distribution system and ultrafiltrated water were collected and disinfected with four disinfectants (concentrations were set 0.2-1 mg/L as Cl2. The study had several findings. First, disinfectants expanded lag phases and shortened generation times of the microbiome. Reduction in culturability, substrate responsiveness, respiratory activity, membrane potential and integrity subsequently occurred with increasing disinfection concentration. Second, the disinfectant decay rate decreased with initial disinfection concentration, and the effective disinfection phase (heterotrophic plate count (HPC) was less than 100 cfu/mL) was longer in water samples with lower organic matter. Moreover, the disinfection process was divided into an effective phase and an invalid phase (HPC>100 cfu/mL). Then a disinfection efficiency model was built and the regulation of disinfection by-products (DBPs) production was studied in chlorinated water samples, which provides a general method for other disinfectant studies. The average trihalomethanes (THMs) production during the effective phase (marked as THM/th) and THMs production during the invalid phase (marked as ΔTHM) were proposed to evaluate the DBPs production. The level of THM/th and ΔTHM were lower in ultrafiltrated water than those in tap water. THM/th were negatively correlated with initial chlorine concentration while ΔTHM were positively correlated with initial chlorine concentration. Finally, for the purpose of raising disinfection efficiency and decreasing DBPs, we propose periodic pulse disinfection.

Effects of phosphate and hydrogen peroxide on the performance of a biological activated carbon filter for enhanced biofiltration.

Biofilm formation on biofilters can influence their hydraulic performance, thereby leading to head loss and an increase in energy use and costs for water utilities. The effects of a range of factors, including hydrogen peroxide and phosphate, on the performance of biological activated carbon (BAC) and biofilm formation were investigated using laboratory-scale columns. Head loss, total carbohydrates, and proteins were reduced in the nutrient-enhanced, oxidant-enhanced, and nutrient + oxidant-enhanced BAC filters. However, there were no changes in the removal of dissolved organic matter, trihalomethane formation potential, or selected trace organic contaminants. The biofilm formation on polyvinyl chloride and stainless steel coupons using the laboratory biofilm reactor system was lower when the effluent from a nutrient-enhanced column was used, which indicated that there was less biofilm formation in the distribution systems. This may have been because the effluent from the nutrient-enhanced column was more biologically stable. Therefore, enhanced biofiltration could be used not only to reduce head loss in biofilters, but also to delay biofilm formation in distribution systems.

Assessment of the air quality in 20 public indoor swimming pools located in the Northern Region of Portugal.

Air exposures occurring in indoor swimming pools are an important public health issue due to their popularity and regular use by the general population, including vulnerable groups such as children and elderly people. More comprehensive information on indoor air quality (IAQ) in swimming pools is thus needed in order to understand health risks, establish appropriate protective limits and provide evidence-based opportunities for improvement of IAQ in these facilities. In this context, twenty public indoor swimming pools located in the Northern Region of Portugal were examined in two sampling campaigns: January-March and May-July 2018. For each campaign, a comprehensive set of environmental parameters was monitored during the entire period of the facilities' operating hours of a weekday, both indoors and outdoors. In addition, four air (1-h samplings) and water samples were collected. Findings show that comfort conditions, ultrafine particles number concentrations and exposure to substances in the indoor air (concentration and composition) is likely to vary greatly from one public indoor swimming pool to another. Trihalomethanes (THM) and dichloroacetonitrile were the predominant disinfection by-products identified in the indoor air but other potentially hazardous volatile organic compounds, such as limonene, 1,2,4-trimethylbenzene, 2,2,4,4,6,8,8-heptamethylnonane, 2- and 3-methylbutanenitrile, acetophenone, benzonitrile, and isobutyronitrile were found to have relevant putative emission sources in the environment of the swimming pools analyzed. Furthermore, indicators of poor ventilation conditions (namely carbon dioxide, relative humidity and existence of signs of condensation in windows) and some water-related parameters (THM levels, conductivity and salinity) were found to be determining factors of the measured airborne THM concentrations that appeared to significantly potentiate the exposure. In summary, this work provides evidence for the need to establish adequate standards for the comprehensive evaluation of IAQ in public swimming pools, in order to guide further development of evidence-based prevention/remediation strategies for promoting healthy environments in swimming pools.

Trihalomethane yields from twelve aromatic halogenated disinfection byproducts during chlor(am)ination.

As the first identified category of disinfection byproducts (DBPs), trihalomethanes (THMs) have received continuous attention. Previous studies have demonstrated that the transformation of aromatic halogenated DBPs during chlor (am)ination resulted in the formation of THMs, which may occur in both water treatment plants and drinking water distribution systems. In this study, THM yields from aromatic chlorinated/brominated DBPs during chlorination and aromatic iodinated DBPs during chloramination were investigated. The trichloromethane (TCM) yields from 3,5-dichloro-4-hydroxybenzaldehyde, 3,5-dichlorosalicylic acid, 2,6-dichloro-4-nitrophenol, and 2,4,6-trichlorophenol were in the range of 0-11.4%, 0-8.4%, 0-6.4%, and 0-17.8%, respectively. The THM4 (TCM, bromodichloromethane (BDCM), dibromochloromethane (DBCM), and tribromomethane (TBM)) yields from 3,5-dibromo-4-hydroxybenzaldehyde, 3,5-dibromosalicylic acid, 2,6-dibromo-4-nitrophenol, and 2,4,6-tribromophenol were in the range of 0-12.9%, 0-27.0%, 0-8.6%, and 0-29.4%, respectively. The TCM and triiodomethane (TIM) yields from 3,5-diiodo-4-hydroxybenzaldehyde, 3,5-diiodosalicylic acid, 2,6-diiodo-4-nitrophenol, and 2,4,6-triiodophenol were in the range of 0-5.2%, 0-7.0%, 0-2.2%, and 0-10.6%, respectively. After 72 h, TCM yields from aromatic chlorinated DBPs were generally higher than that from their brominated analogues; TBM yields from aromatic brominated DBPs were significantly lower than TCM yields, BDCM yields, and DBCM yields; and among aromatic halogenated DBPs, 2,4,6-trihalophenol had the highest THM yields while 2,6-dihalo-4-nitrophenol had the lowest THM yields. Moreover, the results revealed that alkaline conditions and higher temperatures favored the THM yields from the twelve aromatic halogenated DBPs during chlor (am)ination, and chlorine/monochloramine dose affected the yields and speciation of THMs from the aromatic halogenated DBPs.

Fluorescence spectroscopy for assessing trihalomethane precursors removal by MIEX resin.

This study investigated the applicability of fluorescence excitation-emission matrix spectroscopy (EEMS) to assess total trihalomethane formation potentials (TTHMFPs) and the ability of magnetic ion exchange (MIEX®) resin to reduce TTHMFP. We treated a surface water and secondary wastewater effluent with MIEX mimicking full-scale operation by repeatedly exposing the same resin batch to additional feed water, with batches ranging from 500 to 5,000 resin bed volumes. Results showed that MIEX was more effective at removing or reducing ultraviolet absorbance (UVA254), dissolved organic carbon (DOC), and TTHMFP in surface water than in secondary effluent. The greater UVA254, DOC and TTHMFP removal for surface waters was explained by the stronger affinity of MIEX for terrestrial dissolved organic matter (DOM) compared to microbial DOM. Fluorescence EEMS results showed that the ratio between terrestrial and microbial fluorescent signals of DOM was significantly greater in surface water than in secondary effluent. Fluorescence surrogate parameters were strongly correlated with TTHMFP, namely, fluorescence intensity of humic-like peak C (R2 = 0.98, p < 0.01), protein-like peak T (R2 = 0.96, p < 0.01), and fulvic-like peak A (R2 = 0.87, p < 0.01). Correlations between fluorescence surrogate parameters and TTHMFP were substantially stronger than correlations between DOC and TTHMFP. Overall, the results indicate that fluorescent parameters extracted from EEMS data can be used as quick surrogate parameters to monitor TTHMFP for a diverse group of raw and MIEX-treated waters.

Extraction and Trace Analysis of Trihalomethanes in Water Samples Using Zein@Fe3O4 Nanocomposite.

This study presents a simple dispersive solid phase extraction (DSPE) technique combined with headspace thermal desorption (HSTD) for extraction and determination of the most significant trihalomethanes (THMs), bromodichloromethane, bromoform, chloroform and dibromochloromethane, in water samples by using Zein@Fe3O4 nanocomposite coupled with gas chromatography/micro electron capture detection (GC-MECD). Various parameters affecting the DSPE-HSTD performance were investigated and optimized. The obtained results revealed that under optimum conditions, LOD and LOQ values were in the range of 0.1-0.36, 0.3-1.08 µg L-1, respectively. The intra-day and inter-day precisions of the method at a concentration of 10 µg L-1 for each analyte (n = 5) were obtained in the range of 5.69-6.70% and 6.12-7.34%, respectively. Finally, the proposed method was successfully applied for extraction and determination of four THMs in drinking water samples.

Advantages of a ClO2/NaClO combination process for controlling the disinfection by-products (DBPs) for high algae-laden water.

Chlorine dioxide (ClO2) has been widely used in the process of preoxidation and disinfection as an excellent water treatment reagent. However, the inorganic by-products produced by ClO2, such as chlorite (ClO2-) and chlorate (ClO3-) are harmful to human health, and this has become a potential problem when using ClO2 in drinking water treatment. In this study, ClO2 alone and a ClO2/NaClO combination process were carried out to evaluate the algae removal efficiency of the treatment and the formation of disinfection by-products (DBPs: chlorite, chlorate, trihalomethanes and haloacetic acids) for high algae-laden water with 124.16 µg L-1 chlorophyll a (Chl.a) content. The results show that disinfection with 1.5 mg L-1 ClO2 alone results in a ClO2- concentration exceeding 0.7 mg L-1. ClO2 preoxidation/ClO2 disinfection is applicable for the control of effluent quality, but the ClO2- concentration still has an excessive risk when using 0.8 mg L-1 and 0.6 mg L-1 ClO2 for the two process, respectively. In the ClO2/NaClO combination process, the ClO2- concentration is below 0.6 mg L-1, and trihalomethane (THM) and haloacetic acid (HAA) concentrations are lower than 60% of the maximum contaminant levels (MCLs) set by the World Health Organization (WHO). Further, the formation of ClO2- is more effectively controlled by NaClO preoxidation/ClO2 disinfection than ClO2 preoxidation/NaClO disinfection.

Formation of iodinated trihalomethanes during chlorination of amino acid in waters.

Chlorination is essential to provide safe drinking water. However, this process leads to the formation of disinfection byproducts (DBPs). In this study, tryptophan (Trp) has been selected as a precursor to conduct the chlorine disinfection. Moreover, the factors that affect the formation of trihalomethanes (THMs) and iodinated trihalomethanes (I-THMs) are investigated. The formation pathway of Trp chlorination is proposed based on the intermediate products identified. According to the experimental results, the formation of THMs and I-THMs during Trp chlorination fitted a new first-order kinetic model. The dosage of chlorine, temperature, pH and the ratio of bromide and iodide had major influence on the formation of THMs and I-THMs during chlorination. In addition, the inhibition of luminescent bacteria Vibrio fischeri in the water sample increased during Trp chlorination.

Computational investigations on the HO2 + CHBr2O2 reaction: mechanisms, products, and atmospheric implications.

Using quantum chemistry methods, mechanisms and products of the CHBr2O2 + HO2 reaction in the atmosphere were investigated theoretically. Computational result indicates that the dominant product is CHBr2OOH + O2 formed on the triplet potential energy surface (PES). While CBr2O + OH + HO2 produced on the singlet PES is subdominant to the overall reaction under the typical atmospheric condition below 300 K. Due to higher energy barriers surmounted, other products including CBr2O2 + H2O2, CBr2O + HO3H, CH2O + HO3Br, CHBrO + HO3 + Br, and CHBr2OH + O3 make minor contributions to the overall reaction. In the presence of OH radical, CHBr2OOH generates CHBr2O2 and CBr2O2 + H2O subsequently, which enters into new Br-cycle in the atmosphere. The substitution effect of alkyl group and halogens plays negligible roles to the dominant products in the RO2 + HO2 (X = H, CH3, CH2OH, CH2F, CH2Cl, CH2Br, CH2Cl, and CH2Br) reactions in the atmosphere.

Effects of chlorination on the fluorescence of seawater: Pronounced changes of emission intensity and their relationships with the formation of disinfection byproducts.

Chlorination of coastal (CS) and deep ocean (DO) seawater was accompanied by a prominent decrease (of up to 70%) of the intensity of its emission which was measured using a 315 nm excitation wavelength. Deconvolution of the emission spectra of CS and DO seawater showed that these spectra comprised three Gauss-shaped bands. The intensities of two of these bands decreased rapidly as the halogenation proceeded. For both DO and CS seawater, two stages of changes of their fluorescence were observed. The first stage in which the relative changes of the fluorescence intensity (ΔF/F) were between zero to 0.30 and 0.40 was not accompanied by the release of individual disinfection byproduct (DBP) species. For ΔF/F values above the corresponding thresholds, the relative changes of fluorescence intensity were well correlated with the concentrations of individual DBP species such as trihalomethanes and haloacetonitriles. R2 values for CHBr3, CHBr2Cl and CHBrCl2 formed in DO seawater were 0.83, 0.80 and 0.68, respectively while for CS seawater, the corresponding R2 values were 0.91, 0.93 and 0.92. The presented data demonstrate that the intrinsic chemistry of DBP formation and dissolved organic matter (DOM) halogenation in seawater can be well quantified based on the examination of changes of its fluorescence. This approach can also be employed for practical monitoring of changes of properties of marine DOM and generation of DBPs in desalination, marine aquaculture and other processes.