Yields Of Disinfection Byproducts Research Articles

A universal model to predict yields of THMs and HAAs based on UV–Visible absorption spectra

Differential absorption spectroscopy (DAS) quantifies changes in the UV–Visible absorbance of dissolved organic matter (DOM) caused by reactions of its chromophores. As a result of its precision and sensitvity, DAS serves as a powerful tool for characterizing the formation of disinfection by-products (DBPs) in generated in DOM chlorination reactions. However, the nonlinear relationship between the intensity of DAS and DBP concentrations as well as the need to develop site-specific fitting parameters limit its practical applications. This study investigated the physico-chemical nature of DAS of chlorinated DOM through experimental measurements and theoretical calculations. Results of this study provide molecular-level evidence that electrophilic substitution reactions involving DOM reactive sites result in the emergence of DAS feaures ascribed to the "fast" chromophores. The ring opening in the cyclic enones-like structures which can be present either in the original DOM or are generated as intermediates in its chlorination, leads to the emergence of DAS features associated with the "slow" chromophores and high yields of DBPs. The kinetic study of chlorination of real waters reveals a strong linear relationship (R2 > 0.91) between ln([DBP]) and the long-wavelength (λ > 325 nm) parameter of the DAS, notably (ln(-DA350)). This relationship varies among different water sources due to the differences in the heterogeneity of Band A3 whose maximum is near 350 nm. Band A3 is one of the Gaussian bands that comprise the overall UV–Visible spectrum of DOM. A new function (f(−DA350)) is proposed in this study to quantify DBP formation. This function, which is determined by the Band A3's area, allows establishing a universal linear relationship between f(−DA350) and ln([THMs]), as well as f(−DA350) and ln([HAAs]), across various water sources. The findings of this study will stimulate further development of spectroscopy-based DBP monitoring technology for monitoring and optimization of water disinfection processes.

The convergence of 2,6-dichloro-1,4-benzoquinone in the whole process of lignin phenol precursor chlorination

The formation and decomposition of 2,6-dichloro-1,4-benzoquinone, an emerging disinfection byproduct (DBP), was studied in the chlorination of lignin phenol precursors. The results show that DCBQ and the related hydroxyl DCBQ (DCBQ-OH) acts as the intermediate products of the chlorination process of the three typical lignin phenol precursors (p-hydroxybenzoic acid, protocatechuic acid, and gallic acid). The contributions of lignin phenol precursors to the overall formation of the targeted DBPs were determined based on the observed abundances of individual lignin phenols and their DBP yields. DCBQ and DCBQ-OH were generated within 2–6 h, the relative abundance of the yields of mol carbon atoms in DCBQ corresponding to the mol carbon atoms in the three model precursors (DCBQ-C) was about 0.01%–14.37% under different pH conditions. With the chlorination reaction time increased (after two or four h), the concentrations of DCBQ and DCBQ-OH entirely decreased, and the decomposition of DCBQ do not follow a pseudo-first-order kinetics during chlorination. Conversely, the decomposition of DCBQ generated from p-hydroxybenzoic acid followed a pseudo-second-order kinetics. Moreover, the formation of trichloromethane (TCM), dichloroacetic acid (DCAA), and trichloroacetic acid (TCAA) was also detected during the chlorination. The contribution of the decomposed DCBQ was mainly to TCAA and the unknown DBPs within 2–12 h, and DCBQ decomposition pathway was affected by pH. Moreover, except for DCBQ/DCBQ-OH and TCM/HAAs, there were still 73.6%–92.41% unknown products (including non-halogenated aromatic DBPs and chlorine-substituted DBPs) needing to identify during the chlorination process for lignin phenols. Overall, revealing the formation and decomposition of DCBQ during the chlorination of lignin phenol precursors would contribute to the effective development of drinking water treatment processes for the removal of highly toxic intermediates generated during disinfection.

Removal of algae and algogenic odor compounds via combined pre-chlorination and powdered activated carbon adsorption for source water pretreatment

This study investigated the combination sequence and time interval of chlorination and powdered activated carbon (PAC) adsorption for the control of algae inactivation, algogenic odor removal, and disinfection by-product (DBP) formation. Results indicated that pre-chlorination/post-PAC exhibited the highest algae removal efficiency in all sequential combinations of PAC adsorption and chlorination, while it had displayed slight effect on the removal of DBPs. The evaluated sequential combinations all had significant effect on the removal of odor. Nevertheless, prolonged time interval between chlorination and PAC adsorption exhibited enhanced control of algae and odor compounds in all experiments; with increasing time interval from 0 to 15 min in pre-chlorination/post-PAC process, the removal efficiency of Chl-a, algal cell viability, GSM, and 2-MIB increased by 46%, 15%, 15% and 23%, respectively. In the combined processes, the odor removal efficiency was positively correlated with PAC dosage but negatively correlated with chlorine dosage. Furthermore, PAC addition could effectively reduce the total DBP yields, especially the N-DBPs. This study can provide a better understanding of improving in-situ operation of the pre-chlorination and PAC dosing systems for source water pretreatment.

Formation characteristics of disinfection byproducts from four different algal organic matter during chlorination and chloramination

Algal organic matter (AOM) has become an important precursor of disinfection byproducts (DBPs) in multiple drinking water sources. In this study, the formation of DBPs during chlorination and chloramination of AOMs from four algal species (Microcystis aeruginosa, Chlorella vulgaris, Scenedesmus obliquus, and Cyclotella sp.) under different conditions (disinfectant doses 4.0–8.0 mg/L as Cl2, pH 6.0–8.0, and bromide 0–1.0 mg/L) were simultaneously investigated. Some common and specific characteristics of DBP formation have also been identified. The yields of total DBPs from the four AOMs were 3.28 × 102–6.00 × 102 and 1.97 × 102–3.70 × 102 nmol/mg C during chlorination and chloramination, respectively. The proportions of haloacetic acids (HAAs) in total DBPs were approximately ≥50%. Increasing disinfectant doses or pH only enhanced the yields of trihalomethanes (THMs) during chlorination but enhanced the yields of THMs, HAAs and dihaloacetonitriles (DHANs) during chloramination. Increasing bromide concentrations enhanced THM yields but decreased HAA yields during chlorination and chloramination, in addition to the shift from chlorinated DBPs to brominated DBPs. The DHAN yields of the four AOMs slightly decreased with bromide levels during chlorination, whereas different AOMs showed different trends with bromide levels during chloramination. During chlorination, C. vulgaris and S. obliquus AOMs generated higher THM and DHAN yields (at 4.0–5.0 mg/L as Cl2) than the other AOMs. During chloramination, M. aeruginosa AOM generated higher THM and HAA yields than the other AOMs (at 0.1 mg/L bromide). Cyclotella sp. AOM had the highest THM-bromine substitution factors during chlorination and the highest DHAN-bromine substitution factors during both chlorination and chloramination (at 0.1 mg/L bromide).

Kinetics and Transformations of Diverse Dissolved Organic Matter Fractions with Sulfate Radicals.

Dissolved organic matter (DOM) scavenges sulfate radicals (SO4•-), and SO4•--induced DOM transformations influence disinfection byproduct (DBP) formation when chlorination follows advanced oxidation processes (AOPs) used for pollutant destruction during water and wastewater treatment. Competition kinetics experiments and transient kinetics experiments were conducted in the presence of 19 DOM fractions. Second-order reaction rate constants for DOM reactions with SO4•- (kDOM,SO4•-) ranged from (6.38 ± 0.53) × 106 M-1 s-1 to (3.68 ± 0.34) × 107 MC-1 s-1. kDOM,SO4•- correlated with specific absorbance at 254 nm (SUVA254) (R2 = 0.78) or total antioxidant capacity (R2 = 0.78), suggesting that DOM with more aromatics and antioxidative moieties reacted faster with SO4•-. SO4•- exposure activated DBP precursors and increased carbonaceous DBP (C-DBP) yields (e.g., trichloromethane, chloral hydrate, and 1,1,1-trichloropropanone) in humic acid and fulvic acid DOM fractions despite the great reduction in their organic carbon, chromophores, and fluorophores. Conversely, SO4•--induced reactions reduced nitrogenous DBP yields (e.g., dichloroacetonitrile and trichloronitromethane) in wastewater effluent organic matter and algal organic matter without forming more C-DBP precursors. DBP formation as a function of SO4•- exposure (concentration × time) provides guidance on optimization strategies for SO4•--based AOPs in realistic water matrices.

The effect of coagulation on the removal of algogenic organic matter and the optical parameters for predicting disinfection byproducts

Algae-derived disinfection byproducts (DBPs) are receiving increasing attention. Coagulation is the first water treatment section in removing algogenic organic matter (AOM). However, there is a significant knowledge gap in the effects of coagulation on DBPs produced from AOM. In this study, in view of the multi-component AOM, several analysis methods were combined to investigate the changes in AOM of Microcystic aeruginosa during the coagulation treatment, including ultraviolet–visible absorbance, multi-peaks Gaussian fitting method based on differential absorption spectroscopy, Excitation-emission matrix, and Fourier transform infrared spectroscopic analysis. To identify the characteristic parameters that could indicate the formation of DBPs, the yields of twenty-one DBP species produced from the residual AOM after the coagulation treatment were investigated. The correlations between DBPs and the spectral parameters were also analyzed. The results showed that aluminum salt coagulant could significantly remove protein-like compounds, chlorophyll, and phycocyanin in AOM, but it had a limited ability to precipitate AOM. With the increase of aluminum sulfate coagulant, the yields of DBPs produced from the residual extracellular organic matter decreased, while those produced from the residual intracellular organic matter decreased firstly and then gradually increased. The Pearson’s correlation results showed that the combination of fluorescent regions of protein-like and humic acid-like could be used as an optical surrogate for predicting the formation of DBPs.

Variations of disinfection byproduct precursors through conventional drinking water treatment processes and a real-time monitoring method

In this investigation, raw water (RW), settled water (SW), and filtered water (FW) collected from a drinking water treatment plant were fractionated into 24 natural organic matter (NOM) fractions with varying molecular weights and hydrophobicity. The yields of disinfection byproducts (DBPs) obtained during the chlorination of the NOM fractions were explored. Results revealed that the 0–1 kDa, 5–10 kDa, and hydrophobic DBP precursors dominated RW. Hydrophobic fractions cannot be effectively removed, which contributed to the high DBP precursors remaining in the FW. The optional optical parameters, including UVA (UV340, UV360, and UV380), UVB (UV280, UV300, and UV310), and UVC (UV254, UV260, and UV272), were analyzed to determine the DBP yields during chlorination of different NOM fractions. Results revealed that UVC could be applied to indicate the regulated DBP yields of the humified precursors. Contrary to the generally accepted view, for biologically derived precursors, their regulated DBPs and dichloroacetonitrile correlated better with UVA (e.g. UV340). Moreover, PARAFAC analysis was applied to decompose an array of 24 EEM spectra. Good linear correlations were found between the PARAFAC components and most DBP yields. Furthermore, four fluorescence parameters were proposed via a modified fluorescence picking method, which can serve as excellent surrogates of PARAFAC components. These fluorescence parameters were found to be effective in indicating most DBP yields. Finally, the fluorescence intensity at excitation wavelength/emission wavelength = 310/416 nm was found to be a promising built-in parameter for the real-time monitoring of DBP precursors, regardless of the humification degree of the precursors.

Impact of simulated wildfire on disinfection byproduct formation potential

AbstractWildfires are complex phenomena that have served a vital role in ecosystem function for millennia. However, thermal alterations to dissolved organic matter's (DOM) solubility and chemical features can change disinfection byproduct (DBP) formation dynamics. Physicochemical changes to DOM are influenced by several factors, the most prominent being heating temperature. In this study, mineral soil samples were collected from fire‐prone areas, artificially heated in a muffle furnace to simulate wildfire heating, and leached. As heating temperature increased, chloroform and dichloroacetic acid yields decreased and increased, respectively. Of particular interest was the stimulation of dichloroacetonitrile, a highly toxic and unregulated DBP, at moderate heating temperatures. To demonstrate further insight into the chemical attributes of wildfire‐impacted DOM, optical properties were used as proxy measurements. This work provides water utilities with information on how wildfires can alter DBP formation potential, and a means to investigate correlations between intrinsic optical measurements and DBP yields.

Formation of disinfection byproducts during chlorination of mixed nitrogenous compounds in swimming pools

Disinfection byproducts (DBPs) in swimming pool waters are receiving increasing attention because of their toxicity and widespread occurrence. Current studies rarely investigate the formation of DBPs from typical precursors in swimming pools under mixed exposure. They also rarely investigate the formation of carbonaceous DBPs (C-DBPs) and nitrogenous DBPs (N-DBPs) simultaneously. In this study, the formation of C-DBPs and N-DBPs were investigated during chlorination of mixed precursors (i.e., tryptophan, urea, creatinine, and ammonia). The effects of precursors and operation parameters were also investigated. Among the four precursors, tryptophan had the highest DBP formation potential. Urea and ammonia restrained the formation of C-DBPs but promoted the formation of more toxic N-DBPs. C-DBP yields were significantly higher than N-DBP yields under all experimental conditions. Longer reaction time and higher chlorine dosage promoted the formation of C-DBPs, while higher temperature decreased the concentration of N-DBPs. The presence of bromide not only improved the sum yields of DBPs, but also shifted chlorinated DBPs to brominated species.

Mechanistic study on chlorine/nitrogen transformation and disinfection by-product generation in a UV-activated mixed chlorine/chloramines system

The conversion mechanisms of chlorine species (including free chlorine, monochloramine (NH2Cl), dichloramine, and total chlorine), nitrogen species (including ammonium (NH4+), nitrate (NO3−), and nitrite (NO2−)) as well as the formation of disinfection by-products (DBPs) in a UV-activated mixed chlorine/chloramines system in water were investigated in this work. The consumption rates of free chlorine and NH2Cl were significantly promoted in a HOCl/NH2Cl coexisting system, especially in the presence of UV irradiation. Moreover, the transformation forms of nitrogen in both ultrapure and HA-containing waters were considerably affected by UV irradiation and the mass ratio of free chlorine to NH2Cl. NO3− and NO2− can be easily produced under UV irradiation, and the removal efficiency of total nitrogen with UV was obvious higher than that without UV when the initial ratio of HOCl/NH2Cl was less than 1. The roles of different radicals in the degradation of free chlorine, NH2Cl and NH4+ were also considered in such a UV-activated mixed chlorine/chloramines system. The results indicated that OH• was important to the consumption of free chlorine and NH2Cl, and showed negligible influence on the consumption of NH4+. Besides, the changes of DOC and UV254 in HA-containing water in UV-activated mixed chlorine/chloramines system indicated that the removal efficiency of DOC (24%) was much lower than that of UV254 (94%). The formation of DBPs in a mixed chlorine/chloramines system was also evaluated. The yields of DBPs decreased significantly as the mass ratio of HOCl/NH2Cl varied from 1 : 0 to 0 : 1. Moreover, compared to the conditions without UV irradiation, higher DBPs yields and DBP-associated calculated toxicity were observed during the UV-activated mixed chlorine/chloramine process.

Characteristics of low and high SUVA precursors: Relationships among molecular weight, fluorescence, and chemical composition with DBP formation

Disinfection by-products (DBPs) formed upon water treatment is an emerging issue worldwide. While monitoring of DBP precursors can easily be achieved for high specific UV absorbance (SUVA) organic (>6 L/mg·m), low and extremely low SUVA precursors (<2 L/mg·m) are difficult to monitor or even to predict their DBP formation behaviour. This study investigated the relationships among NOM characteristics, such as molecular weight (MW), fluorescence, and chemical composition, with DBP formation resulting from the chlorination of relatively high and low SUVA precursors. High SUVA precursors were formed by C-rich substances (82–85% of total mass) corresponding with high C/N and C/O (>100 and >5, respectively). Such precursors exhibited the fluorescence of long-wavelength humic-like signal and occurred at a high MW range (>30 kDa). By contrast, low SUVA precursors were either N-rich and/or O-rich substances, associated with much lower carbon content (40–70%). Low SUVA, N-rich precursors particularly also occurred at a high MW region (>100 kDa) and produced a strong protein-like fluorescence signal. When SUVA values of O-rich precursors were extremely low (<1 L/mg·m) they were accompanyied by short-wavelength humic-like fluorescence. During DBP tests, high SUVA produced only high yields of carbonaceous DBPs (e.g trichloromethane, haloacetic acids, haloketones), whereas low SUVA N-rich precursors yielded high levels of both C and NDBPs (e.g. haloacetonenitrile, chloropicrin). By contrast, extremely low SUVA precursors produced significantly low levels of both C and NDBPs (total < 30 μg/mgC). Furthermore, 19 of 20 regression models of DBP formation using log-transformed MW gave R2 = 0.50–0.97. The strong regressions and correlations of NOM characteristics with DBPs in this study provide a better understanding of the influence of precursors characteristics on DBP monitoring, especially for low SUVA NOM.

Formation and interdependence of disinfection byproducts during chlorination of natural organic matter in a conventional drinking water treatment plant.

It is crucial to explore the source, formation process and interdependence of disinfection byproducts (DBPs) to reduce their risk on public health. In this investigation, a source water was chlorinated to evaluate the initial formation rates and the maximum yields of trichloromethane (TCM), dichloroacetic acid (DCAA), and trichloroacetic acid (TCAA) based on a hyperbola model. The results showed that TCM achieved the highest initial formation rate and maximum theoretical concentration compared with DCAA and TCAA. The TCM yield can be used to forecast the yields of DCAA and TCAA throughout the whole reaction process, and the yields of chloral hydrate (CH), dichloroacetonitrile (DCAN) and 1,1,1-trichloropropanone (1,1,1-TCP) within the initial reaction stage. Besides, the raw water, settled water and filtered water collected from a drinking water treatment plant were divided into five fractions, respectively, by ultrafiltration membranes to evaluate their DBP formation after chlorination. Compared with the medium molecular weight species, high and low molecular weight organic matters exhibited relatively high specific regulated and unregulated DBP yields (expressed as μg/mg C), respectively. Humic acid-like compositions predominantly contributed to regulated DBP yields, while soluble microbial by-product-like compounds preferentially generated DCAN. The correlation study revealed that the TCM could also serve as an indicator for the measured DBPs from chlorination of sample fractions with different molecular weight. Finally, it was found that the theoretical cytotoxicity was enhanced during chlorination of filtered water compared with chlorination of settled water.

UV-assisted chlorination of algae-laden water: Cell lysis and disinfection byproducts formation

Chlorination of algae-laden water under UV irradiation was studied in bench scale. An obvious synergistic effect between UV light (at 254 nm) and chlorine was obtained due to the formation of HO, which promoted the degradation of Microcystis aeruginosa. During this process, sequential UV/chlorine and UV irradiation were included, and UV/chlorine stage accounted for 86% of total algae removal with 50 mg/L chlorine. The removal performance was positively related to the chlorine dose in the range of 5–50 mg/L. The presence of chloride had little influence, whereas ammonia significantly inhibited the algae removal as chlorine was quickly transformed to chloramine. The integrity of algae cells was disrupted immediately, along with an instant release of algal organic matter which was synchronously degraded by UV/chlorine. The emission scanning electron microscopy results further confirm the occurrence of serious cell lysis. Moreover, a large amount of chlorinated disinfection byproducts (DBPs) produced during the UV/chlorine process. But the final yields of DBPs from chlorination of algae suspension over a period of 23 h storing in dark surpassed that after UV/chlorine treatment. This work suggests a promising technique for the treatment of algae-laden water by using UV/chlorine.

The contribution of atmospheric particulate matter to the formation of CX3R-type disinfection by-products in rainwater during chlorination

Atmospheric particulate matter (PM) can be scavenged by rainfall and contribute dissolved organic matter (DOM) to rainwater. Rainwater may serve as a part or the whole of drinking water sources, leading to the introduction of PM-derived DOM into drinking water. However, little information is available on the role of PM-derived DOM as a remarkable precursor of CX3R-type disinfection by-products (DBPs) in rainwater. In this study, samples were collected from ten occurrences of rainfall in Shanghai and batch experiments were executed to explore the contribution of PM-derived DOM to CX3R-type DBP formation in rainwater and to further understand some of unknowns regarding its characteristics. Results revealed that a part of PM was scavenged by rainfall and the scavenge performance was better for smaller PM. The formation potentials (FPs) of individual CX3R-type DBP were similar among size-isolated PM. TCM was predominant (around 0.5–4.5 μg-C/mg-C) and TCAA was the secondary (around 0.6–3.2 μg-C/mg-C) among all detectable CX3R-type DBPs. Based on the PM removal data and DBP FP results, the contribution of PM-derived DOM to CX3R-type DBP formation in rainwater was modeled. Furthermore, aromatic proteins and soluble microbial product-like compounds were found to be significant compositions, which were reported to be DBP precursors. And low molecular weight (< 10 kDa) DOM derived from total PM and rainwater exhibited higher CX3R-type DBP FPs. DOM fractions with higher SUVA254 and SUVA285 values gave relatively higher yields of CX3R-type DBPs, indicating that aromatic compounds played an important role in DBP formation.

Evaluation of disinfection by-products (DBPs) formation potential in ANAMMOX effluents.

Disinfection by-products (DBPs), major health concerns in the potable reuse of municipal wastewater effluent, are process-related in wastewater treatment systems. Anammox is a promising and increasingly-applied technology for nitrogen removal in wastewater. In this study, the relationship between DBP formation potential and the anammox process has been investigated based on a lab-scale sequencing batch reactor (SBR). Excitation and emission matrix (EEM) fluorescence spectroscopy was employed to identify the compositions of the DBP precursors. The results showed that the effluents from the anammox SBR could yield both carbonaceous and nitrogenous DBPs after chlorination. Trichloromethane (TCM) was the dominant product among all DBPs detected. The anammox effluent has a low specific TCM formation potential of 0.778 μmol/mmol C and a trichloronitromethane (TCNM) formation potential of 0.0725 μmol/mmol C, leading to a TCM and TCNM formation potential ratio of 10.7. We found that substrate utilization of anammox did not enhance DBP yields, and the DBP formation potential decreased after 10 hour starvation. High pH conditions stimulated the production of TCM precursors in the anammox reactor. Humic acid-like and protein-like substances were identified in the EEM spectra of anammox effluents.

Comparison of the effects of chloramine and chlorine on the aromaticity of dissolved organic matter and yields of disinfection by-products

This study compared effects of chlorination and chloramination on the chromophores of dissolved organic matter (DOM) and attendant formation of disinfection by-products (DBPs) in raw and treated surface waters. Comparison of the differential absorbance spectra of chloraminated and chlorinated waters shows that interactions of chloramine with DOM chromophores result in changes that are in many respects similar to those observed for chlorine although the extent of degradation of DOM chromophores and the attendant decrease of DOM aromaticity by chloramine are less pronounced than that caused by free chlorine. The degradation of DOM chromophores caused by the examined disinfectants indicated that in both cases a gradual decrease of DOM took place. Decreases of DOM aromaticity estimated based on the changes of DOM absorbance at 254 or 280 nm were correlated with chlorine consumption in a similar way for both examined disinfectants. Correlations between changes of DOM absorbance and yields of dihaloacetic acids (DHAA) were also similar for chlorination and chloramination. This was interpreted to indicate that the generation of DHAA proceeds via the degradation of the reactive sites associated with DOM chromophores irrespective of whether these sites are engaged by chlorine or chloramine. Correlations between the decrease of DOM aromaticity and formation of other DBP (e.g. trihalomethanes - THM, trihaloacetic acids - THAA and dihaloacetonitriles - DHAN) for chloramine and chlorine were also observed but, as opposed to the observations for DHAA, the correlations between degradation of DOM aromaticity and yields of THM, THAA or DHAN were different for chlorination and chloramination.

Effects of Joint-reaction Combined by Ozonation and Coagulation on Aquatic Organic Matters

Variations of residual ozone concentration in pure water and Al2(SO4)3 solution were studied. The spectral characteristics, contents of organic compounds and disinfection by products (DBPs) yields in preozonated, preozonated coagulated (POC) and ozonated combined coagulated (OC) waters were detected by differential absorbance(DA), three dimensional fluorescence excitation-emission matrix spectroscopy (3D-EEM), GC and TOC. The purpose of the work was to investigate the effects of ozonation combined with coagulation on their oxidation extents of organic matter and the production of DBPs. Studies showed that there were remarkable differences between the two processes, POC and OC, which proved the existence of joint interaction of ozone and coagulant. The joint interaction involved the following aspects. 1 Decomposition rate of ozone was improved; and the free radical production was increased during OC compared with POC. Comparing to ozone alone, 15.2% and 23.9% more radical capture with ozone 2mg·L-1, Al3+ 1 mg·L-1, 3 mg·L-1 were detected. 2 The difference of OC and POC was found in that organic matter removal of OC was lower than that of POC. The pathways of OC and POC showed difference, which resulted in differences of reaction between organic matter and disinfectant, as well as yields of DBPs. OC removed UV254 and DOC more efficiently than single ozonation or single coagulation; but less efficiently than POC. DCAAFP (Dichloroacetic acid formation potential) and TCAAFP (Trichloroacetic acid formation potential) were 47 μg·L-1 and 20.5 μg·L-1 respectively after treatment by POC with O3 1mg·L-1and Al3+1mg·L-1, and chloroform formation potential (CFFP) was 97.8 μg·L-1, which were 51%, 64.6% and 41.5% respectively lower than those in the raw water. Under the same dose conditions, DCAAFP, TCAAFP and CFFP after OC were 48.4 μg·L-1, 21.4 μg·L-1 and 117.3 μg·L-1, respectively, which were 49.6%, 63% and 29.5% lower than those in raw water. The difference between the efficiencies of POC and OC would be enlarged with increase of coagulant dose under the same ozone dose. Considering its safety and efficiency, the ozone dosage, adding spot and coagulant species must be taken into account when combined treatment of preozonation and coagulation is used; further investigations are also needed.

Disinfection byproduct formation in drinking water sources: A case study of Yuqiao reservoir

This study investigated the potential formation of disinfection byproducts (DBPs) during chlorination and chloramination of 20 water samples collected from different points of Yuqiao reservoir in Tianjin, China. The concentrations of dissolved organic matter and ammonia decreased downstream the reservoir, while the specific UV absorbance (SUVA: the ratio of UV254 to dissolved organic carbon) increased [from 0.67 L/(mg*m) upstream to 3.58 L/(mg*m) downstream]. The raw water quality played an important role in the formation of DBPs. During chlorination, haloacetic acids (HAAs) were the major DBPs formed in most of the water samples, followed by trihalomethanes (THMs). CHCl3 and CHCl2Br were the major THM species, while trichloroacetic acid (TCAA) and dichloroacetic acid (DCAA) were the major HAA species. Chloramination, on the other hand, generally resulted in lower concentrations of THMs (CHCl3), HAAs (TCAA and DCAA), and haloacetonitriles (HANs). All the species of DBPs formed had positive correlations with the SUVA values, and HANs had the highest one (R2 = 0.8). The correlation coefficients between the analogous DBP yields and the SUVA values in chlorinated samples were close to those in chloraminated samples.

Molecular and Spectroscopic Characterization of Water Extractable Organic Matter from Thermally Altered Soils Reveal Insight into Disinfection Byproduct Precursors.

To characterize the effects of thermal-alteration on water extractable organic matter (WEOM), soil samples were heated in a laboratory at 225, 350, and 500 °C. Next, heated and unheated soils were leached, filtered, and analyzed for dissolved organic carbon (DOC) concentration, optical properties, molecular size distribution, molecular composition, and disinfection byproduct (DBP) formation following the addition of chlorine. The soils heated to 225 °C leached the greatest DOC and had the highest C- and N-DBP precursor reactivity per unit carbon compared to the unheated material or soils heated to 350 or 500 °C. The molecular weight of the soluble compounds decreased with increasing heating temperature. Compared to the unheated soil leachates, all DBP yields were higher for the leachates of soils heated to 225 °C. However, only haloacetonitrile yields (μg/mgC) were higher for leachates of the soils heated to 350 °C, whereas trihalomethane, haloacetic acid and chloropicrin yields were lower compared to unheated soil leachates. Soluble N-containing compounds comprised a high number of molecular formulas for leachates of heated soils, which may explain the higher yield of haloacetonitriles for heated soil leachates. Overall, heating soils altered the quantity, quality, and reactivity of the WEOM pool. These results may be useful for inferring how thermal alteration of soil by wildfire can affect water quality.

Developing LED UV fluorescence sensors for online monitoring DOM and predicting DBPs formation potential during water treatment

Online monitoring dissolved organic matter (DOM) is urgent for water treatment management. In this study, high performance size exclusion chromatography with multi-UV absorbance and multi-emission fluorescence scans were applied to spectrally characterize samples from 16 drinking water sources across Yangzi River and Huai River Watersheds. The UV absorbance indices at 254 nm and 280 nm referred to the same DOM components and concentration, and the 280 nm UV light could excite both protein-like and humic-like fluorescence. Hence a novel UV fluorescence sensor was developed out using only one UV280 light-emitting diode (LED) as light source. For all samples, enhanced coagulation was mainly effective for large molecular weight biopolymers; while anion exchange further substantially removed humic substances. During chlorination tests, UVA280 and UVA254 showed similar correlations with yields of disinfection byproducts (DBPs); the humic-like fluorescence obtained from LED sensors correlated well with both trihalomethanes and haloacetic acids yields, while the correlation between protein-like fluorescence and trihalomethanes was relatively poor. Anion exchange exhibited more reduction of DBPs yields as well as UV absorbance and fluorescence signals than enhanced coagulation. The results suggest that the LED UV fluorescence sensors are very promising for online monitoring DOM and predicting DBPs formation potential during water treatment.