Preparation and characterisation of new-polyaluminum chloride-chitosan composite coagulant

In this study, the formulation of a novel polyaluminum chloride-chitosan composite coagulant that improves the coagulation process for natural organic matter (NOM) removal was investigated. The performance of the composite coagulant was tested using two water sources (synthetic and natural water) to develop a better understanding on the behaviour of the composite coagulant. Fourier Transform-Infra red (FT-IR) spectroscopy, ferron analysis and zeta potential studies were performed to characterise the composite coagulant. FT-IR analysis showed that there is an intermolecular interaction between Al species and chitosan molecules, while ferron analysis indicated that the distributions of Al_a, Al_b, and Al_c in PACl-chitosan are different from those in PACl. At a low Al dosage (2.16 mg L⁻¹), a much higher removal of NOM from synthetic water, as evidenced from UV₂₅₄ and Dissolved Organic Carbon (DOC) measurements, was achieved by the composite coagulants in comparison to that removed by PACl or PACl and chitosan added separately. For natural water from the Myponga Reservoir, both polyaluminum chloride (PACl) and PACl-chitosan composite coagulants demonstrated similar dissolved organic carbon (DOC) percentage removal, whereas PACl-chitosan gave a slight improvement in removing the UV₂₅₄ absorbing components of NOM.     

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

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

Degradation of 32 emergent contaminants by UV and neutral photo-fenton in domestic wastewater effluent previously treated by activated sludge

This study focuses on the removal of 32 selected micropollutants (pharmaceuticals, corrosion inhibitors and biocides/pesticides) found in an effluent coming from a municipal wastewater treatment plant (MWTP) based on activated sludge. Dissolved organic matter was present, with an initial total organic carbon of 15.9 mg L⁻¹, and a real global quantity of micropollutants of 29.5 μg L⁻¹. The treatments tested on the micropollutants removal were: UV-light emitting at 254 nm (UV₂₅₄) alone, dark Fenton (Fe^2+,3+/H₂O₂) and photo-Fenton (Fe^2+,3+/H₂O₂/light). Different irradiation sources were used for the photo-Fenton experiences: UV₂₅₄ and simulated sunlight. Iron and H₂O₂ concentrations were also changed in photo-Fenton experiences in order to evaluate its influence on the degradation. All the experiments were developed at natural pH, near neutral. Photo-Fenton treatments employing UV₂₅₄, 50 mg L⁻¹ of H₂O₂, with and without adding iron (5 mg L⁻¹ of Fe²⁺ added or 1.48 mg L⁻¹ of total iron already present) gave the best results. Global percentages of micropollutants removal achieved were 98 and a 97% respectively, after 30 min of treatments. As the H₂O₂ concentration increased (10, 25 and 50 mg L⁻¹), best degradations were observed. UV₂₅₄, Fenton, and photo-Fenton under simulated sunlight gave less promising results with lower percentages of removal.The highlight of this paper is to point out the possibility of the micropollutants degradation in spite the presence of DOM in much higher concentrations.     

Tracking natural organic matter (NOM) in a drinking water treatment plant using fluorescence excitation-emission matrices and PARAFAC

Natural organic matter (NOM) in water samples from a drinking water treatment train was characterized using fluorescence excitation emission matrices (F-EEMs) and parallel factor analysis (PARAFAC). A seven component PARAFAC model was developed and validated using 147 F-EEMs of water samples from two full-scale water treatment plants. It was found that the fluorescent components have spectral features similar to those previously extracted from F-EEMs of dissolved organic matter (DOM) from diverse aquatic environments. Five of these components are humic-like with a terrestrial, anthropogenic or marine origin, while two are protein-like with fluorescence spectra similar to those of tryptophan-like and tyrosine-like fluorophores. A correlation analysis was carried out for samples of one treatment plant between the maximum fluorescence intensities (F_max) of the seven PARAFAC components and NOM fractions (humics, building blocks, neutrals, biopolymers and low molecular weight acids) of the same sample obtained using liquid chromatography with organic carbon detection (LC-OCD). There were significant correlations (p < 0.01) between sample DOC concentration, UVA₂₅₄, and F_max for the seven PARAFAC components and DOC concentrations of the LC-OCD fractions. Three of the humic-like components showed slightly better predictions of DOC and humic fraction concentrations than UVA_254. Tryptophan-like and tyrosine-like components correlated positively with the biopolymer fraction. These results demonstrate that fluorescent components extracted from F-EEMs using PARAFAC could be related to previously defined NOM fractions and that they could provide an alternative tool for evaluating the removal of NOM fractions of interest during water treatment.     

Biosorption processes in biomembrane systems during water treatment of surface water sources

The characteristics of a system with bioactive powdered activated carbon and microfiltration have been studied under conditions of the aerobic treatment of natural water from the water storages of Guan Ting (China), the Moskva River, and the Yauza River (Russia). The removal of organic matter in the system was estimated in terms of the permanganate oxidizability and UV absorption at λ = 254 nm (UV₂₅₄) and λ = 410 nm (UV₄₁₀). The average removal efficiency amounted to 68.42, 75.61, and 87.50%, respectively, at water temperature 10°C. The water treatment process (at 20°C) began immediately after the start-up of the plant at the expense of the adsorption on activated carbon that guaranteed a high speed of removal of organic pollutants in the absence of mature microflora. By the time the adsorption capacity of carbon was exhausted, the microflora was able to mature ensuring in combination with the powdered activated carbon a high speed of removal. In order to guarantee the biological stability of water, the removal degree of assimilable organic carbon amounted to 60.2% and the purified water met the requirements of the recommended criterion (100 mg acetate-C/dm³).     

Evaluations of the TiO2/simulated solar UV degradations of XAD fractions of natural organic matter from a bog lake using size-exclusion chromatography

This work reports on the changes in compositions of humic acids (HAs) and fulvic acids (FAs) during photocatalytic degradation. The HAs and FAs were obtained from the XAD-resin fractionation of natural-organic matter (NOM) from a bog lake (Lake Hohloh, Black Forest, Germany). Degussa P-25 titanium dioxide (TiO₂) in a suspension and a solar UV simulator (batch reactor) were used in the experiments. The photocatalytic degradation of the HAs and FAs were monitored using size-exclusion chromatography (SEC) equipped with dissolved organic carbon (DOC) and ultraviolet (UV₂₅₄) detection (SEC-DOC and SEC-UV₂₅₄) and UV–Vis spectrophotometry. The evolutions of the photocatalytic degradations of the HA and FA fractions were selective. The photocatalytic degradation started with the degradations of high molecular weight compounds with relatively high UV₂₅₄ absorbances in the HA and FA fractions to yield low molecular weight compounds showing less specific UV₂₅₄ absorbances. Observance of the same tendency for the original NOM from Lake Hohloh indicates that these XAD-fractions still having complex compound mixtures. However, the larger molecular weight fractions of the FAs showed higher preferential adsorptions onto TiO₂, which caused their faster degradation rates. Furthermore, FAs showed a greater reduction of the total THM formation potential (TTHMFP) and the organic halogen compounds adsorbable on activated carbon formation potential (AOXFP), in comparison with the HAs.     

Comparative effect of simulated solar light,UV, UV/H2O2 and photo-Fenton treatment (UV–Vis/H2O2/Fe) in the Escherichia coli inactivation in artificial seawater

Innovative disinfection technologies are being studied for seawater, seeking a viable alternative to chlorination. This study proposes the use of H₂O₂/UV₂₅₄ and photo-Fenton as disinfection treatment in seawater. The irradiations were carried out using a sunlight simulator (Suntest) and a cylindrical UV reactor. The efficiency of the treatment was compared for Milli-Q water, Leman Lake water and artificial seawater. The presence of bicarbonates and organic matter was investigated in order to evaluate possible effects on the photo-Fenton disinfection treatment. The photo-Fenton treatment, employing 1 mg L⁻¹ Fe²⁺ and 10 mg L⁻¹ of H₂O₂, led to the fastest bacterial inactivation kinetics. Using H₂O₂/UV₂₅₄ high disinfection rates were obtained similar to those obtained with photo-Fenton under UV₂₅₄ light. In Milli-Q water, the rate of inactivation for Escherichia coli was higher than in Leman Lake water and seawater due to the lack of inorganic ions affecting negatively bacteria inactivation. The presence of bicarbonate showed scavenging of the OH^• radicals generated in the treatment of photo-Fenton and H₂O₂/UV₂₅₄. Despite the negative effect of inorganic ions, especially HCO₃^-, the disinfection treatments with AOPs in lake water and seawater improved significantly the disinfection compared to light alone (simulated sunlight and UV₂₅₄). In the treatment of photo-Fenton with simulated sunlight, dissolved organic matter had a beneficial effect by increasing the rate of inactivation. This is associated with the formation of Fe³⁺-organo photosensitive complexes leading to the formation of ROS able to inactivate bacteria. This effect was not observed in the photo-Fenton with UV₂₅₄. Growth of E. coli surviving in seawater was observed 24 and 48 h after treatment with UV light. However, growth of surviving bacteria was not detected after photo-Fenton with UV₂₅₄ and H₂O₂/UV₂₅₄ treatments.     

Bio-diatomite dynamic membrane reactor for micro-polluted surface water treatment

This work investigated the feasibility of treating micro-polluted surface water for drinking water production with a bio-diatomite dynamic membrane reactor (BDDMR) at lab-scale in continuous-flow mode. Results indicate that the BDDMR was effective in removing COD_Mn, DOC, UV₂₅₄, NH₃-N and trihalomethanes' formation potential (THMFP) at a hydraulic retention time (HRT) of 3.5 h due to its high concentrations of mixed liquor suspended solids (MLSS) and mixed liquor volatile suspended solids (MLVSS). The removal of pollutants was mainly ascribed to microbial degradation in BDDMR because the dynamic membrane alone was much less effective in pollutant removal. Though the diatomite particles (5-20 μm) were much smaller in size than the aperture of the stainless steel support mesh (74 μm), microorganisms and their extracellular polymer substances could bind these particles tightly to form bio-diatomite particles which were completely retained by the support mesh. The analysis of molecular weight (MW) distribution by gel permeation chromatography (GPC) shows that the BDDMR could effectively remove the hydrophilic fraction of dissolved organic materials present in the raw water.     

Degradation of emergent contaminants by UV,UV/H2O2 and neutral photo-Fenton at pilot scale in a domestic wastewater treatment plant

This study focuses on the removal of 22 selected micropollutants in an effluent from a municipal wastewater treatment plant (MWTP) at pilot scale. A reactor of 37 L with five low pressure mercury lamps emitting at 254 nm (UV₂₅₄) was used. The 22 micropollutants include 15 pharmaceuticals, 2 X-Ray contrast medias, 1 corrosion inhibitor and 4 biocides/pesticides. Five of these 22 compounds were used as indicative substances as proposed by the Swiss Federal Office for the Environment (FOEN) (carbamazepine, diclofenac, sulfamethoxazole, benzotriazole and mecoprop).     

Electrochemical oxidation of trace organic contaminants in reverse osmosis concentrate using RuO2/IrO2-coated titanium anodes

During membrane treatment of secondary effluent from wastewater treatment plants, a reverse osmosis concentrate (ROC) containing trace organic contaminants is generated. As the latter are of concern, effective and economic treatment methods are required. Here, we investigated electrochemical oxidation of ROC using Ti/Ru_0.7Ir_0.3O₂ electrodes, focussing on the removal of dissolved organic carbon (DOC), specific ultra-violet absorbance at 254 nm (SUVA₂₅₄), and 28 pharmaceuticals and pesticides frequently encountered in secondary treated effluents. The experiments were conducted in a continuously fed reactor at current densities (J) ranging from 1 to 250 A m⁻² anode, and a batch reactor at J = 250 A m⁻². Higher mineralization efficiency was observed during batch oxidation (e.g. 25.1 ± 2.7% DOC removal vs 0% removal in the continuous reactor after applying specific electrical charge, Q = 437.0 A h m⁻³ ROC), indicating that DOC removal is depending on indirect oxidation by electrogenerated oxidants that accumulate in the bulk liquid. An initial increase and subsequent slow decrease in SUVA₂₅₄ during batch mode suggests the introduction of auxochrome substituents (e.g. -Cl, NH₂Cl, -Br, and -OH) into the aromatic compounds. Contrarily, in the continuous reactor ring-cleaving oxidation products were generated, and SUVA₂₅₄ removal correlated with applied charge. Furthermore, 20 of the target pharmaceuticals and pesticides completely disappeared in both the continuous and batch experiments when applying J ≥ 150 A m⁻² (i.e. Q ≥ 461.5 A h m⁻³) and 437.0 A h m⁻³ (J = 250 A m⁻²), respectively. Compounds that were more persistent during continuous oxidation were characterized by the presence of electrophilic groups on the aromatic ring (e.g. triclopyr) or by the absence of stronger nucleophilic substituents (e.g. ibuprofen). These pollutants were oxidized when applying higher specific electrical charge in batch mode (i.e. 1.45 kA h m⁻³ ROC). However, baseline toxicity as determined by Vibrio fischeri bioluminescence inhibition tests (Microtox) was increasing with higher applied charge during batch and continuous oxidation, indicating the formation of toxic oxidation products, possibly chlorinated and brominated organic compounds.     

Spectrometric characterization of effluent organic matter of a sequencing batch reactor operated at three sludge retention times

Effluent organic matter (EfOM) from activated sludge systems is composed primarily of influent refractory compounds, residual degradable substrate, intermediate products and soluble microbial products (SMPs). Depending on operational conditions (hydraulic and sludge retention time (SRT)), the quantity and quality of EfOM significantly changes. The main objective of this research was to quantify and characterize the EfOM of a lab-scale activated sludge sequencing batch reactor (SBR), which was operated at three SRTs and fed glucose, an easily biodegradable substrate. EfOM was followed with two direct-quantification methods (chemical oxygen demand (COD) and dissolved organic carbon (DOC)), three spectrometric methods (ultraviolet absorbance at 254 nm (UVA₂₅₄), excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC)) and three organic matter (OM) indices (specific UVA₂₅₄ (SUVA), SUVA-COD, COD/DOC ratio). The significant increment of UVA₂₅₄ and OM indices after treatment indicated an accumulation of refractory high-molecular-weight humic-like compounds in the EfOM, which demonstrated that EfOM was composed mainly by SMPs and not glucose. On the other hand, as the SRT increased, the amount of EfOM decreased, but SUVA, SUVA-COD and fluorescence intensity increased; these trends indicated the accumulation of SMPs of increased molecular weight and aromaticity. Increasing SRT in the SBRs reduced the amount of EfOM, but increased its aromaticity and reactivity. Visual analysis of EfOM EEMs showed two protein- and one humic-like peak, which were attributed to SMPs generated within the SBRs. PARAFAC determined that a two-component model best represented EfOM EEMs. The two-components from PARAFAC were mathematically correlated to the visually identified protein- and humic-like SMPs peaks.     

Disinfection by-product formation following chlorination of drinking water: Artificial neural network models and changes in speciation with treatment

Artificial neural network (ANN) models were developed to predict disinfection by-product (DBP) formation during municipal drinking water treatment using the Information Collection Rule Treatment Studies database complied by the United States Environmental Protection Agency. The formation of trihalomethanes (THMs), haloacetic acids (HAAs), and total organic halide (TOX) upon chlorination of untreated water, and after conventional treatment, granular activated carbon treatment, and nanofiltration were quantified using ANNs. Highly accurate predictions of DBP concentrations were possible using physically meaningful water quality parameters as ANN inputs including dissolved organic carbon (DOC) concentration, ultraviolet absorbance at 254 nm and one cm path length (UV₂₅₄), bromide ion concentration (Br⁻), chlorine dose, chlorination pH, contact time, and reaction temperature. This highlights the ability of ANNs to closely capture the highly complex and non-linear relationships underlying DBP formation. Accurate simulations suggest the potential use of ANNs for process control and optimization, comparison of treatment alternatives for DBP control prior to piloting, and even to reduce the number of experiments to evaluate water quality variations when operating conditions are changed. Changes in THM and HAA speciation and bromine substitution patterns following treatment are also discussed.     

Investigating dissolved air flotation performance with cyanobacterial cells and filaments

Dissolved air flotation (DAF) performance with two different naturally occurring cyanobacterial morphologies was investigated with respect to the biomass removal efficiency, the toxin release to water and the coagulant demand by different water background natural organic matter (NOM). Coagulation (C)/Flocculation (F)/DAF bench-scale experiments (2 min coagulation at 380 s⁻¹ with polyaluminium chloride (0.5-4 mg/L Al₂O₃, the dose depending on the water NOM content); 8 min flocculation at 70 s⁻¹; 8 min DAF with 5 bar relative pressure and 8% pressurised recycle) were performed with single cells of Microcystis aeruginosa and Planktothrix rubescens filaments spiked in synthetic waters with different NOM contents (hydrophobic vs. hydrophilic NOM; moderate (2-3 mgC/L) vs. moderate-high concentration (ca. 6 mgC/L)). For both morphologies, the results show no apparent cyanobacterial damage (since the water quality did not degrade in dissolved microcystins and the removal of intracellular microcystins matched the removal of chlorophyll a) and high biomass removal efficiencies (93-99% for cells and 92-98% for filaments) provided optimal coagulant dose for chlorophyll a removal was ensured. Charge neutralisation by the polyaluminium chloride was the main coagulation mechanism of the M. aeruginosa cells and most likely also of the P. rubescens filaments. The specific coagulant demand was severely affected by NOM hydrophobicity, hydrophobic NOM (with a specific UV_254nm absorbance, SUVA, above 4 L/(m mgC)) requiring ca. the triple of hydrophilic NOM (SUVA below 3 L/(m mgC)), i.e. 0.7 vs. 0.2-0.3 mg Al₂O₃/mg DOC.     

Continuous fluorescence excitation-emission matrix monitoring of river organic matter

Real-time fluorescence monitoring has been mostly performed in marine systems, with little progress being made in the application of fluorescence excitation-emission matrix (EEM) spectroscopy, especially for freshwater monitoring. This paper presents a two weeks experiment where real-time fluorescence EEM data have been obtained for Bourn Brook, Birmingham, UK, using an in-situ fibre-optic probe. Fluorescence EEMs were measured every 3 min for two weeks, with control ‘grab’ samples every hour analyzed for fluorescence EEMs as well as pH, conductivity and dissolved organic carbon. Comparison of real-time and control samples showed an excellent agreement, with no evidence of fibre-optic probe fouling. EEMs of different character were identified using self-organizing maps, which demonstrated seven clusters of fluorescence EEMs which related to the intensity of fluorescence and relative intensities of peak T₁ and T₂ vs. peak C and peak A fluorescence. Fluorescence intensity of peaks A and C were observed to increase with rainfall, and a diesel pollution event was detected through an increase in T₂ fluorescence.     

A comparison of pilot-scale photocatalysis and enhanced coagulation for disinfection byproduct mitigation

This study evaluated pilot-scale photocatalysis and enhanced coagulation for their ability to remove or destroy disinfection byproduct (DBP) precursors, trihalomethane (THM) formation potential (FP), and THMs in two Arizona surface waters. Limited photocatalysis (<5 kWh/m³) achieved reductions in most of the DBP precursor parameters (e.g., DOC, UV₂₅₄, and bromide) but led to increased chlorine demand and THMFP. In contrast, enhanced coagulation achieved reductions in the DBP precursors and THMFP. Extended photocatalysis (<320 kWh/m³) decreased THMFP once the energy consumption exceeded 20 kWh/m³. The photocatalytic energy requirements for THM destruction were considerably lower (EEO = 20-60 kWh/m³) than when focusing on precursor destruction and THMFP. However, rechlorination increased the total THM (TTHM) concentration well beyond the raw value, thereby negating the energy benefits of this application. Enhanced coagulation achieved consistent 20-30% removals of preformed THMs. Outstanding issues need to be addressed before TiO₂ photocatalysis is considered feasible for DBP mitigation; traditional strategies, including enhanced coagulation, may be more appropriate.     

Solar treatment of cork boiling and bleaching wastewaters in a pilot plant

This paper reports on cork boiling and bleaching wastewaters treatment by solar photocatalytic processes, TiO₂/UV and Fe²⁺/H₂O₂/UV (TiO₂-only for bleaching wastewater), in a pilot plant with compound parabolic collectors. The photo-Fenton reaction (k = 0.12 L/kJ_UV, r₀ = 59.4 mg/kJ_UV) is much more efficient that TiO₂ photocatalysis and TiO₂ + S₂O₈²⁻ (k = 0.0024 L/kJ_UV, r₀ = 1.36 mg/kJ_UV), leading to 94% mineralization of the bleaching wastewater after 31.5 kJ_UV/L, consuming 77.1 mM of H₂O₂ (3.0 mmol/kJ_UV) and using 20 mg/L of iron. For the cork boiling wastewater, after a slow initial reaction rate, the DOC degradation curve shows a first-order kinetics behaviour (k = 0.015 L/kJ_UV, r₀ = 20.8 mg/kJ_UV) until 173 kJ_UV/L (≈300 mg C/L). According to the average oxidation state (AOS), toxicity profiles, respirometry and kinetic results obtained in two solar CPCs plants, the optimal energy dose estimated for phototreatment to reach a biodegradable effluent is 15 kJ_UV/L and 114 kJ_UV/L, consuming 33 mM and 151 mM of H₂OT:/PGN/ELSEVIER/WR/web/00007490/₂, achieving almost 49% and 48% mineralization of the wastewaters, respectively for the cork bleaching and boiling wastewaters.     

Evaluation of UV/H2O2 treatment for the oxidation of pharmaceuticals in wastewater

Advanced oxidation treatment using low pressure UV light coupled with hydrogen peroxide (UV/H₂O₂) was evaluated for the oxidation of six pharmaceuticals in three wastewater effluents. The removal of these six pharmaceuticals (meprobamate, carbamazepine, dilantin, atenolol, primidone and trimethoprim) varied between no observed removal and >90%. The role of the water quality (i.e., alkalinity, nitrite, and specifically effluent organic matter (EfOM)) on hydroxyl radical (OH) exposure was evaluated and used to explain the differences in pharmaceutical removal between the three wastewaters. Results indicated that the efficacy of UV/H₂O₂ treatment for the removal of pharmaceuticals from wastewater was a function of not only the concentration of EfOM but also its inherent reactivity towards OH. The removal of pharmaceuticals also correlated with reductions in ultraviolet absorbance at 254 nm (UV₂₅₄), which offers utilities a surrogate to assess pharmaceutical removal efficiency during UV/H₂O₂ treatment.     

Effects of ozone and ozone/peroxide on trace organic contaminants and NDMA in drinking water and water reuse applications

An ozone and ozone/peroxide oxidation process was evaluated at pilot scale for trace organic contaminant (TOrC) mitigation and NDMA formation in both drinking water and water reuse applications. A reverse osmosis (RO) pilot was also evaluated as part of the water reuse treatment train. Ozone/peroxide showed lower electrical energy per order of removal (EEO) values for TOrCs in surface water treatment, but the addition of hydrogen peroxide increased EEO values during wastewater treatment. TOrC oxidation was correlated to changes in UV₂₅₄ absorbance and fluorescence offering a surrogate model for predicting contaminant removal. A decrease in N-nitrosodimethylamine (NDMA) formation potential (after chloramination) was observed after treatment with ozone and ozone/peroxide. However, during spiking experiments with surface water, ozone/peroxide achieved limited destruction of NDMA, while in wastewaters net direct formation of NDMA of 6-33 ng/L was observed after either ozone or ozone/peroxide treatment. Once formed during ozonation, NDMA passed through the subsequent RO membranes, which highlights the significance of the potential for direct NDMA formation during oxidation in reuse applications.     

Comparison of advanced oxidation processes for the removal of natural organic matter

This study examined the impact of UV, ozone (O₃), advanced oxidation processes (AOPs) including O₃/UV, H₂O₂/UV H₂O₂/O₃ in the change of molecular weight distribution (MWD) and disinfection by-product formation potential (DBPFP). Bench-scale experiments were conducted with surface river water and changes in the UV absorbance at 254 nm (UV₂₅₄), total organic carbon (TOC), trihalomethane and haloacetic acid formation potential (THMFP, HAAFP) and MWD of the raw and oxidized water were analyzed to evaluate treatment performance. Combination of O₃ and UV with H₂O₂ was found to result in more TOC and UV₂₅₄ reduction than the individual processes. The O₃/UV process was found to be the most effective AOP for NOM reduction, with TOC and UV₂₅₄ reduced by 31 and 88%, respectively. Application of O₃/UV and H₂O₂/UV treatments to the source waters organics with 190-1500 Da molecular weight resulted in the near complete alteration of the molecular weight of NOM from >900 Da to <300 Da H₂O₂/UV was found to be the most effective treatment for the reduction of THM and HAA formation under uniform formation conditions. These results could hold particular significance for drinking water utilities with low alkalinity source waters that are investigating AOPs, as there are limited published studies that have evaluated the treatment efficacy of five different oxidation processes in parallel.     

Effects of UV 254 irradiation on residual chlorine and DBPs in chlorination of model organic-N precursors in swimming pools

Ultraviolet (UV) irradiation is commonly applied as a secondary disinfection process in chlorinated pools. UV-based systems have been reported to yield improvements in swimming pool water and air chemistry, but to date these observations have been largely anecdotal. The objectives of this investigation were to evaluate the effects of UV irradiation on chlorination of important organic-N precursors in swimming pools.Creatinine, L-arginine, L-histidine, glycine, and urea, which comprise the majority of the organic-N in human sweat and urine, were selected as precursors for use in conducting batch experiments to examine the time-course behavior of several DBPs and residual chlorine, with and without UV₂₅₄ irradiation. In addition, water samples from two natatoria were subjected to monochromatic UV irradiation at wavelengths of 222 nm and 254 nm to evaluate changes of liquid-phase chemistry. UV₂₅₄ irradiation promoted formation and/or decay of several chlorinated N-DBPs and also increased the rate of free chlorine consumption. UV exposure resulted in loss of inorganic chloramines (e.g., NCl₃) from solution. Dichloromethylamine (CH₃NCl₂) formation from creatinine was promoted by UV exposure, when free chlorine was present in solution; however, when free chlorine was depleted, CH₃NCl₂ photodecay was observed. Dichoroacetonitrile (CNCHCl₂) formation (from L-histidine and L-arginine) was promoted by UV₂₅₄ irradiation, as long as free chlorine was present in solution. Likewise, UV exposure was observed to amplify cyanogen chloride (CNCl) formation from chlorination of L-histidine, L-arginine, and glycine, up to the point of free chlorine depletion. The results from experiments involving UV irradiation of chlorinated swimming pool water were qualitatively consistent with the results of model experiments involving UV/chlorination of precursors in terms of the behavior of residual chlorine and DBPs measured in this study.The results indicate that UV₂₅₄ irradiation promotes several reactions that are involved in the formation and/or destruction of chlorinated N-DBPs in pool settings. Enhancement of DBP formation was consistent with a mechanism whereby a rate-limiting step in DBP formation was promoted by UV exposure. Promotion of these reactions also resulted in increases of free chlorine consumption rates.