Using Fractionated Natural Organic Matter to Quantitate Organic Byproducts of Ozonation

An improved procedure was used to isolate and fractionate natural organic matter (NOM) in water for subsequent ozonation and disinfection by-product (DBP) and color removal quantisation. Isolated NOM fractions from two different sources, accounting for approximately 50 to 60% of the dissolved organic material and 60 to 75% of the color, were characterized and then ozonated under conditions approximating those encontered during drinking water treatment. The natural waters also were ozonated. Organic DBPs of either health concern or which may contribute to biological instability of finished water were investigated, including aldehydes, oxoacids and low molecular weight carboxylic acids. pH and ozone dosage were the parameters having the greatest effect on DBP formation. On the basis of UV absorbance measurements, the fulvic acid fractions studied taken together accurately represented the natural water and may be the primary sources of precursor material for aldehydes and oxoacid DBPs. However, as yet unidentified NOM fractions contribute significantly to carboxylic acid formation upon ozonation.     

Characteristics of Natural Organic Matter and Formation of Chlorinated Disinfection By-Products from Two Source Waters that Respond Differently to Ozonation

This study investigated the characteristics of natural organic matter (NOM) in two different raw surface water sources that respond differently to ozonation: one for which ozonation decreases the disinfection by-product (DBP) formation potentials (i.e., Capilano Reservoir, Vancouver, Canada), and one for which ozonation does not (i.e., South Thompson River, Kamloops, Canada); and evaluated the effect of ozonation on these characteristics and on the DBP formation potential of the different size and polar fractions of the NOM. Although the South Thompson River and the Capilano Reservoir waters had relatively similar total organic carbon concentrations, the characteristics of the NOM (e.g., size and polar distribution, specific UV absorption), in these water sources differed significantly. In general, no clear and consistent trend was observed with respect to the tendency of different size and polar fractions of NOM to generate DBPs. Nonetheless, the results from the present study suggest that hydrophobic NOM has a higher tendency to form DBPs. In addition, when considering individual size and polar fractions, specific UV absorption was a good overall indicator of the DBP formation potential for a given water source. The effect of ozonation on South Thompson River and Capilano Reservoir waters also differed significantly. For both source waters, ozonation appeared to have a greatest effect on the more hydrophilic fractions, generally increasing the DBP formation potential of the smaller more hydrophilic NOM, while generally decreasing that of the larger more hydrophilic NOM. The beneficial effect of ozonation on reducing haloacetic acid (HAA) formation potentials was due to a reduction in both the dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) formation potentials, while the negative effect of ozonation on increasing HAA formation potentials was due to an increase in the DCAA formation potentials. The results from the present study clearly indicate that the use of ozone as a primary disinfectant does not necessarily reduce the DBP formation potential of NOM in all water sources, further demonstrating the complex structure of NOM and the fact that NOM from different sources cannot be simply treated as one entity and compared with one another.     

Evaluation of the performance of tight-UF membranes with respect to NOM removal using effective MWCO, molecular weight, and apparent diffusivity of NOM

Concepts for the effective MWCO of tight-UF membranes, and apparent diffusion coefficients for NOM, were introduced to determine the mechanisms influencing NOM removal and to explain the various behaviors of NOM removal by UF membranes with different hydrophobicities, permeability, and surface charges. Colloidal NOM (COM) and non-colloidal hydrophobic NOM (NCD HP) constituents were chosen for the evaluation of two different UF membranes. For a relatively hydrophobic, relatively high permeability, and less negatively charged UF membrane, the hydrophobic fractions of COM were preferentially removed and were also removed by a size exclusion mechanism (i.e., both hydrophobic interaction and size exclusion mechanisms). The NCD HP exhibited no such preferential removal of the hydrophobic fractions, but could be removed by a size exclusion mechanism (i.e., only size exclusion mechanism). With a relatively hydrophilic, relatively low permeability, and more negatively charged UF membrane, COM exhibited no preferential removal of the hydrophobic fractions, but could be removed by a size exclusion mechanism (i.e., only size exclusion mechanism). Whereas the hydrophobic fractions of the NCD HP were preferentially removed, these could not be removed by a size exclusion mechanism (i.e., only hydrophobic interaction mechanism). The apparent diffusion coefficients of NOM, as determined from NOM diffusion experiments using a diffusion cell equipped with a regenerated cellulose membrane, were much lower than those calculated by the Stokes-Einstein relation. The diffusion coefficient of NOM is expected to be used to predict and explain NOM transport behaviors in tight-UF membranes.     

Effects of Ozonation on Molecular Weight Distribution of Humic Substances and Coagulation Processes – A Case Study: The Úzquiza Reservoir Water

In this article the influence of preozonation on the effectiveness of NOM removal via coagulation processes will be studied (focusing on the influence of the calcium hardness) as well as changes in MW (molecular weight) distribution of humic substances caused by ozonation. Additionally, THMFP removal in both ozonation and preozonation-coagulation processes is assessed. Three different types of water have been used in this study: a natural water from the Úzquiza Reservoir (Burgos, Spain), a synthetic water prepared using natural fulvic acids extracted from the Úzquiza Reservoir and a synthetic water prepared using a commercially supplied humic acid. Molecular weights of humic substances were determined using high-performance size exclusion chromatography (HPSEC); average molecular weights calculated for the unozonated humic substances are 4500 Da for the commercial humic acids and 1000 Da for the natural fulvic acids extracted from the Úzquiza Reservoir. Preozonation shifted the molecular weight distribution of humic substances (both humic and fulvic acids) towards lower average molecular weight values. For the natural water from the Úzquiza Reservoir (with low levels of calcium hardness and hydrophobic fraction (humic substances) being the main fraction of NOM), preozonation has a negative effect on the effectiveness of the coagulation process for NOM removal: the percentages of TOC removal via coagulation decrease with increasing ozone dosage; the maximum TOC removal (33%) is achieved for the unozonated water. Also for this water, ozonation reduced 5–25% of THMFP with ozone doses varying from 0.25 to 2.5 mg O₃/L. A preferential THMFP removal, that is to say, higher reduction in THMFP (43%) relative to TOC (28%) is achieved by the coagulation-flocculation process; this also occurs when preozonation is used, independently of ozone dosage.     

Optimization of NOM Removal during Water Treatment

Abstract

The aim of this paper is to describe the removal efficiency of individual fractions of natural organic matter (NOM) and the aluminum transformation during treatment of two types of surface water with an increased concentration of NOM of various origins. The coagulation conditions (dose of destabilization reagent and reaction pH value) were optimized for the best NOM and aluminum removal. The results show that the NOM removal efficiency depends on the NOM character, using destabilizing reagents and reaction conditions. The optimized doses of destabilization reagents influence especially the removal of hydrophilic charged (CHA) and very hydrophobic acids (VHA) fractions during treatment of both types of raw water. In contrast to this, the removal of hydrophilic neutral (NEU) fraction is very low (? _NEU =0.13–0.22). The optimal destabilization reagent dosage is characterized by the lowest content of the total reactive aluminum concentration and relatively low concentration of dissolved organic aluminum.     

Catalytic ozonation of natural organic matter on alumina

The paper aims to show the potential of catalytic ozonation in the presence of alumina for the removal of natural organic mater from drinking water. An investigation into the efficiency of catalytic ozonation, ozonation by-products formation and their biodegradability was the main goal of the paper. Characterisation of fresh and worn alumina was also conducted. The results clearly indicated the high activity of alumina over a long period of time, which is crucial in water treatment technology. The application of alumina to the ozonation system doubled the efficiency of NOM removal from water when compared to ozonation alone. Furthermore, catalytic ozonation resulted in lower by-products and biodegradable organic carbon formation.     

Kinetics of Natural Organic Matter as the Initiator,Promoter, and Inhibitor,and Their Influences on the Removal of Ibuprofen in Ozonation

Natural organic matter (NOM) can simultaneously act as the initiator, promoter and inhibitor in water ozonation. This study presents an explicit method that can be used to determine these rate constants via the integration of the transient steady-state hydroxyl radical (?OH) model, the R_ct concept and the pseudo first-order ozone decomposition model. The theoretical background of this method was provided, and the method was validated with model compounds. The rate constants of three NOM isolates were determined using the developed method. With these rate constants, the influences of NOM on the degradation of ibuprofen, an ?OH-reactive pharmaceutical compound, can be quantitatively described. [Supplementary materials are available for this article. Go to the publisher's online edition of Ozone Science &; Engineering for the following free supplemental resources: tables, figures, and equations.]     

Reaction Mechanisms for DBPS Reduction in Humic Acid Ozonation

In this study, XAD-8 resins were used to extract the natural organic matter (NOM) from samples collected at the intake of Feng Yuan Water Treatment Plant (in central Taiwan) into five groups: humic acids, fulvic acids, hydrophobic neutrals, hydrophobic bases, and hydrophilic fractions. Quantitative results show that hydrophobic and hydrophilic fractions contribute 44.2% and 55.5% of NOM, individually. Ozonation processes will significantly reduce both disinfection by-products formation potential (DBPFP) and average molecular weight of the humic acid sample. Additionally, double carbon bonds are broken up so that hydrophobic fractions were converted to hydrophilic fractions by ozonation leading to the reduction of DBPFP.     

Degradation and Transformation of Organic Compounds in Songhua River Water by Catalytic Ozonation in the Presence of TiO2/Zeolite

This paper presents experimental results of the catalytic ozonation of Songhua River water in the presence of nano-TiO₂ supported on Zeolite. The removal efficiency of TOC and UV₂₅₄, the variation of AOC and molecular weight distribution of organics was studied. Results showed that TOC and UV₂₅₄ removal efficiency by ozone was improved in the presence of TiO₂/Zeolite, and increased by 20% and 25%, respectively. The part of organic compounds less than 1000 Da increased in ozonation, but decreased in catalytic ozonation. The AOC of water increased in catalytic ozonation, and the increase of AOC was particularly obvious when ozone dose increased from 28.8 mg·L^?1 to 46.6 mg·L^?1. The degradation and transformation of organic compounds was analyzed by means of GC-MS. The total number of organic compounds was reduced from 50 in the untreated water to 36 and 20, respectively, in ozonation and catalytic ozonation. The removal efficiency of the total organic compounds peak area in ozonation and catalytic ozonation were 23.5% and 62.5%, respectively. Most of the hydrocarbons could be removed easily in ozonation and catalytic ozonation. The organic compounds having hydroxyl, carboxyl or carbonyl groups were hard to be removed in ozonation, but could be removed efficiently in the presence of TiO₂/Zeolite.     

Changes in NOM Fractionation through Treatment: A Comparison of Ozonation and Chlorination.

NOM isolation and fractionation to provide insight into the effectiveness of ozonation vs. conventional water treatment was done. In this research, the dissolved portion of natural organic matter (NOM) or dissolved organic matter (DOM) at two surface drinking water treatment plants that treat the same source water was fractionated by resin adsorption. The first treatment plant uses conventional treatment (coagulation, sedimentation, and filtration) with intermediate free chlorination and post chlorination while the second plant uses conventional treatment with pre and intermediate ozonation, and multi-media filtration unit operation. Several different sampling locations within each plant were selected for DOM isolation and fractionation into six fractions (hydrophobic acid, neutral and base, and hydrophilic acid, neutral, and base). The effectiveness of each treatment plant on the oxidation and removal of each organic fraction are discussed. Oxidation by ozone leads to better overall performance in the removal of DOM.     

典型水处理工艺处理黄浦江原水有机物变化规律初探

该文从分子量转化的角度对水体中有机物在水处理工艺过程中的转化进行了研究.针对特定的水质特征(小分子有机物居多),比较了3种不同的氧化剂(臭氧、氯和高锰酸钾)对有机物分子量(molecular weight,MW)的转化情况.试验证实臭氧氧化可明显减少MW＞30 kDa的有机物含量,进一步通过絮凝沉淀和过滤工艺可使MW＞...     

Natural organic matter (NOM) fouling in low pressure membrane filtration — effect of membranes and operation modes

The objective of this study was to evaluate the effects of operating modes, membrane materials and pore size on natural organic matter (NOM) fouling. A range of flat sheet microfiltration (MF) and ultrafiltration (UF) membranes were tested under conditions of various constant pressure and constant flux filtration modes. Based on experimental filtration profiles, molecular weight (MW) distributions of NOM obtained using high performance size exclusion chromatography (HPSEC) and autopsies of fouled membranes using force emission scanning electron microscopy (FESEM), it was concluded that medium to low MW component of NOM (300–1,000 Da) is responsible for the initiation of fouling, where bulk of the fouling observed is due to very high MW ‘colloidal’ NOM (>50,000 Da). This two stage fouling phenomenon was in good agreement with classical blocking laws. As a general observation hydrophilic membranes were less prone to NOM fouling. A comparison of constant pressure and constant flux tests confirmed that modest constant flux, as used in industry, provided the most beneficial conditions.     

Degradation of Refractory Organic Pollutants by Catalytic Ozonation—Activated Carbon and Mn-Loaded Activated Carbon as Catalysts

A novel catalyst for the ozonation process was prepared by loading manganese on the granular activated carbon (GAC). Nitrobenzene was used as a model refractory organic micropollutant in this study. The catalytic activity of GAC and the Mn-loaded GAC were studied respectively. The removal efficiency of nitrobenzene by Mn-loaded GAC catalyzed ozonation could reach 34.2–49.9%, with the oxidation efficiency being about 1.5–2.0 times higher than that achieved in GAC catalyzed ozonation and 2.0–3.0 times higher than that achieved by ozonation alone. The effect of pH and the t -butanol on the GAC/ozone process was discussed. The optimum condition for preparing the catalyst was studied.     

Ozone,Oxalic Acid,and Organic Matter Molecular Weight – Effects on Coagulation

Ozonation breaks long chain natural organic matter (NOM) into smaller, more oxygenated compounds such as oxalic acid. The purpose of this study was to evaluate the effects of such transformations on coagulation in high dissolved organic carbon synthetic waters with model particles. Results indicate that the presence of oxalic acid adversely affects the removal of turbidity and organic carbon by coagulation and filtration. The results also show that larger (higher molecular weight) organic matter is easier to remove by coagulation than lower molecular weight organic matter. In both cases, ozonation results in an increase in the optimum coagulant dose or a decrease in the amount of turbidity and TOC removal at a given coagulant dose.     

Application of combined coagulation-ultrafiltration membrane process for water treatment

The objectives of this research are to identify the membrane fouling potential due to different fractions of NOM and correlate the physicochemical properties of NOM and membranes with the adsorption of humic substances on membrane and investigate the mechanism of coagulation affecting UF, and find the optimum conditions of the combined of coagulation with UF membrane filtration for NOM removal. For Nakdong river water, the humic acid fraction was the most reactive precursor fraction for the formation of the ratio of THMFP/DOC (STHMFP) and TOXFP/DOC (STOXFP). The result of adsorption kinetics tests showed that hydrophobic organics adsorbed much more quickly than hydrophilic organics on both membranes. Thus, hydrophobic compounds exhibited a preferential adsorption onto membrane. In case of the effect of membrane properties on the adsorption of organic fractions, the adsorption ratio (C₁/C_e) was greater for the hydrophobic membrane than for the hydrophilic membrane regardless of the kind of organic fractions. For combined coagulation with membrane process, flux reduction rate showed lower than the UF process alone. Also, the rate of flux decline for the hydrophobic membrane was considerably greater than for the hydrophilic membrane. Applying the coagulation process before membrane filtration showed not only reduced membrane fouling, but also improved removal of dissolved organic materials that might otherwise not be removed by the membrane. That is, during the mixing period, substantial changes in particle size distribution occurred under rapid and slow mixing conditions due to the simultaneous formation of microflocs and NOM precipitates. Therefore, combined pretreatment using coagulation (both rapid mixing and slow mixing) improved not only dissolved organic removal efficiency but also DBP (Disinfection By-Product) precursor's removal efficiency.     

Combined Ozonation Using Alumino-Silica Materials for the Removal of 2,4-Dimethylphenol from Water

This study deals with an advanced oxidation process combining adsorption and ozonation for treating petrochemical effluents. The compound 2,4-dimethylphenol (DMP) was the paradigm molecule and faujasite-Y, mordenite, ZSM-5 and γ-alumina were tested. Single ozonation showed rapid DMP degradation but limited by gas to liquid ozone transfer. No catalytic effect occurred during ozonation combined with any of the adsorbents: DMP removal was not accelerated. However, a good synergistic effect was observed for TOC removal with γ-alumina, yet the various zeolites are less efficient. Some specific oxidation by-products produced during ozonation are eliminated by adsorption in the presence of γ-alumina, although they persist in the other cases.     

Intrinsic Activity of SBA-like Silica in the Catalytic Ozonation of Organic Pollutants

Hydrothermal synthesis using two gel compositions: i. 1 SiO₂: 0.059 P123: 56.130 HCl: 607.638 H₂O; ii. 1 SiO₂: 0.006 P123: 0.013 F127: 42.439 HCl: 442.876 H₂O, resulted in highly crystalline SBA-15 and SBA-16 like silica with intrinsic activity in the catalytic ozonation of oxalic acid (OA), phenol (φ-OH) and Orange G (OG) in water at room temperature. X-ray diffraction, nitrogen adsorption–desorption, transmission and scanning electron microscopies revealed highly ordered mesoporous structure, with large surface area, regular channels and uniform particle size. UV-Vis analysis provided faster, more precise and reliable assessments of the decomposition yield and process selectivity than the conventional and laborious method of Chemical Oxygen Demand (COD). The ozone reactivity was found to be favored by increasing size of the organic substrate. OG and phenol decomposition required shorter ozonation time (20, 15 min, respectively) than OA, involving mainly phenyl ring hydroxylation and cleavage. Measurements through thermal programmed desorption of carbon dioxide and water revealed that the catalytic activity of the SBA samples involves adsorption via both acid-base and hydrophobic interactions. Suitable SBA modifications allow tailoring these interactions for even faster ozonation without persistent traces of short chain derivatives.     

Catalytic Ozonation of Gasoline Compounds in Model and Natural Water in the Presence of Perfluorinated Alumina Bonded Phases

Gasoline compounds are one of the most widespread causes of soil and groundwater contamination. Their degradation in model and natural waters due to catalytic ozonation in the presence of perfluorooctylalumina (PFOA) is presented and discussed in this paper. The results obtained clearly indicate that the PFOA/O₃ system is effective mainly for ether (MTBE and ETBE) removal from both model and natural water. The catalytic activity of PFOA is not so significant in the case of BTEX ozonation. An investigation into by-product formation has shown that the concentration of both carboxylic acids (mainly oxalic acid) and carbonyl compounds (mainly acetone) increases after catalytic ozonation when compared with ozonation alone. A decrease of formic acid and formaldehyde takes place after the PFOA/O₃ system as opposed to the usage of ozonation alone.     

Crystal structure and surface species of CuFe2O4 spinel catalysts in steam reforming of dimethyl ether

The application of catalytic ozonation processes for the decolourisation and mineralisation of coloured aqueous solutions was studied. One acid azo dye, CI Acid Blue 113, and two reactive dyes, CI Reactive Yellow 3 and CI Reactive Blue 5, with azo and anthraquinone chromophores, respectively, were used as representative textile dyes. The catalytic activities of activated carbon, cerium oxide and a ceria-activated carbon composite were evaluated in the removal of the selected dyes. In all cases, with an initial dye concentration of 50 mg/L, a complete decolourisation was achieved by single ozonation in short reaction times (less than 10 min). The ceria-activated carbon composite allowed the highest removal of total organic carbon. For dye concentrations of 50 mg/L, mineralisation degrees of 100%, 98% and 97% were achieved with the composite after 2 h of reaction, respectively for CI Reactive Blue 5, CI Acid Blue 113 and CI Reactive Yellow 3. The activity of the catalyst containing cerium was affected by the presence of carbonate and bicarbonate ions due to their scavenging effect towards hydroxyl radicals; for example the mineralisation degree of CI Reactive Blue 5 (C₀ = 300 mg/L) after 120 min of reaction was only 63%, contrasting with the value of 85% obtained in the absence of carbonates. All the catalytic systems were evaluated in the treatment of textile effluents, collected before or after conventional biological treatment. Catalytic ozonation was proven to be effective when used as tertiary treatment for bio-treated effluents.     

Comparison of Activated Carbon and Hydrophobic Zeolite Efficiencies in 2,4-Dichlorophenol Advanced Ozonation

This study aims at comparing the removal of 2,4-dichlorophenol (2,4-DCP) by 3 methods; adsorption using hydrophobic zeolite (faujasite) or activated carbon (S-23 and L-27), conventional ozonation and hybrid adsorption/ozonation treatment. On the one hand, the three materials correctly adsorb 2,4-DCP; however the adsorption kinetics using zeolite is very low. On the other hand, ozonation totally removes 2,4-DCP after 1 h experiment and the simultaneous combination of adsorbent and ozone does not change the 2,4-DCP degradation. But, though ozonation and hybrid process appear to be equivalent for 2,4-DCP removal, activated carbons are able to decompose ozone and to improve chemical oxygen demand (COD) removal, whereas the zeolite does not show this catalytic effect. Similar results were also observed in a former study with nitrobenzene. Adsorbent degradation is evaluated by Brunauer, Emmet and Teller (BET) and differential thermogravimetric (DTG) analysis, which evidence that Faujasite and S-23 activated carbon are resistant to ozone exposure whereas the pore volume and the surface area of L-27 activated carbon decrease during ozonation.