The Effect of Ozonation on the Removal of Organics by Coagulation – Flocculation

We present here some works which take place in the particular framework of the study of drinking water treatment of reservoir waters which contain high concentrations of organics, mainly humic substances. Previous studies on coagulation of fulvic acid solutions have proved that the optimal removal of organic matter was reached at acidic pH with 2 mg of ferricion per mg or organic carbon (summarized in this paper). The main question in this study is to know what is the impact of preozonation on the removal of organics by iron (III) coagulation.

The study of the behavior of organics, in terms of UV-absorbance and TOC measurements was made on three aquatic fulvic acids and on two raw waters. The experiments carried out with fulvic acids showed that preozonation (at 0.5 mg O₃/mg C) of fulvic acid appeared to have shifted the region of the optimal DOC removal towards the higher coagulant dose. Furthermore, increasing ozone doses led to a slight decreasing of coagulation efficiency at constant coagulant dose. With two raw waters, preozonation at low ozone doses (0.2 mg 0₃/mg C) was found to improve very slightly the elimination of organic matter, while high ozone doses (0.9 mg O₃/mg C) led to a disturbance of TOC elimination by iron coagulation.     

Flocculation Effects of Ozone

There are numerous reports on coagulation/flocculation effects of preozonation, which cannot be interpreted by one single mechanism. About 7 basic processes are presently discussed. This paper presents results from drinking and wastewater treatment, indicating that preozonation effects can be explained with algae flocculation, with the destabilization of particles, and with polymerization of the dissolved organics. In view of the complexity of the systems, it is anticipated that several processes can be responsible, leading to an optimum ozone dosage.     

Ozonation/Post-Chlorination of Humic Acid: A Model for Predicting Drinking Water Disinfection By-Products

Experiments were performed to evaluate disinfection by-products in model humic acid solutions which were ozonated at three different ozone to carbon levels and then chlorinated. These experiments were conducted in order to help understand whether the ozone/post-chlorination process alters the amount and type of mutagenic by-products formed, from those produced by chlorination of humic acid alone. Disinfection by-products were identified by gas chromatography/mass spectrometry (GC/MS). Samples of clarified and sand-filtered Mississippi River water at a pilotscale drinking water treatment plant in Jefferson Parish, Louisiana, that were ozonated and post-disinfected with chlorine, also were analyzed by GC/MS. A comparison of the by-products in the pilot plant study versus those in our laboratory study showed that similar compounds were produced. The effect of bromide ion in the pilot plant water on by-product formation also is discussed.     

Ozonation Enhancement with Nonpolar Bonded Alumina Phases

This article presents the results obtained for humic acid (HA) degradation in drinking water by means of an ozonation process in the presence of a nonpolar bonded alumina phase. It was observed that (perflurooctylalumina) (PFOA) is characterized by its high adsorption capacity toward HA. The adsorption properties of bare alumina and alumina modified with perfluorooctanoic acid appeared to differ significantly toward the various organic substances examined. The ozonation process carried out in the presence of PFOA was found to be more efficient for the removal of HA from water than the other two examined ozonation systems: ozonation alone and ozonation in the presence of bare alumina; however, a catalytic activity of bare alumina cannot be denied. The effect of by-products formation and changes in the molecular size distribution of HA were studied in the case of all three examined ozonation systems. The influence of catalyst dosage and ozonation time was also investigated.     

Effects Of Catalysts During Ozonation Of Salicylic Acid,Peptides And Humic Substances In Aqueous Solution

The oxidation of two model molecules (salicylic acid and a peptide) and humic substances in aqueous solution was studied using ozone in the presence of various catalysts. Experiments were performed in reactors operated either in batch (TOC_o = 2.5 mg C.L^?1) or in semi-continuous flow mode (TOC_o = 42 mg C.L^?1).     

混凝及其与粉末活性炭联用去除水中腐殖酸的研究

以模拟腐殖酸水样为研究对象 ,重点考察并讨论了硫酸铝为絮凝剂时 ,硫酸铝投加量、水样pH值及加入粉末活性炭等因素对混凝去除腐殖酸效果的影响。结果表明在一定的絮凝剂投加量和pH范围内 ,混凝可以有效地去除水样中的腐殖酸 ,当硫酸铝投加量为 5 0mg·L-1,pH =7时 ,去除率达到 99% ;通过助凝作用 ,粉末活性炭可以显著地强化混凝对腐殖酸的去除     

Mineralization of Ibuprofen and Humic Acid through Catalytic Ozonation

Advanced oxidation methods are used to remove traces of pharmaceuticals from aquatic environments. The application of a catalyst improves the total organic carbon removal during ozonation of pharmaceuticals in water. The aim of this study was to use MnO₂-CuO/ γ-Al₂O₃ catalyst for ozonation of ibuprofen (5 mgL^?1) and evaluate the effect of the presence of humic acid in the removal process. The presence of the catalyst increased the mineralization percentage of ibuprofen from 27% for noncatalytic ozonation to 55% in the presence of catalyst. The presence of humic acid increased noncatalytic mineralization by 10%. The reusability and stability of the catalyst, and its ability to adsorb reaction by-products were demonstrated.     

Ozonation of VOC's in the Presence of Humic Acid and Soils

The oxidation of several VOCs in the presence of humic acid and soil is described in this paper. It was found that while ozone does react appreciably with humic acid, as indicated by significant changes in the spectral characteristics of humic acid, the TOC levels in these solutions changed by only 3‰ or less. The oxidation of four olefinic VOCs occurred in solutions containing up to 120 mg/L humic acid, however, the extent to which each of the compounds reacted is very much compound specific. The effect of pH and ozone dosage on these reactions was considered. The effects of pH were weak for all compounds except trichloroethane. Ozone dosage had a significant effect on the extent to which each of the VOCs was oxidized, although no simple relationship between ozone dosage and the amount of VOC which reacted could be obtained. Complete oxidation of dy–dichloroethylene by ozone (22 mg/L) occurred in solutions containing 1.0 g of Eustis soil suspended in 10.0 mL water. However, only 40‰ oxidation of tetrachloroethylene was achieved using an ozone dosage of 17.3 mg/L when 1.0 g of Eustis soil was present. The results obtained in this study strongly suggest that the influence of free radicals, generated during the decomposition of ozone, on the oxidation of VOCs is significant. The work described here suggests that ozone may be applicable for the treatment of contaminated soils and waters containing high concentrations of matter.     

Study of the Catalytic Ozonation of Humic Substances in Water and Their Ozonation Byproducts

It is shown that using transition metals, especially Mn(II) and Ag(I), during ozonation of humic substances in water allows important reductions in the content of organic matter. Characterization of the organic compounds resulting from ozonation was made by concentrating the sample through liquid-liquid extraction or derivation with PFBOA.HCl, along with the GC/MS and GC/ECD techniques. In total, 110 different organic compounds were identified using GC/MS; mainly carboxylic acids, aromatics, hydrocarbons, aldehydes, ketones, and furan-carboxylic acids. The percentages of elimination or formation levels reached during ozonation are discussed.     

Influence of Ozonation of Humic and Fulvic Acids on Diuron Adsorption on Activated Carbon

The effect of ozonation on the competitor effect of humic and fulvic acids against diuron in adsorption on activated carbon in drinking water process has been studied. Ozonation treatment allows the removal of herbicides from drinking waters by modification of humic and fulvic acids structures. These latest are responsible for their adsorption variation on activated carbon. An ozone dose similar to that used in industrial pre-ozonation (1.3?mg ozone/l) does not cause significant transformations of humic and fulvic acids which could decrease their competitor effect and increase significantly the adsorption capacity of the activated carbon for a well-adsorbed pesticide like diuron.     

容量法测定腐植酸复肥中腐植酸含量

现行标准GB11957-1989对腐植酸复肥中腐植酸测定方法操作步骤繁,手续多,耗时长。本文以容量法测定腐植酸复肥中腐植酸。总体方差0.087%,实验方法与标准方法不存在显著性差异;本方法操作手续简便,具有较好的准确度和精密度。结果满意。     

The Effect of Ozone on the Reversibility of Floc Breakage: Suspensions with High Humic Acid Content

The effects of pre-ozonation and humic acid concentration on the formation, breakup and reformation of flocs generated using aluminium sulphate and polyaluminium chloride was investigated using conventional jar test procedure and by continuous optical monitoring. Using a range of different humic acid and ozone concentrations, it was found that increasing either concentration was detrimental to floc formation, leading to reduced turbidity removal. Once ruptured, only limited regrowth of flocs occurred, indicating irreversible floc breakage. The findings showed that the use of pre-ozonation did not provide beneficial results to improve turbidity removal. Nevertheless, improved dissolved organic carbon removal was achievable.     

Iron and Manganese Removal with Ozonation in the Presence of Humic Substances

The conditions for the removal of iron and manganese contained in slightly mineralized water, rich in humic substances, were determined in a case where an intermediate oxidation was provided in a conventional potabilization line comprising a coagulationflocculation stage with iron salts.

The experiments were conducted both on a synthetic water, with or without addition of humic substances, and on raw water from the Moulin-Papon dam. While iron was easily removed by simply increasing the pH measurement from 8.2 to 8.5 without intermediate oxidation, ozonation applied to water with a pH of nearly 8.4 did not enable the manganese to be removed with a low ozone dose (about 1 mg/L) unless a significant amount of bicarbonates (120 to 130 mg/L as CaCO₃) were injected prior to the ozonation-filtration stage.

As it removes the manganese from the water, intermediate ozonation also removes the abatement of organics on the filters, and lowers the THM buildup potential.     

Ozonation of Humic Substances: Effects on Molecular Weight Distributions of Organic Carbon and Trihalomethane Formation Potential

Four different sources of humic substances were studied to determine the effects of ozonation on molecular weight-distributions, based on dissolved organic carbon (DOC) and trihalomethane formation potential (THMFP). Solutions of two soil-derived fulvic acids and a one soil-derived humic acid, as well as dissolved organic matter (DOM) associated with a natural water source were studied. Both gel permeation chromatography (GPC) and ultrafiltration (UF) were employed to define apparent molecular weight (AMW). Applied ozone doses ranged from 2.0 to 2.5 mg O₃/mg DOC. Overall samples of untreated and ozonated waters, as well as individual molecular weight fractions, were characterized according to DOC, UV absorbance, and THMFP. Ozonation resulted in a significant disappearance of higher AMW material with a corresponding increase in lower AMW material. Although little overall reduction in DOC concentration was observed, significant overall reductions in UV absorbance and THMFP levels were observed.     

Removal of Atrazine Through Ozonation in the Presence of Humic Substances

The presence of pesticides in water sources and their removal by treatment processes is of particular interest currently to water companies and research scientists. Although operators and scientists are debating whether the related standards and legislation are too stringent, the current European Drinking Water Directive stipulates a maximum contaminant level (MCL) of 0.1 μg/L for an individual pesticide. Atrazine is amongst the most frequently identified pesticides in water supply sources. Since conventional treatment processes (chlorination, coagulation and filtration) are unable to reduce this micropollutant to an acceptable concentration, two advanced technologies are being investigated extensively; namely, adsorption onto activated carbon, and ozonation, particularly ozone combined with hydrogen peroxide. As for ozonation, several authors (Glaze et al., 1987; McGuire and Gaston, 1988; Terashima, 1988; Ferguson et al., 1991) have reported that the removal of refractory organics (e.g., 2-methyl isoborneol – MIB and geosmin) by ozone appears to be more effective in natural waters than in pure water solution; this was attributed to the action of natural organic material in water (such as humic substances) which promotes the radical reactions of ozone. In other more fundamental studies (Staehelin and Hoigné, 1985; Xiong and Legube, 1991), humic substances were speculated to be involved in radical decomposition of ozone in solution.     

Sequential Oxidation of Humic Acids by Ozonation and Photocatalysis

In this study, humic acids, the natural polymerized organic compounds which are responsible for the formation of disinfection by-products such as haloacetic acids and trihalomethanes upon chlorination, are oxidized in a sequential system incorporating ozonation and photocatalysis. Titanium dioxide is used as photocatalyst in the photocatalytic oxidation phase. Humic acid degradation kinetics is evaluated both for ozonation and photocatalysis. The Freundlich adsorption model is used for defining the adsorption characteristics of humic acid solutions on the photocatalyst after the ozonation step. The Langmuir-Hinshelwood model is also studied for explaining the adsorptive and photocatalytic removal of humic acids.     

The Ozonation of Glyoxylic Acid in Aqueous Solution: Chemical Products and Kinetics Evolution

The ozonation of glyoxylic acid in aqueous solution is investigated in semicontinuous and continuous reacting systems to follow the evolution of both chemical products and kinetics. Evidence is given of formation of small amounts of formic acid and -of the promoting effect of peroxidic intermediates upon oxalic acid ozonation. Kinetic results indicate that the ozonation process develops according to a radical chain mechanism initiated by ozone attack on glyoxylic acid.     

反向悬浮聚合法合成腐植酸基复合高吸水性树脂的研究

以腐植酸与丙烯酰胺为原料,采用反向悬浮聚合法制备了一种腐植酸基复合高吸水性树脂聚丙烯酰胺-腐植酸钠(PAM-NaHA),分别研究了交联剂、引发剂用量及聚合温度对树脂吸水率的影响,以及树脂对沙土吸水保水性能的促进作用.结果表明:当n(MBAA)∶n(AM)=0.0005、n(APS)∶n(AM)=0.008、聚合温度为6...     

Heterogeneous Catalytic Ozonation with Supported Titanium Dioxide in Model and Natural Waters

This paper presents the results obtained with heterogeneous catalytic ozonation in which model and natural waters are ozonated in the presence of supported titanium dioxide (TiC₂) as a solid catalyst. The conditions in preparing the supported catalyst are experimentally optimized. The efficiencies of three catalyst supports (attapulgyte, alumina and silica gel) for organic matter oxidation have been compared. The TiC₂ supported in alumina calcined at 500[ddot]C compacted to granular form with a particle diameter about 2-4 mm is demonstrated to be the best catalyst on the removal total organic carbon (TOC) by ozone.     

Identification of Oxidation Intermediates in Humic Acid Oxidation

The effects of using ultraviolet irradiation (UV), ozone (O₃) and the combined O₃-UV advanced oxidation process (AOP) on humic acid (HA), which is regarded as the main disinfection by-products (DBPs) precursor, have been evaluated and compared. In particular, aromatic acids, short-chain aldehydes and carboxylic acids were measured. The purpose of this study was to determine the different classes and yields of oxidation intermediates, compare O₃, UV and O₃-UV for HA removal, as well as investigate the effects of O₃, irradiation time, UV intensity on the mineralization of HA. Based on that, the knowledge gap of DBPs generation was made up. The results showed that by UV irradiation and O₃ oxidation, HA broke down into smaller molecules that were more hydrophilic, namely formaldehyde, acetaldehyde, propaldehyde, butyraldehyde, glyoxal, methyl-glyoxal, formic, acetic, fumaric, benzoic, phthalic, protocatechuic and 3-hydroxybenzoic acids. Meanwhile, unsaturated conjugated double bonds in the structure of HA were destroyed, which lead to UV₂₅₄ a slight decrease. Due to the synergistic effect of O₃-UV, DOC and UV₂₅₄ significantly decreased and remained stable after the reaction of 10 min, indicating that O₃-UV system had stronger potential of mineralization and lower nonselectivity. Besides, the kinds and concentration levels of the intermediates were obviously reduced with light intensity increasing. Hydroxyl radical (^.OH) could mineralize some organics that could not be mineralized by O₃.