Systematic Approach to Quantify Adsorption and Biodegradation Capacities on Biological Activated Carbon Following Ozonation

The goal of this research was to develop a systematic approach to quantify adsorption and biodegradation capacities on biological activated carbon (BAC). The role of absorption and biodegradation on BAC was studied using a continuous column. Several media, i.e., granular activated carbon (GAC), seeded glass bead and seeded GAC, and a target compound (p-hydroxybenzoic acid) were selected. Before breakthrough, the effluent of the GAC column contained a small amount of p-hydroxybenzoic acid that contributed the greatest amount of organic carbon to the effluent of the glass bead column, which suggests that adsorption should be the prevailing mechanism for removal the p-hydroxybenzoic acid, and biodegradation should be responsible for reducing the ozonation intermediates. Also, the bioactivity approach (biomass respiration potential, BRP) of BAC can not only reveal the importance of biodegradation mechanisms for the intermediates of ozonation, but also quantify the extent of the adsorption or biodegradation reaction occurring on BAC.     

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.     

Ozone: A Means of Stimulating Biological Activated Carbon Reactors

To reduce the formation of chlorination byproducts in drinking water, the European strategy consists in developing techniques for the removal of organic matter. No chlorine is added to the water until the end of the treatment line, allowing a great reduction of the chlorine dose applied. Delaying the chlorination also improves the biological assimilation of organics within the filters. Identification of the basic properties (i.e., molecular weight, biodegradability) of the molecules which react with chlorine shows that the combination of ozone and biological activated carbon (BAC) filtration is an efficient and economical technique for the removal of these undesirable byproducts. More and more, drinking water suppliers are faced with the worrisome problem of chlorinated byproducts. This concern was prompted largely by the degradation of raw waters. Chlorinated byproducts are caused by the effect of chlorine on organic matter dissolved in water.     

Adsorption and Microbiological Mechanisms for Removal of Natural Organics in Granular Activated Carbon Columns

Performance data for GAC columns treating surface water are analyzed to determine the relative importance of physical adsorption and biological activity, with and without pre-ozonation. Kinetic and equilibrium adsorption parameters for the source water are used in the Homogeneous Surface Diffusion model to predict GAC performance over 83 weeks. The model underestimates removal of TOC for ozonated and unozonated streams by 46% and 28%, respectively, which is attributed to omission of biological removal in the model.     

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.     

The Influence of H2O2 in Ozonation Treatment: Experience of the Water Supply Service of Florence,Italy

This paper reports on the use of ozone in the Water Supply Service of Florence (Italy). The addition of hydrogen peroxide at the end of ozonation treatment has proved particularly efficient for controlling bromates and brominated organic byproducts. Significant differences regarding the formation of oxygenated organic compounds were not observed.     

Ozonation of Cyanide Catalyzed by Activated Carbon

In this work, the removal of cyanide from aqueous solutions was accomplished by using the synergetic effect of activated carbon and an oxidizing agent. A basic-character coconut shell activated carbon (CAC) was used; experiments were conducted in a semi-batch reactor, at 25 °C, initial pH of 11.5, and using cyanide solutions with initial concentration up to 1200 mg/mL. In particular, the beneficial effect of an oxidizing agent such as air, oxygen or ozone on the removal of cyanide by CAC was evaluated. At the optimum operating conditions found in this study, 1200 mg/mL of cyanide were totally decomposed in about 3 h, by using 1 g of CAC and about 2 mgO₃/min. The experimental results were rationalized based on different mechanisms reported in the literature. The findings provide the basis to optimize the removal of cyanide from aqueous solutions in mining or metallurgical effluents by using the synergetic effect of CAC and ozone.     

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.     

Diuron Multilayer Adsorption on Activated Carbon from CO2 Activation of Grape Seeds

Granular activated carbons were obtained from grape seeds by pyrolysis at 600°C and subsequent physical activation with CO₂ (750–900°C, 1–3 h, 25–74% burn-off). The carbon and ash content increased during the activation, reaching values of 79.0% and 11.4%, respectively. Essentially microporous materials with BET surface areas between 380 and 714 m²/g were obtained. The performance of the activated carbon in the adsorption of diuron in aqueous phase was studied within the 15–45°C temperature range. Equilibrium data showed that the maximum uptake increased with temperature from 120 to 470 µmol/g, also evidencing some dependence of the adsorption mechanism on temperature. Data were fitted to five isotherm models [Langmuir, Freundlich, Dubinin–Radushkevich, BET, and GAB (Guggenheim, Anderson, and de Boer)]. Kinetic data were analyzed using first- and second-order rate equations and intraparticle diffusion model. The second-order rate constant values obtained (2.8–13.5 × 10^?3 g/µmol min) showed that the hollow core morphology of the material favors the adsorption kinetics.     

Removal Of Residual Organics From Drinking Water By Ozonation And Activated Carbon Filtration: A Pilot Plant Study

The effects of ozonation, granular (GAC) and biological activated carbon (BAC) in the removal of natural organic matter and precursors of disinfection byproducts from drinking water were studied on pilot scale. Ozonation was determined to be the best method to reduce concentrations of the precursors of AOX, chloroform and mutagenicity, whereas BAC removed organic matter the most effectively. Reductions in TA100 mutagenicity were an average 40%, 4%, 26% in ozonated, GAC and BAC filtered water, respectively. Average reductions of AOX levels were similar at 48%, 7% and 35%, respectively. The chloroform formation potential always increased after GAC filtration.     

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.     

Formaldehyde Formation During Ozonation Of Drinking Water

Partial oxidation of natural organic material during ozonation produces oxygenated by-products of low molecular weight. Formaldehyde, being the most common oxygenated by-product of ozone, is considered to be a problematic compound by the water industry due to its potential adverse health effects. This research attempts to provide specific information on the effects of water quality parameters, specifically, pH and alkalinity, the structure of humic material, and the operational parameters, e.g., ozone dosage and contact time, on generation of formaldehyde. The results showed that ozonation caused almost an immediate formation of formaldehyde, which reached a peak value, and then started to decrease with continued ozonation. Ozonation of aqueous fulvic acid produced higher concentrations of formaldehyde compared to other types of humic material. Formaldehyde formation was suppressed by high bicarbonate levels, and enhanced at higher pH. Formaldehyde accumulation was more dramatic at low ozone dosages.     

Application of Perfluorooctylalumina in the Ozonated Decomposition of Humic Acids

The present study deals with the application of ozone with perfluorooctylalumina in humic acids decomposition. Ozonation with perfluorooctylalumina addition destroys the complex structures in humic acids into relatively simple ones and color removal based on ADMI (American Dye Manufacture Index) measurement was greater than 95% in all tests. The rate of humic acids decomposition was described by using a first-order rate expression with respect to the decrease of A₂₅₄. A central pH level (pH 7) and perfluorooctylalumina addition is helpful in humic acids decomposition. The modified-Nernst equation could be used to predict humic acids decomposition at varying reaction conditions.     

Effect of Catalytic Ozonation Coupling with Activated Carbon Adsorption on Organic Compounds Removal Treating RO Concentrate from Coal Gasification Wastewater

This paper reports a novel system of catalytic ozonation coupling with activated carbon adsorption for removing the organic compounds treating in the RO concentrate from coal gasification wastewater. The effect of ozone dosage, catalyst dosage, reaction time, influence pH, and temperature on organic compounds removal were examined for the processes. In the catalytic ozonation process, increasing solution pH, dosages ozone, and catalyst were statistically significant for improving the performance. In addition, the high salinity with chloride concentration of 15 g/L could reduce the catalyst specific surface area by 18%. Thus, high salinity showed negative influence on the catalytic effect in TOC removal. Regarding activated carbon adsorption process, modified activated carbon by NaOH revealed advantages in adsorbing organic compounds treating catalytic ozonation effluent. With the ozone dosage of 120 mg/L, catalyst dosage of 2.0 g/L, catalytic ozonation reaction time of 1 h, and modified activated carbon adsorption time of 1 h, the average TOC removal efficiencies were maintained at the stable level of 58% with the TOC concentration of 26 mg/L.     

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.     

Impact of Drinking Water Preozonation on Granular Activated Carbon Quality and Performance

A bench-scale laboratory system was set up to study the impact of residual ozone on the properties and performance of granular activated carbon (GAC). Simulating a carbon service life of two years, the study demonstrated that the effect of residual ozone was minimal and was the same as aerated or nitrogen-purged waters. Dissolved oxygen did modify the surface properties of GAC, with some impact on the adsorptive properties of exposed carbon. However, after thermal reactivation, the physical and adsorptive properties were comparable to reactivated virgin carbon.     

The Influence of Ozone,Oxygen and Chlorine on Biolocical Activity on Biological Activated Carbon

A laboratory study was conducted into the effects of the treatment of activated sludge effluent with different oxidants on the biodegradability of the organic substances. It was found that, under the experimental conditions described, ozone increased the biodegradability, whereas chlorine had no apparent significant effect. The effect of continuous oxidative pretreataent of activated sludge effluent on microbial populations and the biological activated carbon used subsequently in the process also was studied. It was found that ozone, particularly at a dosage of about 5 mg/L promoted biological activity, while chlorine and oxygen (in addition to the dissolved oxygen already in the effluent) had no significant effect on the biological population size.     

活性炭纤维在吸附领域的应用

活性炭纤维是一种新型高效吸附材料。本文阐述了活性炭纤维的结构与吸附性能间的关系，并介绍了它在吸附领域的应用。     

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.     

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.