THE USE OF OZONATION TO REDUCE THE POTENTIAL FOR FORMING TRIHALOMETHANE COMPOUNDS IN CHLORINATING RESORCINOL, PHLOROGLUCINOL AND 1,3 CYCLOHEXANEDIONE

This study concerns the ozonation of Resorcinol, Phloroglucinol and 1,3 Cyclohexanedione in the presence of bromide ion in a bubble column, prior to chlorination. Preozonation in aqueous solutions reduces the potential for forming chlorinated trihalomethane compounds. At organic concentrations greater than 10^-4 M a short ozonation time increases the potential for forming trihalo compounds. At longer ozonation times the reverse is true. Finally the influence of mass transfer and chemical reaction on the ozone absorption rate have been evaluated following the film theory.     

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.     

Performance evaluation of ozonation and an ozone/hydrogen peroxide process toward development of a new sewage treatment process—Focusing on organic compounds and emerging contaminants

Performance of ozonation and an ozone/hydrogen peroxide process under a new concept centering on ozonation and/or ozone/hydrogen peroxide processes in sewage treatment processes comprising only physical and chemical processes are discussed, with focus on the removal of matrix organic compounds and emerging contaminants. Matrix organic compounds of filtrated primary sewage effluents were removed to as low as 3.2 mgC/L in the ozone/hydrogen peroxide process at an ozone consumption of around 400 mg/L. Linear relationships between ozone consumption and removal amounts of organic compounds were observed, in which the amounts of ozone required to remove 1 mg of organic carbon were 9.5 and 8.3 mg (2.4 and 2.1 mol-O₃/mol-C) in ozonation and the ozone/hydrogen peroxide process, respectively. Ratios of hydroxyl radical exposure to ozone exposure were in the order of 10^–9 to 10^–8 for ozonation and 10^–7 to 10^–6 for the ozone/hydrogen peroxide process. Experiments and a kinetic evaluation showed that ozonation and/or the ozone/hydrogen peroxide process have high elimination capability for emerging contaminants, even in primary sewage effluent with the thorough removal of matrix organic compounds. Newly found reaction phenomena, the temporal increase and decrease of dissolved ozone and accumulation of hydrogen peroxide in the early stage of oxidation with the continuous feeding of hydrogen peroxide, were presented. Possible reaction mechanisms are also discussed.     

Ozonation of estrone, estradiol, diethylstilbestrol in waters

The ozonation of three environmental endocrine disrupters (EDCs), estrone(E₁), estradiol(E₂), and diethylstilbestrol(DES), in aqueous solutions were investigated. Batch experiments were carried out to research the effect of initial EDCs concentrations, initial pH values and ozone dosages on the degradation efficiency. At pH 9.0, the degradation efficiency of estrone (E₁) reached to 94% after 8 min; diethylstilbestrol could be totally degraded after 6 min, and even estradiol was completely degraded after only 4 min. After 6 min for ozonation, the degradation efficiency of E₂ was nearly 48% with ozone dosage of 0.13 mg min^− 1. Compared with the ozone dosage of 0.38 mg min^− 1, E₂ entirely degraded after 6 min. Ozone dosage on degradation of E₁ was in a similar way. DES had analogous rule. At four different concentration solutions (5-20 mg L^− 1) of EDCs exposed to ozone, the higher the initial EDCs concentration, the lower EDCs degradation efficiency was obtained. During the ozonation process, the rapid decreasing of pH and the sharp increasing of electrical conductivity indicated the higher polarity by-products were produced during ozonation, which was confirmed by high performance liquid chromatography (HPLC) analysis. The results could provide some useful information for the potential treatment of EDCs by ozonation in waters.     

Combined biological–chemical (Ozone) treatment of wastewaters containing chloroguaiacols

Biological degradation of chloroguaiacols contained in sulphite pulp chlorine bleaching wastewater was studied in four parallel biological fluidised bed reactor systems—one single aerobic, one single anaerobic and two combined anaerobic–aerobic reactors. At low loading rates, trichloroguaiacols were removed nearly quantitatively. 4,5-Dichloroguaiacol was only partly removed. At high loading rates the anaerobic–aerobic recycle reactor removed individual guaiacols more than the other reactors. Only 4,5,6-trichloroguaiacol was removed best by the anaerobic–aerobic reactors in series. Even mixed culture biofilms adapted during several years of continuous operation did not satisfactorily remove these compounds. Synthetic wastewater, containing chlorinated guaiacols, treated with ozone produced formate and oxalate and quantitatively inorganic chloride. Combined ozonation–biotreatment in two reactors in series as well as in a recycle system allowed complete removal of all individual chlorinated guaiacols (< 1 μmol m^?3 remained). The efficiency of non-purgable organic carbon removal could be increased from ≤0.55 to about 4 mol carbon mol^?1 ozone by combination of ozonation with biotreatment. Simultaneously, the efficiency of removal of chlorinated guaiacols was increased by a factor of 10, which is essential for industrial application.     

Pyruvic Acid Removal from Water by the Simultaneous Action of Ozone and Activated Carbon

Activated carbon (AC) has been used to catalyze the ozonation of pyruvic acid in water. Pyruvic acid conversions were found to be 9 and 37% after 90 min of single ozonation and single adsorption with 40 gL^?1 AC, respectively, while 82% was reached at the same conditions during the AC catalytic ozonation. Also, for similar conditions, mineralization reached values of 67% in the AC catalytic ozonation against hardly 5% in the non-catalytic experiment. The process likely develops through both adsorption of ozone and pyruvic acid on the AC surface and generation of hydroxyl radicals that eventually is the responsible oxidizing species. Rate constants for both non-catalytic ozonation and AC-Ozone catalytic surface reaction, at 20°C and pH 7.5, were found to be 0.025 min^?1 and 87.9 Lg^?1s^?1, respectively. For AC concentrations higher than 2.5 gL^?1 gas-liquid mass transfer of ozone constituted the limiting step. At lower concentrations, internal diffusion plus surface reaction controlled the process rate.     

Cost analysis for the degradation of highly concentrated textile dye wastewater with chemical oxidation H2O2/UV and biological treatment

The efficiency and cost‐effectiveness of H₂O₂/UV for the complete decolorization and mineralization of wastewater containing high concentrations of the textile dye Reactive Black 5 was examined. Oxidation until decolorization removed 200–300 mg g^?1 of the dissolved organic carbon (DOC). The specific energy consumption was dependent on the initial dye concentration: the higher concentration required a lower specific energy input on a weight basis (160 W h g^?1 RB5 for 2.1 g L^?1 versus 354 W h g^?1 RB5 for 0.5 g L^?1). Biodegradable compounds were formed, so that DOC removal could be increased by 30% in a following biological stage. However, in order to attain 800 mg g^?1 overall mineralization, 500 mg g^?1 of the DOC had to be oxidized in the H₂O₂/UV stage. A cost analysis showed that although the capital costs are much less for a H₂O₂/UV stage compared to ozonation, the operating costs are almost double those of ozonation. Thus, while H₂O₂/UV can compete with ozonation when the treatment goal only requires decolorization, ozonation is more cost‐effective in this case when mineralization is desired. Copyright © 2006 Society of Chemical Industry     

Effect of stream segregation on ozonation for the removal of significant COD fractions from textile wastewater

Ozonation was tested on selected streams of cotton finishing textile plant wastewater for optimizing chemical oxygen demand (COD) removal. For this purpose, significant COD fractions in the wastewater were experimentally identified and the effect of ozone on these fractions was investigated. Ozonation experiments were performed with a 1 dm³ sample volume. Ozone treatment of batches of raw wastewater provided, at a rate of 62 mg min^?1 and a gas feeding time of 15 min, achieved complete colour removal but only 21% COD reduction. Increasing the feeding time to 30 min slightly increased the COD removal to 32%. At this feeding time, removal of the readily biodegradable COD was 60%, but soluble inert COD reduction remained at 16%, indicating selective preference of ozone for simpler compounds. At low concentrations, ozone was mainly influential on soluble COD compounds. Longer feeding times also affected particulate compounds, resulting in the solubilization of the COD fractions. Pre‐ozonation of the dye‐house wastewater, as a segregated stream, proved much more effective in the breakdown of refractory organic compounds, rendering the overall plant effluent more amenable to biological treatment. © 2002 Society of Chemical Industry     

Ozonation of sunflower oil: Spectroscopic monitoring of the degree of unsaturation

Consumption of ozone by unsaturated FA moieties of sunflower oil (SFO) was monitored by ¹H NMR and FTIR spectroscopy. Degradation of linoleate was found to be 1.5 and 1.8 times higher than oleate when SFO was ozonized in the absence and presence of water, respectively. Products of ozonation in both cases include aldehydes and ozonides with 1,2,4-trioxolane ring. Hydroxyl-containing compounds, which could be carboxylic acids and/or hydroperoxides, were also detected in samples ozonized in the presence of water. The extent of ozonation had very little effect on the aldehyde/ozonide ratio obtained from NMR spectra, especially in the ozonation of neast SFO. The aldehyde/ozonide ratios obtained regardless of the extent of ozonation were 10.5:89.5 and 46.6:53.4 for SFO ozonized in the absence and presence of water, respectively.     

Comparison Of Ozonation Kinetic Data From Film and Danckwerts Theories

Danckwerts and film theories have been compared through the aqueous ozonation kinetic study of three organics: crotonic, cinnamic and 0hydroxycinnamic acids. At the conditions investigated, these compounds are removed from water exclusively by direct reactions with ozone and the kinetic regime of ozone absorption corresponds to a fast second order irreversible reaction. In this regime, Danckwerts theory provides wider possibilities than film theory for the determination of the rate constant and individual liquid side mass transfer coefficients. The ozonation reactor was operated as an agitated cell to determine the rate constant and as an agitated tank to obtain the mass transfer coefficient. Rate constants were found to increase with increasing pH. At _pH 7 the ozone reactivity of these compounds was in the following increasing order: Cinnamic acid <? crotonic acid <? o‐hydroxycinnamic acid. At _pH 3 differences in reactivity were not significant.     

The pH Dependence and Effects of the Oxidative Products of Some Aromatic Compounds in Ozonation under Irradiation

Some aromatic compounds (o–nitrotoluene, p–nitrotoluene–2–sulfonic acid, and p–medthylaniline–3–sulfonic acid), were ozonized under UV irradiation separately, and the oxidative efficiencies of these reactions were studied. In order to ensure continued oxidation, it is advantageous to choose a proper pH value so as to fit the requirements of the chain reaction and also diminish the amound of HO. scavengers such as CO₃ ⁼ and HCO₃ ^? in oxidation Products. Removal of carbon dioxide could be effected by acidification of the reaction mixture. In order to decrease the inhibiting effect of the oxidation products, it is advisable to vary the pH value at different stages of UV ozonation. Many refractory organics usually encountered in industrial wastewater may resist degradative oxdation by ozonation alone, but can be destroyed rapidly by UV–radiation combined with ozonation.     

pH Effect on Ozonation of Ampicillin: Kinetic Study and Toxicity Assessment

Ampicillin (AP) is a penicillin-type antibiotic and one of the most widely used bacteriostatic antibiotics in human and veterinary medicine. A kinetic study was performed under different pH conditions (5, 7.2, and 9) to determine the degradation efficiency of AP by ozonation. The second-order rate constants for the direct reaction of AP with ozone were measured to be 2.2 ?5.4×10⁵ M^?1s^?1 under the pH conditions tested. The rate constants were greater at higher pH. The potential toxicity of the AP intermediates formed after ozonation under the various pH conditions were examined using a bioluminescence assay on Vibrio fischeri species. The biodegradability of the AP degraded products was also determined by measuring the BOD₅/COD of the ozonated samples under the different pH conditions. A lower biodegradability and acute toxicity was observed at the lowest pH (pH 5). These results suggest that higher pH conditions are needed for the removal of AP by ozonation in order to mitigate the residual toxicity that can remain even after complete removal of the parent compound by ozonation.     

Ozonation of the reactive dye intermediate 2‐naphthylamine 3,6,8‐trisulphonic acid (K‐Acid): kinetic assessment,ozonation products and ecotoxicity

Ozonation of the commercially important, recalcitrant reactive dye intermediate 2‐naphthylamine 3,6,8‐trisulphonic acid (K‐Acid) was investigated. Ozonation performance was examined by following ozone absorption rates and K‐Acid, chemical oxygen demand and total organic carbon removals. Mean oxidation states and unidentified organic products were also determined. At pH 3, where direct ozone reactions are dominant, the second‐order rate constant between K‐Acid and molecular ozone was determined as 20 m ^?1 s^?1 for steady‐state aqueous ozone concentration. The competition kinetics approach was also adopted where a reference compound, phenol, and K‐Acid were subjected to ozonation. By applying this method, the second‐order reaction rate constant was found to be 76 m ^?1 s^?1. Common oxidation products formed during ozonation at pH 3, pH 7 and pH 7 with 1 mm hydrogen peroxide were identified as methoxy‐phenyl‐oxime, phenol, benzene, benzaldehyde and oxalic acid via high‐performance liquid chromatography and gas chromatography/mass spectrometry analyses. Continuous nitrate and sulphate evolution were observed during K‐Acid ozonation as a consequence of the abrupt release and subsequent oxidation of its amino and sulphonate groups. The number and amount of reaction products were most intensive for K‐Acid ozonation at pH 7 with 1 mm hydrogen peroxide. According to the acute toxicity tests conducted with Vibrio fischeri, ozonation products were not less toxic than the original K‐Acid solution that caused only 15% inhibition.     

Are the Results of Ozonation of Model Compounds at High Concentrations Transferable to the Conditions of Drinking Water Treatment With Ozone?

Organic compounds of the different classes of substances (isobarbituric acid, citraconic acid and o-chlorophenol) were ozonized while varying their initial concentrations (c = 10^-3 to 10^-5 mol/L) at pH 7. In the case of isobarbituric acid at 10-3 mol/L, formyloxaluric acid, oxaluric acid, and formic acid were identified. At an initial concentration of 10^-3 mol/L, alloxanic acid and oxalic acid were formed in addition to oxaluric acid and formic acid. In both cases, the rates of elimination are similar.After ozonation of citraconic acid (c = 10^-5 mol/L, pH 7), the following oxidation products were identified: glyoxylic, acetic, formic, oxalic, pyruvic, and hydroxypyruvic acids.     

Mathematical Modeling and Simulation of Ozonation Processes in a Downstream Static Mixer with Sieve Plates

New standards for drinking water disinfection require better optimization of the ozonation stage on the basis of the concentration×contact time (CT) concept, and production of ozone from pure oxygen at higher concentrations presumes application of the new type of contactors operating efficiently at lower gas/liquid volumetric ratios. One possible construction to meet these requirements is a downstream static mixer with sieve plates. At higher flow rates of liquid in this mixer, the interfacial area may reach 10,000m²/m³ at energy dissipation 1–5kW/m³. Due to the very intensive hydrodynamic regime the ozone utilization degree in the gas phase reaches 98–100% in natural lake water ozonation. Mathematical simulation of lake water ozonation in this mixer indicated that the process proceeds mostly in the diffusion or kinetic regime depending on the operating parameters. The dominating parameters besides the sieve geometry are the liquid flow rate in the holes of the sieves and the volumetric liquid/gas ratio.     

Bromate control in phenol-contaminated water treated by UV and ozone processes

Formation of bromate is of a great concern whenever ozone-based technologies are used for treating highly bromide-containing water ever since bromate was classified as a potential carcinogen. Saudi Arabian groundwater is coincidentally high in bromide content, and the potential of forming bromate during the treatment of such water is high. This study investigated the extent of bromate formation under different treatment conditions of ozone-based Advanced Oxidation Processes (AOPs) when used for the treatment of phenol-contaminated water. The results of the study showed that continuous ozonation at a rate of 1 L/min has completely removed 50 ppm of phenol from contaminated water in less than 5 min. However, as high as 8.85 ppm of bromate (BrO₃⁻) was detected when treating the water which has high concentration of bromide ion (5 ppm). Results also showed that by adjusting the pH to 6 and adding ammonia (NH₃) at a dosage of 1.5 ppm, bromate formation was diminished drastically to non-detected levels.     

Systematic Analysis of the Biochemical Characteristics of Activated Sludge During Ozonation for Lowering of Biomass Production

Properties of activated sludge during ozonation were analyzed. The structure and surface characteristics altered with the increase of ozone dosage. At low ozone dosage, the floc structure was completely dismantled. Floc fragments reformed through reflocculation at an ozone dosage greater than 0.20 g O₃·g^?1 mixed liquor suspended solids (MLSS). Inactivation of microorganisms in the activated sludge mixture was caused by ozonation. Microbial growth decreased by up to 65% compared to the control. Simultaneously, 92.5% of nucleotide and 97.4% of protein in microbial cells of the sludge were released. Organic substance, nitrogen and phosphorus were released from the sludge during the ozonation process. The initial value of soluble chemical oxygen demand (SCOD) was 72 mg·L^?1. When the ozone dosage was 0.12 g O₃·g^?1 MLSS, the value of SCOD rapidly reached 925 mg·L^?1, increased by almost 12-fold. Simultaneously, 54.7% of MLSS was reduced. The composition of MLSS was changed, indicating that the inner water of cells and volatile organic substance decreased during the ozonation process.     

Evaluation Of Genotoxicity Of Bromate Ion Produced During Ozonation

Bromate ion formation during ozonation processes in water works is regarded as an issue of great interest because of its potential for carcinogenicity. In this research, genotoxicity of bromate ion was investigated by the umu-test using Salmonella typhimurium TA 1535/pSK1002. The time-course study showed that the umuC gene related to error-prone repair of damaged DNA was induced by bromate ion after 12 hours exposure of the test strain. However, a further study revealed that this induction was inactivated by metabolism with rat liver microsome when bromate ion concentration was less than 0.88 mg BrO₃ ^?/mg as protein of the S9 fraction. This inactivation was assumed to depend on -SH compounds in liver microsome.     

Kinetics Analysis on the Ozonation of MIB and Geosmin

The ozonation of 2-methylisoborneol (MIB) and geosmin was investigated in both pure and raw water. In a semi-batch reactor, a series of experiments was performed to determine the effect of pH on the ozonation of MIB and geosmin. The results show that pH has a significant effect on the ozonation of both compounds, which supports the theory that OH radical plays an important role on the destruction of MIB and geosmin. Compared with MIB, geosmin is more readily destroyed by ozonation. The ozonation kinetics follow approximately a first-order equation with respect to MIB and geosmin at the pH of 5, 7 and 9, and their rate orders of C_O3 at pH 7 are 0.44 and 0.61, respectively. Ozonation of organic matters in the water decreases the ozone concentration leading to a lower removal of MIB and geosmin; at the same time, the formation of OH radical initiated by the organic matters accelerates the ozonation of MIB and geosmin. The ozonation of MIB and geosmin spiked in raw water, settled water and pure water shows that background organics have no significant effect on the removal of MIB and geosmin; hence, the simplified rate equations acquired in pure water may have potential application in real water.     

CORRELATION OF THE ASYMMETRIC AND SYMMETRIC POO- FREQUENCIES WITH THE IONIC POTENTIAL OF THE METAL ION IN COMPOUNDS OF ORGANOPHOSPHORUS ACID EXTRACTANTS : A SHORT REVIEW*

ABSTRACT

The correlation between [(VASYM(POO^-) - VASYM (POO^-)], Av, and the ionic potential of the metal ion in metal compounds of alkylsubstituted diphosphonic acid extractants is reviewed. Similar correlations of the ionic potential of the metal ion with Δv in organosubstituted monophosphate, organosubstituted monophosphonate, carbonate and nitrate compounds have been previously demonstrated. In this paper, we discuss the origin, general validity, and utility of the correlation for organophosphorus compounds. Far-infrared and ⁵⁴Fe -labeled data were used to identify metal-oxygen stretching vibrations and establish that for some metal ions, e.g., Fe(III) and possibly Th(IV), the metal-oxygen interaction has substantial covalent character. The correlation appears to be valid not only for materials in which the metal-oxygen interaction is predominantly ionic, but also for compounds characterized by a covalent metal-oxygen bonding as well as for polymeric materials, providing the POO^- stretching vibrations are assignable. The