Ozonation of an azo dye C.I. Remazol Black 5 and toxicological assessment of its oxidation products

The effect of ozonation (20.5 mgl(-1)) on the degradation processes of an azo dye, Remazol Black 5 (RB5; CI) was studied. Conventional parameters such as chemical oxygen demand (COD), total organic carbon (TOC), pH, conductivity, colour removal, biodegradability (BOD(5/28)), and toxic potential of the dye and its degradation products were monitored during the process. The results obtained indicated that ozonation is a highly effective way to remove the colour of a corresponding dye solution. However, a considerable organic load still remained as indicated by high COD and TOC residues. The COD, TOC reductions were about 40% and 25% for 6 h ozonation of 2 gl(-1) RB5 aqueous solution. During the ozonation process the rapid decrease of pH and the sharp increase of conductivity indicated the formation of acidic by-products and small fragments and ions which were identified by high performance ion chromatography. The BOD28 data revealed that first by-products after partial ozonation (10-150 min) of RB5 were more biodegradable than the parent compound and ozonation can enhance the biodegradability of azo dyes. During the first 150 min of total 360 min of oxidation, the formation of first by-products with high toxic potential took place as it could be confirmed by two acute toxicity-screening tests, the bioluminescence test (Vibrio fischerii) and the neutral red cytotoxicity assay (rat hepatoma cells). The significant enhancement of microbial biodegradability after long-term ozonation could also be seen as a decrease of toxic intermediates in correlation with the ozonation time as indicated in BOD28 biological degradation test results.     

Ozonation of hydrolyzed azo dye reactive yellow 84 (CI).

The combination of chemical and biological water treatment processes is a promising technique to reduce recalcitrant wastewater loads. The key to the efficiency of such a system is a better understanding of the mechanisms involved during the degradation processes. Ozonation has been applied to many fields in water and wastewater treatment. Especially for textile mill effluents ozonation can achieve high color removal, enhance biodegradability, destroy phenols and reduce the chemical oxygen demand (COD). However, little is known about the reaction intermediates and products formed during ozonation. This work deals with the degradation of hydrolyzed Reactive Yellow 84 (Color Index), a widely used azo dye in textile finishing processes with two monochlorotriazine anchor groups. Ozonation of the hydrolyzed dye in ultra pure water was performed in a laboratory scale cylindric batch reactor. Decolorization, determined by measuring the light absorbance at the maximum wavelength in the visible range (400 nm), was almost complete after 60 and 90 min with an ozone concentration of 18.5 and 9.1 mg/l, respectively. The TOC/TOC0 ratio after ozonation was about 30%, the COD was diminished to 50% of the initial value. The BOD5/COD ratio increased from 0.01 to about 0.8. Oxidation and cleavage of the azo group yield nitrate. Cleavage of the sulfonic acid groups of aromatic rings caused increases in the amount of sulfate. Formic acid and oxalic acid were identified as main oxidation products by high performance ion chromatography (HPIC). The concentrations of these major products were monitored at defined time intervals during ozonation.     

Advanced oxidation processes in azo dye wastewater treatment.

The chemical degradation of synthetic azo dyes color index (C.I.) Acid Orange 7, C.I. Direct Orange 39, and C.I. Mordant Yellow 10 has been studied by the following advanced oxidation processes: Fenton, Fenton-like, ozonation, peroxone without or with addition of solid particles, zeolites HY, and NH4ZSM5. Spectrophotometric (UV/visible light spectrum) and total organic carbon measurements were used for determination of process efficiency and reaction kinetics. The degradation rates are evaluated by determining their rate constants. The different hydroxyl radical generation processes were comparatively studied, and the most efficient experimental conditions for the degradation of organic azo dyes solutions were determined.     

Ozonation of Cationic Red X-GRL in aqueous solution: degradation and mechanism

Ozonation of the azo dye Cationic Red X-GRL was investigated in a bubble column reactor at varying operating parameters such as oxygen flow rate, temperature, initial Cationic Red X-GRL concentration, and pH. The conversion of dye increased with the increasing of pH and oxygen flow rate. As the reaction rate constant and the volumetric mass transfer coefficient increase while the ozone equilibrium concentration decreases with the temperature, there is a minimum conversion of dye at 25 degrees C. The increasing of initial dye concentration leads to a decreasing conversion of dye while the ozonation rate increases. The formation of intermediates and the variation of pH, TOC, and nitrate ion during ozonation were investigated by the use of some analytical instruments such as GC/MS, GC, and IC. The intermediates of weak organic acids lower the pH value of the solution. The probable degradation mechanism of the Cationic Red X-GRL in aqueous solution was deliberated with the aid of Molecular Orbital calculations. The N(12)-C(13) site in Cationic Red X-GRL, instead of the N(6)-N(7) site, is found to be the principal site for ozone cycloaddition in the degradation processes. During the degradation process, among the six nitrogen atoms of Cationic Red X-GRL, one is transferred into a nitrate ion, one is converted into an amine compound, and the remaining four are transformed into two molecules of nitrogen.     

Ozonation of azo dye in a semi-batch reactor: a determination of the molecular and radical contributions

Azo dye ozonation was carried in a semi-batch reactor to evaluate both the molecular and radical contributions of ozone on the dye decay. From two mass balance equations, the simultaneous determination of mass transfer, self-decomposition and solubility parameters of ozone were determinated; thus establishing the steady state conditions in the experimental system. The results of kinetic studies showed that the decay of azo dye was a pseudo-first-order reaction with respect to dye concentration and the overall rate constant increased with an increase in the pH, however declined with an increase in the dye concentration. Furthermore, from the overall rate constants obtained at various pH values a mathematical analysis of dye decay was performed, which provides a practical new method to quantify the radical and molecular contributions in the ozonation of azo dyes.     

Mechanism of decolorization and degradation of CI Direct Red 23 by ozonation combined with sonolysis

The decolorization and degradation of CI Direct Red 23, which is suspected to be carcinogenic, were investigated using ozonation combined with sonolysis. The results showed that the combination of ozonation and sonolysis was a highly effective way to remove color from waste water. The operational parameters, namely concentration of the dye, pH, ozone dose and ultrasonic density, were investigated during the process. The decolorization of the dye followed pseudo-first-order kinetics. Increasing the initial concentration of Direct Red 23 led to a decreasing rate constant. The optimum pH for the reaction was 8.0, and both lower and higher pH decreased the removal rate. The effect of the ozone dose on the dye decolorization was much greater than that of the sonolysis density. Intermediates such as naphthalene-2-sulfonic acid, 1-naphthol, urea and acetamide were detected by gas chromatography coupled with mass spectrometry in the absence of pH buffer, while nitrate and sulfate ions and formic, acetic and oxalic acids were detected by ion chromatography. A tentative degradation pathway was proposed without any further quantitative analyses. During the degradation, all nitrogen atoms and phenyl groups of Direct Red 23 were degraded into urea, nitrate ion, nitrogen and formic, acetic and oxalic acids, etc.     

Photo-Fenton-assisted ozonation of p-Coumaric acid in aqueous solution

The degradation of p-Coumaric acid present in olive oil mill wastewater was investigated as a pretreatment stage to obtain more easily biodegradable molecules, with lower toxicity that facilitates subsequent anaerobic digestion. Thus, photo-Fenton-assisted ozonation has been studied and compared with ozonation at alkaline pH and conventional single ultraviolet (UV) and acid ozonation treatments. In the combined process, the overall kinetic rate constant was split into various components: direct oxidation by UV light, direct oxidation by ozone and oxidation by hydroxyl radicals. Molecular and/or radical ozone reaction was studied by conducting the reaction in the presence and absence of tert-butylalcohol at pHs 2, 7 and 9. Ozone oxidation rate increases with pH or by the addition of Fenton reagent and/or UV radiation due to generation of hydroxyl radicals, *OH. Hydrogen peroxide and ferrous ion play a double role during oxidation since at low concentrations they act as initiators of hydroxyl radicals but at high concentrations they act as radical scavengers. Finally, the additional levels of degradation by formation of hydroxyl radicals have been quantified in comparison to the conventional single processes and an equation is proposed for the reaction rate as a function of studied operating variables.     

Decolorization and degradation of H-acid and other dyes using ferrous-hydrogen peroxide system

In this study, advanced oxidation process utilizing Fenton's reaction was investigated for the decolorization and degradation of two commercial dyes viz., Red M5B, Blue MR and H-acid, a dye intermediate used in chemical industries for the synthesis of direct, reactive and azo dyes. Effect of Fe2 +, H2O2, pH, and contact time on the degradation of the dyes was studied. Maximum color and COD removal was obtained for Red MSB, H-acid and Blue MR at 10-25 mg/l of Fe2+ dose and 400-500 mg/l of H2O2 dose at pH 3.0. The initial oxidation reaction was found to fit into first order rate kinetics and the rate of oxidation of H-acid was higher than the other dyes. Release of chloride and sulfate from the Fenton's treated Red M5B dye and sulfate from H-acid and Blue MR indicates that the dye degradation proceeds through cleavage of the substituent group.     

Enhanced biodegradation of azo dyes using an integrated elemental iron-activated sludge system: I. Evaluation of system performance.

The objective of this research is to evaluate an integrated system coupling zero-valent iron (Fe(0)) and aerobic biological oxidation for the treatment of azo dye wastewater. Zero-valent (elemental) iron can reduce the azo bond, cleaving dye molecules into products that are more amenable to aerobic biological treatment processes. Azo dye reduction products, including aniline and sulfanilic acid, were shown to be readily biodegradable at concentrations up to approximately 25 mg/L. Batch reduction and biodegradation data support the proposed integrated iron pretreatment and activated sludge process for the degradation of the azo dyes orange G and orange I. The integrated system was able to decolorize dye solutions and yield effluents with lower total organic carbon concentrations than control systems without iron pretreatment. The success of the bench-scale integrated system suggests that iron pretreatment may be a feasible approach to treat azo dye containing wastewaters.     

Enhanced ozonation of simulated dyestuff wastewater by microbubbles

The ozonation of synthetic wastewater containing azo dye, CI Reactive Black 5, was investigated using a microbubble generator and a conventional bubble contactor. The microbubble generator produced a milky and high intensity microbubble solution in which the bubbles had a mean diameter of less than 58 microm and a numerical density of more than 2.9 x 10(4) counts ml(-1) at a gas flow rate of less than 0.5 l min(-1). Compared with the bubble contactor, the total mass transfer coefficient was 1.8 times higher and the pseudo-first order rate constant was 3.2-3.6 times higher at the same initial dye concentration of 100 mg l(-1), 230 mg l(-1) and 530 mg l(-1) in the proposed microbubble system. The amount of total organic carbon removed per g of ozone consumed was about 1.3 times higher in the microbubble system than in the bubble contactor. The test using terephthalic acid as the chemical probe implied that more hydroxyl radicals were produced in the microbubble system, which contributed to the degradation of the dye molecules. The results suggested that in addition to the enhancement of mass transfer, microbubbles, which had higher inner pressure, could accelerate the formation of hydroxyl radicals and hence improve the oxidation of dye molecules.     

直接红染料的臭氧脱色与中间产物研究

以直接红B模拟染料废水为研究对象，考察了臭氧化过程中染料溶液的吸光度和TOC的变化，同时利用离子色谱仪和GC/MS对染料的降解过程进行了分析，最后用发光细菌法检测了染料溶液急性毒性的变化。结果表明，臭氧对染料的降解符合一级反应动力学，20 min时对染料的脱色率达到99.2%；反应40 min后TOC减少32.55%，染料分子有97.8%的S被氧化为SO^2-₄，偶氮键被臭氧化为N₂，分子中的仲胺基小部分转化成游离NH⁺₄和NO^-₃；在臭氧化过程前期新生成的醛类和酰胺类物质使溶液急性毒性迅速上升，25 min后溶液毒性开始逐渐下降。     

Formation of oxidation by-products of the iodinated X-ray contrast medium iomeprol during ozonation

The present work describes the investigation of the formation of oxidation by-products of the iodinated X-ray contrast medium (ICM) iomeprol during ozonation in water treatment. Bench-scale investigations revealed that ICM can be partly oxidized during ozonation processes, whereas the ionic diatrizoic acid showed the lowest reactivity. Iomeprol, as a representative of ICM, was not fully mineralized during ozonation. Thus, unknown oxidation by-products were formed. Aqueous solutions of iomeprol were treated by ozonation in order to assess the formation of oxidation by-products. The by-products were characterized by different liquid chromatography methods including detection of single-stage mass spectra, product ion mass spectra, and induced in-source fragmentation for analysis of iodine containing oxidation by-products. Aldehyde and carbonyl containing compounds were proposed to be among the stable by-products. A derivatization step confirms that the aldehyde and carbonyl moieties are major functional groups in oxidation by-products of iomeprol. Furthermore, oxidation by-products of iomeprol were detected at the outlet of an ozone reactor at a full-scale waterworks. However, the toxicological relevance of the by-products is a major future research tasks.     

Decolorization of mixtures of different reactive textile dyes by the white-rot basidiomycete Phanerochaete sordida and inhibitory effect of polyvinyl alcohol

We tried to decolorize mixtures of four reactive textile dyes, including azo and anthraquinone dyes, by a white-rot basidiomycete Phanerochaete sordida. P. sordida decolorized dye mixtures (200 mg l-1 each) by 90% within 48 h in nitrogen-limited glucose-ammonium media. Decolorization of dye mixtures needed Mn2+ and Tween 80 in the media. Manganese peroxidase (MnP) played a major role in dye decolorization by P. sordida. Decolorization of dye mixtures by P. sordida was partially inhibited by polyvinyl alcohol (PVA) that wastewaters from textile industries often contain. This was caused by an inhibitory effect of PVA on the decolorization of Reactive Red 120 (RR120) with MnP reaction system. Second addition of Tween 80 to the reaction mixtures in the presence of PVA improved the decolorization of RR120. These results suggest that PVA could interfere with lipid peroxidation or subsequent attack to the dye.     

Degradation of nitrogen containing organic compounds by combined photocatalysis and ozonation

The combination of TiO2-assisted photocatalysis and ozonation in the degradation of nitrogen-containing substrates such as alkylamines, alkanolamines, heterocyclic and aromatic N-compounds has been investigated. A laboratory set-up was designed and the influence of the structure of the N-compound, the TiO2 and ozone concentration on the formation of breakdown products were examined. The experimental results showed that a considerable increase in the degradation efficiency of the N-compounds is obtained by a combination of photocatalysis and ozonation as compared to either ozonation or photocatalysis only. The mineralization of the model substances was monitored by measurements of the TOC and ion-chromatographic determinations of the formed NO2- and NO3-. The temporal changes of concentrations of breakdown products, such as NH4+, short chain alkyl- and alkanolamines were determined by single column ion chromatography (SCIC) and as well as by electrospray mass spectrometry (EI-MS).     

Decomposition of phorate in aqueous solution by ozonation

Phorate (O,O-diethyl S-ethylthiomethyl phosphorodithioate) dissolved in aqueous solution was almost completely decomposed by ozonation to form various species within 10 minutes of reaction time for the experimental conditions examined in this research. The generation rate of sulfate was found to be fairly independent of solution pH value. However, the formation of phosphate and carbonate was more favorable for alkaline solutions where hydroxyl free radical is the primary oxidative species. The reaction rates increased with initial gaseous ozone concentrations, indicating the reaction was mass transfer-controlled within the experimental range of this research. Combining the analytical results by various instruments, including gas chromatograph equipped with an electron ionization detector (GC-EID), high performance liquid chromatography (HPLC), ion chromatography (IC), and total organic carbon (TOC), the temporal sequence of phorate ozonation was proposed in this study. The oxidation of sulfur atoms on the phosphorus-sulfur double bond or carbon-sulfur-carbon bond by ozonation was found to occur at first to form sulfate and various intermediates.     

Degradation of reactive dyes I. A comparative study of ozonation, enzymatic and photochemical processes

The environmental problems associated with textile activities are represented mainly by the extensive use of organic dyes. A great number of these compounds are recalcitrant and shown carcinogenic or mutagenic character. In this work three processes were studied for degradation of an anthraquinone dye (C.I. reactive blue-19). The ozonation process leads to complete decolorization with a very short reaction time; however, effective mineralization of the dye was not observed. The enzymatic process promotes quick decolorization of the dye; nevertheless, maximum decolorization degrees of about 30% are insignificant in relation to the decolorization degree achieved by the other processes. The best results were found for the photocatalytical process. The use of ZnO or TiO2 as photocatalysts, permits total decolorization and mineralization of the dye with reaction times of about 60 min.     

催化臭氧化降解技术中的两个问题

探讨了有机物特性及中间产物H₂O₂在催化臭氧化中的作用。结果表明，有机物在自由基链反应过程中的特性直接影响催化臭氧化的降解效率。当目标有机物是对链反应具有促进作用的甲酸时，自由基引发反应可以明显提高甲酸的臭氧化效率。当目标有机物是对自由基链反应具有抑制剂作用的乙酸时，O₃和Fe²⁺/O₃对乙酸有着相似的降解效率。以上结果表明，自由基引发反应并不是臭氧化降解效率提高的充分条件。另外，当臭氧化过程有H₂O₂产生时，必须考虑类Fenton反应对臭氧化效率的影响。     

Degradation of anthraquinone dye C.I. Reactive Blue 19 in aqueous solution by ozonation

This study investigated the degradation of anthraquinone reactive dye C.I. Reactive Blue 19 (RB-19) with initial concentration of 100 mg L⁻¹ in aqueous solution by ozone oxidation. The results of UV/VIS and FTIR spectra showed that the anthraquinone structures, nitrogen linkages and amino groups of RB-19 were destroyed under direct ozone reaction. The identification by LC–MS and GC–MS analyses indicated that some organic acids (e.g., phthalic acids) and 1,3-indanone could be the primary degradation products, respectively. The Microtox toxicity of the ozonated RB-19 solution initially increased but subsequently decreased when ozonation time increased. This detoxification accompanied biodegradability enhancement revealed by BOD/COD ratio increasing from 0.15 to 0.33 after 10 min of ozonation.     

Novel imazethapyr detoxification applying advanced oxidation processes

Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O?), and hydrogen peroxide tied to UV-irradiation (H?O?/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed. Ozonation joined to UV-irradiation (O?/UV), ozonation joined to titanium dioxide photo-catalysis (TiO?/UV+O?), sole photo-catalysis (TiO?/UV), and photo-catalysis reinforced with hydrogen peroxide-oxidation (TiO?/UV+H?O?) were characterized by a faster degradation and rapid formation of a lot of small molecules, which were quickly degraded to complete mineralization. The most effective oxidation methods were those using titanium dioxide photo-catalysis enhanced either by ozonation or hydrogen peroxide. Most of all, these last processes were useful to avoid the development of dangerous by-products.     

Mineralization of C.I. Reactive Yellow 84 in aqueous solution by sonolytic ozonation

The operational parameters and mechanism of mineralization of C.I. Reactive Yellow 84 (RY84), one of the azo dyes, in aqueous solution were investigated using sonolytic ozonation (US/O(3) oxidation). Of the pseudo-first-order degradation rate constants of TOC reduction, 9.0 x 10(-4), 7.3 x 10(-3) and 1.8 x 10(-2)min(-1) were observed with US, O3, and a combination of US and O3, respectively. These results illustrate that ozonation combined with sonolysis for removal of TOC is more efficient than ozonation alone or ultrasonic irradiation alone without considering the operating costs. With the initial pH value at 10.0, the ozone dose at 4.5 g h(-1), the energy density of ultrasound at 176 W l(-1), and the initial concentration of RY84 at 100 mg l(-1), the extent of mineralization measured as TOC loss was maximized. The variation of the concentrations of related ions (oxalate, formate, acetate, NO3(-), NO2(-), NH4(+), Cl(-), and SO4(2-)) during the reaction process was monitored. Other organic intermediates detected by GC/MS were N-methyleneaniline, phthalic acid, 4-hydroxyphthalic acid, isocyanatobenzene, aniline, 4-iminocyclohexa-2,5-dien-1-one, butene diacid and urea. Based on these findings, a tentative degradation pathway was proposed.