Degradation of 4-chlorophenol in aqueous solution by γ-radiation and ozone oxidation

The degradation of 4-chlorophenol (4-CP) by using gamma rays generated by a ⁶⁰Co source in the presence of O₃ was investigated. The radiolysis of 4-CP and the kinetics of 4-CP mineralization were analyzed based on the determination of total organic carbon (TOC). The influence of initial 4-CP concentration and the free radicals scavengers (such as NaHCO₃ and t-butanol) on the 4-CP degradation was also studied. The results showed that when the radiation rate was 336 Gy·min⁻¹, 4-chlorophenol at concentration of 10 mg·L⁻¹ could be completely degraded at the radiation dose of 2 kGy. The degradation of 4-chlorophenol could be described by a first-order reaction model, the rate constant of 4-CP degradation by combined ozonation and radiation was 0.1016 min⁻¹, which was 2.4 times higher than the sum of radiation (0.0294 min⁻¹) and ozonation (0.0137 min⁻¹). It revealed that the combination of radiation and ozonation resulted in synergistic effect, which can remarkably increase the degradation efficiency of 4-CP.     

Degradation of 4-Chlorophenol by High-Voltage Pulse Corona Discharges Combined with Ozone

Degradation of aqueous 250 mg/L 4-chlorophenol (4-CP) by high-voltage pulse corona discharges combined with ozone was investigated to gain insight into factors affecting enhancement of the combined system. High-voltage pulse corona discharges, ozonation, and a combination of the two were used to facilitate the degradation of aqueous 4-CP. Experimental results indicate that the treatment of 4-CP using a combination of high-voltage pulse corona discharges and ozonation within 30 min resulted in the almost degradation (96%) and a 51% reduction of the chemical oxygen demand (COD). This apparent synergistic effect may be attributed to the enhancement of ozone decomposition. The degradation of aqueous 4-CP by high-voltage pulse corona discharges combined with ozone was found to be affected by ozone concentration, substrate concentration, and interelectrode separations. The increase of ozone concentration leads to an increase of 4-CP conversion and COD removal. The conversion of 4-CP decreased with increase in 4-CP concentration and interelectrode separations.     

The Role of Sulphate and Phosphate Ions in the Recovery of Benzoic Acid Self-Enhanced Ozonation in Water Containing Bromides

The ozonation of aromatic compounds in low-pH water is ineffective. In an acidic environment, the decomposition of ozone into hydroxyl radicals is limited and insufficient for the degradation of organic pollutants. Radical processes are also strongly inhibited by halogen ions present in the reaction medium, especially at low pH. It was shown that even under such unfavorable conditions, some compounds can initiate radical chain reactions leading to the formation of hydroxyl radicals, thus accelerating the ozonation process, which is referred to as so-called “self-enhanced ozonation”. This paper presents the effect of bromides on “self-enhanced ozonation” of benzoic acid (BA) at pH 2.5. It is the first report to fully and quantitatively describe this process. The presence of only 15 µM bromides in water inhibits ozone decomposition and completely blocks BA degradation. However, the effectiveness of this process can be regained by ozonation in the presence of phosphates or sulphate. The addition of these inorganic salts to the bromide-containing solution helps to recover ozone decomposition and BA degradation efficiency. As part of this research, the fractions of hydroxyl, sulphate and phosphate radicals reacting with benzoic acid and bromides were calculated.     

Antioxidant,antimicrobial, and tyrosinase inhibition activities of acetone extract of <Emphasis Type="Italic">Ascophyllum nodosum</Emphasis>

The search for new antioxidants of natural origin derived from plants and seaweeds is still very important at present. In our study, the acetone extract of A. nodosum was investigated for its potential use as a natural antioxidant, natural feed additive with antibacterial activity and as a tyrosinase inhibitor. This study could be useful in the context of improved utilization of the A. nodosum extract in the food and cosmetics industry, being not only economically advantageous but also environmentally friendly. Extracts showed antioxidant activity with application of different methodologies: 1,1-diphenyl-2-picrilhydracil DPPH· radicals scavenging (39 %, 4 mg of freeze-dried sample), β-carotene-linoleic acid antioxidant assay (11 %, 4 mg of freeze-dried sample), O₂· radicals scavenging activity (IC₅₀ 0.43 mg mL⁻¹), OH· radicals scavenging activity (IC₅₀ 1.55 mg mL⁻¹), and iron chelation ability (IC₅₀ 0.56 mg mL⁻¹). The extract showed considerable antibacterial activity being more effective against gram-positive bacteria (Micrococcus luteus, Staphylococcus aureus) than against gram-negative bacteria (Escherichia coli, Enterococcus aerogenes). Results of tyrosinase assay for the acetone extract of Ascophyllum nodosum presented 65.6 % inhibition of tyrosinase activity at the IC₅₀ value of 0.1 mg mL⁻¹. The outcomes of our study support potential utilization of this brown seaweed as a source of natural antioxidants. Antioxidant activity of the studied seaweed can be apparently explained by the free radicals scavenging activity, particularly related to the mechanisms of O₂⁻· radicals scavenging activity, OH· radicals inactivation, and iron chelation ability.     

Enhanced degradation of 2,4-dinitrotoluene by ozonation in the presence of manganese(II) and oxalic acid

Manganese catalytic ozonation of 2,4-dinitrotoluene (DNT) in the presence of oxalic acid was studied. The addition of manganese ion (Mn²⁺) or oxalic acid alone in ozonation process did not enhance DNT degradation, but the addition of Mn²⁺ coupled with oxalic acid accelerated degradation of DNT. The DNT degradation efficiency was influenced by carbonate in the catalytic ozonation process. Kinetics study showed that Mn²⁺ catalytic ozonation significantly promoted the decomposition of ozone. Experimental results of electron spin resonance (ESR) demonstrated that addition of Mn²⁺ and oxalic acid produced much hydroxyl radicals in catalytic ozonation system than that in single ozonation system. These results suggested that catalytic ozonation followed hydroxyl radical-type mechanism. Mn²⁺ promoted decomposition of ozone to produce hydroxyl radical and it was oxidized into manganese oxide. Manganese oxide was reduced into Mn²⁺ by oxalic acid, which is the key step of catalytic process. Based on above results, a cycle catalytic mechanism of Mn²⁺ was proposed. Intermediates were determined by HPLC and GC–MS, and they mainly included aromatic organics and aliphatic carboxylic acids.     

Behavior of two different constituents of natural organic matter in the removal of sodium dodecylbenzenesulfonate by O3 and O3-based advanced oxidation processes

The objective of this study was to analyze the role played by two components of natural organic matter (NOM), gallic acid (GAL) and humic acid (HUM), in the removal of the surfactant sodium dodecylbenzenesulfonate (SDBS) from waters by O(3)-based oxidation processes, i.e., O(3)/H(2)O(2), O(3)/granular activated carbon (GAC), and O(3)/powdered activated carbon (PAC). It was found that the presence of low concentrations of these compounds (1 mg/L) during SDBS ozonation increases both the ozone decomposition rate and the rate of SDBS removal from the medium. Because of the low reactivity of SDBS with ozone, these effects are mainly due to an increase in the transformation rate of ozone into HO(*) radicals. Results obtained demonstrate that the presence of GAL and HUM during SDBS ozonation increases the concentration of O(2)(-*) radicals in the medium, confirming that GAL and HUM act as initiating agents of ozone transformation into HO(*). It was also found that this effect was smaller with a larger molecular size of the acid. Presence of GAL and HUM during SDBS removal by O(3)/H(2)O(2), O(3)/GAC, and O(3)/PAC systems also increases the SDBS degradation rate, confirming the role of these compounds as initiators of ozone transformation into HO(*) radicals.     

Ozone generation on the lead dioxide electrodes in a sulfuric acid solution at potentials of 2 to 3 V

The electrochemical synthesis of ozone is studied on lead dioxide electrodes in sulfuric acid solutions. The two maximums of the current efficiency for ozone (CEO) observed at 2–3.5 V are largely due to the participation of various chemisorbed particles in the ozone synthesis. In the vicinity of the first CEO maximum at lead dioxide, ozone forms only in a discharge of water molecules with the participation of adsorbed oxygen-containing radicals. In the potential range of the second maximum, the adsorbed anion radicals, e.g., ·HSO₄ and ·SO₄, also take part in the reaction of ozone generation. At the electrode not subjected to anodic polarization, CEO is considerably higher than that on the preliminarily polarized electrode. On the basis of the experimental data, schemes for the ozone evolution at PbO₂ in sulfuric acid at 2 to 3 V are proposed.     

A pathway of free radical generation via copper corrosion and its application to oxygen and ozone activation for the oxidative destruction of organic pollutants

This study investigated the commercially available zero-valent copper powder and copper foil to activate molecular oxygen (O₂) and ozone for the degradation of organic pollutants. Under aerobic atmospheric conditions, copper powder effectively removed 50 mg/L of acetaminophen (ACT) within 2 h, though the degradation rate using the foil was less than 20% of the powder. However, copper foil activated ozone to effectively degrade ACT. The total organic carbon (TOC) removal reached a high of 58.3% at a catalyst concentration of 40 g/L, but only 26.8% with ozone alone. The initial solution pH and dosage of copper foil were key operational parameters affecting the ozone activation process. H₂O₂ and Cu(I) were important intermediates in the process as hydroxyl radicals (^·OH) were identified via EPR (electron paramagnetic resonance) experiments and free radical scavengers. The generation of ^·OH was attributed to a Fenton-like reaction between Cu(I) and H₂O₂; this free-radical generation mechanism differs from typical transition metal oxide catalysts. This study outlines a promising approach to significantly increase the generation of ^·OH and effectively remove refractory organic compounds. Furthermore, these copper products are applied in structural components of practical water treatment. Thus, the study of corrosion resistance to oxygen and ozone in aqueous solution have both a practical and theoretical significance. It was determined that copper products were resistant to oxygen corrosion in aqueous solution, but not resistant to ozone corrosion.     

Species transformation and structure variation of fulvic acid during ozonation

The species transformation and structure variation of fulvic acid (FA) during ozonation were investi- gated in this study. The molecular weight (MW) distribution, the species of intermediate products and the variation of polar functional groups were studied by ultrafiltration, gas chromatography/mass spectrometry (GC/MS) and titration analyses respectively. The average MW of FA decreased signifi- cantly during ozonation. The amount of polar functional groups (carboxylic and phenolic (ph-OH) groups) per unit DOC (mol/kg C) increased with increasing ozonation time. Furthermore, GC/MS ex- periments demonstrated the formation of polar species (e.g., hexadecanoic acid, benzoic acid and oc- tadecanoic alcohol) and less-polar species (e.g., aliphatic hydrocarbons and butanedioic acid, bis(2-methylpropyl) ester). Electron spin resonance (ESR) measurements proved the presence of ·OH radicals in the ozonation system. Based on our experimental results, it appears that the oxidations by ozone molecule and ·OH radicals were responsible for the transformation of organics (FA and its oxi- dation products) during ozonation. These two oxidants showed significant influence on organics transformation and exhibited different mechanisms contributing to these processes.     

The kinetics and mechanism of oxidation of isopropanol with the hydrogen peroxide-vanadate ion-pyrazine-2-carboxylic acid system

The vanadate anion in the presence of pyrazine-2-carboxylic acid (PCA) was found to effectively catalyze the oxidation of isopropanol to acetone with hydrogen peroxide. The electronic spectra of solutions and the kinetics of oxidation were studied. The conclusion was drawn that the rate-determining stage of the reaction was the decomposition of the vanadium(V) diperoxo complex with PCA, and the particle that induced the oxidation of isopropanol was the hydroxyl radical. Supposedly, the HO^· radical detached a hydrogen atom from isopropanol, and the Me₂ C^· (OH) radical formed reacted with HOO^· to produce acetone and hydrogen peroxide. The electronic spectra of solutions in isopropanol and acetonitrile and the dependences of the initial rates of isopropanol oxidation without a solvent and cyclohexane oxidation in acetonitrile on the initial concentration of hydrogen peroxide were compared. The conclusion was drawn that hydroxyl radicals appeared in the oxidation of alkanes in acetonitrile in the decomposition of the vanadium diperoxo complex rather than the monoperoxo derivative, as was suggested by us earlier.     

4-氯酚稀水溶液的脉冲辐解研究

利用脉冲电子束进行了多种条件下4－氯酚稀水溶液的脉冲辐解研究,对其瞬态光谱中的主要吸收峰作了归属,并初步考察了这些瞬态物种的生长、衰减等行为,研究表明,·OH基与4－氯酚在碱性条件下反应生成氯代酚氧基,速率常数为4.14×10^9L/(mol·s),在酸性条件下要经过OH-adducts;H原子与4-氯酚反应生成H-adducts的速率常为2.0×10^9L/(mol·s),产物可通过双分子二级反应逐步脱氯;eaq^-可直接从4-氯酚分子夺氯,反应速率常数为1.82×10^9/L(mol·s)。     

Hydroxylamine Reactions with Peroxide Products of Alkenes Ozonolysis

Reactions were studied of peroxide ozonolysis products obtained from linear and cyclic alkenes with hydroxylamine prepared in situ from NH₂OH·HCl by hydrogen chloride neutralization with sodium acetate. A one-pot reactions sequence was performed: alkene oxidation with ozone → reduction to a carbonyl compound with hydroxylamine → condensation of the carbonyl compound with hydroxylamine providing a possibility of direct transformation of alkenes in keto- and aldoximes excluding the stage of preparation and isolation of the carbonyl compound.     

Submerged Arc Breakdown of Methylene Blue in Aqueous Solutions

Low voltage, low energy submerged pulsed arcs between a pair of carbon or iron electrodes with a pulse repetition rate of 100?Hz, energies of 2.6?C192?mJ and durations of 20, 50 and 100???s were used to remove methylene blue (MB) contamination from 30?ml aqueous solutions. The MB concentration decreased exponentially with rates of 0.0006?C0.0143?s^?1 during processing with the carbon electrode pair. With the iron electrodes, the MB concentration initially decreased faster (0.030?s^?1) than with the carbon electrodes, but later saturated. However when microparticles produced with the iron electrodes were periodically filtered, the high removal rate was maintained. Under these conditions, the volume of water which can be treated per unit energy expenditure was much higher with the submerged arc than with other plasma processes. A kinetic model based on MB degradation by OH· radicals formed by the discharge was formulated. The higher initial MB removal rate with iron electrodes is explained by additional OH· production from Fenton??s reaction between Fe⁺⁺ and H₂O₂ produced by the discharge. This rate is maintained if the eroded iron particles are filtered, but if eroded iron particles accumulate, degradation slows down and stops, possibly because the iron particles catalytically decompose H₂O₂ and hence stops Fenton??s reaction, and either directly or via increased Fe⁺⁺ dissolved from the particles, scavenge the OH· radicals.     

Water-soluble cobalt complexes with 1-hydroxyethylydenediphosphonic acid and 2-aminoethanol

The reaction of an aqueous suspension of basic cobalt carbonate CoCO₃·4Co(OH)₂·3H₂O with equimolar amount or two-fold excess of 1-hydroxyethylydenediphosphonic acid (H₄L) has yielded crystalline CoH₂L and amorphous Co(H₃L)₂ products, respectively. The interaction of poorly soluble CoH₂L complex with 2-aminoethanol has resulted in the formation of amorphous water-soluble CoH₂L·H₂NCH₂CH₂OH·6Н₂О complex; the latter loses 5 water molecules at heating and is converted into CoH₂L·H₂NCH₂CH₂OH·Н₂О. The study of agrochemical effects of Co(H₃L)₂ and CoH₂L·H₂NCH₂CH₂OH·6Н₂О has revealed their advantage over the conventional salt form (cobalt sulfate) reflected in the reduced phytotoxicity of the element. The prepared compound containing 2-aminoethanol (solubility promotor) has revealed better performance.     

Oxidation of 4-Nitrotoluene by Ozone in Acetic Anhydride in the Presence of Manganese Sulfate

The reaction of 4-nitrotoluene oxidation with ozone in acetic anhydride in the presence of MnSO₄and sulfuric acid was studied. The main reaction product is 4-nitrobenzyl acetate, the yield of which is 63.2%. Based on an analysis of the experimental data, a mechanism of the catalytic ozonation of 4-nitrotoluene in acetic anhydride was proposed.     

CoAl_2O_4/蜂窝陶瓷催化剂的制备及其催化臭氧化性能

采用涂覆法制备了CoAl_2O_4/蜂窝陶瓷催化剂。利用X射线衍射、N_2吸附-脱附和透射电镜等方法对所制备的催化剂进行了表征,并分析了其催化臭氧化降解对苯二酚的效能。结果表明,CoAl_2O_4/蜂窝陶瓷的晶相属于典型的尖晶石结构,具有较大的比表面积、孔容和孔径,分别达到77 m~2·g~(-1)、0.001 7 cm~3·g~(-1)和3.9 nm。CoAl_2O_4/蜂窝陶瓷催化臭氧化对苯二酚的去除率高达81.2%,COD去除率可达47.7%。在叔丁醇存在的条件下,对苯二酚的去除率显著下降,说明CoAl_2O_4/蜂窝陶瓷催化臭氧化遵循羟基自由基机理。     

CoAl2O4/蜂窝陶瓷催化剂的制备及其催化臭氧化性能

采用涂覆法制备了CoAl₂O₄/蜂窝陶瓷催化剂。利用X射线衍射、N₂吸附-脱附和透射电镜等方法对所制备的催化剂进行了表征,并分析了其催化臭氧化降解对苯二酚的效能。结果表明,CoAl₂O₄/蜂窝陶瓷的晶相属于典型的尖晶石结构,具有较大的比表面积、孔容和孔径,分别达到77 m²·g^-1、0.001 7 cm³·g^-1和3.9 nm。CoAl₂O₄/蜂窝陶瓷催化臭氧化对苯二酚的去除率高达81.2%,COD去除率可达47.7%。在叔丁醇存在的条件下,对苯二酚的去除率显著下降,说明CoAl₂O₄/蜂窝陶瓷催化臭氧化遵循羟基自由基机理。     

An HPLC assay of hydroxyl radicals by the hydroxylation reaction of terephthalic acid

An HPLC assay for hydroxyl radicals is described. The hydroxyl radical was trapped by terephthalic acid (non-fluorescent), and 2-hydroxyl terephthalic acid (fluorescent) was quantitated by HPLC-fluorescence detection. At a terephthalic acid concentration of 4.25 mmol/L, the hydroxyl radical formed in the Fenton reaction was successfully assayed in the concentration range of hydrogen peroxide of 2.5-50 micro mol/L, where the concentration of Fe(II) was 50 micro mol/L. The fluorescence of 2-hydroxy terephthalate was stable at 24 h, and its detection limit by this method was 5 nmol/L (100 fmol).     

Analysis of p-chlorobenzoic acid in water by liquid chromatography-tandem mass spectrometry

para-Chlorobenzoic acid (p-CBA) is typically used as a probe compound to indirectly quantify hydroxyl radicals formed during advanced oxidation processes used in drinking water and wastewater treatment. A method has been developed for the sensitive analysis of p-CBA in water using liquid chromatography-tandem mass spectrometry (LC-MS/MS). A reporting limit in water of 100 ng/L was determined for the method, which is 40-fold lower than the 4.0 microg/L reporting limit of the widely used liquid chromatography with UV detection (LC-UV) method. The method was found to be robust in difficult matrices such as wastewater and highly selective, unlike LC-UV which relies on non-specific detection at 234 nm. The detection of p-CBA below 1 microg/L during bench-scale ozonation of wastewater after hydrogen peroxide addition was demonstrated. Duplicate samples were analyzed by LC-MS/MS and LC-UV and results were found to be comparable at concentrations quantifiable by both methods.     

Fe-Mn-Cu-Ce/Al2O3 as an efficient catalyst for catalytic ozonation of bio-treated coking wastewater: Characteristics,efficiency, and mechanism

It is important to develop a catalyst that has high catalytic activity and can improve the degradation efficiency of refractory organic pollutants in the catalytic ozonation process. In this study, Fe-Mn-Cu-Ce/Al₂O₃ was synthesised via impregnation calcination for catalytic ozonation of bio-treated coking wastewater. The physical and chemical characteristics of the catalysts were analysed using X-ray diffraction (XRD), X-ray fluorescence spectrometry (XRF), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and Brunauer–Emmett–Teller nitrogen adsorption–desorption methods. The effects of catalyst dosage, pH, and reflux ratio on the degradation efficiency of wastewater were examined in laboratory-scale experiments. The chemical oxygen demand (COD) removal rate of bio-treated coking wastewater was estimated to be 52.76 % under optimal conditions. The experiments on the catalytic mechanism demonstrated that the surface hydroxyl formed by the Lewis acid sites on the surface of the catalyst can react with ozone as the active site forming the active oxygen (·OH, ·O₂^–, and ¹O₂), thereby efficiently degrading the organic pollutants in coking wastewater. Furthermore, a pilot-scale experiment on the catalytic ozonation of bio-treated coking wastewater was carried out using an Fe-Mn-Cu-Ce/Al₂O₃ catalyst, while the effects of the initial pollutant concentration, ozone concentration, and gas flow on the COD removal rate were studied on a pilot scale. It was found that the COD removal rate of the wastewater was ～ 60 % under optimal parameters. After the treatment, the wastewater steadily reached the coking wastewater discharge standard (COD < 80 mg/L), while the operating cost of catalytic ozonation reached ～ 0.032$/m³, thereby paving the way toward economic engineering applications. The COD degradation kinetics in the bio-treated coking wastewater followed pseudo-second-order kinetics. Three-dimensional fluorescence and gas chromatography–mass spectrometry revealed that macromolecular organic pollutants in the bio-treated coking wastewater were greatly degraded. In summary, Fe-Mn-Cu-Ce/Al₂O₃ exhibited good reusability, high catalytic activity, and low cost and has a wide application prospect in the treatment of coking wastewater.