Application of Fenton, photo-Fenton, solar photo-Fenton, and UV/H2O2 to degradation of the antineoplastic agent mitoxantrone and toxicological evaluation

In the present study, selected advanced oxidation processes (AOPs)—namely, photo-Fenton (with Fe²⁺, Fe³⁺, and potassium ferrioxalate—FeOx—as iron sources), solar photo-Fenton, Fenton, and UV/H₂O₂—were investigated for degradation of the antineoplastic drug mitoxantrone (MTX), frequently used to treat metastatic breast cancer, skin cancer, and acute leukemia. The results showed that photo-Fenton processes employing Fe(III) and FeOx and the UV/H₂O₂ process were most efficient for mineralizing MTX, with 77, 82, and 90 % of total organic carbon removal, respectively. MTX probably forms a complex with Fe(III), as demonstrated by voltammetric and spectrophotometric measurements. Spectrophotometric titrations suggested that the complex has a 2:1 Fe³⁺:MTX stoichiometric ratio and a complexation constant (K) of 1.47 × 10⁴ M^–1, indicating high MTX affinity for Fe³⁺. Complexation partially inhibits the involvement of iron ions and hence the degradation of MTX during photo-Fenton. The UV/H₂O₂ process is usually slower than the photo-Fenton process, but, in this study, the UV/H₂O₂ process proved to be more efficient due to complexing of MTX with Fe(III). The drug exhibited no cytotoxicity against NIH/3T3 mouse embryonic fibroblast cells when oxidized by UV/H₂O₂ or by UV/H₂O₂/FeOx at the concentrations tested.     

Degradation of ethylenethiourea pesticide metabolite from water by photocatalytic processes

In this study, photocatalytic (photo-Fenton and H₂O₂/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H₂O₂). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H₂O₂]₀ = 400 mg L^?1. The photo-Fenton process mineralized 70% of the ETU with [H₂O₂]₀ = 800 mg L^?1 and [Fe²⁺] = 400 mg L^?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H₂O₂ from 800 mg L^?1 to 1200 mg L^?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H₂O₂ and photo-Fenton processes were determined to be 6.2 × 10^?4 mg L^?1 min^?1 and 7.7 × 10^?4 mg L^?1 min^?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.     

Stability of 6:2 fluorotelomer sulfonate in advanced oxidation processes: degradation kinetics and pathway

Perfluorooctane sulfonate (PFOS), a widely used mist suppressant in hard chrome electroplating industry, has been listed in the Stockholm Convention for global ban. 6:2 Fluorotelomer sulfonate (6:2 FTS) acid and salts have been adopted as alternative products in the market, but no data about their abiotic degradation has been reported. In the present study, the degradability of 6:2 FTS potassium salt (6:2 FTS-K) was evaluated under various advanced oxidation processes, including ultraviolet (UV) irradiation, UV with hydrogen peroxide (H₂O₂), alkaline ozonation (O₃, pH = 11), peroxone (O₃/H₂O₂), and Fenton reagent oxidation (Fe²⁺/H₂O₂). UV/H₂O₂ was found to be the most effective approach, where the degradation of 6:2 FTS-K followed the pseudo-first-order kinetics. The intermediates were mainly shorter chain perfluoroalkyl carboxylic acid (C₇ to C₂), while sulfate (SO₄ ^2?) and fluoride (F^?) were found to be the final products. The high yields of SO₄ ^2? and F^? indicate that 6:2 FTS-K can be nearly completely desulfonated and defluorinated under UV/H₂O₂ condition. The degradation should firstly begin with the substitution of hydrogen atom by hydroxyl radicals, followed by desulfonation, carboxylation, and sequential “flake off” of CF₂ unit. Compared with PFOS which is inert in most advanced oxidation processes, 6:2 FTS-K is more degradable as the alternative.     

Degradation of bisphenol A by the UV/H2O2 process: a kinetic study

A theoretical and experimental study of bisphenol A (BPA) degradation by the UV/H₂O₂ process in water is presented. The effects of the H₂O₂ concentration and the specific rate of photon emission (E_P,0) on BPA degradation were investigated. A kinetic model derived from a reaction sequence was employed to predict BPA and hydrogen peroxide concentrations over time using an annular photochemical reactor in batch recirculation mode. The local volumetric rate of photon absorption (LVRPA) inside the photoreactor was computed using a Line Source with Parallel Plane emission model (LSPP). From the proposed kinetic model and the experimental data, the second order rate constants of the reactions between hydroxyl radicals and the main reacting species (H₂O₂ and BPA) were estimated applying a nonlinear regression method. A good agreement between the kinetic model and experimental data, for a wide range of operating conditions, was obtained. For BPA, H₂O₂, and TOC concentrations, the calculated root means square errors (RMSE) were 2.3?×?10^??2, 9.8?×?10^??1, and 9.0?×?10^??2 mmol L^??1, respectively. The simplified kinetic model presented in this work can be directly applied to scaling-up and reactor design, since the estimated kinetic constants are independent of the reactor size, shape, and configuration. Further experiments were made by employing low BPA initial concentration (100 μg L^??1) in water and real wastewater. A lower degradation rate of BPA was observed in the real wastewater, although the UV/H₂O₂ process has also been able to completely degrade the target pollutant in less than 1 h.

     

The use of artificial neural network (ANN) for the prediction and simulation of oil degradation in wastewater by AOP

The application of advanced oxidation process (AOP) in the treatment of wastewater contaminated with oil was investigated in this study. The AOP investigated is the homogeneous photo-Fenton (UV/H₂O₂/Fe⁺²) process. The reaction is influenced by the input concentration of hydrogen peroxide H₂O₂, amount of the iron catalyst Fe⁺², pH, temperature, irradiation time, and concentration of oil in the wastewater. The removal efficiency for the used system at the optimal operational parameters (H₂O₂?=?400 mg/L, Fe⁺²?=?40 mg/L, pH?=?3, irradiation time?=?150 min, and temperature?=?30 °C) for 1,000 mg/L oil load was found to be 72 %. The study examined the implementation of artificial neural network (ANN) for the prediction and simulation of oil degradation in aqueous solution by photo-Fenton process. The multilayered feed-forward networks were trained by using a backpropagation algorithm; a three-layer network with 22 neurons in the hidden layer gave optimal results. The results show that the ANN model can predict the experimental results with high correlation coefficient (R ²?=?0.9949). The sensitivity analysis showed that all studied variables (H₂O₂, Fe⁺², pH, irradiation time, temperature, and oil concentration) have strong effect on the oil degradation. The pH was found to be the most influential parameter with relative importance of 20.6 %.     

Electro-oxidation of the dye azure B: kinetics,mechanism, and by-products

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (^?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ^?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?10⁹ M^?1 s^?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.     

Degradation kinetics of anthracene by ozone on mineral oxides

To further understand the role of substrates on the heterogeneous reactions of polycyclic aromatic hydrocarbons, the reactions of ozone with anthracene adsorbed on different mineral oxides (SiO₂, α-Al₂O₃ and α-Fe₂O₃) and on Teflon disc were investigated in dark at 20 °C. No reaction between ozone and anthracene on Teflon disc was observed when the ozone concentration was ～1.18 × 10¹⁴ molecules cm^?3. The reactions on mineral oxides exhibited pseudo-first-order kinetics for anthracene loss, and the pseudo-first-order rate constant (k_1,obs) displayed a Langmuir–Hinshelwood dependence on the gas-phase ozone concentration. The adsorption equilibrium constants for ozone (K_O3) on SiO₂-1, SiO₂-2, α-Al₂O₃ and α-Fe₂O₃ were (0.81 ± 0.26) × 10^?15 cm³, (2.83 ± 1.17) × 10^?15 cm³, (2.48 ± 0.77) × 10^?15 cm³ and (1.66 ± 0.45) × 10^?15 cm³, respectively; and the maximum pseudo-first-order rate constant (k_1,max) on these oxides were (0.385 ± 0.058) s^?1, (0.101 ± 0.0138) s^?1, (0.0676 ± 0.0086) s^?1 and (0.0457 ± 0.004) s^?1, respectively. Anthraquinone was identified as the main surface product of anthracene reacted with ozone. Comparison with previous research and the results obtained in this study suggest that the reactivity of anthracene with ozone and the lifetimes of anthracene adsorbed on mineral dust in the atmosphere are determined by the nature of the substrate.     

Role of some organic inhibitors on the oxidation of dissolved sulfur dioxide by oxygen in rainwater medium

In August 2012, eight rainwater samples were collected and analyzed for pH and metal ions, viz., iron, copper, and manganese. The pH was within the range 6.84–7.65. The rate of oxidation of dissolved sulfur dioxide was determined using these rainwater samples as reaction medium. Kinetics was defined by the rate law: ?d[S(IV)]/dt = R _o = k _o[S(IV)]], where k _o is the first-order rate constant and R _o is the rate of the reaction. The effect of two volatile organic compounds—ethanol and 2-butanol—was examined and found to inhibit the oxidation as defined by the rate law: k _obs = k _o/(1 + B [Inh]), where k _obs is the first-order rate constant in the presence of the inhibitor, [Inh] is the concentration of the inhibitor, and B is the inhibitor parameter—an empirical constant. In the pH range of collected rainwater samples, the values of first-order rate constants ranged from 3.1?×?10^?5 to 1.5?×?10^?4 s^?1 at 25 °C. The values of inhibition parameter were found to be (5.99?±?3.91?×?10⁴) (ethanol) and (3.95?±?2.36)?×?10⁴ (2-butanol) at 25 °C.     

Photocatalytic mineralization of glyphosate in a small-scale plug flow simulation reactor by UV/TiO2

The present work involves the photocatalytic mineralization of glyphosate on a plug flow reactor by UV/TiO₂. The effect of catalyst loading shows an optimal value (0.4 g L^?1) which is necessary to mineralize glyphosate. The kinetic rate of glyphosate mineralization decreases with the increasing initial concentration of glyphosate, and the data can be described using the first-order model. An alkaline environment is conducive to glyphosate mineralization. The mineralization efficiency increases with elevated flow rate to 114 mL min^?1, which is followed by a decrease with a further increase in flow rate due to the reduction of the residence time. The presence of external oxidants (K₂S₂O₈, H₂O₂ and KBrO₃) and photosencitizer (humic acid) can significantly enhance glyphosate mineralization. Photocatalysis oxidation ability of the three studied oxidants decrease in the order of: S₂O₈ ^2? > BrO₃ ^? > H₂O₂. Finally, the Langmuir–Hinshelwood (L-H) model was used to rationalize the mechanisms of reactions occurring on TiO₂ surfaces and L-H model constants were also determined.     

Kinetics of the gas-phase reactions of alkylnaphthalenes with O3, N2O5 and OH radicals at 298 ± 2 K

Rate constants for the gas-phase reactions of the OH radical with 1-methylnaphthalene and of N₂O₅ with 1- and 2-methylnaphthalene and 2,3-dimethylnaphthalene have been determined at 298 ± 2 K by use of relative rate techniques. The rate constants determined were: for the reaction of OH radicals with 1-methylnaphthalene, (5.30 ± 0.48) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹; for the reaction of N₂O₅ with 1-methylnaphthalene, 2-methylnaphthalene and 2,3-dimethylnaphthalene, (3.3 ± 0.7) × 10⁻¹⁷, (4.2 ± 0.9) × 10⁻¹⁷ and (5.7 ± 1.9) × 10⁻¹⁷ cm³ molecule⁻¹ s⁻¹, respectively. In addition, an upper limit to the rate constant of 1.3 × 10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ was measured for the reaction of O₃ with 1-methylnaphthalene at 298 ± 2 K. These data, when combined with data from previous literature, allow the atmospheric gas-phase removal processes of these alkylnaphthalenes to be quantified.     

Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River,São Paulo,Brazil)

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO^●), singlet oxygen (¹O₂), and triplet excited states of chromophoric dissolved organic matter (³CDOM^*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23?±?0.07)?×?10^–2 and (7.99?±?1.61)?×?10^–3 mol Einstein^?1, respectively. In contrast, reactions with HO^● radicals and ³CDOM* dominate their degradation, with ¹O₂ exhibiting rates three to five orders of magnitude lower. The values of k_IMD,HO● and k_AMT,HO● were (3.51?±?0.06)?×?10⁹ and (4.97?±?0.37)?×?10⁹ L mol^?1 s^?1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with k_IMD,3AQ2S*?=?(1.02?±?0.08)?×?10⁹ L mol^?1 s^?1 and k_IMD,3CBBP*?=?(3.17?±?0.14)?×?10⁸ L mol^?1 s^?1; on the contrary, the values found for AMT are close, k_AMT,3AQ2S*?=?(8.13?±?0.35)?×?10⁸ L mol^?1 s^?1 and k_AMT,3CBBP*?=?(7.75?±?0.80)?×?10⁸ L mol^?1 s^?1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO₃^?, NO₂^?, CO₃^2?, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.

     

Electrooxidation of industrial wastewater containing 1,4-dioxane in the presence of different salts

The treatment of 1,4-dioxane solution by electrochemical oxidation on boron-doped diamond was studied using a central composite design and the response surface methodology to investigate the use of SO₄ ^2? and HCO₃ ^? as supporting electrolytes considering the applied electric current, initial chemical oxygen demand (COD) value, and treatment time. Two industrial effluents containing bicarbonate alkalinity, one just carrying 1,4-dioxane (S1), and another one including 1,4-dioxane and 2-methyl-1,3-dioxolane (S2), were treated under optimized conditions and subsequently subjected to biodegradability assays with a Pseudomonas putida culture. Electrooxidation was compared with ozone oxidation (O₃) and its combination with hydrogen peroxide (O₃/H₂O₂). Regarding the experimental design, the optimal compromise for maximum COD removal at minimum energy consumption was shown at the maximum tested concentrations of SO₄ ^2? and HCO₃ ^? (41.6 and 32.8 mEq L^?1, respectively) and the maximum selected initial COD (750 mg L^?1), applying a current density of 11.9 mA cm^?2 for 3.8 h. Up to 98 % of the COD was removed in the electrooxidation treatment of S1 effluent using 114 kWh per kg of removed COD and about 91 % of the COD from S2 wastewater applying 49 kWh per kg of removed COD. The optimal biodegradability enhancement was achieved after 1 h of electrooxidation treatment. In comparison with O₃ and O₃/H₂O₂ alternatives, electrochemical oxidation achieved the fastest degradation rate per oxidant consumption unit, and it also resulted to be the most economical treatment in terms of energy consumption and price per unit of removed COD.     

Effect of ethylenediamine-N,N′-disuccinic acid on Fenton and photo-Fenton processes using goethite as an iron source: optimization of parameters for bisphenol A degradation

The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H₂O₂ decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H₂O₂ concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical (^?OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of ^?OH. The presence of EDDS decreases the reactivity of goethite toward H₂O₂ because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H₂O₂ and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O ₂ ^?? to generate Fe(II) species from Fe(III) reduction. Low concentrations of H₂O₂ (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.     

Fenton-like degradation of nalidixic acid with Fe3+/H2O2

The Fenton-like degradation of nalidixic acid was studied in this work. The effects of Fe³⁺ concentration and initial H₂O₂ concentration were investigated. Increasing the initial H₂O₂ concentration enhances the degradation and mineralization efficiency for nalidixic acid, while Fe³⁺ shows an optimal concentration of 0.25 mM. A complete removal of nalidixic acid and a TOC removal of 28 % were achieved in 60 min under a reaction condition of [Fe³⁺]?=?0.25 mM, [H₂O₂]?=?10 mM, T?=?35 °C, and pH?=?3. LC–MS analysis technique was used to analyze the possible degradation intermediates. The degradation pathways of nalidixic acid were proposed according to the identified intermediates and the electron density distribution of nalidixic acid. The Fenton-like degradation reaction of nalidixic acid mainly begins with the electrophilic attack of hydroxyl radical towards the C₃ position which results in the ring-opening reaction; meanwhile, hydroxyl radical attacking to the branched alkyl groups of nalidixic acid leads to the oxidation at the branched alkyl groups.     

Remediation of acid mine drainage (AMD)-contaminated soil by Phragmites australis and rhizosphere bacteria

Experiments were conducted to assess the impact of citric acid (CA) and rhizosphere bacteria on metal uptake in Phragmites australis cultured in a spiked acid mine drainage (AMD) soil. Rhizosphere iron-oxidizing bacteria (Fe(II)OB) enhanced the formation of Fe plaque on roots, which decreased the uptake of Fe and Mn. CA inhibited the growth of Fe(II)OB, decreased the formation of metal plaque, raised the metal mobility in soil, and increased the accumulation of metals in all tissues of the reeds. The higher the CA dosage, the more metals accumulated into reeds. The total amount of metals in reeds increased from 7.8?±?0.5?×?10^?6 mol plant^?1 (Mn), 1.4?±?0.1?×?10^?3 mol plant^?1 (Fe), and 1.0?±?0.1?×?10^?4 mol plant^?1 (Al) in spiked soil without CA to 22.2?±?0.5?×?10^?6 mol plant^?1 (Mn), 3.5?±?0.06?×?10^?3 mol plant^?1 (Fe), and 5.0?±?0.2?×?10^?4 mol plant^?1 (Al) in soil added with 33.616 g C₆H₈O₇·H₂O for per kilogram soil. CA could be effective at enhancing the phytoremediation of metals from AMD-contaminated soil.     

Kinetics of the oxidation of hydrogen sulfite by hydrogen peroxide in aqueous solution:: ionic strength effects and temperature dependence

Conductometry was used to study the kinetics of the oxidation of hydrogen sulfite, HSO⁻₃, by hydrogen peroxide in aqueous non-buffered solution at the low concentration level of 10⁻⁵–10⁻⁶ M, typically found in cloud water. The kinetic data confirm that the rate law reported for the pH range 3–6 at higher concentration levels, rate=k_H·[H⁺]·[HSO⁻₃]·[H₂O₂], is valid at the low concentration level and at low ionic strength I_c. At 298 K and I_c=1.5×10⁻⁴ M, third-order rate constant k_H was found to be k_H=(9.1±0.5)×10⁷ M⁻² s⁻¹. The temperature dependence of k_H led to an activation energy of E_a=29.7±0.9 kJ mol⁻¹. The effect of the ionic strength (adjusted with NaCl) on rate constant k_H was studied in the range I_c=2×10⁻⁴–5.0 M at pH=4.5–5.2 by conductometry and stopped-flow spectrophotometry. The dependence of k_H on I_c can be described with a semi-empirical relationship, which is useful for the purpose of comparison and extrapolation. The kinetic data obtained are critically compared with those reported earlier.     

4种高级氧化法处理高浓度正丙醇废水的动力学比较

研究了1%和10%(V/V)模拟正丙醇废水在UV/TiO2体系、UV/H2O2体系、Fe2+/H2O2体系和UV/TiO2/Fe2+/H2O2体系等4种工艺条件下的降解动力学过程,对比了降解动力学特点及工艺参数对动力学常数的影响,优化工艺参数。结果表明,UV/TiO2体系和Fe2+/H2O2体系的降解过程可分为零级反应阶段和一级反应阶段,转折点分别在反应开始后2 h和氧化剂浓度为6.7 g/L,UV/H2O2体系和UV/TiO2/Fe2+/H2O2体系分别符合零级反应和一级反应规律;相同工艺参数条件下,6 h反应后,组合工艺UV/TiO2/Fe2+/H2O2体系在处理效率达85%,比前3个体系分别高52.0%、8.3%和32.0%,与UV/TiO2体系和Fe2+/H2O2体系的处理效率之和持平,其协同效应提高了速率常数,在目标物浓度降低时依然可维持较高降解速率。而目标物浓度提高10倍后,UV能量利用率提高35.5倍,氧化剂用量是Fe2+/H2O2体系的1/7.1。     

Efficient removal of insecticide “imidacloprid” from water by electrochemical advanced oxidation processes

The oxidative degradation of imidacloprid (ICP) has been carried out by electrochemical advanced oxidation processes (EAOPs), anodic oxidation, and electro-Fenton, in which hydroxyl radicals are generated electrocatalytically. Carbon-felt cathode and platinum or boron-doped diamond (BDD) anodes were used in electrolysis cell. To determine optimum operating conditions, the effects of applied current and catalyst concentration were investigated. The decay of ICP during the oxidative degradation was well fitted to pseudo-first-order reaction kinetics and absolute rate constant of the oxidation of ICP by hydroxyl radicals was found to be k _abs(ICP)?=?1.23?×?10⁹ L mol^?1 s^?1. The results showed that both anodic oxidation and electro-Fenton process with BDD anode exhibited high mineralization efficiency reaching 91 and 94 % total organic carbon (TOC) removal at 2 h, respectively. For Pt-EF process, mineralization efficiency was also obtained as 71 %. The degradation products of ICP were identified and a plausible general oxidation mechanism was proposed. Some of the main reaction intermediates such as 6-chloronicotinic acid, 6-chloronicotinaldehyde, and 6-hydroxynicotinic acid were determined by GC-MS analysis. Before complete mineralization, formic, acetic, oxalic, and glyoxylic acids were identified as end-products. The initial chlorine and organic nitrogen present in ICP were found to be converted to inorganic anions Cl^?, NO₃ ^?, and NH₄ ⁺.     

Kinetic studies of O3 reactions with 3-bromopropene and 3-iodopropene in the temperature range 288–328 K

The kinetics of the reactions of O₃ with 3-bromopropene and 3-iodopropene has been studied over the temperature range of 288–328 K at atmospheric pressure. The results obtained for the room temperature rate constants are (1.88 ± 0.22) × 10^?18 and (3.52 ± 0.43) × 10^?18 cm³ molecule^?1 s^?1, and the proposed Arrhenius expressions are k = (3.47 ± 1.28) × 10^?15 exp[(?2233 ± 110)/T] and k = (8.17 ± 2.12) × 10^?14 exp[(?2991 ± 80)/T] cm³ molecule^?1 s^?1 for 3-bromopropene and 3-iodopropene, respectively. The atmospheric chemical lifetimes of these two compounds with O₃ were also estimated from these values.