Decomposition of phenylarsonic acid by AOP processes: degradation rate constants and by-products

The paper presents results of the studies photodegradation, photooxidation, and oxidation of phenylarsonic acid (PAA) in aquatic solution. The water solutions, which consist of 2.7 g dm^?3 phenylarsonic acid, were subjected to advance oxidation process (AOP) in UV, UV/H₂O₂, UV/O₃, H₂O₂, and O₃ systems under two pH conditions. Kinetic rate constants and half-life of phenylarsonic acid decomposition reaction are presented. The results from the study indicate that at pH 2 and 7, PAA degradation processes takes place in accordance with the pseudo first order kinetic reaction. The highest rate constants (10.45?×?10^?3 and 20.12?×?10^?3) and degradation efficiencies at pH 2 and 7 were obtained at UV/O₃ processes. In solution, after processes, benzene, phenol, acetophenone, o-hydroxybiphenyl, p-hydroxybiphenyl, benzoic acid, benzaldehyde, and biphenyl were identified.     

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.     

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.     

Performance evaluation of the UV/H2O2 process on selected nitrogenous organic compounds: reductions of organic contents vs. corresponding C-, N-DBPs formations

The presence of various organic contaminants in water sources is of concern due to their direct threats to human health and potential to react with disinfectants to form carcinogenic byproducts including trihalomethanes, haloacetic acids and nitrosamines in finished water. This study applied both medium-pressure and low-pressure ultraviolet light coupled with hydrogen peroxide (UV/H₂O₂) to evaluate its efficacy for degradation of selected nitrogenous organic compounds and corresponding disinfection byproduct (DBP) formation. Six organic compounds were chosen as target precursors based on their nitrogen contents and molecular structures. The results showed that higher oxidation capacity resulted in better reduction of organic matters and DBP formation potentials (DBPFPs). However, insufficient contact time and oxidant doses could lead to a rise of DBPFPs in the early stages of UV/H₂O₂ reactions. A greater percentage removal was achieved for organic carbon than organic nitrogen after UV/H₂O₂ treatment, especially for compounds with complicated structure such as diltiazem. During the UV/H₂O₂ treatment, the intermediate products include tertiary amine, dimethyl amine (DMA) or DMA-like structures, which are N-nitrosodimethylamine (NDMA) precursors after chlorination or chloramination. Furthermore, it was observed that using dissolved organic nitrogen and DMA to predict NDMAFP could lead to biased conclusions because of the complex nature of nitrogenous matters in aqueous environments.     

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。     

Photochemical degradation of ciprofloxacin in UV and UV/H2O2 process: kinetics, parameters, and products

Photochemical degradation of fluoroquinolone ciprofloxacin (CIP) in water by UV and UV/H₂O₂ were investigated. The degradation rate of CIP was affected by pH, H₂O₂ dosage, as well as the presence of other inorganic components. The optimized pH value and H₂O₂ concentration were 7.0 and 5 mM. Carbonate and nitrate both impeded CIP degradation. According to liquid chromatography–tandem mass spectrometry analysis, four and 16 products were identified in UV and UV/H₂O₂ system, respectively. Proposed degradation pathways suggest that reactions including the piperazinyl substituent, quinolone moiety, and cyclopropyl group lead to the photochemical degradation of CIP. Toxicity of products assessed by Vibrio qinghaiensis demonstrated that UV/H₂O₂ process was more capable on controlling the toxicity of intermediates in CIP degradation than UV process.     

Photooxidative removal of the herbicide Acid Blue 9 in the presence of hydrogen peroxide: modeling of the reaction for evaluation of electrical energy per order (EEO)

The present work deals with photooxidative removal of the herbicide, Acid Blue 9 (AB9), in water in the presence of hydrogen peroxide (H₂O₂) under UV light illumination (30 W). The influence of the basic operational parameters such as amount of H₂O₂, irradiation time and initial concentration of AB9 on the photodegradation efficiency of the herbicide was investigated. The degradation rate of AB9 was not appreciably high when the photolysis was carried out in the absence of H₂O₂ and it was negligible in the absence of UV light. The photooxidative removal of the herbicide was found to follow pseudo-first-order kinetic, and hence the figure-of-merit electrical energy per order (E_Eo) was considered appropriate for estimating the electrical energy efficiency. A mathematical relation between the apparent reaction rate constant and H₂O₂ used was applied for prediction of the electricity consumption in the photooxidative removal of AB9. The results indicated that this kinetic model, based on the initial rates of degradation, provided good prediction of the E_Eo values for a variety of conditions. The results also indicated that the UV/H₂O₂ process was appropriate as the effective treatment method for removal of AB9 from the contaminated wastewater.     

Determination of direct photolysis rate constants and OH radical reactivity of representative odour compounds in brewery broth using a continuous flow-stirred photoreactor

A method based on photolysis was developed for the appropriate treatment of organic pollutants in air exhausting from breweries upon wort decoction, and thereby causing smell nuisance. A continuous flow stirred photoreactor was built-up exclusively, allowing OH radicals to react with selected odorous compounds contained in exhaust vapours, such as: 2-methylpropanal, 3-methylbutanal, 2-methylbutanal, 3-methyl-1-butanol, n-hexanal, 2-methylbutyl isobutyrate, 2-undecanone, phenyl acetaldehyde, myrcene, limonene, linalool, humulene, dimethylsulphide, and dimethyltrisulphide. These substances were quantified in brewery broth before and after UV irradiation using high-resolution gas chromatography–mass spectrometry (HRGC–MS). For odour analysis, high-resolution gas chromatography-flame ionisation detection (HRGC-FID) coupled with sensory methods was used. Determined quantum yields of about 10⁻³ for phenyl acetaldehyde, myrcene, and humulene pointed out that direct photolysis contributed to their decay. Quantum yields of below 10⁻⁴ for the other substances indicated that UV irradiation did not contribute significantly to their degradation processes. Hydroxyl radical reaction rate constants and Henry constants of organic compounds were also measured. Substances accompanied with low Henry constants converted rapidly, whereas those with higher ones, relatively slowly. Determined aroma values concluded that after UV–H₂O₂ treatment, only dimethylsulphide and myrcene remained as important odorous compounds, but in significantly reduced concentrations. The UV–H₂O₂ treatment of brewery broth has been proved effective to reduce smell-irritating substances formed upon wort decoction.     

Photochemical degradation of atrazine in UV and UV/H2O2 process: pathways and toxic effects of products

The degradation of atrazine in aqueous solution by UV or UV/H₂O₂ processes, and the toxic effects of the degradation products were explored. The mineralization of atrazine was not observed in the UV irradiation process, resulting in the production of hydroxyatrazine (OIET) as the final product. In the UV/H₂O₂ process, the final product was ammeline (OAAT), which was obtained by two different pathways of reaction: dechlorination followed by hydroxylation, and the de-alkylation of atrazine. The by-products of the reaction of dechlorination followed by hydroxylation were OIET and hydroxydeethyl atrazine (OIAT), and those of de-alkylation were deisopropyl atrazine (CEAT), deethyl atrazine (CIAT), and deethyldeisopropyl atrazine (CAAT). OIAT and OAAT appeared to be quite stable in the degradation of atrazine by the UV/H₂O₂ process. In a toxicity test using Daphnia magna, the acute toxic unit (TUa) was less than 1 of TUa (100/EC₅₀, %) in the UV/H₂O₂ process after 30 min of reaction time, while 1.2 to 1.3 of TUa was observed in the UV process. The TUa values of atrazine and the degradation products have the following decreasing order: OIET> Atrazine> CEAT≈CIAT> CAAT. OIAT and OAAT did not show any toxic effects.     

Degradation of diethyl phthalate (DEP) by vacuum ultraviolet process: influencing factors,oxidation products,and toxicity assessment

The vacuum ultraviolet (VUV) process, which can directly produce hydroxyl radical from water, is considered to be a promising oxidation process in degrading contaminants of emerging concern, because of no need for extra reagents. In this study, the influencing factors and mechanism for degradation of diethyl phthalate (DEP) by the VUV process were investigated. The effects of irradiation intensity, inorganic anions, natural organic matter (NOM), and H₂O₂ dosage on the performance of VUV process were evaluated. The results showed that DEP could be more efficiently degraded by the VUV process compared with ultraviolet (UV)-254-nm irradiation. The presence of HCO₃^?, NO₃^? and NOM in the aqueous solutions inhibited the degradation of DEP to a different degree, mainly by competing hydroxyl radicals (HO^?) with DEP. Degradation rate and removal efficiency of DEP by VUV process significantly enhanced with the addition of H₂O₂, while excess H₂O₂ dosage could inhibit the DEP degradation. Moreover, based on the identified seven oxidation byproducts and their time-dependent evolution profiles, a possible pathway for DEP degradation during the VUV process was proposed. Finally, the ecotoxicity of DEP and its oxidation byproducts reduced overall according to the calculated results from Ecological Structure Activity Relationships (ECOSAR) program. The electrical energy per order (EE/O) was also assessed to analysis the energy cost of the DEP degradation in the VUV process. Our work showed the VUV process could be an alternative and environmental friendly technology for removing contaminants in water.

     

Transformation of sulfaquinoxaline by chlorine and UV light in water: kinetics and by-product identification

Sulfaquinoxaline (SQX) is an antimicrobial of the sulfonamide class, frequently detected at low levels in drinking and surface water as organic micropollutant. The main goal of the present study is the evaluation of SQX reactivity during chlorination and UV irradiations which are two processes mainly used in water treatment plants. The SQX transformation by chlorination and UV lights (254 nm) was investigated in purified water at common conditions used for water disinfection (pH =?7.2, temperature =?25 °C, [chlorine] =?3 mg L^?1). The result shows a slow degradation of SQX during photolysis compared with chlorination process. Kinetic studies that fitted a fluence-based first-order kinetic model were used to determine the kinetic constants of SQX degradation; they were equal to 0.7?×?10^?4 and 0.7?×?10^?2 s^?1corresponding to the half time lives of 162 and 1.64 min during photolysis and chlorination, respectively. In the second step, seven by-products were generated during a chlorination and photo-transformation of SQX and identified using liquid chromatography with electrospray ionization and tandem mass spectrometry (MS-MS). SO₂ extrusion and direct decomposition were the common degradation pathway during photolysis and chlorination. Hydroxylation and isomerization were observed during photodegradation only while electrophilic substitution was observed during chlorination process.     

Fog Chemistry at an Urban Midwestern Site

This work investigates the oxidative aging of preformed secondary organic aerosol (SOA) derived from α-pinene ozonolysis (～100 ppb_v hydrocarbon [HC_x] with excess of O₃) within the University of California–Riverside Center for Environmental Research and Technology environmental chamber that occurs after introduction of additional hydroxyl (OH) and nitrate (NO₃) radicals. Simultaneous measurements of SOA volume concentration, hygroscopicity, particle density, and elemental chemical composition (C:O:H) reveal increased particle wall-loss-corrected SOA formation (1.5%, 7.5%, and 15.1%), increase in oxygen-to-carbon ratio (O/C; 15.6%, 8.7%, and 8.7%), and hydrophilicity (4.2%, 7.4%, and 1.4%) after addition of NO (ultraviolet [UV] on), H₂O₂ (UV on), and N₂O₅ (dark), respectively. The processing observed as an increase in O/C and hydrophilicity is attributed to OH and NO₃ reactions with first-generation vapor products and UV photolysis. The rate of increase in O/C appears to be only sufficient to achieve semivolatile oxygenated organic aerosol (SV-OOA) on a day time scale even at the raised chamber radical concentrations. The additional processing with UV irradiation without addition of NO, H₂O₂, or N₂O₅ is observed, adding 5.5% wall-loss-corrected volume. The photolysis-only processing is attributed to additional OH generated from photolysis of the nitrous acid (HONO) offgasing from chamber walls. This finding indicates that OH and NO₃ radicals can further alter the chemical composition of SOA from α-pinene ozonolysis, which is proved to consist of first-generation products.

Implications: Secondary organic aerosol (SOA) may undergo aging processes once formed in the atmosphere, thereby altering the physicochemical and toxic properties of aerosol. This study discusses SOA aging of a major biogenic volatile organic compound (VOC; α-pinene) after it initially forms SOA. Aging of the α-pinene ozonolysis system by OH (through NO or H₂O₂ injection), NO₃ (through N₂O₅ injection), and photolysis is observed. Although the reaction rate appears to be only sufficient to achieve semivolatile oxygenated organic aerosol (SV-OOA) level of oxygenation on a 1-day scale, it is important that SOA aging be considered in ambient air quality models. Aging in this study is attributed to further oxidation of gas-phase oxidation products of α-pinene ozonolysis.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air &; Waste Management Association for information on the referenced α-pinene ozonolysis reaction and chamber reactor temperature.     

Removal of AOX, total nitrogen and chlorinated lignin from bleached Kraft mill effluents by UV oxidation in the presence of hydrogen peroxide utilizing TiO2 as photocatalyst

Background, aim, and scope  The pulp and paper industry is the sixth largest polluter discharging a variety of gaseous, liquid, and solid wastes into the environment. Effluents from bleached Kraft mill effluents (BKME) are polluting waters to a great extent These effluents cause considerable damage to the receiving waters if discharged untreated since they have high levels of biological oxygen demand (BOD), chemical oxygen demand (COD), chlorinated compounds (measured as AOX), suspended solids (mainly fibers), fatty acids, tannins, resin acids, lignin and its derivatives, sulfur and sulfur compounds, etc. This study aimed to remove adsorbed organic halogen (AOX), total nitrogen, and lignin-degrading products in the wastewater (4,500 m³/h) from the paper mill in the pulp and paper industry, which is discharged to sea from a plant located in western Turkey. Materials and methods  The photocatalytic degradation of AOX, total nitrogen, and chlorinated lignin in BKME have been investigated in different parameters, such as time, H₂O₂ and TiO₂ concentration. In addition, for investigating the effect of chlorine on the removal of lignin, pure lignin solution was prepared in equal amounts to chlorinated lignin degradation products found in BKME. The same experiments were conducted for this solution. Experiments were carried out in photocatalytic reactor made of Pyrex glass. The mercury lamp was used as a radiation source. All irradiation was carried out under constant stirring. The existence of dissolved O₂ is an important factor which increases the photocatalytic degradation. Hence, we used an air pump for the aeration of the wastewater solutions. The temperature of the wastewater was controlled and adjusted to 25°C by thermostat pump in conjunction with a cooler. At the end of all experiments, AOX, total nitrogen and lignin concentrations were analyzed according to standard methods. All experiments were performed in duplicate and average values were used. Results and discussion  When the effect of H₂O₂ and time were investigated, it was observed that the AOX concentration increased from 3.0 to 11.0 mg/L by only UV. However, when H₂O₂ was added, AOX concentration decreased from approximately 3.0 to 0.0 mg/L. The optimal conditions for the removal of AOX appear to be an initial H₂O₂ concentration of 20.0 mL/L and reaction time of 50 min. In addition, at the same experiment conditions, it was seen that the total nitrogen concentration decreased from 23.0 to 15.0 mg/L by only UV and by increasing H₂O₂ concentration, the concentration of 20.0 mL/L H₂O₂ appears to be optimal (9.0 mg/L). The AOX, total nitrogen and lignin degradation products and pure lignin go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. The kinetics for the degradation of AOX, total nitrogen and lignin degradation products followed a pseudo-first order law with respect to the products, and the degradation rates (min⁻¹) for the UV/TiO₂/H₂O₂ system were higher than that of the corresponding values for the UV/H₂O₂ system. Conclusions  The AOX, total nitrogen and lignin concentration go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. It was found that the UV/TiO₂/H₂O₂ system has proved capable of the degradation of total nitrogen as well as chlorinated and degraded lignin in BKME. Recommendations and perspectives  The photocatalytic process can be considered a suitable alternative for the remove of some compounds from the BKME. Nevertheless, further studies should be carried out to confirm the practical feasibility of BKME. Another result obtained from the study is that pre-purification carried out with UV/TiO₂/H₂O₂ photocatalytic process may constitute an important step for further purification processes such as adsorption, membrane processes, etc.     

二氧化钛纳米管光催化降解水中百草枯

二氧化钛纳米管被用于光催化氧化水体中的百草枯,对光催化反应条件、常见Fe3+离子的干扰情况和百草枯光催化降解动力学规律进行了研究。结果表明,浓度为25 mg/L的百草枯溶液,在二氧化钛纳米管(TNT)1.0 g/L,H2O20.5 mL/50 mL,pH=5.0的最优光催化氧化条件下,经过30 min反应可以被100%从水体中去除,表现出非常高的光催化降解效率;动力学方程拟合表明,百草枯光催化氧化反应符合拟一级动力学规律,动力学方程为ln(C0/C)=1.0267t-0.1282,反应速率常数K为1.0267 h-1;双氧水存在时常见的Fe3+能够进一步提高百草枯光催化降解率;该光催化反应体系对低浓度百草枯废水有很好的处理效果,预示着光催化氧化技术适合地表或地下水体中百草枯的去除。     

组合方法去除新型采油污水中有机污染物的研究

含聚丙烯酰胺采油污水的有效处理是近年来困扰油田三次采油生产的一个难题。研究采用移动床生物膜技术与O3/UV/H2O2高级氧化技术的组合方法来处理含聚丙烯酰胺采油污水。实验结果表明,移动床生物膜技术可以有效去除污水中的石油类有机物,但对聚丙烯酰胺几乎无效果。O3/UV/H2O2高级氧化技术可以降解污水中的聚丙烯酰胺。组合方法处理后的含聚丙烯酰胺采油污水水质可以达到污水综合排放标准中的一级要求。     

Fe(III)–EDDS complex in Fenton and photo-Fenton processes: from the radical formation to the degradation of a target compound

The present work compares the efficiency of homogenous Fenton and photo-Fenton processes in the presence of Fe(III)–EDDS complex under different experimental conditions. 4-tert-Butylphenol (4-t-BP), which is one of the endocrine disrupting chemicals, was used as a model pollutant to investigate the Fenton and photo-Fenton application. The efficiency of homogenous photo-Fenton process was significantly much higher than homogenous Fenton process, which is due to the rapid formation of Fe²⁺ under UV irradiation of the iron complex and the photochemical formation of HO^? from the photolysis of the complex Fe(III)–EDDS. Through the degradation of 4-t-BP, the effect of Fe(III)–EDDS concentration, H₂O₂ concentration, pH, and oxygen was investigated in both processes. Such trend was also correlated with pH calculating the polychromatic Fe²⁺ quantum yield formation at pH 4.0, 6.0, and 8.6. The results showed that at high Fe(III)–EDDS and H₂O₂ concentrations, a negative effect was found. By the way, the Fenton process was found to be enhanced at basic pH. These results can be very useful for the use and optimization of such iron complex in water treatment process as function of different physico-chemical conditions.     

Photolysis of atrazine in aqueous solution: role of process variables and reactive oxygen species

Photochemical advanced oxidation processes have been considered for the treatment of water and wastewater containing the herbicide atrazine (ATZ), a possible human carcinogen and endocrine disruptor. In this study, we investigated the effects of the photon emission rate and initial concentration on ATZ photolysis at 254 nm, an issue not usually detailed in literature. Moreover, the role of reactive oxygen species (ROS) is discussed. Photon emission rates in the range 0.87?×?10¹⁸–3.6?×?10¹⁸ photons L^?1 s^?1 and [ATZ]₀?=?5 and 20 mg L^?1 were used. The results showed more than 65 % of ATZ removal after 30 min. ATZ photolysis followed apparent first-order kinetics with k values and percent removals decreasing with increasing herbicide initial concentration. A fivefold linear increase in specific degradation rate constants with photon emission rate was observed. Also, regardless the presence of persistent degradation products, toxicity was efficiently removed after 60-min exposure to UV radiation. Experiments confirmed a noticeable contribution of singlet oxygen and radical species to atrazine degradation during photolysis. These results may help understand the behavior of atrazine in different UV-driven photochemical degradation treatment processes.     

Heterogeneous UV/Fenton degradation of bisphenol A catalyzed by synergistic effects of FeCo2O4/TiO2/GO

A new method for bisphenol A (BPA) degradation in aqueous solution was developed. The characteristics of BPA degradation in a heterogeneous ultraviolet (UV)/Fenton reaction catalyzed by FeCo₂O₄/TiO₂/graphite oxide (GO) were studied. The properties of the synthesized catalysts were characterized using scanning electron microscopy, X-ray diffraction, and vibrating sample magnetometry. FeCo₂O₄ and TiO₂ were grown as spherical shape, rough surface, and relatively uniform on the surface of GO (FeCo₂O₄/TiO₂/GO). Batch tests were conducted to evaluate the effects of the initial pH, FeCo₂O₄/TiO₂/GO dosage, and H₂O₂ concentration on BPA degradation. In a system with 0.5 g L⁻¹ of FeCo₂O₄/TiO₂/GO and 10 mmol L⁻¹ of H₂O₂, approximately 90 % of BPA (20 mg L⁻¹) was degraded within 240 min of UV irradiation at pH 6.0. The reused FeCo₂O₄/TiO₂/GO catalyst retained its activity after three cycles, which indicates that it is stable and reusable. The heterogeneous UV/Fenton reaction catalyzed by FeCo₂O₄/TiO₂/GO is a promising advanced oxidation technology for treating wastewater that contains BPA.

     

Degradation of chlordecone and beta-hexachlorocyclohexane by photolysis, (photo-)fenton oxidation and ozonation

Intensive use of chlorinated pesticides from the 1960s to the 1990s has resulted in a diffuse contamination of soils and surface waters in the banana-producing areas of the French West Indies. The purpose of this research was, for the first time, to examine the degradation of two of these persistent pollutants – chlordecone (CLD) and beta-hexachlorocyclohexane (β-HCH) in 1 mg L^?1 synthetic aqueous solutions by means of photolysis, (photo-) Fenton oxidation and ozonation processes. Fenton oxidation is not efficient for CLD and yields less than 15% reduction of β-HCH concentration in 5 h. Conversely, both molecules can be quantitatively converted under UV-Vis irradiation reaching 100% of degradation in 5 h, while combination with hydrogen peroxide and ferrous iron does not show any significant improvement except in high wavelength range (>280 nm). Ozonation exhibits comparable but lower degradation rates than UV processes. Preliminary identification of degradation products indicated that hydrochlordecone was formed during photo-Fenton oxidation of CLD, while for β-HCH the major product peak exhibited C₃H₃Cl₂ as most abundant fragment.