Sunlight-driven environmental photodegradation of 2-chlorobiphenyl (PCB-1) in surface waters: kinetic study and mathematical simulations

Environmental Science and Pollution Research - Polychlorinated biphenyls (PCBs) are a family of highly toxic, resistant, and persistent organic pollutants, among which 2-chlorobiphenyl (PCB-1) is...     

Degradation and mineralization of sulcotrione and mesotrione in aqueous medium by the electro-Fenton process: a kinetic study

Introduction

The degradation and mineralization of two triketone (TRK) herbicides, including sulcotrione and mesotrione, by the electro-Fenton process (electro-Fenton using Pt anode (EF-Pt), electro-Fenton with BDD anode (EF-BDD) and anodic oxidation with BDD anode) were investigated in acidic aqueous medium.

Methods

The reactivity of both herbicides toward hydroxyl radicals was found to depend on the electron-withdrawing effect of the aromatic chlorine or nitro substituents. The degradation of sulcotrione and mesotrione obeyed apparent first-order reaction kinetics, and their absolute rate constants with hydroxyl radicals at pH?3.0 were determined by the competitive kinetics method.

Results and discussion

The hydroxylation absolute rate constant (k _abs) values of both TRK herbicides ranged from 8.20?×?10⁸ (sulcotrione) to 1.01?×?10⁹ (mesotrione) L?mol^?1?s^?1, whereas those of the TRK main cyclic or aromatic by-products, namely cyclohexane 1,3-dione , (2-chloro-4-methylsulphonyl) benzoic acid and 4-(methylsulphonyl)-2-nitrobenzoic acid, comprised between 5.90?×?10⁸ and 3.29?×?10⁹?L?mol^?1?s^?1. The efficiency of mineralization of aqueous solutions of both TRK herbicides was evaluated in terms of total organic carbon removal. Mineralization yields of about 97?C98% were reached in optimal conditions for a 6-h electro-Fenton treatment time.

Conclusions

The mineralization process steps involved the oxidative opening of the aromatic or cyclic TRK by-products, leading to the formation of short-chain carboxylic acids, and, then, of carbon dioxide and inorganic ions.     

Photochemical behaviour of carbendazim in aqueous solution

To elucidate the photochemical behaviour of carbendazim (or MBC) in superficial waters, photolysis studies have been carried out in aqueous solutions at several pH using a UV light source (high pressure mercury arc lamp) or a solar light simulator (xenon arc lamp). The kinetics of photodecomposition of carbendazim was determined using HPLC-DAD and the identification of photoproducts was carried out with HPLC-MS (ESI negative and positive mode). According to the experimental results carbendazim is a rather stable molecule in the dark or in environmental conditions. The pH influence of the environmental medium on the photodegradation rate has been confirmed. The photochemical process can be considerably accelerated in alkaline solutions using HPK-quartz irradiation (quantum efficiency at pH 9 phi = 3.1 x 10(-3) degraded molecule per absorbed photon) while the photodegradation is not as efficient under a simulated sun irradiation (quantum efficiency in the suntest phi = 10(-4) at pH 7). Three photoproducts have been tentatively identified in pure water: 2-aminobenzimidazole, benzimidazole isocyanate and monocarbomethoxy-guanidine (issued from the cleavage of the benzimidazole ring). The last one seems very stable and could be accumulated in the environment.     

磺胺二甲嘧啶在水溶液中的光化学降解

研究了4种光源(高压汞灯、氙灯、紫外灯和太阳光)下磺胺二甲嘧啶(SM2)的光化学降解(简写为光解)动力学.结果表明:(1)4种光源下,SM2的光解符合一级动力学方程,光解速率常数依次为紫外灯＞高压汞灯＞氙灯＞太阳光.(2)在相同条件下,SM2的光解速率常数随着初始浓度的增加而减小.(3)SM2在不同pH的缓冲溶液下的光...     

Photochemical transformation of azoxystrobin in aqueous solutions

The photochemical behaviour of azoxystrobin fungicide (AZX) in water was studied under laboratory conditions. Photodegradation was initiated using a solar simulator (xenon arc lamp) or a jacketed Pyrex reaction cell equipped with a 125 W, high-pressure mercury lamp. HPLC/MS analysis (APCI and ESI in positive and negative modes) was used to identify AZX photoproducts. The calculated polychromatic quantum efficiencies (phi) of AZX at pH 4.5, 7 and 9 were 5.42 x 10(-3), 3.47 x 10(-3) and 3.06 x 10(-3) (degraded molecules per absorbed photon), respectively. The relatively narrow range of values indicates the stability of AZX with respect to photodegradation in the studied pH range. Results from the HPLC/MS analysis suggest that the phototransformation of AZX proceeds via multiple, parallel reaction pathways including: (1) photo-isomerization (E-->Z), (2) photo-hydrolysis of the methyl ester and of the nitrile group, (3) cleavage of the acrylate double bond, (4) photohydrolytic ether cleavage between the aromatic ring giving phenol, and (5) oxidative cleavage of the acrylate double bond.     

Photochemical nitrosation of dimethylamine in aqueous solution containing nitrite

Dimethylamine was found to be nitrosated photochemically in aqueous solution containing nitrite both by the irradiation with a high pressure mercury lamp and by the exposure to sunlight to give nitrosodimethylamine, a well-known carcinogen. The nitrosation occurred more readily at alkaline pH than at acidic and neutral pH. These findings suggest that nitrosodimethylamine is produced photochemically under natural environmental conditions.     

Photochemical transformation of the thyroid hormone levothyroxine in aqueous solution

Purpose  

The direct aqueous photolysis of the thyroid hormone levothyroxine (T₄) has been studied.     

Photochemistry and environment IV- Photochemical behaviour of monochlorophenols in dilute aqueous solution

The photochemical behaviour of chlorophenols is different to that of non-halogenated phenols. In the former, the first step is a C-Cl bond scission, which is not influenced by oxygen. Chlorine is converted into hydrochloric acid. For monochlorophenols, the position of the chlorine on the ring strongly influences the transformation. In the molecular form, 2-chlorophenol is converted into pyrocatechol. In the anionic form however, it is reduced in a cyclopentadienic acid which dimerizes according to a Diels-Alder reaction. The irradiation of 3-chlorophenol leads to resorcinol whatever the pH. This would appear to suggest a photohydrolysis mechanism. With 4-chlorophenol, the photochemical conversion is not so specific. Hydroquinone is formed (mainly in aerated solution), along with polyphenolic oligomers. A radical mechanism is proposed.     

Photochemical processing of aldrin and dieldrin in frozen aqueous solutions under arctic field conditions

Organochlorine (OC) contaminants are transported to the Polar Regions, where they have the potential to bioaccumulate, presenting a threat to the health of wildlife and indigenous communities. They deposit onto snowpack during winter, and accumulate until spring, when they experience prolonged solar irradiation until snowmelt occurs. Photochemical degradation rates for aldrin and dieldrin, in frozen aqueous solution made from MilliQ water, 500 μM hydrogen peroxide solution or locally-collected melted snow were measured in a field campaign near Barrow, AK, during spring-summer 2008. Significant photoprocessing of both pesticides occurs; the reactions depend on temperature, depth within the snowpack and whether the predominant phase is ice or liquid water. The effect of species present in natural snowpack is comparable to 500 μM hydrogen peroxide, pointing to the potential significance of snowpack-mediated reactions. Aldrin samples frozen at near 0 °C were more reactive than comparable liquid samples, implying that the microenvironments experienced on frozen ice surfaces are an important consideration.     

Fe and UV-enhanced ozonation of chlorophenolic compounds in aqueous medium

Mono-, di- and trichlorophenol including different isomers were degraded by O₃, O₃ + UV and O₃ + UV + Fe³⁺. Disappearance rates are nearly identical among three ozonations. Whereas TOC elimination was not completed by ozone alone. UV illumination accelerated TOC elimination rate and the addition of Fe³⁺ (O₃ + UV + Fe³⁺) further accelerated it. TOC elimination rates among different chlorophenols were in the order of mono > di > tri. The effect of Fe³⁺ was largest on the degradation of trichlorophenol. Hydroxylated aromatics, organic acids, formaldehyde and acetone were detected as intermediates.     

Photochemical ozone creation potentials for oxygenated volatile organic compounds: sensitivity to variations in kinetic and mechanistic parameters

The sensitivity of Photochemical Ozone Creation Potentials (POCP) to a series of systematic variations in the rates and products of reactions of radical intermediates and oxygenated products is investigated for the C₄ alcohols, 1-butanol (n-butanol) and 2-methyl-1-propanol (i-butanol), using the recently developed Master Chemical Mechanism (MCM) as the base case. The POCP values are determined from the calculated formation of ozone in the boundary layer over a period of approximately five days along an idealised straight line trajectory, using a photochemical trajectory model and methodology described in detail previously. The results allow the relative impacts on calculated ozone formation of various classes of chemical reaction within the degradation chemistry to be assessed. The calculated POCP is found to be very insensitive to many of the changes investigated. However, it is found to be sensitive to variations in the rate coefficient for the initiating reaction with OH (k_OH), although the sensitivity decreases with increasing k_OH. The POCP appears to vary approximately linearly with k_OH at low values (i.e. k_OH less than ca. 4×10^-13 cm³ molecule^-1 s^-1), whereas at high reactivities (i.e. k_OH greater than ca. 4×10^-11 cm³ molecule^-1 s^-1), the calculated POCP value is comparatively insensitive to the precise value of k_OH. The POCP is also very sensitive to mechanistic changes which influence the yields of unreactive oxygenated products (i.e. those with OH reactivities below ca. 10^-12 cm³ molecule^-1 s^-1), for example acetone. The propensity of the organic compound to produce organic nitrates (which act as comparatively unreactive reservoirs for free radicals and NO_x) also appears to have a notable influence on the calculated POCP. Recently reported information relevant to the degradation of oxygenated VOCs is then used to update the chemical schemes for the 17 alcohols and glycols, 10 ethers and glycol ethers, and 8 esters included in the MCM, and new schemes are incorporated for dimethoxy methane (CH₃OCH₂OCH₃) and dimethyl carbonate (CH₃OC(O)OCH₃), which are proposed fuel additives. New or updated POCP values are calculated for all 37 oxygenated VOCs and, where applicable, these are compared with the previous POCP values and reported Maximum Incremental Reactivity (MIR) values.     

Removal of congo red from aqueous solution by bagasse fly ash and activated carbon: kinetic study and equilibrium isotherm analyses

Present investigation deals with the utilisation of bagasse fly ash (BFA) (generated as a waste material from bagasse fired boilers) and the use of activated carbons-commercial grade (ACC) and laboratory grade (ACL), as adsorbents for the removal of congo red (CR) from aqueous solutions. Batch studies were conducted to evaluate the adsorption capacity of BFA, ACC and ACL and the effects of initial pH (pH(0)), contact time and initial dye concentration on adsorption. The pH(0) of the dye solution strongly affected the chemistry of both the dye molecules and BFA in an aqueous solution. The effective pH(0) was 7.0 for adsorption on BFA. Kinetic studies showed that the adsorption of CR on all the adsorbents was a gradual process. Equilibrium reached in about 4h contact time. Optimum BFA, ACC and ACL dosages were found to be 1, 20 and 2 g l(-1), respectively. CR uptake by the adsorbents followed pseudo-second-order kinetics. Equilibrium isotherms for the adsorption of CR on BFA, ACC and ACL were analysed by the Freundlich, Langmuir, Redlich-Peterson, and Temkin isotherm equations. Error analysis showed that the R-P isotherm best-fits the CR adsorption isotherm data on all adsorbents. The Freundlich isotherm also shows comparable fit. Thermodynamics showed that the adsorption of CR on BFA was most favourable in comparison to activated carbons.     

Photochemical degradation of 1,3-dinitrobenzene in aqueous solution in the presence of hydrogen peroxide

A study on the destruction of 1,3-dinitrobenzene (1,3-DNB) in aqueous solution was carried out under ultraviolet (UV) irradiation alone and UV irradiation in the presence of hydrogen peroxide (H2O2). The combination of UV and H2O2 is significantly effective in degrading 1,3-DNB in terms of initial reaction rate and the mineralization of organic carbons. The photodegradation process can be influenced in certain extent by increasing the content of H2O2 and the acidity of reaction matrices. It was found that a variety of phenolic intermediates and inorganic acid were formed via hydroxyl radicals attacking the parent compound. The UV/H2O2 oxidation of 1,3-DNB was characterized by pseudo-zero order reaction for the degradation of 1,3-DNB with a 20 times enhanced rate constant of 1.36 x 10(-7) Ms(-1) and the initial rate constant was dependent on the initial concentration of 1,3-DNB.     

Fenton氧化水中间氯硝基苯的动力学与机制研究

结合Fenton氧化反应动力学模型研究了Fenton氧化水中间氯硝基苯(m-ClNB)的影响因素和降解机制.结果表明:(1)反应初始pH、H2O2浓度、Fe2+浓度、污染物初始浓度和反应温度对m-ClNB的降解均有明显影响.在反应初始pH为3.5、m-ClNB初始摩尔浓度为0.444mmol/L、H2O2摩尔浓度为21.55mmol/L、Fe2+摩尔浓度为0.054mmol/L、反应温度为(25土1)℃的条件下,m-ClNB的去除效果较好.(2)建立了Fenton氧化m-ClNB的准一级反应动力学模型,且m-ClNB的降解与该模型拟合良好.基于不同反应温度时的准一级反应速率常数(kap),得到了m-ClNB降解的阿累尼乌斯公式,且活化能为36.51kJ/mol.(3)气相色谱(GC)/质谱(MS)和高效液相色谱(HPLC)/MS分析表明,Fenton氧化m-ClNB的主要产物有4-氯-2-硝基苯酚及其同分异构体、羟基乙酸、草酸、丁二酸、丙二酸、6-氯己酸、乙醛酸、2,2-二羟基丙二酸和2-乙基丙二酸等.     

Photocatalytic degradation of triclocarban in aqueous solution using a modified zeolite/TiO2 composite: kinetic,mechanism study and toxicity assessment

Environmental Science and Pollution Research - The current work aimed to investigate the degradation of the triclocarban (TCC) in aqueous solution using a modified zeolite/TiO2 composite (MZTC)...     

Sorption of the herbicides diquat and difenzoquat from aqueous medium by polymeric resins in the presence of sodium dodecylsulfate: Kinetic and mechanistic study

The goal of this work was to propose a novel method for the solid-phase extraction of the herbicides diquat (DQT²⁺) and difenzoquat (DFQT⁺) from aqueous medium using polymeric Amberlite XAD-2 and XAD-4 resins in the presence of sodium dodecylsulfate (SDS). The addition of SDS to the medium was of fundamental importance in order to allow the formation of a negatively charged surface able to sorb the cationic solutes. Several factors that could influence the sorption process, such as SDS concentration in the medium, sorbent mass, pH, ionic strength, and initial concentration of the solutes were investigated. Kinetic studies were also performed to model the system and to identify the mechanisms that operate the sorption process of the herbicides. SDS concentration in the medium presented remarkable influence on the extraction efficiency, achieving maximum values when the ratios [SDS]/[herbicide] were approximately 90, for XAD-2, and 22 and 11 for DQT²⁺ and DFQT⁺, respectively, for XAD-4. The sorption process followed a pseudo second-order kinetic in all cases studied. It was also found that an intraparticle diffusion process controlled exclusively the sorption of the herbicides by the Amberlite XAD-2 and XAD-4 resins in the first 15 min, becoming less active with time.     

Degradation of clofibric acid in acidic aqueous medium by electro-Fenton and photoelectro-Fenton

Acidic aqueous solutions of clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid), the bioactive metabolite of various lipid-regulating drugs, have been degraded by indirect electrooxidation methods such as electro-Fenton and photoelectro-Fenton with Fe(2+) as catalyst using an undivided electrolytic cell with a Pt anode and an O(2)-diffusion cathode able to electrogenerate H(2)O(2). At pH 3.0 about 80% of mineralization is achieved with the electro-Fenton method due to the efficient production of oxidant hydroxyl radical from Fenton's reaction between Fe(2+) and H(2)O(2), but stable Fe(3+) complexes are formed. The photoelectro-Fenton method favors the photodecomposition of these species under UVA irradiation, reaching more than 96% of decontamination. The mineralization current efficiency increases with rising metabolite concentration up to saturation and with decreasing current density. The photoelectro-Fenton method is then viable for treating acidic wastewaters containing this pollutant. Comparative degradation by anodic oxidation (without Fe(2+)) yields poor decontamination. Chloride ion is released during all degradation processes. The decay kinetics of clofibric acid always follows a pseudo-first-order reaction, with a similar rate constant in electro-Fenton and photoelectro-Fenton that increases with rising current density, but decreases at greater metabolite concentration. 4-Chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol, along with carboxylic acids such as 2-hydroxyisobutyric, tartronic, maleic, fumaric, formic and oxalic, are detected as intermediates. The ultimate product is oxalic acid, which forms very stable Fe(3+)-oxalato complexes under electro-Fenton conditions. These complexes are efficiently photodecarboxylated in photoelectro-Fenton under the action of UVA light.     

Use of activated Chromolaena odorata biomass for the removal of crystal violet from aqueous solution: kinetic,equilibrium, and thermodynamic study

Environmental Science and Pollution Research - In the present study, biomass from the Chromolaena odorata plant’s stem was activated using sulfuric acid to adsorb crystal violet (CV) dye. The...