Degradation and by-product formation of diazinon in water during UV and UV/H(2)O(2) treatment

Kinetics and degradation products resulting from the application of UV and UV/H(2)O(2) to the US EPA Contaminant Candidate List pesticide diazinon were studied. Batch experiments were conducted with both monochromatic (low pressure [LP] UV 253.7 nm) and polychromatic (medium pressure [MP] UV 200-300 nm) UV sources alone or in the presence of up to 50 mg l(-1) H(2)O(2), in a quasi-collimated beam apparatus. Degradation of diazinon by both UV and UV/H(2)O(2) exhibited pseudo first order reaction kinetics, and quantum yield of 8.6 x 10(-2) and 5.8 x 10(-2) mol E(-1) for LP and MP lamps respectively. Photolysis studies under MP UV lamp showed 2-isopropyl-6-methyl-pyrimidin-4-ol (IMP) to be the main degradation product of diazinon at aqueous solution pH values of 4, 7 and 10. Trace levels up to 1.8 x 10(-3) microM of diazinon oxygen analogue diethyl 2-isopropyl-6-methylpyrimidin-4-yl phosphate (diazoxon) were detected only during the UV/H(2)O(2) reaction. Decay of both products was observed, as the UV/H(2)O(2) reaction prolonged, yet no mineralization was achieved over the UV fluence levels examined. Photolysis kinetics, quantum yield and UV/H(2)O(2) degradation of the reaction product IMP was determined using MP UV lamp at pH values of 4, 7 and 10.     

Effectiveness of UV-based advanced oxidation processes for the remediation of hydrocarbon pollution in the groundwater: a laboratory investigation

The effectiveness of advanced oxidation processes in a batch and a flow reactor was investigated for the remediation of hydrocarbon pollution in the groundwater underlying a petrochemical industrial site. The main organic contaminants present in the groundwater were MTBE, benzene, alkyl-benzenes and alkyl-naphthalenes. Experimental results with a batch reactor showed that for all the organic contaminants the removal efficiency order is UV/TiO2 approximately UV/H2O2>UV (medium-pressure) in a synthetic aqueous solution, compared to UV/H2O2>UV (medium-pressure)>UV/TiO2 for the real polluted groundwater. The much lower performance of UV/TiO2 with respect to UV/H2O2 was inferred to the matrix of the groundwater, i.e. the salt content, as well as the organic and particulate matter. In fact, it is likely that the salts and dissolved organic matter quench the superoxide anion O2(-) and hydroxyl radicals just formed at the surface of the TiO2 catalyst. MTBE was the hardest compound to remove with each of the investigated treatments. UV and UV/TiO2 treatments were not able to reach a residual concentration of 10 microg/L (set by Italian legislation) even after 180 min. As for the UV/H2O2 process, only the MTBE degradation rate resulted affected by the initial H2O2 concentration, while for other compounds a complete removal was obtained within 20 min even with the lowest H2O2 concentration used (0.13 g/L). Only after 120 min of treatment, with an initial H2O2 concentration of 0.13 g/L, did the residual MTBE concentration fall below the above reported maximum admissible concentration. Instead, by using an initial concentration of 2g/L a residual concentration lower than 5 microg/L was obtained after just 30 min of reaction. The UV/H2O2 process was also investigated with a flow reactor. Results showed that it was more efficient than the batch reactor for removing MTBE, in terms of reaction time and initial H2O2 concentration required. This is consistent with the higher power of the UV lamp and with the different geometry of the flow reactor, which has a much shorter optical path than the batch reactor. By-product characterisation was also performed showing that t-butyl-formate and low molecular weight organic acids are formed as intermediate and final by-products, respectively. Finally, a preliminary evaluation of the operational cost of the UV/H2O2 process showed a value of 1.7 euro/m3 under the optimised condition.     

Oxidation of cyanide in aqueous solution by chemical and photochemical process

Cyanide waste is found predominantly in industrial effluents generated from metallurgical operations. The toxicity of cyanide creates serious environmental problems. In this paper, oxidation of cyanide in aqueous solution was investigated using chemical and photochemical process. Chemical oxidation was studied at room temperature using H2O2 as oxidant and Cu2+ as catalyst. Photochemical oxidation was studied in an annular type batch photoreactor of 1l capacity using 25 W low-pressure (81.7% transmission at 254 nm wavelength) ultraviolet (UV) lamp along with H2O2 as oxidant. The effect of Cu2+ catalysis was also studied. It was observed that in absence of UV source, the degradation of cyanide by H2O2 alone was very slow, whereas copper ions accelerated the rate of reaction thereby acting as catalyst. Copper formed a complex with cyanide ion, i.e. tetracyanocuprate which had greater affinity for H2O2. Cyanate hydrolysis was also favoured by copper ions. As Cu2+ ion concentration was increased, rate of degradation also increased. Photochemical oxidation by H2O2 and Cu2+ was found to be the best system for cyanide degradation. CN- (100 mg/l) was degraded to non-detectable level in 9 min at pH 10.0 with optimum H2O2 dose of 35.5 mM and Cu2+ dose of 19 mg/l. Reaction kinetics of cyanide oxidation was found to be pseudo-first order and the rate constant has been determined for different processes.     

Application of Box-Wilson experimental design method for the photodegradation of bakery's yeast industry with UV/H2O2 and UV/H2O2/Fe(II) process

Decolorization and mineralization of bakery's yeast industry effluent by photochemical advanced oxidation processes (AOPs) utilizing UV with hydrogen peroxide and Photo-Fenton, were investigated in a laboratory scale photo-reactor equipped with a 16 W low-pressure mercury vapor lamp. The Box-Wilson experimental design method was employed to evaluate the effects of major process variables (e.g. pH, oxidant dose, and irradiation time) on the decolorization efficiency. Response function coefficients were determined by regression analysis of the experimental data and prediction results agreed with the experimental results. The optimum hydrogen peroxide concentration and irradiation time were found to be 5 mM and 50 min at pH 3, respectively, for UV/H2O2 process. In the Photo-Fenton process application, maximum decolorization efficiency (96.4%) was obtained at the optimum reaction conditions that were 100 mM H2O2 and 1 mM Fe(II) doses at pH 3, and 10 min of irradiation time.     

Comparison of four advanced oxidation processes for the removal of naphthenic acids from model oil sands process water

Four advanced oxidation processes (UV/TiO(2), UV/IO(4)(-), UV/S(2)O(8)(2-), and UV/H(2)O(2)) were tested for their ability to mineralize naphthenic acids to inorganic carbon in a model oil sands process water containing high dissolved and suspended solids at pH values ranging from 8 to 12. A medium pressure mercury (Hg) lamp was used, and a Quartz immersion well surrounded the lamp. The treatment goal of 5mg/L naphthenic acids (3.4 mg/L total organic carbon (TOC)) was achieved under four conditions: UV/S(2)O(8)(2-) (20mM) at pH 8 and 10, and UV/H(2)O(2) (50mM) at pH 8 (all with the Quartz immersion well). Values of electrical energy required to meet the treatment goal were about equal for UV/S(2)O(8)(2-) (20mM) and UV/H(2)O(2) (50mM) at pH 8, but three to four times larger for treatment by UV/S(2)O(8)(2-) (20mM) at pH 10. The treatment goal was also achieved using UV/S(2)O(8)(2-) (20mM) at pH 10 when using a Vycor filter that transmits light primarily in the mid and near UV, suggesting that that treatment of naphthenic acids by UV/S(2)O(8)(2-) using low pressure Hg lamps may be feasible.     

Co3+掺杂LaFeO3的制备及光催化降解硝基苯的性能研究

以La(NO3)3、Fe(NO3)3.9H2O和Co(NO3)2.6H2O为原料,采用柠檬酸络合法制备了纯LaFeO3和掺杂Co3+的LaFeO3纳米粉体,通过XRD和SEM等手段对样品进行表征,以硝基苯为目标降解物,考察催化剂的光催化降解活性。研究表明:煅烧温度为800℃时制备的LaFeO3样品对硝基苯溶液的脱色率达47.02%;而采用Co3+的掺杂增强了LaFeO3的光吸收特性,对LaFeO3的光催化性能有较大促进作用,且掺杂量为5%时效果最好,光降解时间1h时,对硝基苯的降解率可达76.26%。     

Photocatalytic degradation of azo dyes using Au:TiO2, gamma-Fe2O3:TiO2 functional nanosystems

We report photocatalytic degradation studies on Navy Blue HE2R (NB) dye on significant details as a representative from the class of azo dyes using functional nanosystems specifically designed to allow a strong photocatalytic activity. A modified sol-gel route was employed to synthesize Au and gamma-Fe2O3 modified TiO2 nanoparticles (NPs) at low temperature. The attachment strategy is better because it allows clear surface of TiO2 to remain open for photo-catalysis. X-ray diffraction, Raman and UV-VIS spectroscopy studies showed the presence of gold and iron oxide phases along-with the anatase TiO2 phase. TEM studies showed TiO2 nanocomposite particles of size approximately 10-12 nm. A detailed investigation on heterogeneous photocatalytic performance for Navy Blue HE2R dye was done using the as-synthesized catalysts Au:TiO2 and gamma-Fe2O3:TiO2 in aqueous suspension under 8 W low-pressure mercury vapour lamp irradiation. Also, the photocatalytic degradation of Amranth and Orange G azo dyes were studied. The surface modified TiO2 NPs showed significantly improved photocatalytic activity as compared to pure TiO2. Exposure of the dye to the UV light in the presence of pure and gold NPs attached TiO2 catalysts caused dye degradation of about approximately 20% and approximately 80%, respectively, in the first couple of hours. In the presence of gamma-Fe2O3 NPs attached TiO2, a remarkable approximately 95% degradation of the azo dye was observed only in the first 15 min of UV exposure. The process parameters for the optimum catalytic activity are established which lead to a complete decoloration and substantial dye degradation, supported by the values of the Chemical Oxygen Demand (COD) approximately 93% and Total Organic Carbon (TOC) approximately 65% of the treated dye solution after 5 hours on the employment of the UV/Au:TiO2/H2O2 photocatalytic process.     

Photodegradation and toxicity changes of antibiotics in UV and UV/H(2)O(2) process

The photodegradation of three antibiotics, oxytetracycline (OTC), doxycycline (DTC), and ciprofloxacin (CIP) in UV and UV/H(2)O(2) process was investigated with a low-pressure UV lamp system. Experiments were performed in buffered ultrapure water (UW), local surface water (SW), and treated water from local municipal drinking water treatment plant (DW) and wastewater treatment plant (WW). The efficiency of UV/H(2)O(2) process was affected by water quality. For all of the three selected antibiotics, the fastest degradation was observed in DW, and the slowest degradation occurred in WW. This phenomenon can be explained by R(OH,UV), defined as the experimentally determined OH radical exposure per UV fluence. The R(OH,UV) values represent the background OH radical scavenging in water matrix, obtained by the degradation of para-chlorobenzoic acid (pCBA), a probe compound. In natural water, the indirect degradation of CIP did not significantly increase with the addition of H(2)O(2) due to its effective degradation by UV direct photolysis. Moreover, the formation of several photoproducts and oxidation products of antibiotics in UV/H(2)O(2) process was identified using GC-MS. Toxicity assessed by Vibrio fischer (V. fischer), was increased in UV photolysis, for the photoproducts still preserving the characteristic structure of the parent compounds. While in UV/H(2)O(2) process, toxicity increased first, and then decreased; nontoxic products were formed by the oxidation of OH radical. In this process, detoxification was much easier than mineralization for the tested antibiotics, and the optimal time for the degradation of pollutants in UV/H(2)O(2) process would be determined by parent compound degradation and toxicity changes.     

Development of HPLC/ESI-MS and HPLC/1H NMR methods for the identification of photocatalytic degradation products of iodosulfuron

In the present study, HPLC/ESI-MS and stopped-flow HPLC/1H NMR methods were developed and applied to separate and characterize the byproducts arising from TiO2-catalyzed photodegradation of the herbicide iodosulfuron methyl ester (IOME) in aqueous solution under UV irradiation. Prior to identification, irradiated solutions of IOME (200 and 1000 mg.L(-1)) were concentrated by solid-phase extraction using two cartridges: Isolute C18 and Isolute ENV+. Analytical separation was achieved on a C18 reversed-phase column with ACN/H2O (HPLC/MS) or ACN/D2O (HPLC/NMR) as mobile phase and a linear gradient with a chromatographic run time of 35 min. The combination of UV and MS data allowed the structural elucidation of more than 20 degradation products, whereas 1H NMR data permitted an unequivocal confirmation of the identities of major products and the differentiation of several positional isomers, in particular, the hydroxylation isomers. The obtained results permitted us to propose a possible degradation scheme and to put in evidence the presence of privileged sites for the attack of OH radicals. This work shows, for the first time, the application of combined HPLC with UV, MS, and NMR detection for complete structural elucidation of photocatalytic degradation products, and it will be of particular value in studies on the elimination of pollutants in aqueous solutions by photocatalysis.     

Photodegradation of 17beta-estradiol in water by UV-vis/Fe(III)/H2O2 system

Photodegradation of 17beta-estradiol (E2) in aqueous solutions by UV-vis/Fe(III)/H(2)O(2) system, namely Photo-Fenton system, was preliminarily investigated under a 250 W metal halide lamp (lambda > or = 313 nm). The influences of initial pH value, initial concentration of H(2)O(2) and E2 on photodegradation efficiency of E2 were discussed and the amount of CO(2) produced by the photodegradation reaction was measured. The results indicates that E2 could be decomposed efficiently in UV-vis/Fe(III)/H(2)O(2) system. Under the condition of 10.0 micromol L(-1) Fe(III), 1000 micromol L(-1) H(2)O(2) and pH 3.0, the degradation efficiency of 18.4 micromol L(-1) E2 reach 75.2% after the irradiation of 160 min. Over the range of pH 3.0-6.0, the higher acidity, the higher the degradation efficiency of E2 and initial reaction rate are. The degradation efficiency of E2 increases with increasing of initial concentration of H(2)O(2) and with decreasing of initial concentration of E2. The E2 mineralization efficiency increases with reaction time but the mineralization efficiency was lower. When the initial concentration of Fe(III) and H(2)O(2) were 10.0 and 1000 micromol L(-1), respectively, the mineralization efficiency of 18.4 micromol L(-1) E2 solution with pH 3.0 was only 21.6% after 160 min irradiation. It is suggested that the mineralization occurred probably only at aromatic ring.     

Photodegradation of methyl tert-butyl ether (MTBE) by UV/H2O2 and UV/TiO2

Two UV-based advanced oxidation processes (AOPs), UV/H2O2 and UV/TiO2, were tested in batch reactor systems to evaluate the removal efficiencies and optimal conditions for the photodegradation of methyl tert-butyl ether (MTBE). The optimal conditions at an initial MTBE concentration of 1 mM ([MTBE]0=1 mM) were acidic and 15 mM H2O2 in UV/H2O2 system, and pH 3.0 and 2.0 g/l TiO2 in UV/TiO2 suspended slurries system under 254-nm UV irradiation. Under the optimal conditions, MTBE photodegradation during the initial period of 60 min in UV/H2O2 and UV/TiO2 systems reached 98 and 80%, respectively. In both systems, MTBE photodegradation decreased with increasing [MTBE]0. While MTBE photodegradation rates increased with increasing dosage of H2O2 (5-15 mM) and TiO2 (0.5-3 g/l), further increase in the dosage of H2O2 (20 mM) or TiO2 (4 g/l) adversely reduced the MTBE photodegradation. Pseudo first-order kinetics with regard to [MTBE] can be used to describe the MTBE photodegradation in both systems. The pseudo first-order rate constants linearly increased with the increase in the molar ratio of [H2O2]0 to [MTBE]0 in UV/H2O2 system and linearly increased with the decrease in [MTBE]0 in UV/TiO2 system.     

Removal and degradation pathway study of sulfasalazine with Fenton-like reaction

The Fenton-like degradation of sulfasalazine solution is studied in this work. The effects of reaction parameters such as Fe(3+) concentration, initial H(2)O(2) dosage and the reaction temperature are evaluated. For sulfasalazine of 100mg/L, the removal of sulfasalazine, chemical oxygen demand (COD) and total organic carbon (TOC) reached 99.5%, 84.2% and 41% in 60 min with 0.20mM Fe(3+) and 16 mM H(2)O(2) at 35°C, respectively. The complexed Fe(3+) presents a reaction constant of 0.062 min(-1)mM(-1) while that of free Fe(3+) is 2.526 min(-1)mM(-1) for sulfasalazine degradation. LC-MS technology was used to analysis the possible degradation intermediates. The degradation of sulfasalazine principally begins with the attack of hydroxyl radical on the azo-group as well as the sulfanilamido group. Both intramolecular rearrangement and bimolecular reaction occur simultaneously after the hydroxyl radical attack. Further attack of the active oxidative species results in the cleavage of the aromatic rings and the production of CO(2). The degradation of industrial sulfasalazine wastewater with a COD of 3425 mg/L has also been achieved by Fenton reaction with different dosage of H(2)O(2). Relatively better removal efficiency is observed at moderate Fe/H(2)O(2) molar ratio from 1/5 to 2/5 for industrial sulfasalazine wastewater treatment.     

Photooxidative degradation of 4-nitrophenol (4-NP) in UV/H2O2 process: influence of operational parameters and reaction mechanism

The photooxidative degradation of 4-nitrophenol (4-NP) was studied in the UV/H2O2 process. The effects of applied H2O2 dose, initial 4-NP concentration and UV light intensity have been studied. Degradation was complete in 13 min and follows apparent first-order kinetics. The removal efficiency of 4-NP depends on the operational parameters and increases as the initial concentration of H2O2 and light intensity are increased but it decreases when the initial concentration of 4-NP is increased. From HPLC analysis, major intermediate products were hydroxyl derivatives of 4-NP as a result of photooxidative hydroxylation.     

Photodegradation of Reactive Black 5, Direct Red 28 and Direct Yellow 12 using UV, UV/H(2)O(2) and UV/H(2)O(2)/Fe(2+): a comparative study

The photodegradation of three commercially available dyestuffs (C.I. Reactive Black 5, C.I. RB5, C.I. Direct Yellow 12, C.I. DY12, and C.I. Direct Red 28, C.I. DR28) by UV, UV/H(2)O(2) and UV/H(2)O(2)/Fe(II) processes was investigated in a laboratory-scale batch photoreactor equipped with an 16W immersed-type low-pressure mercury vapour lamp. The experimental results were assessed in terms of absorbance and total organic carbon (TOC) reduction. The initial concentration was kept constant at 100 mg l(-1) for all dyes. Initial results showed that, color removal efficiencies by UV or H(2)O(2) alone were negligible for all dyes. Almost complete disappearance of C.I. RB5 (99%) and DY12 (98%) in UV/H(2)O(2) process was possible to achieve after 60 min of irradiation. The maximum color removal efficiency of C.I. DR28 after 60 min of irradiation, however, was only 40% and reached a maximum value of 70% after 120 min of irradiation. Corresponding mineralization efficiencies were 50, 55 and 7-12%, respectively. The addition of Fe(II) to the system, so-called the photo-Fenton process, greatly enhanced the color removal, the efficiencies being 98, 88 and 85% for C.I. RB5, C.I. DY12 and C.I. DR28 only after 5 min of irradiation. Corresponding mineralization efficiencies were 98% for 45 min irradiation, 100% for 60 min irradiation and 98% for 90 min irradiation, respectively. However, marginal benefit was less significant in the higher range of both H(2)O(2) and Fe(II). Furthermore, decreases in both decolorization and mineralization were observed at higher concentrations of oxidant and catalyst due to the scavenging effect of excess H(2)O(2) and OH radicals. The degradation of all dyes was found to follow first-order reaction kinetics.     

Photochemical degradation of diethyl phthalate with UV/H2O2

The decomposition of diethyl phthalate (DEP) in water using UV-H2O2 process was investigated in this paper. DEP cannot be effectively removed by UV radiation and H2O2 oxidation alone, while UV-H2O2 combination process proved to be effective and could degrade this compound completely. With initial concentration about 1.0mg/L, more than 98.6% of DEP can be removed at time of 60 min under intensity of UV radiation of 133.9 microW/cm2 and H2O2 dosage of 20mg/L. The effects of applied H2O2 dose, UV radiation intensity, water temperature and initial concentration of DEP on the degradation of DEP have been examined in this study. Degradation mechanisms of DEP with hydroxyl radicals oxidation also have been discussed. Removal rate of DEP was sensitive to the operational parameters. A simple kinetic model is proposed which confirms to pseudo-first order reaction. There is a linear relationship between rate constant k and UV intensity and H2O2 concentration.     

Decolorization of azo dye acid black 1 by the UV/H2O2 process and optimization of operating parameters

An advanced oxidation process, UV/H2O2, was applied for decolorization of a di-azo dye (acid black 1). The effects of operating parameters such as hydrogen peroxide dosage, UV dosage and initial dye concentration, on decolorization have been evaluated. The acid black 1 solution was completely decolorized under optimal hydrogen peroxide dosage of 21.24 mmol/l and UV dosage of 1400 W/l in less than 1.2 min. The decolorization rate followed pseudo-first order kinetics with respect to the dye concentration. The rate increased linearly with volumetric UV dosage and nonlinearly with increasing initial hydrogen peroxide concentration. It has been found that the degradation rate increased until an optimum of hydrogen peroxide dosage, beyond which the reagent exerted an inhibitory effect. For real case application, an operation parameter plot of rate constant was developed. To evaluate the electric power and hydrogen peroxide consumption by UV/H2O2 reactor, 90% color removal was set as criteria to find the balance between both factors.     

Kinetics and mechanism of degradation of p-chloronitrobenzene in water by ozonation

The kinetics and mechanism of p-chloronitrobenzene (pCNB) degradation by ozone were investigated. With reference compounds, nitrobenzene (NB) and chlorobenzene (CB), reaction rate constants of pCNB with O3 and OH were measured by means of competition kinetics (mixtures of pCNB and NB, or pCNB and CB), with the rate constants being, 1.6 L mol(-1) s(-1), 2.6 x 10(9) L mol(-1) s(-1), respectively. During the ozonation process of pCNB, an increase of chloride and nitrate ions in the water sample solution was observed, which is consistent with the decrease in pCNB concentration. But the total organic carbon (TOC) removal rate is not consistent with the pCNB elimination rate indicating only part of pCNB was mineralized and thus presumably some intermediate products were formed. The pCNB degradation intermediate products were analyzed by gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), high performance liquid chromatography (HPLC) and ion chromatography (IC). The main intermediate products were phenol, p-chlorophenol, p-nitrophenol, 2-chloro-5-nitrophenol, 5-chloro-2-nitrophenol, 5-nitro-catechol, para-benzoquinone, 5-nitro-1,2,3-trihydroxy phenol, trihydroxy semiquinone, glycolic acid, oxalic acid, hydroxybutanoic acid, mesoxalic acid, tartrouic acid, malonic acid, maleic acid, hydroxymalonic acid, tartaric acid, malic acid, ketoglutaric acid and muconic acid. From the identified reaction products, a possible degradation pathway for the ozonation of pCNB has been proposed.     

Oxidative degradation of dimethyl phthalate (DMP) by UV/H(2)O(2) process

The photochemical degradation of dimethyl phthalate (DMP) in UV/H(2)O(2) advanced oxidation process was studied and a kinetic model based on the elementary reactions involved was developed in this paper. Relatively slow DMP degradation was observed during UV radiation, while DMP was not oxidized by H(2)O(2) alone. In contrast, the combined UV/H(2)O(2) process could effectively degraded DMP, which is attributed to the strong oxidation strength of hydroxyl radical produced. Results show that DMP degradation rate was affected by H(2)O(2) concentration, intensity of UV radiation, initial DMP concentration, and solution pH. A kinetic model without the pseudo-steady state assumption was established according to the generally accepted elementary reactions in UV/H(2)O(2) advanced oxidation process. The rate constant for the reaction between DMP and hydroxyl radical was found to be 4.0 x 10(9) M(-1)s(-1) through fitting the experimental data to this model. The kinetic model could adequately describe the influence of key factors on DMP degradation rate in UV/H(2)O(2) advanced oxidation process, and could serve as a guide in designing treatment systems for DMP removal.     

Catalysis of advanced oxidation reactions by ultrasound: a case study with phenol

The present study is about the enhancement in ozone-mediated degradation and UV (254nm) photolysis of phenol in aqueous solutions by 300kHz acustic cavitation and the selection of operating parameters for optimum phenol removal efficiency. The method was based on monitoring of the concentration of phenol during 90min exposure to ozonation, sonication, UV photolysis, O(3)/ultrasound, UV/ultrasound and O(3)/UV/ultrasound operations. It was found that ozonation at alkaline pH was an effective method of phenol destruction, but it was considerably more effective when applied simultaneously with ultrasonic irradiation. The observed synergy particularly at alkaline pH was attributed to combined effects of: (i) increased ozone mass transfer (upon hydrodynamic shear forces created by ultrasonic bubbles) and (ii) excess hydroxyl radical formation (upon thermal decomposition of ozone in the gaseous cavity bubbles). Degradation of phenol by photolysis alone was negligible, while combination of UV-irradiation and ultrasound rendered considerable degrees of decay. The synergy here was explained by excess hydroxyl radicals that are formed by photolysis of ultrasound-generated H(2)O(2). Maximum rate of phenol degradation was observed in case of combined application of ozone, UV and ultrasound at basic pH.     

Electrochemical monitoring of proton transfer across liquid/liquid interfaces on the surface of graphite electrodes

Equilibrium partitioning of HClO4 between aqueous solutions and benzonitrile (BN) or nitrobenzene (NB) was measured and used to evaluate the pKa of the acid in the two organic solvents. The potential drop across the BN/ H2O interface was evaluated from the known potential drop across the NB/H2O interface and the voltammetrically measured formal potential of a ferrocenium/ferrocene redox couple confined within thin layers of the two organic solvents. The voltammetric reduction of tetrachloro-1, 4-benzoquinone in thin layers of BN was used to monitor changes in the concentration of protons in the layer during proton-consuming faradaic reactions. The rate of proton transfer from the aqueous to the nonaqueous phase across the BN/H2O interface was shown to be adequate to sustain proton-consuming reactions at the electrode/BN interface.