Sonochemical effectiveness factor (e(US)) in the reactors for wastewater treatment by sono-Fenton oxidation: novel considerations.

A comprehensive algorithm was recently proposed for calculation of the sonochemical effectiveness factor and wastewater treatment modeling. The presented approach implies that ultrasound is an auxiliary source of free radicals in Fenton type reactions; introduction of ultrasound represents an enhancement of pollutant degradation rates. The sonochemical effectiveness factor was introduced in kinetic models as the eUS factor (Grcic et al., 2012 [1]). As a substantial follow-up, this study presents novel considerations. The eUS factor was modeled as a function of employed frequency, actual cavitation-related power intensity of ultrasound and a portion of the cavitationally active zone, i.e. dimensionless active volume. The effect of temperature was disregarded in the present model considerations. Cavitationally active zone in reactors was determined based on the erosion of aluminum foil, resulting in cone-shaped space arising from transducer. In the present study, sonochemical treatment of industrial wastewater containing HCOONa as organic pollutant was performed using different equipment: ultrasonic baths (UB1, UB2 and UB3), cylindrical reactor with homogenizer (HCR) and three-frequency hexagonal cell, i.e. ultrasonic pilot reactor prototype (PP). Explored frequency range was from 20 to 120 kHz. Homogeneous and heterogeneous Fenton-type sonochemical processes, US/Fe(II)(FeSO4,aq.)/H2O2 and US/Fe(II)(steel-plate)/H2O2, respectively, applied to industrial wastewater were investigated in terms of mineralization kinetics. Newly modeled eUS factor was introduced in corresponding kinetic models and the overall model was validated. Kinetic parameters of Fenton process were treated as independent of ultrasound, since eUS factor consists of cavitation-related phenomena responsible for the mineralization rate enhancement. In average, a 21% increase of mineralization efficiency was achieved using a single frequency, while more than 70% increase can be achieved by combining 20, 68 and 120 kHz in PP.

Kinetic modeling and synergy quantification in sono and photooxidative treatment of simulated dyehouse effluent.

The aim of this work was to explore the application of sulfate radical based advanced oxidation processes: photooxidation (UV/PMS/PS), sonooxidation (US/PMS/PS) and combined sono-photooxidation (US/UV/PMS/PS) for the mineralization of simulated dyehouse effluent (WW); using peroxymonosulfate (PMS) and persulfate (PS) as oxidants. Experiments were performed in a reaction vessel of a defined geometry and axially positioned source of UV-C radiation, all placed in the ultrasonic bath (35 kHz). Mathematical model of the process was developed according to the proposed degradation scheme. Decomposition of dyestuff (C.I. Reactive Violet 2, RV2 and C.I. Reactive Blue 7, RB7), surfactant (linear alkylbenzene sulfonate; hereafter: LAS) and auxiliary organic components was explored in three types of model wastewater: WW, simulated effluent excluding inorganic species (WW-IS) and model solution that consists of a specific compound (hereafter: compound model solutions). The influence of inorganic matrix (Cl(-), CO(3)(2-)/HCO(3)(-)) was studied due to the corresponding quenching affinity toward HO and SO(4)(-) radicals. The efficiency of applied processes was evaluated and the response to combined phenomena (cavitation and irradiation) was quantified as synergy index, f(Syn). Sono-photooxidative treatment (US/UV/PMS/PS) of WW resulted in a partial mineralization and partial decolourization; approximately 40% of initial TOC and 30% of initial RB7 remained after 60 min of treatment, while RV2 and LAS molecule were completely decomposed. Circumstantially, the combined process increased the mineralization efficiency by a factor of 3 (f(Syn) = 3.026).

Photooxidation of benzene-structured compounds: influence of substituent type on degradation kinetic and sum water parameters.

The combined influence of substituent type and UV/H(2)O(2) process parameters on the degradation of four aromatic water pollutants was investigated using modified 3(3) full factorial design and response surface methodology. Degradation kinetics was described by the quadratic polynomial model. According to the applied ANOVA, besides pH and [H(2)O(2)], model terms related with the pollutant structure are found to be significant. Different optimal operating conditions and values of observed degradation rate constants were determined for each of the pollutants indicating that the type of substituent influences the overall process effectiveness over structurally defined degradation pathway. Biodegradability (BOD(5)/COD) and toxicity (TU) were evaluated prior to the treatment and at the reference time intervals t(1/2)(P), t(3/4)(P), t(1/4)(OC) and t(1/2)(OC) corresponding to the real time required to reduce the concentration of parent pollutant and organic content for 1/2, 3/4, 1/4 and 1/2 of initial amount. The observed differences are correlated to the structural differences of studied aromatics.

Global parameter of ultrasound exploitation (GPUE) in the reactors for wastewater treatment by sono-Fenton oxidation.

Modeling of the sonochemical reactors presents a great challenge due to issues related to the experimental investigation and description of the primary effects of the ultrasound. The main idea proposed in this work was to establish an algorithm consisting of the viable laboratory analyses and basic elements of chemical reaction engineering. In this paper, a novel modeling approach is presented. Proposed approach is characterized by the following; ultrasound was investigated as an auxiliary source of energy and the kinetic constants determined for the basic oxidation reactions, i.e. Fenton type oxidation were treated as independent of the ultrasound. Sonochemical effectiveness factor is expressed as a global parameter of the ultrasound exploitation (GPUE) that was introduced in the kinetic model as the e(US) factor. Factor e(US) is modeled as a function of employed frequency, actual power of the transducer, portion of the cavitationally active zone, i.e. dimensionless active volume and the average temperature in the reactor. Lumped system has been assumed. In order to obtain all the necessary data, the experimental study included different sets of experiments. The kinetics of the sonochemical processes, e.g. US/Fe(2+)/H(2)O(2), US/Fe(2+)/S(2)O(8)(2-), US/Fe(2+)/HSO(5)(-) was investigated in the term of mineralization of model wastewaters containing different types of organic pollutants. The Weissler dosimetry and peroxodisulfate decomposition upon sonication, were used to facilitate the determination of e(US). They follow zero order kinetics, thus can be used as a model reaction to reflect all the primary effects of ultrasound and to establish the empirical correlation for e(US) calculation. Finally, GPUE has been introduced in the adequate kinetic models and the overall model was validated.

Low frequency US and UV-A assisted Fenton oxidation of simulated dyehouse wastewater.

The scope of the present study was to explore the treatment possibilities for the simulated dyehouse wastewater (WW) by the Fenton oxidation ultrasonic (US) or UV-A assisted. Composition of WW included reactive azo dye, C.I. Reactive Violet 2 (RV2), anionic surfactant (LAS) and auxiliary chemicals. An emphasis was put on the influence of the LAS on the treatment efficiency. To explore the pseudo-catalytic effect of LAS and reagent dosages on the extents of decolourization and mineralization, different experimental design techniques were utilized. Box-Behnken design was used as a base for optimization and determination of the influencing factors; numerical (Fe(2+/3+), H(2)O(2) and LAS concentration) and categorical factors (iron oxidation state and type of additional energy; US or UV-A). Furthermore, a mixture design methodology was applied. This two-step optimization approach lead to a single optimal point for two advanced oxidation processes studied in comparison. Models describing the dependency of the overall efficiency on influencing factors were obtained. Application of US/Fe(2+)/H(2)O(2) and UV-A/Fe(2+)/H(2)O(2) processes for the treatment of WW was assessed. Only 26% of mineralization was achieved by Fenton process alone applied for the treatment of the dyehouse effluent in 10-fold dilution, while 43% of mineralization was achieved by US or UV-A assisted Fenton after the 60 min.

Role of quantum dots nanoparticles in the chemical treatment of colored wastewater: catalysts or additional pollutants.

The objective of the study was to investigate the presence and the activity of quantum dots nanoparticles in colored wastewaters. The special interest is devoted to the investigation of their role in the typical treatment of water or wastewater, studying their influence on the effectiveness of applied treatments methods. The standard chemical processes for water treatment and disinfection (direct UV photolysis and direct ozonation) were applied for the degradation of colored organic pollutant, reactive azo dye, in the presence/absence of CdSe/ZnS core-shells quantum dots. The obtained results indicated that investigated nanoparticles inhibit the overall efficiency of applied processes, especially in the case of direct UV photolysis, although catalytic effect might be expected in part due to the semiconductor nature of quantum dots. Such results lead to a conclusion that CdSe/ZnS nanoparticles behave as additional pollutants in the system. They should be removed from the system prior the treatment, because their presence could decrease the efficiency, i.e., prolong the time of treatment and correspondingly increase the costs of the treatment process.

Photooxidation processes for an azo dye in aqueous media: modeling of degradation kinetic and ecological parameters evaluation.

Three photooxidation processes, UV/H(2)O(2), UV/S(2)O(8)(2-) and UV/O(3) were applied to the treatment of model wastewater containing non-biodegradable organic pollutant, azo dye Acid Orange 7 (AO7). Dye degradation was monitored using UV/VIS and total organic carbon (TOC) analysis, determining decolorization, the degradation/formation of naphthalene and benzene structured AO7 by-products, and the mineralization of model wastewater. The water quality during the treatment was evaluated on the bases of ecological parameters: chemical (COD) and biochemical (BOD(5)) oxygen demand and toxicity on Vibrio fischeri determining the EC(50) value. The main goals of the study were to develop an appropriate mathematic model (MM) predicting the behavior of the systems under investigation, and to evaluate the toxicity and biodegradability of the model wastewater during treatments. MM developed showed a high accuracy in predicting the degradation of AO7 when considering the following observed parameters: decolorization, formation/degradation of by-products and mineralization. Good agreement of the data predicted and the empirically obtained was confirmed by calculated standard deviations. The biodegradability of model wastewater was significantly improved by three processes after mineralizing a half of the initially present organic content. The toxicity AO7 model wastewater was decreased as well. The differences in monitored ecological parameters during the treatment indicated the formation of different by-products of dye degradation regarding the oxidant type applied.

The comparison of photooxidation processes for the minimization of organic load of colored wastewater applying the response surface methodology.

In this comparative study, the effectiveness of three photooxidation processes (UV/H(2)O(2), UV/S(2)O(8)(2-) and UV/O(3)) for degradation of an azo dye model pollutant was investigated using several process parameters. The process parameters such as initial pH, the concentrations of oxidant in the reactor inlet stream and the type of oxidant were considered. In order to investigate the influence of cross-factor effects of process parameters, the full factorial design was applied with three factors (two numeric and one categorical) at three levels combined with response surface modeling. The ANOVA results (R(2), F, p) showed high accuracy of developed quadratic model for the zero-order mineralization rate constants of AO7 model wastewater. Among process parameters studied, the type of oxidant and the concentration of oxidant were shown to be the most influential parameters of studied photooxidation processes. The highest rate of mineralization of AO7 model wastewater, k(obs)=7.507×10(-7) M s(-1), was obtained for UV/O(3) process at the initial pH 10 and oxidant reactor input rate of 0.6 mM min(-1). However, when comparing the operating costs for each process studied, it was evident that UV/H(2)O(2) process is 1.6 times less expensive than UV/O(3) process considering the mineralization of organic content of AO7 model wastewater.

QSAR modeling of acute toxicity on mammals caused by aromatic compounds: the case study using oral LD50 for rats.

The goal of the study was to predict toxicity in vivo caused by aromatic compounds structured with a single benzene ring and the presence or absence of different substituent groups such as hydroxyl-, nitro-, amino-, methyl-, methoxy-, etc., by using QSAR/QSPR tools. A Genetic Algorithm and multiple regression analysis were applied to select the descriptors and to generate the correlation models. The most predictive model is shown to be the 3-variable model which also has a good ratio of the number of descriptors and their predictive ability to avoid overfitting. The main contributions to the toxicity were shown to be the polarizability weighted MATS2p and the number of certain groups C-026 descriptors. The GA-MLRA approach showed good results in this study, which allows the building of a simple, interpretable and transparent model that can be used for future studies of predicting toxicity of organic compounds to mammals.

Minimization of organic content in simulated industrial wastewater by Fenton type processes: a case study.

Pre-treatment of simulated industrial wastewaters (SIM1, SIM2 and SIM3) containing organic and inorganic compounds (1,2-dichloroethane, sodium formate, sodium hydrogen carbonate, sodium carbonate and sodium chloride) by oxidative degradation using homogeneous Fenton type processes (Fe2+/H2O2 and Fe3+/H2O2) has been evaluated. The effects of initial Fe2+ and Fe3+ concentrations, [Fe2+/3+], type of iron salt (ferrous sulfate vs. ferric chloride), initial hydrogen peroxide concentration, [H2O2], on mineralization extent, i.e., total organic content (TOC) removal, were studied. Response surface methodology (RSM), particularly Box-Behnken design (BBD) was used as modelling tool, and obtained predictive function was used to optimize the overall process by the means of desirability function approach (DFA). Up to 94% of initial TOC was removed after 120 min. Ferrous sulfate was found to be the most appropriate reagent, and the optimal doses of Fe2+ and H2O2 for reducing the pollutant content, in terms of final TOC and sludge production were assessed.

Prediction of rate constants for radical degradation of aromatic pollutants in water matrix: a QSAR study.

We present the results of the QSAR/QSPR study on the degradation rate constants of 78 aromatic compounds by the hydroxyl radicals in water. A genetic algorithm and multiple regression analysis were applied to select the descriptors and to generate the correlation models. Additionally to DRAGON descriptors, the parameters from quantum-chemical calculations at semiempirical and at density functional theory level (B3LYP/6-31G(d,p)) were applied. The most predictive model is a four-variable model that had a good ratio of the number of variables and the predictive ability to avoid overfitting. As it was expected, the main contribution to the degradation rate was given by the E(HOMO) parameter. Additionally, a number of topological descriptors in selected models showed an importance of polarizability term regarding the degradation rate of compounds. Overall, the applied GA-MLRA approach with the use of quantum-chemical and DRAGON generated descriptors showed good results in this study. The obtained statistically robust structure-degradation rate model can be used for future studies of the presence of organic compounds in the environment, and especially their degradation by hydroxyl radicals as a part of a water/wastewater treatment.

Decolourization and mineralization of commercial reactive dyes by using homogeneous and heterogeneous Fenton and UV/Fenton processes.

The oxidative decolourization and mineralization of three reactive dyes in separately prepared aqueous solutions C.I. Reactive Yellow 3 (RY3), C.I. Reactive Blue 2 (RB2) and C.I. Reactive Violet 2 (RV2) by using homogeneous and heterogeneous Fenton and UV/Fenton processes have been investigated. The effects of H(2)O(2), Fe(2+) and Fe(0) concentrations, Fe(2+)/H(2)O(2) and Fe(0)/H(2)O(2) molar ratios at pH 3 and T=23+/-1 degrees C have been studied. Optimal operational conditions for the efficient degradation of all three dye solutions (100 mg L(-1)) were found to be Fe(2+)/H(2)O(2)=0.5mM/20mM and Fe(0)/H(2)O(2)=2mM/1mM. The experimental results showed that the homogeneous Fenton process employing UV irradiation was the most effective. By using this process, the high levels of mineralization (78-84%) and decolourization (95-100%) were achieved. Pseudo-first-order degradation rate constants were obtained from the batch experimental data.

Application of multi-criteria decision-making on strategic municipal solid waste management in Dalmatia, Croatia.

The efficiency of providing a waste management system in the coastal part of Croatia consisting of four Dalmatian counties has been modelled. Two multi-criteria decision-making (MCDM) methods, PROMETHEE and GAIA, were applied to assist with the systematic analysis and evaluation of the alternatives. The analysis covered two levels; first, the potential number of waste management centres resulting from possible inter-county cooperation; and second, the relative merits of siting of waste management centres in the coastal or hinterland zone was evaluated. The problem was analysed according to several criteria; and ecological, economic, social and functional criteria sets were identified as relevant to the decision-making process. The PROMETHEE and GAIA methods were shown to be efficient tools for analysing the problem considered. Such an approach provided new insights to waste management planning at the strategic level, and gave a reason for rethinking some of the existing strategic waste management documents in Croatia.

Comparative study of UV/TiO2, UV/ZnO and photo-Fenton processes for the organic reactive dye degradation in aqueous solution.

In this study advanced oxidation processes (AOPs), UV/TiO(2), UV/ZnO and photo-Fenton, were applied in order to degrade C.I. Reactive Red 45 (RR45) dye in aqueous solution. The effects of key operating parameters, such as initial pH, catalyst and hydrogen peroxide dosage as well as the effect of initial dye concentration on decolorization and mineralization extents were studied. Primary objective was to determine the optimal conditions for each of the processes. The influence of added zeolite on the process efficiency was also studied. UV/vis spectrophotometric and total organic carbon (TOC) measurements were performed for determination of decolorization and mineralization extents. It has been found that photo-Fenton process was the most efficient with 74.2% TOC removal and complete color removal achieved after a 1h treatment.

Advanced oxidation processes in azo dye wastewater treatment.

The chemical degradation of synthetic azo dyes color index (C.I.) Acid Orange 7, C.I. Direct Orange 39, and C.I. Mordant Yellow 10 has been studied by the following advanced oxidation processes: Fenton, Fenton-like, ozonation, peroxone without or with addition of solid particles, zeolites HY, and NH4ZSM5. Spectrophotometric (UV/visible light spectrum) and total organic carbon measurements were used for determination of process efficiency and reaction kinetics. The degradation rates are evaluated by determining their rate constants. The different hydroxyl radical generation processes were comparatively studied, and the most efficient experimental conditions for the degradation of organic azo dyes solutions were determined.

Fe-exchanged zeolite as the effective heterogeneous Fenton-type catalyst for the organic pollutant minimization: UV irradiation assistance.

The issue of investigations in this study was an application of heterogeneous Fenton-type catalyst, Fe-exchanged zeolite FeZSM5, for the minimization of phenol and overall organic content in the model wastewater. Applied treatment systems included variation of heterogeneous and homogeneous Fenton-type catalyst with and without the assistance of UV irradiation, FeZSM5/H2O2, Fe2+/H2O2/NH4ZSM5, Fe3+/H2O2/NH4ZSM5, UV/FeZSM5/H2O2, UV/Fe2+/H2O2/NH4ZSM5 and UV/Fe3+/H2O2/NH4ZSM5. Processes efficiency was evaluated on the basis of phenol removal, mineralization extent, H2O2 consumption and concentration of iron ions in the bulk after the treatment. By all applied systems, complete phenol removal was achieved in less than 30 min of treatment time. Systems including heterogeneous Fenton-type catalyst showed somewhat lower mineralization efficiency in comparison to the corresponding systems applying homogeneous Fenton-type catalysts and the addition of synthetic zeolite NH4ZSM5. Significantly lower concentration of iron ions in the bulk after the treatment could give these systems, particularly UV/FeZSM5/H2O2, a great advantage over the homogeneous Fenton-type systems.

Photo-assisted Fenton type processes for the degradation of phenol: a kinetic study.

In this study the application of advanced oxidation processes (AOPs), dark Fenton and photo-assisted Fenton type processes; Fe(2+)/H(2)O(2), Fe(3+)/H(2)O(2), Fe(0)/H(2)O(2), UV/Fe(2+)/H(2)O(2), UV/Fe(3+)/H(2)O(2) and UV/Fe(0)/H(2)O(2), for degradation of phenol as a model organic pollutant in the wastewater was investigated. A detail kinetic modeling which describes the degradation of phenol was performed. Mathematical models which predict phenol decomposition and formation of primary oxidation by-products: catechol, hydroquinone and benzoquinone, by applied processes were developed. The study also consist the modeling of mineralization kinetic of the phenol solution by applied AOPs. This part, besides well known reactions of Fenton and photo-Fenton chemistry, involves additional reactions which describe removal of iron from catalytic cycle through formation of ferric complexes and its regeneration induced by UV radiation. Phenol decomposition kinetic was monitored by HPLC analysis and total organic carbon content measurements (TOC). Complete phenol removal was obtained by all applied processes. Residual TOC by applied Fenton type processes ranged between 60.2 and 44.7%, while the efficiency of those processes was significantly enhanced in the presence of UV light, where residual TOC ranged between 15.2 and 2.4%.

UV-based processes for reactive azo dye mineralization.

In the present study, advanced oxidation processes, UV/H2O2, UV/O3, and UV/H2O2/O3 have been applied to bleach and degrade organic dye C.I. Reactive Red 45 in water solution. Influence of pH and hydrogen peroxide dosage on process efficiency was investigated. The rate of color removal was studied by measuring the absorbance at the characteristic wavelength while mineralization rates were obtained on the basis of total organic carbon (TOC) and adsorbable organic halides (AOX) measurements. Complete bleaching was achieved by all applied processes after 60 min while the maximal mineralization extent depended on the reaction conditions for each of the processes. It has been found that UV/H2O2/O3 process was the most efficient with 61.1% TOC removal and 72.0% AOX removal, respectively, achieved after a 1-h treatment. Time required for complete mineralization of RR45 by UV/H2O2 and UV/H2O2/O3 processes was determined as well.

Decomposition of phenol by hybrid gas/liquid electrical discharge reactors with zeolite catalysts.

Application of hybrid gas/liquid electrical discharge reactors and a liquid phase direct electrical discharge reactor for degradation of phenol in the presence and absence of zeolites have been investigated. Hybrid gas/liquid electrical discharges involve simultaneous high voltage electrical discharges in water and in the gas phase above the water surface leading to the additional OH radicals in the liquid phase and ozone formation in the gas phase with subsequent dissolution into the liquid. The role of applied zeolites, namely NH4ZSM5, FeZSM5 and HY, were also studied. Phenol degradation and production of primary phenol by-products, catechol and hydroquinone, during the treatment were monitored by HPLC measurements. The highest phenol removal results, 89.4-93.6%, were achieved by electrical discharge in combination with FeZSM5 in all three configurations of corona reactors. These results indicate that the Fenton reaction has significant influence on overall phenol removal efficiency in the electrical discharge/FeZSM5 system due to the additional OH radical formation from hydrogen peroxide generated by the water phase discharge.

Influence of iron on degradation of organic dyes in corona.

In this work application of AOPs such as Fenton process, aqueous phase high voltage electrical discharge (corona) and their combination have been studied for colored wastewater treatment. Experiments were conducted on water solutions of four different organic dyes, two azo dyes C.I. Mordant Yellow 10 (MY10) and C.I. Direct Orange 39 (DO39), and two reactive of azo type C.I. Reactive Red 45 (RR45) and C.I. Reactive Blue 137 (RB137). The efficiency of studied AOPs has been estimated on the bases of UV-vis spectrophotometric and TOC measurements. The rate constants in the kinetic model have been determined. Experimental data have been compared with the developed mathematical model.