Oxidative decomposition and mineralization of caffeine by advanced oxidation processes: The effect of hybridization.

The study consists of a detailed investigation of the degradability of the emerging water contaminant-caffeine by homogeneous and heterogeneous Advanced Oxidation Processes (AOP's), estimation of a synergy index for each hybrid operation thereof, and proposing the most plausible reaction mechanisms that are consistent with the experimental data. It also encompasses evaluation of the effect of the water matrix represented by carbonate species and humic acids, as strong scavengers of hydroxyl radicals. The results showed that single AOP's such as sonolysis (577 kHz) and photolysis with H2O2 provided complete caffeine elimination, but they were insufficient for the mineralization of the compound. Hybrid AOP's were considerably more effective, particularly when operated at a heterogeneous mode using commercial TiO2. The most effective hybrid process was UV-H2O2/TiO2, which provided more than 75% TOC decay at the minimum test doses of the reagent and catalyst. While the addition of ultrasound to the process significantly increased the rate of caffeine decomposition, it reduced the overall degradation of the compound to 64% in terms of TOC decay. The antagonistic effect was attributed to the formation of excess H2O2, and the presence of cavity clouds and/or high density layers that inhibited the transmission of UV light. The effect of natural water ingredients was found to reduce the reaction rates, signifying the major contribution of hydroxyl radicals to the destruction of caffeine. The proposed reaction mechanisms based on OH radical attack and the calculated energy barriers were in good agreement with the experimentally detected reaction byproducts.

Sonochemical decay of C.I. Acid Orange 8: effects of CCl4 and t-butyl alcohol.

Sonochemical degradation of aryl-azo-naphthol dyes represented by C.I. Acid Orange 8 was investigated at 300 kHz to assess the operational parameters and the impacts of rate enhancers (CCl(4)) and rate inhibitors (t-butyl alcohol). It was found that the degradation of the dye was accelerated with increased concentrations of CCl(4) via the accumulation of reactive chlorine species and the hindrance of OH radical combination reactions with atomic hydrogen. The addition of t-butyl alcohol at all test concentrations inhibited the degradation of the dye regardless of the quantity of OH radicals (or H(2)O(2)) in solution. The inhibition was explained by the competition of the dye and t-butyl alcohol at the gas-liquid interface. Finally, the rate of dye degradation in the presence of both reagents at their effective concentrations was found to be considerably slower than that with CCl(4), showing that the formation of reactive chlorine species was remarkably suppressed by the rapid reaction of t-butyl alcohol at the gas-liquid interface.

Optimization of methylparaben degradation by sonocatalysis.

Sonocatalytic degradation of methylparaben (MPB) in the presence of a low-cost clay mineral (sepiolite) was optimized using a multivariable center composite design protocol based on response surface methodology (RSM). Using the data generated with varying MPB concentrations, pH, frequency and catalyst dose, two semi-empirical expressions were developed to describe the relation between the apparent reaction rate constant of the parent compound and the most significant control variables. It was found that ultrasonic power, pH, sepiolite dose and its interactions with time and pH were the most significant parameters influencing the rate of MPB decay under high frequency ultrasound. The models also showed that the rate constant was a convex function of time, as it decreased during the first 35-min of sonolysis and increased thereafter, indicating the formation and depletion of competing oxidation byproducts. Finally, the models predicted that the rate of MPB decay was a maximum either at alkaline pH and a high sepiolite dose (k = 1.68 × 10-1 min-1), or at acidic pH and a considerably lower dose of the mineral (k = 1.48 × 10-1 min-1).

Sonochemical and sonocatalytic destruction of methylparaben using raw, modified and SDS-intercalated particles of a natural clay mineral.

The first part of the study is about the degradation of a common PPCP-methylparaben by high-frequency ultrasound to highlight the operation parameters, the reaction sites, the oxidation byproducts and the role of OH radicals. The second part covers the catalytic effect of a highly abundant and cost-effective clay mineral-sepiolite, and investigates the role of surface modification and SDS-composites of the clay in improving the efficiency of the degradation reactions. It was found that the compound (C0 = 10 mg L-1) was readily and totally decomposed by 30-min sonication at neutral pH, producing phenolic and aliphatic intermediates, but with insignificant mineralization. The major reaction site was the bubble-liquid interface, where the reactions were governed by OH radical attack. Modification of the sepiolite surface by pre-sonication in an ultrasonic bath improved the rate of reaction and the degree of TOC decay. Further modification by the synthesis of 20-min sonicated (200 kHz bath) SDS-intercalates of the clay was found to yield significant enhancement in the rate of target compound decomposition and the fraction of TOC decay, provided that the reaction was operated at acidic pH.

Ultrasonic destruction of bisphenol-A: the operating parameters.

Degradation of bisphenol-A (BPA) by ultrasonic irradiation at 300 kHz was investigated at varying substrate concentrations, pH, hydroxyl radical scavengers and sparge gases. It was found that increases in BPA initial concentration slowed down the reaction rate, but enhanced the sonochemical product yield. Both the rate of reaction and the product yield were adversely affected by pH elevation above the neutral level. The degree of BPA decay was fastest in the presence of air due to the formation of acids and excess radicals, and slowed down as the gas was replaced by argon and oxygen. The impact of large concentrations of hydroxyl radical scavengers such as carbonate and t-butanol was to decrease the rate of degradation, particularly when the scavenger concentration was considerably larger than that of BPA, and the deceleration was more remarkable in the presence of t-butanol than in that of carbonate.

Ultrasound-assisted advanced oxidation processes for water decontamination.

The study reflects a part of my experience in sonochemistry and ultrasound-assisted advanced oxidation processes (AOPs) acquired during the last fifteen years with my research team. The data discussed were selected from studies with azo dyes, endocrine disrupting compounds and analgesic/anti-inflammatory pharmaceuticals, which are all classified as "hazardous" or "emerging" contaminants. The research focused on their treatability by ultrasound (US) and AOPs with emphasis on the mineralization of organic carbon. Some of the highlights as pointed out in the manuscript are: i) ultrasound is capable of partially or completely oxidizing the above contaminant groups if the operating conditions are properly selected and optimized, but incapable of mineralizing them; ii) the mechanism of degradation in homogeneous solutions is OH-mediated oxidation in the bulk solution or at the bubble-liquid interface, depending on the molecular properties of the contaminant, the applied frequency and pH; iii) US-assisted AOPs such as ozonation, UV/peroxide, Fenton and UV/Fenton are substantially more effective than ultrasound alone, particularly for the mineralization process; iv) catalytic processes involving TiO2, alumina and zero-valent iron and assisted by ultrasound are promising options not only for the destruction of the parent compounds, but also for the mineralization of their oxidation byproducts. The degradation reactions in heterogeneous solutions take place mostly at the catalyst surface despite the high-water solubility of the compounds; v) sonolytic modification of the above catalysts to reduce their particle size (to nano-levels) or to decorate the surface with metallic nanoparticles increases the catalytic activity under sonolysis, photolysis and both, and improves the stability of the catalyst.

Single, simultaneous and sequential applications of ultrasonic frequencies for the elimination of ibuprofen in water.

The study is about the assessment of single and multi-frequency operations for the overall degradation of a widely consumed analgesic pharmaceutical-ibuprofen (IBP). The selected frequencies were in the range of 20-1130kHz emissions coming from probes, baths and piezo-electric transducers attached to plate-type devices. Multi-frequency operations were applied either simultaneously as "duals", or sequentially at fixed time intervals; and the total reaction time in all operations was 30-min. The work also covers evaluation of the effect of zero-valent iron (ZVI) on the efficiency of the degradation process and the performance of the reaction systems. It was found that low-frequency probe type devices especially at 20kHz were ineffective when applied singly and without ZVI, and relatively more effective in combined-frequency operations in the presence of ZVI. The power efficiencies of the reactors and/or reaction systems showed that 20-kHz probe was considerably more energy intensive than all others, and was therefore not used in multi-frequency operations. The most efficient reactor in terms of power consumption was the bath (200kHz), which however provided insufficient mineralization of the test chemical. The highest percentage of TOC decay (37%) was obtained in a dual-frequency operation (40/572kHz) with ZVI, in which the energy consumption was neither low nor exceptionally too high. A sequential operation (40+200kHz) in that respect was more efficient, because it required much less energy for a similar TOC decay performance (30%). In general, the degradation of IBP increased with increased power consumption, which in turn reduced the sonochemical yield. The study also showed that advanced Fenton reactions with ZVI were faster in the presence of ultrasound, and the metal was very effective in improving the performance of low-frequency operations.

Catalytic ozonation of paracetamol using commercial and Pt-supported nanocomposites of Al2O3: The impact of ultrasound.

The study is the assessment of commercial γ-Al2O3 and its sonolytically modified nanocomposite in catalytic ozonation of paracetamol (PCT), which is an emerging water contaminant and a highly reactive compound with ozone. The results showed that commercial alumina was ineffective regardless of the solution pH, due to the low affinity of the catalyst surface for PCT and the high reactivity of the solute with molecular ozone. The modified catalyst, which was synthesized by decoration of the original surface with nanoparticles of platinum provided considerable improvement in the performance of the catalyst, particularly in mineralization of the target compound. The presence of OH scavenging agents in solution markedly retarded the rate of PCT oxidation and organic carbon decay, to signal the importance of radical-mediated reaction mechanisms on the degradation of the compound. Finally, the attempt to accelerate the reactions by running them in the presence of ultrasound was found inadequate for the early oxidation, but highly adequate for the longer mineralization process. The failure was attributed to the diffusion of a large fraction of ozone into the gaseous cavity bubbles (reduced probability of direct reactions) and the extreme conditions of cavitation collapse that partially damaged the catalyst surface. The success (in mineralization) was explained by the shift of the reaction site from the bulk solution (poor adsorption on catalyst surfaces) to the solid surface and the gaseous cavity bubbles (via enhanced hydrophobicity), both being considerably more active reaction media.

Reprint of: Decomposition of PPCPs by ultrasound-assisted advanced Fenton reaction: A case study with salicylic acid.

The study is about the degradation of a widely used pharmaceutical and personal care product-salicylic acid by sonocatalysis, and the experimental design of the reaction system. The first part of the study consists of sonication (572kHz) in the presence of zero-valent iron (ZVI) with or without H2O2 to select and optimize the operational parameters as frequency, time, initial solute concentration, dose of reagents and pH. The second part consists of the use of response surface methodology and multiple regression to develop an experimental design modeland to assess the individual and interactive effects of pH, power (Po), ZVI dose and H2O2. The results showed that the optimal conditions predicted by the model without defining any restrictions are: pH=2.0, Po=120W, ZVI=24mgL-1, which provide total salicyclic acid and 48% TOC decay. However, the prediction implies intensive consumption of energy and reagents, and must therefore be modified by restricting the value of TOC decay to a lower value and that of pH to a higher one. Cross-validation tests showed that the prediction accuracy of the model was considerably high with 5.0-9.4% deviation from the experimental data.

Decomposition of PPCPs by ultrasound-assisted advanced Fenton reaction: A case study with salicylic acid.

The study is about the degradation of a widely used pharmaceutical and personal care product-salicylic acid by sonocatalysis, and the experimental design of the reaction system. The first part of the study consists of sonication (572kHz) in the presence of zero-valent iron (ZVI) with or without H2O2 to select and optimize the operational parameters as frequency, time, initial solute concentration, dose of reagents and pH. The second part consists of the use of response surface methodology and multiple regression to develop an experimental design modeland to assess the individual and interactive effects of pH, power (Po), ZVI dose and H2O2. The results showed that the optimal conditions predicted by the model without defining any restrictions are: pH=2.0, Po=120W, ZVI=24mgL-1, which provide total salicyclic acid and 48% TOC decay. However, the prediction implies intensive consumption of energy and reagents, and must therefore be modified by restricting the value of TOC decay to a lower value and that of pH to a higher one. Cross-validation tests showed that the prediction accuracy of the model was considerably high with 5.0-9.4% deviation from the experimental data.

Hydroxyl radical-mediated degradation of diclofenac revisited: a computational approach to assessment of reaction mechanisms and by-products.

Advanced oxidation processes (AOPs) are based on the in situ production of hydroxyl radicals (•OH) and reactive oxygen species (ROS) in water upon irradiation of the sample by UV light, ultrasound, electromagnetic radiation, and/or the addition of ozone or a semiconductor. Diclofenac (DCF), one of the emerging organic contaminants (EOC), is of environmental concern due to its abundancy in water and is known to be subjected to AOPs. The current study uses density functional theory (DFT) to elucidate the mechanisms of the reactions between •OH and DCF leading to degradation by-products, P1-P9. The initial encounter of DCF with •OH is proposed to lead to either the abstraction of a hydrogen or the addition of the hydroxyl radical to the molecule. The results showed that OH addition radicals (R add) are both kinetically and thermodynamically favored over H abstraction radicals (R abs). The intermediate radicals give degradation by-products by subsequent reactions. The by-products P7 and P8 are easily formed in agreement with experimental findings. Finally, acute toxicities at three trophic levels are estimated with the Ecological Structure Activity Relationships program. DCF and most of the by-products were found to be harmful to aquatic organisms, P9 being the only by-product that is not harmful at all three trophic levels.

Ultrasonic destruction of phenol and substituted phenols: a review of current research.

Phenol and some of its derivatives such as chlorophenol and nitrophenol have received considerable attention from environmental scientists and engineers, due to their undesirable effects in the water environment, where they end up as a result of improper disposal methods. As a consequence, research has been conducted all around the world with the common goal of reducing their concentrations to allowable limits or converting them to non-toxic, non-hazardous forms that may easily be handled by natural decay processes. Some of this research has focused on ultrasonic techniques, which currently appears to present a convenient but as yet unproven method for large scale water remediation. The goal of this study is to identify and review some of these studies that are directly related with the use of ultrasound in decontaminating effluents with phenol residuals and to summarize the main points of interest and problems encountered.

Enhanced photo-degradation of paracetamol on n-platinum-loaded TiO2: The effect of ultrasound and OH/hole scavengers.

Elimination/mineralization of paracetamol (PCT) was investigated by catalytic oxidation under ultrasound, UV and both. The catalyst was synthesized by immobilization of nPt on TiO2 to benefit from the ability of Pt to facilitate charge transfer processes and to separate e(-)/h(+) pairs. It was found that increasing the Pt-loading enhanced the rate of sonochemical reactions, but retarded that of photolytic reactions, due to reduced UV absorption on the surface. Simultaneous application of sonolysis and photolysis was synergistic due to disaggregation of the particles and homogenization of the active species over the catalyst surface. The decay of PCT was highly dependent on the availability of OH, as the reactions were nearly terminated in the presence of a strong OH scavenger-2-propanol. However, a remarkable rate enhancement was observed in the presence of a suitable dose of I(-), which scavenges both OH and hvb(+). The result was explained by the production of excess radicals upon sonolysis of iodide solutions, and the reactivity of PCT with them. Finally, carbon mineralization was significantly hindered in the presence of both scavengers due to increased competition for OH and inefficient formation of hydroquinone arising from reduced availability of hvb(+).

Impacts of pH and molecular structure on ultrasonic degradation of azo dyes.

Sonochemical bleaching of monoazo dyes was investigated by irradiating 30 microM solutions of two "aryl-azo-naphthol" type model dyes in acidic, neutral and basic conditions using a 300 kHz emitter. It was found that the rate of bleaching in all cases was first order with respect to the maximum absorption of the dye in the visible band, and accelerated with increased acidity. The inhibition observed at alkaline conditions was attributed to the formation of anionic dye structures and their competition with the dye and its intermediate oxidation products for hydroxyl radicals, which are the major precursors of azo dye oxidation in sonicated water. Decolorization of the dyes was also related to the size of the molecule and the type or position of substituents about azo bonds. Comparison of color decay rates at similar conditions showed that the dye with a simple structure, low molecular mass and one ortho-substituent (hydroxyl) about the azo bond bleached considerably faster than the one having a more complicated structure (higher mass) and an additional o-substituent to the azo bond other than the OH group.

Sonochemical degradation of diclofenac: byproduct assessment, reaction mechanisms and environmental considerations.

The study covers a thorough assessment of the overall degradation of diclofenac-Na (DCF) by high-frequency ultrasound, focusing particularly on identification, interpretation, and characterization of the oxidation byproducts and their reaction mechanisms. It was found that sonication of 5 mg L(-1) DCF at near neutral pH rendered complete conversion of the compound, 45 % carbon, 30 % chlorine, and 25 % nitrogen mineralization. Density functional theory (DFT) calculations confirmed the experimentally detected major byproduct 2,6-dichloroaniline, the formation of which was explained by OH• addition to the ipso-position of the amino group. The stability of UV absorption at around 276-280 nm throughout reaction was in agreement with the detected byproduct structures, i.e., the presence of amino/amine groups and phenolic, aniline, benzene, and quinine-type derivatives, which all absorbed at around the same band. Microtox toxicity of the reactor aliquots at early reaction showed that initially the reaction products, specifically 1-(2,6-dichlorophenyl)-2-indoline-one, were very toxic; subsequently toxicity exhibited a fluctuating pattern, and a steady declination towards the "non-toxic" level was observed only after 90 min. Oxygen uptake analysis also revealed the formation of harmful products at early reaction, but the reactor was totally biodegradable upon 1-h sonication.

More on sonolytic and sonocatalytic decomposition of Diclofenac using zero-valent iron.

The study is an extension of our previous work on sonolytic and sonocatalytic decomposition of Diclofenac-Na (DCF) to depict and highlight further operation parameters of significance, and to assess the effect of a novel home-made catalyst made of magnetic nanoparticles of zero-valent iron (ZVI). It was found that high-frequency was more effective than power ultrasound (20 kHz), and the efficiency was a maximum at 861 kHz, acetate-buffered pH 3.0 and air bubbling provided that samples were prepared from a pre-heated stock solution to enhance solubility of the compound. As such, 40-min sonication rendered nearly complete transformation of DCF to intermediate products that were more biodegradable than itself, but with little mineralization of organic carbon. Catalytic sono-treatment showed that the effect of the catalyst was largest in a non-buffered acidic solution and the rate of DCF elimination increased with increasing concentrations of solids up to a "critical" mass, above which it declined via the coalescence of particles and bubbles. Sonocatalysis using the "effective" solid mass also enhanced the overall degradation or mineralization of the compound as portrayed by the accumulation of chloride and nitrate ions in solution after prolonged contact. The production of excess H(2)O(2) during catalysis with ZVI was attributed to the presence of additional and major routes of (·)OH and/or H(2)O(2) formation (other than water pyrolysis). The initial rate of DCF degradation in the presence of nanoparticles was found highly sensitive to the mass of solids in solution, declining sharply as the mass exceeded a "critical" effective level. A catalyst efficacy factor was defined as a function of the initial mass ratio of Fe(0) to DCF and found to be one order of magnitude larger than that obtained by using commercial microparticles with a threefold larger Fe content. The result signifies that the role of aqueous Advanced Fenton reactions (Fe(0)/H(2)O(2)) was less significant in the presence of nanoparticles relative to that of heterogeneous reactions with reactive Fe and oxygen species on the massive surface areas with enriched reaction/adsorption and nucleation sites.

The occurrence and fate of anti-inflammatory and analgesic pharmaceuticals in sewage and fresh water: treatability by conventional and non-conventional processes.

The presence of pharmaceutical (PhAC) residues in the environment is an emerging issue due to their continuous and uncontrolled release (via excretion from medical care) to the water environment and detrimental effects on aquatic organisms at low concentrations. A large fraction of PhAC pollution in water is composed of anti-inflammatory (AI) and analgesic (AN) drugs, which are rapidly excreted in urine. The present review is aimed to emphasize the occurrence of AI/AN wastes in sewage and fresh water bodies, their impacts on non-target organisms, and conversion or elimination by chemical, biochemical and physical treatment methods. The first part of the study is devoted to a critical review of most common AI/AN drugs and the relative efficiency of some selected sewage and drinking water treatment operations for their elimination/separation from aqueous systems. The second part focuses on pilot- or lab-scale applications of various advanced oxidation processes that are promising solutions to the ultimate degradation and/or conversion of such medical residues in effluents of drinking water treatment plants (DWTPs) and wastewater treatment plants (WWTPs) to less harmful and non-toxic products.

Degradation of diclofenac in water by homogeneous and heterogeneous sonolysis.

The study is about the degradation of a widely used anti-inflammatory drug-diclofenac (DCF) by high frequency ultrasound to select the operating conditions and to improve the process efficiency by the addition of iron species. The initial concentration, pH and frequency of operation that rendered maximum degradation of the drug were 30 µM, 3.0 and 861 kHz, respectively. The efficacy (EF) of each additive was expressed by a "yield factor" defined as the change in DCF concentration in 1-h sonication per unit mass of Fe in the reactor. Estimated values of EF were 41.54, 1.65 and 0.02 µM mg(-1), respectively for non-reactive iron superoxide nanoparticles (NPI), reactive divalent iron (DVI) and reactive zero-valent iron (ZVI). The remarkably high yield in presence of NPI was attributed to the synergy of nanotechnology and ultrasound; i.e. combined effects of massive surface area, excess cavitation nuclei, enhanced mass transfer and continuous cleaning of the metal surface. Total mineralization after 90 min sonication of DCF in the presence of 8.9 mM ZVI, 0.01 mM DVI and 0.001 mM NPI were 22%, 43% and 30%, respectively. Although DVI provided a larger degree of mineralization, the efficiency of NPI was still higher owing to its 10-fold lower effective dose.

Impact of dilution on the transport of poly(acrylic acid) supported magnetite nanoparticles in porous media.

This paper investigates the impact of dilution on the mobility of magnetite nanoparticles surface coated with poly(acrylic acid) (PAA). Transport experiments were conducted in a water-saturated sand-packed column for input nanoparticle solutions with total Fe concentrations ranging from 100 to 600mg/L. Particle size analysis of the synthesized nanoparticle solutions showed that PAA provides good size stability for Fe concentrations as low as about 1mg/L. Time-moment analysis of the nanoparticle breakthrough curves, on the other hand, revealed that nanoparticle mass recovery from the column decreased consistently with dilution, with greater attenuation, sharper fronts and longer tails compared to that of the tracer. Particle size analysis of the eluted solutions shows that the nanoparticle size is negatively correlated with nanoparticle concentration. Modeling results suggest that the decrease in nanoparticle mobility with input concentration can be represented using a kinetic time-dependent deposition term with finite deposition capacity and a kinetic detachment term. For field applications, the increase in particle size and detachment resulting from dilution means reduced transport efficiency of nanoparticles and reaction potential with travel distance.

Sonolytic and sonocatalytic degradation of azo dyes by low and high frequency ultrasound.

The study describes degradation of two azo dyes at low and high frequency ultrasound (US) to compare their reactivity and to assess the impacts of frequency, OH, chemical structure and soluble/nonsoluble additives. Low frequency US alone was found totally ineffective for bleaching the dyes even after 2-h irradiation, while high frequency provided significant color decay in 30-min contact. The result was attributed to larger number of oscillations at high frequency that allowed a larger fraction of OH ejection to the bulk liquid. The difference in the rates of dye degradation was due to different substituents around the azo bonds that dictated the reactivities of the dyes with OH and other species. The performance of low frequency US was remarkably improved and exceeded that of high frequency in the presence of CCl(4), nano-sized TiO(2) and zero-valent copper. The effect was attributed to the advantage of low frequency for long bubble-life time, high collapse temperatures, turbulent flow conditions and high sonoluminescence intensity. The efficacies of the additives in terms of the reduction in dye concentration per unit mass of additive were: TiO(2)>CCl(4)>Cu, regardless of the dye structure and the operation frequency. Much better performance of TiO(2) than Cu was attributed to its larger surface area with a slight positive charge on it and to the effect of stable sonoluminescence that may have induced photocatalytic properties on semiconductor surface.