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 HO provided complete caffeine elimination, but they were insufficient for the mineralization of the compound.

Hydroxyl radical-mediated degradation of salicylic acid and methyl paraben: an experimental and computational approach to assess the reaction mechanisms.

Advanced oxidation processes (AOPs) using various energy sources and oxidants to produce reactive oxygen species are widely used for the destruction of recalcitrant water contaminants. The current study is about the degradation of two emerging pollutants-salicylic acid (SA) and methyl paraben (MP)-by high-frequency ultrasonication followed by identification of the oxidation byproducts and modeling of the reaction mechanisms using the density functional theory (DFT). The study also encompasses prediction of the aquatic toxicity and potential risk of the identified byproducts to some aquatic organisms bussing the ECOSAR (Ecological Structure Activity Relationships) protocol.

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.

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 (C = 10 mg L) was readily and totally decomposed by 30-min sonication at neutral pH, producing phenolic and aliphatic intermediates, but with insignificant mineralization.

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 HO 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 (P), ZVI dose and HO.

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 HO 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 (P), ZVI dose and HO.

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.

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.

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

The study is the assessment of commercial γ-AlO 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.

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.

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.

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.

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.

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.

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.

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.

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.

Sonochemical destruction of nonylphenol: effects of pH and hydroxyl radical scavengers.

Nonylphenols are water-stable endocrine disrupting compounds that inhibit the growth of sewage bacteria in biological processes. The study describes the decomposition of 4-n-nonylphenol (NP) in water by 20 kHz ultrasound with emphasis on the impacts of pH, concentration and OH scavengers. It was found that the rate of degradation was accelerated by alkalinization, but more so by the addition of hydroxide alkalinity than carbonate.

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).

Synthetic endocrine disruptors in the environment and water remediation by advanced oxidation processes.

The present study is an overview of the literature on classes and types of compounds described as "endocrine disruptors" and their treatability in water by advanced oxidation processes, which generate hydroxyl radicals in water. The review is limited to details of the destruction of three classes of endocrine disruptors, namely bisphenols, alkylphenols and phthalates, which are among the most highly suspected endocrine disrupting compounds that interfere with the hormonal system of wildlife. It was found that photocatalysis with titanium dioxide was the most frequently tested advanced oxidation method most likely due its potential to render complete mineralization.

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.

Experimental and modeling approach to decolorization of azo dyes by ultrasound: degradation of the hydrazone tautomer.

Sonochemical bleaching of monoazo dyes C.I. Acid Orange 7 and C.

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.

Degradation of reactive azo dyes by UV/H2O2: impact of radical scavengers.

Hydroxyl radical (*OH) scavenging effects of carbonate (CO3(2-)), bicarbonate (HCO3-) and chloride (Cl-) ions on the performance of an ultraviolet light-hydrogen peroxide (UV/H2O2) advanced oxidation process were investigated using a reactive azo dye, C.I. Reactive Red 141 as the model compound.

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.