Sonochemical and photosonochemical degradation of 4-chlorophenol in aqueous media

The degradation of 4-chlorophenol (4-CP) in aqueous media by 516 kHz ultrasonic irradiation was investigated in order to clarify the degradation mechanism. The degradation of concentrated 4-CP solution by means of ultrasound, UV irradiation and their combined application was also studied. The obtained results indicate that *OH radical are the primary reactive species responsible for 4-CP ultrasonic degradation. Very little 4-CP degradation occurs if the sonolysis is carried out in the presence of the *OH radical scavenger tert-butyl alcohol, also indicating that little or no pyrolysis of the compound occurs. The dominant degradation mechanism is the reaction of substrate with *OH radicals at the gas bubble-liquid interface rather than high temperature direct pyrolysis in ultrasonic cavities. This mechanism can explain the lower degradation rate of the ionic form of 4-CP that is partly due to the rapid dissociation of *OH radicals in alkaline solutions. The sonochemical destruction of concentrated 4-CP aqueous solution is obtained with low rate. Coupling photolysis with ultrasound irradiation results in increased efficiency compared to the individual processes operating at common conditions. Interestingly, the photosonochemical decomposition rate constant is greater than the additive rate constants of the two processes. This may be the result of three different oxidative processes direct photochemical action, high frequency sonochemistry and reaction with ozone produced by UV irradiation of air, dissolved in liquid phase because of the geyser effect of ultrasound streaming. Additionally, the photodecomposition, at 254 nm, of hydrogen peroxide produced by ultrasound generating *OH radical can partly explain the destruction enhancement.     

Sonolysis of 4-chlorophenol in aqueous solution: effects of substrate concentration, aqueous temperature and ultrasonic frequency

The sonolysis of 4-chlorophenol (4-CP) in O2-saturated aqueous solutions is investigated for a variety of operating conditions with the loss of 4-CP from solution following pseudo-first-order reaction kinetics. Hydroquinone (HQ) and 4-chlorocatechol (4-CC) are the predominant intermediates which are degraded on extended ultrasonic irradiation. The final products are identified as Cl-, CO2, CO, and HCO2H. The rate of 4-CP degradation is dependent on the initial 4-CP concentration with an essentially linear increase in degradation rate at low initial 4-CP concentrations but with a plateauing in the rate increase observed at high reactant concentrations. The results obtained indicate that degradation takes place in the solution bulk at low reactant concentrations while at higher concentrations degradation occurs predominantly at the gas bubble-liquid interface. The aqueous temperature has a significant effect on the reaction rate. At low frequency (20 kHz) a lower liquid temperature favours the sonochemical degradation of 4-CP while at high frequency (500 kHz) the rate of 4-CP degradation is minimally perturbed with a slight optimum at around 40 degrees C. The rate of 4-CP degradation is frequency dependent with maximum rate of degradation occurring (of the frequencies studied) at 200 kHz.     

Sonochemical and sonophotocatalytic degradation of malachite green: the effect of carbon tetrachloride on reaction rates

A comparative study between the sonolytic, photocatalytic and sonophotocatalytic oxidation processes of aqueous solutions of malachite green was carried out in the presence of carbon tetrachloride, under a low power ultrasonic field (<15 W) and using titanium dioxide as a photocatalyst. The effect of a number of parameters such as ultrasonic intensity, TiO2 crystalline structure and the presence of CCl4 were studied using an inexpensive reactor. Enhanced rates of sonolytic degradation of malachite green in the presence of CCl4 were demonstrated. On the other hand, the simultaneous use of sonolysis and photocatalysis in the presence of CCl4 does not improve the degradation rate of malachite green in comparison with the one obtained using only sonolysis, but it makes possible a faster oxidative degradation of some reaction intermediaries. Finally, in air saturated solutions both processes, the sonolytic and the photocatalytic one, follow a first-order rate law.     

Sonochemical degradation of chlorophenols in water

Sonochemical degradation of dilute aqueous solutions of 2-, 3- and 4-chlorophenol and pentachlorophenol has been investigated under air or argon atmosphere. The degradation follows first-order kinetics in the initial state with rates in the range 4.5-6.6 microM min-1 under air and 6.0-7.2 microM min-1 under argon at a concentration of 100 microM of chlorophenols. The rate of OH radical formation from water is 19.8 microM min-1 under argon and 14.7 microM min-1 under air in the same sonolysis conditions. The sonolysis of chlorophenols is effectively inhibited, but not completely, by the addition of t-BuOH, which is known to be an efficient OH radical scavenger in aqueous sonolysis. This suggests that the main degradation of chlorophenols proceeds via reaction with OH radicals; a thermal reaction also occurs, although its contribution is small. The addition of appropriate amounts of Fe(II) ions accelerates the degradation. This is probably due to the regeneration of OH radicals from hydrogen peroxide, which would be formed from recombination of OH radicals and which may contribute a little to the degradation. The ability to inhibit bacterial multiplication of pentachlorophenol decreases with ultrasonic irradiation.     

Improvement in sonochemical degradation of 4-chlorophenol by combined use of Fenton-like reagents

Studies on the sonolysis of a wide range of organic compounds have demonstrated that ultrasonic irradiation has potential for decomposition of organic pollutants in hazardous wastewater. However, the ultrasonic irradiation alone cannot provide high enough rate of decomposition to be used practically. One of the solutions to increase the degradation efficiency is to combine the ultrasound application with other advanced chemical oxidation processes (AOPs). In this study, in order to increase the efficiency of ultrasonically assisted degradation of organic pollutants in water, we examined effects of three kinds of solid Fe-containing catalysts, namely iron powder, basic oxygen furnace (BOF) slag and mill scale on the degradation rate of 4-CP (4-chlorophenol) in aqueous solutions containing hydrogen peroxide. In the experiments, 4-CP was considered as a model organic compound. All three Fe-containing matters when react with hydrogen peroxide are involved in the Fenton-like reaction system, which is one of the promising AOPs. The results showed that both the iron powder and mill scale additions can accelerate the degradation of 4-CP, although the effect is dependent on the solution pH. All 4-CP could be decomposed for 2 min at pH=3 and for 1h at pH=5.6. On the other hand, the BOF slag had no catalysis effect on the 4-CP degradation because of higher concentration of calcium and lower concentration of iron.     

p-Aminophenol degradation by ozonation combined with sonolysis: operating conditions influence and mechanism

The degradation of p-aminophenol (PAP) in aqueous solution by sonolysis, by ozonation, and by a combination of both was investigated in laboratory-scale experiments. Operation parameters such as pH, temperature, ultrasonic energy density and ozone dose were optimized with regard to the efficiency of PAP removal. The concentration of PAP during the reaction was detected by high-pressure liquid chromatography. The concentrations of ammonium ions and nitrate ions were monitored during the degradation. Intermediate products such as 4-iminocyclohexa-2,5-dien-1-one, phenol, but-2-enedioic acid, and acetic acid were detected by gas chromatography coupled with mass spectrometry. The degradation rate of PAP was higher in the combined system than in the linear combination of separate experiments. The degradation efficiency was decreased rapidly when n-butanol was added to the combined reaction system, which showed that some radical reaction might proceed during the laboratory experiments.     

The kinetics and mechanism of ultrasonic degradation of p-nitrophenol in aqueous solution with CCl4 enhancement

The ultrasonic degradation of p-nitrophenol (p-NP) in aqueous solution with CCl₄ enhancement was studied. The effects of operating parameters such as CCl₄ dosage, ultrasonic power, media temperature, the initial concentration of p-NP and initial pH value of the aqueous solution on the degradation of p-NP were investigated, and the enhancement mechanism of CCl₄ for p-NP sonolysis was also discussed. The results showed that the sonochemical degradation of p-NP was obviously enhanced by adding CCl₄. It attributed to the increase OH radicals concentration in the presence of CCl₄ as a hydrogen atom scavenger, and the formation of some oxidizing agents such as free chlorine and chlorine-containing radicals. The degradation of p-NP follows a pseudo-first-order kinetics. The degradation rate of p-NP increased with decreasing the temperature, the initial pH value of the solution and decreasing the initial concentration of p-NP. It was also found that p-NP can be mineralized in this process.     

Protonation of norharmane as a sonochemical dosimeter for organic media. The effect of temperature

The sonolysis of different organic and aqueous media in the presence of norharmane produce its protonation. This simple and reversible reaction is particularly suitable as a dosimetric reaction in order to measure the relative amount of cavitation induced by the ultrasonic irradiation in non aqueous solutions. The protonation rate increases when small amounts of chloroform are added to the solution. The frequency (20 and 475 kHz) and temperature effects on the reaction rate are also studied. Our results show that sonication of aqueous solutions at high frequency leads to a strongly oxidant medium.     

Sonolysis of aqueous 4-nitrophenol at low and high pH

The sonolysis of 4-nitrophenol in argon-saturated aqueous solution has been studied at 321 kHz. In order to evaluate separately the effect of OH radicals that are formed in the cavitational bubble and part of which react in the aqueous phase with this substrate, radiolytic studies in N2O-saturated solutions were carried out for comparison. A detailed product study of the sonolysis of 4-nitrophenol solutions shows that at pH 10, where 4-nitrophenol is deprotonated (pKa = 7.1), its sonolytic degradation is fully accounted for by OH-radical-induced reactions in the aqueous phase. At this pH, the sonolytic yield of H2O2 resulting from OH radical recombination in the solution, measured as a function of the 4-nitrophenol concentration, is reduced in line with the scavenging capacity of the 4-nitrophenolate. In contrast, at pH 4 the formation of H2O2 is already fully suppressed when the solution is 7 x 10(-4) mol dm-3 in 4-nitrophenol, and oxidative-pyrolytic degradation predominates, as exemplified by the large yields of CO and CO2 which are accompanied by a large H2 yield. The basis of this difference in behavior is a hydrophobic enrichment of 4-nitrophenol (which is undissociated at pH 4) at the interface of the cavitational bubble by a factor of about 80. The pH dependence of the yields of the pyrolytic products reflects the hydrolytic equilibrium concentration of 4-nitrophenol. The paper also demonstrates that the complexity of this sonochemical system precludes its use a gauge to determine the temperature in the interior of the cavitational bubble.     

Sonolysis of per- and poly fluoroalkyl substances (PFAS): A meta-analysis

Human ingestion of per- and polyfluoroalkyl substances (PFAS) from contaminated food and water is linked to the development of several cancers, birth defects and other illnesses. The complete mineralisation of aqueous PFAS by ultrasound (sonolysis) into harmless inorganics has been demonstrated in many studies. However, the range and interconnected nature of reaction parameters (frequency, power, temperature etc.), and variety of reaction metrics used, limits understanding of degradation mechanisms and parametric trends. This work summarises the state-of-the-art for PFAS sonolysis, considering reaction mechanisms, kinetics, intermediates, products, rate limiting steps, reactant and product measurement techniques, and effects of co-contaminants. The meta-analysis showed that mid-high frequency (100 – 1,000 kHz) sonolysis mechanisms are similar, regardless of reaction conditions, while the low frequency (20 – 100 kHz) mechanisms are specific to oxidative species added, less well understood, and generally slower than mid-high frequency mechanisms. Arguments suggest that PFAS degradation occurs via adsorption (not absorption) at the bubble interface, followed by headgroup cleavage. Further mechanistic steps toward mineralisation remain to be proven. For the first time, complete stoichiometric reaction equations are derived for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) sonolysis, which add H₂ as a reaction product and consider CO an intermediate. Fluorinated intermediate products are derived for common, and more novel PFAS, and a naming system proposed for novel perfluoroether carboxylates. The meta-analysis also revealed the transition between pseudo first and zero order PFOA/S kinetics commonly occurs at 15 – 40 µM. Optimum values of; ultrasonic frequency (300 – 500 kHz), concentration (>15 – 40 μM), temperature (≈20 °C), and pH range (3.2 – 4) for rapid PFOX degradation are derived by evaluation of prior works, while optimum values for the dilution factor applied to PFAS containing firefighting foams and applied power require further work. Rate limiting steps are debated and F⁻ is shown to be rate enhancing, while SO₄²⁻ and CO₂ by products are theorised to be rate limiting. Sonolysis was compared to other PFAS destructive technologies and shown to be the only treatment which fully mineralises PFAS, degrades different PFAS in order of decreasing hydrophobicity, is parametrically well studied, and has low-moderate energy requirements (several kWh g⁻¹ PFAS). It is concluded that sonolysis of PFAS in environmental samples would be well incorporated within a treatment train for improved efficiency.     

Exploring the effects of pulsed ultrasound at 205 and 616 kHz on the sonochemical degradation of octylbenzene sulfonate

Compared to continuous wave (CW) ultrasound, pulsed wave (PW) ultrasound has been shown to result in enhanced sonochemical degradation of octylbenzene sulfonate (OBS). However, pulsed ultrasound was investigated under limited pulsing conditions. In this study, pulse-enhanced degradation of OBS was investigated over a broad range of pulsing conditions and at two ultrasonic frequencies (616 and 205 kHz). The rate of OBS degradation was compared to the rate of formation of 2-hydroxyterephthalic acid (HTA) following sonolysis of aqueous terephthalic acid (TA) solutions. This study shows that sonication mode and ultrasound frequency affect both OBS degradation and HTA formation rates, but not necessarily in the same way. Unlike TA, OBS, being a surface active solute, alters the cavitation bubble field by adsorbing to the gas/solution interface of cavitation bubbles. Enhanced OBS degradation rates during pulsing are attributed to this adsorption process. However, negative or smaller pulse enhancements compared to enhanced HTA formation rates are attributed to a decrease in the high-energy stable bubble population and a corresponding increase in the transient bubble population. Therefore, sonochemical activity as determined from TA sonolysis cannot be used as a measure of the effect of pulsing on the rate of degradation of surfactants in water. Over relatively long sonolysis times, a decrease in the rate of OBS degradation was observed under CW, but not under PW conditions. We propose that the generation and accumulation of surface active and volatile byproducts on the surface and inside of cavitation bubbles, respectively, during CW sonolysis is a contributing factor to this effect. This result suggests that there are practical applications to the use of pulsed ultrasound as a method to degrade surface active contaminants in water.     

Secondary sonochemical effect on Mo-catalyzed bromination of aromatic compounds

The Molybdate-catalyzed bromination of various aromatic compounds in the presence of KBr/H(2)O(2) in an aqueous/chloroform biphasic system occurred under ultrasonic irradiation, whereas the reaction did not take place under conventional mechanical stirring (1400 rpm). The sonochemical activation was found to be of secondary effect, attributed to lowering pH by sonolysis of CHCl(3)-H(2)O solvents mixture.     

Sonolysis of an aqueous mixture of trichloroethylene and chlorobenzene

The effect of the initial concentration on the ultrasonic degradation of two volatile organic compounds trichloroethylene (TCE) and chlorobenzene (CB) was investigated. At higher concentrations, slower sonolysis rates were obtained due to the lowering of the average specific heat ratio gamma of the gas inside the cavitation bubbles. Furthermore, the effect of different concentrations of CB on the sonolysis of 3.34 mM TCE and the effect of different concentrations of TCE on the sonolysis of 3.44 mM CB was examined. The presence of CB lowered the sonolysis rate of TCE, while the sonolysis rate of CB did not decrease by TCE addition. An even higher sonolysis rate was obtained for 3.44 mM CB in the presence of 0.84 mM TCE than without TCE. The explanation for the different effects of both volatile organics on each other's sonolysis rate is thought to be the difference in reaction rate of TCE and CB with the radicals formed during sonolysis. The effect of TCE on the sonolysis rate of CB by lowering the gamma value is compensated by an increased indirect degradation of CB by radicals formed out of TCE. The decreased thermal degradation and the increased indirect radical degradation of CB in the presence of TCE is demonstrated by determining the kinetics of the degradation products styrene and dichlorobenzene.     

Sonochemical degradation of various monocyclic aromatic compounds: relation between hydrophobicities of organic compounds and the decomposition rates

Various aromatic compounds, i.e., nitrobenzene, aniline, phenol, benzoic acid, salicylic acid, 2-chlorophenol, 4-chlorophenol, styrene, chlorobenzene, toluene, ethylbenzene and n-propylbenzene were decomposed under identical ultrasonic irradiation conditions. The relationships between the initial rates of degradation of these aromatic compounds and their physicochemical parameters were systematically investigated. It was revealed that some correlations between the degradation rates and parameters of volatility, Henry's law constant and vapor pressure, were observed only in the limited high range of parameters. It was suggested that the Henry's law constant and vapor pressure had influenced on the rate of degradation for some of the tested aromatic compounds. In contrast, better correlations between the initial rates of degradation and hydrophobic parameters, water solubility and LogP (water-octanol partition coefficient), were observed over the wide range of chosen parameters. These results meant that the hydrophobicity of the compounds significantly affected their accumulation at the gas-liquid interface of the bubbles and it was the most important factor for the sonochemical degradation of aromatic compounds. In particular, for the sonolysis of water-insoluble organic compounds, LogP was found to be the representative parameter for understanding the hydrophobic properties of water-insoluble compounds.     

Phenol degradation under visible light irradiation in the continuous system of photocatalysis and sonolysis

The combination of photocatalysis under visible light irradiation and sonolysis in the continuous system has been used to degrade an aqueous solution of phenol. ZnFe₂O₄/TiO₂–GAC was employed as the photocatalysts which were obtained by sol–gel process and characterized by spectroscopic X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray microanalyses (SEM–EDX) and Brunauer–Emmett–Teller sorptometer (BET). It was observed that the rates of phenol degradation were affected by the initial pH value of phenol solution, salt addition, gas supplying and the recycling times of the recovered photocatalyst. The kinetic law for the phenol degradation can be apparently expressed as the first-order with respect to the concentration of phenol. Degradation of phenol solution in the continuous system, i.e., photocatalysis and sonolysis has synergistic effect in comparison with the photocatalytic reaction and sonolysis, respectively.     

A systematic study of the degradation of dimethyl phthalate using a high-frequency ultrasonic process

A comprehensive study of the sonochemical degradation of dimethyl phthalate (DMP) was carried out using high-frequency ultrasonic processes. The effects of various operating parameters were investigated, including ultrasonic frequency, power density, initial DMP concentration, solution pH and the presence of hydrogen peroxide. In general, a frequency of 400 kHz was the optimum for achieving the highest DMP degradation rate. The degradation rate was directly proportional to the power density and inversely related to the initial DMP concentration. It was interesting to find that faster removal rate was observed under weakly acidic condition, while hydrolysis effect dominated in extreme-basic condition. The addition of hydrogen peroxide can increase the radical generation to some extent. Furthermore, both hydroxylation of the aromatic ring and oxidation of the aliphatic chain appear to be the major mechanism of DMP degradation by sonolysis based on LC/ESI-MS analysis. Among the principle reaction intermediates identified, tri- and tetra-hydroxylated derivatives of DMP, as well as hydroxylated monomethyl phthalates and hydroxylated phthalic acid were reported for the first time in this study. Reaction pathways for DMP sonolysis are proposed based on the detected intermediates.     

Sonolysis of chlorobenzene in aqueous solution: organic intermediates

The ultrasonic degradation of 1.72 mM chlorobenzene was investigated. The sonolysis of chlorobenzene followed first-order kinetics. The influence of the pH of the aqueous solution and the effect of the saturating gás, air or argon, was measured. No pH effect was noticed, and saturation with the monoatomic argon accelerated the degradation. Furthermore, the addition of the radical scavenger benzoate demonstrated that no significant degradation took place in the bulk solution. For air-saturated solutions, the following organic degradation products were identified: methane, acetylene, butenyne, butadiyne, benzene, chlorophenols, phenylacetylene and other chlorinated and non-chlorinated monocyclic and dicyclic hydrocarbons. For argon-saturated solutions, the same products were found, except for the chlorophenols. The presence of the chlorophenols in the case of air-saturation only demonstrated the interaction between the radicals formed and oxygen, and no direct degradation by OH. radicals. The kinetics of several organic degradation products and chloride were determined for the sonolysis of air- and argon-saturated solutions.     

Degradation of orange-G by advanced oxidation processes

The degradation and mineralization of orange-G (OG) in aqueous solutions by means of ultrasound irradiation at a frequency of 213 kHz and its combination with a heterogeneous photocatalyst (TiO₂) were investigated. The effects of various operational parameters such as, the concentration of the dye and solution pH on the degradation efficiency were studied. The degradation of the dye followed first-order like kinetics under the conditions examined. The sonolytic degradation of OG was relatively higher at pH 5.8 than that at pH 12. However, an alkaline pH was favoured for the photocatalytic degradation of OG using TiO₂. Total organic carbon (TOC) measurements were also carried out in order to evaluate the mineralization efficiency of OG using sonolysis, photocatalysis and sonophotocatalysis. The hybrid technique of sonophotocatalytic degradation was compared with the individual techniques of photocatalysis and sonolysis. A simple additive effect was observed during the sonophotocatalytic oxidation of OG using TiO₂ indicating that the combined treatment offers no synergistic enhancement. TOC results also support the additive effect in the dual treatment process.     

A combination of ultrasound and a bio-catalyst: removal of 2-chlorophenol from aqueous solution

Phenolic compounds have become a cause for worldwide concern due to their persistence, toxicity and health risks. This paper reports a three-step approach to remove 2-chlorophenol from dilute aqueous solution and compares each technique. The first step utilizes Horse Radish Peroxidase (HRP) in presence of hydrogen peroxide to oxidize this organic pollutant (enzyme treatment). For a more efficient removal of 2-chlorophenol, it is necessary to add the enzyme solution gradually to the contents of the reactor instead of rapid addition. The second step, involving ultrasonic waves eliminated 2-chlorophenol through hydroxyl radical generated by the cavitation process (sono-degradation). In the third step, a combination of ultrasonic waves and enzyme was used (sono-enzyme degradation). It should be mentioned that, the enzyme can be active in the presence of ultrasonic waves under the proper sonication. The degradation has been studied at different temperatures, intensities of irradiation, and concentrations of enzyme. The rate of degradation exhibited pseudo-first order behavior and the combination method was more effective than sonolysis and enzyme treatment individually.     

Sonolytic degradation of endocrine disrupting chemical 4-cumylphenol in water

The sonolytic degradation of endocrine disrupting compound 4-cumylphenol (4-CyP) in aqueous solution was investigated. The influence of operating parameters for sonication process such as 4-CyP initial concentration, frequency, power, pH, temperature and saturating gas was examined. The extent of degradation was inversely proportional to the initial substrate concentration. The rate of 4-CyP degradation was frequency dependent. The degradation rate increased proportionally with increasing ultrasonic power from 20 to 100 W and temperature in the range of 20-50°C. The most favorable degradation pH was acidic media. Destruction in the presence of saturating gas follows the order: argon>air>nitrogen. The 4-CyP degradation was inhibited in the presence of nitrogen gas owing to the free radical scavenging effect in vapor phase within the bubbles of cavitation. The ultrasonic degradation of 4-CyP was clearly promoted in the presence of bromide anions and the promoting effect on degradation increased with increasing bromide concentration. At low 4-CyP concentration (0.05 mg L(-1)), bicarbonate ion drastically enhanced the rate of 4-CyP degradation. Experiments conducted using pure and natural water demonstrated that the sonolytic treatment was more efficient in the natural water compared to pure water.