Dissolved organic matter inhibition of sonochemical degradation of aqueous polycyclic aromatic hydrocarbons

Sonochemical degradation of aqueous polycyclic aromatic hydrocarbons (PAHs) was found to be rapid in the absence of other dissolved compounds (k = 0.006-0.015 s-1). In the presence of 20 mg Cl-1 fulvic acid, first-order PAH degradation rate constants decreased from 2.3- to 3.7-fold. Similar results were obtained with added benzoic acid, a crude analog for fulvic acid. In natural waters, PAH degradation was almost completely inhibited. Analysis of the kinetic behavior and reaction products indicates that PAHs are most likely degraded through a radical cation mechanism. Hydroxyl radical appeared to play an insignificant role in the degradation. Inhibited degradation was probably the result of either altered cavitation processes or isolation of the PAH away from cavitation sites.     

Sonolytic degradation of halogenated organic compounds in groundwater: mass transfer effects

Organic pollutants in liquid exposed to acoustic waves behave differently according to their physical and chemical properties. Laboratory batch experiments of sonication for the degradation of trichloroethylene (TCE) and ethylene dibromide (EDB) were carried out in groundwater at 20 kHz, and 12.5 and 35 W/cm(2). A theoretical model for the batch sonication system was derived to examine the mass transfer dependency of the ultrasonic degradation. Experimental results were supported with model predictions suggesting that both liquid phase diffusion coefficient and Henry's law constant are important parameters for the sonolytic degradation of the halogenated organic compounds in groundwater. When compared with the effect of the diffusion coefficient, Henry's constant exerts a greater influence on sonolytic degradation. When Henry's constant exceeds a value of 1 (volume/volume ratio), however, it no longer has much influence on the degradation process. The results also suggest that degradation is enhanced with an increase in ultrasonic power probably due to a greater bubble residence time and the formation of larger bubble at high-energy intensities.     

Sonochemical degradation of PAH in aqueous solution. Part I: monocomponent PAH solution

The sonolysis of selected monocomponent PAH aqueous solution is studied at 20 and 506 kHz in the microg l(-1) range. The highest activity observed at 506 kHz, compared to 20 kHz, is tentatively explained by examination of the physical characteristics of bubbles (size and life-time) as well as by the calculation of the number of bubble at both frequency (5 x 10(3)bubbles l(-1) at 20 kHz and 4.5 x 10(9)bubbles l(-1) at 506 kHz). It is demonstrated that the main mechanism of sonodegradation is the pyrolysis of PAHs in the heart of the cavitation bubbles, and that a possible PAH oxidation by means of HO degrees appears as a minor way, since gaseous byproducts such as CO, CO2, C2H2 and CH4 have been detected. Correlations have been found by examination of kinetic variations in terms of the physical-chemical properties of PAHs. The rate constants of PAH degradation increase when the water solubility, the vapour pressure and the Henry's law constant increase.     

Comparison of ultrasonic degradation rates constants of methylene blue at 22.8 kHz, 127 kHz, and 490 kHz

Techniques such as solvent extraction, incineration, chemical dehalogenation, and biodegradation have been investigated for the degradation of hazardous organic compounds. We found ultrasound to be an attractive technology for the degradation of hazardous organic compounds in water. However, the effects of ultrasonic frequency on degradation rate constants were not investigated quantitatively. In this study, the degradation process of a model for hazardous organic compound methylene blue was investigated using ultrasonic irradiation. The study focused on the effects of ultrasonic frequency and ultrasonic power on the degradation rate constant. The apparent degradation rate constants were estimated based on time dependence of methylene blue concentration assuming pseudo-first-order kinetics for the decomposition. A linear relationship between the apparent degradation rate constant and ultrasonic power was identified. In addition, the apparent degradation rate constants at frequencies of 127 and 490 kHz were much larger than those at 22.8 kHz. A relationship between the apparent degradation rate constant and the sonochemical efficiency value (SE value) was also found. Based on these results, a simple model for estimating the apparent degradation rate constant of methylene blue based on the ultrasonic power and the SE value is proposed in this study.     

Synergistic,aqueous PAH degradation by ultrasonically-activated persulfate depends on bulk temperature and physicochemical parameters

Coupling ultrasound with other remediation technologies has potential to result in synergistic degradation of contaminants. In this work, we evaluated synergisms from adding high-power ultrasound (20 kHz; 250 W) to activated persulfate over a range of bulk temperatures (20–60 °C). We studied the aqueous degradation kinetics of three polycyclic aromatic hydrocarbons (PAHs: naphthalene, phenanthrene, and fluoranthene) treated by ultrasound-alone, heat-activated persulfate, and combined ultrasonically-activated persulfate (US-PS). At 20 °C, observed US-PS rate constants strongly correlated with Wilke-Chang diffusion coefficients. This correlation indicates PAH molecules diffuse to the bubble-water interface prior to reaction with sulfate radicals (SO₄⁻) generated at the interface. At higher temperatures, observed US-PS rate constants appear to be a more complicated function of temperature and diffusion coefficients. Synergy indexes for PAHs with fast diffusion coefficients were greatest at 20 °C. Fluoranthene, the largest and most hydrophobic PAH, had a maximum synergy index at 30 °C; it benefited from additional thermal persulfate activation in bulk solution. Fluoranthene synergy indexes, however, decreased above 30 °C and became antagonistic at 60 °C. Electron paramagnetic resonance (EPR) spin trapping was used to quantify hydroxyl radical (OH) produced from acoustic cavitation in the absence of persulfate. These data showed consistent OH production from 20 to 60 °C, indicating PAH antagonisms at 60 °C were not due to lower bubble collapse temperatures. Instead, the results suggest that PAH antagonisms are caused by increased radical–radical recombination as bulk temperature increases. In effort to develop an efficient, combined remediation technology, this work suggests bulk temperatures between 20 and 40 °C maximize US-PS synergisms.     

Ultrasonic degradation of N-di and trihydroxy benzoyl chitosans and its effects on antioxidant activity

Modified chitosans with 3,4-dihydroxy benzoyl groups (CS-DHBA) and 3,4,5-trihydroxy benzoyl groups (CS-THBA) were synthesized and their chemical structures were determined by Fourier transform infrared (FT-IR) and ¹H nuclear magnetic resonance (¹H NMR) spectroscopy. Then, ultrasonic degradation of CS, CS-DHBA and CS-THBA in 1% acetic acid solution was investigated. The kinetics studies of degradation were followed by gel permeation chromatography (GPC). The results indicated that the weight-average molecular weight of chitosan decreased obviously after ultrasound treatment, but molecular weights of CS-DHBA and CS-THBA decreased slowly with increasing sonication time. Degradation kinetics model based on 1/M_t−1/M₀ = kt was used to estimate the degradation rate constant. It was found that the rates of degradation of CS-DHBA and CS-THBA are lower than CS, and follow the order: CS₄ > CS₈ > CS₁₂ > CS-THBA₄ > CS-THBA₈ ≈ CS-DHBA₄ > CS-THBA₁₂ > CS-DHBA₈ > CS-DHBA₁₂. The antioxidant activity of the CS, CS-DHBA and CS-THBA before and after sonication was investigated by the radical scavenging activity method using 1,1-diphenyl-2-picrylhydrazyl (DPPH). The DPPH scavenging free radical capacity of CS-THBA and CS-DHBA increased up to 89% and 74% respectively, when the concentration reached 6 μg/ml. The ultrasonic treatment of CS-DHBA and CS-THBA after 30 min decreased the DPPH free radical scavenging activity but ultrasonic treatment of CS increased the DPPH free radical scavenging activity.     

Luminescencence determination of ecotoxicants in protein-based media

The structural changes in the protein macromolecules caused by polycyclic aromatic hydrocarbon (PAH) ecotoxicants were studied using the data on intrinsic fluorescence of proteins and fluorescence of PAH molecules introduced into proteins. A luminescence method for PAH determination in proteins was developed and used to study the interaction of two PAHs (pyrene and anthracene) with proteins of two types (bovine serum albumin and human serum albumin). The results were interpreted using the Stern–Volmer fluorescence quenching model. The association constants and the number of binding sites in the protein–ligand complexes were calculated. The binding of PAHs with proteins was described based on the static version of quenching with formation of nonfluorescent complexes of protein fluorophores with PAHs.     

Degradation of azo dye direct sky blue 5B by sonication combined with zero-valent iron

The degradation of azo dye direct sky blue 5B by sonication combined with zero-valent iron (US-Fe(0))was investigated and an evident synergistic effect was observed. The synergetic effect is mainly due to the increase of ()OH radical concentration from Fenton's reaction. The ()OH radical concentrations in sole sonication and US-Fe(0) process were detected by using terephthalic acid as a fluorescent probe and found that ()OH radicals were generated continuously during sonication and the production of ()OH radicals in US-Fe(0) process was much higher than that in sole sonication. The degradation of direct sky blue 5B followed a pseudo-first-order kinetics and the degradation rate constants were found to be 0.0206 and 0.169 min(-1) with sole sonication and US-Fe(0) process respectively. It was also found that the degradation ratio of direct sky blue 5B increased with the increase of zero-valent iron dosage and decrease of pH value of the dye aqueous solution. The degradation mechanism of direct sky blue 5B with US-Fe(0) process was discussed by the changes of UV-Vis spectrogram of the dye during degradation. The dramatic changes of UV spectra showed a disappearance of both azo and aromatic groups during the degradation.     

The sono-degradation of phenanthrene in an aqueous environment

Polynuclear aromatic hydrocarbon (PAH) contamination has spread throughout the globe with background levels now found in virtually all sections of the ecosystem and environment. The mutagenic and/or carcinogenic properties attributed to many of these compounds, and frequency of occurrence and concentration in the environment, has driven research into safe methods of removing contamination, whilst avoiding the use of harmful solvents or the formation of even more hazardous compounds. Ultrasound is currently used in industry and research to propagate and accelerate chemical reactions, opening reaction pathways which otherwise would not be observed. In the study of the degradation of PAHs through ultrasonic irradiation, the breakdown of an aqueous solution of phenanthrene in a sonochemical reactor utilising a 30 kHz probe system, operating in batch mode, has been investigated. The phenanthrene molecule was studied and used as a model PAH molecule. It was chosen due to the structural similarities to many of the higher order PAHs currently recognised as being hazardous to health. The influence of several parameters on the degradation of phenanthrene are reported (power ultrasound energy, temperature and light). Qualitative analysis using HPLC and quantitative analysis using UV/Vis photo-spectrometry confirmed that a 88% reduction in the peak observed phenanthrene concentration was achieved over 240 min of sonocation. Whilst there was the potential for the formation of recalcitration and rearrangement products, no higher order PAHs were observed and a 80% reduction in total monitored UV fluorescence and hence, aromaticity/conjugation, was observed.     

Critical factors in sonochemical degradation of fumaric acid

The effects of critical factors such as Henry’s Law constant, atmospheric OH rate constant, initial concentration, H₂O₂, FeSO₄ and tert-butanol on the sonochemical degradation of fumaric acid have been investigated. The pseudo first-order rate constant for the sonochemical degradation of 1 mM fumaric acid is much lower than those for chloroform and phenol degradation, and is related to solute concentration at the bubble/water interface and reactivity towards hydroxyl radicals. Furthermore, fumaric acid is preferentially oxidized at the lower initial concentration. It is unreactive to H₂O₂ under agitation at room temperature. However, the degradation rate of fumaric acid increases with the addition of H₂O₂ under sonication. 0.1 mM of fumaric acid suppresses H₂O₂ formation thanks to water sonolysis, while degradation behavior is also dramatically affected by the addition of an oxidative catalyst (FeSO₄) or radical scavenger (tert-butanol), indicating that the degradation of fumaric acid is caused by hydroxyl radicals generated during the collapse of high-energy cavities.