Application of the general rate law model to the sonolytic degradation of nonvolatile organic pollutants in aqueous media.

The pseudo-first and pseudo-second order equations have been the most commonly used models to characterize the sonolytic disappearance kinetics of nonvolatile pollutants in aqueous media. In this work, the general rate law model, i.e., pseudo-nth order kinetics equation, was applied for the first time to the sono-decomposition of different nonvolatile organic pollutants, naphthol blue black (NBB), furosemide (FSM), 4-isopropylphenol (4-IPP), and rhodamine B (RhB), in water. It was shown that the general rate law for a chemical reaction would apply to the kinetics of sonochemical decomposition. It is not feasible to set the order of ultrasonic pollutant degradation kinetics to pseudo-first or pseudo-second, as is typically used in numerous studies. The sonochemical oxidation reaction has a fractional order, the order is often non-integer, which frequently indicates a complex sonolytic decomposition reaction mechanism. The degradation mechanism of NBB and RhB does not change with the initial substrate concentration. They are ultrasonically degraded by hydroxyl radicals both in the bulk liquid solution and at the liquid/bubble interfacial layer. The destruction mechanism of FSM and 4-IPP changes as the initial contaminant concentration changes. At low initial substrate concentrations, these pollutants are oxidized mainly by reaction with hydroxyl radicals in the bulk liquid solution and at the interfacial shell of the cavitation bubbles. At high initial substrate concentrations, FSM and 4-IPP are degraded by thermal destruction in the liquid/bubble interfacial layer and by •OH radicals both in the bulk liquid solution and at the liquid/bubble interfacial layer. Additionally, the pseudo-nth order model predicts very well the sonolytic degradation at various sonication frequencies and intensities. The general rate law expression should be used to assess the real kinetics order of the sonolytic destruction process without any predetermined assumptions or constraints.

Sonochemical advanced oxidation process for the degradation of furosemide in water: Effects of sonication's conditions and scavengers.

The intensive consumption of pharmaceuticals and drugs in the last decades has led to their increased concentrations in wastewaters from industrial sources. The present paper deals, for the first time, with the sonochemical degradation and mineralization of furosemide (FSM) in water. FSM is a potent loop diuretic used to treat fluid build-up due to heart failure, liver scarring, or kidney disease. The influence of several operating parameters such as acoustic intensity, ultrasonic frequency, initial FSM concentration, solution's pH, nature of the dissolved gas (Ar, air and N2) and radical scavengers (2-propanol and tert-butanol) on the oxidation of FSM was assessed. The obtained results showed that the degradation rate of the drug increased significantly with the increase of the acoustic intensity in the range of 0.83 to 4.3 W cm-2 and decreased with the augmentation of the frequency in the range of 585-1140 kHz. It was also found that the initial rate of the sonolytic degradation of FSM increased with the increase of its initial concentration (2, 5, 10, 15 and 20 mg/L). The most significant degradation was achieved in acidic conditions at pH 2, while in terms of saturating gas, the rate of FSM degradation decreased in the order of Ar > air > N2. The FSM degradation experiments with radical scavengers showed that the diuretic molecule degraded mainly at the interfacial region of the bubble by hydroxyl radical attack. Additionally, in terms of acoustic conditions, the sono-degradation of 30.24 µmol L-1 of FSM solution demonstrate an optimal performance at 585 kHz and 4.3 W/cm2, the results indicated that even if the ultrasonic action eliminated the total concentration of FSM within 60 min, a low degree of mineralization was obtained due to the by-products formed during the sono-oxidation process. The ultrasonic process transforms FSM into biodegradable and environmentally friendly organic by-products that could be treated in a subsequent biological treatment. Besides, the efficiency of the sonolytic degradation of FSM in real environmental matrices such as natural mineral water and seawater was demonstrated. Consequently, the sonochemical advanced oxidation process represent a very interesting technique for the treatment of water contaminated with FSM.

Ultrasound/chlorine sono-hybrid-advanced oxidation process: Impact of dissolved organic matter and mineral constituents.

In this work, after exploring the first report on the synergism of combining ultrasound (US: 600 kHz) and chlorine toward the degradation of Allura Red AC (ARAC) textile dye, as a contaminant model, the impact of various mineral water constituents (Cl-, SO42-, NO3-, HCO3- and NO2-) and natural organic matter, i.e., humic acid (HA), on the performance of the US/chlorine sono-hybrid process was assessed for the first time. Additionally, the process effectiveness was evaluated in a real natural mineral water (NMW) of a known composition. Firstly, it was found that the combination of ultrasound and chlorine (0.25 mM) at pH 5.5 in cylindrical standing wave ultrasonic reactor (f = 600 kHz and Pe = 120 W, equivalent to PA âˆ¼ 2.3 atm) enhanced in a drastic manner the degradation rate of ARAC; the removal rate being 320% much higher than the arithmetic sum of the two separated processes. The source of the synergistic effect was attributed to the effective implication of reactive chlorine species (RCS: Cl, ClO and Cl2-) in the degradation process. Radical probe technique using nitrobenzene (NB) as a specific quencher of the acoustically generated hydroxyl radical confirmed the dominant implication of RCS in the overall degradation rate of ARAC by US/chlorine system. Overall, the presence of humic acid and mineral anions decreased the efficiency of the sono-hybrid process; however, the inhibition degrees depend on the type and the concentration of the selected additives. The reaction of these additives with the generated RCS is presumably the reason for the finding results. The inhibiting effect of Cl-, SO42-, NO3- and NO2- was more pronounced in US/chlorine process as compared to US alone, whereas the inverse scenario was remarked for the effect of HA. These outcomes were associated to the difference in the reactivity of HA and mineral anions toward RCS and OH oxidizing species, in addition to the more selective character of RCS than hydroxyl radical. The displacement of the reaction zone with increasing the additive concentration may also be another influencing factor that favors competition reactions, which subsequently reduce the available reactive species in the reacting medium. The NMW exerted reductions of 43% and 10% in the process efficiency at pH 5.5 and 8, respectively, thereby confirming the RCS-quenching mechanism by the water matrix constituents. Hence, this work provided a precise understanding of the overall mechanism of chlorine activation by ultrasound to promote organic compounds degradation in water.

Efficient Photocatalytic Degradation of Organic Pollutant in Wastewater by Electrospun Functionally Modified Polyacrylonitrile Nanofibers Membrane Anchoring TiO2 Nanostructured.

In this study, polyacrylonitrile (PAN_P) nanofibers (NFs) were fabricated by electrospinning. The PAN_P NFs membrane was functionalized with diethylenetriamine to prepare a functionalized polyacrylonitrile (PAN_F) NFs membrane. TiO2 nanoparticles (NPs) synthesized in the laboratory were anchored to the surface of the PAN_F NFs membrane by electrospray to prepare a TiO2 NPs coated NFs membrane (PAN_Coa). A second TiO2/PAN_P composite membrane (PAN_Co) was prepared by embedding TiO2 NPs into the PAN_P NFs by electrospinning. The membranes were characterized by microscopic, spectroscopic and X-ray techniques. Scanning electron micrographs (SEM) revealed smooth morphologies for PAN_P and PAN_F NFs membranes and a dense cloud of TiO2 NPs on the surface of PAN_Coa NFs membrane. The attenuated total reflectance in the infrared (ATR-IR) proved the addition of the new amine functionality to the chemical structure of PAN. Transmission electron microscope images (TEM) revealed spherical TiO2 NPs with sizes between 18 and 32 nm. X-ray powder diffraction (XRD) patterns and energy dispersive X-ray spectroscopy (EDX) confirmed the existence of the anatase phase of TiO2. Surface profilometry da-ta showed increased surface roughness for the PAN_F and PAN_Coa NFs membranes. The adsorption-desorption isotherms and hysteresis loops for all NFs membranes followed the IV -isotherm and the H3 -hysteresis loop, corresponding to mesoporous and slit pores, respectively. The photocatalytic activities of PAN_Coa and PAN_Co NFs membranes against methyl orange dye degradation were evaluated and compared with those of bare TiO2 NPs.The higher photocatalytic activity of PAN_Coa membrane (92%, 20 ppm) compared to (PAN_Co) NFs membrane (41.64%, 20 ppm) and bare TiO2 (49.60%, 20 ppm) was attributed to the synergy between adsorption, lower band gap, high surface roughness and surface area.

Galvano-Fenton Engineering Solution with Spontaneous Catalyst's Generation from Waste: Experimental Efficiency, Parametric Analysis and Modeling Interpretation Applied to a Clean Technology for Dyes Degradation in Water.

In this paper, the degradation of the diazo dye naphthol blue black (NBB) using the Galvano-Fenton process is studied experimentally and numerically. The simulations are carried out based on the anodic, cathodic, and 34 elementary reactions evolving in the electrolyte, in addition to the oxidative attack of NBB by HO• at a constant rate of 3.35×107 mol-1·m3·s-1 during the initiation stage of the chain reactions. The selection of the operating conditions including the pH of the electrolyte, the stirring speed, and the electrodes disposition is performed by assessing the kinetics of NBB degradation; these parameters are set to 3, 350 rpm and a parallel disposition with a 3 cm inter-electrode distance, respectively. The kinetics of Fe(III) in the electrolyte were monitored using the principles of Fricke dosimetry and simulated numerically. The model showed more than a 96% correlation with the experimental results in both the blank test and the presence of the dye. The effects of H2O2 and NBB concentrations on the degradation of the dye were examined jointly with the evolution of the simulated H2O2, Fe2+, and HO• concentrations in the electrolyte. The model demonstrated a good correlation with the experimental results in terms of the initial degradation rates, with correlation coefficients exceeding 98%.

A Novel Energy-from-Waste Approach for Electrical Energy Production by Galvano-Fenton Process.

A novel approach allowing the production of electrical energy by an advanced oxidation process is proposed to eliminate organic micropollutants (MPs) in wastewaters. This approach is based on associating the Galvano-Fenton process to the generation of electrical power. In the previous studies describing the Galvano-Fenton (GF) process, iron was directly coupled to a metal of more positive potential to ensure degradation of organic pollutants without any possibility of producing electrical energy. In this new approach, the Galvano-Fenton process is constructed as an electrochemical cell with an external circuit allowing recovering electrons exchanged during the process. In this study, Malachite Green (MG) dye was used as a model of organic pollutant. Simultaneous MG degradation and electrical energy production with the GF method were investigated in batch process. The investigation of various design parameters emphasis that utilization of copper as a low-cost cathode material in the galvanic couple, provides the best treatment and electrical production performances. Moreover, these performances are improved by increasing the surface area of the cathode. The present work reveals that the GF process has a potential to provide an electrical power density of about 200 W m-2. These interesting performances indicate that this novel Energy-from-Waste strategy of the GF process could serve as an ecological solution for wastewater treatment.

Insight into the impact of excluding mass transport, heat exchange and chemical reactions heat on the sonochemical bubble yield: Bubble size-dependency.

Numerical simulations have been performed on a range of ambient bubble radii, in order to reveal the effect of mass transport, heat exchange and chemical reactions heat on the chemical bubble yield of single acoustic bubble. The results of each of these energy mechanisms were compared to the normal model in which all these processes (mass transport, thermal conduction, and reactions heat) are taken into account. This theoretical work was carried out for various frequencies (f: 200, 355, 515 and 1000 kHz) and different acoustic amplitudes (PA: 1.5, 2 and 3 atm). The effect of thermal conduction was found to be of a great importance within the bubble internal energy balance, where the higher rates of production (for all acoustic amplitudes and wave frequencies) are observed for this model (without heat exchange). Similarly, the ignorance of the chemical reactions heat (model without reactions heat) shows the weight of this process into the bubble internal energy, where the yield of the main species (OH, H, O and H2) for this model was accelerated notably compared to the complete model for the acoustic amplitudes greater than 1.5 atm (for f = 500 kHz). However, the lowest production rates were registered for the model without mass transport compared to the normal model, for the acoustic amplitudes greater than 1.5 atm (f = 500 kHz). This is observed even when the temperature inside bubble for this model is greater than those retrieved for the other models. On the other hand, it has been shown that, at the acoustic amplitude of 1.5 atm, the maximal production rates of the main species (OH, H, O and H2) for all the adopted models appear at the same optimum ambient-bubble size (R0 ~ 3, 2.5 and 2 µm for, respectively, 355, 500 and 1000 kHz). For PA = 2 and 3 atm (f = 500 kHz), the range of the maximal yield of OH radicals is observed at the range of R0 where the production of OH, O and H2 is the lowest, which corresponds to the bubble temperature at around 5500 K. The maximal production rate of H, O and H2 is shifted toward the range of ambient bubble radii corresponding to the bubble temperatures greater than 5500 K. The ambient bubble radius of the maximal response (maximal production rate) is shifted toward the smaller bubble sizes when the acoustic amplitude (wave frequency is fixed) or the ultrasound frequency (acoustic power is fixed) is increased. In addition, it is observed that the increase of wave frequency or the acoustic amplitude decrease cause the range of active bubbles to be narrowed (scenario observation for the four investigated models).

A comprehensive numerical analysis of heat and mass transfer phenomenons during cavitation sono-process.

The present study treats the effects of mass transport, heat transfer and chemical reactions heat on the bubble dynamics by spanning a range of ambient bubble radii. The thermodynamic behavior of the acoustic bubble was shown for three wave frequencies, 355, 515 and 1000 kHz. The used acoustic amplitude ranges from 1 to 3 atm. It has been demonstrated that the ambient bubble radius, R0, of the maximal response (i.e., maximal bubble temperature and pressure, Tmax and Pmax) is shifted toward lower values if the acoustic amplitude (at fixed frequency) or the ultrasonic frequency (at fixed amplitude) are increased. The range of the ambient bubble radius narrows as the ultrasonic frequency increases. Heat exchange at the bubble interface was found to be the most important mechanism within the bubble internal energy balance for acoustic amplitudes lower than 2.5 and 3 atm for ultrasonic frequencies of 355 and 515 kHz, respectively. For acoustic amplitudes greater or equal to 2.5 and 3 atm, corresponding to 355 and 515 kHz, respectively, mass transport mechanism (i.e., evaporation and condensation of water vapor) becomes dominant compared to the other mechanisms. At 1000 kHz, the mechanism of heat transfer persists to be dominant for all the used acoustic amplitudes (from 1 to 3 atm). Practically, all the above observations were maintained for bubbles at and around the optimum bubble radius, whereas no significant impact of the three energetic mechanisms was observed for bubbles of too lower and too higher values of R0 (limits of the investigated ranges of R0).

Acoustic cavitation events and solvation power of ionic liquid in a novel hybrid technique: A concept proposal toward a green pathway for cellulose decomposition.

The present paper reports a numerical investigation of the feasibility of a hybrid concept associating the 1-Butyl-3-methylimidazolium Acetate [C4mim][CH3COO] to sonication, in terms of cavitation formation and generated extreme conditions allowing cellulose decomposition in the second reactivity site. The results of the proposed model revealed an acoustic power threshold of 1.8 atm, in order to expect a transient cavitation in the ionic liquid, leading to harsh conditions of 1559.8 K and 49 bar within the bulk volume of the acoustic cavitation bubble. The spatial and temporal variation of the temperature was simulated within the bulk volume of the bubble as well as in the thermal boundary layer jointly with the chemical kinetics. The first stage of the polymerization reduction was clearly attained and demonstrated through the decomposition rate of cellulose and the molar rate of emergence of anhydrocellulose, reaching the respective orders of magnitude of 1.71 × 104 mol/m3⋅s and 7.91 × 104 mol/m3⋅s.

Energy balance of high-energy stable acoustic cavitation within dual-frequency sonochemical reactor.

The acoustic cavitation bubble as an open energetic system is the seat of conversion of various forms of energy accompanying the bubble oscillation. The energy conversion would explain specific dynamical, thermal and kinetical behaviors. In the present paper, the energy balance related to a stable bubble irradiated by dual-frequency field is simulated numerically and interpreted in accordance with the phenomena occurring inside it. The study particularly focuses on the comparison of the energetic behavior of high-energy stable cavitation with bubbles that are non-active in sonochemistry, submitted to couples of 35, 140, 300 and 515 kHz. The simulation results revealed that pressure forces work is the major energetic input during the bubble oscillation lifetime, while the main energetic loss comes from heat transfer by diffusion and enthalpy loss accompanying water condensation. Besides, high rates of condensation of water molecules and low amounts of accumulated energy inside the bubble volume were identified as the key factors preventing the achievement of the sonochemical activity threshold.

How do dissolved gases affect the sonochemical process of hydrogen production? An overview of thermodynamic and mechanistic effects - On the "hot spot theory".

Although most of researchers agree on the elementary reactions behind the sonolytic formation of molecular hydrogen (H2) from water, namely the radical attack of H2O and H2O2 and the free radicals recombination, several recent papers ignore the intervention of the dissolved gas molecules in the kinetic pathways of free radicals, and hence may wrongly assess the effect of dissolved gases on the sonochemical production of hydrogen. One may fairly ask to which extent is it acceptable to ignore the role of the dissolved gas and its eventual decomposition inside the acoustic cavitation bubble? The present opinion paper discusses numerically the ways in which the nature of dissolved gas, i.e., N2, O2, Ar and air, may influence the kinetics of sonochemical hydrogen formation. The model evaluates the extent of direct physical effects, i.e., dynamics of bubble oscillation and collapse events if any, against indirect chemical effects, i.e., the chemical reactions of free radicals formation and consequently hydrogen emergence, it demonstrates the improvement in the sonochemical hydrogen production under argon and sheds light on several misinterpretations reported in earlier works, due to wrong assumptions mainly related to initial conditions. The paper also highlights the role of dissolved gases in the nature of created cavitation and hence the eventual bubble population phenomena that may prevent the achievement of the sonochemical activity. This is particularly demonstrated experimentally using a 20 kHz Sinaptec transducer and a Photron SA 5 high speed camera, in the case of CO2-saturated water where degassing bubbles are formed instead of transient cavitation.

Acoustic frequency and optimum sonochemical production at single and multi-bubble scales: A modeling answer to the scaling dilemma.

The present work consists of an innovative approach aiming to address the scalability dilemma of the sonochemical activity dependency of acoustic frequency. The study originates from the discordance of observations between the theoretical investigations of the sonochemical activity of the single acoustic cavitation bubble in function of the acoustic frequency, in one hand, and the experimental findings regarding the optimal frequency condition, mainly in terms of pollutant degradation, in the other hand. A single bubble and an up-scaled model of the sonochemical activity are suggested and simulations were conducted based on both of them over the frequencies 20, 200, 300, 360, 443, 500, 600 and 800 kHz under an oxygen atmosphere. The results reveal that the sonochemical production at single bubble scale is monotonously decreasing with the increase of frequency, while all the products demonstrate an absolute optimum of sonochemical production at 200 kHz, except HO• that attains its maximum molar yield under 300 kHz. Besides, the production of the predominant species, namely HO2•, HO• and O3, manifests a clear rebound at 500 kHz. All the present results were compared to and confirmed by experimental findings, while the scalability of the concentrations of sonochemically produced species was discussed using a parameter we introduced as "the mass focusing factor".

Influence of processing conditions on the synergism between UV irradiation and chlorine toward the degradation of refractory organic pollutants in UV/chlorine advanced oxidation system.

The synergy of applying UV/chlorine advanced oxidation process (AOP) for the degradation of organic pollutants was usually reported. However, very limited information is available on the influence of processing conditions on the resulted synergism. In this work, C.I. reactive green 12 (RG12), a refractory textile dye, has been selected as a pollutant model to examine the synergism dependence of operational conditions in UV/chlorine AOP. Initial tests conducted with 500 µM of chlorine and 20 mg L-1 of RG12 have resulted in a high synergy index (SI) of 3. Operating conditions sensitively affect the value of SI. This latter increased with increasing initial chlorine and RG12 concentrations up to certain optimums at 500 µM of chlorine and 20 mg L-1 of RG12 and decreased afterward. The best SI value, i.e. 3, was obtained at pH 5, followed by pH 7 (SI = 2.2) and then pH 9-10.5 (SI ~ 2). On the other hand, the synergistic index decreased importantly from 3 at 25 °C to only 1.2 at 55 °C. Finally, by using different radical scavengers, it was found that among various suspected oxidants, only ●OH and Cl2●- play a key role in the synergistic effect between UV and chlorine toward RG12 degradation.

Biocompatible Polymers and their Potential Biomedical Applications: A Review.

BACKGROUND: Biocompatible polymers are gaining great interest in the field of biomedical applications. The term biocompatibility refers to the suitability of a polymer to body and body fluids exposure. Biocompatible polymers are both synthetic (man-made) and natural and aid in the close vicinity of a living system or work in intimacy with living cells. These are used to gauge, treat, boost, or substitute any tissue, organ or function of the body. A biocompatible polymer improves body functions without altering its normal functioning and triggering allergies or other side effects. It encompasses advances in tissue culture, tissue scaffolds, implantation, artificial grafts, wound fabrication, controlled drug delivery, bone filler material, etc. OBJECTIVES: This review provides an insight into the remarkable contribution made by some well-known biopolymers such as polylactic-co-glycolic acid, poly(ε-caprolactone) (PCL), polyLactic Acid, poly(3- hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), Chitosan and Cellulose in the therapeutic measure for many biomedical applications. METHODS: Various techniques and methods have made biopolymers more significant in the biomedical fields such as augmentation (replaced petroleum based polymers), film processing, injection modeling, blow molding techniques, controlled / implantable drug delivery devices, biological grafting, nano technology, tissue engineering etc. RESULTS: The fore mentioned techniques and other advanced techniques have resulted in improved biocompatibility, nontoxicity, renewability, mild processing conditions, health condition, reduced immunological reactions and minimized side effects that would occur if synthetic polymers are used in a host cell. CONCLUSION: Biopolymers have brought effective and attainable targets in pharmaceutics and therapeutics. There are huge numbers of biopolymers reported in the literature that has been used effectively and extensively.

Simultaneous deconvolution of the bivariate distribution of molecular weight and chemical composition of polyolefins made with ziegler-natta catalysts.

Polyolefins made with Ziegler-Natta catalysts have non-uniform distributions of molecular weight (MWD) and chemical composition (CCD). The MWD is usually measured by high-temperature gel permeation chromatography (GPC) and the CCD by either temperature rising elution fractionation (TREF) or crystallization analysis fractionation (CRYSTAF). A mathematical model is needed to quantify the information provided by these analytical techniques and to relate it to the presence of multiple site types on Ziegler-Natta catalysts. We developed a robust computer algorithm to deconvolute the MWD and CCD of polyolefins simultaneously using Flory's most probable distribution and the cumulative CCD component of Stockmayer's distribution, which includes the soluble fraction commonly present in linear low-density polyethylene (LLDPE) resins and have applied this procedure for the first time to several industrial LLDPE resins. The deconvolution results are reproducible and consistent with theoretical expectations.