Sonocatalytical degradation enhancement for ibuprofen and sulfamethoxazole in the presence of glass beads and single-walled carbon nanotubes

Sonocatalytic degradation experiments were carried out to determine the effects of glass beads (GBs) and single-walled carbon nanotubes (SWNTs) on ibuprofen (IBP) and sulfamethoxazole (SMX) removal using low and high ultrasonic frequencies (28 and 1000 kHz). In the absence of catalysts, the sonochemical degradation at pH 7, optimum power of 0.18 W mL⁻¹, and a temperature of 15 °C was higher (79% and 72%) at 1000 kHz than at 28 kHz (45% and 33%) for IBP and SMX, respectively. At the low frequency (28 kHz) H₂O₂ production increased significantly, from 10 μM (no GBs) to 86 μM in the presence of GBs (0.1 mm, 10 g L⁻¹); however, no enhancement was achieved at 1000 kHz. In contrast, the H₂O₂ production increased from 10 μM (no SWNTs) to 31 μM at 28 kHz and from 82 μM (no SWNTs) to 111 μM at 1000 kHz in the presence of SWNTs (45 mg L⁻¹). Thus, maximum removals of IBP and SMX were obtained in the presence of a combination of GBs and SWNTs at the low frequency (94% and 88%) for 60 min contact time; however, >99% and 97% removals were achieved for 40 and 60 min contact times at the high frequency for IBP and SMX, respectively. The results indicate that both IBP and SMX degradation followed pseudo-first-order kinetics. Additionally, the enhanced removal of IBP and SMX in the presence of catalysts was because GBs and SWNTs increased the number of free OH radicals due to ultrasonic irradiation and the adsorption capacity increase with SWNT dispersion.     

Efficient sonochemical degradation of perfluorooctanoic acid using periodate

A rapid and efficient treatment method, using periodate (PI) for sonochemical oxidation of persistent and bioaccumulative perfluorooctanoic acid (PFOA) was developed. With an addition of 45 mM PI, 96.5% of PFOA was decomposed with a defluorination efficiency of 95.7% after 120 min of ultrasound (US). The removals of PFOA were augmented with an increase in PI doses. In all the PI + US experimental runs, decomposition efficiencies were essentially similar to those of defluorination, indicating that PFOA was decomposed and mineralized into fluoride ions. Lower solution pHs resulted in an increase in decomposition and defluorination efficiencies of PFOA due to acid-catalyzation. Dissolved oxygen increased the amount of IO₄ radicals produced, which consumed the more effective IO₃ radicals. Consequently, presence of oxygen inhibited the destruction of PFOA. The PFOA degradation rates with different gases sparging are in the following order: nitrogen > air > oxygen. Effects of anions follow the Hofmeister effects on PFOA degradation (i.e., Br⁻ > none ⩾ Cl⁻ > SO₄²⁻). Br⁻ could react with OH to yield radical anion Br₂⁻ that enhances the PFOA degradation. A reaction pathway was also proposed to describe the PI oxidation of PFOA under US irradiation.     

SonoFenton degradation of an azo dye,Direct Red

The degradation of a reactive azo dye, Direct Red 81 (DR81), by Fenton process and in conjunction with sonolysis (SonoFenton) was studied. The synergistic effect of Fenton process and sonolysis enhanced the degradation of Direct Red 81 in aqueous solutions and the reaction followed the mechanism of hydroxyl radical (HO) oxidation. The influence of the initial substrate concentration, pH and catalyst loading on the rate of decolorisation were studied. The dye decolorisation followed apparent first order kinetics. The optimum conditions for decolorisation were pH = 3.0, [Fe²⁺] = 0.2 g/l, [H₂O₂] = 5.1 × 10⁻³ mol/l and ultrasonic frequency = 120 kHz, 60 W. These conditions yielded 99% decolorisation of DR81 within 75 min. The sonolytic degradation products of DR81 were identified using Electrospray Ionization-Mass Spectrometry (ESI-MS). The presence of CO₃²⁻, HCO₃⁻, Cl⁻, NO₃⁻, and SO₄²⁻ ions in the dye solution did not have a considerable effect on the decolorisation efficiency. This study demonstrates that Fenton and SonoFenton methods can effectively decolorize DR81 dye in waste water. The dye concentration used in this study is higher compared to earlier studies illustrating the effective mineralization by the SonoFenton process. The mechanism of dye degradation is also proposed.     

Production of pyrite nanoparticles using high energy planetary ball milling for sonocatalytic degradation of sulfasalazine

Sonocatalytic performance of pyrite nanoparticles was evaluated by the degradation of sulfasalazine (SSZ). Pyrite nanoparticles were produced via a high energy mechanical ball milling (MBM) in different processing time from 2 h to 6 h, in the constant milling speed of 320 rpm. X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FT-IR) analysis and Brunauer–Emmett–Teller (BET) confirmed the production of pyrite nanoparticles during 6 h of ball milling with the average size distribution of 20–80 nm. The effects of various operational parameters including pH value, catalyst amount (mg/L), SSZ concentration (mg/L), ultrasonic frequency (kHz) and reaction time on the SSZ removal efficiency were examined. The obtained results showed that the maximum removal efficiency of 97.00% was obtained at pH value of 4, catalyst dosage of 0.5 g/L, SSZ concentration of 10 mg/L and reaction time of 30 min. Experimental results demonstrated that the kinetic of the degradation process can be demonstrated using Langmuir–Hinshelwood (L-H) kinetic model. The effect of different inorganic ions such as Cl⁻, CO₃²⁻ and SO₄²⁻ was investigated on the L-H reaction rate (k_r) and adsorption (K_s) constants. Results showed that the presence of the mentioned ions significantly influenced the L-H constants. The impact of ethanol as a OH radical scavenger and some enhancers including H₂O₂ and K₂S₂O₈ was investigated on the SSZ removal efficiency. Accordingly, the presence of ethanol suppressed SSZ degradation due to the quenching of OH radicals and the addition of K₂S₂O₈ and H₂O₂ increased the SSZ removal efficiency, due to the formation of SO₄⁻ and additional OH radicals, respectively. Under the identical conditions of operating parameters, pyrite nanoparticles maintained their catalytic activity during four consecutive runs.     

Synergistic degradation of antibiotic norfloxacin in a novel heterogeneous sonochemical Fe0/tetraphosphate Fenton-like system

In this study, synergistic degradation of antibiotic norfloxacin (NOR) was obtained in a novel sonochemical ultrasound/zero-valent iron/tetraphosphate system (US/ZVI/TPP). Compared to three common organic ligands (EDTA, EDDS, and DTPA), TPP could perform more excellently in activation of O₂ to produce reactive oxidative species (ROS) and lead to efficient Fenton-like oxidative degradation of NOR in the sonochemical in situ chemical oxidation (ISCO) system. An optimized initial condition was obtained as 10 mg/L NOR, 0.3 mM TPP, 1 g/L ZVI and initial pH 7, and the US/ZVI/TPP system would effectively degrade NOR with relative low dosage of ZVI and ligand as well as broad pH work range 3–9. It was found that three ROS (OH, O₂⁻ and H₂O₂) instead of OH only would participate in the NOR degradation, while the in situ generation of H₂O₂ during the series of Fe-TPP reactions should be more critical. Fourteen organic intermediates and four inorganic products were detected during the NOR decomposition, suggesting that two main degradation pathways would occur under OH oxidation via cleavage of the piperazine ring and defluorination of the benzene ring, respectively. Finally, an integrated reaction mechanism in the US/ZVI/TPP system was proposed including solid-liquid interfacial iron corrosion as well as bulk homogenous oxygen activation and Fenton reactions, wherein US would play mechanically and chemically promotional roles. Besides, triple-repeated treatments suggested the relative long-term re-usage of ZVI particles and low effluent dissolved iron (<0.6 mg/L).     

Sonocatalytic rapid degradation of Congo red dye from aqueous solution using magnetic Fe0/polyaniline nanofibers

Nano-sized magnetic Fe⁰/polyaniline (Fe⁰/PANI) nanofibers were used as an effective material for sonocatalytic degradation of organic anionic Congo red (CR) dye. Fe⁰/PANI_, was synthesized via reductive deposition of nano-Fe⁰ onto the PANI nanofibers at room temperature. Prepared catalyst was characterized using HR-TEM, FE-SEM, XRD, FTIR instruments. The efficacy of catalyst in removing CR was assessed colorimetrically using UV–visible spectroscopy under different experimental conditions such as % of Fe⁰ loading into the composite material, solution pH, initial concentration of dye, catalyst dosage, temperature and ultrasonic power. The optimum conditions for sonocatalytic degradation of CR were obtained at catalyst concentrations = 500 mg.L⁻¹, concentration of CR = 200 ppm, solution pH = neutral (7.0), temperature = 30 °C, % of Fe⁰ loading = 30% and 500 W ultrasonic power. The experimental results showed that ultrasonic process could remove 98% of Congo red within 30 min with higher Q_max value (Q_max = 446.4 at 25 °C). The rate of degradation of CR dye was much faster in this ultrasonic technique rather than conventional adsorption process. The degradation efficiency declined with the addition of common inorganic salts (NaCl, Na₂CO₃, Na₂SO₄ and Na₃PO₄). The rate of degradation suppressed more with increasing salt concentration. Kinetic and isotherm studies indicated that the degradation of CR provides pseudo-second order rate kinetic and Langmuir isotherm model compared to all other models tested. The excellent high degradation capacity of Fe⁰/PANI under ultrasonic irradiation can be explained on the basis of the formation of active hydroxyl radicals (OH) and subsequently a series of free radical reactions.     

Unusual oxygen re-equilibration kinetics of TiO2−δ

Oxygen re-equilibration kinetics, along with the equilibrium conductivity, have been measured on undoped, single-crystal TiO_2−δ, by a four-probe d.c. conductivity relaxation technique, against oxygen partial pressure in the range of − 16 < log(P_O2/atm) ≤ 0 at different temperatures in the range of 1173 ≤ T/K ≤ 1373. The isothermal conductivity varies as σ ∝ P_O2^m with m ≈ − 1/4, − 1/5 and − 1/6 in turn with increasing P_O2 up to 1 atm, suggesting a sequential variation of the majority ionic disorder types from Ti_i to Ti_i to V_O, respectively. Contrary to the conventional knowledge that due to the local (defect) equilibrium postulate there should be one and only one chemical diffusivity or single relaxation time for a binary oxide, the oxygen re-equilibration kinetics has turned out to be twofold with two different relaxation times depending on oxygen activities. This is interpreted as being due to the independent relaxation of each sublattice of TiO₂ in an oxygen activity gradient applied, indicating a failure of local equilibrium during oxygen re-equilibration. From the two different relaxation times the chemical diffusion coefficients of component Ti and O are separately evaluated and subsequently, their self-diffusion coefficients. The latter are found to be in a good agreement with the literature data.     

Intramolecular motion in the triptycenegermanyl radical: single crystal EPR study at variable temperature and DFT calculations

X-irradiation of single crystals of Tp–GeH₃ (Tp: triptycene) led to the trapping of the radical Tp–GeH₂. The angular variations of the resulting EPR spectra were recorded at 300 and 77 K. The drastic temperature dependence of the spectra was caused by both a strong anisotropy of the g-tensor and a rotation of the GeH₂ moiety around the C–Ge bond. The determination of the EPR tensors as well as the analysis of this motion required to take the presence of disorder in the crystal into account. In accordance with DFT calculations, Tp–GeH₂ is shown to be pyramidal and to adopt, in its lowest energy structure, a staggered conformation. Rotation around the C–GeH₂ bond is blocked at 90 K and is almost free above 110 K. The experimental barrier, obtained after simulation of the EPR spectra as a function of the rotational correlation time, is equal to 1.3 kcal mol⁻¹, which is slightly inferior to the barrier calculated by DFT (3.6 kcal mol⁻¹). Calculations performed on Tp–CH₃, Tp–GeH₃ and Tp–GeH₂ show that the rotation barrier ΔE_rot around the C–Ge bond drastically decreases by passing from the germane precursor to the germanyl radical and that ΔE_rot increases by passing from the germane to its carbon analogous. Structural parameters involved in these barrier differences are examined.     

Ultrasound (US), Ultraviolet light (UV) and combination (US + UV) assisted semiconductor catalysed degradation of organic pollutants in water: Oscillation in the concentration of hydrogen peroxide formed in situ

Application of Advanced Oxidation Processes (AOP) such as sono, photo and sonophoto catalysis in the purification of polluted water under ambient conditions involve the formation and participation of Reactive Oxygen Species (ROS) like OH, HO₂, O₂⁻, H₂O₂ etc. Among these, H₂O₂ is the most stable and is also a precursor for the reactive free radicals. Current investigations on the ZnO mediated sono, photo and sonophoto catalytic degradation of phenol pollutant in water reveal that H₂O₂ formed in situ cannot be quantitatively correlated with the degradation of the pollutant. The concentration of H₂O₂ formed does not increase corresponding to phenol degradation and reaches a plateau or varies in a wave-like fashion (oscillation) with well defined crests and troughs, indicating concurrent formation and decomposition. The concentration at which decomposition overtakes formation or formation overtakes decomposition is sensitive to the reaction conditions. Direct photolysis of H₂O₂ in the absence of catalyst or the presence of pre-equilibrated (with the adsorption of H₂O₂) catalyst in the absence of light does not lead to the oscillation. The phenomenon is more pronounced in sonocatalysis, the intensity of oscillation being in the order sonocatalysis > photocatalysis ⩾ sonophotocatalysis while the degradation of phenol follows the order sonophotocatalysis > photocatalysis > sonocatalysis > sonolysis > photolysis. In the case of sonocatalysis, the oscillation continues for some more time after discontinuing the US irradiation indicating that the reactive free radicals as well as the trapped electrons and holes which interact with H₂O₂ have longer life time (memory effect).     

Mechanism and dynamic study of reactive red X-3B dye degradation by ultrasonic-assisted ozone oxidation process

The effectiveness of ozone combined with ultrasound techniques in degrading reactive red X-3B is evaluated. A comparison among ozone (O₃), ultrasonic (US), ozone/ultrasonic (O₃/US) for degradation of reactive red X-3B has been performed. Results show that O₃/US system was the most effective and the optimally synergetic factor reaches to 1.42 in O₃/US system. The cavitation of ultrasound plays an important role during the degradation process. It is found that 99.2% of dye is degraded within 6 min of reaction at the initial concentration of 100 mg·L⁻¹, pH of 6.52, ozone flux of 40 L·h⁻¹ and ultrasonic intensity of 200 W·L⁻¹. Ozonation reactions in conjunction with sonolysis indicate that the decomposition followed pseudo-first-order reaction kinetics but the degradation efficiencies are affected by operating conditions, particularly initial pH and ultrasonic intensity. A kinetic model is established based on the reaction corresponding to operational parameters. In addition, the main reaction intermediates, such as p-benzoquinone, catechol, hydroquinone, phthalic anhydride and phthalic acid, are separated and identified using GC/MS and a possible degradation pathway is proposed during the O₃/US process.     

Sonocatalytic removal of ibuprofen and sulfamethoxazole in the presence of different fly ash sources

We examined the feasibility of using two types of fly ash (an industrial waste from thermal power plants) as a low-cost catalyst to enhance the ultrasonic (US) degradation of ibuprofen (IBP) and sulfamethoxazole (SMX). Two fly ashes, Belews Creek fly ash (BFA), from a power station in North Carolina, and Wateree Station fly ash (WFA), from a power station in South Carolina, were used. The results showed that >99% removal of IBP and SMX was achieved within 30 and 60 min of sonication, respectively, at 580 kHz and pH 3.5. Furthermore, the removal of IBP and SMX achieved, in terms of frequency, was in the order 580 kHz > 1000 kHz > 28 kHz, and in terms of pH, was in the order of pH 3.5 > pH 7 > pH 9.5. WFA showed significant enhancement in the removal of IBP and SMX, which reached >99% removal within 20 and 50 min, respectively, at 580 kHz and pH 3.5. This was presumably because WFA contains more silicon dioxide than BFA, which can enhance the formation of OH radicals during sonication. Additionally, WFA has finer particles than BFA, which can increase the adsorption capacity in removing IBP and SMX. The sonocatalytic degradation of IBP and SMX fitted pseudo first-order rate kinetics and the synergistic indices of all the reactions were determined to compare the efficiency of the fly ashes. Overall, the findings have showed that WFA combined with US has potential for treating organic pollutants, such as IBP and SMX, in water and wastewater.     

Improvement of sonochemical degradation of Brilliant blue R in water using periodate ions: Implication of iodine radicals in the oxidation process

In this paper, the effect of periodate (IO₄⁻) on the ultrasonic degradation at 300 kHz of Brilliant Blue R (BBR), an organic dye pollutant, was investigated. The experiments were realized in the absence and presence of periodate for various operating conditions including initial solution pH (2–8) and delivered ultrasonic power (20–80 W). It was found that periodate greatly enhanced the sonochemical degradation of BBR. The degradation rate increased significantly with increasing IO₄⁻ concentration up to 10 mM and decreased afterward. With 10 mM of periodate, the degradation rate was 2.4-fold higher than that with ultrasound alone. The chemical probes experiments showed that periodate activation into free radicals (IO₃, IO₄ and OH) takes place by sonolysis and iodine radicals contribute significantly in the oxidation process. It was found that the periodate-enhanced effect was strongly experimental parameters dependent. The advantageous effect of periodate increased significantly with decreasing power and the best enhancing effect was obtained for the lowest power. Correspondingly, the periodate-enhanced effect increased with pH increase in the range 2–8 and it was more remarkable at near alkaline condition (pH 8). A reaction scheme for periodate sonolysis was proposed, for the first time, discussed and then used for interpreting the obtained results.     

Magnetic Pd@Fe3O4 composite nanostructure as recoverable catalyst for sonoelectrohybrid degradation of Ibuprofen

In the present research, the degradation of an emerging pharmaceutical micro-pollutant, Ibuprofen (IBP) by using Pd@Fe₃O₄ and a hybrid sono-electrolytical (US/EC) treatment system has been demonstrated for the first time. The magnetically separable nanocomposite, Pd@Fe₃O₄ catalyst was synthesized following co-precipitation method to enhance the efficiency of US/EC system. The synthesized catalyst showed a strong reusable property even after applying for five times and in all the five cases, 100% degradation of IBP was maintained. It not only enhanced the IBP degradation rate, but also reduced the energy consumption of the system by ∼35%. Its strong magnetization value of 64.27 emu g⁻¹ made it easily separable. Hence, a comprehensive knowledge on the application of combined energy based US/EC system and magnetically separable multifunctional catalysts for degradation of intractable pollutants like Ibuprofen was achieved, assuring that US/EC can be an effective option for IBP treatment.     

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.     

Ultrasonic assisted-Fenton-like degradation of nitrobenzene at neutral pH using nanosized oxides of Fe and Cu

Ultrasonic-assisted heterogeneous Fenton reaction was used for degradation of nitrobenzene (NB) at neutral pH conditions. Nano-sized oxides of α-Fe₂O₃ and CuO were prepared, characterized and tested in degradation of NB (10 mg L⁻¹) under sonication of 20 kHz at 25 °C. Complete degradation of NB was effected at pH 7 in presence of 10 mM H₂O₂ after 10 min of sonication in presence of α-Fe₂O₃ (1.0 g L⁻¹), (k = 0.58 min⁻¹) and after 25 min in case of CuO (k = 0.126 min⁻¹). α-Fe₂O₃ showed also effective degradation under the conditions of 0.1 g L⁻¹ oxide and 5.0 mM of H₂O₂, even though with a lower rate constant (0.346 min⁻¹). Sonication plays a major role in enhancing the production of hydroxyl radicals in presence of solid oxides. Hydroxyl radicals-degradation pathway is suggested and adopted to explain the differences noted in rate constants recorded on using different oxides.     

Development of an empirical kinetic model for sonocatalytic process using neodymium doped zinc oxide nanoparticles

The degradation of Acid Blue 92 (AB92) solution was investigated using a sonocatalytic process with pure and neodymium (Nd)-doped ZnO nanoparticles. The nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The 1% Nd-doped ZnO nanoparticles demonstrated the highest sonocatalytic activity for the treatment of AB92 (10 mg/L) with a degradation efficiency (DE%) of 86.20% compared to pure ZnO (62.92%) and sonication (45.73%) after 150 min. The results reveal that the sonocatalytic degradation followed pseudo-first order kinetics. An empirical kinetic model was developed using nonlinear regression analysis to estimate the pseudo-first-order rate constant (k_app) as a function of the operational parameters, including the initial dye concentration (5–25 mg/L), doped-catalyst dosage (0.25–1 g/L), ultrasonic power (150–400 W), and dopant content (1–6% mol). The results from the kinetic model were consistent with the experimental results (R² = 0.990). Moreover, DE% increases with addition of potassium periodate, peroxydisulfate, and hydrogen peroxide as radical enhancers by generating more free radicals. However, the addition of chloride, carbonate, sulfate, and t-butanol as radical scavengers declines DE%. Suitable reusability of the doped sonocatalyst was proven for several consecutive runs. Some of the produced intermediates were also detected by GC–MS analysis. The phytotoxicity test using Lemna minor (L. minor) plant confirmed the considerable toxicity removal of the AB92 solution after treatment process.     

Determination of nitrofurans in feeds based on silver nanoparticle-catalyzed chemiluminescence

A highly sensitive chemiluminescence (CL) method for the determination of nitrofurans (NFs) was developed based on the enhancement of CL intensity of luminol–H₂O₂–NFs system by silver nanoparticles (AgNPs). It was supposed that the oxygen-related radicals of OH and superoxide radical (O₂^?) could be produced when NFs reacted with H₂O₂. Furthermore, the enhancement mechanism was originated from the reinforcer of AgNPs, which could catalyze the generation of the OH radical. Then OH radicals reacted with luminol anion and HO₂^? to form luminol radical (L^?) and O₂^?. The excited state 3-aminophthalate anion was obtained in the reaction of L^? and O₂^?, which was the emitter (luminophor) in the luminol–H₂O₂ CL reaction system and the maximal emission of the CL spectrum was at 425 nm. The experiments of scavenging oxygen-related radicals were done to confirm these reactive oxygen species participated in the CL reaction. The limits of detection (LOD) (S/N=3) were 8×10^?7 g mL^?1 for furacilin, 8×10^?8 g mL^?1 for furantoin, 4×10^?8 g mL^?1 for furazolidone and 2×10^?7 g mL^?1 for furaltadone. The proposed method was successfully applied to the determination of NFs in feeds and pharmaceutical samples.     

Heterogeneous sono-Fenton-like process using nanostructured pyrite prepared by Ar glow discharge plasma for treatment of a textile dye

The plasma-treated pyrite (PTP) nanostructures were prepared from natural pyrite (NP) utilizing argon plasma due to its sputtering and cleaning effects resulting in more active surface area. The NP and PTP were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Brunauer–Emmett–Teller (BET) and scanning electron microscopy (SEM) methods. The performance of the PTP was greater than NP for treatment of Reactive Red 84 (RR84) by the heterogeneous sono-Fenton process. The optimum amounts of main operational parameters were obtained as PTP of 4 g/L, initial dye concentration of 10 mg/L, pH of 5, and ultrasonic power of 300 W after 120 min of reaction time. Also, the effects of enhancers, and inorganic salts and t-butanol as hydroxyl radical scavengers on the degradation efficiency were investigated. Gas chromatography–mass spectroscopy analysis (GC–MS) was applied for detection of some degradation intermediates. Environmentally friendly plasma modification of the NP, in situ production of H₂O₂ and OH radicals, low leached iron concentration and repeated reusability at the milder pH are the significant benefits of the PTP utilization.     

Effect of nitrate ions on the efficiency of sonophotochemical phenol degradation

A sonophotochemical oxidation process has been used for the treatment of an aqueous solution of phenol. The aim of this work is to evaluate the effect of nitrate ions on hydroxyl radical production and on phenol oxidation. It has been demonstrated that ultrasound can produce NOx (nitrate and nitrite), with a production rate of 2.2 μM min⁻¹. The photolysis of nitrate can significantly improve the hydroxyl radical production. The apparent rate constant for hydroxyl radical production increased from 0.0015 min⁻¹ to 0.0073 min⁻¹ while increasing initial nitrate concentration from 0 to 0.5 mM. The concentration of hydroxyl radical was directly proportional to the initial nitrate concentration. Using US/UV process, the apparent reaction rate constant of phenol degradation in the presence of nitrate reached 0.020 min⁻¹, which was relatively lower than the value obtained (0.027 min⁻¹) in the absence of nitrate. It appeared that, nitrate ions can inhibit the sonochemical degradation of organic compounds such as phenol.