Removal of dinitrotoluenes in wastewater by sono-activated persulfate

Oxidative degradation of dinitrotoluenes (DNTs) in wastewater was performed using persulfate anions combined with ultrasonic irradiation, wherein a synergistic effect is observed. The batch-wise experiments were carried out to elucidate the influence of various operating parameters on sono-activated persulfate oxidation, including ultrasonic power intensity, persulfate anion concentration, reaction temperature and acidity of wastewater. It is noteworthy that the nitrotoluene contaminants could be almost completely eliminated by virtue of sono-activated persulfate oxidation, wherein sulfate radicals serve as principal oxidants, of which amounts are significantly enhanced via addition of sodium sulfate. Based on the results given by gas chromatograph-mass spectrometer (GC-MS), it is postulated that the methyl group of DNTs preliminarily underwent oxidation pathway into dinitrobenzoic acid, followed by decarboxylation to form 1,3-dinitrobenzene (DNB). In sum, the sono-activated persulfate oxidation is a promising method for treatment of nitrotoluenes in wastewater.     

Ultrasound and heat enhanced persulfate oxidation activated with Fe0 aggregate for the decolorization of C.I. Direct Red 23

Effluents from the paper printing and textile industries are often heavily contaminated with azo dyes. Azo dyes are difficult to oxidize biologically. This work investigated the decolorization of an azo dye, C.I. Direct Red 23 (DR23), by persulfate (PS) activated with Fe⁰ aggregates (PS/Fe⁰). Ultrasound (US) and heat were used as enhancement tools in the PS oxidation system. Neither US-activated PS nor thermally activated PS was effective in oxidizing DR23. However, the decolorization was significantly enhanced by PS/Fe⁰ combined with US (PS/Fe⁰/US) or heat (PS/Fe⁰/55 °C). Approximately 95% decolorization of 1 × 10⁻⁴ M DR23 was achieved within 15 min in the PS/Fe⁰/US system at an initial pH of 6.0, PS of 5 × 10⁻³ M, Fe⁰ of 0.5 g/L and US irradiation of 106 W/cm² (60 kHz). Complete decolorization was achieved within 10 min in the Fe⁰/PS/55 °C system. The rate of decolorization doubled when US was introduced in the PS/Fe⁰ system during the treatment of different initial dye concentrations. The dependence of dye and true color (ADMI) depletion on PS concentration has been discussed. DR23 was completely degraded based on the disappearance of aromatic groups of UV–vis spectra and the variation of TOC mineralization. The observed pseudo-first-order decolorization rate was substantially enhanced by increasing temperature. The Arrhenius activation energy for the PS activated with Fe⁰ was estimated as 8.98 kcal/mol, implying that higher temperature is beneficial for the DR23 decolorization. The addition of US into the PS/Fe⁰ system did not incur a substantial increase in electricity, whereas the mineralization of DR23 occurred quickly. Thus, both PS/Fe⁰/US and heated PS/Fe⁰ systems are practically feasible for the effective degradation of the direct azo dye in textile wastewater.     

Intensification of sonochemical degradation of ammonium perfluorooctanoate by persulfate oxidant

Ammonium perfluorooctanoate (APFO) is an emerging environmental pollutant attracting significant attention due to its global distribution, high persistence, and bioaccumulation properties. The decomposition of APFO in aqueous solution with a combination of persulfate oxidant and ultrasonic irradiation was investigated. The effects of operating parameters, such as ultrasonic power, persulfate concentration, APFO concentration, and initial media pH on APFO degradation were discussed. In the absence of persulfate, 35.5% of initial APFO in 46.4 μmol/L solution under ultrasound irradiation, was decomposed rapidly after 120 min with the defluorination ratio reaching 6.73%. In contrast, when 10 mmol/L persulfate was used, 51.2% of initial APFO (46.4 μmol/L) was decomposed and the defluorination ratio reached 11.15% within 120 min reaction time. Enhancement of the decomposition of APFO can be explained by acceleration of substrate decarboxylation, induced by sulfate radical anions formed from the persulfate during ultrasonic irradiation. The SO₄^−•/APFO reactions at the bubble-water interface appear to be the primary pathway for the sonochemical degradation of the perfluorinated surfactants.     

Degradation of amoxicillin in aqueous solution using sulphate radicals under ultrasound irradiation

Degradation of the antibiotics amoxicillin in aqueous solution using sulphate radicals under ultrasound irradiation was investigated. The preliminary studies of optimal degradation methodology were conducted with only oxone (2KHSO₅·KHSO₄·K₂SO₄), cobalt activated oxone (oxone/Co²⁺), oxone + ultrasonication (oxone/US) and cobalt activated oxone + ultrasonication (oxone/Co²⁺/US). The chemical oxygen demand (COD) removal efficiency were in the order of oxone < oxone/Co²⁺ < oxone/US < oxone/Co²⁺/US for the amoxicillin solution. The variables considered for the effect of degradation were the temperature, the power of ultrasound, the concentration of oxone, as well as catalyst and the initial amoxicillin concentration. More than 98% of COD removal was achieved within 60 min under optimum operational conditions. Comparative analysis revealed that the sulfate radicals had the high oxidation potential and the use of ultrasound irradiation reduced the energy barrier of the reaction and increased the COD removal efficiency of organic pollutants. The degradation of amoxicillin follows the first-order kinetics.     

Mild corrosion behavior on sulphurized steel surface during friction

After treatment by low temperature ion sulphuration, the solid lubrication sulphuration layers (FeS films) were produced on the AISI 1045 and stainless steel. A mass of corrosion peeling pits occurred on the worn scars of 1045 steel sulphuration layer after wear test, whereas none of them on the stainless steel one. AFM was used to observe the morphology of sulphuration layer, SEM equipped EDS was utilized to analyze the morphologies and compositions of worn scars. XPS and XRD were employed to detect the valence states of sulphuration layer and its worn scars, as well as the phase structures. The results showed that during friction, under the frictional heat, the sulfate radical with mild corrosion was produced, so that the 1045 steel without any anti-corrosion was corroded in some certain, meanwhile the stainless steel was not corroded depending on its excellent corrosion resistance.     

苯快速反应点火特性的光谱研究

利用由单色谱仪、压力传感器以及示波器组成的测试系统, 测定了高温激波管中苯快速反应的几个重要产物：H,C₂和CH的点火延迟时间和出现的顺序。提出了一种在入射激波条件下确定含能材料冲击点火延迟时间的新方法,并介绍了苯在快速反应中碳生成的微观反应机理。 研究表明: 无论马赫数如何改变,H原子总是最先出现,说明苯在快速反应过程中,首先断裂的C—H键,而不是C—C键。利用较早出现的反应中间产物H原子来测定苯的点火延迟时间更为准确。利用单色谱仪技术能较好地研究苯的快速反应点火特性,新方法与国内外常用的全色光技术相比可明显减少实验量。     

Kinetics for the reaction of phenyl radical with phenylacetylene and styrene

The kinetics for the reactions of C₆H₅ with phenylacetylene and styrene have been measured by CRDS in the temperature range 297-409 K under an Ar pressure of 3.6 Torr. The total rate constants can be given by the following Arrhenius expressions (in units of cm³ mol⁻¹ s⁻¹): k₁(C₆H₅ + C₆H₅C₂H) = 10^13.0±0.1exp [−(2430 ± 150)/RT] and k₂(C₆H₅ + C₆H₅C₂H₃) = 10^13.3±0.1 exp [−(2570 ± 180)/T]. Additional DFT and MP2 calculations have been carried out to assist our interpretation of the measured kinetic data. The addition of C₆H₅ to the terminal CH_x (x = 1 or 2) sites is predicted to be the dominant channel for both reactions. The calculated bimolecular rate constants are in reasonable agreement with experimental values for the temperature range studied.     

Sonodegradation of 17α-ethynylestradiol in environmentally relevant matrices: laboratory-scale kinetic studies

The sonochemical degradation of 17α-ethynylestradiol (EE2) in secondary treated effluents was investigated. Ultrasound irradiation was provided by a horn-type sonicator operating at 80 kHz. The effect of various operating conditions such as estrogen concentration (25-160 μg/L), power density (18-46 W/L), liquid bulk temperature (15-60 °C), gas sparging (air, oxygen, and helium), solution pH (3 and 7.8), as well as the addition of radical promoters (hydrogen peroxide) or catalysts (TiO₂ and Fe²⁺) on degradation kinetics was evaluated. Changes in estrogen concentration were followed by high performance liquid chromatography and the yeast estrogen screening (YES) assay. EE2 degradation in the range 25-110 μg/L follows first order kinetics in regard to its concentration, while lower order kinetics occur at higher concentrations. The reaction rate increases linearly with applied power and decreases exponentially with temperature at the conditions in question. Continuous sparging of air or oxygen has little effect on the kinetics relative to air-equilibrated conditions, while helium has a marginally positive effect. The inorganic and organic contents of the wastewater matrix appear to promote degradation at inherent conditions in comparison to experiments in ultrapure water. Nevertheless, the addition of H₂O₂ (8.6 and 86 mg/L), Fe²⁺ (2.5-25 mg/L) or TiO₂ (50-2000 mg/L) has no or, in some cases, adverse effect on kinetics.     

水辅助下的OH自由基与CH3OOH气相反应机理的理论研究

利用量子化学计算方法对单个水分子不存在与存在的情况下OH自由基与CH3OOH的气相氢抽取反应进行了理论研究。在BHandHLYP/6-311++G(2df,2pd)理论水平下优化了所有驻点的几何构型,在此基础上利用CCSD(T)/cc-pVTZ方法对所有驻点的单点能重新进行了计算。计算结果表明,OH自由基与CH3OOH反应的主要通道是OH自由基抽取CH3OOH中的-OH基团上的H原子。在单个水分子存在的情况下,反应的主要通道没有改变,但是水化过渡态的能量显著地降低,显然单个水分子对OH+CH3OOH反应具有催化效应。     

水辅助下的OH自由基与CH_3OOH气相反应机理的理论研究

利用量子化学计算方法对单个水分子不存在与存在的情况下OH自由基与CH3OOH的气相氢抽取反应进行了理论研究.在BHand HLYP/6-311++G(2df,2pd)理论水平下优化了所有驻点的几何构型,在此基础上利用CCSD(T)/cc-p VTZ方法对所有驻点的单点能重新进行了计算.计算结果表明,OH自由基与CH3OOH反应的主要通道是OH自由基抽取CH3OOH中的-OH基团上的H原子.在单个水分子存在的情况下,反应的主要通道没有改变,但是水化过渡态的能量显著地降低,显然单个水分子对OH+CH3OOH反应具有催化效应.