一种检测低浓度化学需氧量的双波长光谱方法

提出了一种基于双波长光谱法快速测定低污染水样的化学需氧量(COD)的方法.结果表明:对低COD样品采用440和560 nm双波长的测定方法可有效地提高可靠性和检测灵敏性.该法的灵敏度(即定量检测下限)为8.6 mg·L-1;在低COD范围标样(≤100mg·L-1)的准确性对比测定相对标准误差在2%～15%的范围内.另外,该方法不需要用标准样品进行校正,可以通过光谱法检测消解液中重铬酸根的消耗直接计算出样品的COD值,使实验步骤得到了进一步的简化.     

Ultrasound assisted method to increase soluble chemical oxygen demand (SCOD) of sewage sludge for digestion

The aim of this study was to clarify the possibilities to increase the amount of soluble chemical oxygen demand (SCOD) and methane production of sludge using ultrasound technologies with and without oxidising agents. The study was done using multivariate data analyses. The most important factors affected were discovered. Ultrasonically assisted disintegration increased clearly the amount of SCOD of sludge. Also more methane was produced from treated sludge in anaerobic batch assays compared to the sludge with no ultrasonic treatment. Multivariate data analysis showed that ultrasonic power, dry solid content of sludge (DS), sludge temperature and ultrasonic treatment time have the most significant effect on the disintegration. It was also observed that in the reactor studied energy efficiency with high ultrasound power together with short treatment time was higher than with low ultrasound power with long treatment time. When oxidising agents were used together with ultrasound no increase in SCOD was achieved compared the ultrasonic treatment alone and only a slight increase in total organic carbon of sludge was observed. However, no enhancement in methane production was observed when using oxidising agents together with ultrasound compared the ultrasonic treatment alone. Ultrasound propagation is an important factor in ultrasonic reactor scale up. Ultrasound efficiency rose linearly with input power in sludge at small distances from the transducer. Instead, ultrasound efficiency started even to decrease with input power at long distances from the transducer.     

Trivalent manganese as an environmentally friendly oxidizing reagent for microwave- and ultrasound-assisted chemical oxygen demand determination

In the present work manganese(III) has been used as oxidant and microwave radiation and ultrasound energy have been assessed to speed up and to improve the efficiency of digestion step for the determination of chemical oxygen demand (COD). Microwave (MW) and ultrasound-assisted COD determination methods have been optimized by means of experimental design and the optimum conditions are: 40 psi pressure, 855 W power and 1 min irradiation time; and 90% of maximum nominal power (180 W), 0.9 s (s^?1) cycles and 1 min irradiation time for microwaves and ultrasound, respectively. Chloride ion interference is removed as hydrochloric acid gas from acidified sample solutions at 150 °C in a closed reaction tube and captured by bismuth-based adsorbent suspended above the heated solution. Under optimum conditions, the evaluated assisted digestion methods have been successfully applied, with the exception of pyridine, to several pure organic compounds and two reference materials. COD recoveries obtained with MW and ultrasound-assisted digestion for five real wastewater samples were ranged between 86–97% and 68–91%, respectively, of the values obtained with the classical method (open reflux) used as reference, with relative standard deviation lower than 4% in most cases. Thus, the Mn(III) microwave-assisted digestion method seems to be an interesting and promising alternative to conventional COD digestion methods since it is faster and more environmentally friendly than the ones used for the same purpose.     

基于拉曼光谱的海水COD检测方法的研究

海水的化学需氧量大小直接决定海水水质的污染程度,传统的紫外-可见光波段检测时荧光干扰较大,近红外光波段检测时,水分子红外吸收峰影响较严重。提出一种基于拉曼光谱的海水化学需氧量检测方法,以不同浓度的模拟海水样本为被测对象,确定特征拉曼位移为981.6 cm-1,对拉曼光谱预处理后,通过偏最小二乘法对拉曼光谱的相对强度与碱性高锰酸钾法检测得到的海水化学需氧量进行回归建模。实验结果显示,训练集和预测集相关系数达到0.99,验证集决定系数可达到0.990 9,预测均方根误差为0.79 mg/L。     

Electrosynthesis of hydrogen peroxide via the reduction of oxygen assisted by power ultrasound

The electrosynthesis of hydrogen peroxide using the oxygen reduction reaction has been studied in the absence and presence of power ultrasound in a non-optimized sono-electrochemical flow reactor (20 cm cathodic compartment length with 6.5 cm inner diameter) with reticulated vitreous glassy carbon electrode (30 x 40 x 10 mm, 10 ppi, 7 cm(2)cm(-3)) as the cathode. The effect of several electrochemical operational variables (pH, volumetric flow, potential) and of the sono-electrochemical parameters (ultrasound amplitude and horn-to-electrode distance) on the cumulative concentration of hydrogen peroxide and current efficiency of the electrosynthesis process have been explored. The application of power ultrasound was found to increase both the cumulative concentration of hydrogen peroxide and the current efficiency. The application of ultrasound is therefore a promising approach to the increased efficiency of production of hydrogen peroxide by electrosynthesis, even in the solutions of lower pH (<12). The results demonstrate the feasibility of at-site-of-use green synthesis of hydrogen peroxide.     

High UV absorption efficiency of nanocrystalline ZnO synthesized by ultrasound assisted wet chemical method

Ultrasound assisted wet-chemical method has been carried out to incorporate different metal and non-metal ions such as; Li, S and Ag into ZnO. Characteristic studies on the structural and optical properties of the samples especially; the ultra-violet (UV) light absorption have been carried out. X-ray diffraction (XRD) analysis shows the formation of hexagonal crystal structure of ZnO along with changes in crystallinity and micro-strain with impurity doping. The morphology of the doped samples changes from particle like structure to flower and rod like structures showing the influence of dopant ions on nano ZnO growth. Infra-red (IR) transmittance spectra give information about the presence of metal–oxygen bond along with other stretching and bending modes. UV–visible absorption studies show the narrowing and sharpening of UV absorption band along with a blue shift for the doped samples. This shows the intensification in the excitonic absorption in ZnO after doping specific elements which will find application in UV blocking agents. Photoluminescence (PL) measurement shows the presence of excitonic emission and emissions due to intrinsic defects and external impurities in UV and visible regions respectively. These emission bands show a change in their position and intensity which has been explained on the basis of the existence of impurity levels in the band gap of ZnO.     

近红外透射和紫外吸光度法检测水质化学需氧量的研究

化学需氧量(COD)是表征水体中有机物污染程度的一个综合性指标.基于光电检测技术发展起来的红外透射法和紫外吸光度法相较于传统湿化学法有着精度高,速度快,非接触,无二次污染等优点.以邻苯二甲酸氢钾配置的标准液为实验对象,分别采用近红外透射法和紫外吸光法采集标准液的近红外光谱和紫光吸光度光谱,对光谱进行不同的预处理后运用偏...     

Enhancing the formation of tetragonal phase in perovskite nanocrystals using an ultrasound assisted wet chemical method

Synthesis of highly-pure tetragonal perovskite nanocrystals is the key challenge facing the development of new electronic devices. Our results have indicated that ultrasonication is able in enhancing the formation of tetragonal phase in perovskite nanocrystals. In the current research, multicationic oxide perovskite (ATiO₃; A: Ba, Sr, Ba_0.6Sr_0.4) nanopowders are synthesized successfully by a general methodology without a calcination step. The method is able to synthesize high-purity nanoscale ATiO₃ (BaTiO₃, SrTiO₃, Ba_0.6Sr_0.4TiO₃) with tetragonal symmetry at a lower temperature and in a shorter time span in contrast to the literature. To reach an in-depth understanding of the scientific basis of the proposed methodology, in-detail analysis was carried out via XRD, FTIR, FT-Raman, FE-SEM and HR-TEM. The effects of the sonication time and sonication (bath) temperature on the tetragonality of nanoscale products were examined. Furthermore, Raman spectroscopy provides clear evidence for local tetragonal symmetries, in particular when a band is observed at 310 cm⁻¹.     

Some studies of ultrasound assisted filtration rates

Some recent experimental results of ultrasonically assisted pressure filtration rates through sintered brass and woven stainless steel filters are presented. The liquids studied are clean motor oil (Velocite Mobil No. 6) and slurries formed by adding aluminium powder or hollow glass spheres to the motor oil. Relations between the parameters: pressure drop across the filter, ultrasonic field intensity and the ratio of particle to pore diameter are investigated. Previous explanations on the mechanisms leading to observed flow rate increase by ultrasonic irradiation, given by various authors, are critically evaluated in the light of new observations. These include the critical frequency theory, the influence of cavitation and microstreaming and the influence of turbulence. Some essential relations between parameters influencing the flow rate which still need a systematic investigation are emphasized. It is concluded that the use of ultrasound in pulsed mode operation may be the way out of the present stagnation in the field.     

Pulsed ultrasound assisted dehydration of waste oil

A method to aid the separation of the oil phase from waste oil emulsion of refineries had been developed by using a pulsed ultrasonic irradiation technology. Compared with conventional continuous ultrasonic irradiation, it is found that pulsed ultrasonic irradiation is much better to make water drop coalescence and hence dehydration of waste oil. The effects of ultrasonic irradiation parameters on waste oil dehydration are further discussed. The orthogonal experiment is also designed to investigate the degrees of influence of ultrasonic parameters and the optimal technological conditions. Under the optimal experimental conditions, the water content of waste oil is decreased from 65% to 8%, which thereby satisfies the requirements of refineries on the water content of waste oil after treatment (<10%).     

Various aspects of ultrasound assisted emulsion polymerization process

In this paper, the effects of ultrasonic (US) power, pulse ratio, probe area and recipe composition were investigated on two process responses namely, monomer (methyl methacrylate, MMA) conversion and electrical energy consumption per mass of product polymer (PMMA). Pulsed mode US is more suitable than continuous mode US for emulsion polymerization. The probe (tip) area has little effect on the yield of polymerization when comparing 19 and 13 mm probes, 13 mm probe performing slightly better for high conversion levels. Meanwhile, large probe area is beneficial for high conversion efficiency of electric energy to US energy as well as for high radical generation yield per energy consumed. The conversion increased slightly and electrical energy consumption decreased substantially by using a recipe with high SDS and monomer concentrations. Conclusions presented in this paper may be useful for scale-up of US assisted emulsion polymerization.     

Use of ultrasound in chemical synthesis

A review is presented giving details of the use and effects of ultrasound chemical synthesis. This paper is designed to introduce the reader to the field of sonochemistry as applied to chemical synthesis and more details of the mechanisms and theories of sonochemistry will be given in a future special issue of Ultrasonics.     

Direct contact ultrasound assisted freezing of chicken breast samples

Nowadays, rapid freezing is sought to favor the formation of small ice crystals. Several studies have shown that the application of ultrasounds (US) accelerates the processes of energy and mass transfer when they are applied through immersion systems. However, there are hardly any studies on its application in direct systems without the use of a liquid medium for its transmission. Therefore, the objective of this work was to evaluate the potential of the application of US for improving the freezing process of chicken breast samples. First, the application of intermittent US treatments at different net sonication times of 7, 17, 37, 50 and 67% during the freezing of distilled water samples in a conventional freezer was evaluated. It was observed that net sonication times of 37, 50 and 67% reduced the phase change period by 30.0, 21.4, 27.0%, respectively. The effective freezing time was also reduced by 12.4 and 12.8% by applying net sonication times of 37 and 50%. Considering these results, an intermittent US treatment with a net sonication time of 37% was chosen for chicken breast freezing in an air-forced cooling tunnel at ambient temperatures from −13 to −22 °C. The length of all the freezing phases was reduced upon application of US, leading to an overall process time reduction of approx. 11%. On the other hand, no significant differences were found either in the Water Holding Capacity (WHC) or Cooking Loss (CL) values between control and US assisted frozen chicken breast samples. Furthermore, in vitro experiments showed that US-assisted freezing did not influence protein digestibility of chicken meat samples.This study demonstrates the potential of the application of US by direct contact to favor energy transfer processes during freezing of water and chicken breasts samples. However, its effect on the quality of the frozen products should be further studied.     

Direct pyrolysis and ultrasound assisted preparation of N,S co-doped graphene/Fe3C nanocomposite as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions

Bifunctional electrocatalysts to enable efficient oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential for fabricating high performance metal–air batteries and fuel cells. Here, a defect rich nitrogen and sulfur co-doped graphene/iron carbide (NS-GR/Fe₃C) nanocomposite as an electrocatalyst for ORR and OER is demonstrated. An ink of NS-GR/Fe₃C is developed by homogeneously dispersing the catalyst in a Nafion containing solvent mixture using an ultrasonication bath (Model-DC150H; power − 150 W; frequency − 40 kHz). The ultrasonically prepared ink is used for preparing the electrode for electrochemical studies. In the case of ORR, the positive half-wave potential displayed by NS-GR/Fe₃C is 0.859 V (vs. RHE) and for the OER, onset potential is 1.489 V (vs. RHE) with enhanced current density. The optimized NS–GR/Fe₃C electrode exhibited excellent ORR/OER bifunctional activities, high methanol tolerance and excellent long-term cycling stability in an alkaline medium. The observed onset potential for NS–GR/Fe₃C electrocatalyst is comparable with the commercial noble metal catalyst, thereby revealing one of the best low-cost alternative air–cathode catalysts for the energy conversion and storage application.     

Improvement of biological activity by low energy ultrasound assisted bioreactors

Bioreactors are broadly applied in biotechnology and wastewater treatments. The so-called advanced bioreactor systems should be optimised in a more compact, more efficient and more effective form. One method of optimisation is the improvement of the solid-liquid interface of the sludge flocs and the mass transfer rate of gas and nutrients in the liquid. This could be obtained by the intake of ultrasound in the bioreactor at a frequency of 25 kHz and a power input of 0.3 Wl-1. An increase in the biological activity of the process investigated with alternating ultrasound as well as a decrease without ultrasound were measured.     

Synthesis and characterisation of nanohydroxyapatite using an ultrasound assisted method

Nanostructured hydroxyapatite (HAP) was prepared by a wet precipitation method using Ca(NO₃) and KH₂PO₄ as the main material and NH₃ as the precipitator under ultrasonic irradiation. The Ca/P ratio was set at 1.67 and the pH maintained at a minimum of 9. The temperature conditions and ultrasound influences were investigated using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and Fourier transform infrared spectroscopy (FT-IR). The results showed that Nano-HAP can be obtained by this method and the particles were achieved to around 30 nm.     

A novel ultrasound assisted method in synthesis of NZVI particles

This research is about a novel ultrasound assisted method for synthesis of nano zero valent iron particles (NZVI). The materials were characterized using TEM, FESEM, XRD, BET and acoustic PSA. The effect of ultrasonic power, precursor/reductant concentration (NaBH₄, FeSO₄·7H₂O) and delivery rate of NaBH₄ on NZVI characteristics were investigated. Under high ultrasonic power the morphology of nano particles changed from spherical type to plate and needle type. Also, when high precursor/reductant and high ultrasonic power was used the particle size of NZVI decreased. The surface area of NZVI particles synthesized by ultrasonic method was increased when compared by the other method. From the XRD patterns it was found also the crystallinity of particles was poor.     

Reagent generation for chemical analysis assisted by ultrasonic irradiation

Few methods, such as coulometrics, have been developed to produce reagents in situ for analytical purposes. In this work the concept related to the generation of ultrasound-assisted reagents was exploited to yield oxidizing species in batch and flow systems of analysis. To evaluate the efficiency of ultrasound-assisted reagent generation, the conversion of Fe(2+) to Fe(3+) associated with the 1,10-o-phenantroline spectrophotometric method was tested to compare the oxidizing power of the produced species from pure water and aqueous solutions saturated with CCl(4) or CHCl(3) irradiated ultrasonic waves. Irradiation processes were conducted with an ultrasonic bath (40 kHz and 140 W). The borosilicate reactor was used in the batch studies, while the PTFE tube reactor was used for setting up the flow system, with the temperature during irradiation being controlled using a thermostatic bath. The sonochemical production of oxidizing agents was demonstrated to be efficient for chemical analysis in batch and flow systems. This technique was exemplified by oxidation of iodide and ferrous ions. It was observed that after 120 min of sonication approximately 40 microg of Fe(2+) was quantitatively oxidized to Fe(3+). Similar result was obtained by the irradiation of iodine in aqueous-organic medium.     

Laser assisted chemical vapour deposition of silicon oxide layers

This paper focuses on the deposition of silicon oxide thin films, using laser assisted CVD based on a CO₂ laser, and on the feasibility of the process for coating porous silicon samples. Scanning electron and atomic force microscopy were used to analyse the morphology and microstructure of the films, while structure and chemical composition were determined by Fourier transform infrared and Rutherford backscattering spectroscopy. Two-wavelength ellipsometry was used for thickness and refractive index evaluation. The photoluminescence of SiO₂/PS was measured and compared with that of uncoated samples.     

Searching for quarks: a quantum chemical assisted approach

The evidence for quarks as the basic blocks of matter come only from very expensive experiments, performed in very large particle accelerators. An alternative method of detection is to look for changes in spectroscopic properties that could be influenced by fractionally charged nuclei formed with the ‘wrong’ number of quarks. Although this proposal has already been made by many authors, they were not able to provide feasible and easily interpretable experiments to detect quarks in matter. In this paper, we present the results of configuration interaction (CI) calculations for the transition energies and optical oscillator strengths associated with inner shell electronic spectra of molecular nitrogen made of fractionally charged nuclei. It is shown that these bands can be used as fingerprints characterizing the presence of quarks in matter.