Development of a high-pressure asher focused microwave system for sample preparation

The development of high-pressure Asher focused microwaves (HPA-FMs), a novel approach to microwave assisted digestion, is described. The system uses focused microwaves, at 2.45 GHz, to improve digestion capability with up to 650 W microwave power concentrated into six quartz pressure vessels containing samples and nitric acid. The device combines microwave heating with high-pressure vessel technology (reactions can be conducted at pressures and temperatures up to 130 bar and 320 °C, respectively). Methodology was developed using powdered biological reference material. The residual carbon content of digested bovine liver sample was determined by Coulometry after combustion in an oxygen stream to evaluate the effectiveness of the decomposition procedure. With this new decomposition device, organic material is totally oxidized with nitric acid in a single-step digestion.     

Microwave digestion of environmental and natural waters for selenium speciation

A microwave preparation procedure is proposed for selenium speciation in natural and drinking waters. Different chemical reagents were tested, and the conditions for Se speciation were optimized. The effect of the different reagents on various oxidation states of selenium under microwave digestion conditions was investigated. Most of the Se(-II) was converted to selenite when digested with HNO3 and <20% to selenate. The digestion with H2O2/H2SO4 can change most Se species into Se(IV). The concentration of Se(IV) in the samples was then determined by HPLC with a fluorescence detector after derivatization with 2,3-diamino-naphthalene (DAN). The microwave preparation procedure allows Se speciation in water samples. Se(IV) was determined after concentrating the sample under nitrogen protection. The amount of Se(IV) and Se(VI) was measured by adding an equal volume of concentrated hydrochloric acid to water sample to reduce Se(VI) to Se(IV). Then the amount of Se(VI) can be calculated by subtraction. The total selenium can be determined after digestion with H2O2/H2SO4, or after digestion with HNO3 followed by reduction with concentrated hydrochloric acid. Selenium (-II, 0) was calculated by subtracting inorganic Se(IV+VI) from the total. Detection limits of 0.0066 ng and 0.0096 ng Se were obtained for HNO3 and H202/H2SO4 as digestion reagents, respectively. The total Se in the four water samples tested range from 0.20 to 0.90 microg L(-1). Among them the dominant form was Se(VI) with the exception of pond waters where Se(-II) predominated.     

微波消解-等离子体光谱法测定钒氮合金中硅、锰、磷、铝

建立了微波消解等离子体光谱法直接同时测定钒氮合金中Si、Mn、P、Al四种杂质元素的新方法。至目前为止,此方法未见报道。通过对微波消解试样参数、基体效应、光谱干扰、等离子体测定条件等多方面的考察,优选了检测条件。方法简便快捷、易于实际操作。各杂质离子平均回收率为95%~111%,相对标准偏差RSD小于3%。     

A device for sampling and determination of total particulate mercury in ambient air

A miniaturized device, which serves as both particulate trap and pyrolyzer for airborne particulate mercury species, is described. It has been used in combination with amalgamation/thermal desorption/cold vapor atomic fluorescence spectrometry detection for the determination of total particulate mercury (TPM) associated with atmospheric aerosols. A standard reference material (SRM 1633b, NIST) has been used for validating of the pyrolysis technique, and a relative error smaller than 3% has been obtained. Contrary to most methods currently employed, this new technique does not require any sample preparation (e.g., extraction/digestion), no manual sample transfer or sample handling, and no addition of chemicals or reagents. Hence the risk of contamination is low. The time for complete analysis is less than 10 min per sample. The concentrations of TPM determined in metropolitan Toronto ranged from 3 to 91 pg m(-)(3) with standard deviations of <±2 pg m(-)(3) for simultaneous sets of four samples. These atmospheric TPM concentration values fall within the range reported in the literature. Good agreement was obtained by the three methods compared in a field study at Ny-?lesund (78°54'N, 11°53'E), Svalbard. The elevated values of TPM concentrations obtained using the method developed in this work may arise from the Arctic springtime conversion of atmospheric mercury from gas-phase to particulate-phase Hg species.     

微波消解-ICP-AES法测定茶叶中钾、钠、磷、硫、铁、锰、铜、锌、钙、镁方法研究

通过优化微波消解条件,并根据不同元素性质,调谐ICP-AES工作条件至最佳,实现了茶叶中K、Na、P、S以及Fe、Mn、Cu、Zn、Ca、Mg 10种元素的同时测定。10种元素测定结果 RSD%为0.67(Cu)～5.57(Na),回收率为84.0%(Na)～101.5%(Fe),检出限为0.001(Mn)～0.029(S)μg·g-1,表明该方法准确可靠,能够满足茶叶中K、Na、P、S、Fe、Mn、Cu、Zn、Ca、Mg分析要求。     

Rapid online nonenzymatic protein digestion combining microwave heating acid hydrolysis and electrochemical oxidation

We report an online nonenzymatic method for site-specific digestion of proteins to yield peptides that are well suited for collision-induced dissociation tandem mass spectrometry. The method combines online microwave heating acid hydrolysis at aspartic acid and online electrochemical oxidation at tryptophan and tyrosine. The combined microwave/electrochemical digestion is reproducible and produces peptides with an average sequence length of 10 amino acids. This peptide length is similar to the average peptide length of 9 amino acids obtained by digestion of proteins with the enzyme trypsin. As a result, the peptides produced by this novel nonenzymatic digestion method, when analyzed by electrospray ionization mass spectrometry, produce protonated molecules with mostly +1 and +2 charge states. The combination of these two nonenzymatic methods overcomes shortcomings with each individual method in that (i) peptides generated by the microwave-hydrolysis method have an average amino acid length of 16 amino acids and (ii) the electrochemical-cleavage method is unable to reproducibly digest proteins with molecular masses above 4 kDa. Preliminary results are presented on the application and utility of this rapid online digestion (total of 6 min of digestion time) on a series of standard peptides and proteins as well as an Escherichia coli protein extract.     

The Reduction of Uncertainties for Absolute Piston Gage Pressure Measurements in the Atmospheric Pressure Range

NIST pressure calibration services with nitrogen are now based on two transfer standard piston gages for which the effective areas have been determined by calibration with the manometer developed at NIST for gas thermometry. Root-sum-squared three sigma uncertainties for the areas for the two gages are 3.05 ppm and 4.18 ppm.     

Electrothermal atomic absorption spectrometric determination of total and hexavalent chromium in atmospheric aerosols

A method was developed which allow separate determination of Cr(VI) and total Cr from the same minute sample of atmospheric aerosols. Cr(VI) was leached was with 0.1M Na(2)CO(3) and the total Cr concentrations were determined after acid digestion. The method was validated by the analysis of certified reference materials, CRM 545, Mess-3 and Pacs-2 with good agreement between certified and found values. Cr concentrations in air samples taken around the chromium smelter show concentrations that exceed the maximum allowed levels in 8h with higher values closer to the smelter. The limit of detection (LOD) of the method for Cr(VI) determination in air samples was found to be 0.2 ng m(-3), i.e. lower than offered by the commonly preferred spectrophotometric and colorimetric techniques.     

Electrochemical degradation of aromatic amines on BDD electrodes

The electrochemical oxidation of four aromatic amines, with different substituent groups, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid (A1), 5-amino-2-methoxybenzenesulfonic acid (A2), 2,4-dihydroxyaniline hydrochloride (A3) and benzene-1,4-diamine (A4), was performed using as anode a boron-doped diamond electrode, commercially available at Adamant Technologies. Tests were run at room temperature with model solutions of the different amines, with concentrations of 200 ppm, using as electrolyte 0.035 M Na(2)SO(4) aqueous solutions, in a batch cell with recirculation, at different current densities (200 and 300 A m(-2)). The following analyses were performed with the samples collected during the assays: UV-Vis spectrophotometry, chemical oxygen demand (COD), total organic carbon (TOC), total Kjeldahl nitrogen, ammonia nitrogen, nitrates and HPLC. Results have shown a good electrodegradation of all the amines tested, with COD removals, after 6 h assays, higher than 90% and TOC removals between 60 and 80%. Combustion efficiency (η(C)), which measures the tendency to convert organic carbon to CO(2), was also determined for all the amines, being η(CA1)<η(CA2)<η(CA3)<η(CA4)=0.99.     

Influence of leachate recirculation on aerobic and anaerobic decomposition of solid wastes

In this study, the effect of leachate recirculation on aerobic and anaerobic degradation of municipal solid wastes is determined by four laboratory-scale landfill reactors. The options studied and compared with the traditional anaerobic landfill are: leachate recirculation, landfill aeration, and aeration with leachate recirculation. Leachate quality is regularly monitored by the means of pH, alkalinity, total dissolved solids, conductivity, oxidation-reduction potential, chloride, chemical oxygen demand, ammonia, and total Kjeldahl nitrogen, in addition to generated leachate quantity. Aerobic leachate recirculated landfill appears to be the most effective option in the removal of organic matter and ammonia. The main difference between aerobic recirculated and non-recirculated landfill options is determined at leachate quantity. Recirculation is more effective on anaerobic degradation of solid waste than aerobic degradation. Further studies are going on to determine the optimum operational conditions for aeration and leachate recirculation rates, also with the operational costs of aeration and recirculation.     

Microwave-assisted sample combustion: a technique for sample preparation in trace element determination

A novel digestion procedure based on sample combustion ignited by microwave radiation is proposed for organic samples. Certified samples of bovine liver, pig kidney, and skim milk were used as examples to demonstrate the performance of the proposed procedure. Cadmium and copper were determined in these samples by electrothermal atomic absorption spectrometry. Samples (between 50 and 250 mg) were wrapped with paper and placed on a homemade quartz holder that was positioned inside to quartz vessels used in a commercial microwave oven. Ammonium nitrate solution was added to the paper, and vessels were pressurized with oxygen to 15 bar. The rotor containing four vessels was placed inside the oven, and microwave radiation was applied for 20 s at 1400 W. Combustion was complete in few seconds, and an additional reflux step, which was optional, was applied. The agreement to the certified values was between 96 and 105% for both analytes. Only with the combustion step, the residual carbon (RC) was below 1.3%. The RC decreased to less than 0.4% when an additional reflux step with concentrated nitric acid was applied.     

微波消解磷钼蓝光度法测定燃料油中的磷

研究了微波消解燃料油样品的体系和程序,建立了燃料油中磷含量的测定新方法-磷钼蓝光度法。结果表明,在最佳实验条件下,磷的线性范围为0～1．0μg／mL,RSD为2．06～2．47％,回收率为99．13％～104．10％。方法具有高准确度和低检出限,适用于燃料油中磷的测定。     

Application of methods (sequential extraction procedures and high-pressure digestion method) to fly ash particles to determine the element constituents: a case study for BCR 176

Sequential extraction procedures and the high-pressure digestion method were selected to determine the element constituents of fly ash samples. Sequential extraction is one of the most useful methods used to measure the various elements from municipal solid waste incineration ash and contaminated soils. The extract from each step is analyzed using various techniques and equipment, and the results are then evaluated. In this work, a six-step extraction procedure modified from that of Tessier et al. and Wang et al. was performed and applied to the certified reference material BCR 176 (city waste incineration ash). Analyses were carried out by various techniques such as inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma-mass spectrometry (ICP-MS), scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX), and X-ray powder diffraction (XRPD) to evaluate the characteristics of fly ash. The extraction efficiency of many elements was higher than 80%, and the relative standard deviations (RSD) for recovery of most elements were within 10%. In addition, an H(2)O(2)+HNO(3)+HF mixed acid digestion solution processed using a low-temperature evaporation procedure was selected as the optimal process for fly ash digestion. The results of this work provide information on the chemical composition, distribution, and potential mobility of the investigated elements.     

Dependence of nitriding degree of Ti surface by non-LTE nitrogen plasma on various plasma parameters

Experiments of plasma nitriding of titanium are carried out by two plasma sources. One is a microwave discharge plasma source under several Torr, and the other is a nitrogen arc jet generated under atmospheric pressure followed by rapid expansion into a gas wind tunnel. The relationship between the surface density of nitrogen atoms in the α-Ti and various plasma parameters is systematically studied. For the microwave nitrogen plasma, it is found that the effect of the vibration temperature is the most essential for the surface nitriding, whereas the effect of electron temperature, density and rotation temperature is less remarkable. It is also found that the higher vibration temperature of the microwave discharge nitrogen plasma makes the target temperature higher, and consequently, the surface density of atomic nitrogen remarkably increased. However, the effect of target temperature is less remarkable for the arc jet nitrogen plasma.     

电感耦合等离子体质谱法测定聚丙烯(PP)餐盒中铅的总量

采用HNO3 —H2 O2 微波消解电感耦合等离子体质谱法(ICP-MS) 测定PP 餐盒中的铅含量,测定结果显示相对标准偏差为3. 8%,检出限为0. 05 mg/ L,结果表明该方法具有简便、快速、准确、灵敏度高等优点,适合于PP 餐盒中铅含量的测定。     

Microwave plasma removal of sulphur hexafluoride

Sulphur hexafluoride (SF(6)) gas is a common pollutant emitted during the plasma etching of thin films and plasma cleaning chemical vapor deposition (CVD) production processes used in the semiconductor industry. In this paper a method using microwave (2.45GHz frequency) plasmas sustained at atmospheric pressure for the abatement of SF(6) is investigated experimentally for various gas mixture constituents and operating conditions, with respect to its ability to decompose SF(6) to less harmful molecules. The destruction and removal efficiencies (DRE) of plasma abatement of SF(6) at concentrations between 1.7 and 5% in nitrogen in the presence of water vapor were studied as a function of the total gas flow rate and microwave power. Water vapor proved to be an effective source of free radical species that reacts with the radicals and ions resulting from SF(6) fragmentation in the plasma and also, it proved to reduce the process by-products. It was measured that approximately 25% of the initial SF(6) is converted to SO(2). Destruction and removal efficiencies of SF(6) up to 99.9% have been achieved.     

微波消解地质样品方法探讨

该文利用UltraCLAVE微波消解仪对地质样品进行消解,提出消解用酸的种类和用量,以及消解过程中的一些注意事项。方法优化微波消解的实验条件,速度快,污染少,操作简便安全,消解能力强且效果好,能满足地质样品简单、快速、批量分析的要求。     

Optimization of microwave assisted digestion procedure for the determination of zinc, copper and nickel in tea samples employing flame atomic absorption spectrometry

The present paper describes the development of a microwave assisted digestion procedure for the determination of zinc, copper and nickel in tea samples employing flame atomic absorption spectrometry (FAAS). The optimization step was performed using a full factorial design (2(3)) involving the factors: composition of the acid mixture (CMA), microwave power (MP) and radiation time (RT). The experiments of this factorial were carried out using a certified reference material of tea GBW 07605 furnished by National Research Centre for Certified Reference Materials, China, being the metal recoveries considered as response. The relative standard deviations of the method were found below 8% for the three elements. The procedure proposed was used for the determination of copper, zinc and nickel in several samples of tea from Turkey. For 10 tea samples analyzed, the concentration achieved for copper, zinc and nickel varied at 6.4-13.1, 7.0-16.5 and 3.1-5.7 (microg g(-1)), respectively.     

Speciation of heavy metals in sediment by conventional, ultrasound and microwave assisted single extraction methods: a comparison with modified sequential extraction procedure

Sequential extraction procedure proposed by the European Standards, Measurements and Testing (SM&T) Program, formerly the Community Bureau of Reference (BCR), has been applied for the heavy metals (HMs) partitioning in fresh water lake sediment samples. The results obtained by conventional sequential extraction BCR method (SEB) for Cd, Cu, Cr, Ni, Pb and Zn were compared with those estimated from three alternative single extractions, conventional (CSE), ultrasonic (USE) and microwave assisted (MSE), using identical operating conditions applied in each individual BCR fraction and validated by the CRM BCR 701. Extractable HMs contents obtained by all compared methodologies were measured by atomic absorption spectrometery. With the use of compromised sonication and microwave conditions, steps 1-3 of the sequential extraction (excluding the hydrogen peroxide digestion in step 3) could be completed between 15-30 min using ultrasonic bath, while 60-120 s were required for MSE. The total extractable metal contents obtained by three single extractions ranged from 75.1% to 114.0% except Cr in first step, which was extracted (125.3%) by MSE method as compared to those obtained by SEB procedure. The precision of the proposed BCR single extraction methods (expressed as RSD%) was found in the range of (3.99-9.6%) for all metals.     

Energy utilization and recirculation of currant-finishing wastewater

In this study, a new method for the treatment of currant-finishing wastewater was proposed in the context of the "clean technology" concept. This method consisted of two stages. In the first stage, the currant-finishing wastewater was recirculated in the currant-wash process and in the second stage this wastewater was utilized for the production of energy through anaerobic digestion. Recycling ratios from 0 to 95% were examined. By increasing the recycling ratio, effluent's COD increased from 3808 to 43,722mg/l, effluent's BOD from 681 to 5378mg/l, total sugars from 2.57 to 42.13g/l, total phosphorous from 0.79 to 5.14mg/l and total Kjeldahl nitrogen from 7.36 to 51.9mg/l while fresh water addition decreased from 6 to 0.3kg per kg of currants processed. The optimum recycling ratio range for the wastewater energy utilization proved to be 30-40%. In this range, the mass of COD and sugars digested was maximized resulting in the highest biogas production. Thus, the proposed system could be promising since water consumption is minimized and wastewater energy utilization is achieved rendering the process almost energetically self-sufficient.