A microwave-powered thermospray nebulizer for liquid sample introduction in inductively coupled plasma atomic emission spectrometry

A new thermospray nebulizer based on the absorption of microwave radiation (MWTN) by aqueous solutions of strong acids is presented for the first time. To this end, a given length of the sample capillary is placed inside the cavity of a focused microwave system. A small piece of a narrower capillary tubing is connected at the tip of the sample capillary, outside the microwave cavity, to build up pressure. Drop size distributions of primary aerosols are exhaustively measured in order to evaluate the influence of several experimental variables (microwave power, liquid flow, irradiation length, inner diameter of the outlet capillary, nature and concentration of the acid) on the characteristics of the primary aerosol that are related to the emission signal. These experiments have been performed mainly to increase our understanding of the microscopic process of this new type of aerosol generation. A standard Meinhard nebulizer was employed for comparison. Under the best conditions the entire aerosol volume is contained in droplets smaller than 20 μm compared with 45% of the volume of the aerosol generated by the Meinhard. Hence, higher analyte and aerosol transport rates are to be expected for the MWTN compared with the Meinhard nebulizer. As any highly efficient nebulizer, MWTN requires a desolvation unit. For solutions 0.75 M in strong acid, the new nebulizer improves sensitivity (1.0-2.8 times), limits of detection (1.2-3.0 times), and background equivalent concentration (0.9-2.0 times) as compared to the standard Meinhard nebulizer, features many of the advantages of the conventional thermospray nebulizer, and overcomes some of its drawbacks (MWTN does not show corrosion problems and works at lower pressure, the aerosol characteristics are not modified when the PTFE capillary is replaced).     

A multimicrospray nebulizer for microwave-induced plasma mass spectrometry

We have developed a nebulizer, called a multimicrospray nebulizer (MMSN), that efficiently introduces analytes for plasma mass spectrometry and plasma emission spectrometry. In this nebulizer, both the sample solution and the nebulizer gas are divided into several streams to produce a multispray. That is, the MMSN is a nebulizer that contains several micronebulization units, each unit including an orifice for passing the nebulizer gas and a capillary for introducing a sample solution. The microspray from each micronebulization unit can be operated at a microliter per minute sample uptake rate to achieve high nebulization efficiency. The multimicrospray nebulizer is capable of introducing more analyte to the plasma compared with a single-orifice micronebulizer, which has a very low sample uptake rate. In this work, an MMSN with three orifices was found to be suitable for microwave-induced plasma mass spectrometry (MIP-MS). The sample uptake rate can be varied within a range of 5-250 microL/min. Therefore, the nebulizer is unique in its ability to deal with various sample volumes and provide high nebulization efficiency. The sensitivity for all elements obtained with the MMSN was higher than that obtained with a conventional concentric nebulizer (CCN), which is difficult to achieve with other types of microintroduction nebulizers. For most elements, the MIP-MS sensitivity was improved about 2-fold at a sample uptake rate of 150 microL/min, a much lower rate than that for the CCN (usually 0.5-1.5 mL/min). The sensitivity for arsenic was improved by a factor of 5. The relative standard deviation was found to be less than 2.0%.     

A large bore-direct injection high efficiency nebulizer for inductively coupled plasma spectrometry

A large bore-direct injection high efficiency nebulizer (IB-DIHEN) is introduced that is less prone to capillary blockage and optimally operates at low nebulizer gas pressures compared with the conventional DIHEN used for inductively coupled plasma (ICP) spectrometries. The aerosol quality is examined using a two-dimensional phase Doppler particle analyzer (2D PDPA), and analytical figures of merits are acquired by ICP mass spectrometry. Compared with the DIHEN, the LB-DIHEN produces larger droplets, but the velocity distributions and mean droplet velocities are narrower and lower, respectively, providing longer residence times for the droplets in the plasma. High RF power (1500 W), low nebulizer gas flow rates (0.25-0.35 L/min), and low solution uptake rates (80-110 microL/min) are required to operate the LB-DIHEN at optimum conditions for ICPMS. Detection limits and sensitivities measured with the LB-DIHEN are superior to those of a conventional nebulizer-spray chamber combination, but precision is inferior. The performance of the LB-DIHEN is further explored in the determination of trace elements in an herbal extract.     

Atmospheric pressure photoionization-mass spectrometry with a microchip heated nebulizer

A novel, microfabricated heated nebulizer chip for atmospheric pressure photoionization-mass spectrometry (APPI-MS) is presented. The chip consists of fluidic and gas inlets, a mixer, and a nozzle etched onto silicon wafer that is anodically bonded to a Pyrex glass wafer, on which an aluminum heater is sputtered. A krypton discharge lamp is used as the source for 10-eV photons to initiate the photoionization process. Dopant, delivered as part of the sample solution, is used to achieve efficient ionization. The use of the microfabricated heated nebulizer with APPI in the analysis of four analytes is demonstrated, and the spectra are compared to those obtained with a conventional APPI source. Ionization in positive and negative ion modes was successfully achieved and the spectra were mainly similar to those obtained with conventional APPI, indicating that the ionization in microfabricated and conventional APPI sources takes place by the same mechanisms. The flow rates with conventional APPI are approximately 100 muL/min, whereas the microchip heated nebulizer allows the use of flow rates 0.05-5 muL/min, thus being compatible with microfluidic separation systems or micro- and nano-LC. A stable signal was demonstrated throughout a 5-h measurement, which proved the excellent stability of the micro-APPI. The same heated nebulizer chip can be used for weeks.     

Bonding mechanism and stress distribution of a glass frit free thick film metallization for AlN-ceramic

Typical thick film pastes applied for the metallization of AlN-ceramics are glass bonding systems. The glass phase responsible for adhesion onto the ceramic unfortunately also acts as a heat barrier and impairs the excellent thermal conductivity of AlN. A new glass frit free conductor paste has been especially developed for the metallization of AlN. A numerical analysis of the stress distribution within the metallized ceramic induced by a continuous as well as a pulsed mode operating heat source has been conducted for this new metallization paste and, for comparison purpose, also for a standard thick film paste by means of a finite element program. In order to determine the physical property data of the phases occurring at the interface between metallization and substrate required for numerical simulation the relevant intermetallic samples have been synthesized.     

Fraunhofer effect atomic absorption spectrometry

The dark lines in the solar spectrum were discovered by Wollaston and cataloged by Fraunhofer in the early days of the 19th century. Some years later, Kirchhoff explained the appearance of the dark lines: the sun was acting as a continuum light source and metals in the ground state in its atmosphere were absorbing characteristic narrow regions of the spectrum. This discovery eventually spawned atomic absorption spectrometry, which became a routine technique for chemical analysis in the mid-20th century. Laboratory-based atomic absorption spectrometers differ from the original observation of the Fraunhofer lines because they have always employed a separate light source and atomizer. This article describes a novel atomic absorption device that employs a single source, the tungsten coil, as both the generator of continuum radiation and the atomizer of the analytes. A 25-microL aliquot of sample is placed on the tungsten filament removed from a commercially available 150-W light bulb. The solution is dried and ashed by applying low currents to the coil in a three-step procedure. Full power is then applied to the coil for a brief period. During this time, the coil produces white light, which may be absorbed by any metals present in the atomization cloud produced by the sample. A high-resolution spectrometer with a charge-coupled device detector monitors the emission spectrum of the coil, which includes the dark lines from the metals. Detection limits are reported for seven elements: 5 pg of Ca (422.7 nm); 2 ng of Co (352.7 nm); 200 pg of Cr (425.4 nm); 7 pg of Sr (460.7 nm); 100 pg of Yb (398.8 nm); 500 pg of Mn (403.1 nm); and 500 pg of K (404.4 nm). Simultaneous multielement analyses are possible within a 4-nm spectral window. The relative standard deviations for the seven metals are below 8% for all metals except for Ca (10.7%), which was present in the blank at measurable levels. Analysis of a standard reference material (drinking water) resulted in a mean percent recovery of 91%. This report attempts to give an historical perspective on the development of a novel atomic spectrometer based on the Fraunhofer effect.     

Tunnel frit: a nonmetallic in-capillary frit for nanoflow ultra high-performance liquid chromatography-mass spectrometryapplications

In this study, an easy method to fabricate a durable in-capillary frit was developed for use in nanoflow liquid chromatography (nanoLC). A small orifice was tunneled into the sol-gel frit during the polymerization process resulting in the simple fabrication of a tunnel frit. A short packing tunnel frit column (2 cm, C(18) particles) was able to sustain over 10,000 psi continuous liquid flow for 10 days without observation of particle loss, and back pressure variation was less than 5%. The tunnel frit was successfully applied to the fabrication of nanoflow ultra high-performance liquid chromatography (nano-UHPLC) trap and analytical columns. In the analysis of tryptic peptides, the tunnel frit trap and analytical columns were demonstrated to have high separation efficiency and sensitivity. In analysis of phosphopeptides, the use of the nonmetallic tunnel frit column showed better sensitivity than the metallic frit column. This design can facilitate the preparation of nano-HPLC and nano-UHPLC columns and the packing material can easily be refilled when the column is severely contaminated or clogged.     

测定汞的原子荧光法和冷原子吸收法比对研究

从监测方法和质量控制的角度出发,比对研究了测定水中汞的原子荧光法和冷原子吸收法,并提出了质量控制指标.研究结果表明:(1)两种方法具有可比性;(2)质量控制指标与样品浓度之间没有明显相关性;(3)对于标准样品,两种方法的室内相对标准偏差(RSD)、室间相对标准偏差(RSD′)和相对误差(RE)结论一致,即RSD≤5％,RSD′≤10.0％,RE≤±15.0％;(4)两种方法的标准样品和实际样品的加标回收率基本一致,为85％～115％,原子荧光法的空白加标回收率略低于冷原子吸收法.     

采用精密印刷技术的玻璃浆料圆片级气密封装

采用先进的丝网印刷设备和精密印刷技术,对MEMS器件玻璃浆料气密封装技术,包括丝网印刷、预烧结和键合工艺等进行了深入研究。采用三种不同线宽的丝网板对二次印刷工艺进行了优化,提高了玻璃浆料的平整度和均匀性。经烧结键合后的封装体具有较高的封接强度(剪切力12kg)及良好的气密性(氦气精检合格率100%),可实现高质量的圆片级气密封装。     

New developments in atomic absorption spectrometry

We consider some new methods and measuring instruments used in atomic absorption spectrometry: flame atomizer/annular-slot burner, rapidly heated graphite furnace with ballast, high resolution spectrometers with continuum source, and also the new standard GOST R 8.649-2008 of January 1, 2010.     

用玻璃粉作粘结剂制备碳纳米管厚膜及其场发射特性

研究了用涂敷法制备的碳纳米管（CNT）厚膜及其场发射特性,裂解法获得的碳纳米管与玻璃粉等混合、研磨,直接涂敷在Si基底上,经烧结后制成碳纳米管厚膜,二极结构测量的结果表明,碳纳米管厚膜有较低的开启电场（1.0～1.25V/μm）,场强为5V/μm时,电流密度达到了50μA/cm^2.该工艺的烧结过程应控制好,加热时间稍长会使CNT厚膜的场发射性能很快下降,时间过长会使CNT处在厚膜表面之下,无法有效发射电子.浆料中的玻璃粉比例增大时,碳纳米管阴极的场发射性能会有所降低.     

Highly sensitive elemental analysis for Cd and Pb by liquid electrode plasma atomic emission spectrometry with quartz glass chip and sample flow

This paper describes the development of a highly sensitive liquid-electrode plasma atomic emission spectrometry (LEP-AES) by combination of quartz glass chip and sample flow system. LEP-AES is an ultracompact elemental analysis method, in which the electroconductive sample solution is put into a microfluidic channel whose center is made narrower (～100 μm in width). When high voltage pulses (1500 V) are applied at both ends of the channel, the sample evaporates locally at the narrow part and generates plasma. By the emission from the plasma, elemental concentration is analyzed. In this paper, the limits of detection (LODs) were investigated in various conditions of accumulation time, material of the chip, and the sample flow. It was found that the long accumulation using the quartz chip with sample flow was effective to improve LOD. Authors suggested that this was because bubbles remaining after each plasma pulse were removed from the narrow channel by sample flow, resulting in highly reproducible plasma generation, to enable a high accumulation effect. Finally, LODs were calculated from a calibration curve, to be 0.52 μg/L for Cd and 19.0 μg/L for Pb at optimized condition. Sub-ppb level LOD was achieved for Cd.     

Development of a digital micromirror spectrometer for analytical atomic spectrometry

A digital micromirror device (DMD) has been incorporated into a novel spectrometer for use in analytical atomic spectrometry. The device can be taken from a commercial computer projector. A protective glass window covering the DMD chip limits the viewable wavelengths to the visible range. The DMD is used to project an image of the light source onto the exit plane of a flat-field spectrograph. A single photomultiplier tube is used for detection. The high switching rate of the micromirrors (15 μs) enables rapid full-spectrum capture, wavelength-modulation, source-modulation, fast narrow-wavelength window scans, and rapid-wavelength "jumping." Calcium, sodium, and potassium have been determined in several standard reference materials (tomato leaves, bovine liver, rice flour, total diet) by flame atomic absorption and emission spectrometry. Absorption sensitivities for each element are near the 0.02 μg/mL level, and detection limits for both absorption and emission are near the 0.01 μg/mL level. Elemental recoveries were within 10% of certified values for most reference materials.     

Continuum source tungsten coil atomic fluorescence spectrometry

A simple continuum source tungsten coil atomic fluorescence spectrometer is constructed and evaluated. The heart of the system is the atomizer: a low-cost tungsten filament extracted from a 150 W light bulb. The filament is resistively heated with a small, solid-state, constant-current power supply. The atomizer is housed in a glass chamber and purged with a 1 L/min flow of a conventional welding gas mixture: 10% H(2)/Ar. A 25 μL sample aliquot is pipetted onto the tungsten coil, the liquid is dried at low current, and then the atomic vapor is produced by applying a current in the range 3.5-5.5 A. The atomization current does not produce temperatures high enough to excite atomic emission. Radiation from a 300 W xenon lamp is focused through the atomic vapor, exciting atomic fluorescence. Fluorescence signals are collected using a hand-held charge-coupled device (CCD) spectrometer. Simultaneous determination of ten elements (Ag, Bi, Cr, Cu, Ga, In, Mg, Mn, and Tl) results in detection limits in the range 0.3 to 10 ng. The application of higher atomization currents (10 A) leads to straightforward detection of atomic emission signals with no modifications to the instrument.