OH在火焰中浓度分布图像及与温度关系的PLIF和CARS研究

用平面激光诱光（ＰＬＩＦ）技术了平面火焰炉、狭缝缝火焰的单脉冲激光诱导ＯＨ荧炙。由平面荧光图可得到氢氧基相对浓度分布和它的宽度。对扩散火焰,高温区在ＯＨ带内侧;ＯＨ带的外侧则是火焰的边界,相干反斯托克斯拉斯拉曼光谱（ＣＡＲＳ）的测量结果对比提出了有力的佐证。湍流火焰的ＰＬＩＦ图则清晰地显示出火焰面的不规则性,氢氧基的ＰＬＩＦ图像是研究火焰结构和流场的有力工具。     

Spectroscopy in separated flames-III Use of the separated nitrous oxide-acetylene flame in thermal emission spectroscopy

The separation of a premixed nitrous oxide-acetylene flame at a modified commercial burner is described. The reducing interconal zone of the fuel-rich separated flame exhibits low radiative background. The reducing atmosphere and high temperature of this flame result in an effective medium for the excitation of the atomic line spectra of the refractory elements. The use of the fuel-rich flame in the flame photometry of these elements has been investigated.     

Graphite-furnace AAS with ultrasonic nebulization

A technique combining ultrasonic nebulization of solutions and graphite-furnace atomic-absorption spectrometry is described. The analytical possibilities of two different techniques are shown. In one the nebulized samples are continuously introduced into a graphite tube operated at constant temperature, and in the other deposited on the inner wall of the graphite tube and heated discontinuously. The method chosen influences the absorption values for several elements. The sensitivity for determination by continuous sampling lies between the values for the normal electrothermal AAS injection technique and flame AAS. Higher sensitivities are obtained with the deposition technique.     

Spectroscopy in separated flames-V The argon- or nitrogen-sheathed nitrous oxide-acetylene flame in flame emission spectroscopy

The separation of the premixed nitrous oxide-acetylene flame by sheathing with argon or nitrogen is described. The interconal zone of the hot, slightly fuel-rich flame exhibits low background and noise levels and an extended reducing atmosphere, providing better conditions for the excitation of atoms of elements which form refractory oxides. The limits of detection found for nine such elements are greatly superior to those obtainable in the conventional unsheathed flame under similar conditions.     

Free-atom formation processes in premixed fuel-rich and stoichiometric oxygen-acetylene flames employed in atomic emission and absorption spectroscopy

Detailed observations on the atomic and molecular absorption and emission spectra of the various zones of premixed oxyacetylene flames are presented. Spatial flame profile data for both the natural flame species and those formed when solutions of metallic salts are nebulized into the flame are interpreted in terms of: (a) the relative concentrations of reactive intermediate and stable species in the various zones; (b) the mechanism of free-atom formation from aerosol droplets; and (c) free-atom depopulation processes. The results of this study clearly show that the striking enhancement in atomic spectra observed in either absorption or emission for many elements in the fuel-rich oxyacetylene flame originate in the favorable chemical environment provided by the interconal zone for the formation and existence of free-atoms.     

Correlation between flame geometry and the absorbance of some elements in the presence of organic solvents

The correlation between the changes in flame geometry and the sensitivity of atomic-absorption determination of silver, copper, iron and lead in the presence of various solvents (water, ethanol, n-propanol, methyl acetate, ethyl acetate and acetone) has been investigated. The flame geometry was studied by the Schlieren technique. Organic solvents, allowing a greater rate of introduction of solution, enable a greater sensitivity to be achieved. However, owing to the expansion of the reaction zone, the increase in sensitivity is not as great as expected from the amount of sample introduced into the flame.     

Atomization efficiencies in halocarbon-loaded acetylene-air flames—I. Monochlorides of readily volatilized elements

Carbon tetrachloride vapour was introduced with a carrier air stream into the mixing chamber of an acetylene-air flame while nebulizing aqueous solutions of several metal salts. The atomic absorption signal was measured under increasing flow rate of the halocarbon vapour at constant fuel-to-oxidant ratio, and the latter parameter was also varied in separate experiments. By applying the theory developed by Sugden and Bulewicz, the exclusive formation of monochlorides in the gaseous phase (presented here, in Part I) and the additional formation of hydroxychlorides and dichlorides (presented in Part II) could be elucidated. From the decrease of the signal measured for the alkali elements of known monochloride dissociation constants and dissociation energies, the temperature and the chlorine concentration present in the observed flame zone could be calculated. It is inferred that only 19% of the total halogen introduced is converted to HCl and Cl species in a slightly fuel-rich flame. The signal depression is stronger in a fuel-lean flame of higher monoatomic chlorine concentration for those elements which have a relatively efficient atomization under these flame conditions. An increase of the electron concentration resulting from the introduction of the halocarbon in an alkali-containing flame was deduced from the experimental findings, in agreement with earlier observations.     

Comparison of atomic fluorescence power efficiencies for the helium-oxygen-acetylene and air-acetylene flames

Power efficiencies for five elements have been measured for the helium-oxygen-acetylene and air-acetylene flames. The increased power efficiencies found in this study for the helium-diluted flame, coupled with its enhanced atom-formation capabilities, suggest that lower atomic fluorescence detection limits should exist. However, in a comparison study with an air-acetylene flame using identical experimental conditions, a decreased atomic fluorescence signal-to-noise ratio was found for most elements in the helium-diluted flame. This decrease is ascribed to greater background emission noise in the hotter helium-diluted flame and decreased nebulization efficiency caused by the low density of the helium-containing nebulizer gas. A comparison of flame emission detection limits for the two flames confirms the increased sensitivity of the hotter helium-oxygen-acetylene flame, despite its lower nebulization efficiency.     

Distribution pattern of REE and other elements in the host rocks of the Gubrunde uranium occurrence,NE Nigeria

Prospecting for high grade uranium deposits in NE Nigeria has over the years among other reasons been handicapped by lack of adequate understanding of the elemental primary dispersion pattern associated with known occurrences in this region. Thirty six samples from a low grade uranium occurrence at Gubrunde consisting of disseminated ores and hostrocks were therefore analyzed for 38 elements by NAA, DNAA, EDXRF and flame AAS techniques. The analytical data were evaluated using multivariate statistical techniques. The results show three element groupings (associations). The first group consists of Pb, Ba, Ce, Sm (LREE), that are enriched with increasing uranium concentration in the mineralized zone and are therefore capable of serving as pathfinder elements for uranium. The second group comprising of MgO, K₂O, CaO, Na₂O and the HREE are depleted in the mineralized zone due to action of hydrothermal fluids and are indicative of altered/mineralized rocks. The third group consists of the rest bulk of elements which feature little or no significant enrichment with increasing uranium but associate with ferruginization (haematite) and possibly refractory minerals.     

Atom-trapping atomic absorption spectrometry of arsenic,cadmium, lead,selenium and zinc in air—acetylene and air—propane flames

Atom trapping atomic absorption spectrometry has been applied to the determination of Cd, Pb, Se and Zn in an air—acetylene flame and arsenic in an air—propane flame to yield sensitivities that are, respectively, 18, 48, 3, 80 and 60-fold better than those of the conventional technique. Slitting down the zone of observation above the atom-trap to measure in the region of highest atom density further increases the sensitivity for Cd, Cu, Pb, Se and Zn by factors of 4.5, 2.5, 2.5, 5.5 and 1.5-fold, respectively. The sensitivity for cadmium may be increased 2-fold by precoating the silica collector tube with 1000 ppm vanadium or 3-fold with 1000 ppm copper.     

spectroscopy in separated flames-VI The argon or nitrogen-sheathed nitrous oxide-acetylene flame in atomic-absorption spectroscopy

The separation of the premixed nitrous oxide-acetylene flame at a 50-mm slot burner by sheathing with argon or nitrogen is described. In comparison with the conventional flame, the interconal zone of the hot, slightly fuel-rich separated flames provides better conditions for the maintenance of free atoms of elements which form refractory oxides. Optimum conditions for the determination by atomic-absorption spectroscopy of the elements Al, Be, Ge, Mo, Si, Ti, V and Zr in both separated and conventional flames at the same burner have been established. Significant improvement in detection limits and sensitivities is obtained in the separated flames.     

Studies towards understanding the mechanism of organic reagent enhancement in flame and plasma atomic absorption spectrometry

A series of organic reagents have been tested in atomic absorption measurement for signal enhancement of metal elements. Organic reagents like tetrabutylammonium bromide are demonstrated to enhance the absorption sensitivity to some specific elements such as calcium and chromium. A group of amines were found to have significant enhancement for chromium and calcium measurements. The function of organic reagents in flame and plasma atomic absorption spectrometry (AAS) was investigated in this work with emphases on mechanism of signal enhancement and interference suppression. An alternative mechanism of organic reagent enhancement in flame and plasma AAS has been suggested based on the experimental results obtained in this work. The reduction environments in flame and plasma produced by the organic reagents are considered as major reason for the signal enhancement.     

Emission spectra of nitrous oxide supported acetylene flames at atmospheric pressure

The emission spectra of a premixed flame of acetylene supported by nitrous oxide have been recorded under different fuel-gas mixture conditions. The emission spectra in these flames of a series of metals, for which it is difficult to obtain a significant population of ground state atoms for atomic absorption spectroscopy in more conventional flames, have also been studied. The red secondary zone which is present in the fuel-rich flames shows emission attributable to long-lived CN and NH species which form a strongly reducing atmosphere to inhibit refractory oxide formation from elements such as molybdenum, titanium and aluminium introduced into the flame. An attempt has also been made to explain some of the reactions which may occur between the flame species above the primary reaction zone.     

缝管原子捕集法中的原子化机理

本文用Ｘ射线衍射分析法研究了１１个元素在开缝石英管中原子捕集与释放机理。Ａｇ和Ｂｉ以金属形式被捕集，而Ｃｄ、Ｃｕ、Ｉｎ、Ｎｉ、Ｓｂ、Ｚｎ、Ｐｂ、Ｃｏ、Ｇａ则以氧化物或硅酸盐形式捕集。这些元素在放时直接从熔融物蒸发原子化。５％乙醇或丙酮能提高大多数元素的灵敏度。大多数元素在Ａｌ２３涂层管上的灵敏度较高，在Ｌａ２Ｏ３涂层管上的检出限较低，精密度较高。     

Periodic trends in sensitivity and its dependence on the properties of pyrolytic and non-pyrolytic graphite in graphite-furnace atomic-absorption spectrometry

The sensitivities for metal determination by GFAAS in the peak-height and integration modes were examined with pyrolytic graphite (PG) and non-pyrolytic graphite (NPG) tubes for 34 elements. It was found that there are periodic trends of the mole sensitivity and the elements can be classified according to whether their sensitivity of determination is enhanced by use of (a) the PG tube (alkali, alkaline-earth and transition metals); (b) the NPG tube (semi-metals); about equally by both tubes (Mg, Zn, Cd, and Pb). The mole sensitivity pM for atomic-absorption spectrometry (AAS) was defined as pM = -log(m(h)/A(w)) where m(h) is the weight of an element corresponding to 1% absorption and A(w) is the atomic weight. It was found that the pM values for graphite furnace AAS have a periodic trend similar to that for flame AAS and atomic-fluorescence spectrometry.     

Quantitative evaluation of atomic absorption error functions

The variation in standard deviation with transmittance for a large number of elements has been expressed in terms of four component error functions, each one characteristic of one (or more) possible sources of noise associated with the measurement of transmittance (or absorbance). The magnitude of the contribution of each of the component functions has been measured quantitatively, and it is shown that the major component in nearly every case is that related to noise associated with the dynamic nature of the flame. For many elements, the smallest relative error occurs at an absorbance between 0·35 and 0·61 units; the range from 0·2 to 0·7 absorbance units (50 × to 200 × the observed analytical sensitivity) is suggested as the most precise working range for a wide variety of elements.     

固定床天然气与煤共气化火焰区温度影响因素的研究

用实验室固定床反应器模拟合成气制备炉，考察了该工艺中不同因素对火焰区温度的影响。实验中首先确定了使火焰区温度最低时的甲烷和氧气相对入口位置，然后在此条件下分别考察了进料中H2O/O2和CH4/O2摩尔比变化对火焰区温度的影响。结果表明，甲烷和氧气相对入口位置平齐时火焰区温度最低，火焰区温度均随进料中CH4/O2和H2O/O2摩尔比的增大而降低。     

Derivative flame atomic absorption spectrometry and its application in trace analysis

Flame atomic absorption spectrometry (FAAS) is an accepted and widely used method for the determination of trace elements in a great variety of samples. But its sensitivity doesn’t meet the demands of trace and ultra-trace analysis for some samples. The derivative signal processing technique, with a very high capability for enhancing sensitivity, was developed for FAAS. The signal models of conventional FAAS are described. The equations of derivative signals are established for FAAS, flow injection atomic absorption spectrometry (FI-FAAS) and atom trapping flame atomic absorption spectrometry (AT-FAAS). The principle and performance of the derivative atomic absorption spectrometry are evaluated. The derivative technique based on determination of variation rate of signal intensity with time (dI/dt) is different from the derivative spectrophotometry (DS) based on determination of variation rate of signal intensity with wavelength (dI/dλ). Derivative flame atomic absorption spectrometry (DFAAS) has higher sensitivity, lower detection limits and better accuracy. It has been applied to the direct determination of trace elements without preconcentration. If the derivative technique was combined with several preconcentration techniques, the sensitivity would be enhanced further for ultra-trace analysis with good linearity. The applications of DFAAS are reviewed for trace element analysis in biological, pharmaceutical, environmental and food samples.     

Control parameters of flame spreading in a fuel container

The processes involved in flame spreading over liquid fuels are subject of this work. A heat and momentum transfer analysis has been undertaken for fuel temperatures below the flash-point that confirms (within this range of temperatures studied in this work) that flame spreading is assisted by a convection pattern ahead of the flame. This assistance mechanism, which is not observed for solid fuels, is the origin (for lower temperatures) of a pulsating behaviour of the flame. A first experimental determination of the characteristic horizontal length of this assistance zone will be given. The analysis of our data lead us to conclude that flame spreading can be reduced by simultaneously preventing the formation of the convection zone and reducing the fuel surface temperature.     

古人类骨骼中微量元素的分析及其与古代食谱的关联

采用等离子体质谱(ICP-Ms)法对三峡地区及长江下游地区出土的古墓中的人体骨骼中的微量元素Zn、Sr、Ba、Ca进行了分析，并与原子吸收光谱(AAS)对照，结果表明：ICP-MS是骨化学微量元素分析很好的方法，它相对FAAS，具有灵敏度高，检出限低，可快速进行多元素检测等优点，对溶液中元素的检出限可达到ng/L数量级，对元素的高含量和低含量都能进行准确测量。本实验以Zn、Sr、Ba、Ca为指示剂，根据其测量结果，还对上述两地区的古人类食谱进行了初步探讨。