Comparison of Detection Limits in Atomic Fluorescence and Absorption Spectroscopy

Dagnall, Taylor, and West have recently compared detection limits for a number of metals in atomic fluorescence and absorption spectroscopy and have concluded that “atomic fluorescence measurements using an electrodeless discharge tube are inherently more sensitive than those obtainable by atomic absorption measurements”. Likewise West and Williams have compared the two techniques for magnesium²and silver³, using high-intensity hollow-cathode lamps as sources, and have found much lower detection limits in fluorescence than in absorption.     

间接原子吸收光谱法测定氢溴酸山莨菪碱

研究了原子吸收光谱法间接测定氢溴酸山莨菪碱。在溶液pH为 5 1～ 5 3,当四苯硼钠过量时可完全沉淀氢溴酸山莨菪碱 ;加入过量的氯化钾沉淀滤液中剩余的四苯硼钠 ;干过滤 ,用原子吸收分光光度计在76 6 5nm波长下测定滤液中过量的钾 ,因四苯硼钠与氢溴酸山莨菪碱和氯化钾均按 1∶1的计量关系生成沉淀 ,可以直接计算得到氢溴酸山莨菪碱的含量。对氢溴酸山莨菪碱注射液进行了测定 ,测定结果准确。方法简单快速 ,回收率在 96 %～ 10 3%之间 ,相对标准偏差为 1 4 %。该方法可进一步推广原子吸收光谱法在其他相关药物测定方面的应用。     

激光烧蚀-双光束二极管激光原子吸收光谱法测定固体样品中的铀同位素比

以两个二极管激光作为光源 ,采用激光烧蚀 双光束二极管激光原子吸收光谱法测定了2 3 5U/ 2 3 8U同位素比。实验对用于样品烧蚀的Nd :YAG激光聚焦点位置进行了优化 ,在同时满足一定原子化程度和较高2 3 5U 6 82 6 736nm信背比的原则下 ,选择了聚焦点位置低于样品表面 0 4cm作为分析条件。测量2 3 5U/ 2 3 8U同位素比的精密度和准确度分别为 5 %和 2 % ,2 3 5U检测限为 18μg·g-1。结果表明 ,双光束检测法能消除激光烧蚀脉冲间信号波动对测量重现性的影响 ,比早先报道的单光束检测法在精密度和准确度上有了很大的改善     

Comparison of Flameless Atomic Absorption Spectroscopy with Neutron Activation Analysis for Vanadium in Beach Asphalt

One of the major arguments against using trace metal characterization as a tool to identify oil spills is lack of reliability of the data. With this in mind, the precision of flameless atomic absorption spectroscopy and of neutron activation analysis was determined for vanadium in crude oil residues. Thirty crude oil residues (beach asphalts) were analyzed by both methods, and the results compared. For neutron activation analysis, the population mean was 195 ppm, and the standard deviation of the method was 5.38 ppm. For flameless atomic absorption spectroscopy, the population mean was 202 ppm, and the standard deviation 19.5 ppm.     

Preatomization Losses in Flameless Atomic Absorption Spectroscopy

A preatomizing (charring) step is customarily used in flameless atomic absorption spectroscopy. Experiments were carried out to investigate the effect of the charring temperature on the final response and to determine at what temperature significant losses were occurring. Four elements of environmental significance (Pb, Cd, Be, V) were investigated in three matrices obtained from air pollution studies.

It was found that Pb and Cd were lost in charring above 500°C and 330°C, respectively, and that the loss rate differed for the different matrices. The maximum charring temperatures for Be and V were 900°C and 1280°C, respectively. Preatomization losses were also examined for Co, Ni, Fe and Cu in aqueous solution. Several effects which could be explained by a change in atomization rate were noted at low charring temperatures.     

一种时间相关吸收光谱技术分析新方法

时间相关吸收光谱技术,如腔衰荡光谱技术(CRDS)和腔衰减相移光谱技术(CAPS),是近三十几年发展起来的一类新型吸收光谱检测技术,它具有探测灵敏度高、响应速度快、不受光源强度起伏变化影响等优点。传统的吸收光谱技术都是基于Lambert-Beer定律,如直接吸收光谱技术(DAS)、波长调制光谱技术(WMS)和腔增强吸收光谱技术(CEAS)等,这类光谱技术在探测物质微弱吸收的时候一旦遇到较强的背景光信号就变得难以测量,而且光源的不稳定性也会对检测带来一定的限制。时间相关吸收光谱技术由于其不受光源强度起伏变化的特点,在很大程度上能够弥补传统吸收光谱技术所存在的缺陷,但其也有自身的局限性。首先在理论上,CRDS和CAPS这两种时间相关吸收光谱技术并不统一,而且在现有光谱理论下,Pulse-CRDS在应用时使用的脉冲光源的脉宽必须远小于谐振腔本身的时间常数,对于长脉宽的脉冲光或者反射率低(小于99.9%)的腔体,现有理论将不再适用;CAPS在应用时光源调制信号必须是周期性的正弦信号或者方波信号,对于其他类型的周期调制信号或者非周期性信号,现有理论并没有涉及。针对上述提到的时间相关吸收光谱技术的局限性,提出了一种新的分析时间相关吸收光谱技术的方法,即利用一阶传递函数,将谐振腔视为一阶传感系统,对时间相关吸收光谱技术理论进行统一解释,在公式推导上证明新方法下的推导结果和现有理论结果的一致性。针对Pulse-CRDS,以高斯脉冲光为例,给出一阶传感理论下的透射光强表达式,并对一系列不同的脉冲宽度γ、谐振腔时间常数τ_real以及从输出信号中拟合而得的时间常数τ_anal进行了模拟仿真。经过分析比较后发现,当γ<0.3τ_real时,τ_anal和τ_real的偏差小于1%;当γ>0.3τ_real时,τ_anal和τ_real的偏差渐渐变大,将不再满足实验条件。为了使Pulse-CRDS在长脉宽脉冲光下也能应用,本文给出了修正函数,使得在脉宽大于腔衰荡时间0.3倍的情况下,经过修正补偿后,衰荡时间的误差小于1%。对于CAPS系统,搭建相应实验平台,LED中心波长选用405 nm,使用方波调制信号,测量不同频率下的入射参考信号与探测信号的相位差和探测信号峰-峰值,通过由一阶传递函数推导而得的相频特性和幅频特性,拟合得到时间常数τ,结果分别为7.24和7.25 μs,残差范围分别为[-0.01, 0.02]和[-0.02, 0.025],两者结果基本一致。实验结果验证了一阶传感系统理论完全适用于时间相关光谱的信号分析,并且一阶传感系统理论还使得时间相关光谱技术的理论得到了统一。     

Evaluation of Carbon Rod Atomizer for Routine Analysis of Vanadium in Crude Oil by Atomic Absorption Spectroscopy

Abstract

The Carbon Rod Atomizer (CRA) was evaluated for routine trace analysis of vanadium in crude oil by atomic absorption spectroscopy with a carbon (graphite) tube as a micro-furnace. Two crude oil samples were analyzed, both by standard addition and standard working curve methods, and the results confirmed by analysis with flame atomic absorption spectroscopy using a fuel-rich nitrous oxide-acetylene flame. Because of the relative involatility of vanadium at the temperature of the CRA, quantitative recoveries of vanadium in crude oil occur only when the vanadium content of the sample injected into the CRA does not exceed the limit of about 1 × 10^?8 g. A sensitivity (weight/1% absorption) of 7.0 × 10^?11 g and detection limit (signal-to-root-mean-square-noise equal to two) of 6.9 × 10^?12 are reported.     

激光长程吸收光谱法测量高分辨率大气吸收光谱

用脉冲可调谐光参量振荡器作光源 ,使用光程长达 1km的 8m长吸收池 ,采用分时复用的单探测器探测方法 ,组成测量系统 ,测量了一系列高分辨率的模拟和实际大气的吸收光谱。系统的灵敏度为 0 .5× 10 - 6cm- 1 ,分辨率为 0 .0 2cm- 1 。 1.315 μm附近实际大气的吸收光谱与HITRAN96模拟结果比较 ,强线符合得很好。水汽光谱的大多数强线的分子线强度相对误差在 10 %以下。     

铀元素的激光诱导击穿光谱测量分析

为促进LIBS技术在微量重金属元素检测以及核污染检测领域的应用,提高检测灵敏度和准确性,采用了激光双脉冲LIBS技术和光电双脉冲LIBS技术,分别对土壤和二氧化硅中的铀元素进行分析。首先,对激光脉冲能量、电压和采集延时等参数进行优化,提高铀元素特征谱线的强度和信噪比;然后在优化实验参数条件下,对含不同浓度铀元素的土壤样品和二氧化硅样品进行激发;选取UII 367.01 nm、 UII 454.36 nm两条铀元素的特征谱线作为分析线,通过铀元素浓度与特征谱线强度的线性关系,建立定标曲线。双脉冲激光激发条件为：激光脉冲1作为预脉冲,主要参数为1 064 nm, 90 mJ, 9.2 ns,激光脉冲2作为再加热脉冲,主要参数为355 nm, 50 mJ, 8 ns,两个脉冲的时间间隔800 ns,光谱采集相对第二个脉冲延时1μs,得到铀元素在土壤和二氧化硅两种样品中的浓度检测下限分别为572和110 mg·kg^-1,拟合优度值R²分别为0.958和0.999。在光电双脉冲激发条件下,激光脉冲作为预脉冲,主要参数为355 nm, 50 mJ, 8 ...     

可调谐二极管激光吸收光谱法测量气体温度

研究了一种新型的非接触式测温技术——可调谐二极管激光吸收光谱(TDLAS)测温技术。介绍了温度测量及调制吸收光谱技术原理,分析了调制幅度对气体温度测量的影响。优选了氧气吸收谱线对13163.78 cm-1和13164.18 cm-1,在搭建的高温实验系统上,实现了气体温度和浓度的同时测量。通过分析实测波形获得了谱线13164.18 cm-1在823~1323 K温度范围内的碰撞展宽系数和温度指数。实验结果表明,在823~1323 K温度范围内,系统温度测量的线性误差为0.65%,最大波动为±15 K。     

Indirect Amplification Determination of Thorium by Atomic Absorption Spectroscopy

Thorium may not be determined by direct atomic absorption spectroscopy in flame media with appreciable sensitivity because of inefficient atomisation. Earlier papers from this laboratory have described indirect amplification procedures for similarly difficult elements e.g. niobium¹ and titanium² by atomic absorption spectroscopy· Madison and Guyon³ have developed a solution spectrophotometric procedure for thorium in which the heteropoly acid complex of thorium with phosphomolybdic acid is formed and reduced to the ‘heteropoly blue’. Strict adherence to time of addition of reagents is required in this procedure, and. it is necessary to effect an initial separation of the thorium from most other cations present in the sample.     

多光程吸收的频率调制光谱

采用可连续调谐的半导体二极管激光器作探测光源,将多光程吸收光谱技术、频率调制光谱技术和相敏检波技术相结合,建立了一套具有高检测灵敏度和分辨率的测量气态分子光谱和进行微量分析的研究装置并利用该装置研究了动态分压强为40Pa和120Pa时,H₂O分子在7462cm^-1和7473cm^-1附近的近红外吸收光谱,检测灵敏度远高于传统吸收光谱技术,为气态分子的光谱研究和微量分析提供了一种高灵敏度的光谱检测方法.     

Continuum Source Atomic Absorption Spectrometry with Commercially Available Instrumentation. A Practical Solution

A calculating method is presented in this paper which may be used to correct for the curvature of the calibration curve in atomic absorption spectrometry due to the non-absorbed light within the monochromator bandpass when a continuum source of radiation is used. Thus a linear absorbance to concentration relationship is obtained. Cu, Cr and Ca have been determined using this method with a D₂ lamp as continuum source. The results agree with those obtained by the traditional method using hollow cathode lamps. The relative differences are below 6.2%. Earlier investigations concerning the use of continuum sources in atomic absorption spectrometry (aas) have shown that in some cases there are good results^1–4. However, there are two problems which are difficult to overcome in continuum source aas. First, a narrow slit must be used in order to obtain a bandpass of a width equivalent to the absorption line. However, in this case the light intensity transmitted to the monochromator and arriving to the detector is so small that the detection limits will be very poor. Of course the transmitted intensity may be increased if a wider slit is used. But in this case, the non-absorptive part on the two sides of the absorption line will also enter the monochromator and fall on the detector. As a result the sensitivity will be degraded and the calibration curve will bend towards the concentration axis. Problems such as those discussed above prevented the current use of continuum source aas. The whole field has been recently reviewd extensively^4a.

In this paper we consider a calculationg method which can overcome the influence of non-absorbed radiation and can also correct the non-linearity of the calibration curve. In the first part of the paper the calculating method is introduced and in the second part some factors affecting the method are discussed and the comparaison of some results obtained by this method and the traditional method are given.     

采用离轴入射的腔增强吸收光谱研究

为了改善腔增强吸收光谱的探测灵敏度和光谱分辨率,通过将激光光束离轴注入光学谐振腔中,减小了谐振腔内振荡,提高了模式密度,使得谐振腔被近似看作为“怀特池”。采用记录波长在扫描过程中实际变化的方法,对光谱数据进行了非线性校正,省去了参考光路的布置,简化了实验光路。对二氧化碳在1．572μm处的一条弱吸收谱线进行了测量,得到了大小为1．98×10^-7cm^-1的最小探测灵敏度。实验结果表明同等实验条件下,光束离轴入射时比正轴入射时的腔增强吸收光谱具有更高的信噪比和光谱分辨率。     

Atomic Absorption Assessment of Mineral Iron Quantity in Ferritin

ABSTRACT

The goal of this work is to study the possibilities for quantitative determination of the number of iron atoms in the mineral core of ferritin by atomic absorption spectroscopy (AAS). Distinctive AAS measurements show iron content between 1000 and 4500 atoms per molecule ferritin.^[ 1-6 McKnight , J. ; White , N. ; Moore , G. R. Effect of copper(II) on the aerobic oxidative uptake of iron(II) by horse spleen ferritin . J. Chem. Soc. 1997 , 21 , 4043 – 4045 . Kyung , S. K. ; Mun , H. R. ; Lee , J. H. Iron cores of tadpole ferritin: Native, reconstituted and recombinant H-chain ferritins . Inorg. Chim. Acta 2000 , 298 , 107 – 111 . Beard , J. L. ; Burton , J. W. ; Theil , E. C. Purified ferritin and soybean meal can be sources of iron for treating iron deficiency in rats . J. Nutr. 1996 , 126 , 154 – 160 . Chasteen , N. D. ; Theil , E. C. Iron binding by horse spleen apoferritin. A vanadyl(IV) EPR spin probe study . J. Biochem. 1982 , 257 , 7672 – 7677 . Treffry , A. ; Harrison , P. M. Incorporation and release of inorganic phosphate in horse spleen ferritin . Biochem. J. 1978 , 171 , 313 – 320 . Harrison , P. M. Ferritin: An iron-storage molecule . Semin. Hematol. 1977 , 14 , 55 – 70 .  ^] This motivated us to investigate the amount of iron in the horse spleen ferritin with atomic absorption spectroscopy under application of the Bulgarian standard BDS EN 14082/2003 Foodstuffs—Determination of Trace Elements—Determination of Lead, Cadmium, Zinc, Copper, Iron and Chromium by Atomic Absorption Spectrometry (AAS) after Dry Ashing.^{[ 7} BDS EN 14082/2003 Foodstuffs—Determination of Trace Elements—Determination of Lead, Cadmium, Zinc, Copper, Iron and Chromium by Atomic Absorption Spectrometry (AAS) after Dry Ashing. www.bds–bds.org . [Google Scholar] ^]

We have obtained as a result 1792 atoms in one ferritin molecule. This result is in accordance with previous results, published by leading researchers.^{[ 4} Chasteen , N. D. ; Theil , E. C. Iron binding by horse spleen apoferritin. A vanadyl(IV) EPR spin probe study . J. Biochem. 1982 , 257 , 7672 – 7677 . [Google Scholar] ^{, 5} Treffry , A. ; Harrison , P. M. Incorporation and release of inorganic phosphate in horse spleen ferritin . Biochem. J. 1978 , 171 , 313 – 320 . [Google Scholar] ^] The investigation of the iron content with AAS under the use of the Bulgarian standard can be a good opportunity to study many other objects of biological interest.     

太赫兹吸收光谱的频率误差修正研究

在用太赫兹时域光谱(THz-TDS)系统测量样品THz吸收光谱的过程中,电光采样系统的采样误差往往导致测得的THz吸收频率与真实值间存在偏差。针对此问题,利用一氧化碳(CO)分子THz吸收峰的分布特性研究了对THz-TDS系统测量数据进行修正、从而提高THz吸收频率测量精度的方法。首先通过实验测得了2.0×105 Pa 压强下CO气体的一系列等间隔分布的THz吸收峰,然后把测得的吸收峰峰位与JPL标准数据库中CO分子的吸收频率进行对比,得到了实验数据的误差值。通过分析误差值随吸收频率的分布规律,发现二者间呈正线性相关,在此基础上拟合得到了实验数据的误差修正模型。用所建立的模型对实验数据进行修正后,最大误差值为3.36 GHz,较修正前降低了两个数量级,表明根据CO分子的THz吸收峰可有效修正THz-TDS系统的测量误差,从而提高THz吸收光谱的精度。本研究对材料分析识别以及分子光谱标准数据库的建立具有重要意义。     

宽谱调谐二极管激光吸收光谱的数据预处理研究

二极管激光吸收光谱以温度扫描实现快速宽谱调谐,其原始数据不便于传统的处理及运算,适当的预处理是进行后续数据处理的基础。在分析了温度调谐数据特征的基础上,利用Savitzky-Golay滤波器去除了波长序列中温度检测噪声的干扰,选择单调的波长区间对信号幅值进行三次样条插值,以固定的波长点对应采样点,得到一组位置固定的幅值序列用于后期处理。此方法将两列检测数据合并为一列,相同的起始点和固定的波长位置不仅将多周期平均后的信噪比提升为原始数据的6倍,也使多组数据的比较及评价成为可能,一致的波长分辨率保证了线形检测的精确度,减小了吸收峰的频带宽度,有助于后续的处理、运算以及评价。     

Half-Width Integral Method for Gas Concentration Measuring in Tunable Diode Laser Absorption Spectroscopy

ABSTRACT

We analyze the influence of random errors and absorption shape fitting errors on gas concentration measurement in tunable diode laser absorption spectroscopy. We then propose a new data processing method according to the characteristic of random errors and fitting absorption shape. This method only uses the integral value within the half width at half maximum of the fitting absorption shape to determine the gas concentration in actual measurements. Meanwhile, the O₂ transition at 13,150.197 cm^?1 is selected to measure the O₂ concentration using this method. Compared with the traditional method, the method established in this paper can accurately measure O₂ concentration.     

基于可调谐激光二极管吸收光谱的乙炔在线检测系统

基于可调谐半导体激光吸收光谱技术,研制了一种近红外乙炔气体检测系统。通过分析近红外波段乙炔分子的吸收谱线特性,选择了1.534 μm附近乙炔分子的吸收峰作为吸收谱线。该系统主要由分布反馈激光器、激光器驱动器、单光程对射式气室、光电探测模块及数字式锁相放大器构成。为了测试该检测系统的性能,配备了乙炔气体样品并开展了气体检测实验。实验结果显示,该系统的最小检测下限为0.02%;在体积分数为0.02%～1%范围内,二次谐波幅值与乙炔气体浓度呈现出良好的线性关系。通过长达20 h的稳定性实验测试了检测系统稳定性。鉴于近红外波段石英光纤传输损耗很小,可以将气室及光路部分与电路部分分离,从而可以进行远程气体检测,这是基于量子级联激光器、热光源的乙炔检测系统难以实现的。该系统采用了自主研制的分布反馈激光器驱动器和锁相放大器,结构简单,性价比高,便与集成,在工业现场乙炔浓度检测方面有着良好的应用前景。     

非理想化学计量比氧化铀的拉曼和红外光谱

测量了七种非理想化学计量比的UO₂+x(0＜x＜0.66)及UO₂和U₃O₇等理想化学计量比氧化铀的拉曼和红外光谱,并进行了对比分析,其中U₃O₇和U₃O₈之间UO₂+x的分子振动光谱为首次报道。拉曼光谱结果显示,随着UO₂+x中x值的增加,UO₂特征峰中的578和1 150 cm-1峰强度快速减弱,当x=0.19时,这两峰基本消失,可视为准完美萤石晶体结构UO₂的标志。445 cm-1峰强度在减弱的同时变宽并偏移,当x=0.32时,该峰已偏移至459 cm-1处,同时在～630 cm-1出现一弱肩峰,这与四方相U₃O₇的特征峰一致。当x≥0.39时,459 cm-1峰发生分裂,在235和754 cm-1处出现新峰并增强,其特征逐渐与正交相的α-U₃O₈接近。但直至x=0.60时,与α-U₃O₈相比其333,397,483和805 cm-1峰仍不突出。红外光谱结果显示,随着UO₂+x中x值的增加,UO₂位于400～570 cm-1区间的强吸收特征谱带逐渐分裂为～421和～515 cm-1两峰并增强,同时UO₂在～700 cm-1的弱吸收峰逐渐消失,～645 cm-1处的肩峰逐渐显现,出现的这三个峰正是U₃O₇的特征红外吸收峰。当x≥0.39时,在744 cm-1出现一强吸收峰并增强,该峰是α-U₃O₈的最强特征峰。但即使x=0.60时,～645 cm-1峰仍然存在,同时～515 cm-1峰也未明显分裂成485和535 cm-1峰,这表明UO_2.60仍处于四方相和正交相的过渡阶段。上述结果表明,随着x值的增加,UO₂+x的晶体结构发生变化,每次变化均在拉曼和红外光谱中得到体现。通过对比各特征峰相对强度和位置的变化情况,可很好区分和表征不同的氧化铀。