对提高放射性同位素测量精度的研究

为评价放射性同位素测量的精度 ,对美国BeckmanLS 65 0 0ScintillationSystem的单标DPM(SLDPM)和AUTODPM两种猝灭校正方法进行了比较。结果显示 ,SLDPM的猝灭校正范围宽(校正范围由校正曲线决定 ) ,猝灭校正精度高 ,并且可以用于测试双标或三标的样品。使用AU TODPM猝灭校正方法进行测试 ,对于低能β射线3H ,在 90 相似文献   

电感耦合等离子体原子发射光谱法测定铜合金中锆量的不确定度评定

讨论了采用电感耦合等离子体发射光谱法测定铜合金中锆量分析结果不确定度产生的原因。建立了数学模型,对测量重复性,标准溶液,标准曲线变动,试液体积,试样称量,数字修约等引起的不确定分量进行评定,计算了合成标准不确定度和扩展不确定度,并给出铜合金中锆量测定结果的报告。评定结果表明:测量重复性,标准曲线线性回归引起的不确定度对总不确定度影响最大。所以在测定中应进行多次平行测定,特别注意标准曲线的校正和绘制校准曲线所用标准样品的选择。     

2011年约稿： 电感耦合等离子体原子发射光谱法测定铜合金中锆量的不确定度评定

讨论了采用电感耦合等离子体发射光谱法测定铜合金中锆量分析结果不确定度产生的原因。建立了数学模型,对测量重复性,标准溶液,标准曲线变动性,试液体积,试样称量,数字修约等引起的不确定分量进行评定,计算了合成标准不确定度和扩展不确定度,并给出铜合金中锆量测定结果的报告。评定结果表明：测量重复性,标准曲线线性回归引起的不确定度对总不确定度影响最大。所以,在测定中应进行多次平行测定,特别注意标准曲线的校正和绘制校准曲线所用标准样品的选择。     

磁学测量系统的功能扩充

以磁学测量系统(magnetic property measurement system, SQUID)为主体,LabVIEW图形化编程语言为软件开发平台,利用magnetic property measurement system(MPMS)的扩展接口,由GPIB卡连接Keithley 2400源表、2182A纳伏表等测量仪表,构建实时输入测量参数、采集环境数据、直观显示测量结果的电学性能测试系统. 系统能准确控制温度、磁场,调节范围广,在温度1.9~400 K、磁场0~7 T的环境下,实现I-V曲线、电阻随温度(R-T)曲线、电阻随磁场(R-H)曲线等的电学性能测量,拓展MPMS磁学测量系统功能和应用研究领域.     

基于激光诱导击穿光谱对钛元素自吸收效应的分析

为了减小谱线自吸收效应对样品物质中元素定量分析带来的干扰,提高激光诱导击穿光谱技术(LIBS)对钢铁中微量元素的检测准确度和精度,以攀钢生铁标准样品作为研究对象,选取Fe(Ⅰ)438.4 nm、Fe(Ⅰ)347.6 nm作为内标线,以原子线Ti(Ⅰ)506.5 nm、离子线Ti(Ⅱ)334.9 nm作为分析线,对Ti元素谱线的自吸收效应进行校正,分别建立内定标曲线,并建立了相应的量化模型。先通过指数函数拟合定标曲线来表征自吸收效应,然后对自吸收效应进行校正。自吸收校正后,Ti两组定标曲线的决定系数R²分别从0.882增加到0.994、0.881增加到0.917,分别提高了12.7%和4.0%。定量分析时,2^#和5^#样品用于验证,结果显示两验证样品中Ti预测浓度的相对误差都降低到了10%以内,预测浓度的相对误差分别减少了72.01%、97.10%,测量精度得到明显提高,并且自吸收校正后的预测浓度近似于等于标准浓度。实验表明,通过指数函数拟合定标曲线的方式来量化自吸收效应,并对其进行校正的方法可以提升对Ti的分析精度,方法为...     

光子计数法及其在分子束反应化学发光光谱测试中的应用

本论文从微弱信号检测技术的角度,对光子计数技术在分子束反应化学发光光谱测试中的应用进行了研究。 根据最灵敏的弱光检测元件--光电倍增管在弱光测量时的输出信号特征,利用甄别器消除光电倍增管打拿极热电子发射等产生的暗计数,并以记录光电子数的数字方法进行测量,使测量信噪比,稳定性、灵敏度得到极大提高, 从而, 使光子计数技术可以达到弱光检测的量子极限。     

金相组织变化对X射线荧光光谱法测定黄铜中铜铅铁的影响及校正

研究了金相组织变化对X射线荧光光谱法测定黄铜中Cu、Pb、Fe的影响。Pb相和Fe相的出现使得Cu的测定结果偏高,Pb和Fe的校准曲线不成一条直线。金相组织的变化导致试样测量表面的元素分布不均匀,从而影响了元素间吸收和增强效应的实际效果,理论α影响系数不再适合校正基体效应。提出了4种数学方法来校正金相组织变化的影响：(1)理论α影响系数和经验影响系数相结合的方法;(2)根据析出相的比例校正校准曲线的斜率;(3)引入二次项校正;(4)根据Pb相的析出情况,以Pb含量0．6％为分隔点,对校准曲线分段。     

钐同位素丰度的绝对测量

建立了钐同位素丰度高精度的质谱测量法。对样品形态选择、离子转换效率、离子传输效率和离子接收效率进行研究,消除了浓缩同位素测量时强峰拖尾对弱峰的干扰及同量异位素干扰。用已知化学纯度的^152Sm、^154Sm两种浓缩同位素,通过化学计量配制人工合成校正样品,测量质谱计的系统误差校正系数,对用该仪器测量的来自不同地域矿物和试剂样品中钐元素天然同位素的丰度比数据进行校正,准确求得钐同位素的丰度。     

连续流动电位溶出分析测定血清中镉,铅

1 引言 本文设计了微机控制的连续流动电位溶出分析系统,并应用此系统测定了血清中镉、铅元素的含量。测定时样品的电积和溶出在两种不同的介质溶液中完成,以消除样品中对溶出有影响的因素,改善溶出的信噪比。测定结果表明测试系统具有样品预处理简单及用量少,测试速度快,自动化程度高等特点,尤其适用于大批量样品的分析。     

原子荧光光谱法测定区域地球化学调查样品中硒的干扰校正

氢化物发生-原子荧光光谱法(HG-AFS)是测定土壤样品中硒(Se)的理想方法，常用SePb合金材质的空心阴极灯为激发光源，无色散系统的AFS测硒时存在铅的光谱干扰，但尚未引起广泛关注。本文研究了高浓度Pb对硒测定的影响，并提出一种干扰校正的方法，可对检测结果进行有效校正。同时对还原剂浓度和消解酸的比例进行了优化，在2~40 ng/mL范围内获得Se标准曲线r2=0.9989，检出限为0.0023 ug/g，方法精密度为2.9-9.8%，准确度ΔlogC小于0.035。对南疆铁门关区域地球化学调查样品进行了测定，校正后Se的检测结果合格率为94.0%。此方法具有操作简单、准确高效，能够有效的校正样品中高浓度Pb的干扰，适合于大批量区域地球化学调查样品的检测。     

A technique for estimating contamination tolerance limits for stable isotope ratio determinations

A model of the interaction between the precision of an isotope ion signal measurement and the accuracy of an isotope ratio determination was developed and used to derive the equations required to calculate the maximum tolerable amount of contamination for stable isotope ratio determinations. Comparison of the calculated tolerance limits and the blank estimated amount of contaminant will establish whether or not a correction for the contribution of the contaminant to the gross signals will be required. The 1000:1 sample-to-contaminant concentration tolerance limit used in stable isotope ratio plasma mass spectrometry will, in some situations, underestimate the contamination error compared to the model calculations.Derivation of the limit equations required an empirically determined relation between the signal strength and the signal's relative standard deviation (signal noise function). A single hyperbolic signal noise function was used to describe the behaviour of isotope ion signals of Ni, Cu, Tl and Pb measured using a plasma source double focusing magnetic sector mass spectrometer. The derivation could be extended to accommodate different signal noise functions.     

Trace 1300气相色谱仪故障排查与期间核查

使用赛默飞Trace 1300气相色谱仪进行环境样品分析过程中,出现了FID信号变弱、点火困难的现象,严重影响检测数据的准确性,干扰正常分析工作。从样品性质、仪器方法的设置、气路系统以及检测系统进行故障排查,确定故障原因为FID喷嘴堵塞,点火线圈锈蚀严重。对维修好后的气相色谱仪进行期间核查,核查结果:基线噪声为0.066 pA,基线漂移(30 min)为0.321 pA,FID检测限为0.094 1 ng/s,定性重复性为0.062%,定量重复性为1.41%,均满足技术指标要求。     

Atomic-fluorescence spectroscopy of magnesium with a high-intensity hollow-cathode lamp as line source

Atomic fluorescence of magnesium is possible in air-propane or air-acetylene flames at 285.21 nm, using a high-intensity hollow-cathode magnesium lamp for excitation. The technique permits determinations of magnesium in the range 0.01–5 p.p.m., i.e. with more than 10 times the sensitivity of the atomic absorption method even for this most sensitive element. The detection limit in either flame is 1 ng/ml (signal: noise ratio 1 : 0.75). In a nitrous oxide-acetylene flame, atomic fluorescence may be carried out with linear signal/concentration dependence up to 100 p.p.m. without interference even from metals such as aluminium, titanium, etc. at a 1000-fold excess ratio to magnesium. A brief comparison is made with atomic absorption using the same source and equipment.     

Noise normalisation in capillary electrophoresis using a diode array detector

When using capillary electrophoresis with a diode array detector, the wavelength at maximum absorbance is often chosen to quantify a given analyte. However, the background noise for every wavelength should be taken into account as it is by maximising the signal to noise ratio that the lowest limit of detection will be obtained. Here, we proposed an algorithm allowing to correct an electropherogram from its background absorption and to estimate the background noise. Applying it to all the electropherograms obtained in each wavelength channel allows obtaining the background noise as a function of the wavelength, which can be used to calculate the signal to noise ratio. This not only allows selecting the best wavelength to maximise the limit of detection of a given analyte, but also to generate a noise normalised base peak electropherogram (nn-BPE). It is shown that the noise normalised base peak electropherograms substantially improve the peaks visualisation. The algorithm is part of a graphic user interface that runs under MatLab environment; it does not require any programming knowledge and is freely available.     

Evaluation and correction of isotope ratio inaccuracy on inductively coupled plasma time-of-flight mass spectrometry

Isotope ratio measurements are found to have systematic bias when using the analog detection mode on an inductively coupled plasma time-of-flight (TOF) mass spectrometer. This bias is dependent upon the value of the ratio, the intensity of the signal, and the gain of the electron multiplier tube. The error should not appear if ion counting is employed instead of analog detection, although analog detection with time-of-flight has other distinct advantages. The cause of this isotope ratio inaccuracy is rooted in disproportionate recording of the analog signal because of the need to filter out noise by blocking analog signals below a threshold voltage. This attenuates smaller signals to a greater degree than larger signals. This variable “detection efficiency” causes a larger systematic error in the isotopic ratio as the isotopic abundances become more disparate. Ratios close to unity are generally accurate within the precision of the measurement. The use of an increased gain on the detector leads to improved ratio accuracy, but at the cost of decreased detector lifetime. This research presents a method of analyzing solutions using natural, known isotopic ratios to produce an efficiency correction curve. The average error of several isotope ratios for a 500 ng/mL solution of various elements with ratios between 3.4 and 10 was found to be 6.5% without correction, 3.0% with increased detector gain, 1.1% with efficiency correction and 0.6% with both increased gain and efficiency correction.     

液相色谱–原子荧光联用仪的校准

介绍液相色谱–原子荧光联用仪的校准方法。液相色谱–原子荧光联用仪的校准主要包括仪器的基线噪声漂移、测量线性、测量重复性和检出限等项目。通过分析实验数据,当仪器基线噪声不大于5 m V,基线漂移不大于50 m V/(30 min),保留时间重复性不大于3%,峰面积重复性不大于5%,仪器测量线性r大于0.995,检出限不高于4 ng/m L时,仪器的计量性能指标正常。据此对影响仪器性能的各个参数进行全面评价,确认各项性能指标控制在合理范围内,以保证液相色谱–原子荧光联用仪性能正常,并对影响仪器性能的各个参数进行准确校准。     

Comparative study on the analytical performance of three waveforms for the determination of several aminoglycoside antibiotics with high performance liquid chromatography using amperometric detection

A preliminary comparative study was carried out on the analytical performances of a new six-potential waveform and other two detection waveforms, triple-potential waveform and quadruple-potential waveform. The analytical performances compared included signal response, background noise, signal/noise ratio and signal stability. Compared with triple-potential waveform and quadruple-potential waveform, the new six-potential waveform had higher signal response, signal/noise ratio, and sensitivity. As for determination reproducibility, the six-potential waveform also exhibited a slightly better performance than the other two waveforms. Under the selected experimental conditions based on the six-potential waveform, there is a linear correlation between peak area and concentration over two to three orders of magnitude for nine aminoglycoside antibiotics with a correlation coefficients better than 0.998 and the detection limits measured as three times the peak height signal-to-noise ratio for the nine aminoglycoside antibiotics were in the range of 0.0198-0.889 microg/mL. The proposed method had been used to analyze real gentamicin sulphate drug sample.     

Use of a spectrally segmented photodiode-array spectrometer for inductively coupled plasma atomic-emission spectroscopy Examination of procedures for the evaluation of detection limits

The utility of a spectrally segmented photodiode array spectrometer was examined by using inductively coupled plasma atomic-emission spectrometry (ICP-AES). The spectrometer used in this study is capable of high resolution (reciprocal linear dispersion of approximately 0.08 nm/mm at 300 nm) over a wide spectral range (190-415 nm). The effect of using spectral peak areas instead of peak heights as a signal definition was examined by using the emission signals from 10 molybdenum lines obtained with various photodiode-array integration periods. In addition, a procedure to determine the detection limits obtainable with such a spectrometer is proposed. It was found that a signal definition involving a summation over a range of 5 pixels offered the best signal-to-noise ratio when the noise was defined as the standard deviation of the residual values from the line fitted to the sideband background level. A detection limit of 6 ng/ml was determined in this way for molybdenum. The multichannel capability of the spectrometer was found to permit continuous background correction, thereby reducing errors caused by low-frequency noise or plasma drift. The linearity of response was found to extend over three orders of magnitude with use of a single integration period. However, by use of different integration periods, the linear range of the detector could be extended to at least four orders of magnitude. The precision (RSD) of the spectrometer for a molybdenum concentration of 0.5 mug/ml was found to be about 3-4% for molybdenum peaks where the background emission was relatively low.     

The Evaluation Method of Smoothing Algorithms in Voltammetry

The criterion for testing the influence of smoothing algorithms for the relevant parameters considered in analytical experiment is presented. The proposed approach assumes that the improvement of the whole set of measured curves should be considered. The calibration curve parameters with confidence intervals, correlation coefficient, detection limit, signal to noise ratio and parameters of recovery function are utilized for the evaluation. Performance of evaluation method is presented for several kinds of experimental noises.     

A Calibration‐Base Method for the Evaluation of the Detection Limit of an Electrochemical Biosensor

The method based on the confidence limits of a regression straight line is applied to the linear portion of the calibration curve of a biosensor in order to determine the limit of detection. A practical application gives a detection limit of an ethanol biosensor greater than that calculated by using the method of the signal‐to‐noise‐ratio, S/N=3, but the value is more reliable because it accounts for the variability in the response at analyte additions. A simple approximation of the method is also presented.