电感耦合等离子体发射光谱法测定大气降水中多种元素

本文研究了长白山自然保护区大气降水（雨水或雪水）中的多元素分析。采用ICP-AES法测定水中的K、Na、Ca、Mg、Mn、Fe、Sr、Ba、Cu、Zn、Ni和V等元素，用干扰系数法对光谱干扰进行修正。为该地区天气环境背景值和大气污染现状提供了富贵资料。

KALMAN FILTERING FOR RESOLUTION OF OVERLAPPING LINES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

A Kalman filter was developed for resolving overlapping lines in inductively coupled plasma atomic emission spectrometry (ICP-AES) and evaluated experimentally with the determination of La in the presence of Ho, and Cu in the presence of Pr. The whiteness of the innovation sequence for an optimal filter was explored to be the criterion for the correction of the wavelength positioning errors which may occur in spectral scans. Under the conditions of the medium-resolution spectrometer and 1.5 pm step size in scans, the filter effectively resolved the Cu/Pr line pair having a small peak separation of 4.8 pm. For the La/Ho line pair with a peak distance of 9.8 pm, an unbiased estimate for La concentration was still obtained even when the signal-to-background ratio was down to 0.048. Favourable detection limits for real samples were achieved. Unstructured backgrounds were modeled theoretically and all spectral scans therefore did not require the correction for solvent.

EVALUATION OF THE RELIABILITY OF KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This paper deals with the evaluation of the reliability of the analytical results obtained by Kalman filtering. Two criteria for evaluation were compared: one is based on the autocorrelation analysis of the innovation sequence, the so-called NAC criterion; the other is the innovations number, which actually is the autocorrelation coefficient of the innovation sequence at the initial wavelength. Both criteria allow compensation for the wavelength positioning errors in spectral scans, but there exists a difference in the way they work. The NAC criterion can provide information about the reliability of an individual result, which is very useful for the indication of unmodelled emissions, while the innovations number should be incorporated with the normalization of the innovations or seek the help of the sequence itself for the same purpose. The major limitation of the NAC criterion is that it does not allow the theoretical modelling of continuous backgrounds, which, however, is convenient in practical analysis and can be taken with the innovations number criterion.

LEAST-SQUARES POLYNOMIAL SMOOTHING FOR INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTRA

The use of least-squres polynomial smoothing in ICP-AES is discussed and a method of points insertion into spectral scanning intervals is proposed in the present paper. Optimal FWHM/SR ratio can be obtained, and distortion of smoothed spectra can be avoided by use of the recommended method.

石油亚砜萃取色谱富集-发射光谱测定氧化钇中镧系杂质

本文提出以石油亚砜萃取色谱法富集-ICP-AES测定高纯氧化钇中痕量镧系杂质。化学分离可将镧系杂质富集40倍,加入0.1～2μg/g镧系杂质,相对标准偏差9％～19%;回收率65％～120％,分离周期5h。

高纯氧化钇中镧、铈、钐、铝、铅和铜的电感耦合等离子体原子发射光谱法测定

本文以纯Y_2O_3中杂质元素的ICP-AES测定为例,研究用数值微分技术解决光谱干扰同题。结果表明,导数光谱法不仅可以有效地消除来自基体的光谱干扰,还能减小谱线干扰对检测能力的影响。当分析物浓度较低时,导数光谱法的加入回收率明显优于离峰分析法,多数情况下也优于在峰法校正光谱干扰时的回收率。

电感耦合等离子体原子发射光谱分析中导数光谱法研究——Ⅰ.光谱干扰校正

本文报道了利用导数光谱法校正ICP-AES中光谱干扰的潜力,讨论了导数光谱法的特点以及它比常用的干扰系数法和离峰分析法具有更大的适用性。

电感耦合等离子体原子发射光谱法中Kalman滤波法解析重叠谱线的研究

考察了Kalman滤波技术校正ICP-AES中谱线重叠干扰的潜力.以新息序列的平均平方和为评价函数优化扫描光谱的峰位,消除扫描过程中可能产生的波长定位误差,从而保证滤波结果的准确性,并使实际检出限显著改善.在中等分辨率光谱仪和扫描步长为1.5pm的条件下,滤波器能有效地分辨峰间距只有4.8pm且峰形基本相同的重叠线对.对峰间距为9.8pm的重叠线对,当线背比低至0.05左右时仍能获得满意结果.连续背景用理论描述,因而样品溶液和纯组分溶液的光谱扫描无需扣除溶剂空白.

EVALUATION OF THE EFFECT OF WAVELENGTH POSITIONING ERRORS ON KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This work evaluates the effect of wavelength positioning errors in spectral scans on analytical results when the Kalman filtering technique is used for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). The results show that a positioning accuracy of 0.1 pm is required in order to obtain accurate and precise estimates for analyte concentrations. The positioning error in sample scans is more crucial than that in model scans. The relative bias in measured analyte concentration originating from a positioning error in a sample scan increases linearly with an increase in the magnitude of the error and the peak distance of the overlapping lines, but is inversely proportional to the signal-to-background ratio. By the use of an optimization procedure for the positions of scans with the innovations number as the criterion, the wavelength positioning error can be reduced and, correspondingly, the accuracy and precision of analytical results improved.

IMPROVEMENT OF SELECTIVITY WITH NUMERICAL DERIVATIVE TECHNIQUES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

One of the most attractive features of derivative spectrometry is its higher resolving power. In the present power, numerical derivative techniques are evaluated from the viewpoint of increase in selectivity, the latter being expressed in terms of the interferent equivalent concentration (IEC). Typical spectral interferences are covered, including flat background, sloped background, simple curved background and various types of line overlap with different overlapping degrees, which were defined as the ratio of the net interfering signal at the analysis wavelength to the peak signal of the interfering line. the IECs in the derivative spectra are decreased by one to two order of magnitudes compared to those in the original spectra, and in the most cases, assume values below the conventional detection limits. The overlapping degree is the dominant factor that determines whether an analysis line can be resolved from an interfering line with the derivative techniques. Generally, the second derivative technique is effective only for line overlap with an overlapping degree of less than 0.8. The effects of other factors such as line shape, data smoothing, step size and the intensity ratio of analyte to interferent on the performance of the derivative techniques are also discussed. All results are illustrated with practical examples.

高纯氧化钪中痕量稀土元素的电感耦合等离子体原子发射光谱分析和稀土元素间的光谱干扰及其校正

本文提出了用 ICP-AES 直接同时测定高纯氧化钪中15个痕量稀士元素的新方法。用PGS-2光栅光谱仪,Plasma Therm ICP-5000D 光源系统,乙醇预去溶进样方式,直接同时测定纯度为99.995%的高纯氧化钪中15个痕量稀土杂质元素,并讨论了稀土元素间的干扰及某些元素的光谱干扰的校正。当样品溶液中稀土总浓度为5mg/ml:时,测定下限为镧、钆、钬和铥0.0002%,镨、钕、铽和镥0.0004%,铕、镝、铒和钇0.0001%、镱0.00004%,铈和钐0.001%。其相对标准偏差为1.7～8.2%。

电感耦合等离子体发射光谱测定稀土铝合金中稀土和非稀土元素

本工作用 ICP-AES 法测定稀土-6063变形铝合金中 La、Ce、Pr、Nd、Sm、Gd、Fe、Mg、Ti、Zn,Cu 和 Mn,本方法不用化学分离,可一次同时测定这些元素,并做了 ICP光源参数、基体量变化、酸度(HCl)变化、稀土总量变化、共存元素 Fe 和 Mg 量的变化对被测元素的影响。本方法速度快、准确度高(除 Cu 稍差)。回收率91.0～110.0%,相对标准偏差±1.4～8.0%。

有机试液的电感耦合等离子体原子发射光谱分析 Ⅰ.实际应用的若干方面

本文从七个方面介绍了ICP-AES在有机试液直接分析中的应用:(1) 油类样品分析;(2) 酒样直接分析;(3) 溶剂萃取分离富集-ICP光谱分析;(4) 基于生成挥发性金属有机化合物的ICP进样方法;(5) 有机试液分析中的其它进样方法;(6) 有机介质中非金属元素的ICP-AES测定;(7) ICP-AES作为色谱法的检测器。

高纯氧化钇的感耦等离子体发射光谱分析及基体效应的研究

以高纯氧化钇中稀土杂质的ICP-AES测定为例,研究了基体对分析元素谱线强度的影响及基体效应与工作条件的关系,指出基体效应除主要来自分析物进样效率的降低外,大量基体进入ICP降低了激发温度并对分析物的电离产生抑制作用,提出用Sc内标法代替通常的基体匹配法来补偿基体效应。进行了折衷条件选择及取样量确定等研究。实样分析表明,内标法和基体匹配法所得结果一致,加入回收率为87—120％,精度也符合分析要求。

感耦等离子体发射光谱法分析稀土元素的研究进展

近年来,感耦等离子体发射光谱法(ICP-AES)用于分析稀土元素的研究很活跃,实际应用日益广泛,有关基础研究也有一定进展。程介克等对此已有概述,认为ICP-AES日益广泛的应用是近期稀土元素分析化学进展的重要特征之一。本文拟从基体效应、光谱干扰及修正、检出限以及实际应用情况等方面,比较详细地评述感耦等离子体发射光谱法分析稀土元素的研究进展及尚待解决的问题。