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。

电感耦合等离子体原子发射光谱法分析稀土元素的研究(Ⅰ)高纯氧化镧中十四种稀土杂质的测定

研究了ICP-AES法测定高纯氧化镧中十四种稀土杂质的方法。利用简单的加热去溶装置成功地测定了99.99％La_2O_3中14种稀土杂质。10mg/ml La_2O_3基体工作曲线下限为(以氧化物百分含量计算)Ce、Pr、Sm_2×10~(-3);Gd、Tb1×10~(-3);Nd,Lu 8×10~(-4),Er,Ho,Dy4×10~(-4); Tm.Eu 2×10~(-4),Yb 8×10~(-5),Y_4×~(-5)。相对标准偏差为2.8—9.7,回收率为85—114％。

Formation of Fe-oxyhydroxides from the East Pacific Rise near latitude 13 degrees N: Evidence from mineralogical and geochemical data

The mineralogical and geochemical characteristics of Fe-oxyhydroxide samples from one dredge station (long. 103 degrees 54.48'W, lat. 12 degrees 42.30'N, water depth 2655 m) on the East Pacific Rise near lat 13 degrees N were analyzed by XRD, ICP-AES, and ICP-MS. Most Fe-oxyhydroxides are amorphous, with a few sphalerite microlites. In comparison with Fe-oxyhydroxides from other fields, the variable ranges in the chemical composition of Fe-oxyhydroxide samples are very narrow; their Fe, Si, and Mn contents were 39.90%, 8.92%, and 1.59%, respectively; they have high Cu (0.88%-1.85%) and Co (65x10(-6)-704x10(-6)) contents, and contain Co+Cu+Zn+Ni > 1.01%. The trace-element (As, Co, Ni, Cu, Zn, Ba, Sr) and major-element (Fe, Ca, Al, Mg) contents of these samples are in the range of hydrothermal sulfide from the East Pacific Rise near 13 degrees N, reflecting that this type of Fe-oxyhydroxide constitutes a secondary oxidation product of hydrothermal sulfide. The Fe-oxyhydroxide samples from one dredge station on the East Pacific Rise near 13 degrees N are lower in Sigma REE (5.44x10(-6)-17.01x10(-6)), with a distinct negative Ce anomaly (0.12-0.28). The Fe-oxyhydroxide samples have similar chondrite-normalized rare-earth-element (REE) patterns to that of seawater, and they are very different from the REE composition characteristics of hydrothermal plume particles and hydrothermal fluids, showing that the REEs of Fe-oxyhydroxide are a major constituent of seawater and that the Fe-oxyhydroxides can become a sink of REE from seawater. The quick settling of hydrothermal plume particles resulted in the lower REE content and higher Mn content of these Fe-oxyhydroxides, which are captured in part of the V and P from seawater by adsorption. The Fe-oxyhydroxides from one dredge station on the East Pacific Rise near 13 degrees N were formed by secondary oxidation in a low temperature, oxygenated environment. In comparison with the elemental (Zn, Cd, Pb, Fe, Co, Cu) average content of hydrothermal sulfide samples from the East Pacific Rise near 13 degrees N, the Zn, Cd, and Pb contents of the Fe-oxyhydroxides are lower, and their Fe, Co, and Cu contents are higher.

中太平洋海区富钴结壳地球化学特征及成因机制

本文利用ICP-AES、EPMA、X-ray衍射等测试技术以及聚类分析和因子分析等多种数理统计方法，系统地对中太平洋海区富钴结壳的元素地球化学特征、矿物组成和微观组构进行了研究，并探讨了其成因机制，获得以下主要认识： 1中太平洋海区富钴结壳类型多样，均为水成成因，其矿物相主要由锰矿物相、铁矿物相和非金属矿物相组成；富钴结壳壳层发育多种原生和次生构造类型。 2磷酸盐化作用不仅强烈改变富钴结壳元素初始含量，而且造成富钴结壳某些元素间的相关性发生改变，这些敏感型元素对可用于指示富钴结壳是否发生磷酸盐化。在不同水深段内，未磷酸盐化型富钴结壳的主要元素随经向、纬向的变化趋势相似，表明其受水体化学障、表面生产力和物质来源等环境参数控制；而随水深的变化则具有区域一致性，表明水体化学具有区域成层性。 3未磷酸盐化富钴结壳稀土元素含量和轻重稀土分馏程度随水深发生规律变化，这种变化不仅与它们在海洋中的含量和行为有关，也与海洋背景颗粒的吸附有关；铈(Ce)在富钴结壳中基本上呈4价，且动力学因素控制了其富集过程，因此Ce异常不能用于指示富钴结壳形成环境的氧化程度。 4基于富钴结壳微层呈锯齿状且同一微层生长速率不同，提出了富钴结壳在各种基底表面生长以及后继发育过程受固液界面双电层控制的发育模式。在富钴结壳整个发育过程中，经历了从贫氧环境向富氧环境的转变，但微环境则呈富氧-低氧过程的交替。 关键词： 富钴结壳；中太平洋；元素地球化学；界面双电层

青藏高原3种秦艽组植物微量元素比较分析

利用全谱直读等离子体发射光谱法（ICP—AES）测定了3种秦艽组植物10种微量元素（Cu，Zn，Fe，Mn，Ni，Co，Sn，V，Al，Ti）的含量，并进行了比较分析。结果表明，所测定元素在3个不同物种内的含量排列顺序基本一致，显示了三者在元素富集方面的相似性。就同一种元素在3个物种内的富集水平而言，以麻花艽根部具有较高含量的元素Cu，Zn，Co，Al和Ti，管花秦艽根部则大量富集了其余5种微量元素，达乌里秦艽对元素的吸收积累能力居中，揭示了不同物种对同一元素富集能力的差异。该研究可为秦艽类植物资源的深入开发利用提供参考。

白刺与枸杞中微量元素含量的对比研究

采用ICP-AES法对生长在同一区域内的白刺与枸杞根茎中的8种微量元素的含量进行了分析测定。结果表明，两种植物根茎中8种元素含量丰富，并且差异明显，为以后的开发利用提供了基础数据。

藏药材麻花艽中铜锌铁锰含量分析

采用ICP-AES法对青海省内采集的麻花艽中的铜、锌、铁、锰的含量进行了测定。结果表明，麻花艽中四种元素含量丰富，各部位含量差异较大，其中基部茎部含量较高，入药部位根部次之，为以后的开发利用提供了基础数据。

藏成药七十味珍珠丸中矿物质元素在体内蓄积性水平研究

名贵藏成药七十味珍珠丸是传统藏药的典型代表,疗效显著.其中矿物类药的大量运用为现代医学科学不可理喻,给传统藏医药学的健康发展带来了困惑.以金诃七十味珍珠丸为研究材料,以Wistar大白鼠为试验对象,用等离子体发射光谱(ICP-AES)和氢化物原子吸收光谱(HAAS)等分析仪器,测定了对照组和给药组实验动物在连续18周试验期间心、肝、肾等组织器官中的矿物质元素含量水平,阐述金诃七十味珍珠丸中矿物质元素在动物主要组织器官中的长期蓄积性及其对生物机体的毒性效应.