Determination of Trace Elements in Vegetable Oils and Biodiesel by Atomic Spectrometric Techniques—A Review

Abstract

The determination of trace elements in edible oils and biodiesel using atomic spectrometric methods is reviewed. Problems related to sample pretreatment for appropriate sample introduction and calibration are addressed as well as the strategies to overcome them. Recent trends aimed at simplifying sample manipulation are presented. The applications and scope of atomic absorption spectrometry (AAS), flame optical emission spectrometry (F-OES), inductively coupled plasma–optical emission spectrometry (ICP-OES), and inductively coupled plasma–mass spectrometry (ICP-MS) techniques for the determination of trace metals in edible oils and biodiesel are discussed, as well as some current instrumental new developments.     

An Overview of the Use of Yttrium for Internal Standardization in Inductively Coupled Plasma–Atomic Emission Spectrometry

Abstract

Internal standardization is a widely used method for compensating nonspectral interference in inductively coupled plasma (ICP) spectrometry. Emphasis is given on the choice of the suitable element and its specific spectral line as an efficient internal standard. This choice is the result of multi-variable evaluations and analytical applications. In inductively coupled plasma–atomic emission spectrometry (ICP-AES) and other spectrometric techniques several spectral lines of the same or different elements have been evaluated as potential internal standards. Yttrium spectral lines fulfill certain prerequisites and they are favored by a large number of researchers. In our discussed review, we present several reports of ICP-AES techniques that employ yttrium as the internal standard. These reports are classified according to specific sample origin and aim of the research.     

悬浮液雾化进样感耦等离子体基本参数研究I.等离子体激发温度测定

研究了悬浮液雾化进样感耦等离子体原子发射光谱基本参数——等离子体激发温度。实验用Ti线为温标线,并采用多谱线法测量溶液雾化进样和0.05％二氧化钛悬浮液雾化进样等离子体激发温度。测定结果显示这两种雾化进样方式的等离子体激发温度接近,为5 000～6 000 K。随感耦等离子体原子发射光谱仪器功率的提高,悬浮液雾化进样等离子体激发温度也相应增大,但增大幅度较小。悬浮液雾化进样等离子体发射光谱分析,若单纯改变仪器功率对于颗粒在等离子体中的原子化效率没有显著的变化,因此对于分析结果没有显著的改善作用。     

Excitation Mechanisms of Copper Ionic and Atomic Lines Emitted from a Low‐Pressure Argon Laser‐Induced Plasma

Abstract

Low‐pressure laser‐induced plasmas generated with a pulsed Nd∶YAG laser have complicated structures both temporally and spatially. The emission characteristics of the plasma are investigated for optimizing the experimental parameters in atomic emission spectrometry. The emission intensities of copper emission lines, measured in a time‐resolved as well as a time‐integrated mode, are strongly dependent on the kind of copper lines, ionic or atomic line, and the excitation energy. Also, the pressure of argon gas is the most important parameter for determining the behavior of these emission lines, including argon lines. Generally, copper ionic lines are dominantly emitted from the initial breakdown zone, because the copper ions are produced mainly in the hot breakdown zone. However, the Cu II 229.44‐nm line is emitted also from the expansion zone of the plasma. It results from an additional excitation process through the charge‐transfer collision particularly effective for the corresponding excited level. In this work, the excitation mechanisms for Cu I, Ar I, and Ar II lines are also discussed. The excitations occurring in the laser‐induced plasma can be well understood by taking the temporal and spatial variations in their intensities into consideration.     

直接进样ICP-OES法测定N-甲基吡咯烷酮(NMP)中的12种杂质元素

建立电感耦合等离子体发射光谱(ICP-OES)法测定N-甲基吡咯烷酮(NMP)中12种杂质元素(Mo, Cr, Zn, Pb, Ni, Mn, Fe, Cu, Ca, Al, Na, K)的分析方法。将NMP用硝酸酸化后直接进样分析,无需对样品进行消解,避免了样品前处理时引入误差的风险。通过优化等离子体工作参数,减轻了有机溶剂对等离子体的负载,确保了等离子体的稳定工作,优化后等离子体射频功率为1 350 W,载气流量为0.40 L·min-1。采用轴向观测方式获取样品原子化或离子化过程中的所有信号,降低了方法的检出限,提高了分析灵敏度。通过选择各元素合适分析谱线、采用附加氧气除积碳并结合背景校正技术消除了各类谱线及背景干扰,选用标准加入法校正了基体效应,抵消了高浓度有机基质对易电离元素产生的干扰。结果表明,标准工作曲线的线性相关系数在0.999 5～1.000 0之间,检出限在3.8～106.4 ng·g-1范围内,各元素的回收率在92.0%～108.0%之间,11次测定的相对标准偏差(RSD)≤4.8%。方法操作简单,无需复杂的样品预处理,分析速度快,测定结果准确可靠,精密度高,完全满足大批量实际产品的分析要求。方法可应用于NMP产品中杂质元素的监测。     

Methodology for the Determination of Stoichiometry and Metal Impurities in New PZT Ceramics by Inductively Coupled Plasma Optical Spectrometry (ICP OES)

ABSTRACT

An inductively coupled plasma optical emission spectrometry (ICP OES) method for Pb, Zr, Ti, Sr, Cr, Fe, Cu, Mn, and Al determination in PZT-ceramics is described. Careful analytical work was carried out in order to evaluate precision, accuracy, and matrix interference. Different procedures were investigated for the ceramics decomposition. Axially viewed plasma operating conditions were evaluated for trace elements (Al, Fe, Cu, Mn, and Cr) in presence of sample matrix. The relative standard deviation (RSD) ranged from 0.7 to 3.9%, whereas the analytes recoveries in the spiked samples ranged from 92 to 119%. The detection limits (LODs) of trace elements ranged from 2.4 to 2.6 µg g^?1. The developed method is useful for evaluating the PZT-ceramics synthesis.     

Dry Ashing Preparation of (Quasi)solid Samples for the Determination of Inorganic Elements by Atomic/Mass Spectrometry

Abstract:

This work presents an overview of the development of dry ashing preparation techniques for solid and quasisolid sample analysis by atomic and inorganic mass spectrometry, including flame/graphite furnace atomic absorption spectrometry, chemical vapor generation atomic absorption/fluorescence spectrometry, and inductively coupled plasma–optical emission/mass spectrometry. This article also summarizes all of the dry ashing methods reported in the past 20 years. The dry ashing methods applied to sample preparation are classified as electrothermal ashing, microwave ashing, oxygen combustion, and other special ashing methods including laser, ultraviolet (UV)/ozone, and plasma. Moreover, the development of relevant devices is discussed in context.     

悬浮液雾化进样感耦等离子体基本参数研究Ⅰ.等离子体激发温度测定

研究了悬浮液雾化进样感耦等离子体原子发射光谱基本参数——等离子体激发温度。实验用“线为温标线，并采用多谱线法测量溶液雾化进样和0．05％二氧化钛悬浮液雾化进样等离子体激发温度。测定结果显示这两种雾化进样方式的等离子体激发温度接近，为5000-6000K。随感耦等离子体原子发射光谱仪器功率的提高，悬浮液雾化进样等离子体激发温度也相应增大，但增大幅度较小。悬浮液雾化进样等离子体发射光谱分析，若单纯改变仪器功率对于颗粒在等离子体中的原子化效率没有显著的变化，因此对于分析结果没有显著的改善作用。     

双频容性耦合等离子体相分辨发射光谱诊断

采用相分辨发射光谱法, 对双频容性耦合纯Ar和不同含O₂量的Ar-O₂混合气体放电等离子体的鞘层激发模式进行了探究. 在射频耦合电源上极板的鞘层区域处观察到两种电子激发模式: 鞘层扩张引起的电子碰撞激发模式和二次电子引起的电子碰撞激发模式; 并发现这两种激发模式均受到低频射频电源周期的调制. 在纯Ar放电等离子体中, 两种激发模式的激发轮廓相似; 而在Ar-O₂混合气放电等离子体中, 随着含O₂量的增加, 二次电子的激发轮廓变弱. 此外, 利用相分辨发射光谱法对不同含O₂量的Ar-O₂混合气放电下Ar的 750.4 nm谱线的平均低频电源周期轴向分布进行了研究, 得到了距耦合电源上极板约3.8 mm处为双频容性耦合射频等离子体的鞘层边界. 关键词： 双频容性耦合等离子体 等离子体鞘层 发射光谱     

Slurry Sampling—An Analytical Strategy for the Determination of Metals and Metalloids by Spectroanalytical Techniques

Abstract

This article critically overviews the state-of-the-art of slurry sampling as an approach for the minimization of sample preparation prior to the determination of metals and metalloids in complex matrices by spectroanalytical techniques. Relevant factors involved in the optimization of slurry-based analytical procedures and the dependence of the quality of the results on the calibration method selected are discussed in detail. The advantages and limitations compared to solid sampling for the analysis of solid matrices are highlighted and discussed.

Analytical applications of slurry sampling reported in the literature emphasizing publications between 2004 and 2009 are comprehensively compiled covering detection by flame atomic absorption spectrometry (FAAS), electrothermal atomic absorption spectrometry (ET-AAS), cold vapor atomic absorption spectrometry (CV-AAS), hydride generation atomic absorption spectrometry (HG-AAS), hydride generation atomic fluorescence spectrometry (HG-AFS), inductively coupled plasma optical emission spectrometry (ICP-OES), and inductively coupled plasma mass spectrometry (ICP-MS).     

Electron density diagnostics by use of a collisional excitation model of the oxygen VI doublet in the solar transition region

ABSTRACT

For spectral diagnostics in the solar transition region under the collision–equilibrium condition, the method for electron density diagnostics by the collisional excitation is discussed in this paper. By using observed signal ratio of spectral lines produced by the oxygen VI ion, we discuss the electron density by this method. We find that this method is valid for a large region of signal ratio (from 2.001 to 4.162). We obtain that the electron density increases with increasing signal ratio of the oxygen VI doublet, and the plasma has an electron density on the order of magnitude of 10⁶–10⁷?cm^?3. This discussion will be significant for study on spectral diagnostics of the solar transition region.     

激光诱导击穿火焰等离子体光谱研究

采用PI-MAX-II型增强型电荷耦合器件, 用Nd:YAG纳秒脉冲激光器输出的1064 nm强光束击穿在一个大气压的空气中燃烧的酒精灯火焰, 对激光诱导击穿酒精灯火焰产生的等离子体光谱进行了初步研究. 根据美国国家标准与技术研究院原子发射谱线数据库, 对等离子体中的主要元素的特征谱线进行了标识和归属. 通过激光诱导击穿空气等离子体光谱、激光诱导击穿酒精灯火焰等离子体光谱、激光诱导酒精喷灯火焰等离子体光谱的对比分析, 发现不同燃烧状况下的光谱中各原子谱线的相对强度是不同的. 这些结果对于使用激光诱导击穿技术分析和研究碳氢燃料在空气中的燃烧特性具有重要的意义和参考价值, 同时也为将该技术应用于燃烧诊断提供了实验依据.     

Application of Multivariate Techniques in Optimization of Spectroanalytical Methods

Abstract

The present article describes fundamentals and applications of multivariate techniques used for the optimization of analytical procedures and systems involving spectroanalytical methods such as flame atomic absorption spectrometry (FAAS), electrothermal atomic absorption spectrometry (ETAAS), inductively coupled plasma optical emission spectrometry (ICP OES), and inductively coupled plasma mass spectrometry (ICP‐MS), considering the main steps of a chemical analysis. This way, applications of experimental designs in optimization of sampling systems, digestion procedures, preconcentration procedures, instrumental parameters of quantification steps of analytical methods, and robustness tests have been summarized in this work.     

电感耦合等离子体-发射光谱法测定海洋沉积物中的常、微量元素

采用电感耦合等离子体-发射光谱法(ICP-OES)测定了海洋沉积物中18种常、微量元素。选择了适宜的标准溶液、溶样方法和分析谱线。该方法检出限低,精密度高,准确度好。采用国家一级标准物质GSMS-1、GSD-9、GSD-11进行测试,分析结果与标准值相吻合,相对误差均小于2.0%。用于黄河口沉积物测试,研究区内沉积物以SiO2和Al2O3为主,两者含量之和在70%左右。     

Slurry Nebulization in Plasmas for Analysis of Inorganic Materials

Abstract

This review summarizes and discusses the preparation of slurries for analysis of inorganic materials by inductively coupled plasma optical emission spectrometry (ICP‐OES) and inductively coupled plasma mass spectrometry (ICP‐MS). Details about the grinding step for slurry preparation, the stabilization of slurries, and the calibration strategies are critically discussed. Typical applications described in the literature and the state‐of‐the‐art including advantages and limitations of slurry analysis are presented.     

Inductively Coupled Plasmas as Excitation Sources for Atomic Fluorescence Spectrometry

The inductively coupled Ar plasma (ICP) is introduced as a multielement excitation source for flame atomic fluorescence spectrometry. The ICP-excited and the EDL-excited atomic fluorescence detection limits are compared for 20 elements.     

Procedures of Separation and Pre‐concentration for Molybdenum Determination Using Atomic Spectrometry—a Review

Abstract

The literature concerning the improvement of atomic and ionic procedures for molybdenum determination through separation and pre‐concentration were updated. Analytical procedures based on flame atomic absorption spectrometry (AAAS), electrothermal or graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma optical emission spectrometry (ICP‐OES), and inductively coupled plasma mass spectrometry were reviewed taking into consideration the preliminary steps, which can enhance the selectivity and sensitivity based on co‐precipitation, solvent extraction, and solid‐phase extraction. Both in‐batch and on‐line procedures were considered.     

Pulsed laser ablation of SiC in a nitrogen atmosphere: formation of CN

Optical emission lines from the plasma generated by a laser ablation process have been investigated to gather information on the nature of the chemical species present. In particular, the experiments were carried out during the laser ablation of a ceramic sintered SiC target, both in vacuum and in presence of controlled nitrogen atmosphere. Time integrated and spatially resolved emission spectra are dominated by the atomic emission lines from silicon and carbon species, either neutral, or singly ionized. When the ablation process was carried out in a nitrogen gas background direct evidence of the formation of the CN molecular specie was found. Fast photography imaging of the expanding plume revealed the formation of a shock wave at nitrogen pressure above 13.3 Pa, with the consequent heating of the shocked region and enhancement of the kinetics of ionization and excitation. Since the C₂ specie was absent, a CN formation mechanism involving atomic carbon and nitrogen in the presence of a shock wave is suggested. PACS 52.38.Mf; 52.50.Jm, 47.40.-x     

用标准加入电感耦合等离子体质谱(ICP-MS)法测定白酒中的锰、铅、铜

在ＩＣＰ－ＭＳ基础上用标准加入法对白酒中的锰、同、铜进行了定量测定。与常见的分析方法相比,这种方法具有方便、准确、快速的优点,与等离子光谱相比,ＩＣＰ－ＭＳ的检出限要低３个数量级。由于果酒,黄酒和饮料的成分与白酒相似,因此这种方法不仅可以用来测定白酒中的微量元素,而且还可以用来测定果酒、黄酒及饮料中的微量元素。     

CO2激光锡等离子体极端紫外及可见光光谱

利用CO2激光烧蚀锡靶产生等离子体,当入射到靶面的单个脉冲能量为400mJ,半峰全宽(FWHM)为75ns时,使用光谱仪和增强型电荷耦合器件(ICCD)采集了等离子体的时间分辨光谱。在局域热平衡假设下,利用谱线的斯塔克展宽和五条Sn II谱线的相对强度计算并得到了等离子体电子密度、电子温度和辐射谱线强度随时间的变化规律;利用掠入射极端紫外平场光栅光谱仪,结合X射线CCD同时探测了光源在6.5～16.8nm波段的时间积分极端紫外辐射光谱。实验结果表明:激光点燃等离子体早期的100ns内有很强的连续谱,此后才能分辨出明显的原子和离子线状谱。在延时0.1～2.0μs的时间区间内,等离子体中的电子温度和密度分别在2.3～0.5eV和7.6×1017～1.2×1016 cm-3范围内,均随时间经历了快速下降,然后再较缓慢下降的过程。激光锡等离子体极端紫外不可分辨辐射跃迁光谱峰值中心位于13.5nm,FWHM为1.1nm。