Recent Advance of Hydride Generation–Analytical Atomic Spectrometry: Part I—Technique Development

Abstract Hydride generation is the most popular and widely used chemical vapor generation technique and is interesting to analytical chemists as an effective sample introduction method, especially for elemental determination and speciation analysis by analytical atomic spectrometry. The present review provides a literature survey on the hydride generation technique coupled to analytical atomic spectrometry during the past several years, covering the literature on both tetrahydroborate-based hydride generation and non-tetrahydroborate-based hydride generation techniques. Development of other related methods coupled to hydride generation for better analytical performance of analytical atomic spectrometry is included as well.     

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.     

Molybdenum,Platinum, and Tantalum Metal Atomizers or Vaporizers in Analytical Atomic Spectrometry

Abstract

The application of metal (tantalum, molybdenum, and platinum) devices in analytical atomic spectrometry is reviewed in this article. These metal devices have been employed in various analytical atomic spectrometric techniques for more than three decades, mainly as electrothermal atomizers or electrothermal vaporizers, in various physical shapes, such as tubes, platforms, loops, and wires (or coils/filaments). Their application spans from atomic absorption spectrometry (AAS), atomic emission spectrometry (AES) atomic fluorescence spectrometry (AFS), inductively coupled plasma atomic emission spectrometry (ICP‐AES) to inductively coupled plasma mass spectrometry (ICP‐MS). The analytical figures of merit and the practical applications reported for these metal devices are reviewed, and the atomization mechanism on these metal atomizers is briefly summarized, too. In addition, other applications of the metal devices are discussed, including analyte preconcentration by electrodeposition and sequential metal vapor elution analysis (SMVEA). Furthermore, the application of these metals in graphite furnaces encompasses the schemes with the metals in the form of furnace linings, platforms, or impregnated salts.     

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).     

Dielectric Barrier Discharge in Analytical Spectrometry

Abstract

Dielectric barrier discharge is a nonequilibrium plasma, and its industrial application has been on a large scale. Similarly, its prominent features of high dissociation ability at low working temperature and low power consumption, simple and adjustable configuration, ambient working conditions, and long lifetime are favorable for developing a wide array of analytical devices as well. This review addresses the basics of dielectric barrier discharge and emphasizes their analytical applications in analytical atomic spectrometry, chemiluminescence, gas chromatographic detectors, ion source for mass spectrometry, and ion mobility spectrometry with 103 references.     

Interfacing Microfluidic Handling with Spectroscopic Detection for Real‐Life Applications via the Lab‐on‐Valve Platform: A Review

Abstract

One of the current needs within the analytical spectrometric community is the development of straightforward and cost‐effective, yet rugged, sample processing procedures aimed at precluding both spectroscopic and nonspectroscopic matrix interferences while fostering concomitant sample enrichment. Illustrated via selected representative examples, this review presents and discusses the current state of the art in implementing miniaturised and automated sample treatments for environmental and biochemical assays via microfluidic systems exploiting the lab‐on‐valve (LOV) platform in hyphenation with syringe pump propelling devices as a front end to a plethora of spectroscopic detection schemes including ultraviolet‐visible (UV‐Vis) spectrometry, spectrofluorimetry, chemiluminescence, atomic absorption spectrometry (AAS), atomic flourescence spectrometry (AFS), and inductively coupled plasma‐atomic emission spectrometry/mass spectrometry (ICP‐AES/MS). In contrast to lab‐on‐a‐chip units, the versatile configuration of the micromachined LOV readily facilitates the implementation of on‐line unit operations at will encompassing not merely the introduction of minute, well‐defined volumes of sample followed by chemical derivatization, but the potential for accommodation of solid‐phase extraction, hydride/vapor generation, precipitation/coprecipitation, and bead injection protocols with no need for chip redesign.     

Atomic spectrometry and atomic mass spectrometry in bioanalytical chemistry

Abstract

Atomic spectrometry and atomic mass spectrometric (MS) techniques have been playing crucial roles in the field of biosciences. They detect elements with relatively high sensitivities and are thus applicable to a wide range of analytical targets. In the past decade, determination of bio-relevant metallic elements continues to be of interest, while particularly noteworthy are methods developed for small molecules, peptides, proteins, nucleic acids and even cells that well exploited the bio-analytical strengths of atomic spectrometry and atomic MS, either in a direct or indirect manner. Quantitation, as well as speciation and imaging analyses are all involved. The present review aims to assimilate recent advances in bio-analysis utilizing atomic spectrometry and atomic MS, primarily covering the period of 2013–2018, in an attempt to provide readers insight into the developing trends of this research frontier. Followed by concluding remarks and perspectives, the applications are divided into the following four catalogs: (i) toxicologically important metal-containing species, with an emphasis on quantitative and imaging analysis; (ii) quantitation of biomolecules using naturally occurring heteroatoms; (iii) exogenous metal ion or nanoparticle tagging-based strategies in bioassays; and (iv) label-free detection of biomolecules.     

Microplasma Technology and Its Applications in Analytical Chemistry

Abstract

This review article describes some existing microplasma sources and their applications in analytical chemistry. These microplasmas mainly include direct current glow discharge (DC), microhollow-cathode discharge (MHCD) or microstructure electrode (MSE), dielectric barrier discharge (DBD), capacitively coupled microplasmas (CCμPs), miniature inductively coupled plasmas (mICPs), and microwave-induced plasmas (MIPs). The historical development and recent advances in these microplasma techniques are presented. Fundamental properties of the microplasmas, the unique features of the reduced size and volume, as well as the advantageous device structures for chemical analysis are discussed in detail, with the emphasis toward detection of gaseous samples. The analytical figures of merit obtained using these microplasmas as molecular/elemental-selective detectors for emission spectrometry and as ionization sources for mass spectrometry are also given in this review article.     

Glow Discharge as a Tool for Surface and Interface Analysis

Abstract

This review article focuses on the analytical capabilities of glow discharge optical emission spectrometry (GD‐OES) and mass spectrometry (GD‐MS) to perform compositional depth profiling (GD‐CDP). The properties of the Grimm‐type glow discharge as well as basic processes of sputtering are described and their influence on the GD as a surface and interface analytical tool are discussed. A series of examples from recent literature ranging from computer hard disks to molecular monolayers on copper substrates are presented to illustrate the excellent depth resolution that can be achieved with GD surface analytical techniques. The conditions for obtaining nanometer or even atomic‐layer depth resolution are discussed. Following this introduction is the possibilities of the technique a selection of applications principally chosen from our laboratories, demonstrating that GD‐OES and GD‐MS can be successfully employed as an analytical tool assisting the development of new materials and coatings. The applications cover common industrial tasks such as heat treatments, studies of diffusion processes at interfaces, and electrochemical depositions for biocompatible material. However, limitations and known artifacts are also discussed.     

Critical Evaluation of Analytical Procedures for the Determination of Lead in Seawater

Abstract: This article presents a critical evaluation of the analytical procedures used for the determination of lead in seawater, which is important because lead is a good indicator of marine pollution caused by human activities. Sampling, storage, and pretreatment techniques are briefly overviewed, including the significance of systematic errors that cannot be corrected later on. The main techniques in this article are electrothermal–atomic absorption spectrometry (ET-AAS), inductively coupled plasma–mass spectrometry (ICP-MS), and voltammetry. Flame atomic absorption spectrometry (FAAS) and inductively coupled plasma–optical emission spectrometry (ICP-OES) are treated as well, although their limits of quantification are not sufficient for a determination of lead in unpolluted seawater. Even when separation and preconcentration techniques are applied, these techniques are only capable of detecting lead in polluted coastal seawater. Separation and preconcentration are actually also required for ET-AAS and ICP-MS in order to determine the lowest concentrations of lead found in unpolluted open-ocean seawater, which is still a challenge for the analytical chemist.     

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.     

Sample Preparation for the Determination of Metals in Food Samples Using Spectroanalytical Methods—A Review

Abstract

The present article gives an overview of recent publications and modern techniques of sample preparation for food analysis employing atomic and inorganic mass spectrometric techniques, such as flame atomic absorption spectrometry, chemical vapor generation atomic absorption and atomic fluorescence spectrometry, graphite furnace atomic absorption spectrometry, inductively coupled plasma optical emission spectrometry, and inductively coupled plasma mass spectrometry. Among the most frequently applied sample preparation techniques for food analysis are dry ashing, usually with the addition of an ashing aid, and acid digestion, preferably with the assistance of microwave energy. Slurry preparation, particularly with the assistance of ultrasound, is increasingly used to reduce acid consumption and sample preparation time. Direct analysis of solid samples is gaining importance in the field of food analysis as it offers the highest sensitivity, avoids the use of acids and other aggressive reagents, makes possible the analysis of micro‐samples, and can be applied for fast screening analysis, e.g., of fresh meat.     

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.     

Determination of Cadmium in Biological Samples

Abstract

Even though normal exposure levels to Cd may be small, the human body is inefficient at excreting the heavy metal, so it slowly accumulates over the period of a lifetime. Eventually, the Cd level in the body may become toxic and give rise to harmful effects. Cadmium exposure could therefore be linked to diseases associated with aging such as osteoporosis, prostate cancer, and pancreatic cancer. These potential links have driven the development of a myriad of analytical techniques for the determination of Cd in biological samples. Natural biological Cd concentrations are typically low, so preconcentration steps and sensitive instruments are frequently a necessity. In addition, the complex matrices of biological specimens such as blood, urine, serum, and tissue often require a form of matrix modification or separation. This review provides an overview of these methods with 200 references from the literature published between 1995 and 2005. The analytical methods for the determination of Cd in biological samples include: spectrophotometry, atomic emission spectrometry, atomic absorption spectrometry, atomic fluorescence spectrometry, inductively coupled plasma mass spectrometry, and electrochemistry. In addition, Cd speciation techniques, using high‐performance liquid chromatography and capillary electrophoresis, are briefly discussed.     

Characterization of Conifers and Their Products by Optical Atomic Spectrometry

Abstract

Conifers are primarily evergreen trees that are widely distributed; admired for their beauty; used as biomonitors for elements; processed for lumber, paper, fuel, and other products; and employed for food and medicinal products. Optical atomic spectrometry includes the widely used elemental analysis techniques of atomic absorption, atomic emission, and atomic fluorescence. This review considers applications of optical atomic spectrometry for conifers and their products. The goal is to assemble these diverse applications to assist analytical chemists and associated scientists in the development of methodology. The conclusion summarizes these studies and forecasts future developments.     

Multielement Analytical Spectroscopy in Plant Ionomics Research

Abstract: The study of the ionome (ionomics) is defined as quantitative and simultaneous measurement of the element composition of living organisms and changes in this composition in response to physiological stimuli, development stage, and genetic modifications (Salt et al., Ann. Rev. Plant Biol., Vol. 59, 2008). The necessity of understanding the regulation processes of elements in the organisms demands determination of many elements in the organism, tissue, and cell (Baxter, Plant Biol., Vol. 12, 2009). A prospect for ionomics is environmental pollution where great variety of conditions and pollutants exist resulting in concentration and interelemental changes in the plant ionome. The capabilities of and problems with several multielement analytical techniques, including instrumental neutron activation analysis (INAA), X-ray fluorescence, inductively coupled plasma–atomic emission spectrometry (ICP-AES), inductively coupled plasma–mass spectrometry (ICP-MS), and atomic absorption spectrometry (AAS), which are adequate and most promising in ionomic and environmental studies of plants, are reviewed. References are confined mainly to the last 10–15 years. Information about concentrations, roles, binding forms, and pollution sources of the elements and comparison between methods with respect to limits of detection, determined elements, interferences, and economic considerations are tabulated. Some combinations of instrumental techniques supplementing each other are highly valued, namely, ICP-MS and ICP-AES and INAA and AAS or ICP-AES.     

Analytical Instrumental Techniques to Study Archaeological Wood Degradation

Abstract

Historically, a very large variety of everyday artifacts were made of wood, which makes them representative of their historical period or social context and valuable for archaeologists and historians. In order to preserve degraded wood and to develop and apply suitable conservation treatments, chemical and physical characterization of archaeological wood is needed. This review provides the reader with a survey on state-of-the-art of instrumental analytical tools available to understand the morphology and the chemical composition of archaeological wood. The focus is on microscopic and spectroscopic techniques such as scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Raman, nuclear magnetic resonance (NMR) and analytical techniques based on pyrolysis, such as direct exposure–mass spectrometry (DE-MS), pyrolysis–mass spectrometry (Py-MS), pyrolysis–gas chromtography–mass spectrometry (Py-GC/MS), with emphasis on their respective potentialities and limitations. The advantages of techniques based on synchrotron radiation are also discussed. In addition, the applicability of each examined technique is illustrated and discussed through specific examples from the literature.     

Recent Achievements in Sample Introduction Systems for Use in Chemical Vapor Generation Plasma Optical Emission and Mass Spectrometry: From Macro- to Microanalytics

Abstract

Chemical vapor generation (CVG) offers several significant advantages for analyses, including efficient matrix separation, which often leads to a reduction of interferences and better detection limits; high transport efficiency of analyte into the atomic spectroscopic detector; in some cases, high selectivity to permit differentiation of chemical species of a particular element and enable use of gas-phase separation methods for speciation of some elements.

The development of CVG techniques from a Marsh test (arsine generation) to a recent device combining vapor generation with multichannel sample introduction systems and separation or preconcentration techniques at the macro- and microscale for use in optical emission and mass spectrometry is reviewed.     

Laser Ablation Inductively Coupled Plasma Mass Spectrometry: Principles and Applications

Abstract

The application of laser ablation inductively plasma mass spectrometry (LA‐ICP‐MS) to the determination of major, minor, and trace elements as well as isotope‐ratio measurements offers superior technology for direct solid sampling in analytical chemistry. The advantages of LA‐ICP‐MS include direct analysis of solids; no chemical dissolution is necessary, reduced risk of contamination, analysis of small sample mass, and determination of spatial distributions of elemental compositions. This review aims to summarize recent research to apply LA‐ICP‐MS, primarily in the field of environmental chemistry. Experimental systems, fractionation, calibration procedures, figures of merit, and new applications are discussed. Selected applications highlighting LA‐ICP‐MS are presented.     

Flame Furnace Atomic Absorption Spectrometry: A Review

Abstract

Flame atomic absorption spectrometry (FAAS) is one of the most widespread traditional analytical techniques for trace element determination, but it often suffers from poor sensitivity due to the low nebulization efficiency and the short residence time of free atoms in the flame. On the basis of conventional FAAS, flame furnace atomic absorption spectrometry (FF-AAS) is developed with a tube (flame furnace) placed on top of the FAAS burner for the atomization. Sample is introduced via beam injection (BIFF-AAS) or thermospray (TS-FF-AAS). Due to the total sample introduction and prolonged residence time of free atoms in the flame furnace, marked sensitivity improvement is obtained for volatile and semivolatile elements over conventional FAAS. TS-FF-AAS can be employed as an element-selective detector for GC, HPLC, or CE for studying of metal speciation analysis and metallomics. In addition, three newly developed sample introduction methods, including ultrasonic nebulization, hydride generation, and pneumatic nebulization, are discussed. The analytical figures of merit and practical applications of FF-AAS in analytical atomic spectrometry are reviewed in this article.