{"title":"Radical theory of hydride atomization and its significance for trace element analysis","authors":"","doi":"10.1016/j.sab.2024.107058","DOIUrl":null,"url":null,"abstract":"<div><div>Extremely low limits of detection in trace element analysis can be achieved when coupling generation of volatile hydrides to the relatively simple methods of analytical atomic spectrometry - atomic fluorescence spectrometry (AFS) or atomic absorption spectrometry (AAS). To reach ideal performance of the whole analytical procedure, the atomizers dedicated for coupling with AAS or AFS (conventional externally heated quartz tubes - CQTA, miniature diffusion flames - MDF and dielectric barrier discharges - DBD) have to be optimized in terms of design as well as of operation parameters. Such an optimization can be made in a straightforward and elegant way based on the knowledge of what really happens in hydride atomizers. The key point which must be taken into account in order to understand what really happens in these atomizers is that their temperature is too low to be compatible with any significant thermal atomization of hydrides. The dramatic disagreement with the many years of experience of observing a complete conversion of hydrides to free atoms is explained by the radical theory of hydride atomization. The presented evidence corroborates the radical theory of hydride atomization in the CQTA. This makes possible optimization of design as well as of operational parameters of this kind of atomizer just on the basis of quantification of distributions of hydrogen radicals which can be determined either experimentally by two-photon absorption laser-induced fluorescence or potentially by numerical simulation. Regarding extension of the radical theory in the CQTA to MDF and DBD atomizers, more experimental evidence on free analyte atom distributions is required either to confirm its validity or to discover reasons for its failure.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":null,"pages":null},"PeriodicalIF":3.2000,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Spectrochimica Acta Part B: Atomic Spectroscopy","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0584854724002039","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"SPECTROSCOPY","Score":null,"Total":0}
引用次数: 0
Abstract
Extremely low limits of detection in trace element analysis can be achieved when coupling generation of volatile hydrides to the relatively simple methods of analytical atomic spectrometry - atomic fluorescence spectrometry (AFS) or atomic absorption spectrometry (AAS). To reach ideal performance of the whole analytical procedure, the atomizers dedicated for coupling with AAS or AFS (conventional externally heated quartz tubes - CQTA, miniature diffusion flames - MDF and dielectric barrier discharges - DBD) have to be optimized in terms of design as well as of operation parameters. Such an optimization can be made in a straightforward and elegant way based on the knowledge of what really happens in hydride atomizers. The key point which must be taken into account in order to understand what really happens in these atomizers is that their temperature is too low to be compatible with any significant thermal atomization of hydrides. The dramatic disagreement with the many years of experience of observing a complete conversion of hydrides to free atoms is explained by the radical theory of hydride atomization. The presented evidence corroborates the radical theory of hydride atomization in the CQTA. This makes possible optimization of design as well as of operational parameters of this kind of atomizer just on the basis of quantification of distributions of hydrogen radicals which can be determined either experimentally by two-photon absorption laser-induced fluorescence or potentially by numerical simulation. Regarding extension of the radical theory in the CQTA to MDF and DBD atomizers, more experimental evidence on free analyte atom distributions is required either to confirm its validity or to discover reasons for its failure.
期刊介绍:
Spectrochimica Acta Part B: Atomic Spectroscopy, is intended for the rapid publication of both original work and reviews in the following fields:
Atomic Emission (AES), Atomic Absorption (AAS) and Atomic Fluorescence (AFS) spectroscopy;
Mass Spectrometry (MS) for inorganic analysis covering Spark Source (SS-MS), Inductively Coupled Plasma (ICP-MS), Glow Discharge (GD-MS), and Secondary Ion Mass Spectrometry (SIMS).
Laser induced atomic spectroscopy for inorganic analysis, including non-linear optical laser spectroscopy, covering Laser Enhanced Ionization (LEI), Laser Induced Fluorescence (LIF), Resonance Ionization Spectroscopy (RIS) and Resonance Ionization Mass Spectrometry (RIMS); Laser Induced Breakdown Spectroscopy (LIBS); Cavity Ringdown Spectroscopy (CRDS), Laser Ablation Inductively Coupled Plasma Atomic Emission Spectroscopy (LA-ICP-AES) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS).
X-ray spectrometry, X-ray Optics and Microanalysis, including X-ray fluorescence spectrometry (XRF) and related techniques, in particular Total-reflection X-ray Fluorescence Spectrometry (TXRF), and Synchrotron Radiation-excited Total reflection XRF (SR-TXRF).
Manuscripts dealing with (i) fundamentals, (ii) methodology development, (iii)instrumentation, and (iv) applications, can be submitted for publication.