Atomic direct sample introduction

Different analytical procedures have been developed for direct atomic spectrometry of solids applicable to inorganic and organic materials in the form of powders, granulate, fibres, foils or sheets. For sample introduction without prior dissolution, a sample can also be suspended in a suitable solvent. Slurry techniques have not been used in relation to polymer/additive analysis. The required amount of sample taken for analysis typically ranges from 0.1 to 10 mg for analyte concentrations in the ppm and ppb range. In direct solid sampling method development, the mass of sample to be used is determined by the sensitivity of the available analytical lines. Physical methods are direct and relative instrumental methods, subjected to matrix-dependent physical and nonspectral interferences. Standard reference samples may be used to compensate for systematic errors. The minimum difficulties cause INAA, SNMS, XRF (for thin samples), TXRF and PIXE. 

The extension of inductively coupled plasma (ICP) atomic emission spectrometry to seawater analysis has been slow for two major reasons. The first is that the concentrations of almost all trace metals of interest are 1 xg/l or less, below detection limits attainable with conventional pneumatic nebulisation. The second is that the seawater matrix, with some 3.5% dissolved solids, is not compatible with most of the sample introduction systems used with ICP. Thus direct multielemental trace analysis of seawater by ICP-AES is impractical, at least with pneumatic nebulisation. In view of this, a number of alternative strategies can be considered ... 

Mass spectrometry is a sensitive analytical technique which is able to quantify known analytes and to identify unknown molecules at the picomoles or femto-moles level. A fundamental requirement is that atoms or molecules are ionized and analyzed as gas phase ions which are characterized by their mass (m) and charge (z). A mass spectrometer is an instrument which measures precisely the abundance of molecules which have been converted to ions. In a mass spectrum m/z is used as the dimensionless quantity that is an independent variable. There is still some ambiguity how the x-axis of the mass spectrum should be defined. Mass to charge ratio should not lo longer be used because the quantity measured is not the quotient of the ion s mass to its electric charge. Also, the use of the Thomson unit (Th) is considered obsolete [15, 16]. Typically, a mass spectrometer is formed by the following components (i) a sample introduction device (direct probe inlet, liquid interface), (ii) a source to produce ions, (iii) one or several mass analyzers, (iv) a detector to measure the abundance of ions, (v) a computerized system for data treatment (Fig. 1.1). 

The fast atom bombardment ionization (FAB) technique is a soft ionization method, typically requiring the use of a direct insertion probe for sample introduction in which a high energy beam of Xe atoms, Cs+ ions, or massive glycerol-NH4+ clusters sputter the sample and matrix from the probe surface (Figure 8). 

Elements such as As, Se and Te can be determined by AFS with hydride sample introduction into a flame or heated cell followed by atomization of the hydride. Mercury has been determined by cold-vapour AFS. A non-dispersive system for the determination of Hg in liquid and gas samples using AFS has been developed commercially (Fig. 6.4). Mercury ions in an aqueous solution are reduced to mercury using tin(II) chloride solution. The mercury vapour is continuously swept out of the solution by a carrier gas and fed to the fluorescence detector, where the fluorescence radiation is measured at 253.7 nm after excitation of the mercury vapour with a high-intensity mercury lamp (detection limit 0.9 ng I l). Gaseous mercury in gas samples (e.g. air) can be measured directly or after preconcentration on an absorber consisting of, for example, gold-coated sand. By heating the absorber, mercury is desorbed and transferred to the fluorescence detector. 

The role of the sample introduction system is to convert a sample into a form that can be effectively vaporized into free atoms and ions in the ICP. A peristaltic pump is typically used to deliver a constant flow or sample solution (independent of variations in solution viscosity) to the nebulizer. Several different kinds of nebulizers are available to generate the sample aerosol, and several different spray chamber designs have been used to modify the aerosol before it enters the ICP Gases can be directly introduced into the plasma, for example, after hydride generation. Solids can be introduced by using electrothermal vaporization or laser ablation. 

From the late 1960s onwards, a number of research groups around the world began to investigate alternatives to pneumatic nebulization for sample introduction, in an attempt to overcome transport efficiency limitations. The most successful approaches were those which involved heating small, discrete liquid samples, and sometimes even solid samples, directly on a metal filament, boat, or cup which could be positioned reproducibly into a flame. However, since the temperature of the metal would be lower than that of the flame itself, the techniques were confined to the determination of relatively easily atomized elements such as arsenic, bismuth, cadmium, copper, mercury, lead, selenium, silver, tellurium, thallium, and zinc. 

M. Segura, Y. Madrid, C. Camara, Evaluation of atomic fluorescence and atomic absorption spectrometric techniques for the determination of arsenic in wine and beer by direct hydride generation sample introduction, J. Anal. Atom. Spectrom., 14 (1999), 131-135. 

H. Matusiewicz, M. Mikolajczank, Determination of As, Sb, Sn, and Hg in beer and wort by direct hydride generation sample introduction - electrothermal AAS, J. Anal. Atom Spectrom., 482 (2001), 652-657. 

The liquid sample introduction system most commonly used on an ICP-MS is very similar to that used on a flame Atomic Absorption Spectrometer or an ICP-OES. Liquid samples can be directly injected using a pneumatic nebulizer and a spray chamber. 

Sample introduction is probably one of the most important stages for reproducible measurements and is related to the efficiency of sample uptake to the plasma source. Normally samples are introduced in solution form and in latter years sample introduction as solids and gases directly or from GC columns is now commonly employed on a routine basis where applicable. Selection for the best sample introduction method needs careful consideration, keeping in mind that the properties of the atomiser will dictate its design and operation. For adequate thermal dissociation, volatilisation, excitation and atomisation of aerosol particles, the efficiency of nebulisation will determine the sensitivity and reproducibility of analyte response. The following requirements must be considered when analysing samples using atomic emission methods ... 

In using atomic spectroscopy analysis the sample introduction is an extension to sample preparation. To understand the limitations of practical sample introduction systems it is necessary to reverse the train of thought, which tends to flow in the direction of sample solution > nebulisation > spray chamber > excitation > atomisation. An introduction procedure must be selected that will result in a rapid breakdown of species in the atomiser to give reproducible results irrespective of the sample matrix. In designing an FI A system to carry out atomic emission and to generate efficient free atom production for excitation the following criteria must be adhered to as closely as possible ... 

For glow discharges and inductively coupled high-frequency plasmas ion generation takes place in the plasmas. In the first case mass spectrometry can be performed directly on solids and in the second case on liquids or solids after sample dissolution. In the various atomic spectrometric methods, real samples have to be delivered in the appropriate form to the plasma source. Therefore, in the treatment of the respective methods extensive attention will be given to the techniques for sample introduction. 

Qian S, Yang P. 1990. Direct determination of selenium in flours by slurry sample introduction and platform graphite furnace atomic absorption spectrometry. Fenxi Huaxue 18(11) 1064-1066. 

The detection systems used with HPLC can be broadly divided into three approaches photometry, plasma techniques (ICPAES, ICPMS), and cold vapour atomic absorption and fluorescence spectroscopy (CV-AAS, CV-AFS). The method with the lowest limits of detection (LOD) with sample introduction via a direct injection nebulizer used ICP-MS. An HPLC system coupled to atmospheric pressirre chemical ionization MS was used to identify methyl mercury spiked into a fish tissue CRM (DORM-1, NRCC). This type of system has a significant advantage over elemental detection methods because identification of the species present is based on their structure, rather than matching the analyte s retention time to that of a standard. 

Mass Spectrometric Detection. The very small volumetric flow rates of less than 1 pi,/min from electrophoresis capillaries make it feasible to couple the effluent directly to the Ionization source of a mass spectrometer. The most common sample-introduction and ionization interface for this purpose is currently electrospray (Section 20B-4), although fast atom bombardment, matrix-assisted laser desorption-ionization (MALDI) spectrometry, and inductively coupled plasma mass spectrometry (ICPMS) have also been used. Because the liquid sample must be vaporized before entering the mass spectrometry (MS) system. 

Liquid solutions are the preferred form for sample introduction into flame and furnace atomizers. Frequently liquid samples can be analyzed directly or with minimal sample preparation, such as filtration to remove solid particles. Typical samples that have been analyzed directly include urine, electroplating solutions, petroleum products, wine, fmit juice and, of course, water and wastewater. If the samples are too concentrated, they may be diluted prior to analysis. If they are too dilute, the solvent may be evaporated or the analyte concentrated by solvent extraction or other methods. 

Although most samples are commonly presented as liquids for atomic emission spectroscopy, direct solid sample analysis has the advantage that no major pretreatment or dissolution steps are required [44]. This minimises dilution errors or contamination from reagents and reduces the reagent and manpower cost per sample. In addition, improved detection Hmits may be obtained if microsamples or microanalysis are possible without any further dilution. However, the analyst has to ensure that the solid material sampled is representative of the bulk material. ICP-AES has generally a remarkable tolerance for total dissolved sohds compared to ICP-MS or flame AAS so that, depending on the overall matrix, between 2 and 25 % suspended sohds can be coped with. Therefore, most of the sohd sample introduction devices described below are dedicated for ICP-AES. 

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