Nebulization thermospray

The nebulization and evaporation processes used for the particle-beam interface have closely similar parallels with atmospheric-pressure ionization (API), thermospray (TS), plasmaspray (PS), and electrospray (ES) combined inlet/ionization systems (see Chapters 8, 9, and 11). In all of these systems, a stream of liquid, usually but not necessarily from an HPLC column, is first nebulized... 

A second form of desolvation chamber relies on diffusion of small vapor molecules through pores in a Teflon membrane in preference to the much larger droplets (molecular agglomerations), which are held back. These devices have proved popular with thermospray and ultrasonic nebulizers, both of which produce large quantities of solvent and droplets in a short space of time. Bundles of heated hollow polyimide or Naflon fibers have been introduced as short, high-surface-area membranes for efficient desolvation. 

Aerosols can be produced as a spray of droplets by various means. A good example of a nebulizer is the common household hair spray, which produces fine droplets of a solution of hair lacquer by using a gas to blow the lacquer solution through a fine nozzle so that it emerges as a spray of small droplets. In use, the droplets strike the hair and settle, and the solvent evaporates to leave behind the nonvolatile lacquer. For mass spectrometry, a spray of a solution of analyte can be produced similarly or by a wide variety of other methods, many of which are discussed here. Chapters 8 ( Electrospray Ionization ) and 11 ( Thermospray and Plasmaspray Interfaces ) also contain details of droplet evaporation and formation of ions that are relevant to the discussion in this chapter. Aerosols are also produced by laser ablation for more information on this topic, see Chapters 17 and 18. 

Many designs of nebulizer are commonly used in ICP/MS, but their construction and mode of operation can be collated into a small number of groups pneumatic, ultrasonic, thermospray, APCI, and electrospray. These different types are discussed in the following sections, which are followed by further sections on spray and desolvation chambers. 

In one sense, the thermospray nebulizer could be considered a pneumatic device, in which a fastflowing argon gas stream is replaced by a very rapidly vaporizing flow of solvent from the sample solution. A typical arrangement of a thermospray device is shown in Figure 19.18. 

Thermospray nebulizers are somewhat expensive but can be used on-line to a liquid chromatographic column. About 10% of sample solution is transferred to the plasma flame. The overall performance of the thermospray device compares well with pneumatic and ultrasonic sprays. When used with microbore liquid chromatographic columns, which produce only about 100 pl/min of eluant, the need for spray and desolvation chambers is reduced, and detection sensitivities similar to those of the ultrasonic devices can be attained both are some 20 times better than the sensitivities routinely found in pneumatic nebulizers. 

Nebulizers are used to introduce analyte solutions as an aerosol spray into a mass spectrometer. For use with plasma torches, it is necessary to produce a fine spray and to remove as much solvent as possible before the aerosol reaches the flame of the torch. Various designs of nebulizer are available, but most work on the principle of interacting gas and liquid streams or the use of ultrasonic devices to cause droplet formation. For nebulization applications in thermospray, APCI, and electrospray, see Chapters 8 and 11. 

A thermospray system is shown schematically in Figure 4.6. This consists of a heated capillary through which the LC eluate flows, with the temperature of this capillary being carefully controlled to bring about around 95% vaporization of the liquid. The vapour so produced acts as a nebulizing gas and aids the break-up of the liquid stream into droplets. 

Atmospheric-pressure chemical ionization (APCI) is another of the techniques in which the stream of liquid emerging from an HPLC column is dispersed into small droplets, in this case by the combination of heat and a nebulizing gas, as shown in Figure 4.21. As such, APCI shares many common features with ESI and thermospray which have been discussed previously. The differences between the techniques are the methods used for droplet generation and the mechanism of subsequent ion formation. These differences affect the analytical capabilities, in particular the range of polarity of analyte which may be ionized and the liquid flow rates that may be accommodated. 

Montaser A, Tan H, lishi II, Nam SFI, CaiM (1991) Argon inductively coupled plasma mass spectrometry with thermospray, ultrasonic, and pneumatic nebulization. Anal Chem 63 2660-2665 Montaser A, Minnich MG, Liu FI, Gustavsson AGT, Browner RF (1998) Fundamental aspects of sample introduction in ICP spectrometry. In Inductively Coupled Plasma Mass Spectrometry. Montaser A (ed), Wiley-VCH, New York, p 335-420... 

At present, the most powerful and promising interfaces for drug residue analysis are die particle-beam (PB) interface that provides online EI mass spectra, the thermospray (TSP) interface diat works well with substances of medium polarity, and more recently the atmospheric pressure ionization (API) interfaces that have opened up important application areas of LC to LC-MS for ionizable compounds. Among die API interfaces, ESP and ISP appear to be the most versatile since diey are suitable for substances ranging from polar to ionic and from low to high molecular mass. ISP, in particular, is compatible with the flow rates used with conventional LC columns (70). In addition, both ESP and ISP appear to be valuable in terms of analyte detectability. These interfaces can further be supplemented by preanalyzer collision-induced dissociation (CID) or tandem MS as realized with the use of triple quadrupole systems. Complementary to ESP and ISP interfaces with respect to the analyte polarity is APCI with a heated nebulizer interface. This is a powerful interface for both structural confirmation and quantitative analysis. 

LC-PB-MS has been investigated as a potential confirmatory method for the determination of malachite green in incurred catfish tissue (81) and of cephapirin, furosemide, and methylene blue in milk, kidney, and muscle tissue, respectively (82). Results showed that the mobile-phase composition, nebulization-de-solvation, and source temperature all play an important role in the sensitivity of the method. The sensitivity increases with decreasing heat capacity of the mobile phase in the order methanol acetonitrile isopropanol water and with decreasing flow rate. A comparison of the PB with the thermospray interface showed that less structural information was provided by the latter, whereas the sensitivity was generally lower with the thermospray interface. 

In the thermospray interface, aqueous mobile phases containing an electrolyte such as ammonium acetate are passed at flow rates of 1-2 ml/min through a heated capillary prior entering a heated ion source. The end of the capillary lies opposite a vacuum line. Nebulization takes place as a result of the disruption of the liquid by the expanding vapor formed at the capillary wall upon evaporation of part of the liquid in the capillary. This results in formation of a supersonic jet of vapor containing a mist of fine, electrically charged droplets. 

The APCI interface uses a heated nebulizer to form a fine spray of the HPLC eluate, which is much finer than the particle beam system but similar to that formed during thermospray. A cross-flow of heated nitrogen gas is used to facilitate the evaporation of solvent from the droplets. The resulting gas-phase sample molecules are ionized by collisions with solvent ions, which are formed by a corona discharge in the atmospheric pressure chamber. Molecular ions, M+ or M , and/or protonated or de-protonated molecules can be formed. The relative abundance of each type of ion depends upon the sample itself, the HPLC solvent, and the ion source parameters. Next, ions are drawn into the mass spectrometer analyzer for measurement through a narrow opening or skimmer, which helps the vacuum pumps to maintain very low pressure inside the analyzer while the APCI source remains at atmospheric pressure. 

Elgersma, J.W., Balke, J. and Maessen, F.J.M.J. (1991) The performance of a low consumption thermospray nebulizer for specific use in micro-HPLC and general use in FI with ICP-AES detection. Spectrochim. Acta, 46B, 1073-1088. 

Saverwyno, S., Zhang, X., Vanhaeke, F., Comelis, R., Moens, L. and Dams, R. (1997) Speciation of six arsenic compounds using high-performance liquid chromatography-inductively coupled plasma mass spectrometry with sample introduction by thermospray nebulization.J. Anal. At. Spectrom., 12, 1047-1052. 

Several cfPcicnt sample introduction systems have been conceived to achieve higher precision, accuracy, and sensitivity, such as thermospray nebulization (TN) [95], ETV [88, 99], and hydraulic high pressure nebulization. The use of desolva-tation devices, for example, ultrasonic nebulization (UN), in combination with... 

M. Parent, H. Vanhoe, L. Moens, R. Dams, Determination of low amounts of platinum in environmental and biological materials using thermospray nebulization inductively coupled plasma-mass spectrometry, Fresenius J. Anal. Chem., 354 (1996), 664D667. 

M.B. Denton, J.M. Freeiin and T.R. Smith, Ultrasonic, Babington and Thermospray Nebulization, in J. Sneddon (Ed.), Sample Introduction in Atomic Spectroscopy, Elsevier, Amsterdam, 1988. 

Nebulization ionization is the process involved in the analyte ionization in thermospray [16] and electrospray [17] interfacing. No primary ionization, i.e., a filament or a discharge electrode, is applied. The ionization mechanism is not fully understood (Ch. 6.3). The general understanding can be snmmarized as follows Upon nebulization, charged droplets of a few pm ID are generated. The fate of these droplets is determined by a nnmber of competing processes, the relative importance of which may dependent on the natnre of the analyte ... 

Over 30 years of liquid chromatography-mass spectrometry (LC-MS) research has resulted in a considerable number of different interfaces (Ch. 3.2). A variety of LC-MS interfaces have been proposed and built in the various research laboratories, and some of them have been adapted by instmment manufacturers and became commercially available. With the advent in the early 1990 s of interfaces based on atmospheric-pressure ionization (API), most of these interfaces have become obsolete. However, in order to appreciate LC-MS, one carmot simply ignore these earlier developments. This chapter is devoted to the older LC-MS interfaces, which is certainly important in understanding the histoiy and development of LC-MS. Attention is paid to principles, instrumentation, and application of the capillary inlet, pneumatic vacuum nebulizers, the moving-belt interface, direct liquid introduction, continuous-flow fast-atom bombardment interfaces, thermospray, and the particle-beam interface. More elaborate discussions on these interfaces can be found in previous editions of this book. 

The thermospray (TSP) interface is widely used for the determination of drug residues in foods. Thermospray is typically used with reversed-phase columns and volatile buffers. Aqueous mobile phases containing an electrolyte, such as ammonium acetate, are passed through a heated capillary prior to entering a heated ion source. As the end of the capillary lies opposite a vacuum line, nebulization takes place and a jet of vapor containing a mist of electrically charged droplets is formed. As the droplets move through the hot source area, they continue to vaporize, and ions present in the eluent are ejected from the droplet and... 

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