Thermospray

Thermospray (TSP) [29-31] unites three modes of operation. In pure TSP, a solution of the analyte and a volatile buffer, usually 0.1 M ammonium acetate, is evaporated from a heated capillary at a flow rate of 1-2 ml min into a heated chamber, hence the term thermospray. As the solvent evaporates, the analyte is forming adducts with ions from the buffer salt. While most of the neutrals are removed by a vacuum pump, the ions are extracted orthogonally from their main axis of motion by use of an electrostatic potential. The ions are transferred into a quadrupole mass analyzer through a pinhole of about 25 pm in diameter (Fig. 11.2). The quadrupole was employed according to its tolerance to poor vac- 

Note Thermospray is not a true API method because the liquid is sprayed into a vacuum of several hundred Pa instead of spraying at atmospheric pressure. 

Again a quadrupole is eiiployed due to its tolerance to poor vacuum conditions. As the pure TSP mode only works with high-polarity solvents in the presence of a buffer salt, modified modes of operation were developed to expand the use of TSP ion sources to lower-polarity systems /) use of an electrical discharge in the vapor phase [35] or ii) an electron-emitting filament as used in El (Chap. 5) or Cl (Chap. 7). With this added versatility, TSP meant a breakthrough for LC-MS [36]. Nonetheless, with the advent of ESI, TSP interfaces vanished rather quickly from the laboratories. 

Diagram of a thermospray source. The chromatographic effluent comes in at (a) the transfer line is suddenly heated at (b) and the spray is formed under vacuum at (c). At (d) the spray goes between a pusher with a positive potential and a negative cone for positive ions. The ions are thus extracted from the spray droplets and accelerated towards the spectrometer (f). At (e), a high-capacity pump maintains the vacuum. 

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For a more detailed description of the ionization process inherent in electrospray, please see Chapter 9, which discusses atmospheric pressure ionization (API), The reader also should compare electrospray with thermospray (see Chapter 11). 

The advent of atmospheric-pressure ionization (API) provided a method of ionizing labile and nonvolatile substances so that they could be examined by mass spectrometry. API has become strongly linked to HPLC as a basis for ionizing the eluant on its way into the mass spectrometer, although it is also used as a stand-alone inlet for introduction of samples. API is important in thermospray, plasmaspray, and electrospray ionization (see Chapters 8 and 11). 

In many applications in mass spectrometry (MS), the sample to be analyzed is present as a solution in a solvent, such as methanol or acetonitrile, or an aqueous one, as with body fluids. The solution may be an effluent from a liquid chromatography (LC) column. In any case, a solution flows into the front end of a mass spectrometer, but before it can provide a mass spectrum, the bulk of the solvent must be removed without losing the sample (solute). If the solvent is not removed, then its vaporization as it enters the ion source would produce a large increase in pressure and stop the spectrometer from working. At the same time that the solvent is removed, the dissolved sample must be retained so that its mass spectrum can be measured. There are several means of effecting this differentiation between carrier solvent and the solute of interest, and thermospray is just one of them. Plasmaspray is a variant of thermospray in which the basic method of solvent removal is the same, but the number of ions obtained is enhanced (see below). 

Schematic diagram of a thermospray ion. source. This source, of current design, also incorporates (a) a discharge electrode so that the source can be operated in plasmaspray mode and (h) a repeller electrode to induce fragmentation. The vaporizer itself can be used as a discharge electrode.

The thermospray process extracts sample molecules from a solvent and turns them into ions. Therefore, the system is both an inlet and an ion source, so a separate ion source is not necessary. 

The thermospray inlet/ion source does not produce a good percentage yield of ions from the original sample, even with added salts (Figure 11.2). Often the original sample is present in very tiny amounts in the solution going into the thermospray, and the poor ion yield makes the thermo-spray/mass spectrometer a relatively insensitive combination when compared with the sensitivity attainable by even quite a modest mass spectrometer alone. Various attempts have been made to increase the ion yield. One popular method is described here. 

Most of the ions produced by either thermospray or plasmaspray (with or without the repeller electrode) tend to be very similar to those formed by straightforward chemical ionization with lots of protonated or cationated positive ions or negative ions lacking a hydrogen (see Chapter l).This is because, in the first part of the inlet, the ions continually collide with neutral molecules in the early part of their transit. During these collisions, the ions lose excess internal energy. 

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. 

The thermospray device produces a wide dispersion of droplet sizes and transfers much of sample solution in unit time to the plasma flame. Therefore, it is essential to remove as great a proportion of the bigger droplets and solvent as possible to avoid compromising the flame performance. Consequently, the thermospray device usually requires both spray and desolvation chambers, especially for analyte solutions in organic solvents. 

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. 

The LC/TOF instmment was designed specifically for use with the effluent flowing from LC columns, but it can be used also with static solutions. The initial problem with either of these inlets revolves around how to remove the solvent without affecting the substrate (solute) dissolved in it. Without this step, upon ionization, the large excess of ionized solvent molecules would make it difficult if not impossible to observe ions due only to the substrate. Combined inlet/ionization systems are ideal for this purpose. For example, dynamic fast-atom bombardment (FAB), plas-maspray, thermospray, atmospheric-pressure chemical ionization (APCI), and electrospray (ES)... 

This method is still in use but is not described in this book because it has been superseded by more recent developments, such as particle beam and electrospray. These newer techniques have no moving parts, are quite robust, and can handle a wide variety of compound types. Chapters 8 through 13 describe these newer ionization techniques, including electrospray, atmospheric pressure ionization, plasmaspray, thermospray, dynamic fast-atom bombardment (FAB), and particle beam. 

To achieve sufficient vapor pressure for El and Cl, a nonvolatile liquid will have to be heated strongly, but this heating may lead to its thermal degradation. If thermal instability is a problem, then inlet/ionization systems need to be considered, since these do not require prevolatilization of the sample before mass spectrometric analysis. This problem has led to the development of inlet/ionization systems that can operate at atmospheric pressure and ambient temperatures. Successive developments have led to the introduction of techniques such as fast-atom bombardment (FAB), fast-ion bombardment (FIB), dynamic FAB, thermospray, plasmaspray, electrospray, and APCI. Only the last two techniques are in common use. Further aspects of liquids in their role as solvents for samples are considered below. 

Thermospray is both a liquid inlet system for a mass spectrometer and, at the same time, an ionization source. 

Plasmaspray, or discharge-assisted thermospray, is a modification of thermospray in which the degree of ionization has been enhanced. 

As the name implies, thermospray uses heat to produce a spray of fine droplets. Plasmaspray does not produce the spray by using a plasma but, rather, the droplets are produced in a thermospray source and a plasma or corona is used afterward to increase the number of ions produced. 

Although this system is simple with no moving parts, unfortunately not many ions from the original dissolved sample are produced, and the thermospray inlet/ion source is not very sensitive considering the achievable sensitivities of standard mass spectrometers. 

To increase the number of ions, a plasma or corona discharge is produced in the mist issuing from the capillary. The electrical discharge induces more ionization in the neutrals accompanying the few thermospray ions. This enhancement increases the ionization of sample molecules and makes the technique much more sensitive to distinguish it from simple thermospray, it is called plasmaspray. 

Thermospray and plasmaspray can be used with both sector and quadrupole instruments. They have been used extensively to couple liquid chromatographs to mass spectrometers. 

A sample to be examined by thermospray is passed as a solution in a solvent (made up separately or issuing from a liquid chromatographic column) through a capillary tube that is strongly heated at its end, so the solution vaporizes and emerges as a spray or mist of droplets. As the droplets... 

LC can be combined with all kinds of mass spectrometers, but for practical reasons only quadrapolar, magnetic/electric-sector, and TOP instruments are in wide use. A variety of interfaces are used, including thermospray, plasmaspray, electrospray, dynamic fast-atom bombardment (FAB), particle beam, and moving belt. 

Thermospray interface. Provides liquid chromatographic effluent continuously through a heated capillary vaporizer tube to the mass spectrometer. Solvent molecules evaporate away from the partially vaporized liquid, and analyte ions are transmitted to the mass spectrometer s ion optics. The ionization technique must be specified, e.g., preexisting ions, salt buffer, filament, or electrical discharge. 

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