Nebulizations

The sample to be analyzed can be dissolved in an organic solvent, xylene or methylisobutyl ketone. Generally, for reasons of reproducibility and because of matrix effects (the surroundings affect the droplet size and therefore the effectiveness of the nebulization process), it is preferable to mineralize the sample in H2SO4, evaporate it and conduct the test in an aqueous environment. 

The detectable limits are given for samples such as they are introduced into the apparatus they should be previously diluted in order to be nebulized. It thereby is useful to apply a dilution coefficient, usually at least 10. The dilution depends on the sample viscosity. 

The sample should be liquid or in solution. It is pumped and nebulized in an argon atmosphere, then sent through a plasma torch that is, in an environment where the material is strongly ionized resulting from the electromagnetic radiation produced by an induction coil. Refer to the schematic diagram in Figure 2.8. 

Data for the several flame methods assume an acetylene-nitrous oxide flame residing on a 5- or 10-cm slot burner. The sample is nebulized into a spray chamber placed immediately ahead of the burner. Detection limits are quite dependent on instrument and operating variables, particularly the detector, the fuel and oxidant gases, the slit width, and the method used for background correction and data smoothing. 

Flame atomization assembly equipped with spray chamber and slot burner. The inset shows the nebulizer assembly. 

Precision For absorbances greater than 0.1-0.2, the relative standard deviation for atomic absorption is 0.3-1% for flame atomization, and 1-5% for electrothermal atomization. The principal limitation is the variation in the concentration of free-analyte atoms resulting from a nonuniform rate of aspiration, nebulization, and atomization in flame atomizers, and the consistency with which the sample is heated during electrothermal atomization. 

Flame Sources Atomization and excitation in flame atomic emission is accomplished using the same nebulization and spray chamber assembly used in atomic absorption (see Figure 10.38). The burner head consists of single or multiple slots or a Meker-style burner. Older atomic emission instruments often used a total consumption burner in which the sample is drawn through a capillary tube and injected directly into the flame. 

The liquid (solvent) that is nebulized should be polar (e.g., water, acetic acid). 

Additional ionization is effected by including radioactive substances or plasma or glow discharges in the evaporation chamber or by electrical charging of the nebulizer. Such techniques are also discussed in Chapters 8 and 11. 

A solution of an analyte in a solvent can be sprayed (nebulized) from an electrically charged narrow tube to give small electrically charged droplets that desorb solvent molecules to leave ions of the analyte. This atmospheric-pressure ionization is known in various forms, the one most relevant to this section being called electrospray. For additional detail, see Chapters 8, 9, and 11. 

As a first stage, the stream of liquid from an HPLC eluant is passed through a narrow tube toward the LINC interface. Near the end of the tube, the liquid stream is injected with helium gas so that it leaves the end of the tube as a high-velocity spray of small drops of liquid mixed with helium. From there, the mixture enters an evacuation chamber (Figure 12.1). The formation of spray (nebulizing) is very similar to that occurring in the action of aerosol spray cans (see Chapter 19). 

A typical arrangement for producing a particle beam from a stream of liquid, showing (1) the nebulizer, (2) the desolvation chamber, (3) the wall heater, (4) the exit nozzle, (5, 6) skimmers 1, 2, (7) the end of the ion source, (8) the ion source, and (9) the mass analyzer. An optional GC inlet into the ion source is shown. 

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... 

Suitable inlets commonly used for liquids or solutions can be separated into three major classes, two of which are discussed in Parts A and C (Chapters 15 and 17). The most common method of introducing the solutions uses the nebulizer/desolvation inlet discussed here. For greater detail on types and operation of nebulizers, refer to Chapter 19. Note that, for all samples that have been previously dissolved in a liquid (dissolution of sample in acid, alkali, or solvent), it is important that high-purity liquids be used if cross-contamination of sample is to be avoided. Once the liquid has been vaporized prior to introduction of residual sample into the plasma flame, any nonvolatile impurities in the liquid will have been mixed with the sample itself, and these impurities will appear in the results of analysis. The problem can be partially circumvented by use of blanks, viz., the separate examination of levels of residues left by solvents in the absence of any sample. 

The nebulization concept has been known for many years and is commonly used in hair and paint spays and similar devices. Greater control is needed to introduce a sample to an ICP instrument. For example, if the highest sensitivities of detection are to be maintained, most of the sample solution should enter the flame and not be lost beforehand. The range of droplet sizes should be as small as possible, preferably on the order of a few micrometers in diameter. Large droplets contain a lot of solvent that, if evaporated inside the plasma itself, leads to instability in the flame, with concomitant variations in instrument sensitivity. Sometimes the flame can even be snuffed out by the amount of solvent present because of interference with the basic mechanism of flame propagation. For these reasons, nebulizers for use in ICP mass spectrometry usually combine a means of desolvating the initial spray of droplets so that they shrink to a smaller, more uniform size or sometimes even into small particles of solid matter (particulates). 

Nebulizers can be divided into several main types. The pneumatic forms work on the principle of breaking up a stream of liquid into droplets by mechanical means the liquid stream is forced through a fine nozzle and breaks up into droplets. There may be a concentric stream of gas to aid the formation of small droplets. The liquid stream can be directed from a fine nozzle at a solid target so that, on impact, the narrow diameter stream of liquid is broken into many tiny droplets. There are variants on this approach, described in the chapter devoted to nebulizers (Chapter 19). 

These factors make it necessary to reduce the amount of solvent vapor entering the flame to as low a level as possible and to make any droplets or particulates entering the flame as small and of as uniform a droplet size as possible. Desolvation chambers are designed to optimize these factors so as to maintain a near-constant efficiency of ionization and to flatten out fluctuations in droplet size from the nebulizer. Droplets of less than 10 pm in diameter are preferred. For flow rates of less than about 10 pl/min issuing from micro- or nanobore liquid chromatography columns, a desolvation chamber is unlikely to be needed. 

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. 

Solutions can be examined by ICP/MS by (a) removing the solvent (direct and electrothermal methods) and then vaporizing residual sample solute or (b) nebulizing the sample solution into a spray of droplets that is swept into the plasma flame after passing through a desolvation chamber, where excess solvent is removed. The direct and electrothermal methods are not as convenient as the nebulization inlets for multiple samples, but the former are generally much more efficient in transferring samples into the flame for analysis. 

In some cases, it may be convenient to dissolve a solid and present it for analysis as a solution that can be nebulized and sprayed as an aerosol (mixed droplets and vapor) into the plasma flame. This aspect of analysis is partly covered in Part B (Chapter 16), which describes the introduction of solutions. There are vaporization techniques for solutions of solids other than nebulization, but since these require prior evaporation of the solvent, they are covered here. There are also many solid samples that need to be analyzed directly, and this chapter describes commonly used methods to do so. 

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. 

The term nebulizer is used generally as a description for any spraying device, such as the hair spray mentioned above. It is normally applied to any means of forming an aerosol spray in which a volume of liquid is broken into a mist of vapor and small droplets and possibly even solid matter. There is a variety of nebulizer designs for transporting a solution of analyte in droplet form to a plasma torch in ICP/MS and to the inlet/ionization sources used in electrospray and mass spectrometry (ES/MS) and atmospheric-pressure chemical ionization and mass spectrometry (APCI/MS). 

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