Direct solids nebulizer

Fig. 70. Direct solids nebulizer. (Reprinted with permission from Ref. [242].)...

Solid foods in powder form can be analyzed directly by means of LA- or ETV-ICP-MS to eliminate time-consuming sample dissolution procedures (see Table 8.2). However, this requires the preparation of homogeneous powdered samples and the subsequent analytical determination is not as straightforward as the one based on liquid sample introduction. Another way to perform direct analysis of solid foods is to grind and suspend them into slurries. The viability of slurry nebulization relies on the ability to prepare samples of fine particle size in a reproducible manner and on the adoption of suitable (e.g., high-solids) nebulizers. Otherwise, slurries can be analyzed by ETV-ICP-MS resorting to the ultrasonic slurry sampling technique [72-74]. 

For oil analysis both flame AAS as well as graphite furnace AAS are important. In the first case nebulizers tolerating suspended particles can be used and in the case of graphite furnace AAS direct solids sampling may be useful so as to avoid the need for sample dissolution as well as to allow coarse metal particles present in used engine oils to be dealt with. 

Sea water and other saline waters pose some problems for the atomization methods. Nebulizers for the ICP tend to become blocked with salt encrustations with a disastrous effect on sensitivity. This can be overcome in direct analysis by flow injection techniques, or by the use of high-solids nebulizers. Dilution also helps here but, of course, degrades the detection limits. The sampling cone in ICPMS equipment is also prone to be gradually occluded when... 

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). 

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. 

For solids, there is now a very wide range of inlet and ionization opportunities, so most types of solids can be examined, either neat or in solution. However, the inlet/ionization methods are often not simply interchangeable, even if they use the same mass analyzer. Thus a direct-insertion probe will normally be used with El or Cl (and desorption chemical ionization, DCl) methods of ionization. An LC is used with ES or APCI for solutions, and nebulizers can be used with plasma torches for other solutions. MALDI or laser ablation are used for direct analysis of solids. 

For the majority of applications, the sample is taken into solution and introduced into the plasma as an aerosol in the argon stream. The sample solution is pumped by a peristaltic pump at a fixed rate and converted into an aerosol by a nebulizer (see atomic absorption spectrometry). Various designs of nebulizer are in use, each having strengths and weaknesses. The reader is directed to the more specialist texts for a detailed consideration of nebulizers. There is an obvious attraction in being able to handle a solid directly, and sample volatilization methods using electric spark ablation, laser ablation and electrothermal volatilization have also been developed. 

The digestion of solid samples to produce a solution is discussed in Section 13.2. For solution-based ICP MS analysis, the liquid is taken up through a thin tube via a peristaltic pump. This feeds directly into the instrument nebulizer, where argon gas is introduced into the liquid and a fine mist of droplets is expelled from the tip of the nebulizer. This sample aerosol is sprayed into the condenser to reduce the size of the droplets, ensuring an even sample loading and preventing cooling of the plasma. About 1% of the sample solution uptake is transported to the plasma torch, and any unused solution is drained away and may be recycled. 

When using PFT with a neutral selector, it is quite difficult to avoid any entrance of the chiral selector into the ionization source, particularly at a high pH, where EOF is important. The use of BGE at low pH and/or coated capillary to minimize EOF is therefore mandatory. However, the coaxial sheath gas, which generally assists the ionization process, leads to an aspirating phenomenon of the chiral selector in the MS direction. Javerfalk et al. were the first to apply PFT with a neutral methyl-/i-CD for the separation of racemic bupivacaine and ropivacaine with a polyacrylamide-coated capillary and an acidic pH buffer (pH 3). Cherkaoui et al. employed another neutral CD (HP-/1-CD) with a PVA-coated capillary for the analysis of amphetamines and their derivatives. To prevent a detrimental aspiration effect, analyses were carried out without nebulization pressure. Numerous other studies presented excellent results such as the enantioselective separation of adrenoreceptor antagonist drugs using tandem mass spectrometry (MS/MS) the separation of clenbuterol enantiomers after solid-phase extraction (SPE) of plasma samples or the use of CD dual system for the simultaneous chiral determination of amphetamine, methamphetamine, dimethamphetamine, and p-hydroxymethamphetamine in urine. 

Atomization—Liquid aerosols of readily melted solids may be generated by direct atomization using, for example, a pneumatic nebulizer such as the Collision. When a pneumatic atomizer is used, the aerosol concentration may be varied by changing the pressure of the atomizer air supply. The mass median diameter of the aerosols produced by the small pneumatic nebulizer is typically in the micrometer range. The direct atomization method was applied to dimethyl-phthalate, a liquid, and dibutyl phosphate, a low-melting solid. 

The introduction of inductively coupled plasma (ICP) in inorganic mass spectrometry means that there is an effective ion source operating at atmospheric pressure. Whereas solid mass spectrometric techniques allow direct analysis of solid samples in ICP-MS, the determination of trace impurities or isotope ratios in solid samples is often carried out after digestion and dissolution of the material. For the determination of trace impurities and isotope ratios in liquids, an additional nebulization... 

Most flame spectrometers use a premix burner, such as that in Figure 21-5, in which fuel, oxidant, and sample are mixed before introduction into the flame. Sample solution is drawn into the pneumatic nebulizer by the rapid flow of oxidant (usually air) past the tip of the sample capillary. Liquid breaks into a fine mist as it leaves the capillary. The spray is directed against a glass bead, upon which the droplets break into smaller particles. The formation of small droplets is termed nebulization. A fine suspension of liquid (or solid) particles in a gas is called an aerosol. The nebulizer creates an aerosol from the liquid sample. The mist, oxi-... 

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. 

The method of sample preparation to be used for a given analysis is governed by the nature and concentration of the analyte, the nature (solid or liquid) and type of matrix, the available sample amount, and also by the instrumental technique employed. Freeze-dried samples will require some form of digestion or dissolution in order to be analyzed by a classic atomic technique (i.e., using nebuliza-tion). Liquids might be analyzed by direct nebulization, but this is not always possible due to matrix interferences. Milk pretreatment may be necessary under such circumstances. 

These direct ion sources exist under two types liquid-phase ion sources and solid-state ion sources. In liquid-phase ion sources the analyte is in solution. This solution is introduced, by nebulization, as droplets into the source where ions are produced at atmospheric pressure and focused into the mass spectrometer through some vacuum pumping stages. Electrospray, atmospheric pressure chemical ionization and atmospheric pressure photoionization sources correspond to this type. In solid-state ion sources, the analyte is in an involatile deposit. It is obtained by various preparation methods which frequently involve the introduction of a matrix that can be either a solid or a viscous fluid. This deposit is then irradiated by energetic particles or photons that desorb ions near the surface of the deposit. These ions can be extracted by an electric field and focused towards the analyser. Matrix-assisted laser desorption, secondary ion mass spectrometry, plasma desorption and field desorption sources all use this strategy to produce ions. Fast atom bombardment uses an involatile liquid matrix. 

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