The Plasma Torch

FIGURE 4.1 ICP-MS system showing location of the plasma torch and RF power supply. 

FIGURE 4.2 Detailed view of plasma torch and RF coil relative to the ICP-MS interface. 

FIGURE 4.3 Photograph of a plasma torch mounted in an instrument. (Courtesy of PerkinElmer, Inc., 2003-2012. All rights reserved. With permission.) 

FIGURE 4.4 A fully demountable ceramic torch. (Courtesy of Glass Expansion, Inc.) 

Ceramic components are also available for most ICP-MS torches. The outer, inner, and sample injector tubes are normally made of quartz, but for some applications, it is beneficial to consider using an alternative material such as ceramic. And if a demountable torch is being used, any or all of the tubes can be replaced. Some of the applications that might benefit from a ceramic torch include  

Practical Guide to ICP-MS A Tutorial for Beginners, Second Edition 

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The degree of ionization increases with temperature, and at 6000-8000 K, where ionization efficiencies are 90 to 95%, nearly all atoms exist as ions in the plasma. Operation of the plasma torch under conditions that produce a cooler flame (cold plasma) has important advantages for some applications, which are discussed after the next section. 

Fundamentally, introduction of a gaseous sample is the easiest option for ICP/MS because all of the sample can be passed efficiently along the inlet tube and into the center of the flame. Unfortunately, gases are mainly confined to low-molecular-mass compounds, and many of the samples that need to be examined cannot be vaporized easily. Nevertheless, there are some key analyses that are carried out in this fashion the major one i.s the generation of volatile hydrides. Other methods for volatiles are discussed below. An important method of analysis uses lasers to vaporize nonvolatile samples such as bone or ceramics. With a laser, ablated (vaporized) sample material is swept into the plasma flame before it can condense out again. Similarly, electrically heated filaments or ovens are also used to volatilize solids, the vapor of which is then swept by argon makeup gas into the plasma torch. However, for convenience, the methods of introducing solid samples are discussed fully in Part C (Chapter 17). 

The volatile hydride (arsine in Equation 15.1) is swept by a. stream of argon gas into the inlet of the plasma torch. The plasma flame decomposes the hydride to give elemental ions. For example, arsine gives arsenic ions at m/z 75. The other elements listed in Figure 15.2 also yield volatile hydrides, except for mercury salts which are reduced to the element (Fig), which is volatile. In the plasma flame, the arsine of Equation 15.1 is transformed into As ions. The other elements of Figure 15.2 are converted similarly into their elemental ions. 

These direct-insertion devices are often incorporated within an autosampling device that not only loads sample consecutively but also places the sample carefully into the flame. Usually, the sample on its electrode is first placed just below the load coil of the plasma torch, where it remains for a short time to allow conditions in the plasma to restabilize. The sample is then moved into the base of the flame. Either this last movement can be made quickly so sample evaporation occurs rapidly, or it can be made slowly to allow differential evaporation of components of a sample over a longer period of time. The positioning of the sample in the flame, its rate of introduction, and the length of time in the flame are all important criteria for obtaining reproducible results. 

Synthetic fused siUcas with low OH levels have also been made experimentally using a CO2 laser instead of the plasma torch (62,63). The glass rate of this process, however, is at least 10 times slower than the plasma approach. 

An ICP-OES instrument consists of a sample introduction system, a plasma torch, a plasma power supply and impedance matcher, and an optical measurement system (Figure 1). The sample must be introduced into the plasma in a form that can be effectively vaporized and atomized (small droplets of solution, small particles of solid or vapor). The plasma torch confines the plasma to a diameter of about 18 mm. Atoms and ions produced in the plasma are excited and emit light. The intensity of light emitted at wavelengths characteristic of the particular elements of interest is measured and related to the concentration of each element via calibration curves. 

The sensitivity, accuracy, and precision of solid-sample analysis have been greatly improved by coupling LA with ICP-OES-MS. The ablated species are transported by means of a carrier gas (usually argon) into the plasma torch. Further atomization, excitation, and ionization of the ablated species in the stationary hot plasma result in a dramatic increase in the sensitivity of the detection of radiation (LA-ICP-OES) or of the detection of ions (LA-ICP-MS). 

In ICP-AES and ICP-MS, sample mineralisation is the Achilles heel. Sample introduction systems for ICP-AES are numerous gas-phase introduction, pneumatic nebulisation (PN), direct-injection nebulisation (DIN), thermal spray, ultrasonic nebulisation (USN), electrothermal vaporisation (ETV) (furnace, cup, filament), hydride generation, electroerosion, laser ablation and direct sample insertion. Atomisation is an essential process in many fields where a dispersion of liquid particles in a gas is required. Pneumatic nebulisation is most commonly used in conjunction with a spray chamber that serves as a droplet separator, allowing droplets with average diameters of typically <10 xm to pass and enter the ICP. Spray chambers, which reduce solvent load and deal with coarse aerosols, should be as small as possible (micro-nebulisation [177]). Direct injection in the plasma torch is feasible [178]. Ultrasonic atomisers are designed to specifically operate from a vibrational energy source [179]. 

Applications Over the last 20 years, ICP-AES has become a widely used elemental analysis tool in many laboratories, which is also used to identify/quantify emulsifiers, contaminants, catalyst residues and other inorganic additives. Although ICP-AES is an accepted method for elemental analysis of lubricating oils (ASTM D 4951), often, unreliable results with errors of up to 20% were observed. It was found that viscosity modifier (VM) polymers interfere with aerosol formation, a critical step in the ICP analysis, thus affecting the sample delivery to the plasma torch [193]. Modifications... 

The DC plasma was introduced as an excitation source for atomic emission spectrometry by Margoshes and Scribner [721] and Korolev and Vainshtein [722], Modified designs have been characterised by a number of other authors [614,719-729]. Commercial equipment is now available from several manufacturers. The principle of the plasma torch arrangement used in these instruments is illustrated in Fig. 5.21 [730]. 

The plasma torch is usually mounted on a circular end wall. The torch is aligned in such a way that waste material falls into the hot zone of the plasma arc. The torch cathode and anode are cooled by forced water flow. In addition, auxiliary cooling of the anode with air can be incorporated in the plasma torch. 

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. 

In either case, a stream of argon gas carries the sample into the plasma torch, where it is ionized at high temperature and injected into the quadrupole mass selector. 

Kleinmann and Svoboda [42] reported direct vaporization of samples into a low-power ICP source from a graphite disc support mounted directly within the body of the plasma torch. Nixon et al. [43] described the use of a tantalum filament electrothermal... 

The plasma torch is a simple device that can reach temperatures of up to 8 000 K. Any element introduced into the torch will start to emit. By comparison, flames used in flame photometry are relatively cool. 

Besides plasmas, which are at the forefront of thermal atomisation devices, other excitation processes can be used. These methods rely on sparks or electrical arcs. They are less sensitive and take longer to use than methods that operate with samples in solution. These excitation techniques, with low throughputs, are mostly used in semi-quantitative analysis in industry (Fig. 15.2). Compared to the plasma torch, thermal homogeneity in these techniques is more difficult to master. 

Mass bias—the condition in which ions of different masses are sampled by the detector at frequencies varying from their expected proportions—is thought to be a result of space-charge effects in the high pressure region immediately downstream of the plasma torch (15). 

There is also a standard test method for determination of major and minor elements in coal ash by inductively coupled plasma (ICP)-atomic emission spectrometry (ASTM D-6349). In the test method, the sample to be analyzed is ashed under standard conditions and ignited to constant weight. The ash is fused with a fluxing agent followed by dissolution of the melt in dilute acid solution. Alternatively, the ash is digested in a mixture of hydrofluoric, nitric, and hydrochloric acids. The solution is analyzed by (ICP)-atomic emission spectrometry for the elements. The basis of the method is the measurement of atomic emissions. Aqueous solutions of the samples are nebulized, and a portion of the aerosol that is produced is transported to the plasma torch, where excitation and emission occurs. Characteristic line emission spectra are produced by a radio-frequency inductively coupled plasma. A grating monochromator system is used to separate the emission lines, and the intensities of the lines are monitored by photomultiplier tube or photodiode array detection. The photocurrents from the detector... 

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