Pneumatic nebulisers

The obvious alternative for the in-line flow-through cell in HPLC-FTIR is mobile-phase elimination ( transport interfacing), first reported in 1977 [495], and now the usual way of carrying out LC-FTIR, in particular for the identification of (minor) constituents of complex mixtures. Various spray-type LC-FTIR interfaces have been developed, namely, thermospray (TSP) [496], particle-beam (PB) [497,498], electrospray (ESP) [499] and pneumatic nebulisers [486], as compared by Som-sen et al. [500]. The main advantage of the TSP-based... 

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]. 

In Figure 8.12, the basic set-up of an ICP-MS instrument is presented as a block diagram, consisting of a sample introduction system, the inductively coupled argon plasma (ICP) and the mass-specific detector. By far the most commonly applied sample introduction technique is a pneumatic nebuliser, in which a stream of argon (typically 1 I.min ), expanding with high... 

The extension of inductively coupled plasma (ICP) atomic emission spectrometry to seawater analysis has been slow for two major reasons. The first is that the concentrations of almost all trace metals of interest are 1 xg/l or less, below detection limits attainable with conventional pneumatic nebulisation. The second is that the seawater matrix, with some 3.5% dissolved solids, is not compatible with most of the sample introduction systems used with ICP. Thus direct multielemental trace analysis of seawater by ICP-AES is impractical, at least with pneumatic nebulisation. In view of this, a number of alternative strategies can be considered ... 

The on-line interface of flow manifolds to continuous atomic spectrometric detectors for direct analysis of samples in liquid form typically requires a nebuliser and a spray chamber to produce a well-defined reproducible aerosol, whose small droplets are sent to the atomisation/ionisation system. A variety of nebulisers have been described for FAAS or ICP experiments, including conventional cross-flow, microconcentric or Babington-type pneumatic nebulisers, direct injection nebuliser and ultrasonic nebulisers. As expected, limits of detection have been reported to be generally poorer for the FIA mode than for the continuous mode. 

On-line coupling between a gas chromatograph and an atomic spectrometry detector is fairly simple. Typically, the output of the CG capillary column is connected to the entrance of the atomisation-ionisation system simply via a heated transfer line. When separation is performed by liquid chromatography (EC), the basic interface is straightforward a piece of narrow-bore tubing connects the outlet of the EC column with the liquid flow inlet of the nebuliser. Typical EC flow rates of 0.5-2 ml min are within the range usually required for conventional pneumatic nebulisation. 

An atomic fluorescence spectrometric determination of selenium was first reported by Dagnall et al. [185] using a dispersive spectrometer equipped with an air-propane flame, giving a detection limit of 0.25 xg/ml of selenium on aspiration of aqueous solutions using a pneumatic nebuliser. Fluorescence from the 204 nm selenium resonance line was observed when the flame was irradiated by radiation from a selenium electrodeless discharge lamp, the optical axis of which was aligned at 90 °C to the optical axis of the monochromator. 

Schramel [103] discusses the conditions for multi-element analysis of over 50 trace elements, giving detection limits. Wolnik [104] described a sample introduction system that extends the analytical capability of the inductively coupled argon plasma/polychromator to include the simultaneous determination of six elemental hydrides along with a variety of other elements in plant materials. Detection limits for arsenic, bismuth, selenium and tellurium range from 0.5 to 3 ng/ml and are better by at least an order of magnitude than those obtained with conventional pneumatic nebulisers, whereas detection limits for the other elements investigated remain the same. Results from the analysis of freeze-dried crop samples and NBS standard reference materials demonstrated the applicability of the technique. Results obtained by the analysis of a variety of plant materials are presented in Table 7.10. 

A heated pneumatic nebuliser is used to produce the aerosol in APCI and the ions are produced by ion-molecule reactions initiated by corona discharges in the ion source region. White et al. (1998) found atmospheric pressure ionisation MS and LC-ICP-MS to be complementary techniques. 

In thermospray interfaces, the column effluent is rapidly heated in a narrow bore capillary to allow partial evaporation of the solvent. Ionisation occurs by ion-evaporation or solvent-mediated chemical ionisation initiated by electrons from a heated filament or discharge electrode. In the particle beam interface the column effluent is pneumatically nebulised in an atmospheric pressure desolvation chamber this is connected to a momentum separator where the analyte is transferred to the MS ion source and solvent molecules are pumped away. Magi and Ianni (1998) used LC-MS with a particle beam interface for the determination of tributyl tin in the marine environment. Florencio et al. (1997) compared a wide range of mass spectrometry techniques including ICP-MS for the identification of arsenic species in estuarine waters. Applications of HPLC-MS for speciation studies are given in Table 4.3. 

Figure 1 Schematic of the nebuliser reactor for the Cu-CI hydrolysis experiments. The pneumatic nebuliser is represented at the top of the reactor.

Figure 3 Effect of different Ar flow rates through the pneumatic nebuliser...

While possible to obtain satisfactory products with the pneumatic nebuliser, the experimental difficulties due to clogging and the strong dependence on many interrelated variables indicated that another type of atomiser should be investigated. An ultrasonic nozzle, in which high frequency electrical energy is converted into vibratory mechanical motion at the same frequency, was therefore examined. The ultrasonic nozzle was chosen because the average droplet size was small, about 25 microns, and... 

Ebdon L. and Cave M. R. (1982) A study of pneumatic nebulisation systems for ICP emission spectrometry, Analyst 107 172-178. 

Dittrich K., Berndt H., Broekaert J. A. C., Schaldach G. and Tolg G. (1988) Comparative study of injection into a pneumatic nebuliser and tungsten coil electrothermal vaporisation for the determination of rare earth elements by inductively coupled plasma optical emission spectrometry, J Anal At Spectrom 3 1105—1110. 

Figure 5 A cut away representation of a typical AAS pneumatic nebuliser-atomiser assembly showing the position of a flow spoiler within the nehuliser chamber.

Prior steps to the stage of atomization in flame are the treatment of the sample, dissolving it in a convenient matrix, and the stage of pneumatic nebulisation. In FAAS the stage of atomization is performed in flame. The temperature of the flame is determined by the fuel/oxidant coefficient. The optimum temperatures depend on the excitation and ionization potentials of the analyte. 

Vapor generation techniques The generation of gaseous analytes from the sample and their introduction into atomisation cells for subsequent absorption spectro-metric determination offers a number of advantages over the conventional sample introduction by pneumatic nebulisation of the sample solution. These include the elimination of the nebuliser, the enhancement of the transport efficiency, which approaches 100 %, and the presentation of a homogenous sample vapor to the atomiser. The most common and versatile techniques for the formation of volatile compounds are the hydride generation technique and the cold vapor technique. 

Browner, R. F., Experimental Evaluation of the Nukiyama-Tanasawa Equation for Pneumatic Nebulisers Used in Plasma Atomic Emission Electroscopy, J. Anal. Atom. Spectrosc., Vol. 6, February 1990, pp. 61-66. 

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