Axially and radially viewed inductively coupled plasmas — a critical review

Abstract

The present status of axially viewed inductively coupled plasmas (ICP) is reviewed with special emphasis placed on the analytical performance of currently available systems. Descriptions are given of the various designs of the plasma–spectrometer configuration. Conventional figures of merit such as limits of detection, background behavior, interferences due to easily ionized elements (EIE), Ca and acids, and the Mg II 280.270 nm/Mg I 285.213 nm intensity ratio, are used to compare the performance of axially viewed and radially viewed ICPs. Various modes of sample introduction, including conventional pneumatic and ultrasonic nebulization (USN), thermospray and a direct injection probe will be described. For axially viewed ICPs, limits of detection (LOD) are improved by factors varying from approximately 2 to 30. Additional improvements by factors of 2–20 can be obtained using USN. The improvement factors generally depend on energy potentials of the spectral lines and the element. Although limits of detection in the presence of Ca and Na are degraded relative to an aqueous solution 10–30-fold, USN LODs using an axially viewed ICP are improved relative to those obtained using a pneumatic nebulizer for solutions containing Ca and Na. With normal aerosol load and under robust plasma conditions (as evidenced by Mg II/Mg I intensity ratios >8), EIE, Ca and mineral acid induced interferences are relatively small and are similar in axial and conventional radial configurations. However, interferences due to Ca are larger than those caused by Na due to the larger amount of energy required to dissociate the matrix. Matrix effects increase considerably when an USN is employed. For robust plasmas, ICP operating conditions and performance for multi-element quantitative analysis do not differ significantly from those of conventional radial configurations. In cases where robustness decreases, matrix interferences should be taken into account when establishing optimum conditions for operation. In robust axially viewed ICPs, a single internal standard can compensate for ionic line intensity suppression due to Na. However, owing to the variable influence of Ca on spectral response, more than one internal standard is required to compensate for these matrix effects. In this situation, linear energy potential-interference functions can be used to improve accuracy using spectral lines varying over wide ranges of energy potentials. In axially viewed ICPs, Mg II/ Mg I ratios vary widely as a function of applied RF power, aerosol flow rates and load, diameter of the central torch injector, and composition of the aspirated solution. The highest values of 9–13 have been observed for a pure aqueous solution using conventional nebulization and argon carrier flow rates (0.5–0.7 ml min −1) and forward powers of 1.2–1.5 kW. Mg II/Mg I ratios decrease when the RF power decreases, when Na and Ca are added to the plasma, and when the aerosol load is increased. A low value of 2 was obtained when the carrier gas flow rate was high and when the aerosol load was high using an USN. The use of a copper metal skimmer below the analytical observation zone to isolate the axial channel of the ICP and to deflect the outer cool fringe results in 5–20 times improvement of the LODs compared to those obtained using a conventional configuration (a normal radially viewed ICP). A direct He purged plasma–spectrometer interface for end-on detection of the vacuum UV (VUV) emission from the axial region of an ICP allows the determination of Cl, Br and other analytes in the μg l −1 range. The characteristics of a secondary discharge at the orifice of a Cu cone when the axial channel of the ICP is extracted into a vacuum chamber will be discussed. The characteristics of the emission in the Mach disk region extracted from the axial column will be surveyed. Several applications and techniques are described: determination of major, minor and trace elements in geological, environmental and biological materials, analysis of brines, nuclear materials and organic solvents and solutions. Several unique techniques are described: elemental speciation, determination of the halides and other analytes with VUV spectral lines using a He purged direct plasma–spectrometer interface. Direct solids analysis using slurries, laser and spark ablation and direct solids insertion further extends the scope of axially viewed ICPs.