Inductively coupled plasma parameters

On the basis of the preceding discussion, it should be obvious that ultratrace elemental analysis can be performed without any major problems by atomic spectroscopy. A major disadvantage with elemental analysis is that it does not provide information on element speciation. Speciation has major significance since it can define whether the element can become bioavailable. For example, complexed iron will be metabolized more readily than unbound iron and the measure of total iron in the sample will not discriminate between the available and nonavailable forms. There are many other similar examples and analytical procedures that must be developed which will enable elemental speciation to be performed. Liquid chromatographic procedures (either ion-exchange, ion-pair, liquid-solid, or liquid-liquid chromatography) are the best methods to speciate samples since they can separate solutes on the basis of a number of parameters. Chromatographic separation can be used as part of the sample preparation step and the column effluent can be monitored with atomic spectroscopy. This mode of operation combines the excellent separation characteristics with the element selectivity of atomic spectroscopy. AAS with a flame as the atom reservoir or AES with an inductively coupled plasma have been used successfully to speciate various ultratrace elements. 

Equation 8.3 relies on the assumption that the calibration parameters hold to the limit of detection, which is not necessarily correct. If the calibration is taken over a very wide range, for example in some element analyses by inductively coupled plasma, the uncertainty is not constant but is proportional to the concentration. In this case it is not possible to estimate the detection limit by equation (8.3). 

A serious problem in LA-ICP-MS described in the literature on many occasions is the time-dependent elemental fraction (so-called ablation fractionation ) occurring during laser ablation and the transport process of ablated material, or during atomization and ionization processes in the inductively coupled plasma.20-22 Numerous papers focus on the study of fraction effects in LA-ICP-MS as a function of experimental parameters applied during laser ablation (such as laser energy, laser power density, laser pulse duration, wave length of laser beam, ablation spot size,... 

HPLC units have been interfaced with a wide range of detection techniques (e.g. spectrophotometry, fluorimetry, refractive index measurement, voltammetry and conductance) but most of them only provide elution rate information. As with other forms of chromatography, for component identification, the retention parameters have to be compared with the behaviour of known chemical species. For organo-metallic species element-specific detectors (such as spectrometers which measure atomic absorption, atomic emission and atomic fluorescence) have proved quite useful. The state-of-the-art HPLC detection system is an inductively coupled plasma/MS unit. HPLC applications (in speciation studies) include determination of metal alkyls and aryls in oils, separation of soluble species of higher molecular weight, and separation of As111, Asv, mono-, di- and trimethyl arsonic acids. There are also procedures for separating mixtures of oxyanions of N, S or P. 

The elements Al, Mn, and Sr were determined by means of a Perkin-Elmer Optima 4300DV inductively coupled plasma emission spectrometry (ICP-AES) instrument (axial mode), equipped with an AS-90 Plus autosampler, a cross-flow nebulizer, and a Scott-type spray chamber in Ryton. The instrumental operating parameters are listed in Table 10.1. 

F. Laborda, M. J. Baxter, H. M. Crew, J. Dennis, Reduction of polyatomic interferences in inductively coupled plasma mass spectrometry by selection of instrumental parameters and using an argon-nitrogen plasma effect on multi-element analyses, J. Anal. Atom. Spectrom., 9 (1994), 727-736. 

Procedure Use an Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES), or equivalent instrumentation with similar capabilities. Follow the instrument manufacturer s instructions for setting instrument parameters for assay of cadmium. Select appropriate background correction points for the cadmium analyte according to the recommendations of the instrument manufacturer. Select analytical wavelengths to yield adequate sensitivity and freedom from interference. 

Vanadium molecular size distributions in residual oils are measured by size exclusion chromatography with an inductively coupled plasma detector (SEC-ICP). These distributions are then used as input for a reactor model which incorporates reaction and diffusion in cylindrical particles to calculate catalyst activity, product vanadium size distributions, and catalyst deactivation. Both catalytic and non-catalytic reactions are needed to explain the product size distribution of the vanadium-containing molecules. Metal distribution parameters calculated from the model compare well with experimental values determined by electron microprobe analysis, Modelling with feed molecular size distributions instead of an average molecular size results in predictions of shorter catalyst life at high conversion and longer catalyst life at low conversions. 

Vaughan M. A., Horlick G. and Tan S. H. (1987) Effect of the operating parameters on analyte signals in inductively coupled plasma mass spectrometry, J Anal At Spectrom 2 765-772. 

Each experiment was accortqjanied the determination of Pd in solution after hot filtration of the solid catalyst at the end of the reaction. Because simple Atomic Absorption Spectroscopy (AAS) was found to not be precise enough for the palladium analysis in this concentration range (detection limit too high.) ICP-OES and/or ICP-MS (Inductively Coupled Plasma - Optical Emission Spectroscopy or Inductively Coupled Plasma - Mass Spectrometry) were applied. To first approximation, the Pd leaching could not be correlated with the properties of the twelve different Pd/C catalysts described above ((1) Correlation of catalyst structure and activity.) There is, however, a strong correlation with the reaction parameters as described below. 

---