第1楼2005/03/25
Discussions:
Discussion (a and b) - The matrix will influence the nebulization efficiency, which is proportional to the signal intensity. Nebulization efficiency is the percent of solution that reaches the plasma. Therefore, if the nebulization efficiency is 1 %, then 99 % of the solution is going to waste and 1 % is making it to the plasma. Typically, nebulized solution 'mist particles' that are greater in diameter than 8 microns will go to waste. If a matrix component changes the efficiency from 1.0 % to 0.8%, then a relative drop of ~ 20 % would be expected from this effect alone. The droplet size distribution of a pneumatic nebulizer is governed by the physical properties of the solution as well as the volume flow rates of liquid (influenced by peristaltic pump speed and tubing diameter) and gas (sample Ar flow rate). The physical properties claimed to influence the droplet size distribution are the surface tension, viscosity, and density. See Inductively Coupled Plasmas in Analytical Atomic Spectrometry; Montaser, A., Golighty, D. W., Eds.; VCH Publishers: New York, 1992 - page 703 for more detail and additional references on this topic.
For the ICP analyst, the most common matrix component that will alter the physical properties of a solution is the acid content. This is not to say that other differences such as the presence of trace organics (added intentionally or not) should not be considered. However, the identity and concentration(s) of one or more acids is an issue that virtually all ICP analysts have to decide upon. The ICP analyst is most commonly involved in the preparation of samples where one or more inorganic mineral acids are required to bring about dissolution of the sample and/or to maintain solution stability of the analyte(s) of interest. The acids most commonly used are HNO3, HCl, HF, HClO4, H2SO4, and H3PO4 and are listed in the order of best to worst.
The effect of acid matrix upon nebulization efficiency is such that a change in acid content from 5 to 10 % v/v will cause a decrease in efficiency of 10 to 35 % depending upon the acid used, nebulizer design and liquid and gas flow rates. Matching the matrix to within 1 % relative is necessary for the most accurate (we use the term "assay") work (i.e., a 5 % HNO3 acid solution would be made to 5.00 ± 0.05 %.
The matrix will influence the plasma temperature, which is related to the signal intensity for ICP-OES. The other effect matrix components have on the ICP cannot be explained by a change in nebulization efficiency. The effect is one where the matrix components give the appearance of taking power away from the plasma (lowering the temperature of the plasma). It has been reported that this effect is related to the excitation potential of the line and that the effect increases as the excitation potential increases. A similar effect would be seen by decreasing the applied RF power or by increasing the sample (nebulizer) Ar flow rate since both result in a reduction of the plasma temperature. Therefore different lines of the same element would be affected differently according to their excitation potentials. In addition, when choosing an internal standard element it follows that the excitation potentials of the internal standard and analyte lines should be as close as possible, unless the calibration standards and samples are matrix matched. See Inductively Coupled Plasmas in Analytical Atomic Spectrometry; Montaser, A., Golighty, D. W., Eds.; VCH Publishers: New York, 1992 - pages 279-281 for more detail and additional references on this topic.
ICP-MS suffers from nonspectral matrix effects. The effect most commonly encountered is referred to as 'quenching' and is thought to be due to defocusing of the ion optics by space charge effects. Generally, as the concentration of the 'matrix element(s)' increases, the analyte signal will be suppressed. Quenching increases in effect as the matrix element absolute concentration increases, the matrix element mass increases and the analyte mass decreases. This effect is absolute in nature and not a function of the relative concentrations of the matrix elements and analyte elements. Therefore, when sensitivity allows, it can be diluted out. It is also greater in effect as the RF power is lowered. The effect is such that an element matrix concentration of 100 ppm can severely suppress a 'cool plasma' (RF power W ~ 800) and has little effect at normal power (an RF power of ~ 1300 W). See Inductively Coupled Plasma Mass Spectrometry; Mantaser, A., Ed.; Wiley-VCH: New York, 1998 - page 543 for more information and additional references.
In the next section, recommendations (c) and (d) will be discussed along with some additional considerations