ICP detection limits

Table 9-5. Practical ICP detection limits in relation to typical concentrations of elements in plant tissues (pg g l).

The section on Spectroscopy has been expanded to include ultraviolet-visible spectroscopy, fluorescence, Raman spectroscopy, and mass spectroscopy. Retained sections have been thoroughly revised in particular, the tables on electronic emission and atomic absorption spectroscopy, nuclear magnetic resonance, and infrared spectroscopy. Detection limits are listed for the elements when using flame emission, flame atomic absorption, electrothermal atomic absorption, argon ICP, and flame atomic fluorescence. Nuclear magnetic resonance embraces tables for the nuclear properties of the elements, proton chemical shifts and coupling constants, and similar material for carbon-13, boron-11, nitrogen-15, fluorine-19, silicon-29, and phosphorus-31. 

Choice of Atomization and Excitation Source Except for the alkali metals, detection limits when using an ICP are significantly better than those obtained with flame emission (Table 10.14). Plasmas also are subject to fewer spectral and chemical interferences. For these reasons a plasma emission source is usually the better choice. 

Samples to be examined by inductively coupled plasma and mass spectrometry (ICP/MS) are commonly in the form of a solution that is transported into the plasma flame. The thermal mass of the flame is small, and ingress of excessive quantities of extraneous matter, such as solvent, would cool the flame and might even extinguish it. Even cooling the flame reduces its ionization efficiency, with concomitant effects on the accuracy and detection limits of the ICP/MS method. Consequently, it is necessary to remove as much solvent as possible which can be done by evaporation off-line or done on-line by spraying the solution as an aerosol into the plasma flame. 

ICP-SFMS (Thermo Finnigan, Flement) with cold vapour generation was developed with a guard electrode and a gold amalgamation device using an Au-sorbent for sample pre-concentration to improve the sensitivity. Instrumental parameters of ICP-SFMS such as take-up time, heating temperature of Au-sorbent, additional gas flow, and sample gas flow were optimized. Detection limit calculated as 3 times the standard deviation of 10 blanks was 0,05 ng/1, RSD = 7-9 %. 

The complex of the following destmctive and nondestmctive analytical methods was used for studying the composition of sponges inductively coupled plasma mass-spectrometry (ICP-MS), X-ray fluorescence (XRF), electron probe microanalysis (EPMA), and atomic absorption spectrometry (AAS). Techniques of sample preparation were developed for each method and their metrological characteristics were defined. Relative standard deviations for all the elements did not exceed 0.25 within detection limit. The accuracy of techniques elaborated was checked with the method of additions and control methods of analysis. 

Inductively coupled plasma-mass spectrometry (ICP-MS) is a multielement analytical method with detection limits which are, for many trace elements, including the rare earth elements, better than those of most conventional techniques. With increasing availability of ICP-MS instalments in geological laboratories this method has been established as the most prominent technique for the determination of a large number of minor and trace elements in geological samples. 

Approximately 70 different elements are routinely determined using ICP-OES. Detection limits are typically in the sub-part-per-billion (sub-ppb) to 0.1 part-per-million (ppm) range. ICP-OES is most commonly used for bulk analysis of liquid samples or solids dissolved in liquids. Special sample introduction techniques, such as spark discharge or laser ablation, allow the analysis of surfaces or thin films. Each element emits a characteristic spectrum in the ultraviolet and visible region. The light intensity at one of the characteristic wavelengths is proportional to the concentration of that element in the sample. 

The strengths of ICP-OES are its speed, wide linear dynamic range, low detection limits, and relatively small interference effects. Automated instruments with... 

Table 1 Typical detection limits (ppb) for iCP-OES (using a pneumatic nabuiizer for sample introduction) of the most sensitive amission line betwean 175 nm and 850 nm for each element.

ICP-OES is one of the most successful multielement analysis techniques for materials characterization. While precision and interference effects are generally best when solutions are analyzed, a number of techniques allow the direct analysis of solids. The strengths of ICP-OES include speed, relatively small interference effects, low detection limits, and applicability to a wide variety of materials. Improvements are expected in sample-introduction techniques, spectrometers that detect simultaneously the entire ultraviolet—visible spectrum with high resolution, and in the development of intelligent instruments to further improve analysis reliability. ICPMS vigorously competes with ICP-OES, particularly when low detection limits are required. 

Reaction experiments were performed at the substrate to catalyst ratios between 250 and 5000 (Table 1). The immobilized catalyst showed a rather constant values of TOP and enantioselectivity in spite of the increase in the S/C ratio, even though these values were slightly lower than those of the homogeneous Ru-BINAP catalyst. After the reaction, the Ru content in the reaction mixture was measured by ICP-AES and was found to be under 2 ppm, the detecting limit of the instrument, indicating the at Ru metal didn t leach significantly during the reaction. These results show that the immobilized Ru-BINAP catalyst had stable activity and enantioselectivity and that the Ru metal complex formed a stable species on the alumina support. 

Another major change was the shift from extensive use of field laboratory exploration techniques to the laboratory techniques hke ICP-AES and INAA. These produce a higher quality data than had resulted from the dc arc and other field techniques, with respect to both repeatability of measurement and improved detection limits. The metrology laboratory certifications for As and Hg in soils and sediments as key environmental toxins provided strong support to mineral exploration programs. 

HPLC (in both NP and RP modes) is quite suitable for speciation by coupling to FAAS, ETAAS, ICP-MS and MIP-MS [571,572]. Coupling of plasma source mass spectrometry with chromatographic techniques offers selective detection with excellent sensitivity. For HPLC-ICP-MS detection limits are in the sub-ng to pg range [36]. Metal ion determination and speciation by LC have been reviewed [573,574] with particular regard to ion chromatography [575]. 

Mono-, di- and tributyltin ion species (in water) have been determined by cation exchange IC-ICP-MS at 0.2 ng detection limits [856]. IC is also particularly useful for HSE purposes, such as the determination of acid gases in the workplace. Applications of IC have been reviewed [857]. 

Table 7.33 reports the main characteristics of GC-ICP-MS. Since both GC and ICP-MS can operate independently and can be coupled within a few minutes by means of a transfer line, hyphenation of these instruments is even more attractive than GC-MIP-AES. GC-ICP-MS is gaining popularity, probably due to the fact that speciation information is now often required when analysing samples. Advantages of GC-ICP-MS over HPLC-ICP-MS are its superior resolution, resulting in sharper peak shapes and thus lower detection limits. GC-ICP-MS produces a dry plasma when the separated species reach the ICP they are not accompanied by solvent or liquid eluents. This reduces spectral interferences. Variations on the GC-ICP-MS... 

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