Other solid sampling approaches

A number of other devices are used for solid sampling, albeit to a much lesser extent than those discussed in the preceding sections. The most salient among them are described below. 

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Application to solid polymer/additive formulations is restricted, for obvious reasons. SS-ETV-ICP-MS (cup-in-tube) has been used for the simultaneous determination of four elements (Co, Mn, P and Ti) with very different furnace characteristics in mg-size PET samples [413]. The results were compared to ICP-AES (after sample dissolution) and XRF. Table 8.66 shows the very good agreement between the various analytical approaches. The advantage of directly introducing the solid sample in an ETV device is also clearly shown by the fact that the detection limit is even better than that reported for ICP-HRMS. The technique also enables speciation of Sb in PET, and the determination of various sulfur species in aramide fibres. ETV offers some advantages over the well-established specific sulfur analysers very low sample consumption the possibility of using an aqueous standard for calibration and the flexibility to carry out the determination of other analytes. The method cannot be considered as very economic. 

Liquid samples, other than those that are inherently liquid, can arise from the solid sample extraction techniques described above. As mentioned previously, sometimes a simple dilute-and-shoot approach can be utilized, i.e., add solvent to the sample and then inject directly into the instrument. Other times, evaporation of residual liquid can be utilized—then the sample is either directly injected, or if the sample is evaporated to dryness, a new solvent can be added. Often, however, the residual matrix causes interference and the following techniques can be employed for further sample cleanup. 

Besides the use of large volume samples, there are also other "brute force" approaches frequently used since the earlier reports of solid-state Mg NMR, including isotopic enrichment and the use of malefic fields as strong as possible.. 39.42,, 45-52 jg doubt that the increase in the... 

Calibration and quantification procedures are easier in LA-ICP-MS compared to other solid-state mass spectrometric techniques because the laser ablation and the ICP ion source operate at normal pressure and the laser ablation of solid samples and ionization of analytes are separated in space and time. Therefore the advantage of solution calibration in ICP-MS can be applied in this solid-state analytical technique. The introduction of solution based calibration, which is only possible in LA-ICP-MS, was an innovative step in the development of this sensitive mass spectrometric technique. A number of different calibration approaches using aqueous standard solutions in the dual gas flow technique have been discussed by various authors.74 75 In the dual gas flow injection technique , the nebulized standard solution and the laser ablated sample material are mixed in the -piece and the two gas flows from the nebulizer (e.g. ultrasonic nebulizer) and laser ablation chamber are added. Using solution based calibration with the addition of a standard solution, Leach et alP determined minor elements in steel reference materials with a relative accuracy of a few %. In comparison to the so-called dual gas flow technique proposed in the literature, where the argon flow rates through the nebulizer and ablation cell add up to 11 min-1 (e.g. 0.451 min-1 and... 

Some confusion may also arise when one does not remember that these expressions strictly refer to mass rather than volume units. The difference is negligible when only aqueous solutions are considered because 1 L is practically equal 1 kg, but it should not be forgotten when other liquid systems are considered. In such cases, mass concentration units (cb or y s) should be used, being the ratio of analyte mass to the volume of liquid sample. Such an approach is particularly incorrect in the case of solid samples when their density differs significantly from unity, and... 

Since the radioactive sample material from most methods of sample preparation is in intimate contact or in actual solution with the phosphor, the detection of emitted particles or radiation is highly efficient and may even approach 100%. Problems of self-absorption of the emissions are thus absent, or considerably smaller than those associated with planchette counting of solid samples. This is of particular importance for the measurement of low energy beta emitters such as tritium and carbon-14. On the other hand, the measurement method has intrinsic drawbacks such as quenching and chemiluminescence. 

Almost all MAE applications involve off-line procedures, and on-line systems have not been utilized in food and agricultural analyses. Only a few approaches involving an on-line system have been published, for example in the determination of organophosphorus compounds in air particulates (21). In this MAE-GC system, an interface based on solid-phase trapping was used. Methanol was as the extraction solvent, and before the solid-phase trap the extract was diluted with water to enable efficient trapping to a polymeric sorbent. The sorbent was then dried with a nitrogen flow and the trapped analytes were eluted with organic solvent to the GC equipped with a PTV injector. A similar system should be applicable to the analysis of other types of solid samples as well. 

A different approach to mathematical analysis of the solid-state C NMR spectra of celluloses was introduced by the group at the Swedish Forest Products Laboratory (STFI). They took advantage of statistical multivariate data analysis techniques that had been adapted for use with spectroscopic methods. Principal component analyses (PCA) were used to derive a suitable set of subspectra from the CP/MAS spectra of a set of well-characterized cellulosic samples. The relative amounts of the I and I/3 forms and the crystallinity index for these well-characterized samples were defined in terms of the integrals of specific features in the spectra. These were then used to derive the subspectra of the principal components, which in turn were used as the basis for a partial least squares analysis of the experimental spectra. Once the subspectra of the principal components are validated by relating their features to the known measures of variability, they become the basis for analysis of the spectra of other cellulosic samples that were not included in the initial analysis. Here again the interested reader can refer to the original publications or the overview presented earlier. ... 

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