Spectroscopy/spectrometry coupled sample preparation

Spectrochemical methods Higher yield ion sources for mass spectrometry Hyphenated techniques, gas or liquid chromatogr hy with inductively coupled plasma emission spectroscopy Minimization of sample preparation... 

This chapter deals mainly with (multi)hyphenated techniques comprising wet sample preparation steps (e.g. SFE, SPE) and/or separation techniques (GC, SFC, HPLC, SEC, TLC, CE). Other hyphenated techniques involve thermal-spectroscopic and gas or heat extraction methods (TG, TD, HS, Py, LD, etc.). Also, spectroscopic couplings (e.g. LIBS-LIF) are of interest. Hyphenation of UV spectroscopy and mass spectrometry forms the family of laser mass-spectrometric (LAMS) methods, such as REMPI-ToFMS and MALDI-ToFMS. In REMPI-ToFMS the connecting element between UV spectroscopy and mass spectrometry is laser-induced REMPI ionisation. An intermediate state of the molecule of interest is selectively excited by absorption of a laser photon (the wavelength of a tuneable laser is set in resonance with the transition). The excited molecules are subsequently ionised by absorption of an additional laser photon. Therefore the ionisation selectivity is introduced by the resonance absorption of the first photon, i.e. by UV spectroscopy. However, conventional UV spectra of polyatomic molecules exhibit relatively broad and continuous spectral features, allowing only a medium selectivity. Supersonic jet cooling of the sample molecules (to 5-50 K) reduces the line width of their... 

Apart from the aforementioned sample preparation techniques (SFE, SPE and SPME), other sample collection modes are coupled directly to spectroscopy (e.g. fast pyrolysis and fast thermolysis-FTIR) and spectrometry (e.g. LD-ITMS). 

Wet chemical methods involve sophisticated sample preparation and standardization with National Bureau of Standards reference materials but are not difficult for the analytical chemist nor necessarily time consuming (Figure 1). The time from sample preparation to final results for various analytical methods, such as GFAA (graphite furnace atomic absorption), ICP (inductively coupled plasma spectroscopy), ICP-MS (ICP-mass spectrometry), and colorimetry, ranges from 0.5 to 5.0 h, depending on the technique used. Colorimetry is the method of choice because of its extreme accuracy. Typical results of the colorimetric analysis of doped oxides are shown in Tables I and II, which show the accuracy and precision of the measurements. 

Many metal analyses are carried out using atomic spectroscopic methods such as flame or graphite furnace atomic absorption or inductively coupled plasma atomic emission spectroscopy (ICP-AES). These methods commonly require the sample to be presented as a dilute aqueous solution, usually in acid. ICP-mass spectrometry requires similar preparation. Other samples may be analyzed in solid form. For x-ray fluorescence, the solid sample may require dilution with a solid buffer material to produce less variation between samples and standards, reducing matrix effects. A solid sample is also preferred for neutron activation analyses and may be obtained from dilute aqueous samples by precipitation methods. 

ICP-OES continues to dominate the market because of its ease of use and relatively low maintenance cost. Inductively coupled plasma mass spectrometry (ICP-MS) is a very powerful state-of-the-art technique used for metal analysis of all kinds of samples but requires highly skilled operators. A vast amount of information is received that is not necessarily required as part of problem-solving or routine support. The cost difference and relative freedom from maintenance problems would favour ICP-OES. This book is aimed at practitioners requiring multi-elemental analysis in industrial, environmental, pharmaceutical and research laboratories, where information on identification and quantification is required on a regular basis. The main focus of this book will be on sample preparation, a topic overlooked in most books on atomic spectroscopy. It is aimed at most ICP-OES and ICP-MS users to show that the instrument is useless unless the sample is prepared in a suitable state that can be used to accurately and precisely quantify the metals present. 

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