Surface mass spectrometry, analytical method

The analytical techniques covered in this chapter are typically used to measure trace-level elemental or molecular contaminants or dopants on surfaces, in thin films or bulk materials, or at interfaces. Several are also capable of providing quantitative measurements of major and minor components, though other analytical techniques, such as XRF, RBS, and EPMA, are more commonly used because of their better accuracy and reproducibility. Eight of the analytical techniques covered in this chapter use mass spectrometry to detect the trace-level components, while the ninth uses optical emission. All the techniques are destructive, involving the removal of some material from the sample, but many different methods are employed to remove material and introduce it into the analyzer. 

Gros M, Petrovic M, Barcelo D (2006) Development of a multi-residue analytical method based on liquid chromatography-tandem mass spectrometry (LC-MS-MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters. Talanta 70 (4) 678-690... 

The method for chloroacetanilide soil metabolites in water determines concentrations of ethanesulfonic acid (ESA) and oxanilic acid (OXA) metabolites of alachlor, acetochlor, and metolachlor in surface water and groundwater samples by direct aqueous injection LC/MS/MS. After injection, compounds are separated by reversed-phase HPLC and introduced into the mass spectrometer with a TurboIonSpray atmospheric pressure ionization (API) interface. Using direct aqueous injection without prior SPE and/or concentration minimizes losses and greatly simplifies the analytical procedure. Standard addition experiments can be used to check for matrix effects. With multiple-reaction monitoring in the negative electrospray ionization mode, LC/MS/MS provides superior specificity and sensitivity compared with conventional liquid chromatography/mass spectrometry (LC/MS) or liquid chromatography/ultraviolet detection (LC/UV), and the need for a confirmatory method is eliminated. In summary,... 

Laser desorption methods (such as LD-ITMS) are indicated as cost-saving real-time techniques for the near future. In a single laser shot, the LDI technique coupled with Fourier-transform mass spectrometry (FTMS) can provide detailed chemical information on the polymeric molecular structure, and is a tool for direct determination of additives and contaminants in polymers. This offers new analytical capabilities to solve problems in research, development, engineering, production, technical support, competitor product analysis, and defect analysis. Laser desorption techniques are limited to surface analysis and do not allow quantitation, but exhibit superior analyte selectivity. 

The impact of an ion beam on the electrode surface can result in the transfer of the kinetic energy of the ions to the surface atoms and their release into the vacuum as a wide range of species—atoms, molecules, ions, atomic aggregates (clusters), and molecular fragments. This is the effect of ion sputtering. The SIMS secondary ion mass spectrometry) method deals with the mass spectrometry of sputtered ions. The SIMS method has high analytical sensitivity and, in contrast to other methods of surface analysis, permits a study of isotopes. In materials science, the SIMS method is the third most often used method of surface analysis (after AES and XPS) it has so far been used only rarely in electrochemistry. 

Wille K, Vanden Bussche J, Noppe H, De Wulf E, Van Caeter P, Janssen CR, De Brabander HF, Vanhaecke L (2010) A validated analytical method for the determination of perfluorinated compounds in surface-, sea- and sewagewater using liquid chromatography coupled to time-of-flight mass spectrometry. J Chromatogr A 1217(43) 6616-6622... 

The most frequently applied analytical methods used for characterizing bulk and layered systems (wafers and layers for microelectronics see the example in the schematic on the right-hand side) are summarized in Figure 9.4. Besides mass spectrometric techniques there are a multitude of alternative powerful analytical techniques for characterizing such multi-layered systems. The analytical methods used for determining trace and ultratrace elements in, for example, high purity materials for microelectronic applications include AAS (atomic absorption spectrometry), XRF (X-ray fluorescence analysis), ICP-OES (optical emission spectroscopy with inductively coupled plasma), NAA (neutron activation analysis) and others. For the characterization of layered systems or for the determination of surface contamination, XPS (X-ray photon electron spectroscopy), SEM-EDX (secondary electron microscopy combined with energy disperse X-ray analysis) and... 

However, tandem mass spectrometry, as a separation technique, does have limitations. It cannot easily differentiate between isomeric and isobaric species, and, in complex matrices, the presence of components with a high surface activity can suppress the ionization of components with a lower surface activity, leading to the nondetection of analytes (66). Therefore, the combination of MS-MS with a readily available chromatographic separation method such as TLC affords analysts real benefits. 

Although a great variety of analytical techniques have been applied to the simultaneous determination of methylxanthines in various matrices, HPLC is the one most frequently used nowadays. Most of the methods are based on reversed-phase HPLC, using ACN, MeOH, or THF in acetate or phosphate buffer as mobile phase and UV spectrophotometric detection (256 -270). Some RP-HPLC methods were proposed in combination with solid-surface room-temperature phosphori-metric detection (271), mass spectrometry (272), or amperometric (273) detection. The separation can also be achieved by RP ion-pair or ion-interaction HPLC (274-277) or micellar HPLC (278). In contrast, in recent years few normal-phase HPLC methods (279) were reported (see Table 5). 

Use of inductively coupled plasma-mass spectrometry (1CP-MS) coupled to a laser-ablation sample introduction system (LA-ICP-MS) as a minimally destructive method for chemical characterization of archaeological materials has gained favor during the past few years. Although still a relatively new analytical technique in archaeology, LA-ICP-MS has been demonstrated to be a productive avenue of research for chemical characterization of obsidian, chert, pottery, painted and glazed surfaces, and human bone and teeth. Archaeological applications of LA-ICP-MS and comparisons with other analytical methods are described. 

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