Thermal Desorption-Mass Spectrometric Techniques

Cotter [1026] has reviewed thermal desorption/ volatilisation for volatility enhancement. Cotter s authoritative coverage includes desorption mechanisms, inert probe desorption and the various interrelations of evaporation of intact neutrals with thermal decomposition. 

Thermal desorption mass spectrometry allows rapid qualitative scanning (2 min) of additive packages [2, 

As most common additives are removed quite readily from rubbers, TD-MS is therefore often the first and preferred approach for qualitative analysis of untreated rubber [745], 

Pleshkova et al. [1031] have used TD-MS to determine the composition of a number of commercial bisphenol A-based polycarbonates. PhOH, p-t-butylphenol, and p-isooctylphenol were determined as the main chain-transfer agents for these polycarbonates. Up to 10 additives with concentrations exceeding 0.05% could be determined in a sample. Mould lubricants of various chemical nature were the main additives found. 

Wunderlich, Thermal Analysis of Polymeric Materials, Springer-Verlag, Berlin (2005). 

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Robbat et al. [50] evaluated a thermal desorption gas chromatographic-mass spectrometric technique for the detection of polychlorobiphenyl in sediments and soils. 

Several original papers must be mentioned that deal with mass spectrometric techniques which the numerous reviews do not comprise. Kaufmann and coworkers268,288 studied the mass spectrometric analysis of carotenoids and some of their fatty acid esters using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry and its post-source-decay (PSD) variant. Some advantages concerning the thermal instability and limited solubility were discussed, but the fragmentation paths of the carotenoid cations were found to be essentially the same as those observed with conventional techniques. 

Bombick DD, Allison A. Desorption/Ionization mass spectrometric technique for the analysis of thermally labile compounds based on thermionic emission materials. Anal Chem. 1987 59 458-66. 

Alternative approaches consist in heat extraction by means of thermal analysis, thermal volatilisation and (laser) desorption techniques, or pyrolysis. In most cases mass spectrometric detection modes are used. Early MS work has focused on thermal desorption of the additives from the bulk polymer, followed by electron impact ionisation (El) [98,100], Cl [100,107] and field ionisation (FI) [100]. These methods are limited in that the polymer additives must be both stable and volatile at the higher temperatures, which is not always the case since many additives are thermally labile. More recently, soft ionisation methods have been applied to the analysis of additives from bulk polymeric material. These ionisation methods include FAB [100] and LD [97,108], which may provide qualitative information with minimal sample pretreatment. A comparison with FAB [97] has shown that LD Fourier transform ion cyclotron resonance (LD-FTTCR) is superior for polymer additive identification by giving less molecular ion fragmentation. While PyGC-MS is a much-used tool for the analysis of rubber compounds (both for the characterisation of the polymer and additives), as shown in Section 2.2, its usefulness for the in situ in-polymer additive analysis is equally acknowledged. 

In direct insertion techniques, reproducibility is the main obstacle in developing a reliable analytical technique. One of the many variables to take into account is sample shape. A compact sample with minimal surface area is ideal [64]. Direct mass-spectrometric characterisation in the direct insertion probe is not very quantitative, and, even under optimised conditions, mass discrimination in the analysis of polydisperse polymers and specific oligomer discrimination may occur. For nonvolatile additives that do not evaporate up to 350 °C, direct quantitative analysis by thermal desorption is not possible (e.g. Hostanox 03, MW 794). Good quantitation is also prevented by contamination of the ion source by pyrolysis products of the polymeric matrix. For polymer-based calibration standards, the homogeneity of the samples is of great importance. Hyphenated techniques such as LC-ESI-ToFMS and LC-MALDI-ToFMS have been developed for polymer analyses in which the reliable quantitative features of LC are combined with the identification power and structure analysis of MS. 

Conventional electron impact or chemical ionization mass spectrometry requires that volatilization precede ionization and this is clearly a limiting factor in the analysis of many biochemically significant compounds. A newer ionization technique, field desorption (FD) (1, 2 ) removes this requirement and makes it possible to obtain mass spectrometric information on thermally unstable or non-volatile organic compounds such as glycoconjugates and salts. This development is particularly significant for those concerned with the analysis of glycolipids and we have therefore explored the suitability of field desorption mass spectrometry (FDMS) for this class of compounds. We have evaluated experimental procedures in order to enhance the efficiency of the ionization process and to maximize the information content of spectra obtained by this technique. 

Solid-Phase Microextraction. Solid-phase microextraction (SPME), used as a sample introduction technique for high speed gc, utilizes small-diameter fused-silica fibers coated with polymeric stationary phase for sample extraction and concentration (33). The trapped analyte can be liberated by thermal desorption. By using a specially designed dedicated injector, the desorption process can be shortened to a fraction of a second, producing an injection band narrow enough for high speed gc. A modified system has been investigated for the analysis of volatile compounds listed in EPA Method 624. Separation of all 28 compounds by ion trap mass spectrometric detector is achieved in less than 150 seconds. 

In recent years, several techniques have been developed for mass spectrometry, whereby samples are ionized and analysed from a condensed phase, without prior volatilization. These desorption techniques have permitted the extension of mass spectrometric analyses to sulfate and glutathione conjugates, as well as to underivatized and labile glucuronic acid conjugates. Primary among these techniques are field desorption 6, plasma desorption (7), laser desorption (8), fast atom bombardment (or secondary ion mass spectrometry with a liquid sample matrix) ( ) and thermospray ionization ( O). The latter can also serve to couple high pressure liquid chromatography and mass spectrometry for analysis of involatile and thermally labile samples. 

The general principle of mass spectrometry (MS) is to produce, separate and detect gas phase ions. Traditionally, thermal vaporization methods are used to transfer molecules into the gas phase. The classical methods for ionization are electron impact (El) and chemical ionization (Cl). Most biomolecules, however, undergo severe decomposition and fragmentation under the conditions of both methods. Consequently, the capabilities of mass spectrometry have been limited to molecules the size of dinucleotides [1]. Analysis of oligonucleotides with a mass range of up to 3000 Da became feasible with the development of plasma desorption (PD) methods [2]. However, until the invention of soft ionization techniques such as ESI- and MALDI MS, mass spectrometric tools were not widely considered for routine applications in biological sciences. 

The rapid development of mass spectrometric technology and the wide field of applications exclude a complete and comprehensive discussion of mass spectrometric possibilities for trace analysis of metals. Therefore, this report will give a brief outline of the principles of mass spectrometry (MS) and the fundamentals of qualitative and quantitative mass spectrometric analysis with emphasis on recent developments and results. The classical methods of analysis of solids, i.e. spark-source MS and thermal ionization MS, as well as newer methods of metal analysis are described. Focal points in this survey of recently developed techniques include secondary ion MS , laser probe MS , plasma ion source MS gas discharge MS and field desorption MS . Here, a more detailed description is given and the merits of these emerging methods are discussed more explicitly. In particular, the results of the FD techniques in elemental analyses are reviewed and critically evaluated. 

In the past several years, a number of new ionization methods in mass spectrometry have been introduced. These new techniques have extended mass spectrometric analysis to a wide variety of labile (thermally unstable), highly polar, and higher molecular weight materials. Field ionization (FI) and field desorption (FD) are two of the pioneering techniques in this list of alternative ionization methods. FI-MS, which was introduced for organic molecules in 1954, was the first soft ionization method. (Soft ionization refers to processes that produce high relative abundances of molecular, or quasimolecular, ions.) FD-MS, which was invented in 1969, was the first desorption/ionization method. (Desorption/ionization refers to processes in which die vaporization/ desorption, and ionization steps occur essentially simultaneously.)... 

Three years earlier, in 2000, Scrivens and Jackson published a review paper with the same title [5], in which revolutionary technical advances in the field were described. In their words, before the so-called revolution, The majority of mass spectrometric studies of polymer systems required optional extraction of the additives from the polymer followed by a chemical or thermal degradation of the polymer itself. Due to partial degradation, the authors make a distinction between direct measurements and indirect measurements [5]. The mass spectra of many synthetic polymers are discussed, but they limit their review to spectra recorded using three ionization techniques, namely field desorption (FD), electrospray ionization (ESI), and matrix-assisted laser desorption/ionization (MALDI). For MS of synthetic polymers prior to the revolution, the authors refer the reader to other sources. 

Steam-solvent distillation using diethyl ether has been used to remove and analyse for odour and taint from additives in food packaging films. Another technique that has been used is vacuum/thermal extraction. This procedure has been applied to polyamides and fluorocarbon polymers. The procedure is used for the direct isolation or release of volatile components from a polymeric matrix and may involve the combined use of vacuum and heat, as for example in the mass spectrometer direct insertion probe or during dry vacuum distillation. Alternatively, the volatiles may be swept from the heated sample by a flow of inert gas for concentration by freeze trapping and/or collection on to a solid adsorbent prior to thermal or solvent desorption for GC or mass spectrometric (MS) examination. 

Principles and Characteristics As well known, transformation of atoms and high mass organic molecules from a surface-adsorbed state into the gas phase (for mass spectrometric detection) may be achieved by various methods, including field desorption, plasma desorption, laser desorption, fast atom bombardment (FAB) and ion sputtering. These techniques address different analytical problem areas. For example, the development of the laser desorption (LD) technique has been prompted by the desire to study thermally labile and high mass compounds by mass spectrometry. 

The elution of the organic compounds collected involves extraction by a solvent (displacement) or thermal desorption. Pentane, CS2 and benzyl alcohol are generally used as extraction solvents. CS2 is very suitable for activated charcoal, but cannot be used with polymeric materials, such as Tenax or Amberlite XAD, because decomposition occurs. As a result of displacement with solvents, the sample is extensively diluted, which can lead to problems with the detection limits on mass spectrometric detection. With solvents additional contamination can occur. The extracts are usually applied as solutions. The readily automated static headspace technique can also be used for sample injection. This procedure has also proved to be effective for desorption using polar solvents, such as benzyl alcohol or ethylene glycol monophenyl ether (1% solution in water, Krebs, 1991). 

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