Liquids spectrometry

Analysis of such cuts by spectrometry requires a preliminary separation by chemical constituents. The separation is generally done by liquid phase chromatography described in article 3.3.5. 

As the temperatures of the distillation cuts increase, the problems get more complicated to the point where preliminary separations are required that usually involve liquid phase chromatography (described earlier). This provides, among others, a saturated fraction and an aromatic fraction. Mass spectrometry is then used for each of these fractions. 

This is an analysis frequently conducted on oil lubricants. Generally, the additive is known and its concentration can be followed by direct comparison of the oil with additive and the base stock. For example, concentrations of a few ppm of dithiophosphates or phenols are obtained with an interferometer. However, additive oils today contain a large number of products their identification or their analysis by IR spectrometry most often requires preliminary separation, either by dialysis or by liquid phase chromatography. 

W. V. Ligon, Jr., Evaluating the Composition of Liquid Surfaces Using Mass Spectrometry, in Biological Mass Spectrometry, Elsevier, Amsterdam, 1990. 

Fast-Atom Bombardment (FAB) and Liquid-Phase Secondary Ion Mass Spectrometry (LSIMS) Ionization... 

A big step forward came with the discovery that bombardment of a liquid target surface by abeam of fast atoms caused continuous desorption of ions that were characteristic of the liquid. Where this liquid consisted of a sample substance dissolved in a solvent of low volatility (a matrix), both positive and negative molecular or quasi-molecular ions characteristic of the sample were produced. The process quickly became known by the acronym FAB (fast-atom bombardment) and for its then-fabulous results on substances that had hitherto proved intractable. Later, it was found that a primary incident beam of fast ions could be used instead, and a more generally descriptive term, LSIMS (liquid secondary ion mass spectrometry) has come into use. However, note that purists still regard and refer to both FAB and LSIMS as simply facets of the original SIMS. In practice, any of the acronyms can be used, but FAB and LSIMS are more descriptive when referring to the primary atom or ion beam. 

In many applications in mass spectrometry (MS), the sample to be analyzed is present as a solution in a solvent, such as methanol or acetonitrile, or an aqueous one, as with body fluids. The solution may be an effluent from a liquid chromatography (LC) column. In any case, a solution flows into the front end of a mass spectrometer, but before it can provide a mass spectrum, the bulk of the solvent must be removed without losing the sample (solute). If the solvent is not removed, then its vaporization as it enters the ion source would produce a large increase in pressure and stop the spectrometer from working. At the same time that the solvent is removed, the dissolved sample must be retained so that its mass spectrum can be measured. There are several means of effecting this differentiation between carrier solvent and the solute of interest, and thermospray is just one of them. Plasmaspray is a variant of thermospray in which the basic method of solvent removal is the same, but the number of ions obtained is enhanced (see below). 

The basic principles of fast-atom bombardment (FAB) and liquid-phase secondary ion mass spectrometry (LSIMS) are discussed only briefly here because a fuller description appears in Chapter 4. This chapter focuses on the use of FAB/LSIMS as part of an interface between a liquid chromatograph (LC) and a mass spectrometer (MS), although some theory is presented. 

To examine a sample by inductively coupled plasma mass spectrometry (ICP/MS) or inductively coupled plasma atomic-emission spectroscopy (ICP/AES) the sample must be transported into the flame of a plasma torch. Once in the flame, sample molecules are literally ripped apart to form ions of their constituent elements. These fragmentation and ionization processes are described in Chapters 6 and 14. To introduce samples into the center of the (plasma) flame, they must be transported there as gases, as finely dispersed droplets of a solution, or as fine particulate matter. The various methods of sample introduction are described here in three parts — A, B, and C Chapters 15, 16, and 17 — to cover gases, solutions (liquids), and solids. Some types of sample inlets are multipurpose and can be used with gases and liquids or with liquids and solids, but others have been designed specifically for only one kind of analysis. However, the principles governing the operation of inlet systems fall into a small number of categories. This chapter discusses specifically substances that are normally liquids at ambient temperatures. This sort of inlet is the commonest in analytical work. 

The term nebulizer is used generally as a description for any spraying device, such as the hair spray mentioned above. It is normally applied to any means of forming an aerosol spray in which a volume of liquid is broken into a mist of vapor and small droplets and possibly even solid matter. There is a variety of nebulizer designs for transporting a solution of analyte in droplet form to a plasma torch in ICP/MS and to the inlet/ionization sources used in electrospray and mass spectrometry (ES/MS) and atmospheric-pressure chemical ionization and mass spectrometry (APCI/MS). 

FAB has evolved, and fast atoms are being replaced by fast ions, such as cesium (Cs+). This variation is called liquid secondary ion mass spectrometry (LSIMS) because the sample solution affords the secondary ion beam while the bombarding ions constitute the primary beam. Spectra... 

Historically, the term SIMS was developed for bombardment of solid surfaces with ions, so, for greater descriptive precision, the name liquid secondary ion mass spectrometry (LSIMS) is better and can be used synonymously with FAB,... 

The term liquid secondary ion mass spectrometry (LSIMS) is sometimes used synonymously with FAB and is preferred by some as being more descriptive, since FAB could apply to bombardment of solid or liquid surfaces and does not indicate the types of secondaries investigated. In practice, little confusion is likely to result from using either term. Strictly, LSIMS can refer to the use of fast ions (FIB). 

Liquid chromatography/mass spectrometry (LC/MS) is an analytical technique combining the advantages of an LC instrument with those of a mass spectrometer. 

Desorption ionization (DI). General term to encompass the various procedures (e.g., secondary ion mass spectrometry, fast-atom bombardment, californium fission fragment desorption, thermal desorption) in which ions are generated directly from a solid or liquid sample by energy input. Experimental conditions must be clearly stated. 

GD/IRMS. glow discharge isotope ratio mass spectrometry HPLC. high-pressure liquid chromatography... 

LC/MS. liquid chromatography and mass spectrometry used as a combined technique... 

LSIMS. liquid-phase secondary ion mass spectrometry... 

Brown, M.A., Liquid Chromatography/Mass Spectrometry Applications in Agricultural, Pharmaceutical and Environmental Chemistry, Oxford University Press, Oxford, 1998. 

Niessen, W.M.A. and van der Greef, J, Liquid Chromatography-Mass Spectrometry, Marcel Dekker, New York, 1992. 

Smith, R.M., Gas and Liquid Chromatography in Analytical Chemistry, Wiley, Chichester, U.K., 1988. Smith, R.M. and Busch, K.L., Understanding Mass Spectra A Basic Approach, Wiley, Chichester, U.K., 1998. Snyder, A.R, Biochemical and Biotechnological Applications of Electrospray Ionization Mass Spectrometry, Oxford University Press, Oxford, 1998. 

Yergey, A.L., Edmonds, C.G., Lewis, I.A.S., and Vestal, M.L., Liquid Chromatography/Mass Spectrometry Techniques and Applications, Plenum Press, New York, 1990. 

Journal of Analysis and Applied Pyrolysis Journal of Chromatographic Science Journal of Chromatography Journal of Environmental Monitoring Journal of Liquid Chromatography Journal of Mass Spectrometry... 

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