Measurement spectrometry

Book topics include practical aspects of spectrometers and spectrometry, sample preparation, chemometrics, and calibration practices reflectance measurements and standard materials measurements. We have placed an emphasis on reflectance and color measurements due to their common usage in today s spectroscopic laboratories. Methods for selecting a measurement technique are included, as well as solar and color measurements. Spectrometry of new materials, ceramics, and textiles are covered by respective experts in their fields. An appendix of practical reference data for UV-VIS, NIR, IR bench top, IR microspectroscopy, and UV Sun Protection Factor (SPF) measurements is included. 

Before ehding this presentation on mass spectrometry, we should cite the existence of spectrometers for which the method of sorting ions coming from the source is different from the magnetic sector. These are mainly quadripolar analyzers and, to a lesser degree, analyzers measuring the ion s time of flight. 

The spectroscopic methods, NMR and mass spectrometry for predicting cetane numbers have been established from correlations of a large number of samples. The NMR of carbon 13 or proton (see Chapter 3) can be employed. In terms of ease of operation, analysis time (15 minutes), accuracy of prediction (1.4 points average deviation from the measured number), it is... 

The method implies injection of a mixture of 3 radioactive tracers each being distributed into one of the 3 phases. The tracers must show such differences in the emitting y-radiation energy spectra that they can be simultaneously detected by on line y-spectrometry. Candidate tracers are Br-82 as bromobenzene for oil, Na-24 or La-140 for water, and Kr-85 for gas. The tracers are injected simultaneously at a constant rate into the flow in the pressurised pipe, and the concentration is detected as series of instantaneous measurements taken downstream as illustrated in figure 2. 

Ions are also used to initiate secondary ion mass spectrometry (SIMS) [ ], as described in section BI.25.3. In SIMS, the ions sputtered from the surface are measured with a mass spectrometer. SIMS provides an accurate measure of the surface composition with extremely good sensitivity. SIMS can be collected in the static mode in which the surface is only minimally disrupted, or in the dynamic mode in which material is removed so that the composition can be detemiined as a fiinction of depth below the surface. SIMS has also been used along with a shadow and blocking cone analysis as a probe of surface structure [70]. 

The major role of TOF-SARS and SARIS is as surface structure analysis teclmiques which are capable of probing the positions of all elements with an accuracy of <0.1 A. They are sensitive to short-range order, i.e. individual interatomic spacings that are <10 A. They provide a direct measure of the interatomic distances in the first and subsurface layers and a measure of surface periodicity in real space. One of its most important applications is the direct determination of hydrogen adsorption sites by recoiling spectrometry [12, 4T ]. Most other surface structure teclmiques do not detect hydrogen, with the possible exception of He atom scattering and vibrational spectroscopy. 

Rutherford backscattering spectrometry is the measurement of the energies of ions scattered back from the surface and the outer microns (1 micron = 1 pm) of a sample. Typically, helium ions with energies around 2 MeV are used and the sample is a metal coated silicon wafer that has been ion implanted with about a... 

There are otlier teclmiques for mass separation such as tire quadmpole mass filter and Wien filter. Anotlier mass spectrometry teclmique is based on ion chromatography, which is also capable of measuring tire shapes of clusters [30, 31]. In tills metliod, cluster ions of a given mass are injected into a drift tube witli well-defined entrance and exit slits and filled witli an inert gas. The clusters drift tlirough tills tube under a weak electric potential. Since the... 

Following the movement of airborne pollutants requires a natural or artificial tracer (a species specific to the source of the airborne pollutants) that can be experimentally measured at sites distant from the source. Limitations placed on the tracer, therefore, governed the design of the experimental procedure. These limitations included cost, the need to detect small quantities of the tracer, and the absence of the tracer from other natural sources. In addition, aerosols are emitted from high-temperature combustion sources that produce an abundance of very reactive species. The tracer, therefore, had to be both thermally and chemically stable. On the basis of these criteria, rare earth isotopes, such as those of Nd, were selected as tracers. The choice of tracer, in turn, dictated the analytical method (thermal ionization mass spectrometry, or TIMS) for measuring the isotopic abundances of... 

Allen, H. C. Brauers, T. Finlayson-Pitts, B. J. Illustrating Deviations in the Beer-Lambert Law in an Instrumental Analysis Laboratory Measuring Atmospheric Pollutants by Differential Optical Absorption Spectrometry, /. Chem. 

A further important use of El mass spectrometry lies in measuring isotope ratios, which can be used in estimating the ages of artifacts, rocks, or fossils. Electron ionization affects the isotopes of any one element equally, so that the true isotope ratio is not distorted by the ionization step. Further information on isotopes can be found in Chapter 46. 

Another type of ion is formed almost uniquely by the electrospray inlet/ion source which makes this technique so valuable for examining substances such as proteins that have large relative molecular mass. Measurement of m/z ratios usually gives a direct measure of mass for most mass spectrometry because z = 1 and so m/z = m/1 = m. Values of z greater than one are unusual. However, for electrospray, values of z greater than one (often much greater), are quite coimnonplace. For example, instead of the [M + H]+ ions common in simple Cl, ions in electrospray can be [M + n-H]- where n can be anything from 1 to about 30. 

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). 

If a sample solution is introduced into the center of the plasma, the constituent molecules are bombarded by the energetic atoms, ions, electrons, and even photons from the plasma itself. Under these vigorous conditions, sample molecules are both ionized and fragmented repeatedly until only their constituent elemental atoms or ions survive. The ions are drawn off into a mass analyzer for measurement of abundances and mJz values. Plasma torches provide a powerful method for introducing and ionizing a wide range of sample types into a mass spectrometer (inductively coupled plasma mass spectrometry, ICP/MS). 

By high-resolution mass spectrometry, ions of known mass from a standard substance can be separated from ions of unknown mass derived from a sample substance. By measuring the unknown mass relative to the known ones through interpolation or peak matching, the unknown can be measured. An accurate mass can be used to obtain an elemental composition for an ion. If the latter is the molecular ion, the composition is the molecular formula. 

The previous discussion has centered on how to obtain as much molecular mass and chemical structure information as possible from a given sample. However, there are many uses of mass spectrometry where precise isotope ratios are needed and total molecular mass information is unimportant. For accurate measurement of isotope ratio, the sample can be vaporized and then directed into a plasma torch. The sample can be a gas or a solution that is vaporized to form an aerosol, or it can be a solid that is vaporized to an aerosol by laser ablation. Whatever method is used to vaporize the sample, it is then swept into the flame of a plasma torch. Operating at temperatures of about 5000 K and containing large numbers of gas ions and electrons, the plasma completely fragments all substances into ionized atoms within a few milliseconds. The ionized atoms are then passed into a mass analyzer for measurement of their atomic mass and abundance of isotopes. Even intractable substances such as glass, ceramics, rock, and bone can be examined directly by this technique. 

Plasma torches and thermal ionization sources break down the substances into atoms and ionized atoms. Both are used for measurement of accurate isotope ratios. In the breakdown process, all structural information is lost, other than an identification of elements present (e.g., as in inductively coupled mass spectrometry, ICP/MS). 

The upper part of the figure illustrates why the small difference in mass between an ion and its neutral molecule is ignored for the purposes of mass spectrometry. In mass measurement, has been assigned arbitrarily to have a mass of 12.00000, All other atomic masses are referred to this standard. In the lower part of the figure, there is a small selection of elements with their naturally occurring isotopes and their natural abundances. At one extreme, xenon has nine naturally occurring isotopes, whereas, at the other, some elements such as fluorine have only one. 

Recently, it has become possible to create isotopes that do not exist naturally. These are the artificial isotopes, and all are radioactive. For example, 13 artificially created isotopes of iodine are known, as well as its naturally occurring monoisotopic form of mass 127. Mass spectrometry is able to measure m/z values for both natural and artificial isotopes. 

This accurate measurement of the ratio of abundances of isotopes is used for geological dating, estimation of the ages of antiquities, testing athletes for the use of banned steroids, examining fine details of chemical reaction pathways, and so on. These uses are discussed in this book under various headings concerned with isotope ratio mass spectrometry (see Chapters 7, 14, 15, 16, 17, 47, and 48). 

Few of the naturally occurring elements have significant amounts of radioactive isotopes, but there are many artificially produced radioactive species. Mass spectrometry can measure both radioactive and nonradioactive isotope ratios, but there are health and safety issues for the radioactive ones. However, modem isotope instmments are becoming so sensitive that only very small amounts of sample are needed. Where radioactive isotopes are a serious issue, the radioactive hazards can be minimized by using special inlet systems and ion pumps in place of rotary pumps for maintaining a vacuum. For example, mass spectrometry is now used in the analysis of Pu/ Pu ratios. 

If a value Rs represents a ratio in a sample(s) as measured by mass spectrometry,... 

This is the basic process in an inductively coupled plasma discharge (ICP). The excited ions can be examined by observing the emitted light or by mass spectrometry. Since the molecules have been broken down into their constituent atoms (as ions) including isotopes, these can be identified and quantified by mass spectrometry, as happens with isotope ratio measurements. 

When multicharged ions are formed, the simple rule of thumb used widely in mass spectrometry that m/z = m because, usually, z = 1 no longer applies for z > 1 then m/z < m, and the apparent mass of an ion is much smaller than its true mass. Accurate mass measurement is much easier at low mass than at high, and the small m/z values, corresponding to high mass with multiple charges, yield accurate values for the high mass. 

A related technique is based on the same principles, only the trap population is measured by means of esr spectrometry (see Magnetic spin resonance) (50). 

For marble provenance studies, the most successful technique seems to be the measurement, through mass spectrometry, of the abundance ratios of the stable isotopes of carbon and oxygen (116). However, no single technique appears to provide unequivocal results, especially in cases such as the different Mediterranean sources, and a combination is often necessary to arrive at an approximate place of origin (117). 

To measure trace metals to the levels required in the guidelines involves the use of state-of-the-art instmmentation such as inductively coupled plasma/mass spectrometry (icp/ms). 

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