Sampling system mass spectrometer

The number and types of pieces of analytical equipment to be integrated into the LIMS (e.g., gas chromatographs, sampling systems, mass spectrometers, etc.). There will also be a requirement to define the means of communication with these pieces of equipment this communication link may be t5q)ically via RS232 or a local area network (LAN). 

Experimental determination of He diffusion was attempted by Duddridge et al. (1991), who injected He-rich gas at a depth of 35 m into permeable limestones cut by a fault. They recorded a pulse of He in shallow soil gas 5-20 hours later within 10 m of the fault suboutcrop and up to 53 hours later 20 m from the fault suboutcrop. However, the concentration increase recorded (0.032 ppm) is well within the error of the analytical system (mass spectrometer with constant pressure inlet, as discussed below, and analytical sensitivity of 0.030 ppm), the data are patchy with many samples showing no pulse, and there is no estimate of background variation or the effect of changing environmental conditions. Conclusions about diffusion rates based on these data may not be reliable. 

Figure 10.1 Conceptual diagram of a molecular beam scattering (MBS) experiment comprised of pulsed beam source, sample target, mass spectrometer detector, and a differentially pumped ultrahigh-vacuum system.

Optimization of ion lens settings is described in considerable detail in Chapter 4. The processes affecting the ion transmission of analyte species are very complex in nature and are difficult to predict based on the operating conditions of the analysis. In addition, the transmission has a dependence on the history of the recent operation of the plasma and mass spectrometer, which may not be reproducible. In summary, the space charge effects, which defocus the ion beam, can severely alter the ion trajectories in the ion lens system. This defocusing can be highly dependent on the matrix of the sample. Some mass spectrometers have dynamically pro-... 

Liquids that are sufficiently volatile to be treated as gases (as in GC) are usually not very polar and have little or no hydrogen bonding between molecules. As molecular mass increases and as polar and hydrogen-bonding forces increase, it becomes increasingly difficult to treat a sample as a liquid with inlet systems such as El and chemical ionization (Cl), which require the sample to be in vapor form. Therefore, there is a transition from volatile to nonvolatile liquids, and different inlet systems may be needed. At this point, LC begins to become important for sample preparation and connection to a mass spectrometer. 

Apart from ES and APCI being excellent ion sources/inlet systems for polar, thermally unstable, high-molecular-mass substances eluting from an LC or a CE column, they can also be used for stand-alone solutions of substances of high to low molecular mass. In these cases, a solution of the sample substance is placed in a short length of capillary tubing and is then sprayed from there into the mass spectrometer. 

Although this system is simple with no moving parts, unfortunately not many ions from the original dissolved sample are produced, and the thermospray inlet/ion source is not very sensitive considering the achievable sensitivities of standard mass spectrometers. 

Special isotope ratio mass spectrometers are needed to measure the small variations, which are too small to be read off from a spectrum obtained on a routine mass spectrometer. Ratios of isotopes measured very accurately (usually as 0/00, i.e., as parts per 1000 [mil] rather than parts per 100 [percent]) give information on, for example, reaction mechanisms, dating of historic samples, or testing for drugs in metabolic systems. Such uses are illustrated in the main text. 

Direct-inlet probe. A shaft or tube having a sample holder at one end that is inserted into the vacuum system of a mass spectrometer through a vacuum lock to place the sample near to, at the entrance of, or within the ion source. The sample is vaporized by heat from the ion source, by heat applied from an external source, or by exposure to ion or atom bombardment. Direct-inlet probe, direct-introduction probe, and direct-insertion probe are synonymous terms. The use of DIP as an abbreviation for these terms is not recommended. 

Sample introduction system. A system used to introduce sample to a mass spectrometer ion source. Sample introduction system, introduction system, sample inlet system, inlet system, and inlet are synonymous terms. 

A mass spectrometer consists of four basic parts a sample inlet system, an ion source, a means of separating ions according to the mass-to-charge ratios, ie, a mass analyzer, and an ion detection system. AdditionaUy, modem instmments are usuaUy suppUed with a data system for instmment control, data acquisition, and data processing. Only a limited number of combinations of these four parts are compatible and thus available commercially (Table 1). 

Mass Spectrometer. The mass spectrometer is the principal analytical tool of direct process control for the estimation of tritium. Gas samples are taken from several process points and analy2ed rapidly and continually to ensure proper operation of the system. Mass spectrometry is particularly useful in the detection of diatomic hydrogen species such as HD, HT, and DT. Mass spectrometric detection of helium-3 formed by radioactive decay of tritium is still another way to detect low levels of tritium (65). Accelerator mass spectroscopy (ams) has also been used for the detection of tritium and carbon-14 at extremely low levels. The principal appHcation of ams as of this writing has been in archeology and the geosciences, but this technique is expected to faciUtate the use of tritium in biomedical research, various clinical appHcations, and in environmental investigations (66). 

Detection limits in ICPMS depend on several factors. Dilution of the sample has a lai e effect. The amount of sample that may be in solution is governed by suppression effects and tolerable levels of dissolved solids. The response curve of the mass spectrometer has a large effect. A typical response curve for an ICPMS instrument shows much greater sensitivity for elements in the middle of the mass range (around 120 amu). Isotopic distribution is an important factor. Elements with more abundant isotopes at useful masses for analysis show lower detection limits. Other factors that affect detection limits include interference (i.e., ambiguity in identification that arises because an elemental isotope has the same mass as a compound molecules that may be present in the system) and ionization potentials. Elements that are not efficiently ionized, such as arsenic, suffer from poorer detection limits. 

A versatile Laser-SNMS instrument consists of a versatile microfocus ion gun, a sputtering ion gun, a liquid metal ion gun, a pulsed flood electron gun, a resonant laser system consisting of a pulsed Nd YAG laser pumping two dye lasers, a non-resonant laser system consisting of a high-power excimer or Nd YAG laser, a computer-controlled high-resolution sample manipulator on which samples can be cooled or heated, a video and electron imaging system, a vacuum lock for sample introduction, and a TOF mass spectrometer. 

It has been reported that exchange of protons activated by enolization can be performed directly in a glass inlet system of the mass spectrometer prior to analysis by heating the sample at about 200° with deuterium oxide vapor for a few minutes. " Exchange has been observed with 2-, 3-, 6-, 11- and 17-keto steroids, but the resulting isotopic purity is usually poor,... 

For capillary columns, the usual practice is to insert the exit end of the column into the ion source. This is possible because under normal operating conditions the mass spectrometer pumping system can handle the entire effluent from the column. It is then only necessary to heat the capillary column between the GC and the MS ion source, taking care to eliminate cold spots where analyte could condense. The interface must be heated above the boiling point of the highest-boiling component of the sample. 

Every mass spectrometer consists of four principal components (Fig 1) (1) the source, where a beam of gaseous ions are produced from the sample (2) the analyzer, where the ion beam is resolved into its characteristic mass species (3) the detector, where the ions are detected and their intensities measured (4) the sample introduction system to vaporize and admit the sample into the ion source. There is a wide variety in each of these components and only those types which are relevant to analytical and organic mass spectrometry will be emphasized in this survey. The instrumentation... 

Qualitative or quantitative mass spectrometric analysis can be made by one of two alternative configurations. Either the sample is decomposed in the high vacuum chamber of the mass spectrometer (MS) itself or reaction proceeds in an external system at higher pressure (e.g. a microbalance)... 

Finally, a quantitative study of these systems is subject to the general limitations when mass spectrometers are used to sample the intermediate... 

---