Mass spectrometry sample introduction system

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... 

Because ICP-MS with different instrumentations and sample introduction systems (besides solution nebulization, also laser ablation or hyphenated methods, such as HPLC, CE, SPME) is today the most frequently used analytical technique for precise and accurate isotope ratio measurements, the following section will mainly focus on this form of mass spectrometry with an inductively coupled plasma source. 

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. 

Elemental mass spectrometry has undergone a major expansion in the past 15-20 years. Many new a, elopments in sample introduction systems, ionization sources, and mass analyzers have been realized. A vast array of hybrid combinations of these has resulted from specific analytical needs such as improved detection limits, precision, accuracy, elemental coverage, ease of use, throughput, and sample size. As can be seen from most of the other chapters in this volume, however, the mass analyzers used to date have primarily been magnetic sector and quadrupole mass spectrometers. Ion trapping devices, be they quadrupole ion (Paul) [1] traps or Fourier transform ion cyclotron resonance (Penning) traps, have been used quite sparingly and most work to date has concentrated on proof of principal experiments rather that actual applications. 

The second major environmental application of FFF has been the use of an element-specific detector, usually in series with a UV detector, to provide elemental composition data along with the PSD. Graphite-furnace atomic absorption spectrometry has been used off-line on fractions collected from the FFF run. However, the multi-element detection, low detection limits and capability to function as an online detector have made inductively coupled plasma mass spectrometry (ICP-MS) the ideal detector for FFE85-86 The sample introduction system of the ICP-MS is able to efficiently transport micron-sized particles into the high-temperature plasma,... 

Buckley WT, Budac JJ, Godfrey DV, et al. 1992. Determination of selenium by inductively coupled plasma mass spectrometry utilizing a new hydride generation sample introduction system. Anal Chem 64(7) 724-729. 

A very useful innovation in sample introduction systems is the use of a gas chromatograph coupled to a mass spectrometer. In effect, the mass spectrometer acts in the role of detector. In this technique, known as gas chromatography-mass spectrometry (GC-MS), the gas stream emerging from the gas chromatograph is admitted through a valve into a tube, where it passes over a molecular leak. Some of the gas stream is thus admitted into the ionization chamber of the mass spectrometer. In this way it is possible to obtain the mass spectrum of every component in a mixture being injected into the gas chromatograph. 

The efficient transfer of an analyte from its original condition to the ionization region of an ion mobility spectrometer (IMS) is the topic of this chapter. Snccessfnl detection and identification of an analyte by IMS depend on many steps but none more important than those by which a sample is introduced into an instrument. IMS instruments are used for the detection and identification of analytes found in air, water, biological fiuids and tissues, industrial solvents and on surfaces. Because ion mobility spectrometry is such a universal analytical instrument, sample introduction methods are diverse and depend on the type of sample analyzed. Atmospheric pressure operation makes IMS suitable for interfacing with several sample introduction systems as a detector as well as a selective filter for mass spectrometric techniques. 

Kambara, H. Sample Introduction System for Atmospheric Pressure Ionization Mass Spectrometry of Nonvolatile Compounds. Analyt. Chemistry 54, 143 (1982). 

ICP is seeing more use as a sample introduction system for various hyphenated techniques. New to the pharmaceutical industry is the use of inductively coupled plasma-mass spectrometry (ICP-MS). ICP-MS offers excellent versatihty and sensitivity to the analyst, and greatly complements any pharmaceutical... 

McLaren, J.W., Lam,J. W., and Gustavsson, A. (1990). Evaluation of a membrane interface sample introduction system for inductively coupled plasma mass spectrometry. Spec-trochim.Acta, Part B 45(9), 1091. 

Debrah, E. and L6gbre, G. (1999) Design and performance of a novel high efficiency sample introduction system for plasma source spectrometry. In Plasma Source Mass Spectrometry (eds J. G. Holland and S. D. Tanner), Royal Society of Chemistry, Cambrigde, pp. 20-6. 

Mass spectrometry is unique among many modern analytical methods in that sample molecules are physically and irretrievably introduced into the instrument. The sample handling devices must be transport devices that accommodate a wide dynamic range of sample quantities, efficiently transporting aU sample molecules from the outside world into the ionization source of the mass spectrometer. Given the diversity of sample types, there is a concurrent diversity of sample introduction systems. 

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 main advantages of the ms/ms systems are related to the sensitivity and selectivity they provide. Two mass analyzers in tandem significantly enhance selectivity. Thus samples in very complex matrices can be characterized quickly with Htde or no sample clean-up. Direct introduction of samples such as coca leaves or urine into an ms or even a gc/lc/ms system requires a clean-up step that is not needed in tandem mass spectrometry (28,29). Adding the sensitivity of the electron multiplier to this type of selectivity makes ms/ms a powerhil analytical tool, indeed. It should be noted that introduction of very complex materials increases the frequency of ion source cleaning compared to single-stage instmments where sample clean-up is done first. 

The impact of this new technique, which was called Accelerator Mass Spectrometry (AMS), on the radiocarbon and archaeologist communities, was immediate and revolutionary. The introduction of AMS is indeed recognized by some as the third revolution in radiocarbon dating[22,23] and it has provided the opportunity to date very precious finds by collecting very small samples. The interest in developing the technique of AMS was so evident that, just few years after the measurements cited above, a first dedicated AMS system (based on a tandem accelerator) was designed and built [24] then, the first dedicated... 

Mass spectrometry is a sensitive analytical technique which is able to quantify known analytes and to identify unknown molecules at the picomoles or femto-moles level. A fundamental requirement is that atoms or molecules are ionized and analyzed as gas phase ions which are characterized by their mass (m) and charge (z). A mass spectrometer is an instrument which measures precisely the abundance of molecules which have been converted to ions. In a mass spectrum m/z is used as the dimensionless quantity that is an independent variable. There is still some ambiguity how the x-axis of the mass spectrum should be defined. Mass to charge ratio should not lo longer be used because the quantity measured is not the quotient of the ion s mass to its electric charge. Also, the use of the Thomson unit (Th) is considered obsolete [15, 16]. Typically, a mass spectrometer is formed by the following components (i) a sample introduction device (direct probe inlet, liquid interface), (ii) a source to produce ions, (iii) one or several mass analyzers, (iv) a detector to measure the abundance of ions, (v) a computerized system for data treatment (Fig. 1.1). 

Advances in TIMS-techniques and the introduction of multiple collector-ICP-MS (MC-ICP-MS) techniques have enabled the research on natural variations of a wide range of transition and heavy metal systems for the first time, which so far could not have been measured with the necessary precision. The advent of MC-ICP-MS has improved the precision on isotope measurements to about 40 ppm on elements such as Zn, Cu, Fe, Cr, Mo, and Tl. The technique combines the strength of the ICP technique (high ionization efficiency for nearly all elements) with the high precision of thermal ion source mass spectrometry equipped with an array of Faraday collectors. The uptake of elements from solution and ionization in a plasma allows correction for instrument-dependent mass fractionations by addition of external spikes or the comparison of standards with samples under identical operating conditions. All MC-ICP-MS instruments need Ar as the plasma support gas, in a similar manner to that commonly used in conventional ICP-MS. Mass interferences are thus an inherent feature of this technique, which may be circumvented by using desolvating nebulisers. 

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