X-ray proton-induced

The determination of cesium in minerals can be accompHshed by x-ray fluorescence spectrometry or for low ranges associated with geochemical exploration, by atomic absorption, using comparative standards. For low levels of cesium in medical research, the proton induced x-ray emission technique has been developed (40). 

There are two principal sources of reliable partitioning data for any trace element glassy volcanic rocks and high temperature experiments. For the reasons outlined above, both sources rely on analytical techniques with high spatial resolution. Typically these are microbeam techniques, such as electron-microprobe (EMPA), laser ablation ICP-MS, ion-microprobe secondary ion mass spectrometry (SIMS) or proton-induced X-ray emission (PIXE). 

Principles and Characteristics Particle-induced X-ray emission spectrometry (PIXE) is a high-energy ion beam analysis technique, which is often considered as a complement to XRF. PIXE analysis is typically carried out with a proton beam (proton-induced X-ray emission) and requires nuclear physics facilities such as a Van der Graaff accelerator, or otherwise a small electrostatic particle accelerator. As the highest sensitivity is obtained at rather low proton energies (2-4 MeV), recently, small and relatively inexpensive tandem accelerators have been developed for PIXE applications, which are commercially available. Compact cyclotrons are also often used. 

Ion beam probes are used in a wide range of techniques, including Secondary Ion Mass Spectroscopy (SIMS), Rutherford backscattering spectroscopy (RBS) and proton-induced X-ray emission (PIXE). The applications of these and number of other uses of ion beam probes are discussed. 

Three analytical techniques which differ in how the primary vacancies are created share the use of such X-rays to identify the elements present. In X-ray fluorescence, the solid sample is irradiated by an X-ray beam (called the primary beam), which interacts with the atoms in the solid to create inner shell vacancies, which then de-excite via the emission of secondary or fluorescent X-rays - hence the name of the technique. The second uses a beam of electrons to create the initial vacancies, giving rise to the family of techniques known collectively as electron microscopy. The third and most recently developed instrumentation uses (usually) a proton beam to cause the initial vacancies, and is known as particle- (or proton-) induced X-ray emission (PIXE). 

C.H. Lochmiiller, J. Galbraith and R. Walter, Trace metal analysis in water by proton-induced x-ray emission analysis of ion-exchange membranes, Anal. Chem., 46 (1974) 440. 

This chapter discusses the range of analytical methods which use the properties of X-rays to identify composition. The methods fall into two distinct groups those which study X-rays produced by the atoms to chemically identify the elements present, and X-ray diffraction (XRD), which uses X-rays of known wavelengths to determine the spacing in crystalline structures and therefore identify chemical compounds. The first group includes a variety of methods to identify the elements present, all of which examine the X-rays produced when vacancies in the inner electron shells are filled. These methods vary in how the primary vacancies in the inner electron shell are created. X-ray fluorescence (XRF) uses an X-ray beam to create inner shell vacancies analytical electron microscopy uses electrons, and particle (or proton) induced X-ray emission (PIXE) uses a proton beam. More detailed information on the techniques described here can be found in Ewing (1985, 1997) and Fifield and Kealey (2000). 

Protons can also be used instead of X-rays or electrons to create the initial vacancies in the inner electron shells, giving rise to a method known as proton induced X-ray emission (PIXE). In these instruments a high intensity, highly focused beam of protons is produced by a van de Graaff accelerator,... 

Buoso, M. C., Fazinic, S., Haque, A. M. I., el al. (1992). Heavy element distribution profiles in archaeological samples of human tooth enamel and dentin using the proton-induced X-ray-emission technique. Nuclear Instruments and Methods in Physics Research B 68 269-272. 

With analytical methods such as x-ray fluorescence (XRF), proton-induced x-ray emission (PIXE), and instrumental neutron activation analysis (INAA), many metals can be simultaneously analyzed without destroying the sample matrix. Of these, XRF and PEXE have good sensitivity and are frequently used to analyze nickel in environmental samples containing low levels of nickel such as rain, snow, and air (Hansson et al. 1988 Landsberger et al. 1983 Schroeder et al. 1987 Wiersema et al. 1984). The Texas Air Control Board, which uses XRF in its network of air monitors, reported a mean minimum detectable value of 6 ng nickel/m (Wiersema et al. 1984). A detection limit of 30 ng/L was obtained using PIXE with a nonselective preconcentration step (Hansson et al. 1988). In these techniques, the sample (e.g., air particulates collected on a filter) is irradiated with a source of x-ray photons or protons. The excited atoms emit their own characteristic energy spectrum, which is detected with an x-ray detector and multichannel analyzer. INAA and neutron activation analysis (NAA) with prior nickel separation and concentration have poor sensitivity and are rarely used (Schroeder et al. 1987 Stoeppler 1984). 

Hansson HC, Ekholm AKP, Ross HB. 1988. Rainwater analysis A comparison between proton-induced x-ray emission and graphite furnace atomic absorption spectroscopy. Environmental Science and Technology 22 527-531. 

Landsberger S, Jervis RE, Kajrys G, et al. 1983. Characterization of trace elemental pollutants in urban snow using proton induced x-ray emission and instrumental neutron activation analysis. Int J Environ Anal Chem 16 95-130. 

J.W. "Elemental Trace Analysis of Small Samples by Proton Induced X-ray Emission" Anal Chem, 1975, 855. 

In a search for sources of alkaline materials in rural air and rain, we have sampled and performed multi-element analyses on ambient particulate matter and potential source materials. Ambient aerosols were sampled daily using single Nuclepore filters or Florida State University "streakers." Samples of soil and unpaved road materials were also collected and analyzed. The samples were analyzed by various multi-element methods, including ion-and proton-induced X-ray emission and X-ray fluorescence, as well as by atomic absorption spectrophotometry. Visual observations, as well as airborne elemental concentration distributions with wind direction and elemental abundances in aerosols and source materials, suggested that soil and road dust both contribute to airborne Ca. Factor analysis was able to identify only a "crustal" source, but a simple mass balance suggested that roads are the major source of Ca in rural central Illinois in summer. 

Johansson, T. B., R. E. Van Grieken, J. W. Nelson, and J. W. Winchester, Elemental Trace Analysis of Small Samples by Proton Induced X-Ray Emission, Anal. Chem., 47, 855-860 (1975). 

Brands proposed a calculation method in the case of segregation A special type of inhomogeneous, particulate objects is the surface analysis by microscopic techniques e.g. analytical electron sj troscopy, laser induced mass spectroscopy or proton-induced X-ray emission. Here the minimum sample size can be translated into the minimum number of specific sample points in the specimen under investigation. 

Mannermaa, J. P, Raisanen, J., Hyvonen-Dabek, M., Spring, E., and Yliruusi, J. (1994), Use of proton-induced X-ray emission (PIXE) analysis in the evaluation of large volume parenteral rubber stoppers, Int. J. Pharm., 103,125-129. 

Quantitative trace element analysis of diamond by LA-ICP-MS using different synthetic multielement carbon based standards (e.g., cellulose pellets) is discussed by Rege et al 2, whereby 13C was used for internal standardization. Concentrations of 41 elements were determined in two fibrous diamonds from Jwaneng Botswana (JWA 110 and 115) by relative sensitivity coefficients measured using the synthetic cellulose standard. The analytical data were verified by means of instrumental neutron activation analysis (INAA) and proton induced X-ray emission (PIXE).72... 

In 2006, Lobinski et al.1 reported on the imaging and speciation analysis of trace elements to study the element distribution, oxidation state, metal site and metal structure in biological environments using mass spectrometric techniques (LA-ICP-MS, SIMS, MALDI-MS) and non-mass-spectrometric techniques such as micro-PIXE (proton induced X-ray emission), XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) -the latter two techniques are very sensitive due the use of a more intense synchrotron beam.1... 

High-resolution compositional measurements are possible through use of a variety of microanalytical methods. Ideally, these should be non-destructive, can be targeted on small areas of sample, and have low minimum detection limits. Electron-probe X-ray microanalysis (EPXMA) and proton-induced X-ray emission (PIXE) techniques have both been used successfully on archaeological sediment thin sections (19, 20). Both techniques yield elemental composition data for a range of elements. EPXMA has the advantage of being nondestructive, whereas PIXE when used on thin-section samples is typically destructive conversely the detection limit for PIXE is lower than EPXMA. 

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