The role of total-reflection X-ray fluorescence in atomic spectroscopy

Abstract Total-reflection X-ray fluorescence (TXRF) is a universal and economic method for the simultaneous determination of elements with atomic numbers > 11 down to the lower pg-level. It is a microanalytical tool for the analysis of small sample amounts placed on flat carriers and for contaminations on flat sample surfaces. Analyses of stratified near-surface layers are made possible by varying the incident angle of the primary beam in the region of total-reflection. This non-destructive method is especially suitable for thin layers of a few nanometres, deposited on wafer material although not usable as a microprobe method with a high lateral resolution. Furthermore, depth profiles of biological samples can be recorded by means of microtome sectioning of only a few micrometres, as, for example in the gradient analysis of human organs. In addition to micro- and surface-layer analysis, TXRF is effectively applied to element trace analysis. Homogeneous solutions, for example aqueous solutions, high-purity adds or body fluids, are pipetted onto carriers and, after evaporation, the dry residues are analysed directly down to the pg ml region. Particularly advantageous is the absence of matrix effects, so that an easy calibration can be carried out by adding a single internal standard element. A digestion or separation step preceding the actual determination becomes necessary if a more complex matrix is to be analysed or especially low detection limits have to be reached. A critical evaluation of the recent developments in atomic spectroscopy places TXRF in a leading position. Its outstanding features compete with those of e.g. electrothermal atomic absorption spectrometry (ETAAS), microwave induced plasma optical emission spectroscopy (MIP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) in the field of micro- and trace analysis and with Rutherford backscattering (RBS) and secondary ion mass spectrometry (SIMS) in the surface-layer analysis.

[1]  R. Klockenkämper,et al.  Determination of trace elements in high-purity aluminium by total reflection X-ray fluorescence after their separation on cellulose loaded with hexamethylenedithiocarbamates , 1989 .

[2]  J. Evans,et al.  A low-pressure beenakker-type microwave-induced helium plasma source as a simultaneous multi-element gas chromatographic detector , 1987 .

[3]  K. Heumann,et al.  Ultra-trace analysis of U, Th, Ca and selected heavy metals in high purity refractory metals with isotope dilution mass spectrometry , 1992 .

[4]  G. Tölg.  Extreme trace analysis of the elements-I Methods and problems of sample treatment, separation and enrichment. , 1972, Talanta.

[5]  M. Bolshov,et al.  Direct ultratrace determination of cadmium in Antarctic and Greenland snow and ice by laser atomic fluorescence spectrometry , 1991 .

[6]  W. Weng,et al.  Multielement analysis of aerosol samples by X-ray fluorescence analysis with totally reflecting sample holders , 1984 .

[7]  D. D. Boer,et al.  Total reflection X-ray fluorescence of single and multiple thin-layer samples , 1991 .

[8]  F. Ames,et al.  Principle and analytical applications of resonance lonization mass spectrometry , 1989 .

[9]  A. Knöchel,et al.  Untersuchungen zur Bestimmung von Spurenelementen in Blutserum mit Hilfe der Totalreflexions-Röntgenfluoreszenzanalyse , 1989 .

[10]  A. Prange,et al.  Determination of trace elements in the water cycle by total-reflection x-ray fluorescence spectrometry , 1987 .

[11]  M. Stoeppler,et al.  Arsenic determination in the ultratrace range by atomic absorption spectrometry after preconcentration of the hydride , 1988 .

[12]  L. Moenke-Blankenburg.  Laser micro analysis , 1986 .

[13]  J. Broekaert.  Trends in optical spectrochemical trace analysis with plasma sources , 1987 .

[14]  K. Niemax,et al.  Optical emission spectrometry and laser-induced fluorescence of laser produced sample plumes. , 1990, Applied optics.

[15]  D. Chambers,et al.  Atomic emission detector for gas chromatography and supercritical fluid chromatography , 1990 .

[16]  H. Schwenke,et al.  Trace Element Analysis using Total-Reflection X-Ray Fluorescence Spectrometry , 1991 .

[17]  R. Vis.  Accelerator based techniques for trace element analysis on the micrometer scale , 1990 .

[18]  V. Penka,et al.  Application of total reflection X-ray fluorescence in semiconductor surface analysis , 1989 .

[19]  A. Bohlen,et al.  Qualitative survey analysis of thin layers of tissue samples , 1987, International archives of occupational and environmental health.

[20]  G. Tölg,et al.  Große Angst vor kleinen Mengen ‐ die Bedeutung der Analytischen Chemie in der modernen Industriegesellschaft am Beispiel der Spurenanalytik der Elemente , 1985 .

[21]  J. Olesik.  Elemental Analysis Using ICP-OES and ICP/MS , 1991 .

[22]  A. Prange,et al.  Determination of trace element impurities in ultrapure reagents by total reflection X-ray spectrometry , 1991 .

[23]  J. Messerschmidt,et al.  A contribution towards the improvement of Se-determination in the pg-region by hydride AAS , 1987 .

[24]  A. Prange,et al.  Determination of trace elements in rainwater by total-reflection x-ray fluorescence , 1985 .

[25]  N. S. Nogar,et al.  Chromium detection by laser desorption and resonance ionization mass spectrometry , 1992 .

[26]  G. Tölg,et al.  Power of Detection and Accuracy in Elemental Trace Analysis , 1987 .

[27]  K. Niemax,et al.  Basic investigations for laser microanalysis: II. Laser-induced fluorescence in laser-produced sample plumes , 1989 .

[28]  G. Weber,et al.  Trace determination of nickel by microwave-induced plasma atomic emission spectrometry after preconcentration of nickel tetracarbonyl on chromosorb , 1990 .

[29]  P. Wylie,et al.  Applications of gas chromatography with an atomic emission detector , 1989 .

[30]  N. Jakubowski,et al.  Microchemical determination of platinum and iridium by glow discharge mass spectrometry , 1991 .

[31]  A. Bohlen,et al.  Simultaneous multielement determination in vegetable foodstuffs and their respective cell fractions by total-reflection X-ray fluorescence (TXRF) , 1990, Zeitschrift fur Lebensmittel-Untersuchung und -Forschung.

[32]  K. Heumann,et al.  Determination of dissolved selenium species in environmental water samples using isotope dilution mass spectrometry. , 1991, Analytical chemistry.

[33]  D. Schmidt,et al.  Application of total reflection X-ray fluorescence analysis for the determination of trace metals in the North Sea , 1989 .

[34]  Peter Schramel,et al.  Einsatz des Hochdruckveraschers HPA nach Knapp [1] für die voltammetrische Bestimmung von Spurenelementen in biologischem Material , 1987 .

[35]  J. Broekaert,et al.  Study of a toroidal argon and a cylindrical helium microwave induced plasma for analytical atomic emission spectrometry-I. Configurations and spectroscopic properties , 1990 .

[36]  J. Broekaert,et al.  Recent developments in atomic spectrometry methods for elemental trace determinations , 1987 .

[37]  A. Bohlen,et al.  Total reflection X-ray fluorescence—an efficient method for micro-, trace and surface layer analysis. Invited lecture , 1992 .

[38]  W. Michaelis,et al.  Multi-element determination of dissolved heavy metal traces in sea water by total-reflection x-ray fluorescence spectrometry , 1985 .

[39]  W. Michaelis.  Multielement analysis of environmental samples by total-reflection X-ray fluorescence spectrometry, neutron activation analysis and inductively coupled plasma optical emission spectroscopy , 1986 .

[40]  H. Tobschall,et al.  An efficient combined procedure for the extreme trace analysis of gold, platinum, palladium and rhodium with the aid of graphite furnace atomic absorption spectrometry and total-reflection X-ray fluorescence analysis , 1989 .

[41]  U. Reus.  Total reflection X-ray fluorescence spectrometry: matrix removal procedures for trace analysis of high-purity silicon, quartz and sulphuric acid , 1989 .

[42]  G. Knapp.  Sample preparation techniques―an important part in trace element analysis for environmental research and monitoring , 1985 .

[43]  D. D. de Boer,et al.  Glancing-incidence x-ray fluorescence of layered materials , 1991 .

[44]  G. Tölg.  Neue Wege zur analytischen Charakterisierung von Reinststoffen , 1979 .

[45]  C. Streli,et al.  Progress in X-ray fluorescence analysis , 1988 .

[46]  L. Moens,et al.  Analytical characterization of artists' pigments used in old and modern paintings by total-reflection X-ray fluorescence , 1993 .

[47]  A. Bohlen,et al.  Multielement speciation in vegetable foodstuffs by gel permeation chromatography (GPC) and total reflection X-ray fluorescence (TXRF) , 1991 .

[48]  A. Bos,et al.  The measurement of position dependent trace element concentrations with micro-proton induced X-ray emission , 1983 .

[49]  H. Aiginger.  Historical development and principles of total reflection X-ray fluorescence analysis (TXRF) , 1991 .

[50]  A. Bohlen,et al.  Quantification in total reflection X-ray fluorescence analysis of microtome sections , 1989 .

[51]  V. Scheuer,et al.  Application of total-reflection X-ray fluorescence spectrometry in material analysis , 1990 .

[52]  S. Haswell,et al.  Application of total-reflection X-ray fluorescence spectrometry to elemental determinations in water, soil and sewage sludge samples , 1991 .

[53]  H. Berndt,et al.  Trace analysis of high-purity iron by total reflection X-ray fluorescence spectrometry , 1990 .

[54]  D. D. Boer,et al.  Glancing-incidence X-ray analysis , 1993 .

[55]  C. Streli,et al.  Instrumental developments in total reflection x-ray fluorescence analysis for K-lines from oxygen to the rare earth elements , 1991 .

[56]  A. Bohlen,et al.  Determination of the critical thickness and the sensitivity for thin-film analysis by total reflection X-ray fluorescence spectrometry , 1989 .

[57]  G. Tölg,et al.  Zur Ursache und Vermeidung systematischer Fehler bei Elementbestimmungen in wäßrigen Lösungen im ng/ml- und pg/ml-Bereich , 1980 .

[58]  P. Hoffmann,et al.  Perspex as sample carrier in TXRF , 1987 .

[59]  A. Sanz-Medel.  Inductively coupled plasma-atomic emission spectrometry: Analytical assessment of the technique at the beginning of the 90's , 1991 .

[60]  E. B. Saloman.  A resonance ionization spectroscopy/resonance ionization mass spectrometry data service. II, Data sheets for Al, Ca, Cs, Cr, Co, Cu, Kr, Mg, Hg and Ni , 1991 .

[61]  R. Grieken,et al.  Total reflection X-ray fluorescence analysis using an extended focus tube for the determination of dissolved elements in rain water , 1991 .

[62]  J. A. C. Broekaert.  Analytische Chemie 1991 , 1992 .

[63]  N. Jakubowski,et al.  Hydraulic high pressure nebulization-application of a new nebulization system for inductively coupled plasma mass spectrometry , 1992 .

[64]  K. Niemax,et al.  Internal standardization in laser induced fluorescence spectrometry of microplasmas produced by laser ablation of solid samples , 1990 .

[65]  A. Prange.  Total reflection X-ray spectrometry: method and applications , 1989 .

[66]  D. Stuewer.  Glow discharge mass spectrometry — A versatile tool for elemental analysis , 1990 .

[67]  A. Bohlen,et al.  Microtome sections of biomaterials for trace analyses by TXRF , 1988 .

[68]  E. Jacob.  Inorganic multielemental analysis by fluorine volatilization systems (FV/FTIR and FV/MS) , 1989 .

[69]  P. Eichinger,et al.  Ultra-trace analysis of metallic contaminations on silicon wafer surfaces by vapour phase decomposition/total reflection X-ray fluorescence (VPD/TXRF) , 1991 .

[70]  R. Klockenkämper.  Über die Repräsentanz von inhomogenen Analysenproben , 1977 .

[71]  H. Schwenke,et al.  X-ray induced fluorescence spectrometry at grazing incidence for quantitative surface and layer analysis , 1991 .

[72]  U. Reus.  Determination of trace elements in oils and greases with total reflection X-ray fluorescence: sample preparation methods , 1991 .

[73]  A. Bohlen,et al.  Microanalysis of solid samples by total-reflection x-ray fluorescence spectrometry , 1987 .

[74]  G. Tölg,et al.  Analytische Chemie 1989 , 1990 .

[75]  R. Gijbels,et al.  Inorganic mass spectrometry , 1989 .

[76]  D. Goetz,et al.  Multielement-Analyse von Müllverbrennungs-Schlacke mit der Totalreflektions-Röntgenfluorescenz (TRFA) , 1987 .

[77]  C. Streli,et al.  A new X-ray tube for efficient excitation of low-Z-elements with total reflection X-ray fluorescence analysis , 1991 .

[78]  G. Tölg.  Where is analysis of trace elements in biotic matrices going to? , 1988 .

[79]  W. Michaelis,et al.  Multi-element determination of trace elements in whole blood and blood serum by TXRF , 1989 .

[80]  J. Broekaert,et al.  Study of a toroidal argon MIP and a cylindrical helium MIP for atomic emission spectrometry—II: Combination with graphite furnace vaporization and use for analysis of biological samples , 1990 .

[81]  C. Boss,et al.  Sensitivity comparison in a microwave-induced plasma gas chromatographic detector: effect of plasma torch design , 1992 .

[82]  R. Grieken,et al.  Determination of rare earth elements in geological materials by total reflection x-ray fluorescence , 1991 .

[83]  G. Tölg,et al.  Determination of selenium at ng/g- and pg/g-levels by hydride generation-atomic absorption spectrometry in biotic materials , 1985 .

[84]  Kay Niemax,et al.  Basic investigations for laser microanalysis: I. Optical emission spectrometry of laser-produced sample plumes , 1989 .

[85]  K. Niemax,et al.  Atomic absorption spectroscopy with tunable semiconductor diode lasers , 1989 .

[86]  P. Burba,et al.  Elementspuren-Bestimmungen (AAS, ICP-OES, TRFA) in natürlichen Wässern nach Voranreicherung: ein Vergleich , 1988 .

[87]  S. Parry.  Activation spectrometry in chemical analysis , 1991 .

[88]  Maria Becker,et al.  Determination of the heavy-metal ion-dose after implantation in silicon-wafers by total reflection X-ray fluorescence analysis , 1991 .

[89]  D. D. Boer.  X-ray standing waves and the critical sample thickness for total-reflection X-ray fluorescence analysis , 1991 .

[90]  G. Weber,et al.  Bestimmung der durch Flavonoide komplexierten Metalle in Zwiebeln mit Totalreflexions-Röntgenfluorescenzanalyse (TRFA) , 1987 .

[91]  K. Danzer,et al.  FANES — Test of applicability for the determination of heavy metals in river water , 1990 .

[92]  A. von Bohlen,et al.  Quantification of biomineralization: an in-vitro tissue culture system and microanalysis of calcium, phosphorus and trace elements by total-reflection X-ray fluorescence. , 1990, Biochemical and Biophysical Research Communications - BBRC.

[93]  H. Schwenke,et al.  Current work on total reflection x‐ray fluorescence spectrometry at the GKSS research centre , 1991 .

[94]  B. Schneider.  The determination of atmospheric trace metal concentrations by collection of aerosol particles on sample holders for total-reflection X-ray fluorescence , 1989 .

[95]  H. Schwenke,et al.  Total reflection X-ray fluorescence spectrometry for quantitative surface and layer analysis , 1991 .

[96]  W. Reuter.  Sputtered neutral mass spectrometry , 1989 .

[97]  P. Wobrauschek,et al.  Analysis of aerosols using total reflection X-ray spectrometry and industrial process monitoring using EDXRF (Energy Dispersive X-ray Fluorescence) , 1987 .

[98]  A. Knöchel.  TXRF, PIXE, SYXRF; Principles, critical comparison and applications , 1990 .

[99]  J. Broekaert,et al.  Comparative study of a beenakker cavity and a surfatron in combination with electrothermal evaporation from a tungsten coil for microwave plasma optical emission spectrometry (MIP-AES). , 1991, Talanta.