Copyright (C) JCPDS-International Centre for Diffraction Data 1999







R. Schramm’, J. Heckel’, K. Molt 2

‘Spectra Analytical Instruments, Kleve, Germany. 2Gerhard-Mercator- University Duisburg, Germany.

Screening is a fast method for qualitative precision quantitative FAST SCREENING

or semi-quantitative

analysis, in contrast to high design to handle both: The analyses of

analysis. This paper presents an instrumental ANALYSIS AND HIGH PRECISION


solids and liquids with real times between 150 and 600 s and a relative error < 10 % for the elements Na up to U will prove the screening method. The analysis of main components in Mn-concentrates within 600 s with a precision in the range of 10.06% will prove the high analysis.

precision quantitative


Screening analysis is a traditional application of energy dispersive x-ray fluorescence [l-3]. In the past, screening meant qualitative analysis or,’ at best, semi-quantitative analysis. In recent

times, the aim of further development of EDXRF spectrometers was improvement of detection limits and sensitivities of the analyzing elements. This resulted in quantitative analysis

comparable with atomic emission or absorption methods for several applications [4]. One of the great disadvantages of common EDXRF systems is long measurement times to get low detection limits and high precision. Also the use of one x-ray tube in a specific excitation arrangement cannot give optimal excitation conditions for light anJ heavy elements. The use of primary beam filters combined with varying tube voltages can improve the situation.

The main goal would be to combine the quantitative analysis with short measurement times to get a quantitative screening analysis. One way this result can be reached is using polarized x-rays

For liquids. the preparation as a pellet would be necessary. This allows for conducting a quantitative screening analysis within a real time between 150 and 600s with a relative error below 10 % for all elements between Na and U.15% for main component analysis. if there is an interest in elements like Na. In contrast to WDXRF systems.Copyright (C) JCPDS-International Centre for Diffraction Data 1999 385 for excitation in an EDXRF system [5-lo]. For high precision analysis the samples were prepared as glass beads. The irradiation chamber could be operated under vacuum or by using a gas purge either with nitrogen or helium. The automatic sample changer could be equipped with 20 samples maximum. simple pouring into a cuvette can be used. Mg and Al. SAMPLE PREPARATION The analytical target of analysis defines the necessary sample preparation technique. the total measurement time (real time) for main components like Mg . By using a BRAGG polarizer in the ED(P)XRF system. This allows the determination of components in different matrices (eg oil and water) using the same calibration. However. The available targets were A1203 and B& used as BARKLA polarizer. MO and Co used as secondary targets. EXPERIMENTAL SET-UP The instrumentation used was a SPECTRO XLAB 2000 equipped with a 400 W Rh end window tube and a Si(Li) detector with a resolution of 148 eV (1000 cps Mn Ka). The high stability of an XRF system generally allows analysis with a precision better than 0. . For quantitative screening analysis with a relative error < 10% the direct measurement of powders should be sufficient. Thus the quantitative screening method achieves results with a relative error < 10% although the matrix of the sample is unknown. The background reduction by using polarized x-rays for excitation results in very low detection limits and high sensitivities. an HOPG (High Oriented Pyrolitic Graphite) - crystal used as BRAGG polarizer and Al. To get a flexible screening method valid for a large number of different matrices the fundamental parameter algorithm was combined with an empiric matrix calibration. the lower sensitivity of common EDXRF systems leads to extremely longer counting times.Fe in a light matrix (eg glass bead) could be decreased to less than 600s [ 111.

Cl. Bi. Pb. Zn. Y. Fe. La. Br. 3current is optimized for each measurement to maximum countrate. Nd. Sb. *liquids. P. MO. Ta. Ge. Zr.Zr (K).141. V. Th. Cd. a main target is saving time and receiving a fast overview of the sample contents. target MO &03 HOPG type of target secondary Barkla Bragg excited elements voltage 35 kV 49. Te. Table 2: Standards used for calibration of powders. As. The non-detectable elements with Z < 11 can be taken into account by using an empiric calibration of the mass absorption coefficient versus the Compton intensity. Cs. Ba. No Standard with the following calibrated elements 1 2 3 4 5 6 7 8 9 10 Term standards Si. TI. Pr . Rb. Ag. The evaluation of the resulting spectra is done by a method based on fundamental parameters. I.5 kV 10’ / 20L kV curren? I Cr . Mn. Ce. Ga. Table 1 shows the excitation conditions used for screening analysis of liquids.Bi (L) Y-Ce Na-V 4mA 6mA 2mA ‘solids. W. Co. Cu. This is analogous to the well-known Compton-Method [ 12. Table 1: Excitation conditions for screening analysis.scattered MO Ka radiation of the MO target for powders and liquids. Sn. Sm. NaBr SARM05 . Nevertheless the high performance of the polarized excitation will achieve concentrations down to the low ppm level. K. powders and pellets. Se. The standard samples shown in Table 2 and 3 are used to calibrate the mass absorption coefficient of the sample versus the Compton . U Ash Portland Cement Basic Slag Sediment Rock Soil Phosphate Rock Bauxite Pyroxenite 876-i BCS372/1 BCS382ll GSDll GSR07-09 GSS6 NBS120c NIST696 NaCI. In. Pr. Ti. Sr. Ca. Nb. Cr. Ni.Copyright (C) JCPDS-International Centre for Diffraction Data 1999 386 RESULTS AND DISCUSSION QUANTITATIVE SCREENING ANALYSIS For screening analysis.

P.0 Figure 2: Calibration of copper in water.lO. Cd.500 pg/g Elements Ag. Br. Figure 1: Calibration of zinc in powder (real time: 150s). Te. ICP Multi Element Standard IV (Merck) Multi Element Standardsolution (Bernd Kraft) Figure 1 and 2 show the calibration curves for Zn in powders and Cu in liquids as examples.and oil based liquids (real time: 200s). I Ag. Al. Ca. Mn.O% 1 . Cone.1000 pg/g 1 .001 .0% 0.Copyright (C) JCPDS-International Centre for Diffraction Data 1999 387 Table 3: No Standards for calibration of liquids. Cu. Zn As.0 Cu [pg/g] certified 1000. . TI.0 100. Ca. In. V. TI Standard 1 2 3 4 5 Conostan S-21 MBH SMIN-5%-4 Laboratorystd. Hg. Fe. MO. Mn. S. 1 . 10. Sb. Cr. Ba. Co. Sn. Sn. Mg.6 show the results of different samples : powder.001 . Cu. K. Ti. Tables 4 . Zn s Cl. Cd. Bi. Fe. Cr. Al. P. Ni.5. Ga. Sr. monophase liquid and polyphase liquid measured as ‘unknown’ and evaluated with the calibrations mentioned.lg/g 0. Ni. Pb. Na.900 l. Ba. Si. Pb. range.

XLA B 2000 known concentrations cont. Mg.2 f 1 161 i2 47.2 + I 21.4 + 3 16k3 22 f 2 60*2 22. . This avoids surface effects. Table 5: Element Results of ICP multi element standard solution I (Merck) (real time: 600s). Table 6: Element Results of a two liquid phased sample. XLA B 2000 cont. apart from preparing . real time 6OOs.3g sample + lg charcoal as adsorbing material. tls/sJ f/J&71 *impurity of charcoal. Al and Si. which have a high influence elements. The calibration used is similar on the determination of light the to the powder calibration. ’ &g/g] 25 + 3 7.Copyright (C) JCPDS-International Centre for Diffraction Data 1999 388 Table 4: Results BCR-176 (ash) prepared as powder (real time: 450s). If there is interest in light elements like Na.1 io. the samples must be prepared as pellets.5 221*2 certified concentrations tw4l1 25 r2.5 20 *2 50*5 2oi2 15oi15 5oi5 2oi2 200 f 20 Cr Mn Fe co Ni Zn Ga Ag Cd Pb ’ counting error (20).5 5 + 0.5 15 *1.

Table 7: Results of GSR-02 prepared as pellet (real time 150s). . Table 7 shows the results of the standard GSR02 (andesite) prepared as pellet in comparison to the certified values.Copyright (C) JCPDS-International Centre for Diffraction Data 1999 389 standards as pellets and measuring in a vacuum. ’ counting error (20).

.19% corresponds to a relative error of 0. To get the precision of the XRF method. Table 8 shows the excitation conditions used for the analysis.5 mA real time 250s 290s Na.13 % which points out the performance and stability of the system.7%. Mg Al .Fe Table 9: Calibration data for Mn concentrates prepared as glass beads. The main uncertainty is the error in the chemical analysis performed to achieve the reference values. This gives a RSD for Mn of 0. The samples were prepared as glass beads. An overview of the achievable precision as a function of concentration is shown in table 11.5 kV current 12. target Al HOPG type of target Secondary Bragg excited elements vo/tage 14. The use of a HOPG . the RMS of 0. For a mean value of 26.crystal as a BRAGG-polarizer resulted in a decrease of measurement time (real time) below 10 minutes.5 kV 14. The calibration of the main component Mn is presented in detail in figure 3. The calibration used was based on the alpha normalization method due to Keith Norrish [16].5 mA 12. a common raw material for production of Fe-alloys. Table 9 shows the calibration parameter for the elements of interest. Table 8: Measurement conditions for analysis of Mn-concentrates.9% Mn. one standard was measured 10 times (table 10). One example is the analysis of the main components in Mnconcentrates.Copyright (C) JCPDS-International Centre for Diffraction Data 1999 390 HIGH PRECISION ANALYSIS The development of ED(P)XRF also makes it possible to achieve high precision analysis [ 151.

05 0.05 certified value tw 8.800 16.04 15.24 f 0.Copyright (C) JCPDS-International Centre for Diffraction Data 1999 391 20.00 certified values 30.10 0.06 s 0.310 k.01 20 .03 36.830 ?r 0.5 . prepared as glass bead.19% Table 10: precision determined for a standard sample of raw material.50 MgO A1203 SiO2 S CaO Mn Fe Table 11: Precision concerning different concentration ranges.002 10. component calculated value I%1 8.3 < 0.530 3.06 3.90 F 0.05 8.28 f 0.06 10.90 8.013 2 0.06 I 0. RMS = 0.319 10. measured 10 times (given error corresponds to 95% confidence limit).5 Standard deviation [%] < 0.14 36. Concentration range 1x1 70-99 40-70 3-40 0.628 k 0.00 for Mn rh] Figure 3: Calibration curve for Mn in Mn-concentrates.97 + 0.

Methods 115.C. R. Nucl.43 1 (1969). Atom. (2) A.297 (1974). 7. (7) J. (8) J. (16) K. Jaklevic. but a reality.. Brumme. Heckel. Piorek. Heckel. X-Ray Anal. Heckel. 30. Vol.T. J. Anal. XRF Technique as a Method of Choice For On-Site Analysis of Soil Contaminants and Waste Material. X-Ray Anal..R. Dzubay. Haschke. X-Ray Anal. J. Chem. M. Schramm. 40. Brumme. Vol. Bragg and Barkla Polarization in EDXRF. Am. The choice between pellets and fusions has to be done carefully. X-Ray Spectrom. REFERENCES (1) S. Harding. (6) E. Screening of Hazardous Waste with an Energy Dispersive X-Ray Fluorescence Spectrometer. Scattered X-Rays as Internal Standard in X-Ray Emission Spectroscopy. Schramm. Taggart. Multi-Element Trace Analysis of Rocks and Soils by EDXRF Using Polarized Radiation. 20 (1991) 287. X-Ray Anal. (11) R. Russell. Adv. J. Gerhard-Mercator-University Duisburg. 33. May .M. especially for high precision analysis. Spectra Analyse 196. James.Copyright (C) JCPDS-International Centre for Diffraction Data 1999 392 CONCLUSION Screening analysis and high precision analysis with the same instrumental design is no longer only a concept. R.281 (1992). Heckel.C. Jr. 1306 (1958). . Willis. Adv. Kemp. Adv. Andermann and J. 1133 (1963). (12) G.. Mineral. An accurate X-ray spectrographic method for the analysis of a wide range of geological samples.P. Using Barkla polarized X-ray radiation in energy dispersive X-RayjZuorescence analysis (EDXRF). Trace Microprobe Tech. 33. J. Jarrett. (13) R. The applications presented serve as examples of the high flexibility concerning different analytical problems and the high performance of the technology. 28.25 (1997). X-ray Anal. Hutton. Vol.639 (1990). Weinert and K. 48. Germany (1995). A. (9) J. Schramm. Diploma thesis. Norrish and J. Schindler. Sample preparation greatly influences the accuracy of the results achieved. Cosmochim Acta 33. 33.. R.655 (1990). 13(2) (1995) 97. J.V. M.647 (1990). accepted for publication (1996).Journal of Analytical Atomic Spectrometry. Matrix Corrections In Trace Element Analysis by X-Ray Fluorescence: Estimation of the Mass Absorption Coefficient by Compton Scattering. Controle d’entre’e de rejets organiques et d’hydrocarbures halogen& par EDXRF. (4) P. Walsh. 5. Adv.June (1997). Jrrner.E. (3) N. Nevertheless. 12. (15) J. M. B. Jacobus.A. (5) T. Heckel. Application of Field Mobile EDXRFAnalysis to Contaminated Soil Characterization. Reynolds. Geochim. the applications can be improved by expanding the number of standards containing additional elements. J. Anal. A Simple Method for Background and Matrix Correction of Spectral Peaks in Trace Element Determination by X-Ray Fluorescence Spectrometry.G. (10) R. Spectrom.W.P. Feather and J. Jnstrum. Vol. 17 (1985). (14) C.41 (1976). Adv.. Principles and Applications of Energy-dispersive Xray Fluorescence Analysis With Polarized Radiation. X-ray Spectrom.

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