Evaluation and improvement of the rapid multi-element determination of trace amounts of pollutants in the media and materials in the iron and steel industry by means of ICP mass spectrometry

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EURO PEAN COMMISSION SCIENCE RESEARCH DEVELOPMENT technical steel research Measurement and analysis Evaluation and improvement of the rapid multi-element determination of trace amounts of pollutants in the media and materials in the iron and steel industry by means of ICP mass spectrometry Report W EUR 18512 EN STEEL RESEARCH EUROPEAN COMMISSION Edith CRESSON, Member of the Commission responsible for research, innovation, education, training and youth DG XII/C.2 — RTD actions: Industrial and materials technologies — Materials and steel Contact: Mr H. J.-L. Martin Address: European Commission, rue de la Loi 200 (MO 75 1/10), B-1049 Brussels — Tel. (32-2) 29-53453; fax (32-2) 29-65987 European Commission 'A m „, W '%pïi ■■ ^­'" Measurement and analysis Evaluation and improvement of the rapid multi-element determination of trace amounts of pollutants in the media and materials in the iron and steel industry by means of ICP mass spectrometry G. Staats, S. Finkeldei Dillinger Hüttenwerke Postfach 1580 D-66748 Dillingen H.-M. Kuss Universität GH Duisburg Lotharstraße 1 D-47057 Duisburg G. Willay, D. Ravaine IRSID Voie Romaine — BP 320 F-57214 Maizières-lès-Metz Cedex M. G. Del Monte, R. Falciarli CSM Via di Castel Romano, 100/102 1-00129 Rome EUR M. Chtaib Luxcontrol SA 1, avenue des Terres Rouges L-4004 Esch-sur-AIzette A.

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EURO PEAN
COMMISSION
SCIENCE
RESEARCH
DEVELOPMENT
technical steel research
Measurement and analysis
Evaluation and
improvement of the
rapid multi-element
determination of trace
amounts of pollutants
in the media and materials
in the iron and steel industry
by means of ICP mass
spectrometry
Report
W
EUR 18512 EN STEEL RESEARCH EUROPEAN COMMISSION
Edith CRESSON, Member of the Commission
responsible for research, innovation, education, training and youth
DG XII/C.2 — RTD actions: Industrial and materials technologies —
Materials and steel
Contact: Mr H. J.-L. Martin
Address: European Commission, rue de la Loi 200 (MO 75 1/10),
B-1049 Brussels — Tel. (32-2) 29-53453; fax (32-2) 29-65987 European Commission
'A m „,
W '%pïi ■■ ^­'"
Measurement and analysis
Evaluation and improvement of the rapid
multi-element determination of trace amounts of
pollutants in the media and materials in the iron and
steel industry by means of ICP mass spectrometry
G. Staats, S. Finkeldei
Dillinger Hüttenwerke
Postfach 1580
D-66748 Dillingen
H.-M. Kuss
Universität GH Duisburg
Lotharstraße 1
D-47057 Duisburg
G. Willay, D. Ravaine
IRSID
Voie Romaine — BP 320
F-57214 Maizières-lès-Metz Cedex
M. G. Del Monte, R. Falciarli
CSM
Via di Castel Romano, 100/102
1-00129 Rome EUR
M. Chtaib
Luxcontrol SA
1, avenue des Terres Rouges
L-4004 Esch-sur-AIzette
A. Gómez Coedo
CENIM
Avenida Gregorio del Amo, 8
E-28040 Madrid
Contract No 7210-GD/114/115/316/411/502/942
1 Aprii 1993 to 31 March 1996
Final report
Directorate-General
Science, Research and Development
1998 EUR 18512 EN LEGAL NOTICE
Neither the European Commission nor any person acting on behalf of the Commission
is responsible for the use which might be made of the following information.
A great deal of additional information on the European Union is available on the Internet.
It can be accessed through the Europa server (http://europa.eu.int).
Cataloguing data can be found at the end of this publication.
Luxembourg: Office for Official Publications of the European Communities, 1998
ISBN 92-828-4695-4
© European Communities, 1998
Reproduction is authorised provided the source is acknowledged.
Printed in Luxembourg
PRINTED ON WHITE CHLORINE-FREE PAPER Table of contents
0 Abstract 8
1 Introduction 9
1.1 Background and generalities
1.2 Expression of needs within steel industry
1.3 Main objective of the project 10
2 ICP-MS Instruments, Ways and Means 1
2.1 Description of the ICP-MS main devices
2.1.1 ICP ion source
2.1.2 Lens system and its influences
2.1.3 Mass filters and ion detection devices
2.1.4 Signal profiles 12
2.2 Other relevant accessories for sample introduction 1
2.2.1 Ultrasonic nebulization «
2.2.2 Hydride generation approach
2.3 LEVIS and data handling5
3 Results6
3.1 Water analysis results by ICP-MS 1
3.2 Routine/ on line determination by ICP-MS8
3.2.1 Thorium and uranium in iron ore and iron ore sinter
3.2.2 Determination of Sb, Bi, Pb and Sn in Steel 20
3.3 Results obtained with "Hydride Generation" method
3.3.1 Study of parameters to correctly generate hydrides5
3.3.2 Results obtained for As on different CRMs with hydride method coupled to ICP-AES 27
3.3.3 Research made on hydride method coupled with ICP-MS
3.3.4 Advantages of the hydride generation method coupled to ICP-MS 32
3.3.5 Limitations of the hydride method 34
3.4 Dust Samples
3.4.1 Sample preparation and homogeneity tests
3.4.2 Analysis of dust samples by XRF
3.4.3s of dust samples by ICP-AES .,,
3.4.4 Analysis of dust samples by ICP-MS 3.4.5 Results on dust samples MS 1 and MS 2 by ICP-MS 40
3.4.6 Analysis of leaching obtained from MS 1 and MS 22
3.4.7 Optimization of sample dissolution procedure3
3.4.8 ICP-MS method for inter-laboratory comparison test 5
3.5 Ultrasonic nebulizer 56
3.5.1 Advantages and limitations of USN5
3.5.2 Water analysis ~η
3.6 Flow injection analysis9
3.6.1 Introduction
3.6.2 FIAS and pneumatic nebulization
3.6.3 FIAS and high pressuren ^
3.7 Spark-ablation as sampling device for ICP-MS analysis of low-alloyed steels 71
3.7.1 Introduction η\
3.7.2 Experimental 72
3.7.3 Discussion3
3.7.4 Partial conclusions
3.8 Laboratory Information Management System (LIMS) 79
3.8.1 Integration of ICP-MS in a LIM-system
oU
3.8.2 Data flow in LIM-system
83
4 Conclusions 85
5 List of references gg
6 List of abbreviations (excepted element and company names) g7 List of tables
Table 1 : Comparison between certified and found values (all in μg/L) for NBS reference sample 1643c.
Table 2: ICP-MS results of an unknown sea water sample
Table 3: Th and U in Dillinger Hüttenwerke iron ore reference materials
Table 4: Th and U in Dillinger Hüttenwerke iron ore sinter reference materials
Table 5: Determination of Sb, Bi, Pb and Sn in steel; isotopes and their abundance
Table 6 a: Results on certified steel reference materials
Table 6 b: Calibration data of one measurement series
Table 7 a: Repeatability of the analytical results on B i and Sb determination in steel
Table 7 b: of the analytical results on Sn and Pb n in steel
Table 8: Results on Sb- and Bi-analysis in steel sample
Table 9: Detection limit (DL) for As in steel as function of concentration of NaBH4
Table 10: Detection limit (DL) for As in steel as function of n of HCl
Table 11 : Comparison of ICP-AES results with direct nebulization and with hydride generator
Table 12: Results for As obtained on different certified reference materials by ICP-MS
Table 13: Results of dust sample MS 1 by XRF
Table 14: Results of dust sample MS 2 by XRF
Table 15: Results of dust 6201 by XRF
Table 16: Results of dust samples MS 1 and MS 2 by ICP-AES
Table 17: Results of dust sample MS 1 by ICP-MS
Table 18: Results of dust sample MS 2 by ICP-MS
Table 19 a: Summarized results of dust sample MS 1 by ICP-MS
Table 19 b: d results of dust sample MS 2 by ICP-MS
Table 20: Results from leaching tests
Table 21: Multielement calibration solutions for quantitative analysis
Table 22: Microwave heating program (3 high-pressure digestion vessels simultaneously)
Table 23: Composition (% m/m) of ECSC 876/1 and Cupola standard reference materials
Table 24: Mineralogicai distribution of the main elements in EAF flue dust
Table 25: Results (% m/m) of ECSC 876/1 for two dissolution procedures
Table 26: Element concentrations of calibration solutions (major elements)
Table 27: Element s of n solutions (minor and trace elements)
Table 28: Intensity ratio USN/PN for two elements using ICP-AES
Table 29: Intensity ratios USN/PN using ICP-MS
Table 30 a: Results for the analyse of real water samples (mg/L) by ICP-MS and ICP-AES
Table 30 b: Results for the analyse of real water samples (mg/L) by ICP-MS and ICP-AES
Table 31 : Optimized FIAS programm for pneumatic nebulization Table 32: Reproducibility test pneumatic nebulizer
Table 33:y test; HPN
Table 34: Background values; FIAS and high pressure nebulization
Table 35: Sensitivity enhancement factors HPN : PN
Table 36: Quantitative element determination by means of HPN-FIA-ICP-AES in steel
Table 37: Comparison of DL in steel achieved for a group of elements by FIA-LC-ICP-AES with PN and
HPN
Table 38: Results (%, n=6) for the analysis of Standard Reference samples SS-456/1 to 460/1
Table 39: Parameters of the calibration curves performed with reference materials BAM 098/1 and
BAS series SS-456/1 to SS-560/1
Table 40: Detection limits DL and precision RSD at concentrations levels of 10 times the DL
Table 41 :n limits DL (Mg/g) for Al, Nb and V obtained with ICP-MS in comparison to ICP-AES. List of figures
Ultrasonic Nebulizer Fig. 1
Fig. 2 Hydride generator VGS 200 equipped with the conventional gas/liquid separator (in glass).
Fig. 3 Diffractogrammes of ECSC 876-1 and Cupola 6201 m standard reference flue dusts
Fig. 4 Percent recoveries of major elements in ECSC 876-1 and Cupola 6201 from different
microwave HNO3 + HCl digestions
Fig. 5: Flow schemes of the FIAS
Fig. 6: Peak height intensity dependance of the analyte signal on the sampling time
Fig. 7: Peak height dependance of the Fe-signal on the desorption time
Fig. 8: Cd calibration curve
Fig. 9: Mnn curve
Fig. 10: Reproducibility test of FIAS-LC-PN-ICP-AES using 1 mg/L Mn-solutions
Fig. 11 :y test of FIAS-LC-HPN-ICP-AES using 50 pg/Ls
Fig. 12: FIAS-LC-HPN-ICP-AES; a) Zn calibration curve; b) corresponding signal intensity peaks.
Fig. 13: FIAS-LC-PN-ICP-AES; a) Pbn curve; b)g signal intensity peaks . .
Fig. 14: Cyclone dimensions
Fig. 15: Intensities versus time profiles for 58Fe, 55Mn, 59Co, 90Zr, 121Sb and HB, from sample SS-459/1
Fig. 16:s versus time profiles for 58Fe, 51V, 27A1, 93Nb, 28Si and 31P, from sample SS-459/1 ...
Fig. 17: Hardware and software configurations for LIM
Fig. 18: Definition window for GBL ICP-MS
Fig. 19: General data flow of major LIM-components.. 0 Abstract
ICP-MS (Inductively Coupled Plasma Mass Sepctrometry) is a powerful and in the meantime
established method for trace and ultra-trace analysis. The aim of this project was to adapte the
capabilities of ICP-MS to the needs within steel industry. For this reason several European
laboratories from France, Germany, Italy, Spain and Luxembourg worked together in an colla­
borative interaction to evaluate and improve the ICP-MS technique.
Corresponding to the growing interest in controlling the environmental pollution caused by
residues from the industry, electric arc furnace dusts were examined. A homogeneity test was
carried out using XRF. A method for trace analysis of electric arc furnace dusts using ICP-MS
was developed and optimised. An inter-laboratory test was performed for trace analysis of two
dust materials using ICP-MS to assure the reliability and the reproducibility of the analytical
procedure. This test indicates satisfactory reproducibility of the results obtained by the same
analytical procedure in different laboratories using different equipment as well as an excellent
performance of the calibration procedure. In addition to this, leaching tests were carried out, in
order to evaluate the mobile fraction of metals in the dust samples.
Besides the development of appropriate sample preparation procedures including preconcen-
tration steps and matrix separation, several tasks for sample introduction as there are coupling
of hydride generation technique, ultra sonic nebulization and FIAS for ICP-MS were suc­
cessfully treated.
The Laboratory Information Management System (LIMS) was modified for adaptation to the
applied ICP-MS technique, to facilitate the integration of the system to support routine analyse
and to fulfil the requirements of the quality assurance procedure.