EXRS 2008

European Conference on
X-Ray Spectrometry

Organized by:

Ruer Bokovi Institute, Zagreb, Croatia
In cooperation with:

Ministry of science, education and sports, Croatia

International Atomic Energy Agency

European X-ray Spectrometry Association

BOOK OF ABSTRACTS
16th 20th June 2008
Cavtat, Dubrovnik, Croatia

ISBN 978-953-6690-73-2
Book of Abstracts, EXRS-2008 European Conference on X-Ray Spectrometry
Publisher: Ruer Bokovi Institute
Editors: Stjepko Fazini, Milko Jaki
Copies: 300
Zagreb, 2008

Abstracts
Oral Sessions

I1
Tracking gold forgeries with X-rays
M. F. Guerra
Centre de Recherche et de Restauration des Muses de France - UMR171 CNRS
Palais du Louvre-Porte des Lions 14, quai Franois Mitterrand
75001 Paris - France
Among the gold objects kept in museums, a few arrived from ancient private
collections or were acquired in the antiquities market. Owing to the attention given
by scholars and connoisseurs to the newly discovered ancient civilizations, some
periods were characterized by a high production of pastiches and fakes. Queries
on the authentication of gold work from these periods are difficult to achieve. The
absence of documents either on the archaeological context of the finds or on the
acquisitions as well as on the restorations carried out in the past complicates the task.
These difficulties increase in the case of exceptional objects and less widespread
civilisations.
In addition to the ability required to recognize and identify genuine items and
fakes, non-destructive elemental analysis and exam can provide major information
on the goldsmiths techniques and on the origin of the metal. The techniques based
on X-rays (radiography, PIXE, SR-XRF, SEM-EDS) are essential for authentication.
By combining exam and analysis with studies on iconography, style and period
and by comparing suspected with genuine objects it is possible to list criteria to
distinguish the fakes. The aim of this work is to show the role of those techniques in
the case of Etruscan and Pre-Columbian pastiches and repaired items from museum
collections.

O1-1
Investigations on ancient Artemision gold objects using
portable -XRF
M. Melcher1,2, B. Bhler3, M. Schreiner1,2 and U. Muss4
Institute of Science and Technology in Art, Academy of Fine Arts, Schillerplatz 3,
1010 Vienna, Austria
2
Institute of Chemical Technologies and Analytics, Vienna University of Technology,
Getreidemarkt 9/164, 1060 Vienna, Austria
3
Vienna Institute for Archaeological Science, Franz Klein-Gasse 1, 1190 Vienna,
Austria
4
sterreichisches Archologisches Institut, Franz Klein-Gasse 1, 1190 Vienna,
Austria
1

Within two measurement campaigns in summer 2006 and 2007 in the

Archaeological Museum of Istanbul and in the Ephesus Museum of Selcuk/Turkey
more than 80 ancient gold objects (e.g. small statuettes, brooches and coins)
from the 8th-6th century BC, were analysed. Therefore, two self-built portable XRF
instruments [1, 2] were used in order to gain information on the chemical composition
and homogeneity of the artifacts discovered during excavations in the sanctuary of
Artemis at Ephesus since the 1960s. The evaluation of the raw data was carried out
using WinAxil software [3] These quantitative results and complementary studies
on the manufacturing techniques of the objects will contribute to our knowledge of
metalworking, trade, as well as the transfer of ideas and technologies at Ephesus
and in Western Asia in the Archaic period.
The XRF data exhibited highly homogeneous alloys in most cases, mainly
consisting of gold (Au), silver (Ag) and copper (Cu). A high compositional variation of
these elements between different objects could be determined: the Au-content ranged
between about 48 and 99.9%, the Ag-concentration between <dl and 51%, while
copper was generally present at a comparably low level between 0.1 and 4.4%.
This has shown us the range of gold alloys represented within the collection
and permitted us to distinguish between natural and artificial gold alloys (including
the identification of refined gold !) and to obtain some information regarding the
provenance of the raw materials (in most cases, presumably Lydia).
In some cases, gold objects which were closely related from a typological,
stylistic and/ or technological point of view, were also very similar in composition,
which differed only in the sub-percent range.
[1] V. Desnica, M. Schreiner, X-Ray Spectrometry 35 (2006), 280-286.
[2] Compact Portable Roentgen Analyzer, within the EU-Project No. SMT4CT98-2237, project coordinator: Prof. Dr. K. Janssens, University of Antwerp
[3] Win Axil X-Ray Analysis Software, Canberra Eurisys Benelux, Belgium
6

O1-2
Discovery of a Hidden Van Gogh Painting by means of HighEnergy XRF mapping
K. Janssens1, J. Dik2, G. Van der Snickt1, L. Van der Loeff3 and K. Rickers4
University of Antwerp, Department of Chemistry, Antwerp, Belgium
Delft University of Technology, Dept. Materials Science, Delft, the Netherlands
3
Krller-Mller Museum, Otterlo, The Netherlands
4
HASYLAB at DESY, Hamburg, Germany
1

The painter Vincent Van Gogh (1853-1890) is generally considered as one

of the most important painters of the 19th-C. As a result, his short but very productive
career is subject of intensive study by art historians, historians, (conservation)
scientists, etc. In the past, traditional radiographies made clear that Van Gogh
covered several of his paintings with a new composition. The recycling of canvases
might have been prompted by his difficult financial situation. In addition, his style
changed so dramatically at certain moments in time that he might have regarded
preceding works of art as obsolete and thus eligible for overpainting.
An examination of the Van Gogh paintings and the corresponding
radiographies of the Krller-Mller museum (NL) confirmed the existence of these
concealed compositions. However, radiographies usually allow only to discern some
coarse outlines but prevent to observe further details. The visualization of such
covered compositions would be of great interest to both Van Gogh specialists as the
public audience.
This talk discusses the first successful attempt to re-establish a hidden
portrait by means of elemental mapping with synchrotron based -XRF. A small
canvas (ca. 30 x 20cm), representing a patch of grass (ca. 1886-87) was transported
to beam line L at the HASYLAB synchrotron facility in Hamburg. A conventional
radiography of this painting reveals the outlines of a human face but no identification
or correlation with the existing oeuvre of the artist was feasible. A square area of ca.
15x15 cm, corresponding with the position of the head, was scanned with a quasi
monochromatic X-ray beam of 35.5 keV of 0.3x-0.3 mm2 cross-section.
One of the (trace) element maps obtained in this manner allows to visualize
the covered portrait of a peasant woman with unprecedented detail. On-going
spectroscopic research is focused on the identification of the nature of the pigmented
compound with which the portrait was painted. Additionally, art historians are currently
involved in a stylistic comparison between Van Goghs existing oeuvre and the newly
revealed portrait, including a re-examination the preserved correspondence of Van
Gogh in an attempt to identify documentary links to this portrait.

O1-3
Archaeological analysis of Roman glassexcavated from Zadar,
Croatia by a newly develped portable XRF spectrometer for
glass
K.Tantrakarn1, N. Kato1, A. Hokura1, Y. Fujii2, S. Gluevi3, and I. Nakai1
1

Department of Applied Chemistry, Tokyo University of Science

(1-3 Kagurazaka, Shinjuku, Tokyo 162-8601 Japan)
2
Universit Degli Studi Roma Tre
3
Archaeological Museum Zadar

A newly developed portable X-ray fluorescence spectrometer has been

evaluated through the on site non-destructive analyses of 109 Roman glass artifacts
excavated at a Roman necropolis found in Zadar, Croatia. The spectrometer has
been designed for on site analysis of archaeological glass objects. The detector unit
consists of X-ray tube with a Pd target operated at up to 40kV, SDD with a MOXTEK
AP3.3 polymer window and an enlargeable vacuum sampling chamber. A capillary
tube or a pyrolytic graphite monochromator can be selected to obtain white X-ray or
Pd K line source. With this system, quantitative analysis of the light elements such
as Na, Mg, and Al, important components of glass as well as heavy trace elements
can be successfully made and the analytical results were used as characterization
of the ancient glass objects.
The glass samples consist of several groups of square jug, small square
flask, large cinerary urn and bell-shaped flask, dating from the 1st century to the
beginning of the 5th century. The obtained results evidenced the use of Natron as
fluxing agent in glass making process. The transition metals such as Mn, Fe, Cu and
Co were found to be responsible for the colors of the pale bluish green, green, purple
and deep blue glass vessels. We focused on the differences in the use of Mn and/
or Sb as decolorizing agent for colorless glass to classify a group of the bell-shaped
flask which is believed to be an original product of at least one local workshop of
Zadar in the Roman period (1) We will discuss the analytical results of the vessels
excavated from 10 different localities along the coast of Croatia.
[1] S. Gluevi, Annales du 14e Congrs, AIHV, (1998), 182-189.

O1-4
Physical and chemical analysis of a 16th century manuscript
M. Costa, M. Manso and M. L. Carvalho
Universidade de Lisboa, Faculdade de Cincias, Centro de Fsica Atmica,
Av. Prof. Gama Pinto 2, 1649-003 Lisboa, Portugal
This work is focused on a 16th century codex of the Chronicle of the Portuguese
king Dom Fernando (1367-1383, b.1345), originally written by Ferno Lopes (c.1380
c.1460), who was officially appointed chronicler of Portugal in 1434. No originals
written by Ferno Lopes are extant, 47 copies remaining today of Chronicle of Dom
Fernando, mostly anonymous and dated from the 16th to the 18th century. Our study
includes microscopic analysis of the codex paper fibers, energy dispersive X-ray
fluorescence analysis of the elemental content of the paper as well as regions where
ink is present. Infrared and mass spectrometry analysis were also used in order to
identify the type of ink used in the manuscript. The microscopic analysis of paper
revealed the presence of textile fibers commonly used in papermaking before the 18th
century. Ink analysis indicated a ferrogallic composition and elemental composition
of the paper suggested three different origins, which has been corroborated by
watermark analysis.

O1-5
Non-destructive determination of the Silver content in Roman
coins dated to 308-310 A.D. by combined use of the PIXE-alpha,
XRF and DPAA techniques
F.P. Romano1,2, A. Esposito2,3, S. Garraffo4, G. Pappalardo.2,3, L. Pappalardo1,2,F.
Rizzo2,3
IBAM-CNR, Catania
INFN Laboratori Nazionali del Sud, Catania
3
Dipartimento di Fisica e Astronomia, Universit di Catania
4
ITABC-CNR, Montelibretti, Roma
1

The quantitative determination of the composition of ancient coins can give

useful information to archaeologists, numismatists and conservators. The use of
non-destructive techniques is preferable especially when a large number of samples
have to be investigated. However analyses have to be performed with caution since
ancient alloys present often surface effects due to corrosion/oxidation processes
or to the manufacturing techniques (the presence of enriched patinas with nobles
metals) that produce meaningful variation of the composition respect with the interior
of the coins.
At the INFN/CNR LANDIS laboratory of Catania, a non-destructive protocol
of analysis, based on the combined use of the portable PIXE-alpha [1] and XRF
spectrometers and of the new DPAA (Deep Protons Activation Analysis) method [2],
was developed for studying the Roman folles dated to 300 330 A.D. belonging
to the Misurata treasure (Lybia), one of the most important finding of coins in the
Mediterranean Area.
The use of the PIXE-alpha system allowed to determine the composition
of the few microns thick silver-enriched patina of the bronze coins while the DPAA
techniques, making use of high energy proton beams, was used to determine the
silver content in the core of the samples, minimizing the surface effects due to the
enriched patina; the XRF techniques was used to explore the composition of the
interface between the patina and the substratum of the coins.
In the present work the data obtained from the analysis of 15 coins dated
back to 308-310 A.D. are presented and discussed; results allowed archaeologists
to make some historical hypothesis about this period of the Roman empire.
[1] L. Pappalardo, F.P. Romano, S. Garraffo, J. de Sanoit, C. Marchetta, G.
Pappalardo, Archaeometry, 45 (2003) 333-339.
[2] G. Pappalardo, A. Esposito, G.A. Cirrone, G. Cuttone, S. Garraffo, L.
Pappalardo, F. Rizzo, F.P. Romano, S. Russo, in press in NIM B.

10

O1-6
-XRF analysis of museum metal collections across the
Mediterranean basin
V. Kantarelou1, A. G. Karydas 1, D. Sokaras1, Ch. Zarkadas1, V. Argyropoulos2, M.
Giannoulaki2, C. Degrigny3, S. Golfomitsou3, L. Mahfoud4 A. Kurdab4, M. Azar4,
Ahmad Almansour5, J. Alshehne5, N. Haddad6, A. Arafat6, M. Bani Hani7, M.S.
Shunnaq7, Z. Al-Saad7, A. Giakoumaki8 and D. Anglos8
Institute of Nuclear Physics, NCSR Demokritos, 15310, Athens, Greece
Dept. of Conservation of Antiquities & Works of Art, T.E.I. of Athens,12210 Ag. Spyridonos,
Aigaleo, Greece
3
Heritage Malta, Conservation Division (HM), Kalkara CSP12, Malta
4
Ministry of Culture, Directorate General of Antiquities & Museums, Syria
5
Department of Material Engineering, Aleppo University, 16108, Aleppo, Syria
6
The Royal Scientific Society (RSS), Al-Jubaiha 11941, Jordan
7
Faculty of Archaeology and Anthropology, Yarmouk University, Jordan
8
Institute of Electronic Structure and Laser, Foundation for Research and Technology Hellas
(IESL-FORTH), P.O. Box 1385 71110 Herakleion, Crete, Greece
1

Micro- X-ray fluorescence spectrometry (-XRF) analysis has been well established
during the last decade as an important diagnostic and analytical tool in archaeological and
conservation science. The availability of relevant commercial and portable units is indicative,
however, research groups have also developed portable setups to meet the needs of cultural
heritage analysis [1-2]. Most of the reported studies have been undertaken in laboratories
without exploring one of the main advantages of the -XRF which is the potential to analyze
in the museum environment systematically collections of artefacts.
Analysis of archaeological and/or historical metal artefacts using micro-XRF
encounters a number of analytical challenges related to the identification of corrosion
products present on the surface, characterization of artefacts details, reliable compositional
analysis etc. The development of analytical methodologies depending on the collection and
the improvement of quantification aspects of the analysis can give important information
about the raw materials, manufacture techniques and state of preservation supporting
archaeometallurgical and conservation studies.
Within the FP6 project PROMET [3], a portable micro-XRF spectrometer, based on
an industrial prototype with customized hardware components was characterized, optimized
and used to analyse metal collections from the Mediterranean basin. More specifically, high-tin
bronze mirrors of the 2nd cent BC from the museum of Ancient Messene in Greece, gilded mild
steel 16th cent armours from the Palace Armoury in Malta, gilded copper and gold artefacts
from the 3rd and 2nd Millennium B.C. from the Damascus National Archaeological Museum in
Syria, Roman copper alloy artefacts from the Umm Qais site and gold Ottoman coins from
the collection of the Numismatic museum of Yarmouk University, Jordan were analysed and
will be presented. In addition, examples of the in situ synergistic use of LIBS and micro-XRF
analysis will be discussed.
[1] L.Cheng, X. Ding, Z. Liu, Q. Pan, X. Chu, Spectrochim. Acta 62B (2007) 817-823.
[2] G. Buzanich, P. Wobrauschek, C. Streli, A. Markowicz, D. Wegrzynek, E. Chinea-Cano,
S. Bamford, , Spectrochim. Acta 62B (2007) 1252-1256.
[3] PROMET, PROtection of METals, FP6-2002-INCO-MPC-1, www.promet.org.gr

11

O1-7
Provenance characterization of iron age ceramics from
archaeological salvage excavations of Baku-Tbilisi-Ceyhan
crude oil pipeline: Case of Erzurum and Erzincan sites (Turkey)
P. Arikan1, B. Ender2, S. Y. enyurt3 and R. Kasap4
Physics Department, Gazi University,Faculty of Arts and Sciences,06500
Teknikokullar,Ankara,Turkey
2
Physics Department, Gazi University, Institute of Science and Technology, Maltepe, Ankara,
Turkey
3
Archaeology Department, Gazi University,Faculty of Arts and Sciences,06500
Teknikokullar,Ankara,Turkey
4
Statistical Department, Gazi University,Faculty of Arts and Sciences,06500
Teknikokullar,Ankara,Turkey
1

The Baku-Tbilisi-Ceyhan (BTC) crude oil pipeline brings oil from the
landlocked Caspian Sea to international markets. 1768 km pipeline winds its way
through the historically fertile countries of Azerbaijan, Georgia and Turkey, considered
to be among the worlds most archaeologically wealthy countries. Turkeys cultural
legacy is not only ancient, but it is also extremely complex. Archaeological salvage
excavations were carried out at 17 sites in Turkey. Research Center for Archaeology
of Gazi University (ARCED) was responsible for the cultural heritage management
in accordance with ESIA.
This study was executed within the scope of the archaeological salvage
excavations of the Baku-Tbilisi-Ceyhan (BTC) crude oil pipeline project. The
qualitative and quantitative results of X-ray fluorescence analysis of thirty eight
ceramic samples, dated to Iron Age, from Buyukardic-Erzincan and Gulludere,
Tasmasor, Tetikom, Magaratepe-Erzurum archaeological sites and statistical
evaluation of elemental XRF results of paste for selected ceramics were presented.
Similarities and correlation between the samples were determined and compared for
the investigation of the raw materials that used for the manufacturing of the ceramics.
Multivariable statistical methods as well as hierarchic cluster and factor analyses
were applied on the data set. In addition, mineral composition was identified for
some samples in this group by means of XRD techniques for particular information.
As a result, two sherds can be classified in different chemical composition while the
others can be considered from similar provenance.
Furthermore, qualitative XRF measurements were accomplished on the
ceramic bottle, metal slag and metal processed pot sherds that recovered from
Buyukardic. The main purpose of these measurements is to prove metallurgical
activities took place on site. The results indicate that the existence of a small scale
metal industry focused on processing iron and copper.
XRF and XRD results presented in this study are in line with the archaeological
results, especially in determination of the local materials and imported objects
which will help to enlight the cultural, social and technical relationships between the
communities.
12

O1-8
Estimation of the interelement effects in applying the X-ray
fluorescence method to the study of cultural heritage materials
A.G. Revenko
Institute of the Earths Crust, SB RAS, Irkutsk, Russia
The particular features of the application of X-ray spectral analysis are
discussed in this report to solve various problems related to the study of materials
and objects which are of archaeological, historical and cultural heritage. The following
objects were considered: glass- and ceramic products, different dishes, Fe-, Cu-, Ag-,
Au-based metal alloys. The study of a chemical composition of particular materials,
for example, several metal ores, obsidian and others is necessary very often in order
to determine raw material sites: pre-historical mines, quarries and others. The X-ray
fluorescence analysis is widely used for the control of chemical compositions of
the materials considered owing to its compliance with these requirements and the
availability of commercial instrumentation for the determination of most elements.
The increasing number of publications on this problematics is noted [1, 2].
The following glass objects are considered: various dishes and ornaments,
colouring pigments for glass, pictures painted on glass, vitreous coatings on
ceramics and others. Main attention is given to the technology of sample preparation
for an analysis and a problem of inhomogeneity of materials under study. The used
techniques are considered in detail for the conversion of experimental intensities into
concentrations of elements determined. The estimates of the theoretical intensities of
the analytical lines of some elements, determined in glass, are presented, as well the
intensities of coherently and incoherently scattered characteristic radiation of X-ray
tube anode (for calculation procedure see [3]). Such estimates were made for the
samples of ancient glass, obsidian, coloured mosaic glass, and glaze. The obtained
data allow to choose the variants for taking into account interelement effects, which
are optimal for each particular case.
[1] Revenko A.G., Revenko V.A. Application of X-ray spectral method of analysis to
the study of cultural heritage materials (Review) // Methods and objects of chemical
analysis. 2007. V. 2. No.1. P. 4-29.
[2] Revenko A.G. Application of X-ray spectral method to the study of cultural heritage
glass materials // Proc. Intern. Conf. Contemp. Phys.-IV ICCP-IV". Ulaanbaatar:
University Press, 2007. P. 225-247.
[3] Revenko A.G. X-ray fluorescence analysis of rocks, soils and sediments // X-Ray
Spectrometry. 2002. V. 31. No. 3. P. 264-273.

13

O1-9
Portable EDXRF/UV-vis spectrometer, two complementary
techniques on a mobile system used for Archaeometry research
on the Noble tomb of Menna TT-69, Gourna, Egypt
F-P. Hocquet1,2 , F. Mathis1,2 , R. Garcia-Moreno2, S. Raakka1,2, M. Hartwig3, D.
Laboury4, K. Leterme4, P. Vandenabeele5, E. Van Elslande6, H.-P. Garnir1 , A.
Marchal1 , M. Clar1, D. Strivay1,2
Institut de Physique Nuclaire,Atomique et de Spectroscopie, University of Lige
(Belgium),2Centre Europen dArchomtrie, University of Lige (Belgium)3School
of Art & Design, Georgia State University (USA),
4
Dpartement des sciences historiques, University of Lige (Belgium)5Laboratory of
Analytical Chemistry, Ghent University (Belgium)
6
Centre de Recherche et de Restauration des Muses de France, CNRS-UMR171
(France)
1

The Noble tomb of Menna (TT69) is one of the finest painted eighteenth
Egyptian dynasty tombs. It is situated in the officials necropolis of Sheikh Abd elQurna In Thebes West. The tomb presents very well conserved paintings on the
walls and ceilings. The two years Menna project is currently underway and is divided
into several phases related to conservation, protection and scientific documentation.
The fieldwork season for Archaeometry research has taken place from November
15 to December 20, 2007. Many different mobile analysis techniques (UV Visible
Near Infrared spectrometry, Infrared spectrometry RAMAN spectroscopy, EDXRF
spectroscopy) were involved in this project and worked in close collaboration.
This scientific physico-chemical material approach will allow objective data to be
contrasted with the formal and technological approach carried out by the Egyptologists
of the Menna project, in order to have a better understanding of the manufacture
processes of the decoration of Menna tomb. This project is the first attempt to carry
out extensive analyses on wall paintings using complementary mobile equipments
in archaeological fieldwork in Egypt. We will present here the technical aspect of the
mobile EDXRF/UV-Vis spectrometer and its contribution to this project. Let us note
that it is also the first time that these two different and complementary techniques are
coupled on a mobile system in this field of research.

14

O1-10
Analysis of paintings from the XIX century Brazilian painter
Rodolfo Amoedo using EDXRF portable system
Cristiane Calza1, Marcelino J. Anjos1,2, Andrea Pedreira3 and Ricardo Tadeu
Lopes1
Nuclear Instrumentation Laboratory. COPPE/UFRJ. P.O. Box: 68509, 21941-972.
Rio de Janeiro. Brazil.
2
Physics Institute. UERJ. Rio de Janeiro. Brazil.
3
National Museum of Fine Arts. Rio de Janeiro. Brazil.

The pigments used in four of the most representative works of the Brazilian
painter Rodolfo Amoedo were identified using EDXRF. The analyzed paintings,
belonging to the National Museum of Fine Arts Collection, were: The Last Tamoyo
(1883), Study of a Woman (1884), Bust of Mrs. Amoedo (1892) and Bad News
(1895).
The analysis of the pigments is important to evaluate the artist working
method and also for restoration and conservation purposes. Furthermore, the
knowledge of the composition allows the pigment characterization through major or
minor constituents and make possible to establish the provenance, historical period
and, consequently, the authenticity of the painting.
Amoedo (1857-1941) was a renowned artist and contributing to the formation
of several painters like Eliseu Visconti and Candido Portinari. In 1878, as student at
the Imperial Academy of Fine Arts, he won the Europe Travel Prize and traveled to
Paris studying at the cole Nationale des Beaux-Arts with the masters Alexandre
Cabanel and Puvis de Chavannes. He returned to Brazil in 1887 and was designated
acting professor at the Imperial Academy and later, in 1893, assistant director. In this
same year, he won a medal at the Chicago International Exhibition.
EDXRF measurements were carried out with a portable system developed
by the Nuclear Instrumentation Laboratory, consisting of an X-ray tube Oxford
TF3005 with tungsten anode, operating at 25 kV and 100 A, and a Si-PIN XR100CR detector (Amptek). Several spectra were obtained, with an acquisition time
of 300 s and a beam collimation of 2 mm. The spectra were analyzed using the
software QXAS-AXIL (IAEA). Some pigments identified were: zinc and lead white,
ochre, umbra, vermilion, Prussian blue, cobalt blue, cadmium yellow, black iron oxide
and manganese violet. In one painting, which had been restored in the XX century,
was identified titanium white in some alteration areas.

15

I2
Quantification in XRF micro-analysis
W. Malzer
Bruker AXS Microanalysis, Schwarzschildstr. 12, 12489 Berlin
Capillary X-ray lenses have triggered major innovations in X-ray spectroscopy.
The combination of these X-ray lenses with a new generation of low power microfocus X-ray tubes and drift chamber detectors enabled tabletop units for micro-XRF
with a few tens of m lateral resolution.
Since the X-ray tube spectrum is altered significantly when the radiation
passes the optical element in the excitation channel, fundamental parameter
methods for the purpose of quantification have to be further developed, A variety of
approaches to determine the altered excitation spectrum have been proposed and
are under development.
A recent development is the additional application of a polycapillary half-lens
in the detection channel. A confocal setup allows for three dimensionally resolved
X-ray spectrometry.
Though they may be regarded as fundamental parameter methods, the
quantification algorithms developed so far for 3D Micro-XRF substantially differ from
the quantification of classical micro-XRF. In addition to the fundamental parameters,
the appropriate modeling of the X-ray lens properties is of great importance for both
fields of micro-XRF.
The author will give an overview on approaches to determine the X-ray lens
properties, which are relevant for quantification. Furthermore, an introduction to the
principles of quantification for 3D micro-XRF will be presented and its peculiarities
will be discussed.

16

O2-1
Reference-free XRF including K- and L-lines
by synchrotron radiation at multiple energy settings
M. Mantler1 and B. Beckhoff 2
Technische Universitt Wien, Wiedner Hauptstr. 8-10, 1040 Wien, Austria
Physikalisch-Technische Bundesanstalt, Abbestr. 2-12, 10587 Berlin, Germany
1

The paper discusses the complex situation that may arise when compound
samples (such as rocks or ceramics) are analyzed by synchrotron radiation. In such
cases several energy settings are often used in order to optimize the excitation of
heavier and lighter elements, and occasionally K- and L-lines of an element are
simultaneously observed. Proper evaluation of the obtained data requires:

A description of the sample composition in terms of multielement
components with known internal stoichiometric relationships, such as oxides, and
reporting results in such terms rather than element contents;

Accounting for the complex processes that are involved in the
excitation of L-lines including cascades of electron transitions and Coster-Kronig/
Auger-processes;

Accounting for a variety of indirect excitation channels including
excitation by electrons;

An iteration algorithm that allows the integration of multiple lines
for each element (such as K- and L-lines) that may be excited by different primary
photon energies and therefore also affected by different secondary effects; and

Availability of a consistent set of fundamental parameters.

Such schemes have already been applied to a variety of samples including

ceramics and other oxide samples and showed that reference free analysis by using
a well calibrated experimental environment is possible within an error-frame of 5-10%
for the main constituents. This paper emphasizes the methodological side of these
techniques and their implementation.

17

O2-2
Quantitative analysis of individual particles on TEM grids
M. Chol, H. Hwang, and C.-U. Ro
Department of Chemistry, Inha University, Yonghyun-dong, Nam-gu, 402-751,
Incheon,South Korea
Electron probe X-ray microanalysis (EPMA) is particularly suited to
characterizing morphology and elemental composition of individual microparticles.
Besides, the use of ultrathin window X-ray detectors offer extended capabilities for
low-Z element analysis. As C, N, and O are common constituents of environmental
particles such as atmospheric aerosols, their detection allows a more realistic
description of samples. A critical aspect of light element analysis however is the
choice of collecting substrate material. Suitable substrates for single particle analysis
by SEM-EDX should ideally not contribute to the electron and X-ray signals. When
compared with commonly used bulk substrates, the use of thin-film substrates such
as TEM grids results in lower X-ray background and thus lower detection limits [1].
Although carbon films of TEM grids offer advantageous characteristics as a collecting
substrate, carbon interference can be quite strong for particle diameters less than 0.5
m [2]. While conventional methods of quantification such as ZAF or normalization
do not account for size-dependent substrate effects, Monte-Carlo simulations can
accurately describe such electron-particle-substrate interactions [1].
In this study, TEM grid-supported C/Formvar film is evaluated for quantitative
analysis of standard particles containing low-Z elements. TEM grids were mounted in
a self-constructed sample holder which minimizes X-ray interferences. A correction
procedure using a Monte Carlo simulation [3] allowing for input of substrate
parameters (film thickness, substrate density, and composition), particle diameter,
elemental intensities and excitation conditions was tested on CaCO3 particles. The
optimized substrate parameters were first determined using experimental data and
Monte-Carlo simulations with different settings. Then carbon and oxygen corrections
were successfully checked on CaSO4 particles using the optimized parameter
settings.
[1] J. I. Goldstein et al.; Scanning Electron Microscopy and X-ray Microanalysis,
2nd ed. (1992) 557 564.
[2] A. Laskin and J.P. Cowin, Analytical Chemistry, 73 (2001) 1023 1029.
[3] C.-U. Ro et al., Analytical Chemistry, 75 (2003) 851 859.

18

O2-3
The necessity of maximum information utilization in x-ray
analysis
T. Papp1,2, J. A. Maxwell1 and A. T. Papp1
Cambridge Scientific, 175 Elizabeth Street, Guelph, ON, N1E 2X5, Canada,
Institute of Nuclear Research of the Hungarian Academy of Sciences
Bem ter 18/c Debrecen, H-4021, Hungary

1
2

There are significant differences in the experimental data needed in the analysis of
x-ray spectra [1]. If we look deep into the problems many of them contradict simple
logic, elemental arithmetic [2], even parity and angular conservation laws [1]. We
have identified that the main source of the problems, other than the human factor,
is rooted in the signal processing electronics.
We have developed a line of fully digital signal processors [1] that not only
have excellent resolution and line shape [3] but also allow proper accounting. This
is achieved by processing all events and separating them into two or more spectra
where the first spectrum is the accepted or good spectrum and the second spectrum
is the rejected spectrum. It is not enough to know that an event was rejected, and
increment the input counter, it is necessary to know, what, why and when it happened,
whether it was pure noise, a noisy or disturbed event, a true event, or any pile up
combination of the above in order to account properly for true event input rate and
processor dead time.
The data processing methodology cannot be established on the partial and
fractional information offered by other approaches. The availability of all the events
allows one to see the other part of the spectrum. To our surprise the total information
explains many of the shortcomings and contradictions of the x-ray database. We call
this a maximum information utilization approach in signal processing.
To supplement the concept of maximum information utilization, we have
developed front end electronics that keep the maximum information from the detector
available for the processor. Also a fundamental parameter XRF program (CSX-XRF)
has been developed to utilize all the information offered by the signal processor
as well as an inverse fundamental parameter program package for equipment
characterization.
[1] T. Papp, A.T. Papp and J.A. Maxwell, Analytical Sciences 21 (2005) 737-745;
and at www.cambridgescientific.net published online
[2] http://www.atomki.hu/ar2005/3_atom_mol/a07.pdf, published online
[3] T. Papp, J.A. Maxwell, A. Papp, Z. Nejedly and J. L. Campbell; Nucl. Inst. And
Meth. B 219-220, (2004) 503, T. Papp, M.-C. Lepy, J. Plagnard, G. Kalinka and E.
Papp-Szabo, X-ray Spectrometry, 2005, 34, 106.

19

O2-4
The quest for a fundamental algorithm in XRF analysis
and calibration
Richard M. Rousseau
Geological Survey of Canada, 601 Booth St., Room 707, Ottawa, Ont., K1A 0E8,
Canada
When the author began his career in X-ray Spectrometry, he was looking for
a XRF analysis method able to analyse any type of bulk and solid samples such as
rocks, ores, cements, metals, etc., prepared either as fused discs, pressed pellets
or metallic specimens.
At that time, a multitude of algorithms relating concentration to intensity had
been proposed to calculate sample compositions. In this case, the problem is to
select the most appropriate one to an analytical context. Another solution is to try
to find a fundamental algorithm, theoretically exact, that would serve as a common
mathematical basis to generate all the models proposed to date and that can be
applied to any analytical context.
The solution proposed by the author is the Fundamental Algorithm (FA) [1].
It was found to be of a sound theoretical foundation from which one can deduce all
the other algorithms proposed up to now [2]. Furthermore, it explains all the XRF
phenomena observed in practice and contains all the XRF knowledge accumulated
since the beginning of the XRF analysis.
The next step is to develop a special calibration procedure [1] to adapt theory
to the experimental data of each spectrometer, knowing very well that theory cannot
account for all variations in all the instrumental parameters.
Finally, it will be shown how to apply the Fundamental Algorithm in practice
to fused discs, pressed pellets and alloys [3]. Three optimized methods will be
presented that cover the complete analytical range (0-100%). The proposed three
approaches combine the practical flexibility of the influence coefficient concept and
the theoretical exactness of the Fundamental-Parameters method.
[1] R.M. Rousseau, Spectrochimica Acta Part B, 61 (2006) 759-777.
[2] R.M. Rousseau and J.A. Boivin, The Rigaku Journal, 15(1) (1998) 13-27.
[3] R.M. Rousseau, The Rigaku Journal, 18(1) (2001) 8-21.

20

O2-5
3D Micro X-ray Fluorescence Spectroscopy Validation of the
three-dimensional model and scattering
I. Mantouvalou1, W. Malzer1, I. Schaumann2, M. Pagels1, L. Lhl1, C.Vogt2 and
B. Kanngieer2
Institute for Optics and Atomic Physics, Technische Universitt Berlin,
Hardenbergstrasse 36, 10623 Berlin, Germany,
2
Institute for Inorganic Chemistry, Leibniz Universitt Hannover, Callinstr. 9, 30167
Hanover, Germany
1

3D micro X-ray fluorescence spectroscopy (3D Micro-XRF) enables threedimensional resolved, nondestructive investigation of elemental distribution in
samples in the micrometer regime. A procedure for the quantitative reconstruction of
the composition of stratified material by means of 3D Micro-XRF has been developed
[1] and validated [2], recently. The procedure is based on a model of the spatial
distribution of the sensitivity of the probing volume defined by the overlapping foci of
the confocal setup.
In this presentation, the validity of the model is shown. As no adequate
reference samples were available for validation, stratified reference material has
been developed that is appropriate for 3D Micro-XRF or other depth-sensitive
X-ray techniques. The samples are made of five polymer layers with varying ZnO
concentration. Measurements have been carried out at the mySpot beamline of the
Berlin synchrotron BESSY. The reconstructed layer thickness and the respective
Zn concentration of the individual layers show an excellent agreement with the
manufacturers values.
As further development of the quantification model the scattering of a sample
was included in the analysis process. With this additional information the overall
density of a layer can be estimated, which leads to a better understanding of the
dark matrix of a sample. As an example highly inhomogeneous parchment samples
will be discussed.
[1] W. Malzer, B. Kanngieer, Spectrochim. Acta, Part B 2005, 60, 1334-1341.
[2] I. Mantouvalou, W. Malzer, I. Schaumann, L. Luhl; R. Dargel, C. Vogt, B.
Kanngiesser, Anal. Chem. 2008; 80(3); 819-826.

21

O2-6
Confocal XRF quantification procedures applied to the cometary
matter returned by NASA's STARDUST mission
T. Schoonjans1, B. Vekemans1, G. Silversmit1, S. Schmitz2, F. Brenker2,
L. Vincze1
X-Ray Micro-Spectroscopy and Imaging Group, Department of Analytical
Chemistry, Ghent University, Krijgslaan 281, B-9000 Gent, Belgium
2
Institut fr Geowissenschaften, Facheinheit Mineralogie Abt. NanoGeoscience,
Altenhferallee 1, D-60438 Frankfurt am Main, Germany
1

Stardust is an interplanetary spacecraft launched on February 7, 1999, by

NASA, whose primary purpose was to investigate the make up of comet Wild2 and
its coma. The spacecraft was equipped with aerogel (highly porous silica foam with
an extremely low density) collectors, in order to facilitate the capture of cometary
dust particles. After the return of Stardust to Earth on January 15, 2006, the acquired
samples were distributed among more than 150 researchers worldwide, including
the X-Ray Micro-Spectroscopy and Imaging group of Ghent University (XMI-UGent)
[1-3].
Each presented sample contains an elongated cavity (called track) produced
by the impact and deceleration of a single comet coma particle through the aerogel.
Multiple experiments were performed on such tracks and their terminal particle at
the ESRF (beamline ID13) using several non-destructive X-ray based methods
such as conventional 2D scanning nano X-ray fluorescence (XRF) and confocal
nano-XRF. The latter technique is characterized by the mounting of a polycapillary
half-lens in front of the detector, thereby effectively reducing the volume defined by
the intersection of the incoming beam and the sample to a volume defined by the
acceptance of the polycapillary. The nanobeam of X-rays was produced by a linear
Fresnel lens assembly which reduced the dimensions of the beam to the 100-200
nm level.
The data has been evaluated using xmi-quant, a software-package dedicated
to the evaluation of confocal XRF spectra, under development at our research
group. This package includes an implementation of the fundamental parameter
method allowing the modeling of the complex STARDUST particles. The presented
quantitative results confirm the earlier findings concerning the presence of Ca-Alrich inclusions in the cometary dust[2].
[1] D. S. Burnett, Science, 314(2006): 1709-1710
[2] D. Brownlee et al., Science, 314(2006): 1711-1716
[3] G. J. Flynn et al., Science, 314(2006): 1731-1735

22

O3-1
Synchrotron radiation induced Total Reflection X-ray
Fluorescence Analysis- absorption spectroscopy ( SRTXRFXAS)
C.Streli1, F.Meirer1, G.Pepponi2, P.Wobrauschek1, U.Fittschen3, J.Broekaert3, Gy.
Zaray4, G.Falkenberg5 MA.Zaitz6
Atominstitut, Vienna Univ. Of Technology, 1020 Vienna, Austria
2
ITC-irst, 38050 Povo (Trento) Italy
3
Department of Chemistry, University of Hamburg, 20146 Hamburg, Germany
4
Dep. of Analytical Chemistry, Etvs University, 1117 Budapest, Hungary,
5
Hamburger Synchrotronstrahlungslabor at DESY, 22607 Hamburg, Germany
6
IBM Microelectronics, Hopewell Junction, NY, USA
1

Synchrotron Radiation induced Total Reflection X-ray Fluorescence Analysis

(SR- TXRF) using a multilayer monochromator allows to achieve detection limits
in the fg range due to the more effective excitation using synchrotron radiation and
the background reduction. TXRF is specially suited for samples where only small
amounts are available. A crystal monochromator selects a smaller energy bandwidth
from the white synchrotron spectrum than the multilayer. Though it reduces the
intensity it allows absorption spectroscopy measurements (XANES) in fluorescence
mode to perform speciation at trace levels. [1-2]
Various applications of K- edge XANES measurements will be shown:
Speciation of Arsenic in xylem sap of cucumber plants at concentration levels of 30
ng/g. [2] , Fe in aerosols collected in a size fractioning impactor, Fe contamination on
Si wafer surfaces at contamination levels of E12 atoms/cm2. Furthermore absorption
effects for higher concentrated standard solutions have been studied and will be
discussed.
[1] C. Streli, G. Pepponi, P. Wobrauschek, C. Jokubonis, G. Falkenberg, G. Zaray,
X-Ray Spectrometry, 2005. 34(5): p. 451-455.
[2] G. Falkenberg, G. Pepponi, C. Streli, and P. Wobrauschek, Spectrochimica Acta
Part B: Atomic Spectroscopy, 2003. 58(12): p. 2239-2244.
[3] F.Meirer, G.Pepponi, C.Streli, P.Wobrauschek, V. G. Mihucz, G.Zray, V. Czech, J.
A. C. Broekaert, U. E. A.Fittschen and G. Falkenberg, Arsenic speciation in cucumber
(Cucumis sativus L.) xylem sap by K edge TXRF-XANES, X-ray spectrometry 36,
408-412, 2007

23

O3-2
High speed 2-dim. X-ray imaging spectroscopy at BESSY and
FLASH
L.Strder1, U. Pietsch2, R. Hartmann3 and C. Bostedt4
MPI Halbleiterlabor, Otto-Hahn-Ring 6, 81739 Munich, Germany
Universitt Siegen, Emmy-Nther-Campus, 57234 Siegen, Germany
3
PNSensor, Rmerstr. 28, 80803 Munich, Germany
4
TU Berlin, Eugene-Wigner-Bldg. EW 3-1,Hardenbergstr. 36, 10623 Berlin,
Germany
1

For experiments at the present and future X-ray lasers (FLASH, LCLS,
XFEL) we are developing large format backside illuminated fully depleted pnCCDs
with column parallel readout. In a first phase a 1024 x 1024 format detector with 75
x 75 m2 pixels will be ready for use in 2009. The detector chip has recently been
fabricated. First basic properties are actually being measured. The full system will
be described in detail and its prospects will be discussed in the light of the potential
applications. In phase II a 2048 x 2048 format system will be made available. The
design of the pnCCD is being finished, fabrication starts in early 2008; the system
could be ready for use in 2011 for phase II.
Recently we have performed two demonstrator experiments with a 256 x
512 format pnCCD system (a) at the white X-ray beam of BESSY with energies up
to 30 keV and (b) with monochromatic radiation of 90 eV at the FLASH X-ray (VUV)
laser. Due to the high frame rate of the pnCCDs the measurements were made in a
full frame mode with up to 500 frames per second. The results of both experiments
will be presented, the propects of future experiments will be discussed. They are
in excellent agreement with the pnCCDs performance in the laboratory. A detailed
analysis of the pnCCD data of both beamline experiments, (a) the X-ray diffraction
experiment at BESSY and the Xe-nanocluster imaging at FLASH will be given.

24

O3-3
Measuring and interpreting X-ray fluorescence from planetary
surfaces
A. Owens1, B. Beckhoff2, G. Fraser3, M. Kolbe2, M. Krumrey2, A. Mantero4,M.
Mantler5, A. Peacock1, M.-G. Pia4, D. Pullan3, G.Ulm2
Science Payload and Advanced Concepts Office, ESA/ESTEC, 2200AG
Noordwijk, The Netherlands
2
Physikalisch-Technische Bundesanstalt, Abbestrasse 2-12, 10587 Berlin,
Germany
3
Dept. Physics and Astronomy, Leicester University, Leicester LE1 7RH, U.K.
4
INFN, Sezione di Genova, Via Dodecaneso 33, 16146 Genova, Italy
5
Technische Universitt Wien, A-1040 Wien, Austria
1

As part of a comprehensive study of X-ray emission from planetary surfaces

and in particular the planet Mercury, we have measured fluorescent radiation from
a number of planetary analogue rock samples using monochromatized synchrotron
radiation provided by the BESSY II electron storage ring. The experiments were
carried out using a purpose built X-ray fluorescence (XRF) spectrometer chamber
developed by the Physikalisch-Technische Bundesanstalt (PTB), Germanys national
metrology institute. The XRF instrumentation is absolutely calibrated and allows for
reference-free quantitation of rock sample composition, taking into account secondary
photon and electron induced enhancement effects. The fluorescence data, in turn,
have been used to validate a planetary fluorescence simulation tool based on the
GEANT4 transport code. This simulation can be used as a mission analysis tool to
predict the time dependent orbital XRF spectral distributions from planetary surfaces
throughout the mapping phase.

25

O3-4
Development of a Low Energy X-ray Fluorescence system with
high spatial resolution
A. Longoni1, R. Alberti1, T. Klatka1, A. Gianoncelli2, D. Bacescu2, A.
Marcello3 and B. Kaulich2,
Politecnico di Milano, Dipartimento di Elettronica e Informazione, Piazza
Leonardo da Vinci, 20133 Milano, Italy and INFN sezione di Milano, via Celoria 16,
20133 Milano, Italy
2
ELETTRA - Sincrotrone Trieste, X-ray Microscopy Section, Strada Statale 14, km
163.5 in Area Science Park, 34012 Trieste-Basovizza, Italy
3
ICGEB - AREA Science Park, Padriciano 99, 34012 Trieste
1

In the present paper we report a recently developed Low Energy X-ray

Fluorescence spectrometer (LEXRF) system combined with a soft X-ray Microscope.
The LEXRF setup is a modular system based on the use of multiple windowless
Silicon Drift Detectors (SDD), with the option of up-scaling it to 8 detectors. The
detectors are read-out by a custom designed fast multichannel acquisition system,
optimized for the use with SDDs [1]. The LEXRF set up has been designed and
adapted to the European TwinMic [2] microscope station located at Elettra synchrotron
light facility in Trieste, Italy. TwinMic is a Transmission X-ray microscope working
in the energy range 200-2000 eV. It is a multipurpose end station that combines
the advantages of full-field imaging and those of Scanning Transmission X-ray
Microscopy (STXM), with easy switch between the two modes. By using zone plate
diffractive optics the X-ray beam can be focused down to sub-100 nm spot size.
The developed XRF system coupled with the STXM operation mode of
TwinMic enables the simultaneous acquisition of XRF maps, absorption images and
phase contrast images [3] with high spatial resolution for the sample under analysis.
This allows combining chemical specificity with morphological information.
Some examples of XRF maps, absorption images and phase contrast images
collected on environmental and biological samples (human cells) will be shown and
discussed. Moreover the design and performances of the developed system will
be presented. Preliminary results include XRF maps of Ca (L and L lines, 341
and 344 eV respectively), Na (K line, 1041eV), Mg (K line 1253 eV) and other
chemical elements.
[1] R.Alberti, S.Buzzetti, C.Fiorini, C.Guazzoni, T.Klatka, P.Lechner, A.Longoni, L.Struder,
IEEE Trans on Nucl. Sci. Volume 54, Issue 3, June 2007, 751-757.
[2] B. Kaulich, D. Bacescu, J. Susini, C. David, E. Di Fabrizio, G.R. Morrison, P. Charalambous,
J. Thieme, T. Wilhein, J. Kovac, D. Cocco, M. Salome, O. Dhez, T. Weitkamp, S. Cabrini, D.
Cojoc, A. Gianoncelli, U. Vogt, M. Podnar, M. Zangrando, M. Zacchigna and M. Kiskinova,
in Proc. 8th Int. Conf. X-ray Microscopy, edited by S. Aoki, Y. Kagoshima & Y. Suzuki
(IPAP,Tokyo,2006), vol.7, pp.22-25.
[3] A. Gianoncelli, G.R. Morrison, B. Kaulich, D. Bacescu, J. Kovac, Applied Physics Letters
Vol. 89, 251117-251119, 2006.

26

O3-5
High resolution X-ray absorption and X-ray emission
spectroscopy of titanium compounds
F. Reinhardt1, B. Beckhoff1, B.Kanngieer2, M. Mller1, B. Pollakowski1 and
G. Ulm1
1

Physikalisch-Technische Bundesanstalt, Abbestr. 2-12, 10587 Berlin, Gemany

2
Technische Universitt Berlin, Institut fr Optik und Atomare Physik,
Hardenbergstr. 36, 10623 Berlin, Germany

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and

high resolution X-ray emission spectroscopy (XES) are powerful tools for the nondestructive chemical speciation of compounds.
The NEXAFS of Ti K- and LII,III-edges of different binary titanium compounds
were investigated and related to L, X-ray emission spectra of the same specimens.
The aim was to compare the information obtained from absorption techniques to those
gained from emission spectroscopy. All measurements took place in the laboratory
of the Physikalisch-Technische Bundesanstalt at the electron storage ring BESSY II.
All measurements in the soft X-ray regime, where the Ti L-shells are located, were
carried out at the plane-grating monochromator beamline for undulator radiation.
The structure of the Ti K-edge was measured at the four crystal monochromator
beamline for dipole radiation.
For the sake of comparison, the compounds were sorted according to the
oxidation state of the bonded titanium. Thus, it is possible to differ between inner
atomic effects due to different oxidation states and external effects related to the ligand
and the crystal structure. It becomes evident, that certain compounds, while nearly
indistinguishable in their K-NEXAFS spectra, still show significant differences in their
emission characteristics. On the other hand, the strength of NEXAFS spectroscopy
for speciation of different site geometries and ligands can be affirmed.

27

O3-6
Reference-free quantification of multielemental nanolayered
systems
M.Kolbe and B.Beckhoff
Physikalisch-Technische Bundesanstalt, Abbestr. 2-12, 10587 Berlin, Germany
Layered systems in the nanometer range acting as conducting or
nonconducting interfaces become more and more important in the semiconductor
industry. The non destructive characterization of such steadily redesigned
nanolayered systems e.g. consisting of transition and noble metals is an important
task. Appropriate reference materials are often not available due to the rapid
developments. Here, reference-free quantification in Xray fluorescence analyses
may be a flexible and reliable solution for this task.
Reference-free XRF requires the accurate knowledge of all experimental
values both in the excitation and detection channels as well as of the fundamental
parameters involved. Due to the use of a set-up with only calibrated devices the
experimental values are well known. The energy-dispersive detectors to record the
fluorescence spectra are calibrated with respect to their efficiency as well as to their
response behavior. The relative uncertainty of the experimentally determined data
in total is about 3 %. Besides contributions from the instrumentation, the relative
uncertainties of the XRF analytical results are furthermore affected by the tabulated
fundamental parameters of the elements, some of which only have estimated
uncertainties.
Using reference-free XRF carried out at BESSY II, different fundamental
parameter databases have been compared and supplemented by own values
determined by transmission measurements of self-supporting one-elemental foils.
These transmission measurements have been carried out with monochromatized
synchrotron radiation of high spectral purity and well-known flux to obtain absorption
correction factors depending on both the exciting and the fluorescent energy.
Moreover the energy dependency of the absorption jump ratio has been included in
the algorithms to further reduce the uncertainties of the standard-free XRF.
With these improvements a significant reduction of the relative uncertainties
for reference-free quantification from XRF measurements can be achieved and is
shown for relevant nanolayered systems and bulk materials in the present work.

28

I4
The latest directions and trends in Ion Beam Analysis of fine
particle air pollution
David D. Cohen
Australain Nuclear Science and Technology Organisation,
PMB1, Menai, NSW, 2234, Australia.
In recent times fine particle air pollution (particles with diameters less than
2.5m, also known as PM2.5) has been related to adverse health outcomes in USA
and Europe, poor visibility in Asia and long range pollution transport. In 1997 the US
EPA introduced a PM2.5 standard of 15 g/m3 for annual average and 65 g/m3 for
24 hour maximum. The 24 goal was reduced to 35 g/m3 in 2006. Several countries
in Europe and Asia have followed suit, in Australia our current PM2.5 goals are 8
g/m3 annual and 25 g/m3 for 24 hour maximum, much tighter than many other
countries. These air pollution goals or standards recognize the deleterious effects
of fine particle pollution.
This paper discusses fine particle characterisation by X-ray and ion beam
analysis (IBA) techniques and recent developments in their application to source
fingerprinting and apportionment. In particular the positive matrix factorisation (PMF)
technique will be discussed and its advantages over chemical mass balance methods
highlighted. Examples of these applications and their potential will be demonstrated
with recent long term datasets obtained in Asia between January 2001 and June
2007. It will also show how wind and back trajectory data can be included to plot
fine particle pollution transport and identify possible sources several thousands of
kilometers from the sampling site.

29

O4-1
Depth investigation of aerosols in PM10-filter with
3D micro particle induced X-ray emission ( 3D Micro PIXE )
R. Schtz1, B. Kanngieer1, A. G. Karydas2, D. Sokaras2,
P. Pelicon3, N. Grlj3,4 and M. itnik3
Institute of Optics and Atomic Physics, Technical University of Berlin, D-10623,
Berlin, Germany
2
Institute of Nuclear Physics, NCSR Demokritos, 153 10 Aghia Paraskevi,
Athens, Greece
3
Joef Stefan Institute, Jamova 39, SI-1000, Ljubljana, Slovenia
4
Primorska Institute of natural sciences and technology, Muzejski trg 2, SI-6000
Koper

The successful implementation of two X-ray lenses in a X-ray Fluorescence set-up

(3D Micro XRF) [1] motivated the establishment of a novel experimental technique, 3D micro
Particle-induced X-Ray emission (3D Micro PIXE). The 3D Micro-PIXE is realized by inserting a
polycapillary X-ray lens in front of the X-ray detector. The intersection of the lens focus (FWHMx
~29 m at 6.4 keV) with the proton micro-beam space distribution (FWHMb ~2 m) creates a
probing micro-volume. By moving the sample in the beam direction or by 2D beam scanning,
depth resolved measurements on elemental distribution become possible at the micrometer
regime, whereas the combination of the two approaches allows 3D elemental analysis. For the
experimental realization of this technique, the nuclear microprobe of the Joef Stefan Institute was
used [2] in order to establish, characterize and apply the confocal setup for 3D Micro PIXE [3].
In the present work, a new application of 3D Micro PIXE is presented in the field of
the environmental science. The 3D site probing of different aerosol particles collected in a
PM10 quartz filter was investigated by 3D Micro PIXE analysis by moving the sample in the
bean direction and performing micro-beam scanning at each position (Figure 1). An analytical
methodology is proposed based on the acquired semi-quantitative information (depth intensity
profiles of sulfur, calcium and iron) that allows the determination of the position of different
aerosol particles within the micro-beam scanned sample volume.
Figure 1:

[1] B. Kanngieer, W. Malzer, I. Reiche, Nucl. Instr. and Meth. B, 2003, 211/2, 259.
[2] P. Pelicon, J. Simi, M. Jaki, Z. Meduni, F. Naab and F.D. McDaniel, Nucl. Instr. and
Meth. B 231 (2005), 53.
[3] A. G. Karydas, D. Sokaras, C. Zarkadas, N. Grlj, P. Pelicon, M. itnik, R. Schtz, W.
Malzer and B. Kanngieer, J. Anal. At. Spectrom., 2007,22,1260-1265

30

O4-2
Theoretical description of 3D MicroPIXE intensities.
Case 1: Layered materials
D. Sokaras1, A.G. Karydas1, W. Malzer2,* and B. Kanngieer 2
Institute of Nuclear Physics, NCSR Demokritos, 153 10 Aghia Paraskevi,
Athens, Greece
2
Institute of Optics and Atomic Physics, Technical University of Berlin, D-10623
Berlin, Germany
* current affiliation: Bruker AXS Microanalysis GmbH
1

In a typical Micro-PIXE set-up the insertion of a polycapillary half-lens,

in front of the X-ray detector in combination with the focused ion beam defines
a confocal geometry and the intersection of two foci a probing micro-volume. By
moving the sample across the probing-volume, the characteristic X-ray intensities
produced only within this probing-volume are detected. This experimental procedure
will result, finally, into intensity profiles versus position. It has been demonstrated
very recently the feasibility of such kind of depth resolved elemental analysis with
Micro-PIXE [1].
This work presents a complete theoretical description of 3D Micro-PIXE
intensities for layered materials. The proposed model utilizes an analytical description
for the energy dependent spatial response function of the X-ray lens at the focal region
in an analogues manner to the one for 3D Micro-XRF [2]. Incorporating together
the beam profile, the probing-volume is analytically described through a sensitivity
function expressed in spatial coordinates. Particle induced X-ray intensities are
calculated taking into account all the well known processes that involve in the PIXE
process (ionization, stopping power, and self-attenuation) and through convolution
with the sensitivity function 3D Micro-PIXE intensities can be simulated. The model
developed accounts for both experimental approaches aiming to depth resolved
analysis in 3D Micro-PIXE, i.e. sample displacement inside the probing volume or
micro-beam scanning inside the lens focus volume. In the first case, simulated indepth intensity profiles are generated, whereas in the second case two dimensional
intensity maps are obtained.
The influence of various experimental parameters (beam energy, spatial
resolution of the X-ray lens, micro-beam dimensions, irradiation and detection angles),
as well as of the sample characteristics like the structure (thickness, composition)
of the individual layers that compose the analyzed sample, on the simulation of the
PIXE intensity profiles is examined and discussed. Examples of the advantages and
benefits of the Micro-PIXE analysis in confocal geometry are given.
[1] A. G. Karydas, D. Sokaras, C. Zarkadas, N. Grlj, P. Pelicon, M. itnik, R.
Schtz, W. Malzer and B. Kanngieer., J. Anal. At. Spectrom., 22 (2007), 1260 1265, DOI: 10.1039/b700851c.
[2] W. Malzer and B. Kanngieer, Spectroch. Acta, 2005, Part B 60, 1334.
31

O4-3
Lapis lazuli characterization at the LABEC external microbeam
S. Calusi1,2, E. Colombo1,2, L. Giuntini3, A. Lo Giudice2, C. Manfredotti1,2, M.
Massi3, G. Pratesi4, E. Vittone1,2
INFN sezione di Torino, via P.Giuria 1, 10125 Torino, Italy
Dipartimento di Fisica Sperimentale and NIS Excellence Centre, Universit di
Torino, via P. Giuria 1, 10125 Torino, Italy
3
Dipartimento di Fisica, Universit and INFN Sezione di Firenze, Via Sansone 1,
50019, Sesto Fiorentino, Firenze, Italy
4
Dipartimento di Scienze della Terra and Museo di Storia Naturale, Universit di
Firenze, via G. La Pira 4, 50121 Firenze, Italy
1

Characterization of stones and minerals is usually carried out with

optical microscopy and in vacuum analytical techniques (e.g. SEM-EDS,
cathodoluminescence) typically requiring some treatments of samples, like slicing
and/or metallization. These treatments are not possible when precious artworks are
to be studied, so that it is necessary to exploit non-destructive techniques like PIXE/
PIGE and ionoluminescence (IL). At the LABEC external scanning microbeam of
Firenze, we started to study raw lapis lazuli samples of different known origins and
precious lapis lazuli artworks of the Collezione Medicea of Museum of Natural History,
University of Firenze, aiming to characterise their composition and provenience.
Thanks to the PIXE/PIGE spectra and to the intercomparison of elemental
maps, we were able to identify minerals constituting the samples and trace elements
in the minerals. Just basing on these results it was possible to interpret IL spectra of
lapis lazuli standards. Since the IL technique is sensitive to chemistry of materials, in
favourable cases, we can recognize minerals and activators in minerals. Thanks to
its high efficiency which permits to get high statistics with low doses, the IL technique
is a powerful tool to analyze lapis lazuli artworks. The minerals in lapis lazuli stones
and the presence of impurities can characterize the provenience of lapis lazuli; for
the Chilean lapis lazuli, we were actually able to point out a clear correlation between
the IL spectrum and the provenience.

32

O4-4
Multiparameter and digital pulse processing for -PIXE
applications
M. Bogovac1, M. Jaksic1, D. Wegrzynek2, A. Markowicz2
Institute R. Boskovic, Zagreb, Croatia
IAEA Laboratories Seibersdorf, IAEA A-1400 Vienna, Austria
1

X-ray detection and measurement using high resolution detectors usually

requires fast and low noise front-end electronics for pulse processing. Programmable
digital filters are superior alternative to the traditional analog electronic counterparts
in terms of throughputs and flexibility. In addition, as a compact alternative to bulky
analog electronics a digital pulse processing can be great benefit in the applications
that needs more detectors.
The implementation of the digital pulse processor on FPGA's has several
benefits, with emphasis on parallelism and amount of functionality that can be
placed into the silicon. In this work a Virtex-4 SX FPGA based PCI card with two
14-bits, 105-MSPS ADCs and two 14-bit DACs was used as a hardware platform
for development of a multi-channel digital pulse processor suitable for -PIXE
applications. Two boards are chained together and signals from four detectors can
be processed simultaneously.
In order to utilize ADCs input range as best as possible a four channel
analog pre-filter has been designed and produced. The pre-filter includes digitally
controlled differentiation, pole-zero cancellation, linear amplification and finally antialiasing filter.
The main FPGA design was divided into two asynchronous clock domains.
The first clock domain, related to the pulse processing, is driven by 105-MHz clock.
It includes (per channel) the following subsystems which name and functionalities
are equal to their analog counterparts: pulse shapers continuously time domain
trapezoidal filters (fast and energy) followed by base line restorer (BLR), pile-up
rejector (PUR), live time corrector (LTC) and pulse height analyzer (PHA). The
second clock domain is driven by 40-MHz clock and includes subsystem blocks for
communication with host computer.

33

O4-5
Trace Element Profiling of Gunshot Residues by PIXE and SEMEDS: A Comparative Study
M. Webb1, D Cox2 and C Jeynes1
University of Surrey Ion Beam Centre, Guildford, GU2 7XH, UK
Advanced Technology Institute, University of Surrey, Guildford, GU2 7XH, UK
1

The identification of gunshot residues found on a suspect has challenged

forensic scientists for many years [1]. SEM-EDS is the technique of choice for
analysing such samples because as well as being non-destructive, the technique
can be used to study the morphology in addition to the composition of the spherical
particles that make up the residue. The technique is used routinely by police authorities
in the UK to identify gunshot residue, and it has been shown that the technique can
be used to distinguish between residues from different types of ammunition powders
[2]. However, it is probably impossible to distinguish between some ammunition
powders using this method [2],[3], particularly for lead free ammunition powders.
In this work, we evaluate the usefulness of particle induced X-ray emission
(PIXE) compared with SEM-EDS for the characterisation of gunshot residues.
Samples of gunshot residue from several different ammunition powders were
collected from different shooters hands by swabbing with carbon tape. Individual
particles of gunshot residue were analysed by SEM-EDS and PIXE using a 2.5MeV
proton beam focussed to 3 microns. The PIXE technique revealed trace elements
in the samples that were not detected by EDS because of the lower sensitivity of the
latter technique. We demonstrate that the PIXE technique can be used to distinguish
between gunshot residues that cannot be resolved using conventional methods.
[1] F S Romolo et al, Identification of Gunshot Residue: a critical review, Forensic
Sci International, 119 (2001) 195-211
[2] Z Brozek-Mucha et al, Evaluation of the possibility of differentiation between
various types of ammunition by means of GSR examination with SEM-EDX
method, Forensic Sci. Int. (2001).39-47
[3] A Martiny et al, SEM/EDS analysis and characterisation of gunshot residues
from Brazilian lead-free ammunition, Forensic Sci. Int. (2007), doi:10.1016/j.
foresciint.2007.07.0050

34

O4-6
EPMA investigations of soil cover in lake Baikal region
O. Yu. Belozerova
Institute of Geochemistry, Siberian Branch, Russian Academy of Sciences,
Favorsky St. 1 A, 664033 Irkutsk, Russia, obel@igc.irk.ru
Soil is an informative indicator of environmental pollution. Therefore,
environmental investigation of soil cover is actual task of soil science and geochemistry.
In this connection, it is very important to have information both about chemical soil
composition and about phase distribution of substance, shapes of phase separation,
sizes and structure of surface.
The results of investigations of soil cover in Baikal Region obtained by X-ray
electron probe microanalysis (EPMA) are presented in this work. Samples of soils
were collected in ecologically clean (background) regions and regions with high
man-caused loading degree.
The EPMA technique is developed for soil particles using Superprobe-733
and JXA-8200 (Jeol Ltd, Japan) devices with energy-dispersive and wavelengthdispersive spectrometers. The surface of particles, shapes of phase separation,
sizes and homogeneity of their distribution were studied using scanning electron
microscope.
The results of investigations indicated that, soil cover consists of mixture
of mineral phases separated as individual particles of different shape and various
sizes. The change of phase and chemical composition of soils from regions with
various man-caused loading degree differs in proportion of natural and anthropogenic
particles. The natural particles of faceted shape are observed in background regions.
They generally include silicate minerals. Industrial regions contain along with natural
particles the anthropogenic particles shaped as rounded, orbicular and irregular
semi-faceted caused by industrial processes. These particles include the phase with
carbon compounds, carbonates, metal oxides, metallic grains and spherules.
Thus, detailed investigations of soil cover in Baikal Region by EPMA allows
identification of basic pollution sources and their influence on the environment and
estimation of anthropogenic accumulation in clear background regions and regions
with high man-caused loading degree.

35

O4-7
Application of X-ray spectroscopy to study of alkali-silicate
glasses irradiated with electrons
O. Gedeon1, K. Jurek2 and I. Drbohlav2
Department of Glass and Ceramics, Institute of Chemical Technology, Technicka
5, 166 28 Prague, Czech Republic
2
Institute of Physics, Academy of Sciences of the Czech Republic, Cukrovarnicka
10, 162 53 Prague, Czech Republic

Glasses are frequently used in the applications where they are exposed to
particle irradiation of different energy (materials for the fixation of radioactive waste,
insulating glass fibres in nuclear power plants, electron multipliers, telescopes located
in open space, etc.). The need of seeking for the limiting glass properties increases
in connection with material-tailoring technologies, which enable to improve the glass
properties (durability, fatigue, weathering, and mechanical properties) and to use
glass in new applications.
Alkali-silicate glasses irradiated with electrons show changes in their
structures, which can be characterized via measuring of intensity of alkali metal
X-ray line. Intensity versus time curve, so called decay curve, can be recorded by
X-Ray spectrometer during the electron bombardment. The decay curve generally
reveals two distinguished parts; the first one is constant or linear and after some
time, called the incubation period, breaks into the exponential-like one.
Potassium silicate glasses were irradiated with 50 keV and 2.5 MeV. The
decay curves were recorded for both pristine glass and that irradiated with highenergy electrons. Both decay curves were compared; the changed incubation times
enabled to estimate the radiation damage caused by 50keV and 2.5MeV. Changes
of composition within and around the exposed volumes were measured by EPMA
(Electron Probe Microanalysis). Absorption spectra of glass irradiated with highenergy electrons in the visible range revealed a clustering in glass. The electron
irradiation is also accompanied with volume changes. AFM revealed volume
contraction at small doses and expansion at high doses.

36

O4-8
Measurement of a certified standard of hydroxyapatite by PIXE,
EDS, and simultaneous PIXE and RBS a comparative study
M. Webb1, S. Coe2, G Grime1 and C Jeynes1
University of Surrey Ion Beam Centre, Guildford, GU2 7XH, UK
Department of Materials Science, University of Nottingham, NG7 2RD, UK
1

Determination of the Ca:P ratio in biomedical samples such as bone is of

interest in biomedicine, and small variations in the Ca:P ratio are frequently studied
in order to understand conditions such as osteoporosis [1]. X-ray spectrometry
methods are particularly suitable for such studies because the mapping capability of
the techniques allows researchers to locate spatial variations in the Ca:P ratio.
In this paper, we will present a comparative study of different X-ray
spectrometry methods (PIXE and EDS) for the determination of the Ca:P ratio in a
certified standard of hydroxyapatite. The certified value was accurately verified by
Rutherford Backscattering Spectrometry (RBS) which is a simply traceable technique
depending on the scattering cross-section given (analytically) by the Coulomb
potential, and typically using a probe beam of 2MeV alpha particles. RBS is one
varant of ion beam analysis (IBA), and PIXE spectra can be collected simultaneously
with RBS spectra.
The Ca:P ratio was measured using EDS, the PIXE code GUPIX [2], and
the newly implemented PIXE module in the IBA DataFurnace code [3,4] which
accurately determines elemental depth profiles by self-consistently fitting the PIXE
and RBS spectra. RBS spectra have depth profile information available directly,
so a PIXE/RBS analysis is very powerful for samples which are not homogeneous
in depth, a common case which can can seriously distort EDS results. It is also
interesting to compare EDS with IBA since the information depth for all the techniques
is different.
[1] W Kaabar, E Daar, M Farquarharson, O Gundogdu, P M Jenneson, M Webb, C
Jeynes and D A Bradley, International Confernce on the Biomedical Applications
of High Energy Ion Beams, August 2007, Surrey, UK (to be published in Applied
Radiation and Isotopes)
[2] J Maxwell, W Teesdale and J Campbell, Nuc, Inst. Methods in Res. B, Vol.
1970, p. 407-421 (1995)
[3] C. Pascual Izarra et al, NIMB, 261 (2007) 426-429
[4] L.Beck et al, NIMB (2008) doi:10.1016/j.nimb.2007.12.091

37

I5
Photoinduced atomic inner-shell processes investigated by
means of high-resolution x-ray spectroscopy
J.-Cl. Dousse
Department of Physics, University of Fribourg, Chemin du Muse 3,
CH-1700 Fribourg, Switzerland
High-resolution x-ray spectroscopy represents a powerful and sometimes
unique tool for the investigation of atomic inner-shell processes. Indeed many
aspects of the mechanisms governing the atomic excitation and decay channels
can be studied by means of this technique which has played a central role in our
present understanding of atomic structures and dynamics. The wealth of x-ray
based applications in many domains of modern physics and other fields of sciences
and technology and the recent advent of new tools such as synchrotron radiation
facilities and heavy-ion storage rings combined with increasingly sophisticated
instrumentation have given a new boost to the domain.
In the first part of the talk, basic aspects of wavelength dispersive instruments
will be presented. Bragg-type and Laue-type spectrometers will be outlined and their
advantages and drawbacks discussed. Two high-resolution crystal spectrometers
constructed in Fribourg will be then described in more details: a Laue-type DuMond
bent crystal spectrometer used for the measurements of photons of energies higher
than 12 keV and a Bragg-type von Hamos bent crystal spectrometer employed for
photon energies between 0.6 keV and 16 keV.
In the second part, examples of some recent projects performed by means of
high-resolution x-ray spectroscopy will be presented. Some typical results obtained
in our long-term work on the metrology of x-ray transitions will be first presented.
Studies concerning the resonant inelastic x-ray scattering (RIXS) and the hypersatellite transitions induced by impact with heavy-ions, electrons and photons will be
then discussed. Finally, before concluding some results concerning the determination
of low-Z trace impurities on the surface of silicon wafers by means of the novel highresolution total reflection x-ray fluorescence (TXRF) technique will be outlined.
[1] B. Perny et al., Nucl. Instrum. Meth. Phys. Res., A 267 (1988) 120.
[2] J. Hoszowska et al., Nucl. Instr. Meth. Phys. Res., A 376 (1996) 129 - 138.

38

O5-1
Large area silicon drift detectors
A. Pahlke, T. Eggert, S. Pahlke, R. Sttter, F. Wiest
KETEK GmbH, Hofer Str. 3, 81737 Munich, Germany
Silicon Drift Detectors (SDDs) are commercially available for more than 10
years. They are widely used in XRF, TXRF, electron microprobe analysis systems
and synchrotron applications.
The big benefit of SDDs compared to other x-ray detectors as Si(Li)s or
pin-diodes is the spectroscopic performance principally being independent of the
sensitive area. As there is a growing demand for larger detector areas, KETEK has
developed SDDs with active areas up to 100 mm.
We will present spectroscopic measurements of SDDs with areas varying
from 10 to 100 mm. Energy resolution below 130 eV for the Manganese K line
and peak to background values of more than 10,000 will be shown for devices with
active areas of 100 mm when cooled down to -60C. Count rate dependency of the
energy resolution and the peak position is shown to be negligible up to count rates
of 100,000 counts per second.
Temperature dependent measurements of the energy resolution will be
shown for different detector areas. We will present improved cooling techniques for
KETEK VITUS modules which allow detector temperatures down to -50C at an
ambient temperature of +20C. Energy resolutions below 135 eV for 100 mm SDDs
and 130 eV for 30 mm devices at -50C are achieved.

39

O5-2
Advances in the technology of silicon drift detectors (SDD) and
multiple element SDD
R. Terborg1 and M. Rohde1
1

Bruker AXS Microanalysis GmbH, Schwarzschildstr. 12, 12489 Berlin, Germany

Over the past few years, Silicon Drift Detectors (SDD) have become more
and more popular in the field of X-ray detection and are about to replace lithiumdrifted silicon detectors (Si(Li)), [1]
Improvement have made it possible for state of the art SDD, as represented
by the forth generation XFlash 4000 series, to exceed the performance of Si(Li) in
almost every respect that matters to analytical x-ray spectrometry. High resolution type
SDD show energy resolutions of 125eV or even better at Mn-K. Optimised detector
radiation entrance windows [2] provide an excellent low energy response with minimal
shelf and tail. Improved electronics with pulsed charge restoration methodology
maintain this energy resolution even at extremely high count rates, allowing all XFlash
detectors to achieve full specification at 100 kcps input count rate.
Multiple element SDD structures with four separate detectors integrated on
one chip provide even higher count rates without increasing pile-up or dead time.
Quad SDD with four separate detectors are capable to deliver up to 1,000,000 cps
output count rate. The multi element concept also allows a larger solid angle without
degrading energy resolution because of a larger effective area, e.g. detectors which
consist of four 10mm (left) and 15mm2 SDD (right), offering effective detector areas
of 40 and 60mm2, respectively.
The especially designed annular QUAD XFlash 4060 with four 15 mm2
SDD centered around a hole for the primary beam can be placed directly before
the sample in order to cover an extremely large solid angle of about 0.9 sr because
of its flat and perpendicular structure and good performance at count rates of up to
500kcps [2], Fig. 1.

Fig. 1. Flat annular detector (QUAD XFlash 4060) which covers a solid angle of 0.9 sr when
placed 5mm above the sample. Left: design, right: sketch of the four detector segments.

[1] R. Terborg, M. Rohde, Microsc. Microanal. 10 (Suppl.2) (2004), 942-943

[2] P. Kotula et al., Proceedings of the ACMM-20 & IUMAS-IV (2008) 50-51
40

O5-3
Silicon drift detector spectrometers for
high count rate XRF applications
S. Barkan1, V. D. Saveliev1, P. Pianetta2, S. Brennan2, C. R. Tull1, L. Feng1, M.
Takahashi1 and H. Ishii3
SII NanoTechnology USA Inc., 19865 Nordhoff St., Northridge, CA 91324, USA
2
Stanford Synchrotron Radiation Laboratory, Menlo Park, CA 94025, USA
3
Lawrence Livermore National Laboratory, Livermore CA 94550, USA

A 50 mm2 silicon drift detector (SDD) has been successfully applied to TXRF
(total reflection x-ray fluorescence), synchrotron and other XRF applications. The
SDD offers a large solid angle, excellent energy resolution (<130 eV FWHM at 5.9
keV, 4-6 s peaking time), and high count rate performance (> 600 kcps throughput
at 0.25 s peaking time).
The SDD has recently been applied to collect synchrotron XRF spectra
in several astrophysics applications. For example, the chemical composition of
particles from the Wild 2 comet, collected and returned to Earth from a NASA
mission, have been analyzed using the SDD in synchrotron XRF techniques at the
Stanford Synchrotron Radiation Laboratory.
Multi-channel XRF spectrometers, offering larger solid angle and higher
count rate performance, have been developed based on multiples of the 50 mm2
SDDs. Two unique multi-element systems have recently been developed and are
currently being used in high count rate synchrotron applications at the Advanced
Photon Source at Argonne National Laboratory.
Results from several XRF applications, using both the single-element and
multi-element SDD spectrometers, will be presented.

41

O5-4
High througput digital pulse processing hardware
Paul A. B. Scoullar1 and Robin J. Evans2
Southern Innovation, Melbourne, Australia
Dept. of Electrical and Electronic Engineering, The University of Melbourne,
Australia
1

Practical applications of X-ray spectrometry frequently require the user to

trade off a substantial degradation of energy resolution in order to achieve an increase
in the detector throughput. Traditional approaches to digital pulse processing allow
this by implementing linear filtering techniques to decrease the required pulseshaping time. However, a point is rapidly reached beyond which the majority of data
is corrupted by pulse pileup degrading the throughput, energy resolution, or both.
This paper presents an optimal pulse detection technology for the processing
of digitised pulse trains from X-ray detectors. Using a multi-stage, nonlinear digital
signal-processing algorithm, this approach is able to decode pileup events in real
time dramatically improving the count-rate, throughput, and resolution performance
of XRF and XRD systems.
The performance of the digital pulse processing technology has been
analysed over a range of input count-rates using a digital nuclear pulse generator.
Results indicate that over a 100-fold increase in input count-rate (from 10 kc/s to
1,000 kc/s) system throughput and energy resolution both degrade by less than
10%.
Implemented on a PCI based computer card, in a Virtex-IV FPGA, the
technology is able to decode pulse pileup events in real-time dramatically improving
the performance of a wide range of X-ray spectrometry systems.

42

O5-5
Enhanced detection sensitivity of micro X-ray Fluorescence by
using advanced X-ray optic chain
N. Gao, Z. Chen, and I. Ponomarev
X-Ray Optical Systems, Inc., East Greenbush, NY, USA
Both polycapillary X-ray optics and doubly curved crystal (DCC) optics have
been widely used in X-ray analytical instruments and a variety of research applications.
A polycapillary optic is a broad-band optic that consists of up to millions of small
channels that are precisely curved to a designed profile to efficiently transmit X-rays
by multiple external total reflections off the inner surface of each individual capillary
channel. The optic collects a large solid angle of X-rays from a divergent X-ray
source and redirects them to either a parallel beam of a focused beam. A focusing
polycapillary optic can generate a focal spot less than 10m while delivering an
X-ray intensity equivalent to a pinhole collimator of millimeters in diameter, making it
an inevitable tool to use for many applications. A doubly curved crystal (DCC) optic,
on the other hand, is a diffractive X-ray optic that collects X-rays from a divergent
X-ray source and redirects a narrow band of them by diffraction to form a focused,
monochromatic beam. The two optic technologies have their own characteristics and
advantages, but also have their limitations. We will report in this paper the use of a
DCC-polycapillary optic chain to achieve a monochromatic beam with the focal spot
size less than 10m and the use of such configuration for micro X-ray fluorescence
applications. The performance will be compared with that of other technologies to
demonstrate the capability of the innovative approach in achieving higher detection
sensitivity, higher measurement precision and other analysis benefits.

43

O5-6
Detection of a heavy metal inclusion in the tissue
with the use of ED XRF approach
V.I.Koudryashov, A.P.Moroz, A.S.Serebryakov and V.Yu.Toropov
JSC Comita, Roentgen str., 1, St.Petersburg, Russia, 197101
Energy Dispersive X-Ray Fluorescence (ED XRF) spectrometer X-Art M
produced by JSC Comita is used to determine position and size of a spherical heavy
metal inclusion formed by injection at a certain depth in the tissue. This problem
appears in Neutron Capture Therapy when the tumor is saturated with 157Gd solution
[1]. It is important to check the real boundaries of the inclusion just before the tumor
is irradiated by neutron flux.
Thick Si(Li) detector in the X-Art M spectrometer allows effective detection
of Gd K, lines excited in the tissue by 241Am source. To interpret the experimental
spectra a new Monte Carlo code is developed which includes non-standard imitation
of the photon path length in the media with variable parameters.
It is shown that the Gadolinium concentration of about 25 mg/ml can be seen
at a depth up to 4 cm in the tissue, and for 80 mg/ml the depth is up to 5 cm.
[1] Y.M.Yevdokimov et al, Int. J. of Biological Macromoleculs, 37 (2005) 165-173

44

O5-7
The difficult way to excellent analytical results
P. De Pape
BRUKER AXS GmbH, stliche Rheinbrckenstrasse 49, 76187 Karlsruhe,
Germany
Everyone who deals with elemental analysis is probably striving after the
most ideal results and thus calibration curves. Sometimes, it is indeed a long and
difficult way obtaining an excellent and trustable result with an X-ray spectrometer
(let it be an ED- or a WD-XRF). Too often, providers of analytical equipment get
confronted with the question or even statement the machine/spectrometer does not
run stable, it gives me wrong results!
There are some steps in the analytical process which have to be taken care
of in order to get precise and accurate results. It is not only measuring a sample and
picking up your results. No, that is only the final step in a process of many actions.
This presentation will deal with the different sources of error which can take
place, before we measure the actual specimen, in the XRF analysis. First of all we
need to take a representative sample and we also need to transform this sample into
an appropriate specimen which we can measure with our spectrometer. Of course,
also the instrument stability will play a role; every equipment needs some basic
maintenance. If we are setting up a calibration line then we must be sure that we
have a set of certified reference materials or at least some standards of which we
know that they are of high quality. And last but not least, we must take care that
we do use the right calibration model; did we calculate line overlaps where it is
necessary, did we calculate matrix effects? It is necessary to check the quality of our
result by means of some standard.
Further, we can not expect the same quality in our results when we compare
the today so popular black box standardless analysis with quantitative analysis.
Nevertheless, today both methods can give us good results, but again we must
realise that analysis with X-ray spectrometers also needs some human input.
In the end WE are the largest source of error.

45

O5-8
Response function of semiconductor detectors : comparison
between experimental measurements and Monte Carlo
simulation
M.-C. Lpy and J. Plagnard
Laboratoire National Henri Becquerel, CEA-LNE, CEA Saclay,
F-91191, Gif-sur-Yvette CEDEX, France
Response function of semiconductor detectors is a key element for accurate
analysis of experimental spectra obtained by X-Ray fluorescence or PIXE. The
interest of the use of monochromatic radiation to accurately know the detector
response function has been previously pointed out.
In the present study, the SOLEX X-ray source [1] is used to produce a
tunable monochromatic X-ray beam in the 1-20 keV range. With this facility, it is
possible to record spectra around the binding energies of the elements constituting
the detector (active crystal, electrode, etc.). The comparison between spectra just
below and above the binding energies allows demonstrating the effects of primary
photons and secondary fluorescence X-rays, Auger electrons and photoelectrons on
the spectrum shape. Indeed, the spectrum shape strongly depends on the photons
and photoelectrons interactions at the level of the semiconductor crystal-electrode
interface.
The PENELOPE Monte Carlo code [2] is used to simulate the spectra
corresponding to experimental conditions, and to follow the interactions of
elementary particles in each constituent of the detector. This is applied to a highpurity germanium detector that has been previously characterized using SOLEX [3]
and whose constituents thicknesses have been measured.
Comparison between experiment and simulation allows validating
assumptions on the composition of the low energy side of the full-energy peak
[1] C. Bonnelle, P. Jonnard, J.-M. Andr, A. Avila, D. Laporte, H. Ringuenet, M.-C.
Lpy, J. Plagnard, L. Ferreux, J. C. Protas, Nuclear Instruments & Methods in Physics
Research A, 516 (2004) 594601.
[2] F. Salvat, J.M. Fernandez-Varea, J. Sempau, OECD/NEA 6222 (2006), ISBN
92-64-02301-1.
[3] J. Plagnard, C. Bobin, M.-C. Lpy, X-Ray Spectrom, 36 (2007) 191-198.

46

O5-9
A new X-ray astronomy spectro-imaging detector based on a
micro-calorimeters array using tantalum absorbers
F. De Moro1, A. Aliane1, A. Gasse1, P Agnese1, H. Ribot1, C. Pigot2, J-L.
Sauvageot2 and V. Szeflinski2
CEA/LETI, MINATEC 17, avenue des martyrs 38054 Grenoble, France.
2
Laboratoire AIM, CEA/DSM - CNRS - Universit Paris Diderot,
DAPNIA/Service d'Astrophysique, Bt. 709, CEA-Saclay, F-91191 Gif-surYvette Cdex, France.
1

For the next generation X-ray space observatories, such as XEUS mission,
cryogenic X-ray microcalorimeter arrays are expected to outperform CCDs in terms
of spectral resolution, energy bandwidth and count rate. In this context, we are now
developing an X-ray spectro-imaging camera operating between 0.05 and 0.1 K [1]
using silicon thermistors thermally and mechanically linked to Ta absorbers.
The camera is a 32x32 pixels matrix with a 500 m pitch. Each pixel is made
of a purified tantalum X-ray absorber thermally linked in a flip chip configuration to
a thermistor. This last is obtained by P and B implantation and high temperature
diffusion in 1.5 m thin and very brittle silicon membranes, electrically connected to
a read out circuit for data processing. Thanks to its high atomic number, a 25 m
thin tantalum foil allows almost complete absorption of photons between 0.1 and 10
keV. Due to the high number of pixels, a flip chip collective hybridization of tantalum
absorbers on brittle implanted silicon thermistors array has been performed with a
pure indium solder. Indium bumps were first fabricated on silicon wafers and then
transferred onto tantalum foils. These were singulated maximizing the filling factor,
i.e. with a minimum space between pixels. Collective hybridization of pixels onto
thermistors array is then carried out using a Suss Microtec FC 150 bonding machine
by a reflow process.
We will first discuss the materials choice and implementation techniques
imposed by the severe detectors specifications. Then we will present in details,
the main challenging technical issues of the construction of the detector. Collective
hybridization of singulated tantalum absorbers on brittle silicon membranes will be
shown. First measurements of the thermal impedance of the link will be presented.
[1] A. Aliane et al, J. Low Temp. Phys., (2008) doi: 10.1007/s10909-007-9664-7

47

O5-10
X-ray Microanalysis by a Transition-Edge Sensor
Microcalorimeter mounted on a low voltage FE-SEM
I. Nakai1, Y. Ono1, Q. Li1, A. Hokura1, Y. Homma1,
K. Tanaka2, Y.Baba2, and S. Nakayama2
1

Faculty of Science, Tokyo University of Science, Shinjuku, Tokyo 162-8601,

Japan
2
SII NanoTechnology Inc.

We have developed an EDS system for scanning electron microscope

utilizing a transition-edge sensor (TES) microcalorimeter X-ray detector and mounted
it on a FE-SEM (JEOL: JSM-7000F). The microcalorimeter is composed of a gold
X-ray absorber, a bilayer Au/Ti thermometer, a heat sink and a thermal isolation
structure with a SiNx membrane. The operating temperature of 100 mK is obtained
via a dilution refrigerator. The achieved energy resolution was 19 eV for Al K (1487
eV) at an acceleration voltage of 5 kV. An EDS spectrum of euxenite, (Y, Ca, U, Th)
Nb2O6, was measured and compared with the SSD data in Fig. 1. TES gives well
resolved peaks of the heavy elements Y,Nb,Th,U as well as the light element of Ca
showing the high resolution of the detector.
The TES system was applied for the first time to reveal the cellular distribution
of Cd in a cadmium hyper-accumulating plant. The elemental maps of the light
element P as well as the heavy elements Cd and Zn were also successfully obtained.
Similarly, the simultaneous analysis of As L and Mg K in an arsenic-accumulating
fern was possible with this system. In addition, a single particle of natural particulate
matter was successfully analyzed by this spectrometer at a low acceleration voltage.
These results suggest that this system has high potential in application to X-ray
microanalysis of environmental samples including various biological samples.

Fig.1-cal EDS spectrum of euxenite, (Y,Ca,U,Th)Nb2O6.

48

O5-11
High-resolution X-ray spectroscopy with the TES
microcalorimeter X-ray detector
T. Jach1, N. Ritchie1 and J. Ullom2
National Institute of Standards and Technology, Gaithersburg, Maryland 20899
USA
2
National Institute of Standards and Technology, Boulder, Colorado, 80305 USA
1

The NIST microcalorimeter x-ray detector using a superconducting

transition edge sensor (TES) has reached a point of practical development at which
we have already carried out programs in x-ray spectroscopy and quantitative x-ray
microanalysis[1,2]. The ability to measure x-ray spectra with relatively high resolution
(up to 4.4 eV) over an extended energy range (8 keV) means that we are able to
resolve spectra due to compositions of multiple chemical elements and to make
intercomparisons of spectral lines. These include both the energies and intensities
of lines and accompanying satellite lines. We describe the current performance of
the detector and applications that we have carried out using electron excitation.
Future improvements in resolution that will allow us to observe oxidation states and
chemical valence features in the x-ray fluorescence spectra will also be described.
[1] T. Jach, J. A. Small, and D. E. Newbury, Adv. X-ray Anal. 48 (2005) 216-218.
[2] T. Jach, N. Ritchie, J. Ullom, and J. A. Beall, Adv. X-ray Anal. 50 (2007) 51-53.

49

O5-12
Calculation of scattering spectra for the determination of the
actual transmission of an X-ray mini-lens for XRF
V.-D. Hodoroaba and M. Procop
Bundesanstalt fr Materialforschung und prfung (BAM), D-12200 Berlin,
Germany
The knowledge of the X-ray excitation spectrum is a prerequisite for XRF
quantification. In the case of small-spot XRF the excitation spectrum is the X-ray
tube spectrum multiplied with the transmission function of the X-ray mini-lens. The
tube spectrum is usually calculated by fundamental equations. The transmission
function is conventionally determined by measuring two scattering spectra with and
without mini-lens and dividing them to each other [1]. The measurement without
mini-lens is costly, requiring a calibrated double collimator to be interchanged with
the mini-lens therefore carried out mostly by manufacturer.
The alternative to the measurement of the scattering spectrum without lens is
its calculation from Rayleigh and Compton scattering of the specimen. The procedure
was verified with an iMOXS X-ray source (IfG, Berlin) with known tube spectrum [2]
and being attached to a SEM equipped with a calibrated EDX spectrometer [3].
The transmission function obtained was in a good agreement with that resulted
from two measured scatter spectra. It will be presented how the procedure exactly
works and how secondary effects not yet included into the scattering model can be
circumvented.
The major benefits of the new procedure are that the user is able quickly
to determine the actual transmission function. This is very likely modified after a
change of the X-ray tube or of the X-ray mini-lens (meanwhile routine practice in our
lab when looking for the optimal excitation). Additionally, the procedure is sensitive
to the effect of possible degradation of the tube target or window.
[1] W. T. Elam et al., US Patent No. 6,845,147, granted on Jan. 18, 2005.
[2] M. Procop, V.-D. Hodoroaba, Microchim. Acta, DOI
s00604-007-0854-4.

10.1007/

[3] F. Scholze and M. Procop, X-Ray Spectrom. 30 (2001) 69.

50

O5-13
X-Ray plasma source for fs-pulses
M. Haschke1, M. Bargheer, W. Mathis, A. Gnther1, W. Mackowiak, F. Tretner1
and F. Oesker1
Institute for Scientific Instruments GmbH, Berlin
Max-Born-Institut, Berlin
Feinmechanik Teltow GmbH

Examination of material structure is possible with X-Ray techniques. A very

often used method is X-Ray diffraction. This method typically gives time averaged
information about the arrangement of atoms in a crystal. But more and more it
will be interesting to see their changes or also changes in electronic structure. In
that case time dependent measurements are necessary. Due to time constants for
these processes in the range of picoseconds and down to femtoseconds special
pump-probe-experiments are used. They need X-Ray sources that generate pulses
of hard X-Rays in the fs-range. X-Ray pulses of this duration can be generated
by beam slicing experiments at synchrotrons, by free electron lasers or by laser
pumped plasma sources. These plasma sources are table top instruments that can
be used in laboratory environment. They produce incoherent pulses with duration in
the range of 100 fs and with up to 107 photons/(pulse*4) and a repetition rate in
the kHz range.
The paper discusses the development of a plasma-X-Ray-source of this type
and their mechanical design. First results of operation will be presented.

51

I6
X-ray phase contrast imaging and tomography of malaria
transmitting mosquitoes
D. Wegrzynek1, 2, E. Chinea-Cano1, A. Markowicz1,2, C. A. Malcolm1, M.
Helinski1, P. Wobrauschek3, Ch. Streli3, N. Zoeger3, R. Simon4, T. Weitkamp4,
Ch. Frieh4
Agencys Laboratories Seibersdorf, International Atomic Energy Agency, A-1400
Vienna, Austria
2
Faculty of Physics and Applied Computer Science, AGH University of Science and
Technology, 30-059 Krakow, Poland
3
Atominstitut der Oesterreichischen Universitaeten, Technische Universitaet Wien,
Stationallee 2, A-1020 Vienna, Austria
4
Forschungszentrum Karlsruhe GmbH, Institute for Synchrotron Radiation,
Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany
1

X-ray phase contrast imaging technique was applied to examine the

morphology of malaria transmitting mosquitoes in support to the development of the
sterile insect technique (SIT) [1, 2]. The aim of the experiment was to detect eventual
damage induced by the sample preparation procedures, to perform X-ray phasecontrast imaging on freshly prepared (not fixed) and live mosquito species, and to
test the new beamline set up.
The ability to perform X-ray phase-contrast imaging of live mosquito
specimens was confirmed. The collected still images provided data on a relatively
large population of mosquitoes. The CT data were very useful to compare selected
mosquito species. They confirmed that the sample preparation procedures are critical
for examining the morphological details. The procedures must by further optimized
in order to stabilize the sample without inducing significant damage. The most
interesting results should be obtained with the high-resolution (~ 0.5 micrometer)
set up. If there are differences between the control and irradiated populations of
mosquitoes they should show up first at the tissue level. Using the high-resolution
set up it should be possible to detect such differences, if present
[1] A.W. Stevenson, T.E. Gureyev, D. Paganin, S.W. Wilkins, T. Weitkamp, A.
Snigirev, C. Rau, I. Snigireva, H.S. Youn, I.P. Dolbnya, W. Yun, B. Lai, R.F. Garrett,
D.J. Cookson, K. Hyodo, M. Ando, Nucl. Instr. Methods in Phys. Res. B 199 (2003)
427435.
[2] M.Q. Benedict, A.S. Robinson, TRENDS in Parasitology 19 (2003) 349-355.

52

O6-1
Combined micro-XRF/XRPD tomography on historical and
modern paint multilayer samples
W. De Nolf1, J. Jaroszewicz1, G. Van der Snickt1, K. Janssens1, S. Farnell2 and
L. Klaassen2
Department of Chemistry, University of Antwerp,Universiteitsplein 1, B-2610,
Wilrijk, Belgium
2
Royal Museum of Fine Arts, Plaatsnijderstraat 1, B-2000 Antwerp, Belgium

The combination of X-ray powder diffraction (XRPD) and X-ray fluorescence

(XRF) used together in a micro-tomography experiment at a synchrotron end station
allows the reconstruction of phase and elemental distributions within objects on
the micro scale [1]. Several parameters can be extracted from the XRD data and
plotted against the tomographic translation and rotation coordinates to construct
sinograms which form the basis for image reconstruction. Using the intensity of
individual (hkl) reflections will result in phase distribution maps in a plane through
the scanned powder sample, i.e. where all crystal orientations are evenly present.
For polycrystalline material with less grains in the x-ray microbeam, the intensity will
depend on the orientation under which the diffractograms are collected. This results
in irregular sinograms, showing strongly fluctuating diffraction intensity as a function
of the object rotation angle, making the reconstruction very difficult.
The Pawley intensity scaling factor can be used instead of individual peak
intensities to smooth out this orientation effect. When performing Rietveld refinement,
additional semi-quantitative information (i.e. phase weight percentages) can be
obtained for the scanned area.
Recent results from tomographic experiments on paint multilayer samples,
performed at HASYLAB Beamline L, are presented. A ~700 m thick car paint was
found to be composed of nine layers, containing six different crystalline compounds.
Furthermore, a paint fragment was investigated from a 17th C. painting from P.P.
Rubens. Reconstruction shows a distinct calcite grounding on which a mixed
hydrocerussite/azurite layer is deposited, which explains the light-blue tint used to
depict the clouded sky in the painting.
[1] W. De Nolf, B. Vekemans, K. Janssens, G. Falkenberg, HASYLAB Annual
Report (2005) 1131-1132

53

O6-2
Three dimensional SR-confocal micro XRF combined with
absorption microtomography on Daphnia magna: Instrumental
developments and recent advances in dataprocessing
Bjrn De Samber1, R. Evens2, T. Schoonjans1, G. Silversmit1, B. Vekemans1,
K. De Schamphelaere2, C. Janssen2, B. Masschaele3, L. Van Hoorebeke3,
K. Rickers4, G. Falkenberg4 and L. Vincze1
X-Ray Microspectroscopy and Imaging (XMI), Ugent, Belgium
Laboratory of Environmental Toxicology and Aquatic Toxicology, Ugent,Belgium
3
Centre for X-Ray Tomography, Ugent, Belgium
4
Hamburger Synchrotronstrahlungslabor at DESY/PETRA III, Germany
1

Daphnia Magna (also called water fleas) are being used to study the mechanism
of intoxication by metals (Zn, Cu, Ni) and to develop so called biotic ligand models (BLMs).
It has been shown that Daphnia magna responds differently to Zn-exposure via the water
and/or via the food [1].
In order to distinguish critical tissue from
whole body accumulation in these small organisms
(~3 mm size), we explored the potential of combined
X-ray techniques as a complementary approach to the
above problem. Fast dynamic 2D micro XRF scanning
and XRF micro CT experiments on Daphnia magna at
Beamline L (HASYLAB, Hamburg, Germany) allowed
the semi-quantitative investigation of the accumulation
of metals within specific organs with microscopic
resolution. Combining these results with micro CT data
sets unravelled the tissue specific 2D/3D distribution of
metals within delicate organic samples on the 3-15 m resolution level in an essentially nondestructive manner [2].
As demonstrated, recent developments at beamline L, involving a dedicated
confocal -XRF set-up with a resolution of 5 m and full 3D dynamic scanning algorithms
allowed to explore microscopic 3D substructures within Daphnia magna (also called topdown methodology) aiding ecotoxicological research towards the tissue and even cellular
level. Three dimensional isosurfaces of the elements of interest were obtained within a
300 m Daphnia magna egg (5m resolution). Moreover, K-means clustering allowed us
to isolate 3D clusters of interest of which the elemental content can be investigated in
closer detail [3]. Finally, using laboratory micro CT (0.9 m resolution) we obtained full 3D
correlation between elemental and absorption datasets on the micrometer scale within
biological samples.
[1] Developments of a chronic zinc biotic ligand model for Daphnia magna, D.G. Heijerick et
al., Ecotoxicology and Environmental Safety (2005) 62: 1-10
[2] Three-dimensional elemental imaging by means of synchrotron radiation micro-XRF:
developments and applications in environmental chemistry, Anal. Bioanal. Chem. (2008)
390:267-271
[3] Processing of three-dimensional microscopic X-ray fluorescence data, B. Vekemans et
al., J. Anal. At. Spectrom. (2004) 19: 1302-1308

54

O6-3
Quantitative elemental imaging of fragments of the Dead Sea
scrolls with a combination of micro-XRF and 3D micro-XRF
B. Kanngieer1, I. Mantouvalou1, T. Wolff 1,2, O. Hahn2, I. Rabin3
and W. Malzer1,*
Institut fr Optik und Atomare Physik, Technische Universitt Berlin,
Hardenbergstrae 36, 10623 Berlin, Germany
2
BAM Bundesanstalt fr Materialforschung und prfung, Unter den Eichen 87,
12205 Berlin, Germany
3
The Jewish National and University Library, Hebrew University - Edmond Safra
campus, Givat Ram, Jerusalem, Israel
1

* current affiliation: Bruker AXS Microanalysis GmbH

With a combination of Micro-XRF and 3D Micro-XRF an investigation of very
inhomogeneous, archaeological samples was carried out. For Micro-XRF a portable
spectrometer [1] was used for which a quantification procedure was developed. 3D
Micro-XRF measurements were performed at the Spot beamline of the synchrotron
storage ring BESSY. The quantification of the elemental depth profiles was obtained
by a self-developed reconstruction algorithm which was validated and applied
recently [2,3]. The combination of both methods allows reliable quantitative elemental
imaging even for very inhomogeneous samples.
The mutual benefits of this combination will be exemplified by the investigation
of some fragments of the Dead Sea Scrolls. It shows its capacity especially for
samples from the field of Cultural Heritage.
[1] O. Hahn, B. Kanngieer, and W. Malzer, Studies in Conservation 50 (2005),
23-32.
[2] I. Mantouvalou, W. Malzer, I. Schaumann, L. Lhl, R. Dargel, C. Vogt, and B.
Kanngieer, Anal. Chem. 80 (2008), 819-826.
[3] B. Kanngieer, I. Mantouvalou, W. Malzer, T. Wolff, O. Hahn, J. Anal. At.
Spectrom., (2008), in press.

55

O6-4
X-Ray fluorescence microtomography analysis under various
excitation conditions
G.R. Pereira1, H.S. Rocha1, M.J. Anjos2, C.A. Prez3, R.T. Lopes1
Nuclear Instrumentation Laboratory, COPPE/UFRJ
P.O. Box 68509, 21941-972, RJ, Brazil
2
Physics Institute, UERJ, RJ, Brazil
3
Brazilian Synchrotron Light Laboratory, Campinas, Brazil
1

X-ray fluorescence microtomography (XRFCT) can be used to investigate

the distribution of the chemical elements inside a sample. This makes it a powerful
tool for several fields of research, like biology, archaeology and medicine. XRFCT
is based on the detection of fluorescence photons emitted by the elements in the
sample. As the energy of photons of fluorescence has a particular value for each
element, is possible to obtain the distribution of all the elements in a sample, since
that a minimum of fluorescence signal is detected.
The main of this work is to compare three different excitation conditions in
XRFCT for analyzing reference samples and to determine the elemental distribution
map in breast tissue samples in order to verify the concentration of some elements
correlated with characteristics and pathology of each tissue observed by the
transmission CT.
The experiments were performed at the X-Ray Fluorescence beamline
(D09B-XRF) of the Brazilian Synchrotron Light Source (LNLS), Campinas, Brazil.
In this works, it was used a multilayer monochromator at photon energies near
12 keV, a monochromatic beam at 9.8 keV using a Si(111) and a white beam for
the excitation of the elements inside the samples. The sample was placed on a
high precision goniometer and translation stages that allow rotating as well as
translating it perpendicularly to the beam. The fluorescence photons were collected
with an energy dispersive HPGe detector placed at 90 to the incident beam, while
transmitted photons were detected with a fast Na(Tl) scintillation counter placed
behind the sample on the beam direction.
The transmission CT images were reconstructed using a filtered-back
projection algorithm and the XRFCT were reconstructed using a filtered-back
projection algorithm with absorption corrections.

56

O7-1
High-energy polarised-beam EDXRF for the determination of
palladium residues arising from catalysts used in the synthesis
of active pharmaceutical ingredients
E. Margu1,2, K.Van Meel3, R.Van Grieken3, C.Fonts1, M.Hidalgo1 and I.Queralt2
Department of Chemistry, University of Girona, Campus Montilivi, 17071 Girona,
Spain.
2
Laboratory of X-Ray Analytical Applications, Institute of Earth Sciences "Jaume
Almera", CSIC, Sol Sabars s/n, 08028 Barcelona, Spain.
3
Department of Chemisrty, University of Antwerp, Universiteitsplein 1, 2610
Antwerp, Belgium.

Pharmaceutical industries are required by legislation to restrict the amounts

of residual metals used as process catalysts in the synthesis of drug substances
[1]. Metals are classified in three categories based on their potential risk to human
health and concentration limits are set according to the maximal daily dose, duration
of treatment, route of administration and permitted daily exposure. For example,
in the case of Platinum Group Elements (Pt, Pd) a limit of 10 mgkg-1 in active
pharmaceutical ingredients (APIs) for oral exposure has been established.
All pharmacopoeias include a test for heavy metals, which is commonly carried
out by sulphide precipitation in a weakly acidic medium. However, such test is not
suitable for quantitative determination of the actual levels of some metal residues such
as Pd and then spectroscopic techniques including atomic absorption spectrometry
or inductively coupled plasma optical emission spectrometry are preferred. However,
numerous drugs are practically insoluble in water, weak acids or alcohols and therefore
laborious sample preparation procedures for the total destruction of the matrix by
mineralization, using corrosive and toxic reagents, are needed.
In the present work, we study the feasibility of using High-Energy PolarisedBeam EDXRF (HE-P-EDXRF) spectrometry as an alternative analytical tool for the
analysis of Pd residues in APIs. The combined use of selective excitation using a
CsI secondary target, a Gd anode X-ray tube and a high-energy Ge semiconductor
detector allowed the determination of Pd in APIs and synthetic cellulose standards
in the low mg kg-1 range. Moreover, typical validation characteristics proposed by
the ICH guide [2] were evaluated to study the real capability of the method for the
intended purpose.
The results obtained show that HE-P-EDXRF is a promising analytical
alternative since it involves a really simple sample preparation (i.e. pelletisation)
without losing analytical performance compared to techniques used in the daily
routine at the pharmaceutical laboratories.
[1] European Agency for the Evaluation of Medicinal Products (EMEA). Guideline
on the specification limits for residues of metal catalysts. London, January 2007.
Doc.Ref.CPMP/SWP/QWP/4446/00 corr.
[2] International Conference on Harmonisation of Technical Requirements for
Registration of Pharmaceuticals for Human Use. Validation of analytical procedures:
Text and methodology Q2(R1).
57

O7-2
Chemical character of BCxNy nanolayers
O. Baake1, P. Hoffmann1, A. Klein1, B. Pollakowski2,
B. Beckhoff2, W. Ensinger1, M. Kosinova3, N. Fainer3, V. Sulyaeva3
and V. Trunova3
Technische Universitt Darmstadt, Institute of Materials Science,
Petersenstr. 23, D-64287 Darmstadt, Germany
2
Physikalisch-Technische Bundesanstalt, Abbestr. 2-12,
D-10587 Berlin, Germany
3
Nikolaev Institute of Inorganic Chemistry SB RAS,
Acad.Lavrentyev Pr. 3, Novosibirsk 630090, Russian Federation

Binary and ternary compounds of the light elements boron, carbon, and
nitrogen were predicted to have extraordinary properties for hard coatings, and as
semiconductors of varying band gaps. Layers of BCxNy were produced in a CVD
process using the precursor trimethylamine borane and inert or reactive gases
as He, N2, and NH3, respectively [1]. These layers deposited on Si wafers were
characterized chemically by TXRF-NEXAFS and XPS. As a result, the chemical
bonds were identified by comparison of the spectra with those of reference materials,
and with spectra from the literature [2].
In the product synthesized without NH3 nearly only B-C bonds could be
characterized. By adding NH3 with a partial pressure of up to about 1.3 Pa to the
precursor a material with atomic relations B:C:N = 2:2:1 was found. Increasing the
partial pressure of NH3 to about 1.7 2.1 Pa the product was enriched in nitrogen
yielding a material with atomic relations B:C:N = 1:1:1.
The ternary products exhibit a hexagonal structure, which can be characterized
as h-BN, in which some of the nitrogen atoms are substituted by carbon atoms. In
the contribution the results will be discussed in detail.
[1] M.Kosinova, N.Fainer, Y.Rumyantsev, E.Maximovski, F.Kuznet-sov, M. Terauchi,
K. Shibata, F.Satoh, in M.Allendorf, F.Maury, F.Teyssandier (Eds.) Chemical Vapor
Deposition XVI and EUROCVD 14, The Electrochemical Society, 708-713(2003)
[2] P.Hoffmann, O.Baake, B.Beckhoff, W.Ensinger, N.Fainer, A.Klein, M.Kosinova,
B.Pollakowski, V.Trunova, G.Ulm, J.Weser, Nucl.Instr. Meth.A 575(2007)78-84

58

O7-3
XUV diffraction from a self-assembled 2D array of close-packed
200nm diameter PMMA Spheres
B Mills1, C F Chau2, E T F Rogers1, J Grant-Jacob1, S L Stebbings3, M
Praeger3, C A Froud6, R T Chapman4, T J Butcher1, D C Hanna1, J J
Baumberg5, W S Brocklesby1, J G Frey4
Optoelectronics Research Center, University of Southampton, UK
School of Electronics and Computer Science, University of Southampton, UK
3
School of Physics and Astronomy, University of Southampton, UK
4
School of Chemistry, University of Southampton, UK
5
School of Nanotechnology, University of Cambridge, UK
6
Rutherford Appleton Laboratory, UK
1

Laser-generated XUV and soft x-ray radiation sources using high-harmonic

generation (HHG), typically producing 10^8 photons per pulse per harmonic (~5nm to ~50nm)
in a coherent low-divergence beam [1], are a promising source for nanometer scale imaging
[2]. Here we present XUV diffraction from a single-layer self-assembled hexagonal-closepacked (HCP) array of 200nm diameter PMMA nanospheres. Such a lattice is too small to
diffract from using visible light, and hence XUV wavelengths are required. Figure (a) shows the
far-field pattern from the single crystal at a 22m focus, and overlaid with 100 mrad contours.
The interference peaks are a convolution of a Bragg peak with both the distribution of lattice
planes (due to crystal defects) and the harmonic spectra. However, as these convolutions
are in orthogonal directions, they can be independently resolved (figures b & c), providing
information on the crystal quality and generated wavelengths.
The far-field diffraction pattern from a single-layer HCP array of spheres is the Fourier
Transform (FT) of a hexagonal grid of delta functions multiplied by the FT of a the scattering
function from a single sphere, which can be calculated using Mie theory. Figure (d) shows,
(+) the measured intensity for each of the eighteen interference peaks for the harmonic at
27.6nm, (.) the theoretical intensity versus angle distribution for a single sphere, and (o) the
predicted intensity at each interference peak. The excellent agreement indicates that Mie
scattering predicts an appropriate form factor for this analysis and enables us to extract the
complex refractive index of PMMA at this wavelength.

[1] E Gibson et. al. Science, 302 (2003), 95-98

[2] D Sayre, H Chapman, J Miao. Acta Cryst, A54 (1998), 232-239

59

O7-4
An EDXRF method for determination of uranium and thorium in
AHWR fuel after dissolution
Sangita Dhara, S. Sanjay Kumar, N.L. Misra and S.K. Aggarwal
Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)
Thorium, uranium and plutonium based fuels are used in nuclear reactors
for electricity generation [1]. X-ray Fluorescence in different geometries: Energy
Dispersive, Total Reflection and Wavelength Dispersive, can be used as a nondestructive, fast technique for bulk analysis of Th, U and Pu in these fuel materials
[2]. The main advantage of X-ray spectrometric methods is that the samples can be
analysed without dissolution. However, such determinations suffer from laborious
sample preparation and are encountered with severe matrix effects. In present work,
an EDXRF method for uranium determination with a special emphasis on Advanced
Heavy Water Reactor (AHWR) fuel using a Jordan Valley EDXRF spectrometer
EX-3600 TEC having a Rh target has been developed. Studies were carried out for
uranium and thorium determinations in the samples in form of solutions. Synthetic
uranium and thorium mixtures covering the U% in (U+Th) from 0 to 70% were
prepared by mixing uranium and thorium standard solutions. Y was added as
internal standard in these solutions. About 20 microlitre of solution was taken on
circular Whatmann 541 filterpaper of 30 mm diameter and dried. From the EDXRF
spectrum of such samples, a calibration plot between the amount of uranium and
intensity ratios of U L / Y K was made. A few synthetic mixtures prepared in similar
way were analysed using this calibration. In order to use this method specifically
for AHWR fuel, synthetic mixtures were prepared in U % range of 1 to 5 % and the
calibration curve obtained from these mixtures was used to analyse a few unknown
samples. The precision of the method for uranium determination was found to be 4 %
(1 RSD) and the results deviated from the expected uranium concentrations within
3 %. Thorium was determined in similar way using uranium as internal standard and
the precision and accuracy values of 5% were achieved. Compared to solid sample
analysis by XRF, this method is fast gives better precision and accuracy, requires
easy sample preparation and avoids laborious and time consuming processes e.g.
grinding and pelletisation. However, it requires dissolution of the sample.
[1] R. K. Sinha, A. Kakodkar Nucl. Eng. and Des., 236 (2006) 683-700.
[2] Rene E. Van Grieken and A. Markowicz, Handbook of X-ray spectrometry, Marcel
and Dekker Inc. New York, 1993.

60

O7-5
Crystallinity measurement of modified SiO2 samples by laser
produced-plasma
A. Lorusso1, V. Nassisi1, A Rain2 and L. Velardi2
1

Department of Physics, Laboratorio di Elettronica Applicata e Strumentazione

LEAS, University of Salento, INFN, 73100 Lecce-I
2
Department of Physics, University of Bari-I

In this work the preliminary results of plasma influence onto SiO2 films and the
glancing-angle X-ray diffraction analyses are reported. The samples were processed
by a Si plasma source which emits ion, clusters and X-rays. We developed a new
apparatus composed of a plasma source having the source target polarized as well
as the substrate support. The plasma source was able to generate ions of some
hundreds eV of intrinsic energy and soft X-rays[1]. The laser source consists of a
KrF excimer laser and a generating vacuum chamber made of stainless steel. The
laser energy was 45 mJ/pulse, providing a laser fluence of about 4.5 J/cm2 and a
power density of 2.25x108W/cm2 by means a convergent lens. The ion dose and the
X-rays energy were estimated by a fast Faraday cup in two separate steps. In order
to highlight changes in the material degree of crystallinity, as-implanted samples
were studied by X-ray diffraction (XRD) in both Bragg and glancing angle geometry
(GAXRD) using a Rigaku D/MAX-Ultima+ diffractometer equipped with a thin film
sample stage and an Eulerian cradle. This analysis, suitable to investigate thin film
properties, is well used to study the superficial implantation profile due to the low
intrinsic energy involved. Fig 1 shows the XRD results obtained from a sample at
three different conditions.

[1] V. Nassisi, A. Pedone and A. Rain, Preliminary experimental results on an

excimer laser ion source, Nucl. Instr. Meth. B188, 267-261 (2002)
61

O7-6
Getting an insight into soft polymeric systems properties
by X- ray techniques
S. Boeykens1 and C. Vzquez 1,2
Laboratorio de Qumica de Sistemas Heterogneos. Facultad de Ingeniera.
Universidad de Buenos Aires. P. Coln 850 (C1063ACU). Buenos Aires, Argentina.
2
Comisin Nacional de Energa Atmica. Av. Gral Paz 1499 (B1650KNA) San
Martn. Buenos Aires. Argentina.
1

Soft polymeric systems include from quasi-homogenous dispersions,

in which the number, the position and the size of pores are fluctuating, to porous
heterogeneous rigid structures. Transport phenomena of dispersed systems
of different nature have recently acquired special meanings for theoretical and
experimental investigation. This is due to the fact that this knowledge is essential in
a great variety of technologies applied to diverse areas of engineering: preparation
of emulsions, gel permeation chromatography, operations of separation and
filtration, enhanced oil recovery, medicinal and cosmetic production, foods, etc. In
order to design technological devices for such purposes, it is necessary to have an
understanding of the transport properties of the diffusing species in a given matrix
(polymer-solvent) which are influenced by changes in structural characteristics.
X-Ray Microfluorescence is a spectrometric technique with high resolution
properties that allows studying dynamic systems. In this work instrumental and
practical parameters were optimized to make possible subsequent transport
properties studies in these systems for varied applications. The originality of
the measurements required the design of a special cell for this type of systems.
Measurements were realized at the D09XRF line in the National Laboratory of
Synchrotron Light, Campinas, Brazil.
Results of Small Angle Scattering Light experiments with different
concentration solutions of scleroglucan (neutral polysaccharide), xanthan (polyanion)
and polyoxyethylene (neutral polyether) of similar molecular mass help us to studying
the structural changes which have polymers and linked with transport properties.
SAXS measurements were performed in the line SAXS2 National Laboratory of
Synchrotron Light, Campinas, Brazil.
Results show that in aqueous solution the scleroglucan has a triple helix
structure that behaves as statistical ball at low concentrations (<0.1%), with the
same structure but with local behavior of rodlike to average concentrations (0, 1%
and 1%) and there are larger aggregates and gels (<1%). The xanthan shows a
similar behavior while the POE presents in all areas of concentration structure of the
statistical sphere with a radius of gyration almost invariant. It has been found that
the semidiluted solutions in all cases are those with higher retention power, it can be
understood on the basis of accessibility to the active sites of the macromolecules.

62

O7-7
Nanoresolution interface studies in thin films by synchrotron
x-ray diffraction and by using x-ray waveguide structure
Z. Erdlyi, C. Cserhti, A. Csik, G.A. Langer, Z. Balogh and D.L. Beke
Department of Solid State Physics, University of Debrecen. P.O.Box 2, H-4010
Debrecen, Hungary
Using computer simulations, it was shown [1] that on nanoscale, for strongly
composition-dependent diffusion coefficients, an initially diffuse A/B interface can
become chemically abrupt even in ideal systems with complete mutual solubility. This
sharpening is surprising at first sight because the macroscopic Fick I law states that
the direction of diffusion is always opposite to the direction of the composition gradient.
This predicted behaviour is interesting not only from fundamental research point of
view, but, if confirmed experimentally, it is very promising in terms of applications
as well. It could provide a useful tool for the improvement of interfaces and offer a
way for fabrication of e.g. better X-ray or neutron mirrors, microelectronic devices
or multilayers with giant magnetic resistance. In this contribution we will present
theoretical results [1] and experimental evidence [2] for interface sharpening. The
latter is shown in situ during heat-treatments at gradually increasing temperatures by
scattering of synchrotron radiation in coherent Mo/V multilayers containing initially
diffuse interfaces.
Moreover, X-ray standing wave technique has been used to measure the
kinetics of CoSi intermetallic phase growth in a-Si/Co/a-Si sandwich structure. The
a-Si/Co/a-Si arrangement were placed into a waveguide structure formed by two Ta
films. X-ray fluorescence and extended X-ray absorption fine structure analysis has
been used in a combination with X-ray standing wave technique for depth profiling
with sub-nanometer resolution. The position and the thickness of the growing CoSi
intermetallic phase have been monitored and thus the kinetics of the growth could
be determined.
[1] Z. Erdlyi, I.A. Szab, D.L. Beke, Phys. Rev. Lett., 89 (2002) 165901
[2] Z. Erdlyi, M. Sladecek, L.-M. Stadler, I. Zizak, G.A. Langer, M. Kis-Varga, D.L.
Beke, B. Sepiol, Science, 306 (2004) 1913-1915

63

O7-8
XANES and EXAFS analyses of
manganese local environment in porous silicate catalysts
N. Novak Tuar1, I. Aron2,3 and V. Kaui1
National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia
2
University of Nova Gorica, Vipavska 13, 5000 Nova Gorica, Slovenia
3
Institute Jozef Stefan, Jamova 39, 1000 Ljubljana, Slovenia

One of the major challenges in environmentally benign catalysis is the

search for highly active and stable catalysts for the selective oxidation of organic
substrates with molecular oxygen [1]. In recent years, manganese(III)-containing
porous catalysts have received considerable attention as catalysts for the selective
oxidation of hydrocarbons using molecular oxygen (air) as the oxidant [2].
Porous silicates are used as catalytic supports in chemical reactions [1]. They
possess pore openings with diameters in the range from 1.2 to 2 nm (microporous)
and 2 to 10 nm (mesoporous). Incorporation of metals into their framework generates
catalytically active sites. Catalytic properties of metal-functionalised porous silicates
depend on the structure type, location and the nature of incorporated metal.
Here we report on synthesis and structure analysis of microporous silicate
catalysts with structure type silicalite-1 and mesoporous silicate structure types
MCM-41 and MCM-48, functionalised by manganese. The porosity of the products
was determined by X-ray powder diffraction (XRD), high-resolution transmission
electron microscopy (HRTEM) and nitrogen adsorption isotherms. The evidence for
the presence of catalytically active Mn sites in the framework was obtained by Mn
K-edge XANES and EXAFS analysis, which provided direct information on valence
state and local environment of Mn in these products. Experiments were performed at
XAFS beamline of synchrotron radiation facility ELETTRA (Trieste, Italy). The analysis
revealed a presence of predominatly Mn3+ cations located at distorted tetrahedral
coordination silicate framework sites in all three structural types. First catalytic tests
of the products revealed successful oxidation of alkyl aromatics hydrocarbons to the
corresponding aromatic ketones by molecular oxygen.
[1] A. Corma, H. Garca, Chem. Rev., 102 (2002) 3837
[2] J. M. Thomas, R. Raja, Catal. Today, 117 (2006) 22

64

I8
The nature of X-ray absorption spectra:
Novel theoretical and experimental tools
Frank M. F. De Groot
Inorganic Chemistry and Catalysis, Utrecht University,
Sorbonnelaan 16, 3584 CA, Utrecht, Netherlands
The theoretical interpretation of X-ray absorption spectroscopy is briefly
introduced. The XAS spectral shape is determined by the empty density of states,
including phenomena such as multiplet effects, charge transfer effects and non-local
screening [1,2].
Multiplet effects are caused by the overlap of core and valence wave
functions. They destroy the interpretation of the XAS spectral shape in terms of the
empty density of states. The 2p XAS spectra of 3d metal systems are dominated by
large 2p3d multiplet effects, yielding many fine details [3]. This allows for the detailed
analysis of the spectral shapes, which in turn gives a precise determination of the
ground state, including phenomena such as differential orbital covalence, the effects
of -bonding and mixed-spin ground state, i.e. a state that is a mixture of two spin
states due to spin-orbit coupling combined with strong covalency.
An important addition to X-ray absorption spectroscopy is the use of highresolution X-ray emission detectors, both in the hard and soft X-ray Resonant X-ray
Emission (RXES) experiments. In this talk, I limit myself to a few cases where
the combination of multiplet effects and coherence plays a role in spectral shape
distortions in XAS. This includes non-linear decay ratios between radiative and
non-radiative channels and the effects of broken coherence in the radiative decay
channels.
Scanning Transmission X-ray Microscopy (STXM) experiments make it
possible to measure metal L edges with a spatial resolution of 20 nm. With the use
of a new in-situ reactor, we have performed STXM experiments at 1 bar and 500 C.
This allows for the in-situ spectroscopic study of a single catalytic nanoparticle (in
action). Recent STXM results show the spatial distribution of the degree of reduction
of iron-oxide nanoparticles.
[1] Frank de Groot and Akio Kotani, Core Level Spectroscopy of Solids (Taylor
and Francis, New York, 2008).
[2] F.M.F. de Groot, Coor. Chem. Rev. 249, 31 (2005)
[3] F.M.F. de Groot, J. Fuggle B. Thole, G. Sawatzky, Phys. Rev. B. 42, 5459 (1990)

65

O8-1
EXAFS measurements at the micrometer-scale spatial resolution
using achromatic multilayer-based focusing optics
E. Ziegler, G. Aquilanti, O. Mathon, S. de Panfilis, P. Van Vaerenbergh
European Synchrotron Radiation Facility, BP 220, 38043, Grenoble cedex,
France
When performing spectroscopy using a microbeam it is crucial to maintain
both the size and the position of the beam fixed during the total acquisition time.
While this constraint applies to both micro x-ray fluorescence and x-ray absorption
spectroscopy techniques, the problem is severer in EXAFS since the energy of the
probe beam is varied. In this context an achromatic focusing optics is preferable.
We have developed a Kirkpatrick-Baez (KB) optics system in which both
mirrors were coated with aperiodic multilayers to increase the collection angle as
compared to total reflection mirrors and to deliver a large energy bandpass (15%)
and. Hence, the KB optics can remain in a steady state, thus preserving the beam
size and position while scanning the x-ray energy with an upstream silicon doublecrystal monochromator.
A series of measurements were performed at various absorption edges (Zn,
As, Se) at the ESRF synchrotron bending-magnet beamline BM5 to demonstrate the
performance of the system in the 6-13 keV energy range [1] and to assess the beam
stability. The relative variation of the size and the position of the microbeam at the
sample never exceeded 7% of the beam nominal size, for typical spot sizes of the
order of 2.0 m (V) and 2.2 m (H). Another set of measurements was performed
at the Fe K-edge at the ESRF BM29 beamline to compare the spectra classically
obtained at an EXAFS beamline, i.e., without focusing, with spectra obtained under
a microfocused beam. When comparing the results in a k3.(k) plot a difference
between the spectra could only be noticed at large k (>15 -1). For high-pressure
experiments where the sample is located inside a pressure cell, the combination of
the large energy range available from a bending-magnet source with a microfocused
achromatic beam is particularly interesting.
[1] E. Ziegler, S. De Panfilis, L. Peverini, P. Van Vaerenbergh, F. Rocca, 9th Int. Conf.
on Synchrotron Radiation Instrumentation, Daegu, Korea, AIP Proc. 879 (2007)
5541 5.

66

O8-2
XAS analysis of Cd coordination in Cd hyperaccumulating
plants
I. Aron1,2, K. Vogel-Miku3, M. Regvar3, P. Kump2, M. Neemer2
and A. Kodre4,2
University of Nova Gorica, Vipavska 13, SI-5000 Nova Gorica, Slovenia
2
Joef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia
3
Biotechnical faculty, Dept. of biology, Vena pot 111, SI-1000 Ljubljana, Slovenia
4
Faculty of Mathematics and Physics, University of Ljubljana, Jadranska 19,
Slovenia
1

Cd pollution of environment results mainly from Cd-containing fertilizers,

smelting and sewage sludge disposal. From the polluted soils Cd can be taken up
by different plants and translocated to the food chains. Cd is extremely toxic even
at low concentrations of a few g g-1 of dry weight (DW). In some plant species (as
for example Thlaspi) Cd absorption from polluted soils is found to be very efficient.
Recently, Thlaspi praecox was shown to hyperaccumulate up to 5960 g g-1 DW of
Cd under field conditions [1]. Such hyperaccumulating plants are a promising way for
metal removal from polluted soil. However, more knowledge on metal accumulation
and detoxification is needed to understand soil-plant interactions for the use of
phytoextraction in practice.
In addition, Thlaspi praecox was found to massively accumulate Cd not only
in roots and leaves, but also in seeds (up to 1350 g g-1 DW), without drastically
affecting seed viability [2]. Micro-PIXE (proton-induced x-ray emission) localization
study showed that Cd is mainly accumulated in the epidermis of cotyledons, away
from photosynthetically active embryonic tissues [2].
In this study we use Cd K-edge EXAFS and XANES analysis of different
organs (roots, shoots, leaves and seeds) of T. praecox to obtain information on
the local structure around Cd cations bound in different plant tissues, in order to
identify the Cd complex responsible for Cd immobilization. X-ray absorption spectra
were measured at BM29 beamline of ESRF and C beamline of HASYLAB. Cd
concentrations in plant organs were determined by XRF analysis.
Comparison of chemical coordination of Cd in different plant organs
gives insight in detoxification mechanism and Cd transporters and/or antioxidantbased defense at the molecular level that contributes efficiently to Cd tolerance in
hyperaccumulating species [3].
[1] K. Vogel-Miku, D. Drobne, M. Regvar, Environmental Pollution, 133 (2005)
233-242
[2] K. Vogel-Miku, P. Pongrac, P. Kump, M. Neemer, J. Simi, P. Pelicon, M.
Budnar, B. Povh, M. Regvar, Environmental Pollution, 147 (2007) 50-59
[3] T. Karlsson, P. Persson, U. Skyllberg, Environ. Sci. Technol. 39 (2005) 3048 - 3055
67

O8-3
Possibilities of polycapillary based -EXAFS at DUBBLE,
a non-fixed exit monochromator bending magnet beamline
G. Silversmit1, B. Vekemans1, S. Nikitenko2, W. Bras2 and L. Vincze1
X-ray Microspectroscopy and Imaging Research Group (XMI), Department of
Analytical Chemistry, Ghent University, Krijgslaan 281 S12, B-9000 Gent, Belgium.
2
Netherlands Organisation for Scientific Research (NWO), DUBBLE @ ESRF, BP
220, 38043 Grenoble CEDEX 9, France.
1

X-ray absorption spectroscopy (XAS) based experimental techniques like

XANES and EXAFS are widely used for structural characterization. Conventional XAS
measurements involve the use of millimetre sized beams. When a microscopically
inhomogeneous sample is measured with such beam dimensions, an average
spectrum over the illuminated area is recorded in which the information on the
local structure is lost. To obtain spatially resolved spectra of such inhomogeneous
samples, beams of micrometer dimensions are needed.
Focusing optics such as compound refractive lenses and Fresnel lenses
are less suitable for XAS due to their achromaticity. A Kirkpatrick-Baez (KB) mirror
system is therefore often used at bending magnet beamlines, but these mirror
systems typically have relatively small acceptances which leaves a large amount
of the available flux unused. Glass polycapillaries are known focussing elements in
for instance in -XRF experiments and can present an alternative focusing optic for
-XAS. The main advantage being the relatively large acceptance angles (some mm
horizontally and vertically). Also their use in -XANES has been demonstrated [1].
A focussing system based on a polycapillary optic was tested at the DUBBLE
(BM26A, ESRF) beamline for transmission and fluorescence EXAFS. Beam sizes
(FWHM) of 12-16m, transmission efficiencies of 25-45% and intensity gain factors,
compared to the non-focussed beam, of about 2000 were obtained in the 7-14keV
energy range. The vertical height variations during a typical EXAFS energy scan
hardly influences the experimental results and positional accuracy, as the focusing
by the polycapillary reduces this vertical movement strongly. Spectra on several
standards were recorded. As a practical application, an As XANES study on plant
roots and stems was performed.
The experiments show that polycapillary optics are suitable focusing
elements for -XANES and -EXAFS at bending magnet beamlines equipped with a
non-fixed exit monochromator.
[1] L. Vincze, F. Wei, K. Proost, B. Vekemans, K. Janssens, Y. He, Y Yan and G.
Falkenberg, J. Anal. At. Spectrom, 17 (2002) 177-182.

68

O8-4
In situ defect microscopy during the electric-field-driven
insulator-to-metal transition in Cr:SrTiO3
B. P. Andreasson1, M. Janousch1, U. Staub1 and G. I. Meijer2
Swiss Light Source, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
IBM Research, Zurich Research Laboratory, 8803 Rschlikon, Switzerland

1
2

SrTiO3 doped with Cr can be conditioned such that it exhibits a bistable

resistance state. Voltage pulses of opposite polarity switch the resistance between a
high-resistance and a low-resistance state, making it a possible material for memory
device applications. X-ray absorption near edge spectroscopy on the Cr K edge
indicates the presence of an oxygen vacancy. Spatially resolved X-ray fluorescence
microscopy images of Cr:SrTiO3 show the introduction and the evolution of oxygen
vacancies during the conditioning process, the electric-field-driven insulator-to-metal
transition. The vacancies are introduced at the anode, diffusing through the crystal
towards the cathode, and thereby creating a conducting path through a network of
locally conducting defects. The spatial distribution of vacancies is explained by a
model describing the electrical breakdown as a percolation process with fractal growth.
The resistance after the transition shows the previously reported bistable state with
highly reproducible resistance switching. Strong differences in the conducting path
are found between samples electrically treated in air and in a hydrogen enriched
atmosphere. In air, the vacancy network seems to rearrange inside the crystal. In
hydrogen, where electrochemistry plays a critical role, the path forms closer to the
surface, (Figure).

Figure: X-ray fluorescence microscopy images of the memory device electrically

treated in air and in a mixture of hydrogen and argon (H2/Ar). In case of air, the
vacancy concentration is highest close to the electrodes; while in the case of H2/
Ar the vacancy concentration shows a higher ridge between the electrodes. This
indicates that the conducting vacancies are closer to the surface in the latter case.

69

O8-5
Non-destructive probing of the chemical state of buried TiOx
nanolayers
Beatrix Pollakowski1, Burkhard Beckhoff1, Stefan Braun2, Peter Gawlitza2, Falk
Reinhardt1 and Gerhard Ulm1
Physikalisch-Technische Bundesanstalt, Abbestr. 2-12, 10587 Berlin, Germany
2
Fraunhofer Institute Material and Beam Technology, Winterbergstr. 28, 01277
Dresden, Germany

Near edge x-ray absorption fine structure (NEXAFS) in combination with

grazing incidence x-ray fluorescence (GIXRF) analysis provides a good approach
for a depth-sensitive characterization of buried nanolayers with respect to both
elemental composition and speciation. This idea offers the specific advantage of a
high tunability of the information depth. The GIXRF regime implicates the occurrence
of the x-ray standing waves (XSW) field above, at and below the surface affecting
directly influence on the fluorescence intensity. The XSW field and the related mean
penetration depth are dependent on both the incident angle and photon energy. The
variation of the photon energy during a NEXAFS study requires to correct the angle
of incidence to keep the mean information depth constant.
The sample system investigated here consists of several 30 nm titanium
nanolayers oxidized to different extents and being buried below 5 nm of carbon. These
layered structures were produced by means of ion beam sputtering deposition. The
measurements were carried out at the plane grating monochromator (PGM) beamline
for undulator radiation in the PTB laboratory at BESSY II, providing tuneable radiation
of both well-known flux and high spectral purity for GIXRF-NEXAFS studies. The
results of angular corrected high-resolution Ti L3,2 edge NEXAFS spectra exhibit
an electronic structure presumably comparable to that measured in total electron
yield (TEY) and confirm the potential of this method. GIXRF-NEXAFS provides a
complementary approach to different non-destructive techniques based on electron
detection, the reach of which restricts the effective detection sensitivity for deeply
buried thin layers.

70

O8-6
Microstructure of quantum dots ensembles by EXAFS
spectroscopy
S.B.Erenburg1, N.V.Bausk1, S.V.Trubina1, A.I.Nikiforov2, A.V.Dvurechenskii2,
V.G.Mansurov2, K.S.Zhuravlev2, S.G.Nikitenko3
Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Russia
2
Institute of Semiconductors Physics SB RAS, Novosibirsk, Russia
3
DUBBLE-CRG & ESRF,Grenoble, France

The Ge/Si and GaN/AlN quantum dots vertical and lateral alignment have
been recently demonstrated. Interpretation of QDs ensembles energy spectra must
take into account the peculiarities of local structure of such formations, due to the
strain field near the interfaces.
Ge or GaN sandwich heterostructures (from 1 up to 20 monolayers) were
prepared by molecular beam epitaxy growing procedure with follow-up deposition
of blocking Si or AlN layers (from 30 up to 500 ). EXAFS spectra of the GeK- and
GaK- edges were measured at the VEPP-3 storage ring of the BINP (Novosibirsk)
and at the DUBBLE beamline of the ESRF (Grenoble) [1,2].
Lowering of the Si spacer deposition temperature from 500C to 300C
leads to a substantial decrease of the diffusion between the Ge- and Si- phases
and the formation of sharp phase boundaries. It was found that the first shell RGa-N
interatomic distance in heterostructure GaN/AlN is 0.02 A smaller compared to
crystalline GaN.
It was established an influence of blocking layers (Si, AlN) thickness and
number of QDs layers (Ge, GaN) in geterosystems, contains vertically aligned
QDs, on the microstructure characteristics of QDs. This result is in accordance
with electron spectroscopy and electron diffraction results. It was found the same,
but more feebly marked results, for GaN/AlN heterostructure. This result suggests
increasing of average GaN clusters size for structures with more thin AlN films.
[1] Simon Erenburg, Nikolai Bausk, Lev Mazalov, et al., J Synchrotron Rad. 10
(2003) 380-383.
[2] S.B.Erenburg, N.V.Bausk, L.N.Mazalov et al., Nucl. Instr. & Meth. Phys. ResA.
543 (2005) 188-193.

71

O8-7
Electronic structure of Copper films in aqueous solutions
S.M. Butorin
Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala, Sweden
Possibility of using x-ray absorption spectroscopy (XAS) and resonant
inelastic x-ray scattering (RIXS) to probe the Cu oxidation state and changes in the
electronic structure during interaction between copper and groundwater solutions
were examined. Surface modifications induced by chemical reactions of oxidized
100 Cu films with Cl, SO42 and HCO3 ions in aqueous solutions with various
concentrations were studied in-situ using liquid cells. Copper corrosion processes in
groundwater were monitored up to 9 days. By comparing Cu 2p - 3d, 4s transitions
for a number of reference substances previously measured, electronic structure
changes of the Cu films were analyzed. The XAS and RIXS spectral shape at the
Cu edge, the chemical shift of the main line for Cu2+, and the energy positions of the
observed satellites served as a tool for monitoring the changes during the reaction.

72

I9
Spin-state studies with X-ray spectroscopy, and
applications to Earth's lower mantle constituents
G. Vank1, J. Badro2,3 and J.-F. Lin4 and J.-P. Rueff5,6
KFKI Research Institute for Particle and Nuclear Physics, P.O. Box 49, H-1525
Budapest, Hungary
2
IMPMC, Universit Pierre et Marie Curie, CNRS, F-75015 Paris, France
3
Minralogie, Institut de Physique du Globe de Paris, CNRS, F-75015 Paris,
France
4
Lawrence Livermore National Laboratory (LLNL), 7000 East Avenue, Livermore,
CA 94550, USA.
5
Synchrotron SOLEIL, LOrme des Merisiers, Saint-Aubin, Bote Postale 48, 91192
Gif-sur-Yvette Cedex, France
6
Laboratoire de Chimie Physique-Matire et Rayonnement, CNRS, Universit
Pierre et Marie Curie, 75005 Paris, France
1

We report on the study of spin-crossover compounds of Fe3+, Fe2+ and Co2+

in their high-spin and low-spin forms to show that hard X-ray spectroscopies provide
sensitivity to the spin state of 3d transition metal ions, combined with unique qualities:
element selectivity, bulk sensitivity, compatibility with extreme conditions (e.g., high
pressure), and relatively straightforward experimental conditions. It is shown that
all features of the X-ray emission spectrum (XES) are sensitive to the spin state.
Variations of the K and the K emission line shapes, which are in agreement with
theory, can be used as quantitative probes of the spin state; it is suggested that
with appropriate reference experiments one can extract the spin momentum for a
general case. Resonant X-ray emission spectra unveil details of the redistribution
of electrons on the 3d levels associated with the spin-state change by revealing
features at the X-ray absorption pre-edge hardly accessible through standard
absorption measurements [1].
The properties of the main constituents of Earths lower mantle, (Mg, Fe)
SiO3 and (Mg, Fe)O are decisive for the inner dynamics of the Earth, which is
driven by the heat transport towards the surface. Both of these minerals contain
iron, which can be either in high or in low spin-state. Different spin states imply
very different physical properties, including density, optical and infrared absorption,
and transport properties. Therefore, reliable geodynamical modelling of the mantle
requires detailed knowledge on the state of iron in these minerals at high pressure
and temperature. To procure such information, we have applied XES to samples at
lower-mantle conditions [2,3].
[1] G. Vank, T. Neisius, G. Molnr, F. Renz, S. Krpti, A. Shukla, F. M. F. de
Groot, J. Phys. Chem. B 110 (2006) 1164711653.
[2] J. Badro, J.-P. Rueff, G. Vank, et al. Science 300 (2003) 789791.; ibid 305
(2004) 383386.
[3] J.-F. Lin, G. Vank, S. D. Jacobsen, V. Iota, V. V. Struzhkin, V. B. Prakapenka,
A. Kuznetsov, C.-S. Yoo, Science 317 (2007) 1740 1743.
73

O9-1
In-situ X-ray analytical methods in applied earth sciences
advantages and shortcomings A. Wittenberg1, A. Scheibner1 and D. Rammlamir1
1

BGR, Stilleweg 2, 30655 Hannover, Germany

X-ray analytical methods are used for a great range of applications in

earth sciences. Uses include qualitative and quantitative element identification and
distribution, mass transport processes, and derivation of phase relationships. Among
these methods, high resolution in-situ energy dispersive X-ray fluorescence analysis
(EDXRF) techniques play an increasing role. They are used to supplement traditional
methods such as wavelength dispersive X-ray fluorescence analysis (WDXRF).
Major advantages include high spatial resolution of the acquired data, strongly
reduced sample preparation and the ability to analyse even very fragile samples
such as wet sediment drill cores. Applications range from screening analyses for
subsequent sampling in isotope studies of hydrothermal fluids over time sequence
analyses of palaeoclimate proxies, to mineral exploration.
We compare and statistically validate classical WDXRF (PANalytical Axios)
measurements, commercial handheld XRF (INNOV-X CLASSIC) and in-situ
-EDXRF analyses (single point and along profiles) [1]. Sensitivity of the methods to
matrix and surface effects as well as to sample inhomogeneity was taken into account.
Sample types include ore, silicates and carbonates and preparation includes sawn
or polished hand specimens, crushed rocks, powder and fusion pellets. Results are
validated by qualitative ICP-OES and ICP-MS analyses.
[1]. Rammlmair D., Wilke M., Rickers K., Schwarzer R. A., Mller A., and
Wittenberg A. (2006) In Handbook of Practical X-Ray Fluorescence Analysis (ed. B.
Beckhoff, B. Kanngieer, N. Langhoff, and R. Wedell), Springer, 640-687.

74

O9-2
Analysis of different U and Pu particles by means of -XRF,
-XANES and -XRD
J. Jaroszewicz1, W. De Nolf1, K. Janssens1, O.C. Lind2, and B. Salbu2
Department of Chemistry, University of Antwerp, Universiteitsplein 1, B2610,
Wilrijk, Belgium
2
Isotope Laboratory, Dep. Of Plant- and Environmental Sciences , Norwegian
University of Life Sciences, P.O. Box 5003, N-1432 s, Norway
1

Due to the crash accidents of two American B-52 bombers carrying plutoniumbearing weapons, large amount of plutonium as well as uranium were dispersed
over a terrestrial area in the Mediterranean village of Palomares (Spain) and on
the sea ice in Bylot Sound (Greenland). Moreover during the Kuwait and Balkan
conflicts depleted uranium (DU) ammunition were expended by NATO forces which
after impact on hard targets generated large amounts of a DU dust contaminated
soil around.
In this work, the study of oxidation states of uranium and plutonium in
individual particles from these four regions were of interest since various oxidation
states can cause different environmental behavior. A number of particles were
repeatedly investigated by means of -XRF and -XANES at the U- and Pu-L3
edges.
By means of these methods, which predominantly provide information on
the chemical state of U and Pu at/near the surface of the particles, we observed that
U was predominantly present as U(IV) , but that higher oxidation of U was partially
apparent especially in the Palomares, Kuwait and Kosovo samples. Due to lack
of suitable reference compounds for Pu, the conclusions concerning Pu were less
certain.
In order to complement this information with data on the entire bulk of the
particles, the same samples were reexamined by means of transmission -XRD.
The 2-pattern obtained from Palomares particle is matching very well to the U4O9
ICDD database entry, but also coinciding adequately well with the pattern of UO2.
PuO2 , a 1:1 solid solution of UO2 and PuO2. Also the actual nature of the uranium
species from Kuwait and Kosovo is more complicated than a simple mixture of two
well-known uranium compounds. The -XRD results from DU samples revealed
presence of several phases such as Ti0.06U0.94, UO2, UO2.34 and Schoepite.

75

O9-3
Heavy metals in soils and their biogeochemistry significance
L. Luo, B. Chu, Y. Liu, X. Wang and Y. Li
National Research Center of Geoanalysis, Beijing, 100037, China,
In order to reveal the environmental and toxic effects of heavy metals in
ecological system on bio-chains and human health, the soil samples were taken
from the farmlands near a Pb mine in the suburban of Nanjing City in the southeast
of China. Biogeochemistry investigation was conducted. Potential pollution was
evaluated by means of x-ray fluorescence spectrometry, several related analytical
techniques and the biogeochemistry methods.
Heavy metals and other minor and trace elements in the soil samples were
determined by a polarized energy dispersive x-ray fluorescence spectrometer.
Powder pellet was used in the sample preparation. Four targets were used to excite
different elements in the samples.
Analytical data and research results show that the high concentrations of
Pb, Cd and As exist in the farmland soils. Some of them exceed the national health
regulation limits. The high concentrations of heavy metals were also detected in
plants, animals and human blood at the same area. That means the heavy metals,
which come from the lead mine, may have potential toxicity effects on the plants and
animals, especially on the human health.

76

O9-4
EDXRF for fingerprinting fine-grained sediment sources in the
Demer basin, Belgium
K. Van Meel1, E. Vanlierde2, A. L. Collins3, W. De Cooman4, Y. Makarovska1, F.
Mostaert5, P. Jacobs2 and R. Van Grieken1
University of Antwerp, Department of Chemistry, Environmental Analysis Group,
Universiteitsplein 1, 2610 Antwerp, Belgium
2
Department of Geology and Soil Sciences, Research Unit of Sedimentary
Geology and Engineering Geology, Ghent University, Krijgslaan 281 S8, 9000
Ghent, Belgium
3
Environment Systems, ADAS, Woodthorne, Wergs Road, Wolverhampton WV6
8TQ, UK
4
Flemish Environmental Agency, DVP Waterbodemmeetnet, Dr. De Moorstraat
24-26, 9300 Aalst, Belgium
5
Flanders Hydraulics Research, Ministry of Flanders, Berchemlei 115, 2140
Borgerhout, Belgium
1

The EU Water Framework Directive demands good water quality by 2015.

In order to meet this target, water managers need reliable information on catchment
sediment dynamics, since sediment represents a key vector governing the transfer
and fate of important pollutants. In order to gain a reliable understanding of sediment
dynamics one must focus on the principal sources involved. Traditional techniques
for investigating sediment provenance face many limitations and constraints. In view
of these problems, sediment fingerprinting is increasingly recognized as a reliable
alternative means of assembling information on sediment sources at catchment
scale.
Sediment source fingerprinting requires analysis of elemental composition
for identifying a range of fingerprint properties for distinguishing different sources.
EDXRF offers potential in this respect. Accordingly, an ongoing study is applying the
fingerprinting approach to investigate sediment sources in the Demer basin, Belgium.
Potential sediment sources were classified as agricultural soils, channel banks
and authigenic sediment produced in-channel due to groundwater upwelling. The
various sources imply different matrices, so developing a robust method, capable of
handling this variety of matrices, was a challenge. The sample matrix is expected to
be composed mostly of low-Z elements, so the high-Z elements can be determined
with a method based on Compton correction. In order to validate this approach an
ICP-AES procedure, involving HF to ensure complete digestion of the matrix, was
used. The agreement with ICP-AES was very satisfying; even low-Z elements could
be determined when applying a correction factor.
The promising results of the validation demonstrate that EDXRF can be
used to generate fingerprint property datasets and thus to support sediment source
fingerprinting studies designed to improve the information available to catchment
managers concerned with diffuse pollution problems.
77

O9-5
External estimation of the quality of content determinations of
a number of elements in GeoPT geological samples by X-ray
fluorescence method
T.Yu. Cherkashina and E.V. Khudonogova
Institute of the Earths Crust, SB RAS, Russia
The authors discuss the results obtained by XRF group of the Analytical
center participated in 13 rounds of an international proficiency testing programme for
analytical geochemistry laboratories (GeoPT) [1]. The analyses were made according
to the requirements that were stated in the Protocol [2]. The tested samples are rocks
of different types. The analyses were carried out by X-ray fluorescence method of
analysis (XRF) using VRA-30 and S4 PIONEER spectrometers [3].
The quality of results of analysis, made by XRF in the Analytical center,
corresponds to II category of accuracy and is assessed by the criterion Z. The
statistical treatment of the analytical results over 13 rounds of this programme has
shown that in most cases the presented results fall into the range Z 2 and
are satisfactory (73%). 15% of the analytical results fall into the range 2<Z< 3,
which are questionable and must be discussed. For some elements determined the
unsatisfactory values of the error of the analytical results (13%), i.e. Z3. The
possible reasons for the significant systematic source of error were judged: contents
of some elements determined are close to detection limits; insufficient number of the
certified reference materials, close in a chemical composition to a matrix of GeoPT
samples; possible inhomogeneous distribution of an element analyzed in a sample;
insufficient consideration of overlapping of analytical lines, which have wavelengths
close to ones of elements determined.
The participation in the GeoPT programme allows to assess the quality of
the determination of contents of a number of trace elements in samples by XRF and
to consider the results of analysis to be satisfactory in most cases. The testing of
our center in the framework of GeoPT programme allowed to compare the obtained
results of routine analysis with the results of other laboratories and exhibited the
need for the improvement of the available measurement techniques.
The work was made under support of RFBR, grant No 07-05-01061.
[1] Khudonogova E.V., Cherkashina T.Yu., Shtelmakh S.I., Revenko A.G. Proceedings
of Conference on X-ray Analysis. Ulaanbaatar, Mongolia. 2006. P. 103-108.
[2] Thompson M. GeoPTTm.. Protocol for the operation of Proficiency testing
scheme // International Association of Geoanalysts. 2002.
[3] A.G. Revenko, E.V. Khudonogova, Budaev D.A., T.Yu. Cherkashina. Analitika i
Kontrol. V. 10 (2006). P. 71-79.
78

O9-6
Elemental analysis of ambient aerosol samples
with synchrotron XRF
A. Richard1, M. Furger2, N. Bukowiecki2, P. Lienemann2, D. Grolimund1, A.S.H.
Prvt1 and U. Baltensperger1
1

Paul Scherrer Institut, 5232 Villigen PSI, Switzerland

2
Empa, 8600 Dbendorf, Switzerland

Samples of ambient aerosols often contain minuscule amounts of trace

elements at or below the detection limit of conventional analysis methods. Synchrotron
x-ray fluorescence spectroscopy (SR-XRF) allows the detection of such small
concentrations of elements (a few g/m3) without further treatment [1,2]. Therefore
the sampling time can be significantly reduced compared to filter analysis and allows
for the detection of diurnal variations. Rotating Drum Impactors (RDIs) were deployed
to collect ambient aerosols in three different size bins (PM10-PM2.5, PM2.5-PM1
and PM1) on a thin Mylar foil. These samples were analyzed subsequently with
SR-XRF at the Swiss Synchrotron Light Source at PSI using monochromatic light of
around 11 keV, and at Hasylab at DESY, Hamburg using a polychromatic beam.
Ambient samples had been collected in three different settings in winter
2006/07 and thus allow for a comparison of different emission scenarios (wood
combustion, abrasion of vehicles, etc). With the analysis at lower excitation
energies the range of elements form Al Ge could be detected while at higher
energies elements up to Ba are detectable. Heavier elements were found mainly
in the largest size fraction, which is usually considered to originate from (mineral)
dust re-suspended into the air or from mechanical abrasion. The smaller particle
size fraction is more typical for combustion processes. Additional measurements
of different wood-burning stoves were performed with a testing set-up. The results
obtained with RDI samples are also compared to complementary measurements.
Results of this analysis will feed into source apportionment studies (applying
positive matrix factorization, PMF) to get more insight into possible sources of
emissions and therewith helping to formulate mitigation strategies.
[1] N. Bukowiecki et al., Environmental Science and Technology 39 (2005)
5754-5762
[2] N. Bukowiecki et al., Spectrochimica Acta Part B, in preparation (2008)

79

I10
The effect of chemical bonding on high-resolution X-ray
spectroscopy
W. T. Elam1,2, Fernando Vila2, Terrence Jach3 and Alan Sandborg1
EDAX, Inc. business unit of Ametek Materials Analysis Division, Mahwah, NJ
07430 USA
2
Applied Physics Lab, Univ. of Washington, Seattle, WA 9852 USA
3
National Institute of Standards and Technology, Gaithersburg, MD 20899 USA
1

The earliest X-ray spectroscopy used wavelength-dispersion, and chemical

effects were observed very early in X-ray emission spectra. However, prediction and
interpretation of these effects remains something of a challenge. The effects can
be grouped into three main categories: changes in the absorption cross sections,
energy shifts, and changes in the basic line shapes. All of these effects are most
pronounced at low energies, where atomic levels involved in the transition are at or
near the bonding/anti-bonding or conduction electron levels. This talk will mostly focus
on the third effect, although the other effects will be mentioned and some surprises
from the first effect, which sometimes confuse the issue, will also be discussed.
Modern theoretical methods are now able to predict chemical effects with improving
precision. We have performed measurements as well as molecular and solid state
simulations on several nitrogen and chromium compounds of molecular and metallic
nature. These simulations used different methodologies and will be compared to
synchrotron and laboratory measurements to see how well the various effects
can be predicted with modern theories, and to illustrate some successes, failures,
and pitfalls. We will also demonstrate how information from different theoretical
methodologies can be integrated to obtain a more complete understanding of the
systems. The measurements are from both electron beam and X-ray excitation, and
all are wavelength-dispersive, high-resolution measurements of the X-ray emission
line shapes. The measurements with electron beam excitation were made on readilyavailable commercial laboratory equipment.

80

O10-1
High-resolution soft X-ray emission spectrometry for the
determination of atomic fundamental parameters related to the
Ni-L fluorescence process
M. Mller1, B.Beckhoff1, B. Kanngieer2, R.Fliegauf1
1 Physikalisch-Technische Bundesanstalt, Abbestr. 2-12, 10587 Berlin, Germany
2 Institute for Atomic Physics, Technical University of Berlin, Hardenbergstr. 36,
10623 Berlin, Germany
The reliability of XRF quantitation, in particular its reference-free variant [1],
strongly depends on the knowledge of the respective atomic fundamental parameters
like fluorescence yields, transition probabilities and Coster-Kronig coefficients. For
an accurate XRF analysis, e.g. involving light matrix elements or transition metal
nanolayers, a reliable determination of these parameters in the soft X-ray range with
small uncertainties is essential.
Measurements based on calibrated instrumentation employing energydispersive detectors can very well contribute to the determination of fundamental
parameters [2]. However, the energy resolution of energy-dispersive detectors is not
sufficient to determine all parameters of interest, especially for the L-fluorescence
lines of transition metals. Hence, a wavelength-dispersive grating spectrometer
(WDS) was designed and built for dedicated experiments at the plane grating
monochromator beamline for undulator radiation of the Physikalisch-Technische
Bundesanstalt at the electron storage ring BESSY II. The WDS was experimentally
characterized with respect to both its detection efficiency and response functions.
This characterization allows for absolute measurements of fundamental parameters
with small relative uncertainties.
As an example, we present a study of the L-fluorescence emission of
Ni and the related transition probabilities. Taking advantage of the tunability of
monochromatized undulator radiation, we could study the evolution of the Ni-L
emission spectra with increasing incident photon energy. In particular, specific
spectral features such as resonant Raman scattering and satellite lines show strong
dependencies with respect to the photon energy of the exciting radiation.
[1] B. Beckhoff, R. Fliegauf, M. Kolbe, M. Mller, J. Weser, G. Ulm, Anal. Chem.79,
7873 (2007)
[2] M. Mller, B. Beckhoff, G. Ulm, B. Kanngieer, Phys. Rev. A 74, 012702 (2006)

81

O10-2
Spectroscopic analysis of the water-window range with Cr/Sc
multilayers
K. Le Guen1, J.-M. Andr1, P. Jonnard1, A. Hardouin2, F. Delmotte2, M.-F. RavetKrill2
Laboratoire de Chimie Physique Matire et Rayonnement, Univ UPMC Paris
06, CNRS UMR 7614, 11 rue Pierre et Marie Curie, F-75231, Paris Cedex 05,
France
2
Laboratoire Charles Fabry de lInstitut dOptique, CNRS, Universit Paris Sud,
Campus Polytechnique, RD 128, F-91127 Palaiseau Cedex, France
1

The water-window range, between the CK (280eV) and OK (530eV)

absorption edges, is difficult to study in WDS analysis due to the lack of efficient
diffractive optics. This is particularly true for the NK emission band, which is presently
analysed by using periodic multilayers having a poor reflectivity (10%) in this photon
energy range. Recently, the use of Cr/Sc multilayers has been suggested to study
the NK emission and theoretical reflectivity as high as 45% is expected.
The aim of this communication is to report on the performances of Cr / Sc
periodic multilayers as Bragg dispersive devices for the analysis in wavelength
dispersive spectrometry of samples containing N or Sc atoms [1], such as BN, CrN,
Sc5Si3 and ScN. The possibility to distinguish the chemical state of the emitting N or
Sc atoms is evidenced by using Johan-type and double-crystal spectrometers.
[1] K. Le Guen et al., Appl. Phys. Lett. 91, 234104 (2007).

82

O10-3
Micro spot analysis using policapillary lens in standard WDXRF
Y. Kataoka, Y. Yamada , H. Homma and H. Kohno
Riagku Industrial Corporation. (14-8 Akaoji-cho, Takatsuki, Osaka 569-1146,
Japan)
The demand of micro spot measurement such as for the analysis of microelectronics devices and parts has increased. X-ray optics using capillary lens is an
effective method to obtain high intensity x-rays for small spot measurement and is
mainly utilized in EDXRF system.
We have developed a WDXRF spectrometer which is added a poly-capillary
lens to a standard sequential spectrometer that enables 100 micro meter spot size
measurement. And this spectrometer can also be used as regular spectrometer. The
spectrometer is equipped with sample stage and electric camera to observe sample
image for point analysis and mapping measurement of small area
Owing to WDXRF type, high spectral resolution and high sensitivity for light
element can be achieved. The measurable energy range is wide from low energy ( e.g.
C-K ) to high energy ( e.g. Sn-K ). The data reduction function of the spectrometer
allows semi-quantitative analysis using fundamental parameter method for bulk and
film in addition to quantitative analysis. Minor elements such as impurities could also
be analyzed in addition to major elements for stoichiometric analysis with high power
of 4kW x-ray tube.
The spectrometer configuration and some application examples will be
presented.

83

O10-4
High resolution X-ray fluorescence study of Sulfur in various
compounds
M. Kavi1, M. itnik1, K. Buar1, A. Miheli1, R.A. Mori2 and P. Glatzel2
J. Stefan Institute, P.O.B. 3000, SI-1000, Ljubljana, Slovenia
European Synchrotron Radiation Facility, BP 220, F-38043 Grenoble Cedex,
France
1

Among the geochemically abundant elements sulfur is characteristic for its

wide range of oxidation states, exhibiting states from 2- to 6+. The inorganic sulfur
species encountered in the nature among other include sulfide (S-2), native sulfur
(S0), sulfite (SO3-2), and sulfate (SO4-2). Due to its important role in the fundamental
mechanisms such as volcano-climatic interactions, genesis of ore deposits as well
as for its role in the industrial glass-forming processes it is extremely important to
study chemical state of sulfur in order to better understand these mechanisms.
In order to determine electronic configuration and coordination geometry
high energy resolution K and K X-ray emission spectra of sulfur in numerous
compounds from sulfides to sulfates were recorded at the ID26 beamline at the
ESRF synchrotron employing Johansson type wavelength dispersive spectrometer.
Excellent energy resolution of our experimental setup enabled precise measurement
of energy shifts and main spectral features. The energy of K emission line clearly
correlates with the valence state of S and can be effectively employed for such
analysis. Much more complex K spectral structures give important information
about local coordination around S. Ab initio quantum-chemical calculations using the
StoBe code, based on density functional theory, were performed in order to explain
the measured K spectral structures.

Figure 1: The comparison between the experimental Na2SO3 spectrum and the theoretical
calculation using the density functional theory (StoBe code), with four sulfite ions and 8
sodium atoms.

84

O10-5
The use of WD-XRS Spectrometry and XRD to prepare a series
of reference materials of geological samples
M.F. Gazulla, M.P. Gmez, M. Ordua, E. Zumaquero and M. Rodrigo
Instituto de Tecnologa Cermica Asociacin de Investigacin de las Industrias
Cermicas. Universitat Jaume I. Castelln, Spain

Reference materials play an important role in geoanalytical laboratories
as materials for calibrating instrumental techniques, and for quality assurance and
control. However, few reference materials are accompanied by analysis certificates
with uncertainties as recommended in the guide for the calculation of uncertainties.
This impedes appropriate traceability in the measurements that are made using
these materials.
In this work, a series of reference materials of geological samples of clays,
kaolin, silica sand, feldspars, dolomite and calcium carbonate have been prepared.

In order to achieve this objective, it has been necessary to attain a number
of specific tasks: a) selection and collection of the geological samples for analysis;
b) preparation of the samples selected for characterisation, which includes:
crushing, quartering and milling, and the determination of particle size distribution;
c) homogeneity test and distribution of the homogeneous material between
the participating laboratories, after evaluation; d) chemical and mineralogical
characterisation using different analytical techniques: Wavelength Dispersive X
Ray Fluorescence Spectrometry (WD-XRF), Inductively Coupled Plasma Optical
Emission Spectrometry (ICP-OES), Atomic Absorption Spectrophotometry (AAS);
thermogravimetric techniques for the determination of loss on ignition (LOI); and X
Ray Diffraction (XRD); e) analysis of the results obtained for each element by the
different chemical analysis techniques by the participating laboratories; f) and finally,
preparation of the reference material with the data obtained in the foregoing phases,
in accordance with ISO Guide 31.

The validation of the methodology used to obtain the chemical composition
was carried out by:
1) using standard reference materials,
2) comparing the results from independent methods (WD-XRF and ICPOES), and,
3) doing an interlaboratory test.

The results show very good agreement between WD-XRF and ICP-OES
methods for all the analysed elements and it was concluded that, for geological
samples, the WD-XRF method is more accurate and reproducible for major and
minor elements, probably due to simple sample preparation needed and the
measurement technique itself.
The XRD allows the mineralogical composition to be known and it is extra useful
information in the certificate of the reference material, for future use, specially when
a material is going to be used as a calibration standard in the WD-XRF method
when the sample preparation is in the pellet form.
85

O10-6
Absolute X-ray wavelength standards to determine the
wavelength of important X-ray lines with double reflection in
single crystal X-ray Spectroscopy
Benjamin S Fraenkel and Zwi H. Kalman
The Laboratory of X-ray and VUV Spectroscopy ,Racah Institute of Physics, The
Hebrew University, Jerusalem, Israel.
An X-ray beam (in the range of about 0.7- 5 Angstrom) reflected twice in one
crystal by two different crystal planes (h,k,I,) and (h',k',I') might be recorded if the indices
of the reflection having the sum of the successive reflections ((h+h'),(k+K'),(I+l)) is
a crystallographically forbidden reflection. This occurs for limited cases of crystal
symmetries [1].
Adjustment for obtaining double reflection is made by rotating the crystal in
the plane of the forbidden reflection to a precalculated azimuthal position, while the
beam makes a Bragg angle with the plane.
Double reflection of a POINT SOURCE yields on a film ( film has the best
resolution) a POINT for every wavelength emitted. A strong point will indicate an
X-ray transition, while a line represents the continuous white spectrum.
For every forbidden reflection there are several double reflections possible.
Let us look at the diamond lattice forbidden reflection (2,0,0). As an example, the
following double reflections represent a multitude of double reflections which may
be used: ((1,1,1),(1,-1,-1)); ((3,1,5), (-1,-1,-5)); ((5,3,1),(-3,-3,-1)). These double
reflections are seen on film as a group of lines of the white spectrum, intersecting
between them [2].
THE WAVELENGTH OF AN INTERSECTION IS A CONSTANT OF THE
CRYSTAL LATTICE. With several such constants on a line of the white spectrum,
they may be used to determine the wavelength value of a point seen on the line, this
point representing a spectral transition. It may be argued that crystal constants are
dependent on X-ray wavelength, but this has been overcome by using a DesLattes
interferometer [3].
For example we obtained on film two intersections along a white spectrum
line at 1.287829 A and 1.280169 A, assuming an agreed upon lattice constant for the
Ge crystal involved. The sharpness of the lines is better than 1/300 of the distance
between those intersections [2]. This was done with a fine focus tube. With a microfocus tube one may expect much better resolution.
The description of obtaining intersections for determining the near absolute
wavelength values of the main lines of Fe XXVI and Fe XXV will be given.
[1] M.Renninger, Z.Phys.106, 141,(1937).
[2] Benjamin S. Fraenkel, J. of X-ray Science and Tech. 5, 341 - 367, (1995).
[3] R.D.DesLattes and A.Hennins, Phys. Rev. letters 31, 972,(1973).
86

I11
Biomedical applications of micro-PIXE
Ph. Moretto
Centre d'Etudes Nuclaires de Bordeaux-Gradignan, CNRS-IN2P3/Universit
Bordeaux 1, BP 120, 33175 Gradignan cedex, France
Nuclear microscopy is a generic term referring to a large panel of ion beam
analysis techniques carried out using light ion micro-beams in the MeV energy range
(typically H+, D+ and He+). After twenty years' experience by world-wide research
groups in the use of those micro-beams, nuclear microscopy is now recognised as a
powerful technique for routine chemical microanalysis and elemental mapping in the
frame of biomedical applications.
The lateral resolution achieved by advanced facilities is about 50 nm in low
current mode for pure imaging and 300 nm in high current mode for trace elements
analysis and mapping. Since MeV ions may induce both nuclear reactions and
ionisation of atomic shells, a non-exhaustive list of available methods includes
PIXE (Particle Induced X-ray Emission), NRA (Nuclear Reaction Analysis), RBS
(Rutherford Backscattering Spectrometry) and STIM (Scanning Transmission Ion
Microscopy). PIXE is the basic method employed for routine elemental mapping.
Numerous applications in biomedicine take advantage of its versatility and easy
operation, either at the tissue or individual cell scale. In addition, micro-PIXE and
other micro-beam techniques complement each other to offer unique information.
This is particularly true for RBS and STIM for sample mass monitoring and ultrastructure elucidation.
The first CENBG micro-beam was commissioned in 1989 at the old Van de
Graaff accelerator. This beam-line was recently transferred on the AIFIRA facility
and a new high resolution line has been constructed. Since the first microprobe was
initially designed for easy and reliable micro-PIXE analysis of biological samples,
biomedicine has been the main research area developed on this system. In this
review, different examples of investigation will be presented with emphasis placed
on dermatology, pathology and pharmacology. Development and prospective studies
of STIM-PIXE Tomography will be also discussed.

87

O11-1
Trace element mapping using hard X-ray nanobeam focused by
a Kirkpatrick Baez mirror system
S. Matsuyama1, M. Shimura2, H. Mimura1, M. Fujii1, H. Yumoto3, S. Handa1, T.
Kimura1, Y. Sano1, M. Yabashi3, Y. Nishino4, K. Tamasaku4, T. Ishikawa4 and K.
Yamauchi1,5
Department of Precision Science and Technology, Graduate School of
Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan
2
Department of Intractable Diseases, International Medical Center of Japan,
1-21-1 Toyama, Shinjuku-ku, Tokyo 162-8655, Japan
3
SPring-8/Synchrotron Radiation Research Institute (JASRI), 1-1-1 Kouto,
Sayoucho, Sayogun, Hyogo 679-5148, Japan
4
SPring-8/RIKEN, 1-1-1 Kouto, Sayoucho , Sayogun, Hyogo 679-5148, Japan
5
Research Center for Ultra-Precision Science and Technology, Graduate School of
Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan
1

X-ray fluorescence spectroscopy is a powerful tool for trace elements

because of non-destructive and high-sensitivity analysis. To visualize elemental
distributions with high resolution and high sensitivity, we developed a Kirkpatrick
Baez mirror system which enables us to utilize hard X-ray nanobeam having a size
of 30 x 50 nm2, and constructed a scanning X-ray fluorescence microscope (SXFM)
with the focusing system, a high resolution scanner and a silicon drift detector in
BL29XUL of SPring-8.
We demonstrated high-resolution elemental mapping using test patterns
having 50-60 nm line widths. As a result, the best spatial resolution was found to be
better than 50 nm. Additionally, we demonstrated application for biological samples,
in which high-sensitivity detection is required. To observe frozen hydrated samples, a
cryogenic system, which is capable of imaging samples at temperature of 120K, was
installed on the scanner. As a result of observation of fast frozen cells at cryogenic
temperature, we could visualize intercellular elemental distributions same as that of
living cells, compared with fixed cells with chemicals.
[1] S. Matsuyama et al., Review of Scientific Instruments, 77 (2006) 103102.
[2] S. Matsuyama et al., Proc. SPIE, 6317 (2006) 631719.
[3] S. Matsuyama et al., Surf. Interface Anal. Accepted (2008).

Fig. Intracellular elemental distributions of fast frozen NIH/3T3 mouse cells. Area:
50 x 50 um2, Exposure: 0.5sec/pix., X-ray energy: 15keV, Temperature: 150K.
88

O11-2
Micro-XRF imaging and micro-XANES analysis of cadmium
hyper-accumulating plant, Arabidopsis halleri ssp. gemmifera,
using high-energy synchrotron radiation
A. Hokura1, N. Fukuda1, N. Kitajima1,2, Y. Terada3, T. Abe4 and I. Nakai1
1

Department of Applied Chemistry, Tokyo University of Science (1-3 Kagurazaka,

Shinjuku, Tokyo 162-8601 Japan)
2
Fujita Co.
3
SPring-8, JASRI
4
RIEKEN

Arabidopsis halleri grows in Europe and are known to contain more than
10,000 mg kg-1 of cadmium and zinc in the shoot [1]. This trait in A. halleri has
the potential to be exploited in phytoremediation, a soft method in which plants
are used for the cleanup of heavy metal-polluted soils. Subspecies of this plant,
Arabis gemmifera, a native species of Japan, is also known as a cadmium and zinc
hyperaccumulator [2]. Since Cd is a highly toxic metal for plants, it is interesting to
reveal the mechanism involved in the Cd accumulation of this plant.
The monochromatic high-energy X-rays (37 keV) focused to a microbeam
(3.8 1.3 m2) with a Kirkpatrick-Baez mirror allows us for the first time to reveal a
striking sub-cellular distribution and the chemical form of cadmium in the cadmium
hyperaccumulating plant, Arabidopsis halleri ssp. gemmifera by detecting the Cd K
line. Micro X-ray fluorescence (-XRF) analysis and micro X-ray absorption nearedge structure (-XANES) analysis were used for the nondestructive analysis of
Cd distribution and chemical form of Cd at a cellular scale in the plant in order to
investigate the accumulation mechanism of Cd. It was clearly observed by twodimensional -XRF imaging that Cd was highly accumulated in a part of the trichomes,
epidermal hairs existing at the surface of leaves. The bases of trichomes contained
Cd, Zn and Mn at a high concentration and these distribution patterns were similar
to each other. These elements were located near the surface of the trichome in the
form of a ring. The -XANES analysis revealed that the majority of Cd exists as
divalent state and bound to O and/or N ligands. This study has demonstrated the
potential of Cd K-edge -XANES spectroscopy, which was applied here for the first
time to plant samples.
[1] H. Kpper, E. Lombi, F. J. Zhao, S. P. McGrath, Planta 212 (2000) 75-84.
[2] H. Kubota, C. Takenaka, Int. J. Phytoremediation 5 (2003) 197-201.

89

O11-3
Quantification of manganese in teeth via wavelength-dispersive
X-ray fluorescence spectrometry: A pilot study
E. Da Silva1,2, A. Pejovi-Mili2 and D. V. Heyd1
1

Department of Chemistry & Biology, Ryerson University, Toronto, Ontario, Canada

M5B 2K3
2
Department of Physics, Ryerson University, Toronto, Ontario, Canada M5B 2K3

With the recent study by Smith and co-workers [1] outlining how classical
biological specimens (i.e. blood, plasma and urine) do not act as viable biomarkers
of manganese exposure, the search for a suitable biomarker has been in place.
Teeth are known to accumulate trace and minor elements during full mineralization
and have a high half-life for trace elements (on the order of 14-24 years). As such,
teeth, in particular baby teeth can potentially be used as a means of studying a
populations environmental exposure to manganese (as well as other trace and
minor elements). Wavelength-dispersive X-ray fluorescence spectrometry (WDXRF)
provides unparalleled resolution of X-ray lines (reducing Mn/Fe line interferences)
and although suffers from relatively high detection limits, a method has been
developed that can be used as a means to quantify manganese in teeth at the
expected concentrations (1-10 ppm). The WDXRF system (Bruker-AXS, S4 Explorer)
equipped with LiF(200), PET and OVO-55 analyzing crystals and an 8 mm mask,
is conveniently able to provide a means of non-destructively and simultaneously
quantifying for the elements between Be-U in the small sample size (~100-300 mg
per tooth) providing a full multielemental analysis of the minor and major elements
(Ca, P, Sr) while also being optimized for the trace quantification of manganese. The
system allows for an adequate estimate of the light element content in teeth which
allows for a standardless algorithm to be used successfully. An investigation into
the use of a standardless algorithm will be reported.
[1] D. Smith, R. Gwiazda, R. Bowler, H. Roels, R. Park, C. Taicher, R. Lucchini,
Americal Journal of Industrial Medicine, 50 (2007) 801-811.

90

O11-4
Human prostate cancer is zinc the prime suspect?
M. Podgrczyk1, W.M. Kwiatek1, J.Duliska-Litewka2, P.M. Laidler2, E.Welter3
The Henryk Niewodniczaski Institute of Nuclear Physics Polish Academy of
Sciences, ul. Radzikowskiego 152, 31-342 Krakw, Poland
2
Chair of Medical Biochemistry, Jagiellonian University Medical College
ul. Kopernika 7, 31-034 Krakw, Poland
3
Hasylab DESY, Notkestr. 85, D-22603 Hamburg, Germany

Prostate cancer is one of the most commonly diagnosed cancers in men

throughout the world. Investigating possible reasons for cancerogenesis process
on molecular level lead to zinc. The suspicion is not groundless for the reason of
unique capability of prostate epithelial cells in accumulating zinc that plays role in a
wide range of cellular processes such as immune system function, antiangiogenesis
or apoptosis. Zinc has a significant antioxidant function and its presence in prostate
cells is strongly connected with their metabolism [1].
Searching irrefutable proofs in that investigation we used synchrotron
radiation based techniques to look insight human prostate cancer tissues and
cultured human prostate cell lines (DU-145, LNCaP and PC-3). Analysis of prostate
tissue samples revealed complexity of structures that can be reflected by bioimaging
methods, while cell culture samples provided areas of required homogeneity. SR
X-Ray Fluorescence analysis let to connect concentration of zinc with pathological
status of tissue (healthy, hyperplastic and cancerous) and obtain bioimaging on
cellular level. X-Ray Absorption Near Edge Spectroscopy (XANES) provided
sophisticated studies of environment of absorbing zinc atom including determination
of Zn K-edge position and local structure description [2].
Role of zinc in prostate cancer etiology is still an open question but the
solution of this riddle seems to be closer.
This work was supported by the European Community under the Contract
RII3-CT-2004-506008 (IA-SFS) (Hasylab project No I-20070071 EC).
[1] Costello L.C., Franklin R.B., Feng P., Mitochondrion 5 (2005): 143-153
[2] W.M. Kwiatek, M. Podgrczyk, J. Duliska-Litewka, P.M. Laidler, E. Welter,
Hasylab Annual Report (2007): 1567-1568

91

O11-5
The role of chemical elements in the formation of aneurism of
aorta (SRXRF)
V.A. Trunova1, V.V. Zvereva1, G.N. Okuneva2, E.N. Levicheva2, I.Yu.Loginova2
A.V. Nikolaev Institute of Inorganic Chemistry, SB RAS, 630090 Novosibirsk,
Lavrentyeva, 3, Russia
2
E.N. Meshalkin Institute of pathology of circulation of the blood, 630055
Novosibirsk, Rechkunovskaja,15, Russia

The efficiency of the surgical treatment of the ascending part of aorta in

many respects depends on the knowledge of pathogenesis of aorta diseases. One
of the reasons of aorta pathology formation is the occurrence of microelements
disbalance. The researches in this direction are not numerous, and the results are
inconsistent. The most part of researches deal with the contents of calcium in an
aorta wall [1]. The analysis of Ca, Mg, Zn, and Cu in aorta wall, atherosclerosis
plaque and aneurism of aorta has shown that concentration of Zn, Cu, Mg, and Ca
in atherosclerosis plaque is higher than in a surrounding tissue [2]. At the same time,
according to the other authors data, the content of Cu, Zn, and Cr in the plaque was
considerably below the norm [3].
The purpose of our research is to reveal the role of the chemical elements
in the development and forming of aneurism of aorta versus the anatomicmorphological changes of its wall. We have revealed the marked disbalance of the
chemical elements expressed disbalance of the chemical elements in a wall of aorta
at patients with aneurism of the ascending part of an aorta and with stratification
of an aorta in comparison with ischemic heart disease patients, that testifies to the
important role of macro- and microelements in the metabolic processes connected
with the formation of aneurysm of aorta. It has been shown, that V, Ni, Cr, Sr, Mn,
Co provide structural integrity of an aorta as the development of aneurysms of aorta
is accompanied by decrease in their concentration. Increased contents of As at an
aneurysm of aorta and, especially, at stratification of its wall testifies to inflammatory
process. It proves to be true morphological data. Probably, such microsomal elements
as Se, As, K, and Rb are markers of aneurysms of aorta.
The given researches are executed by SRXRF method, experimental station
XFA, BINP, Novosibirsk. Measurements have been executed in different conditions
of primary excitation energies.
[1] Marra S.P., Daghlian C.P., Fillinger M.F., Kennedy F. Elemental composition,
morphology and mechanical properties of calcified deposits obtained from abdominal
aortic aneurysms. Acta biomaterialia. 2006; 2: 5: 515-520.
[2] Iskra M., Patelski J., Majewski W. Relationship of calcium, magnesium, zinc and
copper concentrations in the arterial wall and serum in atherosclerosis obliterans
and aneurysm. J. Trace Elem. Med. Biol. 1997; 11(4): 248-252.
[3] Caseanu K.M., Petresu U.Y. Concentration of copper, zinc, chromium, iron and
nickel in the abdominal aorta of patients deceased with coronary heart disease. J.
Trace Elem. Electrolytes Health. 1994; 8(2): 111-114.
92

O12-1
Double 1s ionization of Al and Si by photon and electron impact
J. Hoszowska1, M. Berset1, W. Cao1, J.-Cl. Dousse1, K. Fennane1, Y. Kayser1,
J.-L. Schenker1, J. Szlachetko2,1, M. Szlachetko1 and M. Kavcic3
Department of Physics, University of Fribourg, Chemin du Muse 3, CH-1700
Fribourg, Switzerland
2
European Synchrotron Radiation Facility, BP 220, F-38400 Grenoble, France
3
J.Stefan Institute, P.O. Box 3000, SI-1001 Ljubljana, Slovenia
1

Double ionization leading to an empty 1s shell is a sensitive probe of electron

correlation effects in the initial and final states. For low-Z neutral atoms, experimental
data on double-to-single 1s ionization are scarce or nonexistent.
We report on the energy dependence of the double 1s photon and electron
ionization of metallic Al and Si. The double Kshell vacancy production was studied
by means of high-resolution x-ray emission spectroscopy. Measurements of the
photoinduced x-ray spectra were carried out using the Fribourg high-resolution von
Hamos Bragg curved crystal x-ray spectrometer [1] installed at the ID21 and ID26
beam lines at the ESRF, Grenoble. The electron impact double ionization cross
sections were measured in-house by means of an electron gun. The double to single
1s ionization cross sections were derived from the hypersatellite (1s-21s-12p1/2-1)
K2h to diagram K (1s-12p-1) line intensity ratios as a function of the photon and
electron energy spanning the range from threshold for double ionization to 7 keV for
Al and 10 keV for Si in case of photoionization, and 20 keV for electron impact. It was
found that the maximum values of PKK for electron double ionization are an order of
magnitude lower than those obtained with photons.The energies and linewidths of
the K2h x-ray emission lines were determined. Further, the peak values of the ratio
of double to single ionization cross sections were compared to the Z-dependence
reported in [2] and different theoretical models for double 1s photoionization of Helike atoms. The relative importance of the dynamical electron-electron scattering
contribution to hollow low-Z atom production was evinced.
[1] J. Hoszowska et al., Nucl. Instr. Meth. Phys. Res., A 376 (1996) 129 - 138.
[2] E. P. Kanter et al., Phys. Rev., A 73 (2006) 0227081-02270811.

93

O12-2
Effect of excitation energy on the Pb L/L intensity ratio
N. Sasaki and J. Kawai
Department of Materials Science and Engineering, Kyoto University
Pb L lines overlap with As K lines. The overlapped lines are separated by
a Pb L/L intensity ratio. The L/L intensity ratio is not actually constant, though
the statistical ratio of L/L is 2 [1]. In order to quantify Pb accurately, it is necessary
to know changing factors of the Pb L/L intensity ratio. We have measured
dependence of the Pb L/L intensity ratio on applied voltages of an X-ray tube.
Pb L and L X-ray fluorescence spectra of Pb metal and several compounds were
measured using an energy dispersive X-ray spectrometer with a Rh target X-ray
tube. Changing the applied voltage, the L1, 2 (L3-M5, 4) / L1, 2 (L2-M4, L3-N5) intensity
ratio changed from about L/L = 4 at 15 kV to L/L = 1 at 45 kV (Fig.1). The
calculation values of the Pb L/L intensity ratio of the Pb metal using the Shiraiwas
formula [2] were in good agreement with the experimental ones (Fig.2). The Pb L/
L intensity ratio modifications of metal and compounds were smaller than 5%. We
concluded that the Pb L/L intensity ratio modifications by the applied voltage were
due to the changes of the L3 and the L2 ionization probabilities and that the rate
changes of Auger transitions had little effect on the Pb L/L intensity ratio.

Fig.1 Pb L and L X-ray

fluorescence spectra of Pb metal.

Fig.2 Experimental and calculated

Pb L/L intensity ratios plotted
against the applied voltage.

[1] R. Shioi, N. Sasaki, G. Kinugawa, J. Kawai, Adv. X-ray. Chem. Anal., Japan, 38
(2007) 205 214.
[2] T. Shiraiwa, N. Fujino, Jpn. J. Appl. Phys., 5 (1966) 886 899.

94

O12-3
Helium induced L X-ray production cross-section in Pt and Bi
S. Ouziane1, A. Amokrane1, I. Toumert2 and A. Nourreddine3
Facult de Physique, Universit des Sciences et de Technologie Houari
Boumedine, BP 32, El Alia, Bab Ezzouar 16111 Alger, Algrie.
2
Centre de Recherches Nuclaires dAlger, 2 Bd Frantz Fanon, BP 399, Alger,
Algrie
3
Centre de Recherches Subatomiques (IReS), 67037 Strasbourg cedex 2, France
1

L-Shell X-ray production cross-sections induced by helium on Pt and Bi

elements have been measured in the incident energy range of 2.0 to 3.0 MeV. The
present values will be compared with available data of Vigilante et al [ J. Phys.
B: At. Mol. Opt. Phys. 24 (1991) 2521] and with the theoretical calculations by
ECPSSR model [ W. Brandt and G. Lapicki, Phys. Rev. A23 (1981) 1717]

95

O12-4
On features of extreme X-Ray focusing
S.B. Dabagov1, 2
INFN - Laboratori Nazionali di Frascati, Via E. Fermi 40, I-00044 Frascati (RM),
Italy
2
RAS - P.N. Lebedev Physical Institute, Leninsky Pr. 53, 119991 Moscow, Russia
1

New scientific applications of intense coherent x-ray beams require focusing

of the beams to sub-micron spot sizes. In order to propose suitable technological
solutions for sub-micron x-ray imaging one becomes necessary to understand the
basic features of x-ray focusing at the extreme diffraction limited conditions.
In this report, recent studies on x-ray micro- and nano-focusing by means of
various guide systems, performed by different research groups in the world, will be
analyzed [1]. The fine features of x-ray propagation both in ultra narrow collimators
and at glancing reflection from a smooth surface, plane or curved, can be described
within the unified theory of trapped radiation propagation: surface channeling in
micro-guides and bulk channeling in sub-micron/nano-guides [2].

[1] S.B. Dabagov, and H. Uberall, Nucl. Instr. Meth. A580 (2007) 756.
[2] S.B. Dabagov, Reviews of Topical Problems: Physics Uspekhi 46 (2003) 1053.

96

O12-5
Self enhancement effects on XRF K-lines due to natural width
Jorge E. Fernandez and Viviana Scot
Laboratory of Montecuccolino-DIENCA, Alma Mater Studiorum University of
Bologna, via dei Colli 16, 40136 Bologna, Italy
It is well known that, due to the Heisenbergs uncertainty principle, the
energy levels in the atom are defined within an energy width. Any electronic transition
involving two or more levels shows a natural width given by the sum of the widths of
the participating levels. Moreover, any XRF line appears to have a Lorentzian like
distribution whose FWHM is the natural width.
Since the Lorentzian distribution has long tails on both sides, the tails may
cross above neighbor absorption edges giving rise to enhancement effects of a
certain complexity.
In this article we discuss the self enhancement effects on XRF K-lines in
pure element samples having atomic numbers Z=11-92. This study is performed with
both deterministic and MC calculations.

97

O12-6
A method for measuring K, L and higher shell photoionisation
cross sections at 59.5 keV
H. Erdogan1 and M. Ertugrul2
Pamukkale University, Faculty of Science, Department of Physics, DenizliTURKEY
2
Ataturk University, K.K. Education Faculty, Department of Physics, ErzurumTURKEY
1

A simple and direct method has been developed to measure the K, L and
other higher shell photoionisation cross-sections of several element at 59.5 keV. The
K and Li (i=l, , , ) x-ray intensities emitted by these elements, from irradiating their
samples by the photons of above energy are measured using a Si(Li) spectrometer
system. The K and Li x-ray fluorescence cross sections of the above elements are
determined, after the total K and L shell photoelectric cross sections are evaluated.
The present experimental results are agreed with the theoretical values.

98

O12-7
Intensity distribution of Compton scattered gamma rays from
K-shell electrons using coincidence technique
Bhajan Singh and B.S. Sandhu
Physics Department, Punjabi University, Patiala-147002, India
Compton scattering generally refer to the scattering of photons from free
and stationary electrons. Scattering from bound electrons modifies the general
relationship between energy of the scattered photons and the scattering angle in
a number of ways. Various relativistic and non-relativistic theoretical investigations
of the Compton scattering from bound electrons are based upon either form factor
approximation, which is valid for low photon energy and low binding energy or the
incoherent scattering function approach, whose validity requires that the photon
energy to be appreciably greater than the electron binding energy. Due to different
approximations introduced in various theories, the prediction made by these
calculations is very often in disagreement with each other.
In the present work, the measurements are made to determine the intensity
distribution of Compton scattered photon from K-shell electrons of medium atomic
number elements at 145, 279 and 662 keV gamma photons at scattering angles
ranging from 30 to 150. The scatterer is viewed by two detectors, one sensitive to
characteristic x-rays emitted from the element and the other to the scattered gamma
rays. The scattered photons are detected by a 51 mm diameter and 51 mm thick
NaI(Tl) crystal and the K X-rays are detected by a 38 mm diameter and 2 mm thick
NaI(Tl) crystal. A coincidence set up using Canberra ARC timing amplifiers in the fast
channels and having 30 nsec resolving time is used for recording the events.
The intensity distribution of measured K-shell to free electron Compton
collision, absorption and scattering cross section ratio, dK/dF will be presented
for the energies, elements and scattering angles mentioned above. The general
trend of K-shell to free electron Compton collision cross section ratio increases with
the increase in scattering angle. Our experimental results are compared with the
available theoretical and experimental data.

99

I13
Synchrotron-radiation-based hard X-ray nanobeam
by Kirkpatrick-Baez mirrors
K. Yamauchi1,4, H. Mimura1, S. Matsuyama1, H. Yumoto2, S. Handa1, T. Kimura1,
Y. Sano1, M. Yabashi2, Y. Nishino3, K. Tamasaku3, T. Ishikawa3
Department of Precision Science and Technology, Graduate School of
Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan
2
SPring-8/Synchrotron Radiation Research Institute (JASRI), 1-1-1 Kouto,
Sayoucho, Sayogun, Hyogo 679-5148, Japan
3
SPring-8/RIKEN, 1-1-1 Kouto, Sayoucho , Sayogun, Hyogo 679-5148, Japan
4
Research Center for Ultra-Precision Science and Technology, Graduate School of
Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan
1

We developed a surface-figuring method to realize atomic-level smoothness

and 0.1nm (RMS)-level figure accuracy over the large area of 100mm scale, and
applied the method to fabricate total-reflection optics for hard X-ray nano-focusing
[1]-[3]. The fabricated optics were evaluated at the 1km-long beam-line (BL29-XUL)
of SPring-8, and a nearly diffraction-limited focusing with the spot size of 25nm x
30nm was obtained at the X-ray of 15keV. The fabrication methods, the performances
of the focusing optics, and the application examples will be introduced.
We are now trying to realize sub-10nm X-ray nano-beam in which wavefront error smaller than 0.01nm is required. To evaluate such small phase error, we
developed a novel at-wavelength interferometry using a phase retrieval technique
[4,5]. A compensation method of the phase error was also proposed. The latest
results on the research will be also presented.
[1] Y. Mori et al., Rev. Sci. Instrum., 71 (2000), 4627-4632.
[2] K. Yamauchi et al., Rev. Sci. Instrum., 73 (2002), 4028-4033.
[3] H. Mimura et al., Applied Physics Letters 90, 051903 (2007)
[4] H. Yumoto et al., Rev. Sci. Instrum., 77, 063712 (2006).
[5] H. Mimura et al., Phys Rev A 77, 015812 (2008)

Fig. Focused X-ray beam profiles of the size of 25nm

100

O13-1
SR-XRF analysis of fluid-inclusions in cloudy diamonds from
Koffiefontein, South-Africa
B. Vekemans1, T. Pisternick2, T. Schoonjans1, F. E. Brenker2, A. Szymanski2, W. De
Nolf3, K. Janssens3, J. Harris2,4, R. Tucoulou5, L. Vincze1
XMI, Department of Analytical Chemistry, Ghent University, 9000 Gent, Belgium
Geoscience Institute / Mineralogy, JWG University, 60438 Frankfurt/Main,
Germany
3
MiTAC, Department of Chemistry, Antwerp University, 2610 Wilrijk, Belgium
4
Division of Earth Sciences, University of Glasgow, Glasgow G12 8QQ, Scotland,
UK
5
ID22, ESRF, BP 220, 38043 Grenoble, France

The study of fluid inclusions within diamonds from different locations

around the world gives important information on subduction processes (e. g. of
oceanic lithosphere material) and the diamond growth. For this, cloudy diamonds
from Koffiefontein and Finsch mines were studied systematically at the European
Synchrotron Radiation Facility (ESRF) at the beamlines ID18F and ID22. In addition,
XANES measurements (at HASYLAB beamline L) and Raman Spectroscopy (at JWG
University) were performed on the same inclusion suite to complete the identification
of the inclusions.
To avoid the loss of information when separating the solid part of the
inclusion from the diamond host and releasing the gas and/or fluid content, dedicated
measurement techniques must be applied to study these fluid inclusions in-situ. In
this work, the experiment performed at ID22 to investigate very tiny fluid inclusions in
a specially prepared Koffiefontein diamond (Kf07-4) is demonstrated. The application
of the confocal XRF method appears to be essential to unambiguously retrieve
information from within the diamond needle on the trace element and sub-micron
level. In such way, the distribution of elements such as Cl, Br, K, Ca, Ti, Mn, Fe, Ni
and Cu could be studied in great detail. The extreme in-homogenous distribution
of these elements in a single diamond was surprising. And whether this distribution
indicates immiscibility during entrapment of the fluid phase or subsequent separation
into a solid, fluid and probably gas phase during uplift of the diamond host remains
speculative at the moment and is a matter of our ongoing measurements.
These studies should also provide a standard reference for future
investigations on fluid inclusions entrapped in superdeep diamonds from Kankan
(Guinea) and Juina (Brazil).

101

O13-2
Applications of the remote operation of PIXE and Micro-PIXE
measurements
M. Jaki, M. Bogovac, N. Skukan, I. Bogdanovi Radovi, S. Fazini
Ruer Bokovi Institute, Bijenika 54, 10000 Zagreb, Croatia
Fast internet connections that are available today worldwide are opening
new possibilities in the research and education using accelerator based analytical
techniques. Our newly developed accelerator computer control and recent
improvements in sample positioning and data acquisition systems enabled a long
distance access to experiments performed at accelerator including different aspects
of the application of PIXE technique. At the Laboratory for ion beam interactions of
the Ruer Bokovi Institute, PIXE is applied at three different beamlines. These are
a) the broad beam PIXE vacuum chamber with automatic sample changer, b) the
external beam PIXE system with computer controlled sample stage for large objects
and c) the proton microprobe facility. As each of these systems is equipped with a
dedicated software and hardware for remote operation, PIXE measurements can be
entirely or partially performed from distant locations.
These capabilities have been shown of particular importance for sensitive
microPIXE measurements (e.g. in biomedical applications) when the typical
measurement time needed for low concentrated elements can be achieved only by
overnight measurements. This aspect is also important in collaborative work when
the samples have been sent by experimenter that is not personally present during
the measurements on site. In both cases possibility to be connected to the ongoing
measurement for collaborators from distance locations is of great value. And finally
we will show that this possibility can be easily used for the long distance learning by
access to accelerator operation console and subsequent analysis using PIXE and
RBS techniques.

102

O13-3
Micro-XRF from Carbon upwards with a laboratory x-ray source
S. Sasamori, P. Wobrauschek, C. Streli, N. Zoeger, S. Smolek and F. Meirer
Atominstitut Vienna University of Technology, Vienna, Austria, Stadionallee 2
Micro X-ray fluorescence analysis (-XRF) is widely used for sample
analysis in the m-scale. However, for the analysis of low Z elements (Z<14) the
challenge lies in a very sophisticated experimental set-up. Of particular importance
is an efficient excitation from the source and a good attainable detection of the low
energy photons emitted from the light elements in the sample.
Sample examination under medium vacuum conditions is essential to avoid
undesired effects, which would normally occur in air, such as air scattering of the
primary beam, existence of Ar K-lines and absorption of the fluorescence radiation.
A preferential excitation source is an intensive low-energy photon source, like a Cr
anode 1900 W point focus from a LFF diffraction x-ray tube, which was used in the
work presented.
In order to achieve a micro-spot on the sample (spot size 40m) a polycapillary
(XOS) is used. The detector is a horizontally mounted Peltier cooled SDD with a
300nm ultra thin window (MOXTEK), offering an adequate high efficiency to reach
even down to carbon. The shaped output signal is collected via ADC in a multichannel
analyzer and stored as spectrum of the individually examined pixels. The vacuum
chamber with a 8m Kapton entrance window is closest coupled to a 300 m Be
window of the x-ray tube. The capillary is mounted inside the chamber on an x-z
micro stage to obtain optimal alignment with respect to the x-ray tube. The sample
is fixed on a frame, which can be moved 25 x 25 mm horizontally and vertically
by two computer-controlled x-z micro stages. An additional translation stage allows
adjusting the sample surface in the focus of the polycapillary. The sample surface is
observed through a microscope with a CCD camera.
The following investigations have been performed, utilizing the aforementioned set-up and will be presented as (1) scans across a pattern, that was
applied on a plexiglass reflector by ink jet picodroplets containing Sc; (2) analysis of
the spatial distribution of a 1l Na(F) sample on a Kapton foil; and (3) the elemental
distribution of light elements in a slice of human bone.
Prospects for future improvements of the set-up and its applications will be
presented (see also poster S. Smolek et al).

103

O13-4
3D analysis of biological samples by confocal XRF
Roberto D. Perez1 2 3, Hctor J. Snchez 1 2 , Carlos A. Perez4 and Marcelo Rubio1 2 3
FAMAF, Universidad Nacional de Crdoba, (5000) Ciudad Universitaria, Crdoba,
Argentina.
2
CONICET, Rivadavia 1917, (1033) Buenos Aires, Argentina.
3
CEPROCOR-Agencia Crdoba Ciencia S.E, (5164) Santa Mara de Punilla,
Crdoba, Argentina.
4
Laboratrio Nacional de Luz SncrotronLNLS, POB 6192, 13084-971 Campinas,
SP, Brazil
1

The confocal setup consists of x-ray lenses in the excitation as well as in

the detection channel. In this configuration, a micro volume defined by the overlap
of the foci of both x-ray lenses is analyzed. Scanning this micro volume through the
sample, 1-3 dimensional studies can be performed.
For the confocal setup, we used a commercial glass monocapillary in the
excitation channel and a monolithic half polycapillary in the detection channel. The
polycapillary was home-made by means of drawing of multibundles of glass capillaries
in a heating furnace. The experiment was carried out at the D09B beamline of the
Synchrotron Light National Laboratory (Laboratrio Nacional de Luz Sncrotron,
LNLS) using white beam. A silicon drift x-ray detector of 150 eV resolution at 5.9 keV
was used for detection of fluorescent photons.
A model for a theoretical description of the x-ray fluorescent intensity
registered by a confocal XRF was introduced by Malzer and Kanngieer in 2005
[1]. These authors showed that the scan of the x-ray fluorescent intensity is the
spatial convolution of the sensitivity and the x-ray fluorescence emission rate to the
detector. In a previous work we showed that the convolution theorem can simplify
the calibration and quantification process in confocal XRF [2]. In the present work,
we applied these ideas to analyze samples of aquatic plants and a sample of tooth
by confocal XRF. We showed that confocal XRF can be successfully applied to
help the study of the effects of water bioremediation on aquatic plants. We also
showed that confocal XRF can be used to make topological studies of teeth.
[1] W. Malzer, B. Kanngieer. Spectrochim. Acta, B60 (2005) 1334-1341.
[2] R.D. Prez, H.J. Snchez, C.A. Prez, M. Rubio, in preparation.

104

O13-5
X-ray Fluorecenece Analysis of Liquid/Solid Samples
K. Tsuji and Y. Nishida
Department of Applied Chemistry, Graduate School of Engineering, Osaka City
University, (3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan)
We have applied X-ray fluorescence (XRF) analysis for the direct measurement
of solutions and the solid surface of the samples in the solution [1,2]. A glass guide
tube, which was attached to an X-ray tube, was inserted into the solution. The solid
surface in the solution was irradiated by the primary X-rays. The X-ray fluorescence
was detected through another glass tube by the energy dispersive X-ray detector.
The glass tubes for X-ray irradiation and X-ray detection were combined; therefore,
it was easy to approach this XRF probe to the surface of the sample.
The quantitative analysis of the method was evaluated by using standard
solutions. The lower detection limits for solution samples were in the range of ppm
order. The XRF spectra changed depending on the distance between the XRF
probe and the solid surface in the solution. Usually, the XRF spectrum includes the
information of both the solution and the solid sample. However, by subtracting the
contribution from the solution, the XRF spectrum of the solid surface in the solution
could be obtained. We have also applied the XRF analysis using a needle-type
collimator [3] to know the concentration distribution of elements in the solution.
[1] K. Tsutsumimoto, K. Tsuji, Proposal of XRF analysis for Solid/Liquid Interfaces and
Monitoring Chemical Plating Processes, BUNSEKI KAGAKU, 56 (2007) 499-504.
[2] K. Tsuji, T. Yonehara, K. Nakano, Application of confocal 3D micro XRF for solid/
liquid interface analysis, Ana. Sci., 24 (2008) 99-103.
[3] K. Tsuji, A. Matsuda, K. Nakano, A. Okhrimovskyy, X-ray fluorescence analysis
of soft materials using needle-type collimators enabling greater tolerance in
analysis depth, Spectrochim. Acta B, 61, (2006) 460-464.

105

O13-6
Micro-beam X-ray fluorescence analysis of individual
particles
M. Czyzycki1, M.Bielewski2, D.Wegrzynek1, 3, A.Markowicz1, 3, R.Simon4 and
M.Lankosz1
AGH-University of Science and Technology, Faculty of Physics and Applied
Computer Science, Krakow, Poland
2
European Commission-DG RJC, Institute for Transuranium Elements, P.O. Box
2340, D-76125 Karlsruhe, Germany
3
International Atomic Energy Agency, Agencys Laboratories Seibersdorf, A-1400
Vienna, Austria
4
Institute for Synchrotron Radiation, Forschungszentrum Karlsruhe GmbH,
D-76021 Karlsruhe, Germany
1

Micro-beam x-ray fluorescence spectrometry is one of the basic method

of elemental analysis of minute samples, especially individual particles and grains.
Several methods of correction for absorption and particle shape effects in microbeam x-ray fluorescence analysis were investigated experimentally and with the use
of Monte-Carlo simulation. A fast energy-dispersive, silicon drift detector was used
to measure the primary x-ray beam transmitted through the sample. The absorption
factors were calculated using the data acquired with the SDD. The possibility of
using the coherently and incoherently scattered primary radiation for determining the
mass of individual particles was examined. The proposed methods were validated
with the use of glass micro-spheres of known composition.
Synchrotron radiation x-ray fluorescence confocal imaging is among the
methods, which are able to provide three-dimensional, quantitative information on
the elemental distribution in the probed sample volume with trace level detection
limits. The confocal X-ray fluorescence microscope was applied for 3D micro-XRF
analysis of microscopic inclusions in mineral grains. Intensities correlation method
was applied for determining the concentrations of major and minor elements in
mineral grains.

106

I14
Nanoparticles observed under X-ray grazing incidence
Alex von Bohlen
ISAS Institute for Analytical Sciences, Bunsen-Kirchhoff-Str. 11, 44139 Dortmund,
Germany
Particles, especially the smallest are nowadays of primordial interest.
They are used in many disciplines and in several applications in biology, medicine,
biochemistry, pharmacy, material sciences and also in conservation sciences. Man
is continuously producing nanoparticles. Laser printers, copy machines, Diesel fuel
driven cars, Pt-Pa-Rh catalyst converters built-in in cars, laser applications in medicine
and technology, lasers used for LIBS (Laser Induced Breakdown Spectrometry)
and several other applications produce nanoparticles. They are in terms of their
diameter located in the range below one micrometer. Single members of the finest
fractions, those below 100 nm, are difficult to characterize via conventional methods
of chemical analysis or microscopy if their morphology and/or composition should
not be altered during measurements.
An approach to the chemical characterization as well as some hints about the
morphology of very fine fractions of nanoparticles can be deduced from experiments
using X-ray grazing incidence techniques (TXRF, Total Reflection X-ray Fluorescence
and XSW, X-ray Standing Waves). Some theoretical aspects will be discussed in
detail. Results of modelling and simulation will be compared with the experimental
data obtained from XSW experiments performed at DELTA synchrotron facility.
Advantages and drawbacks will be shown for metallic nanoparticle characterization
using TXRF and XSW. The power of X-ray methods for these purposes will be
compared with those obtained by other technique

107

O14-1
Reference-free TXRF analysis of semiconductor surfaces with
synchrotron radiation
B. Beckhoff , R. Fliegauf, M. Kolbe, M. Mller, J. Weser, G. Ulm
Physikalisch-Technische Bundesanstalt, Abbestrae 2-12, 10587 Berlin, Germany
Total-reflection X-ray fluorescence (TXRF) analysis is a well-established
method to monitor lowest level contamination on semiconductor surfaces. Even
light elements on a wafer surface can be excited effectively when using high-flux
synchrotron radiation in the soft X-ray range. To meet current industrial requirements in
non-destructive semiconductor analysis, the Physikalisch-Technische Bundesanstalt
(PTB) operates dedicated instrumentation for analyzing light element contamination
on wafer pieces as well as on 200 mm and 300 mm silicon wafer surfaces. This
instrumentation [1] is also suited for grazing incidence X-ray fluorescence analysis
(GIXRF) and conventional energy-dispersive X-ray fluorescence (EDXRF) analysis
of buried and surface nanolayered structures, respectively. The most prominent
features are a high vacuum load-lock combined with an equipment front end module
(EFEM) and a UHV irradiation chamber with an electrostatic chuck (ESC) mounted
on an 8-axis manipulator. Here, the entire surface of a 200 mm or a 300 mm wafer
can be scanned by monochromatized radiation provided by the plane grating
monochromator beamline (PGM) for undulator radiation in the PTB laboratory at
the electron storage ring BESSY II. This beamline provides high spectral purity and
high photon flux in the range of 78 eV to 1.86 keV. In addition, absolutely calibrated
photodiodes and Si(Li) detectors are used to monitor the exciting radiant power
respectively the fluorescence and scattered radiation [2]. Furthermore, the footprint
of the excitation radiation at the wafer surface is well known due to beam profile
recordings by a CCD during special operation conditions at BESSY II that allow for
drastically reduced electron beam currents. Thus all the requirements of completely
reference-free quantitation of TXRF analysis are fulfilled and will be presented.
[1] B. Beckhoff, R. Fliegauf, M. Kolbe, M. Mller, J. Weser, G. Ulm, Anal. Chem. 79
(2007) 7873.
[2] M. Mller, B. Beckhoff, G. Ulm, B. Kanngieer, Phys. Rev. A 74 (2006) 012702

108

O14-2
Grazing incidence X-Ray fluorescence characterisation of ultra
shallow junctions in the ANNA consortium
G. Pepponi1, D. Giubertoni1, M. Bersani1, N. Zoeger2, C. Streli2, B. Beckhoff3, P.
Hoenicke3, M. Kolbe3 and M. Mueller3
Fondazione Bruno Kessler, via Sommarive 18, 38100 Povo, Trento, Italy
2
Atominstitut, TU Wien, Stadionallee 2, 1020 Vienna, Austria
3
Physikalisch-Technische Bundesanstalt (PTB), Abbestrae 2-12, 10587 Berlin,
Germany
1

Dopant profiling in ultra shallow junctions in Si and other semiconductor

materials, is a very current problem in applied physics and is well known to the
scientific community involved in the characterization, design, fabrication as well as
simulation of processes and devices in microelectronics [1].
Grazing Incidence X-Ray Fluorescence Analysis (GI-XRF) is known for its
capability of performing qualitative and quantitative elemental analysis of surfaces,
near surface layers, thin films [2]. For the characterisation of ion implants in silicon
wafers it has been shown that it can give quantitative information on the total retained
fluence and on the depth profile shape [3].
A perspective will be given of its use for the characterisation of Ultra Shallow
Junctions within the ANNA project [www.anna-i3.org], an Analytical Network for
Nanotechnology funded by the European Commission under the Framework
Programme 6.
The results of laboratory measurements obtained on arsenic implanted
silicon wafers with a self-developed chamber (Mo K excitation, As K fluorescence
recorded) at the Atominstitut are presented.
A novel evaluation approach based on the coupling of Secondary Ion Mass
Spectroscopy (SIMS) maesured profiles and GI-XRF developed at the Fondazione
Bruno Kessler will be outlined and discussed. In this approach the deeper part of
the SIMS profile is assumed to be accurate whereas the near surface part (where
SIMS is known to have quantification weaknesses) is adjusted using the information
obtained from GI-XRF measurements.
Employing monochromatized undulator radiation at the electron storage ring
BESSY II, the PTB conducted GI-XRF measurements on As implanted 200 mm
silicon wafers at 1540 eV in order to reveal the implantation profile. A routine is
currently developed to calculate and fit this depth profile for the implanted element
using an IMD simulation [4] of the standing wave field inside the silicon wafer. These
measurements are also planned for B implanted wafers.
[1] W., AIP Conf. Proc. 931 (2007) 233-245
[2] D.K.G. de Boer, W.W. van den Hoogenhof, Spectrohimica Acta Part B, 46, 10
(1991) 1323-1331
[3] G. Pepponi, C. Streli, P. Wobrauschek, N. Zoeger, K. Luening, P. Pianetta,
D. Giubertoni, M. Barozzi, M. Bersani, Spectrochimica Acta Part B, 59, 8 (2004)
1243-1249
[4] D.L. Windt, Computers in Physics, 12 (1998) 360-370.
109

O14-3
Trace element analysis and zinc speciation in size-fractionated
aerosol samples using SR-TXRF and XANES
J. Osn1, V. Groma1, F. Meirer2, E. Brcsk,1 S. Trk1, C. Streli,2 P.
Wobrauschek2 and G. Falkenberg3
1

KFKI Atomic Energy Research Institute, P.O. Box 49, H-1525 Budapest, Hungary
Atominstitut der sterreichischen Universitten, TU Wien, Stadionallee 2, A-1020
Vienna, Austria
3
HASYLAB at DESY, Notkestr. 85, D-22607 Hamburg, Germany

The health effects of aerosol depend on the size distribution and the chemical
composition of the particles. Heavy metals of anthropogenic origin are connected to
the fine (PM2.5) and ultrafine (PM1) aerosol fraction. The composition and speciation
of aerosols can be variable in time, due to the time-dependence of anthropogenic
sources as well as meteorological conditions. Synchrotron-radiation totalreflection X-ray fluorescence (SR-TXRF) provides very high sensitivity for aerosol
characterization. X-ray absorption near-edge structure (XANES) spectrometry in
conjunction with TXRF detection can deliver speciation information on heavy metals
in aerosol particles collected directly on the reflector surface. The suitability for SRTXRF for elemental analysis and XANES for zinc speciation in size-fractionated
aerosols from a short sampling period is presented.
Atmospheric aerosol samples were collected at different urban and rural,
continental and marine locations using a 7-stage May cascade impactor having the
opportunity of sampling on Si wafers with high temporal and size resolution. The
measurements were performed at HASYLAB Beamline L using the TXRF vacuum
chamber. For TXRF, the energy of the synchrotron radiation was tuned to 18.4 keV
using the NiC multilayer monochromator. For TXRF-XANES at the Zn K-edge, a
Si(111) monochromator was used. The vertical dimension of the beam was set to
0.5 mm for both cases. Cr standards having a known mass in dimensions identical
to the deposited aerosol particles could be used for calculating the elemental
composition.
For TXRF elemental analysis, detection limits of transition metals in the pg/
m3 range could be reached for a 20-min sampling time in the 0.5-1 m aerosol
fraction. Information on Zn speciation could be obtained from air concentration of Zn
as low as 100 pg/m3. The size distribution of the elemental composition as well as the
Zn speciation was found to be in accordance with the origin of the aerosol samples.

110

O14-4
TXRF cation analysis by anionic membrane collection
V. Hatzistavros, and N. Kallithrakas-Kontos
Technical University of Crete, Analytical and Environmental Chemistry Lab.,
University Campus, GR-73100 Chania, Greece
A new method for the determination of metal cations by anion selective
membranes is presented. The anion selective membranes were composed of polyvinyl
chloride (PVC) as a matrix, Aliquat-336 as anionic extractant, dibutyl phthalate as
plasticizer and various ligands as complexing agents [1]. These membranes were
capable of capturing cationic metals such as Co, Ni, Mn, Fe, Cu, Zn in solutions
that had excess of anionic ligands (cyanides etc). The membranes produced on
the surfaces of quartz reflectors; they were put in the centre of the reflectors as
a ~3 mm diameter liquid spot, they were dried and they were immersed in water
solutions containing various concentrations of metals. By the end of the equilibration
time, the reflectors were left to dry and they were analyzed by Total reflection XRay Fluorescence (TXRF). The effects of various experimental parameters (pH,
equilibration time, metal speciation, competitive cations, and different complexing
ligands) were tested. Minimum detection limits of the order of 1-10 ppb (or even
lower) were achieved.
[1] V. Hatzistavros, P. Koulouridakis, I. Aretaki, N. Kallithrakas-Kontos, Analytical
Chemistry 79 (2007) 2827 - 2832.

111

O14-5
Application of high-resolution grazing emission x-ray
fluorescence (GEXRF) spectroscopy for detction of low level
impurities on Si-wafer.
J. Szlachetko1,2, M. Pajek1, A. Kubala-Kukus1, D. Banas1, W. Cao3, J.-Cl. Dousse3,
J. Hoszowska3, M. Kavcic4, Y. Kayser3, M. Salome2, J. Susini2
Institute of Physics, Swietokrzyska Acdemy, 25-406 Kielce, Poland
European Synchrotron Radiation Facility (ESRF), F-38043 Grenoble, France
3
Department of Physics, University of Fribourg, CH-1700 Fribourg, Switzerland
4
J. Stefan Institute, SI-1001 Ljubljana, Slovenia
1

The production of ultra clean silicon wafers is one of the most important issues
for Si-based microelectronic technology. Application of the TXRF method combined with
intense synchrotron sources offers presently the best possibilities for measuring very low
concentration impurities on Si wafer surfaces. Using the synchrotron x-ray beams the TXRF
sensitivity on the level of 108 atoms/cm2 was achieved [1] at optimized conditions. However, the
synchrotron radiation based TXRF technique, which employs the grazing incident geometry,
cannot benefit from the available micro-focused synchrotron radiation beams for performing
high-resolution 2D mapping of impurities on Si wafer surfaces. Moreover, in standard TXRF
arrangements low-resolution semiconductor silicon detectors are usually used, which limits
in some cases the elemental resolution capabilities and results in poorer detection limits due
to the low-energy tailing of semiconductor x-ray line profiles. Therefore, further development
of new direct techniques to measure the metallic impurities on Si wafers is still a challenging
question.
We report on application of the grazing-emission x-ray fluorescence (GEXRF)
method [2, 3] to measure the x-ray emission from metallic impurities on Si-wafer. The GEXRF
technique was combined with intense synchrotron radiation beam and high-resolution x-ray
detection by employing a von Hamos-type spectrometer. In order to determine the detection
limits for the GEXRF method, the K-, L- and M x-rays of several elements, having x-ray
energies in the range between 1.7 keV and 7 keV, were measured. From the measured x-ray
spectra the GEXRF detection limits on the level of 1012 atoms/cm2 were obtained. By means
of the GEXRF technique the composition, density and thickness of the layers can be deduced
by measuring the intensity evolution around grazing exit angle. Differences between the bulk,
film-like and particle-like layers were clearly observed. Additionally, to test the 2D-mapping
capabilities of the GEXRF method a 1D-scan employing 25 m beam size was performed
using Si wafer with periodic Cr layer.
The further improvement of detection limits for the GXRF technique can be achieved
by applying the vapor phase decomposition (VPD) preconcentration technique. Since a spot
of x-ray synchrotron beam is very small (1mm2) thus the VPD enhancement factor can be up
to five orders of magnitude. Therefore, a combination of the high-resolution GEXRF method
with the VPD technique can lead to the detection limits on the level of 107 atoms/cm2.
This work was partially supported by Swiss National Science Foundation, grant PB
FR2-118665.
[1] P. Pianetta et al., Thin Solid Films 373, 222 (2000).
[2] R.S. Becker, J.A. Golovchenko, J.R. Patel, Phys. Rev. Lett. 50, 153 (1983).
[3] P. K. De Bokx et al., Spectrochim. Acta B52, 829 (1997) .

112

O14-6
A novel approach for chlorine determination in acidic medium
by total reflection X-ray fluorescence
N.L. Misra1, Imre Varga2, Sangita Dhara1 and S.K. Aggarwal1
Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085
(India)
2
Etvs Lornd University, Institute of Chemistry, H-1518 Budapest P.O. Box 32,
Hungary
1

Determination of chlorine at trace levels in different matrices is of importance

in biological, environmental, medical, nuclear and industrial technology. During total
reflection X-ray fluorescence (TXRF) determination of chlorine in acidic solutions
there is appreciable loss of chlorine when the sample is heated on quartz sample
support for sample preparation [1]. This results in lower recovery of chlorine from
nuclear materials e.g. UO2, ThO2 and PuO2 etc. where major matrix is removed using
solvent extraction after dissolution in nitric acid [2]. Silver nitrate has been successfully
applied as a stabilizer for iodine determination by TXRF [3]. In present work, an indirect
novel method of chlorine determination by TXRF has been developed. The method
involves addition of a known excess amount of AgNO3 solution (than that required for
chlorine precipitation as AgCl) to the analyte solution and determination of the excess
(unused) Ag in the filtrate by TXRF using Cd as internal standard. The TXRF spectra
were recorded using an ATOMIKA TXRF spectrometer with W continuum excitation at
50 kV and 38 mA. Amount of Ag present in filtrate was determined by using Ag K and
Cd K line intensities of analyte and internal standard respectively. Concentration of
chlorine in original solution was calculated from the amount of Ag consumed in AgCl
precipitation. The method has been found to have a precision (1 RSD) and accuracy
better than 16% for the samples having chlorine concentration in the range of 15 to
60 g/mL. The method gives satisfactory results in HNO3 medium of acidity up to 4.5
M and is thus suited for the determination of chlorine in nuclear materials after their
dissolution and separation of major matrices: thorium, uranium or plutonium using
tri-n-butyl phosphate. Experiments conducted by using synthetic mixtures of standard
uranium and NaCl solutions have shown encouraging results by this methodology.
Acknowledgements: The authors express their sincere thanks to Indian
National Science Academy, New Delhi and Hungarian Academy of Sciences,
Budapest for the financial support during this work.
[1] Nand Lal Misra, Sangita Dhara, Khush Dev Singh Mudher, Udai Kumar Thakur,
Dipti Shah, R. M. Sawant, K.L. Ramakumar, Suresh K. Aggarwal, Proc. Nuclear
and Radiochemistry Symposium (NUCAR-2007) held at The Maharaja Sayajirao
University of Baroda, Vadodara, Feb 14-17, 2007, 465-466.
[2] R. Klockenkmper, Total Reflection X-ray Fluorescence Analysis, Chemical
Analysis Vol. 140, John Wiley & Sons, New York (1996).
[3] Imre Varga, Iodine determination in dietary supplement products by TXRF and
ICP-AES spectrometry, Microchemical Journal 85, 127-131, 2007
113

Abstracts
Poster Session A

PA-1
Analytical characterization of the ground layer in paint section
of Rubens paintings at El Prado National Museum
M.I. Bez1, J. Ramrez-Castellanos2, M.D. Gayo3,
J.L. Baldonedo4, L. Vidal1 and M.J. Garca1
Dpto. Pintura-Restauracin. Universidad Complutense de Madrid (Espaa)
Dpto. Qumica Inorgnica I. Universidad Complutense de Madrid (Espaa)
3
Laboratorio de Qumica. Museo Nacional del Prado (Espaa)
4
Centro Microscopa y Citometra. Universidad Complutense de Madrid (Espaa)
1

El Prado National Museum collection has several pieces of Rubens artwork,

some of which were painted in Spain during his last two stays at Spanish Royal
Court. However, his other paintings come from Ambers, Belgium, where he usually
used to work. He always used the painting style of his time; such as reddish ochre
grounds from natural colored earths, which have a complex chemical composition.
At present, a multidisciplinary project is being developed in order to clearly
identify the origin of several of Rubens undated paintings at El Prado Museum.
The first step of this project is to carry out a detailed study on two of his paintings
of unknown origin. The data gathered in this study will be compared with the data
obtained from the previously used materials.
The estratigraphic cross-sectional micro samples have been studied by
Scanning Electron microscopy (SEM), high resolution transmission electron
microscopy (HRTEM), and light microscopy (LM). Furthermore, a detailed analytical
study by Energy Dispersive X-ray Spectroscopy (EDS) was carried out.
Results of the well dated canvas entitled El duque de Lerma (1609)
(Ambers) will be presented. Thin samples obtained by cross-sectional method were
embedded in an epoxy resin. Special care must be taken in order to keep the micro
sample unaltered.
Numerous qualitative and semi-quantitative microanalyses by EDS have
been performed in order to locate the pigments and additives used by the artist.
These results show the main and secondary components, such as different types of
feldspars and micas, mixed with very pure iron oxides/hydroxides, silice (quarz and
opal), titanium oxides, calcite and dolomite.

117

PA-2
SR micro-XRD, SR micro-XRF and SR micro-XANES analyses on
degraded Cadmium Sulphide paint samples
Geert Van der Snickt1, J. Jaroszewicz1, W. De Nolf1, K. Janssens1, J. Dik2,
L. Van der Loeff3 and L. Klaassen4
Department of Chemistry, University of Antwerp, Universiteitsplein 1, B2610,
Wilrijk, Belgium
2
Delft University of Technology, Rotterdamseweg 137, NL-2628 AL Delft,
Netherlands.
3
Kroeller-Mueller Museum, Houtkampweg 6, NL-6731 AW Otterlo, the Netherlands.
4
Royal Museum of Fine Arts Antwerp, Plaatsnijdersstraat 2, B-2000, Antwerp,
Belgium.
1

The paintings of the end of the 19th-C and the beginning of the 20th-C
form an interesting field of research as numerous new pigments were developed
by the emerging chemical industry at that time. These new painting materials often
outclassed the traditional pigments with regards to colouring intensity, purity, cost
price, covering power etc. However, not all of these modern pigments appeared
to be chemically stable on the long term. This seems for instance the case for
cadmium yellow, a cadmium sulphide compound invented by Stromey in 1818 and
commercialized around the middle of the 19th-C. Fading of the yellow colour and
loss of adhesion has been reported by several authors, but the exact deterioration
process remains a point of discussion. Both in the Royal Museum of Fine Arts of
Antwerp and in the Kroeller-Mueller Museum, degraded cadmium yellow was found
on paintings of the Belgian avant-garde artist James Ensor (1860-1949). Under the
microscope, the surface of the yellow paint looks dull and flaky; it also displays
cavities, has become brittle and lacks cohesion. However, the most striking feature is
the formation of whitish, semi-transparent protrusions on the surface. The chemical
characterization of both the white globules and the overall degradation process
is obviously of great interest/concern to conservators as it is a warning signal for
ongoing transformations.
The conservators of both museums supplied scrapings/samples of the
surface of the paint containing white globules and some yellow paint. The materials
were examined at the ESRF by means of micro-XRD at beam line ESRF-ID18F
and micro-XRF and micro-XANES at ID21. The collected XRD spectra and maps
show the distribution of cadmium sulfate hydrate (CdSO4.H2O), otavite (CdCO3) and
greenockite (CdS) throughout an assembly of grains isolated from one of the paint
scrapings. Greenockite and otavite was identified in the non-degraded, yellow areas.
By contrast, the whitish/transparent grains are rich of CdSO4.H2O. On the basis of
these findings, the major mechanism for colour change of the yellow CdS could
be identified, i.e.: CdS + 2O2 + H2O CdSO4.H2O. The XANES and XRF maps
collected at ESRF-ID21 confirmed this hypothesis and allowed us also to obtain
information on the depth of the oxidation front.
118

PA-3
EDXRF coupled with vis-RS to study iron-gall inks: laboratory
tests and in situ analysis on Palladios drawings
S. Caglio1 and G. Poldi1, 2
Dipartimento di analisi scientifiche, Open Care, via Piranesi 10, 20123 Milano,
Italy
2
LAM, Universit degli Studi di Bergamo, piazza Vecchia 8, 24129 Bergamo, Italy
1

Different kinds of inks used in drawings, engravings and manuscripts can be

usually distinguished by elemental analyses. In the case of ancient iron-gall inks, also
diverse batches produced in different periods can be recognized because of some
differences in composition. Non invasive methodologies like PIXE [1] and microED-XRF [2] have been successfully used with this aim on manuscripts of Galileo,
Goethe and Mozart.
In this work we show the possibility to use a portable ED-XRF spectrometer
without capillary x-ray optics to study drawings, which limits the analyses to broader
traced lines (about 3 mm). The different kinds of drawing patterns (single lines,
cross-hatchings, liquid shadings of different intensity) suggests the need to use a
preliminary clustering of the investigated points that can be performed on the basis
of colorimetric results achieved by visible Reflectance Spectrometry (vis-RS).
The method has been tested on laboratory test samples with different kinds
of iron-gall ink, then applied in situ to study sixteen drawings of architecture by
Andrea Palladio (1508-1580) belonging to the Pinacoteca Civica di Vicenza (Italy).
A discussion of the method and results is provided.
[1] L. Giuntini et al., Nucl. Instr. and Meth. in Phys. Res. B, 95 (1995) 389-392.
[2] O. Hahn et al., X-ray Spectrom., 33 (2004) 234-239.

119

PA-4
Analysis of pigments on paintings from two churches in
Dubrovnik
D. Mudronja1, S. Fazini2, . Pastuovi2, M. Jaki2, M. Braun1, M. Pusti1
and M. Bonjak1
1

Croatian Conservation Institute, Grkovieva 23, Zagreb, Croatia

2
Ruer Bokovi Institute, Bijenika cesta 54, Zagreb, Croatia

Eight paintings located in two churches in Dubrovnik have been systematically

analyzed by using portable XRF system, proton microprobe, optical and UV
microscopy techniques, with the aim to compare the use of pigments by an author
or authors of the paintings.
Four of investigated paintings, all located in church of st. Blaise, represent
one evangelist. The other four analyzed paintings, located in the church of Lady of
Carmen, are very similar to the first four paintings. They represent the same four
evangelists as the first four paintings from the other church. Since they also look
quite similar to the first set of paintings, there is a common understanding that all
these paintings originate from the same period and that they were painted by the
same author(s).
In our analysis we compared pigments of the four evangelists paintings from
church of st. Blaise with the pigments of the four evangelists paintings from church
of Lady of Carmen. In order to make comparison easier, micro-samples for the
analysis were taken from similar positions on each of two similar evangelist paintings
from two churches. The work presented here is focused on analysis of pigments by
x-ray spectroscopy methods, which is just one aspect of the larger project which
will investigate these paintings in more detail with the final goal to investigate their
attributions to Mattia Preti.

120

PA-5
Monitoring the process of gilding, tarnishing and restoration
of 21st centry daguerreotypes by wavelength-dispersive X-ray
fluorescence spectrometry
E. Da Silva1,2, M. Robinson3, A. Pejovi-Mili2, C. Evans1 and D. V. Heyd1
1

Department of Chemistry & Biology, Ryerson University, Toronto, Ontario, Canada,

M5B 2K3
2
Department of Physics, Ryerson University, Toronto, Ontario, Canada, M5B 2K3
3
School of Image Arts, Ryerson University, Toronto, Ontario, Canada, M5B 2K3

Work announced to the world in 1839 by Louis J. M. Daguerre and

Joseph Nicphore Nipce resulted in the earliest form of photography known as
daguerreotyping. In the daguerreotype process a polished silver plate is exposed to
halogen vapor (I, Br, Cl or a combination thereof) to make the surface light sensitive.
It is then exposed in a camera to form a latent image. The modified silver halide
surface is then developed by exposing it to mercury vapor and the image fixed
by treatment with Na2SO3 (hyposulfite of soda). Toning and strengthening of the
image is achieved by treating the silver surface with a solution of gold chloride.
The image is susceptible to tarnishing when exposed to air and preservation of the
image performed by housing in a tightly sealed case with a protective cover glass.
The brass mats of such housings are a catalyst to tarnishing on the images. As
such, restoration of tarnished, yet delicate and irreplaceable images has become
an area of active research. This study presents the use of wavelength-dispersive
X-ray fluorescence spectrometry (WDXRF) on modern daguerreotypes to monitor
the photographic development process as well as the tarnishing and restoration of
daguerreotypes. The WDXRF system equipped with LiF(200), PET and OVO-55
analyzing crystals provides a means to estimate the relative surface content of various
elements including the light elements, sulfur and the halides. The photographic plate
composed of a copper backing and a silver surface, provides an adequately thick
layer of silver as to attenuate any copper signal from the backing (in comparison
to inherent system Cu contamination) while allowing for signal normalization to the
silver X-ray(s).

121

PA-6
Computed radiography of XIX century Brazilian paintings
Cristiane Calza1, Davi F. Oliveira1, Henrique S. Rocha1, Andrea Pedreira2 and
Ricardo Tadeu Lopes1
Nuclear Instrumentation Laboratory. COPPE/UFRJ. P.O. Box: 68509, 21941-972.
Rio de Janeiro. Brazil.
2
National Museum of Fine Arts. Rio de Janeiro. Brazil.

Four paintings of some of the most representative Brazilian artists from

the XIX century were characterized using Computed Radiography. The analyzed
paintings were: The Model at Rest (Almeida Junior, 1882, 100 x 130 cm); Bad
News (Rodolfo Amoedo, 1895, 100 x 74 cm); Redemption of Can (Modesto
Brocos, 1895, 199 x 166 cm) and Inside the Atelier (Rafael Frederico, 1898, 20.5
x 40.5 cm).
Radiographic techniques have been used in paintings to reveal the extent
of old damages sometimes concealed by past restoration; the successive phases of
the artist creation (preparatory drawing, underpainting and changes of design); the
nature of the support; the canvas weave; presence of lead pigments; crackings and
detachments of ink; losses of support; etc.
The experimental setup consisted of an Oxford X-ray source, operating at 35
kV and 200 A, placed at 85 cm from the painting, a GE CR 50P Portable Computed
Radiography Scanner and a Fuji Imaging Plate detector. The IP detector (35 x 43
cm) was fixed behind the canvas to perform each radiograph. The images were
revealed by introducing the exposed IP in the scanner, which also erased the film
after the image processing.
The radiographic images revealed that the paintings were in a relatively
good state of conservation most of them had been restored during the XX century.
Small regions of losses could be observed and also some details like: the canvas
weave, the wooden support, the nails used to fix the fabric on the wood, the use of
lead white, the characteristic brushing technique of the artists and some changes in
the design. These results together with the EDXRF analyses - have been used to
create a database about the XIX century collection of the National Museum of Fine
Arts, in order to assist restorators, conservators, researchers and students.

122

PA-7
XRF and PIXE analysis of the wooden polychrome altars from
the northern Croatian region
V. Desnica1, K. kari2, D. Mudronja2, M. Bonjak2, S. Fazini3, Z. Pastuovi3
Department for conservation and restoration, Academy of fine arts, Ilica 85,
HR-10000 Zagreb, Croatia
2
Croatian Conservation Institute, Grskoviceva 23, HR-10000 Zagreb, Croatia
3
Laboratory for Ion Beam Interactions, R. Boskovic Institute, Bijenicka 54,
HR-10000 Zagreb, Croatia
1

The aim of this work was the investigation of pigments from five wooden
polychrome altars from parochial churches in northern Croatia. All altars stem from
the famous sculptor's workshop of Frantz Straub, which was active in the 1760s.
Three of these altars from the parochial church of the Blessed Virgin Mary in Klotar
Ivani have been recently restored in the Croatian Conservation Institute. The two
other studied altars were the main altar from the parochial church in Pakrac and the
altar from Velika Ludina. Being important objects for the national cultural heritage an
extensive research on the painted wooden objects was undertaken as a part of the
conservation-restoration process. Among still unresolved questions was whether the
Straub workshop had its own standard collaborating painter(s), or the altars were left
on the intended places unpainted, leaving the work of painting to local artists. Paints
in the palette of each painter have its own characteristic pigments combination and
this fingerprint is even more individualized by trace, impurity elements in pigments
and binders, which are dependent on geographic source of the material, technology
of purification, etc.
To address this problem, an extensive preliminary in-situ pigment
investigation was done using a portable X-ray fluorescence device (XRF). XRF is
a non-destructive, fast and relatively simple analytical method for multi elemental
analysis. In its portable version, used here, it is also a non-invasive method, which
is of particular importance when working on precious artifacts. It reduced sampling
(and related damage to the artifacts) to a minimum. XRF analysis yielded positive
identification of most pigments used.
Only the problems which could not be resolved by this method (organic
materials, pigment layer cross-sections, binders, etc.) were further analyzed using
additional off-site lab methods, primarily micro-PIXE (proton induced X-ray emission)
at the nuclear microprobe of the Rudjer Boskovic accelerator facility, as well as thinlayer chromatography (TLC) and Fourier-transform infrared spectroscopy (FTIR).
The opportunity to research 5 artifacts built by a single outstanding workshop
provided us with new insights into its ways of manufacturing altars, its style and
technologies it used.

123

PA-8
Homogeneity study of modern bronzes for artistic castings
using pixe and plp
D. atovi1, V. Desnica1, L. Valek2, S. Martinez2, S. Fazini3, . Pastuovi3
Department for Conservation and Restoration, Academy of Fine Arts, Ilica 85,
HR-10000 Zagreb, Croatia
2
Department for Electrochemistry, Faculty of Chemical Engineering and
Technology, Savska cesta 16, 10000 Zagreb
3
Laboratory for Ion Beam Interactions, Rudjer Boskovic Institute, Bijenicka 54,
HR-10000 Zagreb, Croatia

Metal casting is the most efficient way of shaping metals both for industrial
purposes, as well as in art modeling. However, when casting an art model in metal,
focus is on shape and form, and quality of a cast is often neglected. Therefore, artistic
casts may vary in composition and structure, and often exhibit poor homogeneity.
Inhomogeneity in composition decreases mechanical properties of a cast alloy, and
also has a negative affect on corrosion resistance of alloy due to formation of anodic
and cathodic places. These can lead to very dangerous local (galvanic) corrosion.
Modern bronzes, cast in typical art foundries today, often show a high degree
of inhomogeneity and various compositions due to many different casting methods in
use and because of often very unrefined temperature control systems in processes
of melting and solidification.
In this work, we have studied several specimens of cast statuary bronzes
and compared the results with the results obtained from the industrial standard
bronze cast. In order to examine distribution of Sn as a major alloying element and
Zn, Pb and Fe as trace elements larger area line scans were performed using PIXE
(proton induced X-ray emission). Furthermore, the PIXE elemental maps allowed
calculation of the homogeneity factor. The areas which have showed large scale
inhomogeneities were subsequently examined by the means of PLP (potentiodynamic
linear polarization) measurements, which were able to confirmed higher potential
appearance of galvanic corrosion for those regions.

124

PA-9
Contribution of tin compounds to protective properties of patina
layers on statuary bronzes
D. atovi1, L.Valek2, V. Desnica1, S. Martinez2, S. Fazini3, . Pastuovi3
Department for Conservation and Restoration, Academy of Fine Arts, Ilica 85,
HR-10000 Zagreb, Croatia
2
Department for Electrochemistry, Faculty of Chemical Engineering and
Technology, Savska cesta 16, 10000 Zagreb
3
Laboratory for Ion Beam Interactions, Rudjer Boskovic Institute, Bijenicka 54,
HR-10000 Zagreb, Croatia

Outdoor bronze statues are usually exposed to aggressive environmental

conditions thus covered with patina layers containing various constituents. Influence
of sulfates is indicated as most important for creating patina layers under urban
conditions.
Majority of corrosion products in patina were identified as copper products
but several studies have indicated the presence of tin compounds within naturally
formed patinas on bronzes in atmospheric environments.
In the present work, contribution of these tin-containing compounds
to the protectiveness of a patina layer on statuary bronze (CuSn6) have been
investigated.
Artificial patina layers have been formed on bronze samples in 15mM
Na2SO4 solution by immersion. The Cu/Sn ratio in patina layer was monitored versus
immersion time using PIXE (proton induced X-ray emission) and the correlation
between immersion time and Cu/Sn ratio was determined.
The protective properties of patina layer have been determined by the method
of electrochemical impedance spectroscopy. To avoid the contribution of increasing
thickness of patina layer to corrosion resistance due to increased immersion time,
the referent set of pure copper samples was immersed in the same solution as
CuSn6 samples and measured at same time.
These measurements helped establish correlation between protective
properties of patina layer and Cu/Sn ratio in patina layer, and gain better understanding
of bronze corrosion in neutral aqueous solutions.

125

PA-10
Physicochemical investigation of late Bronze Age artifacts using
EDXRF Spectrometry
V. Andri1, M. Stojanovi2, S. upi1, D. Jovanovi3
1

VINCA Institute for Nuclear Sciences, Belgrade, Serbia

2
National Museum Belgrade, Serbia
3
City Museum, Vrac , Serbia

The region of Vrako Gorje is exeptional for its large concentracion of

hoards with metal artifacts because it was the crossroad for the trade routs and
conection between the most important metalurgical centres from late Bronze Age
situated between rivers Sava and Danube and Transilvania as a major source of
copper. This hoards consist usualy of varios objects and besides the fragments of
bronze artifacts, very often the ingots of pure copper can be found. A main goal of
this investigatons was to reveal informations regarding used metalurgical processes
in weapon manufacturing ( knives, daggers and spears ) in that period, origin source
of raw materials and trading routes for final products.
Physicochemical investigation process was divided in two phases. First,
undestructive analysis of all artifacts was performed using EDXRF spectrometry with
radioisotope excitation sources 109Cd and 241Am and Si(Li) semiconductor detector.
All the artifacts was cleaned from surface corrosion layer on the investigated area.
With this results we have a good insight in the composition of the analyzed artifacts.
All the artifacts was made from bronze with average copper content of 93% and
average tin content of 6% with arsenic, antimony, lead, iron, silver, zinc and nickel as
minor or trace elements. On the other side analysis of the ingots showed that they
are made of almost pure copper with average content of 97% and with no traces of
tin, lead and antimony. All these results confirmed that the manufacturing process
involved melting and mixing recycled bronze and pure copper ingots for making
suitable material for weapon production.

126

PA-11
Analysis of the enamel of Benvenuto Cellinis Saliera using
XRF, confocal XRF and SEM/EDX
K. Uhlir1, M. Griesser1, H. Hanzer2, P. Wobrauschek3, C. Streli3, G. Buzanich3,
D. Wegrzynek4, A. Markowicz4 and E. Chinea-Cano4
Conservation Science Department, Kunsthistorisches Museum, Burgring 5,
A-1010 Vienna, Austria
2
Restoration Department, Collection of Sculpture and Decorative Arts,
Kunsthistorisches Museum, Burgring 5, A-1010 Vienna, Austria
3
Atomic Institute (ATI) Vienna University of Technology,
Stadionallee 2, A-1020 Vienna, Austria
4
Agencys Laboratories Seibersdorf, International Atomic Energy Agency (IAEA),
Reaktorstrasse 1, A-2444 Seibersdorf, Austria
1

Before re-exhibiting Benevenuto Cellinis Saliera in the permanent exhibitions

of the Kunsthistorisches Museum (KHM) it has to be restored. For this purpose the
compositions of its gold alloy and especially of the differently coloured enamels present
were studied by non-destructive X-ray Fluorescence Analysis (XRF). Using XRF for the
investigation of the enamel is a delicate matter, as the analysis in air leads to absorption
of the x-ray radiation of the light fractions in the matrix - mostly sodium, one of the main
components. To solve this problem a portable prototype XRF-instrument equipped with a
compact vacuum chamber [1-3] to reduce absorption in the excitation and fluorescence
radiation path could be used due to a co-operation with the International Atomic Energy
Agency (IAEA), Seibersdorf Laboratories, and the Atomic Institute of the Austrian
Universities (ATI).
For reasons of comparison some minute enamel chips already detached from
the Saliera were analysed by Scanning Electron Microscopy with Energy Dispersive
X-Ray Detection (SEM/EDX). Additionally, the elemental distribution of one of these minute
enamel chips was verified by confocal XRF performed at the Seibersdorf Laboratories
of the IAEA. A clear insight into the inhomogeneous character of the enamel chips could
be gained. Hence, some differences in the quantitative results of XRF versus SEM/EDX
investigations can be explained.
Although it was possible to perform semi-quantitative analysis on the enamels
of the Saliera using XRF, it became evident during the measurements that some
improvements concerning the shape of the measuring head, and therefore the vacuum
chamber, as well as some technical improvements could lead to better results and easier
accessibility of the different parts of the Saliera and comparable objects. Therefore, a
new research project funded by the FWF (Austrian Science Fond) building an enhanced
version of the vacuum chamber equipped instrument has just started.
[1] P. Wobrauschek, B. Frank, N. Zoeger, C. Streli, N. Cernohlawek, C. Jokubonis,
H. Hoefler, Advanced X-ray Analysis, 48 (2005) 229-235
[2] C. Streli, N. Marosi, P. Wobrauschek, B. Frank, The RIGAKU Journal, 20, No.
2 (2003) 25-29
[3] G. Buzanich, P. Wobrauschek, C. Streli, A. Markowicz, D. Wegrzynek, E.
Chinea-Cano, S. Bamford, Spectrochimica Acta B, special issue of ICXOM 2005,
Frascati, submitted

127

PA-12
Chemical and structural features of the Neolithic pottery from
Alba Iulia-Lumea Noua (Romania) archaeological settlement
S. Varvara1, B. Fabbri2, S. Gualtieri2 and M. Gligor3
Topography Department, 1 Decembrie 1918 University, 11-13 Nicolae Iorga St.,
510009 Alba Iulia, Romania
2
CNR, Institute of Science and Technology for Ceramics, 64 Via Granarolo, 48018
Faenza, Italy
3
Archaeology Department, 1 Decembrie 1918 University, 11-13 Nicolae Iorga St.,
510009 Alba Iulia, Romania
1

The paper focuses on the investigation of the Neolithic pottery discovered at

Alba Iulia-Lumea Noua archaeological settlement, in the middle basin of the Mures
River (Romania) in order to achieve information about the possible provenance
and manufacturing technique used for their production. Four samples of raw clays
originating from different natural deposits situated in the surroundings of the site
have also been analyzed. A multianalytical approach was adopted; chemical,
mineralogical, microstructural and petrographic features of the ceramic bodies
were determined by X-ray fluorescence, X-ray diffraction and optical microscopy,
respectively. Chemical composition of the slips and painting materials was identified
by SEM-EDS analysis.
The petrographic examination of the thin-sections allowed the individuation
of two different types of ceramic bodies, the primary distinction being related with
the presence or absence of different types of bioclasts. In spite of this, most of the
artefacts can be retained of local provenance.
The mineral phases of the ceramic bodies seem to indicate two ranges of
firing temperature; samples with high contents of illite were fired between 600-800C,
while the samples with low quantity of illite at higher temperature.
SEM-EDS and mineralogical analysis of the coatings and decorations
showed that the slips were obtained with specific raw materials, consisting very
probably of carbonatic clays with high content of illite. At the leather hardness state
the surface was polished and painted using iron-rich materials.
The comparison between the chemical composition of the potsherds and
of the raw clays does not show any overlap when major and minor elements are
considered, probably because of the textural and compositional variability of the raw
materials.

128

PA-13
PIXE characterization of particle modified consolidant applied to
quarried limestones
D. Krsti1, M. Jaki2, I. Boievi2 and D. Mudronja3
Arts Academy University of Split, Glagoljaka bb, 21000 Split, Croatia
2
Ruer Bokovi Institute, Bijenika 54, 10000 Zagreb, Croatia
3
Croatian Conservation Institute, Nike Grkovia 23, 10000 Zagreb, Croatia
1

The aim of this work is to evaluate the consolidation performance on different

types of Croatian limestones that were used for monuments in the past. The fresh
quarry samples have been consolidated with Particle Modified Consolidants (PMC)
consisted of a silicate matrix (Conservare OH-100) and colloidal alumina particles
(Al2O3). This composite has been chosen on the basis of a bibliographic research
aimed to better protection from salt crystallization damage [1]. The application
by capillary rise has been taken under laboratory conditions [2]. Different stone
types show different behaviours towards consolidation. Knowledge of consolidant
distribution within the porous stones is important in definition of more appropriate
consolidant for each particular case.
The evaluation of consolidation effect in the samples has been carried out
by the study of the depth profiles and elemental distribution of silicon and aluminium.
Analysis was performed by external beam millibeam as well as with in vacuum
microbeam PIXE spectroscopy. Additionally, the modification of the stone structure
induced by consolidation treatment has been examined by optical and electronic
microscopy. The differences between fresh and strengthen stone samples are
discussed. The results obtained in this investigation are significant because of their
contribution to better understanding of consolidation process in the stone.
This work may have important implication for specific conservation works:
the palace of Dioklecianus in Split, the cathedrals in Trogir and ibenik, and the
Arena (Roman amphitheatre) in Pula.
[1] C. Miliani, M. L. Velo-Simpson, G. W. Scherer, Journal of Cultural Heritage, 8
(2007) 1-6
[2] E. Aggelakopoulou, P. Charles, M. E. Acerra, A. I. Garcia, R. J. Flatt, G. W.
Scherer, Mat. Res. Soc. Symp. Proc. 712 (2002) 15-20

129

PA-14
Ban Chiang pottery from archaeological site of Thailand: study
of firing technique in ancient periods
W. Tanthanuch1, W. Pattanasiriwisawa1, W. Somphon1 and S. Srilomsak2
National Synchrotron Research Center, Nakhon Ratchasima, 30000, Thailand.
School of Ceramic Engineering, Institute of Engineering, Suranaree University of
Technology, Nakhon Ratchasima, 30000, Thailand.
1

The pottery shards excavated from the Ban Chiang archaeological siteUNESCO world heritage, Thailand, are best known for their beautiful designs
painted in red by ancient villagers made. The pottery assemblages are spanned from
pre-Metal, Bronze to Iron Age. With the aim of exploring the firing techniques used
for pottery production in ancient periods, X-ray absorption spectroscopy (XANES
and EXAFS) were used to measure Fe2+ and Fe3+ distribution in pottery and local
coordination environment of Fe atoms. Measurements were carried out at BL8 of
the National Synchrotron Research Center (NSRC), Thailand. Furthermore, a range
of analytical techniques, including XRD, XRF, IR, DTA and TGA were also used for
examination to get more information. Fe K-edge absorption spectra of the mixtures
standard iron compound and the red-clay ceramics fired under control conditions
allow us to determine the ferric/ferrous ratio and firing temperature of pottery shards.
The results revealed that the Pre-metal Age pottery was likely produced under
reducing atmosphere at temperature 1200 oC, while the Bronze and Iron Ages were
produced under partial reducing condition at temperature between 700 and 900 oC.
[1] E. Gliozzo, I. W. Kirkman, E. Pantos, I. Memmi Turbanti, Archaeometry, 46, 2
(2004) 227246.
[2] M. Matsunaga, I. Nakai, Archaeometry, 46,1 (2004) 103114.
[3] M. Wilke, F. Farges, P. E. Petit, G. E. Brown JR, and F. Martin, American
Mineralogist, 86 (2001) 714730.

130

PA-15
Micro-X-ray fluorescence and 3D confocal Micro-X-ray
fluorescence analysis of chinese ancient cultural heritages
Lin Cheng1,2,3, Xunliang Ding1,2,3, Rongwu Li4, Guoxia Li 5
The Key Laboratory of Beam Technology and Material Modification of Ministry of
Education
2
Institute of Low Energy Nuclear Physics , Beijing Normal University
3
Beijing Radiation Center, Beijing, 100875, China
4
Department of Physics, Beijing Normal Unviersity
5
Faculty of physical Engineering,Zhengzhou University,Zhengzhou 450052

Polycapillary X-ray optics can focus the X-ray beam produced from X-ray
sources into micro levels by external total reflected method [1].In this paper, the
setups of micro-X-ray fluorescence (MXRF) and 3D confocal micro-XRF and their
applications of analysis for the Chinese ancient cultural heritages in our Lab were
reported. The micro-XRF system was consisted of a rotating anode X-ray generator,
glass polycapillary X-ray optics, Si-PIN detector, XYZ sample stage, CCD camera
and associated electronics and a piece of ancient porcelain made in Ming Dynasty
decorated with blue-and-white glaze (AD 13681344),Jun porcelain and Ru porcelain
made in Song Dynasty(AD 9601276) were analysis by this instrument. 3D confocal
micro-XRF system was comprised of a low-power MCBM 50 X-ray tube combined
with focused polycapillary optics ( FWHM = 39 m, at 17.4 keV) manufactured by
our Lab. A Peltier cooled Si-PIN diode detector equipped with a polycapillary half
optics (FWHM = 30.9m, at 17.4KeV) in front of Be windows of Si detector. The two
lenses are situated perpendicular to each other in one plane, in such a way that the
intersections of the two focus spots form a confocal volume. Only fluorescent signals
generated in this volume will reach the detector. The depth analysis and elemental
mappings in a certain depth of Chinese ancient bronze plate made in Warring States
(B.C.770-476) and Heqigubronze mirror smelted in Eastern Han (A.D.25-220)
were analysis by this system. The characteristics and results of analysis of Chinese
ancient cultural heritages by micro-XRF and 3D confocal micro-XRF were reported
in this paper, also.
(Endnotes)
1

[] M.A. Kumakhov, E.F. Komarov, Phys. Rep. 191 (1990) 289

131

PA-16
XRF analysis of two terracota polychromated sculptures
by Pietro Torrigiano
A. Kriznar2, M.V. Muoz1, F. de la Paz1, M. A. Respaldiza2 and M. Vega1
Museo de Bellas Artes de Sevilla, Seville, Spain
Centro Nacional de Aceleradores, Universidad de Sevilla, Seville, Spain
1

The name of the sculptor Pietro Torrigiano was very well known already in
the 16th century, when he made most of his important works. Artists as Giorgio Vasari
or Benvenuto Cellini wrote about him in their books. He got his artistic education in
the heart of the Renaissance Italy, in the Academia of Florence, where he studied
under the custody of Bertoldo di Giovanni, together with Michelangelo. His restless
spirit made him travel around Europe, working for noble families, courts and the
catholic church. In 1522 he came to Seville where he carried out his latest, but
majestic artworks. Two of them, made around 1525 by order of Spanish Hieronymus
for their monastery, are exposed today in the Museum of Fine Arts of Seville: San
Jernimo (Saint Hieronymus) and Virgen de Beln (Virgin of Nativity).
Both sculptures were analysed by the non-destructive technique of X-ray
fluorescence. The equipment used has an X-ray tube of 30 kV with anode of W and
one SDD detector with energy resolution of 140 eV. By this technique, used directly
in situ in the exposition room, the support and the pigments were analysed.
The results of the first artwork, San Jernimo, show a great part of modern
materials applied, such as titan-zinc white (denoted by the elements Ti and Zn) or
lithopone (Ba, Zn). The sculpture was restored almost entirely. Its base and the upper
part of the cross are new. The original polychromation, that can still be detected in
some areas, show the use of lead white (Pb), yellow and red ochre (Ca, Fe), cinnabar
(Hg) and umbra (Mn, Fe). The raw material is terracotta (Mg, Al, Si, K, Ca, Mn, Fe),
used as well in the Virgen de Beln sculpture. The spectra of the figure of the Virgin
and child are different as those of the bench under them, which reveals that it is not
original and it was added later. Also in this sculpture modern pigments were found
(titan-zinc white, lithopone, cadmium red) that reveal restoration interventions. The
pigments applied are white lead, red ochre, cinnabar, blue azurite, some copper
based green pigment, umbra and an organic black pigment. Also the presence of
tin-lead yellow was detected. Some parts of the blue Virgins coat are gilded.

132

PA-17
Possibility of punctual XRF analysis for archaelogical pottery
classification
L. Bonizzoni1, A. Galli2 and M. Milazzo1
Istituto di Fisica Generale Applicata, Universit degli Studi di Milano, via Celoria
16, 20133 Milano, Italy
2
INFM and Dipartimento di Scienza dei Materiali, Universit di Milano Bicocca, via
R. Cozzi 53, 20125 Milano, Italy
1

The determination of elemental composition of archaeological pottery, with

particular attention to trace elements, allows the classification of the samples on the
basis of row clay provenance, applying multivariate analysis to the resulting data.
XRF analysis is an appropriate tool if it is possible to grind ceramics and analyze a
sample which is representative of the object. If we deal with particularly well preserved
objects, we are often not allowed to sampling them. Moreover, also moving these
objects from museum should be unfeasible.
The aim of this work is to evaluate if a punctual XRF analysis on integral
objects is adequate to classify row material provenance even if ceramics is not an
homogeneous material. We start from the consideration that, in order to have a good
classification through multivariate analysis, is enough that different measurements
on the same object give raise to the same grouping [1]. So we considered for each
sample several measurement points in polished areas and verified in which cases it
is possible to obtain equivalent quantitative results.
The test was conduct on a large set of samples of depurate Etruscan pottery
and sun-dried (but not fired) pottery from Indonesia. The results were compared with
those obtained with different analytical techniques. The limits and necessary working
conditions are discussed.
[1] E. Marengoet al., Analytica Chimica Acta, 537 (2005) 359 375.

133

PA-18
Wires and granulation in gold jewellery pastiches
V. Virgili1, M.L. Vitobello2 and M.F. Guerra3
University La Sapienza, Piazza Aldo Moro 2, 00186 Rome, Italy
European Jewellery Technology Network, CNR-IENI, Via San Pedrino 19, Paullo
(MI), Italy
3
Centre de Recherche et de Restauration des Muses de France, UMR 171
CNRS, Palais du Louvre - 14, quai Franois Mitterrand, 75001 Paris, France
1

The morphology and the elemental composition of granulation and wires

used in the decoration of ancient gold jewellery items provide information on the
goldsmiths manufacture techniques. The aim of this work is to evaluate how far
ancient goldwork can be authentified by coupling exam of these decoration elements
with analysis of their gold alloys, measured by different analytical techniques.
Granulation welded to gold sheets was produced by jewellers of EC
programme AUTHENTICO [1] with several techniques and gold alloys. The
morphology of both the granules and the joining regions was examined at low
(binocular) and high (SEM) magnification. Gold jewellery items either attributed to the
Etruscans or produced in the 19th century in the Etruscan tradition were examined
at low and high magnification and compared to features. These objects were also
analysed by PIXE with a 3 MeV proton and by SEM-EDX with an Oxford Link ISIS
system. We could show that exam is in some cases sufficient to authenticate the
objects while in the other cases the determination of the composition of the alloys
was required. Results by PIXE and SEM-EDX were compared.
[1] STRP CT-044480: Authentication methodologies for metal artefacts based on
material composition and manufacturing techniques.

134

PA-19
The use of EDXRF in gold alloys analysis: Instrumental set-up
and evaluation
I. Queralt1, A.M. Jurado-Roldn1 and J.Pujol2
Laboratory of X-ray Analytical Applications, Institute of Earth Sciences Jaume
Almera, CSIC, Sol Sabars, s/n 08028 Barcelona, Spain
2
Fischer Instruments, S.A.,Almogvers 157, 3a. Planta, 08018 Barcelona, Spain
1

In this work, we use a conventional low-cost EDXRF instrumentation to

evaluate the performances of this instrumentation for the analysis of different gold
alloys. The potential of X-ray instrumentation for the analysis of precious metals and
gold assaying routine had been recently pointed out [1]-[2].
Some different certified standards of gold alloys were analyzed at different
instrumental conditions in order to determine the accuracy and precision. In the work
we use up to four different primary filters and four different focal spots, modifying
the surface of analysis. The combined use of a motorized X-Y-Z stage and reduced
irradiation area allows us to also determine the homogeneity of gold alloys.
The results exhibit the usefulness of EDXRF for the analysis of gold alloys
al the levels of accuracy required by the official regulations in gold assaying, giving
additional information about the nature and content of gold-accompanying metals
[1] Marucco, A., 2004, Low-energy ED-XRF spectrometry application in gold
assaying. Nuclear Instruments and Methods in Physics Research B, 213:486-490.
[2] Jurado-Lopez, A., Luque de Castro, M.D. and Perez-Morales, R., 2006. Application
of Energy-dispersive X-ray Fluorescence to jewellery Samples determining Gold and
Silver. Gold Bulletin, 39/1: 16-21

135

PA-20
TXRF and underwater archaeology:
revealing the liquid into the bottle
C. Vzquez1,2, D. Elkin3 and S. Boeykens1
Laboratorio de Qumica de Sistemas Heterogneos. Facultad de Ingeniera.
Universidad de Buenos Aires. P. Coln 850 (C1063ACU). Buenos Aires, Argentina.
2
Comisin Nacional de Energa Atmica. Av. Gral Paz 1499 (B1650KNA) San
Martn. Buenos Aires. Argentina.
3
CONICET, 3 de Febrero 1378 (C1426BJN) BuenosAires, Argentina.
1

Each The knowledge of archaeological objects in terms of chemical

composition and or physical properties is mandatory for better understanding
technologies used in the past and preservation and conservation procedures
to be used in the future. These studies permits to answer questions concerned
with the history of civilization by using and developing scientific methods namely
physic chemistry, biology, etc. The tools that archaeometry field needs to achieve
successfully results are in the mostly analytical techniques.
In this paper, the applicability of TXRF as a powerful analytical tool to
discover the composition of a liquid inside a bottle found in the HMS Swift, a British
warship which sank off Patagonia in 1770 is demonstrated. This bottle was found
in the stern of the ship, inside a wooden box and together with assorted elements
which are preliminarily interpreted as personal belongings of one or more officers.
It still had a cork stopper in place and it was filled with a grey dispersion. In order
to characterize the dispersion found in the bottle, a microsample was submitted for
TXRF determination. The collected spectrum clearly showed the presence of Cl and
Hg signals which were quantified using Compton peak as internal standard. After
quantification, results perfectly match with Hg2Cl2 compound which was usually used
as bactericide at those times.
[1] D. Elkin, A. Argeso, M. Grosso, C. Murray, D. Vainstub, R. Bastida, V. DellinoMusgrave, The International Journal of Nautical Archaeology 36 (2007) 3258.

136

PA-21
SEM-EDX analysis of black-appearing Roman glass
S. Cagno1, V. Van der Linden1, O. Schalm1, K. Janssens1,
P. Cosyns2 and K. Nys2
Universiteit Antwerpen (UA), Department of Chemistry, (Universiteitsplein 1,
B-2610 Antwerp, Belgium)
2
Vrije Universiteit Brussel (VUB), Department of Art History and Archaeology,
(Pleinlaan 2, B-1050 Brussels, Belgium)

Artifacts of deeply colored, black-appearing glass were rather popular during

the Roman era, in the form of jewels or tableware. The aim of this work is that of
determining whether compositional changes, i.e. modifications in technology and
raw materials, did occur in the period considered (2nd century BC-4th century AD), by
analyzing a large number of samples originating from various locations in Europe
and in the Levant.
176 samples of deeply colored glass were embedded into acrylic resin, which
was mechanically ground and polished in order to obtain flat surfaces of unaltered
glass. The samples were then analyzed with SEM-EDX; quantitative analysis was
performed by using a standard-less ZAF-model. Further analyses are in progress,
included the trace element analysis via LA-ICP-MS.
The composition of the glass has proven to be that of typical Syro-Levantine
Roman glass, produced by mean of sand and natron in primary workshops in the
Levant. The characteristic black-appearing coloration is the result of the presence
of elevated levels of iron (intense green) or manganese (intense purple). Two ways
of obtaining the dark green hue are identified: this was achieved either by using
quartz-bearing sand that also contained various minerals (and hence containing a
certain percentage of iron), or by adding iron ore to the colorless glass. While the first
method is encountered with samples dated before 150 AD, the second procedure
was used from that period onwards in European objects, possibly a manifestation of
increased glass-working knowledge in the secondary workshops.

137

PA-22
Non-destructive, depth resolved Investigation of corrosion
layers of historical glass objects by 3D micro X-Ray fuorescence
analysis
I. Mantouvalou1, T. Wolff 1,2, W. Malzer1, M. Pagels1, L. Lhl1 , O. Hahn2 and B.
Kanngieer2
Institute for Optics and Atomic Physics, Technische Universitt Berlin,
Hardenbergstrasse 36, 10623 Berlin, Germany,
2
BAM Federal Institute for Materials Research and Testing, Unter den Eichen 87,
12205 Berlin, Germany
1

The investigation of diffusion processes can give insights into the aging
mechanisms of glass artefacts. In order to obtain concentration profiles of mobile
elements, like potassium and calcium, the method of choice should be non-destructive.
Our first results demonstrate the usefulness of the 3D micro X-ray fluorescence
spectroscopy (3D Micro-XRF) measurements for this kind of investigations [1].
"Reverse painting on glass" comprises a special technique of preparation:
glass plates were directly painted with oil- or resin-containing colors. Due to the
fact that acidic materials cause glass corrosion it is assumed that certain binding
media may initiate corrosion processes beginning at the interface glass/binding
material. This leads to "loss of adhesion" inside of reverse-glass paintings, eventually
destroying completely the decoration of the glass objects.
Measurements were carried out on a reverse-glass painting from the 19th
century. The painting shows strong corrosion at several sites. In order to characterize
the dissemination of the corrosion process we studied the composition of the glass
material depending on the distance to the interface glass/binding material within the
glass. Measurements have been carried out at the mySpot beamline of the Berlin
synchrotron BESSY.
We could demonstrate that a corrosion layer has formed between paint and
glass matrix. Lead and mercury ions migrate into the glass matrix originating from
the paint layer (lead white and cinnabar dispersed in oil) whereas lighter elements
such as manganese decrease in the corrosion zone.
[1] B. Kanngieer, I. Mantouvalou, W. Malzer, T. Wolff, O. Hahn, J. Anal. At.
Spectrom., DOI 10.1039/B717286A (2008) - in press

138

PA-23
Nondestructive on site analyses of Islamic glass in Egypt by
using a portable X-ray Fluorescence spectrometer
N. Kato1, Y. Shindo2 and I. Nakai1
1

Dept. of Applied Chemistry, Tokyo University of Science (1-3 Kagurazaka,

Shinjuku, Tokyo 162-8601 Japan)
2
Research Institute for Islamic Archaeology and Culture

When analyzing a large number of archaeological objects in a country like

Egypt, where it is strictly prohibited to take any artifacts to overseas, on site analyses
by using a portable XRF are quite effective. We have developed and brought portable
XRF spectrometers, OURSTEX 100FA series to the Missions research facilities in
Egypt. Adopting Moxtek AP3.3 polymer window for the SDD detector allowed us to
quantify the light elements like Na and Mg from 2006. This study focuses in particular
on Islamic glass excavated in the Raya (8-12th centuries, Director; M. Kawatoko),
one of the important port cities of Red Sea for the East-West maritime trade. Results
of more than 800 samples obtained from a three-year research are summarized.
In the Early Islamic period (eighth to ninth century), the glass based on the
natron as a soda source was mainly produced. Among this type of glass, Egyptian
natron glass objects with high content of Ti, Fe and Zr were characterized in more
detail based on the lime content. Meanwhile, the glass vessels with low content of Ti,
Fe and Zr, and high Ca/Sr ratio seem to be imported from the Syro=Palestine region.
From the ninth century, gradual transition from the natron glass to the plant-ash glass
was observed based on their Mg and K levels. The newly developed XRF for the light
elements made it possible to distinguish them clearly. Furthermore, it was found that
the glass vessels with high MgO/CaO ratio (> 0.45, proportion by wt%) consisted
mainly of colorless cut glass. Our compositional and archaeological insights suggest
the possibility that these colorless vessels were produced in the Mesopotamian
region. By adopting a portable XRF for on site analyses of archaeological samples,
multielemental information from a large number of excavated objects were
obtained.

139

PA-24
A quantification approach for portable -XRF spectrometers
V. Kantarelou, D. Sokaras and A. G. Karydas
Laboratory for Material Analysis, Institute of Nuclear Physics, N.C.S.R Demokritos,
153 10 Aghia Paraskevi, Athens, Greece
In -XRF analysis a polycappilary X-ray lens is usually utilized in the
excitation channel to collect very efficiently, propagate and focus down to few tens
of micrometers the exciting X-ray beam radiation. On the other hand, the X-ray lens
introduces major difficulties in quantification, since its transmission efficiency being
highly dependent on the transmitted X-ray energy results to a significant and not
easily predicted modification of the energy distribution of the primary tube spectrum.
Direct and indirect methods have been proposed towards an analytical description
of the lens transmission efficiency [1-2].
In the present paper we propose a different analytical approach that provides
an analytical description of the lens transmission efficiency. A theoretical FPA model
was developed based on Ebels description for the tube emission spectrum [3] and
on a transmission efficiency expressed as polynomial of 5th degree versus energy.
Measured and theoretically predicted characteristic K- or L- line intensities emitted
by a large set of pure single element or compound targets (1.5 25 keV), with
infinite or very small thickness were compared through X2 minimization procedure
with fitted parameters the coefficients of the transmission efficiency function.
For the measurements a -XRF set-up consisting of a Rh microfocus X-ray tube
operated at 50kV, a polycapillary X-ray lens and a Si-drift X-ray detector was used.
The agreement between theoretical and experimental elemental intensities at the
convergence minimum was equal or better than 10%. The developed FPA model
was next validated in reproducing concentrations of ten NIST and BAM SRM glasses
with deviations less than 10%-15%.
The proposed analytical approach has the advantage that does not require
any removal of the X-ray lens from the -XRF setup configuration and it can be
adapted in commercial -XRF spectrometers supporting a FPA methodology towards
quantification in -XRF analysis.
[1] T. Sun and X. Ding, X-Ray Spectrom., 35 (2006) 120-124
[2] R. Padilla, P.Van Espen, A. Abrahantes, K. Janssens, X-Ray Spectrom. 34
(2005) 19-27
[3] H. Ebel, X-Ray Spectrom. 28, (1999) 255-266.

140

PA-25
Extended calibration procedure for the determination of microXRF excitation spectra
T.Wolff1,2, W. Malzer2,*, I. Mantouvalou2, O. Hahn1 and B. Kanngieer2
1

BAM Federal Institute for Materials Research und Testing, Unter den Eichen 87,
12205 Berlin, Germany
2
Institute for Optics and Atomic Physics, Technische Universitt Berlin,
Hardenbergstrasse 36, 10623 Berlin, Germany,
*
current affiliation: Brucker AXS Microanalysis

Quantitative XRF based on fundamental parameters requires an accurate

knowledge of the excitation spectrum. In case of a conventional setup this spectrum is
given by the x-ray-tube-spectrum and can be calculated. [1]. The use of polycapillary
optics in micro XRF spectrometers changes the spectral distribution of the excitation
radiation. For that reason it is necessary to get access to the transmission function
of the used optic.
Several authors have described experimental methods to determine the
transmission of polycapillary optics for example with pinhole- or knife-edge-scans
or with scatter measurements (e.g. [2]). In all these procedures it is necessary to
remove the optic from the source to measure a pure tube spectrum as reference for
the determination of the transmission function.
Due to the fact, that many commercial spectrometers are not designed
for removing the optic from the x-ray-tube, those methods are often not possible.
Furthermore the transmission depends on the current adjustment of the lens. It
may also change for different tube-operation-voltages. For that reasons a pure
transmission curve, measured under specific conditions, is not the correct function
to determine the actual excitation spectrum.
To overcome these problems a new calibration procedure has been
developed, which allows the user to determine the lens-transmission, without
changing the experimental setup. The result of that calibration is the product of the
geometrical factor and the transmission values for different energies. Fitting those
results with a suitable function, delivers a relative transmission curve, that can be
used to solve the Sherman equations.
The results are compared with experimental determined transmission
functions of the used optic. The quality of the determined excitation spectrum is
verified on the one hand, by a conventional calibration with different standards and
on the other hand by comparing calculated concentration of measured standards
with certified values.
[1] H. Ebel, X-Ray-Spetrom., 28 (1999) 255-266
[2] M. Haschke, M. Haller, X-Ray-Spectrom., 32 (2003), 239-247
141

PA-26
Intelligent computational infrastructure for XRF-based
investigations
E.Cherkashin1, M.Granin1 and T.Cherkashina2
Institute of System Dynamics and Control Theory of SB RAS,
Lermontov str. 134, Irkutsk, Russia, 664033
2
Institute of Earths Crust of SB RAS, Lermontov str. 128, Irkutsk, Russia, 664033
1

The aim of the research is to develop a number of computational technologies

and corresponding software to support interdisciplinary natural science investigations.
The following problems are under consideration:

Consolidation of instrumental and analytical software in a distributed software

environment, supporting automatic data transformation.

High performance computational resources usage, such as GRIDs.

Developing intelligent subsystems in the software allowing automation

of some aspects of creative activity of analysts, such as experiment and
analysis planning, XRF appliance control, data analysis on their quantitative
characteristics, e.g., on the base of expert systems.

Resultant data description, namely, automatic creation of self-describing

electronically reusable hypertext tagged parts of scientific reports, selfadopting user interfaces of the software.

The above mentioned problems connected with increasing the precision

of element concentration determination in samples, automatic analytic techniques
synthesis, and analytic process control and planning, reducing human intervention
during exploration, automatic resultant data processing and visualization, and
consolidation various stages of an interdisciplinary science investigation in one
virtual distributed investigation process.
Some pioneering applications and technologies have been developed,
such as follows. Intelligent application, based on expert system technologies, for an
appliance control and experiment planning, including automatic certified reference
materials choose, system of calibration equation construction based on possible
logical analysis of reciprocal line overlaps. A special microformat is been developing
for data description, which allows to describe resultant data in scientific reports
presented in well-known Internet hypertext format (HTML); microformat technology
is a kind of Semantic Web technologies, a nowadays Internet development direction.
An approach to construct user interface for modularized analytical software has been
proposed, an example of the interface has been developed; the interface allows
user to view the research plan in various detail degree and generate corresponding
repots.
The work is carried out under support of Russian Foundation for
Fundamental Research, grant No 07-05-01061, and Presidium of Russian
Academy of Sciences, scientific program No 16 project No 10.
142

PA-27
Thin film samples as reference samples for micro XRF
R. Simon2, G. Falkenberg3, R. Dietsch1, U. Fittschen4, D. Weissbach1
1

AXO DRESDEN GmbH, Heidenau, Germany; 2Karlsruhe Institute of Technology,

Germany; 3HASYLAB at DESY, Hamburg, Germany; 4University of Hamburg,
Germany

An ideal reference sample for the calibration of the sensitivity of micro-XRF

set-ups has negligible absorption of exciting and fluorescent radiation, high degree
of uniformity and homogeneity and emits a multitude of non overlapping x-ray
fluorescence lines over a broad spectral range with suitable intensity. Free standing
thin films (FSTF) can meet these requirements; unfortunately after the discontinuation
of NIST SRM 1832/1833 suitable reference materials are no longer commercially
available. Therefore a project was started to develop FTSF into functional reference
materials and first test samples have been produced by stacking thin metal films
using PVD at AXO Dresden. As support we used Ultralene foil and recently Si3N4
membranes. The deposition technique assures very homogeneous layers and a
large degree of flexibility regarding the choice of elements and mass densities.
The samples were characterized by ICP-OES at the University of Hamburg
and by micro-XRF at Hasylab and ANKA. The ICP-OES measurements on eight
sample foils show a very good reproducibility of the elemental depositions. The
statistical evaluation of micro-XRF mapping data, obtained with beam sizes of 1.5m
to 100m and beam energies up to 26 keV, limited mass deposition heterogeneities
to below 1% RMS for most elements even at 1.5m resolution. Very recently Si3N4
membranes have been tested as supports, since they can withstand very high
radiation intensities. First XRF measurements indicate that these samples are
equivalent in terms of homogeneity with the polymer foil based samples.
First applications of these FTSF aimed at assessment of absolute lower
detection limit and characterization of depth resolution and sensitivity of confocal
set-ups.

Fig. Micro-XRF measurements of sample sf1 (beam size 5 m, 26 keV excitation

energy, sum spectrum).
143

PA-28
X-ray fluorescence enhancement induced by photo-electrons
secondary excitation
D. Sokaras1, M. Kolbe2, M. Gerlach2, A.G Karydas1, B. Beckhoff2, C. Zarkadas1,*
Institute of Nuclear Physics, N.C.S.R. Demokritos, Aghia Paraskevi, 15310,
Athens, Greece
2
Physikalisch-Technische Bundesanstalt, Abbestr. 2-12, 10587 Berlin, Germany
*current affiliation: PANalytical B.V., 7600AA Almelo, The Netherlands
1

Well established values for the X-ray fundamental parameters are very
important but not enough for an accurate reference-free x-ray fluorescence
quantification analysis. Secondary ionization processes following photon induced
primary ionizations in matter may contribute significantly to the detected fluorescence
radiation introducing significant errors in XRF quantitative analysis, if not taken into
account properly.
In the present work, the relative enhancement to the primary fluorescence
intensity from ionizations induced by secondary photo-electrons is studied both
experimentally and theoretically. Several targets of Mg, Al and Si with few micrometers
thickness and a wide range of exciting monoenergetic X-ray beams (2-30keV) were
utilized in the study. Measurements have been performed in the PTB Laboratory
and at the BAMline wave-length shifter at the synchrotron storage ring BESSY II
with a fully characterized experimental setup of the PTB, consisting of a calibrated
Si(Li) detector, calibrated photodiodes and a well known geometry with calibrated
diaphragms. Experimental values of the relative enhancement to the fluorescence
intensity due to photoelectrons were determined with low uncertainty. Additionally,
intensive Monte Carlo theoretical calculations for all the experimental cases have
been accomplished. The simulation codes have been developed implementing both
Geant4 [1] and Penelope2006 [2] toolkits. The crucial performance of the databases
for electrons ionization cross sections have been tested and evaluated for both codes
using CASINO simulation tool for electron trajectory [3]. The powerful computer
cluster zeus at the Institute of Nuclear Physics (over 60 Xeon processors)
hosted the long time simulation runs (up to 20 billions events per exciting energy).
Experimental measurements and simulations are compared and discussed.
[1] S. Agostinelli et al., Nuclear Instruments and Methods in Physics Research
Section A, 506( 2003), 250-303.
[2] F. Salvat, J.M. Fernandez-Varea, J. Sempau, Proc. Nuclear Energy Agency
Workshop, (2006).
[3] D. Drouin, A. R. Couture, D. Joly, X. Tastet, V. Aimez, R. Gauvin, Scanning, 29
(2007) 92 101.

144

PA-29
New XRF software packages for the application
of the fundamental algorithm in practice
Richard M. Rousseau
Geological Survey of Canada, 601 Booth St., Room 707, Ottawa, Ont., K1A 0E8,
Canada
Newly developed XRF software allows chemical composition calculations
using the Fundamental Algorithm in X-Ray Fluorescence (XRF) analysis. It was
designed by an XRF analyst, for XRF analysts, having in mind their day-to-day
routine XRF analysis. Three different software packages are available: CiROU, CiLT
and CiREG, each one using the same user-friendly Windows-based interface. The
CiROU and CiLT packages allow the XRF analyst in particular to select analytes,
calculate the X-ray tube spectra and theoretical influence coefficients, calibrate, read
files of measured intensities, calculate net intensities and sample compositions, and
print a report. The CiREG package does all the same thing, except by using empirical
influence coefficients.
CiROU is applicable to samples of any composition with the utmost accuracy
that can be obtained from a Fundamental-Parameters method. Its unique calibration
procedure further adds to the accuracy by eliminating the bias between theory and
experimental data. In addition to its unsurpassed accuracy, CiROU is faster than any
other sophisticated program for XRF analysis.
CiLT uses the Lachance-Traill algorithm with theoretical constant influence
coefficients. Consequently it is limited to a smaller range of compositions (0 10%).
It is the optimal program to use with fused discs. In this case, CiLT takes into account
the ratio sample/flux and the composition of the flux. Another fine feature of CiLT is
its capability to manage with accuracy the loss of volatile components during the
preparation of fused discs. No matter that the fused disc is prepared with the burned
sample, or the original one, no matter if the LOI is known or not, CiLT can calculate
in all the cases the sample composition with accuracy.
CiREG uses the Lachance-Traill algorithm with empirical constant influence
coefficients, which are calculated by regression analysis. This program has been
written for application to non-homogeneous materials that cannot be analyzed
from fundamental principles. Surface, particle size and mineralogical effects are
compensated for by comparing the unknowns to a large number of standards similar
to them and prepared in the same way.

145

PA-30
Measurements and Monte Carlo calculations of X-ray
fluorescence K/K ratios for layered specimens
T. Trojek1 and D. Wegrzynek2, 3
Czech Technical University in Prague, Behov 7, 115 19 Praha 1, Czech Republic
2
IAEA Seibersdorf Laboratories, A-2444 Seibersdorf, Austria
3
Faculty of Physics and Applied Computer Science, AGH University of Science and
Technology, Al. Mickiewicza 30, 30-059 Krakow, Poland

The quantitative X-ray fluorescence analysis of an untreated specimen can

be inaccurate due to possible depth inhomogeneous distribution of elements. As
has been already shown in [1], so called depth heterogeneity can be recognized
by means of K/K ratios of all elements identified in a specimen. The principle of
the proposed technique lies in the different attenuation coefficients of the K and
K lines. If an element is present at some depth in the specimen, its characteristic
radiation has to penetrate a thick layer of the matrix, and the characteristic X-ray
intensities can be significantly changed.
This contribution shows how the K/K ratios depend on depth distribution
of elements. The experiments were performed for specimens made of various thick
substrates covered with one or two intermediate thick mono-elemental layers (Ti,
Fe, Ni, and Cu). The K/K ratios of elements present in a substrate and in layers
were measured and then compared with the ratios obtained with the Monte Carlo
computer code MCNPX [2]. Good correspondence between the experimental and
the calculated values was achieved. The results demonstrate also the influence of
inter-layer enhancement effect due to secondary emission of characteristic X-rays.
It has been demonstrated that Monte Carlo simulations with the code
MCNPX make it possible to predict the K/K ratios for arbitrary chosen distribution
of elements in a specimen. The code can be applied to estimate the depth distribution
of elements in a layered sample and for measurements of coating thicknesses, etc.
[1] T. Trojek, T. echk, L. Muslek, Nucl. Instr. and Meth. in Phys. Res. B 263
(2007) 7678.
[2] T. Trojek, T. echk, Nucl. Instr. and Meth. in Phys. Res. B 263 (2007) 7275.

146

PA-31
An algorithm to for calculation of atomic density factors used in
facilitating calculation of x-ray production cross sections from
raw data
K. Streib, T. Alford and J. Mayer
Arizona State University School of Materials, P.O. box 878706, Tempe, AZ
85287-8706 USA
A method is developed for calculating density factors for various crystal
structures which can be easily incorporated into computer software designed
to calculate x-ray production cross sections from raw data, such as x-ray counts
extracted from spectral data. The advantage of this algorithm is that it will aid in the
calculation of x-ray production cross sections from data acquired experimentally, by
allowing the atom density of crystalline substances to be determined from readily
obtained parameters. This method is then used to calculate various density factors
for FCC, BCC, diamond cubic, HCP, and ionic structures. These density factors can
then be used to find x-ray production cross sections.

147

PA-32
Simulation of environmental aerosol loaded filters for ED-XRF
analysis by partial least squares
G. W. W. Wepukhulu1, H. K. Angeyo1, O. A. Mustapha1 and M. Mangala2
Department of Physics, University of Nairobi,
Institute of Nuclear Science and Technology, University of Nairobi,
P.O. Box 30197 00100, Nairobi, Kenya
1

Environmental pollution is a problem of global concern. Its quantitative analysis

requires the use of certified reference materials (CRM) for quality control. This has
remained a difficult analytical problem due to unavailability of such CRMs in required
amounts and lifetime. Analysis of this pollution poses even a greater challenge due
to its multivariate nature. Laboratory reference material (LRM) was simulated for this
purpose. This work details methodology of making such LRMs, spectral acquisition
and resolution, quantification, accuracy, precision and range. The robustness of
partial least squares (PLS) as an alternative quantitative procedure was constructed
for energy dispersive X-ray fluorescence (EDXRF) analysis. EDXRF spectra were
acquired directly and used to build a training set based on the total fluorescence
spectrum after normalization using principle component regression (PCR). Both
standard solutions and analytical-grade salts were used to make a homogenous
mixture that was deposited onto 0.45m membrane filters, dried in ambient air
at standard room conditions of temperature and pressure, and then analyzed by
radioisotope-excited EDXRF spectrometry. Two analytical methods were used and
compared. Unlike Fundamental Parameter Method (FPM), the heavy metal (Ti, V,
Cr, Mn, Fe, Co, Ni, Cu, Zn, Hg and Pb) loadings acquired via PLS demonstrates the
comparative advantage and potential for fast, non-invasive, and accurate EDXRF
analysis of trace metals in environmental aerosols. Homogeneity between filter
loadings was evaluated using relative standard deviation at an average of 5%. The
PLS procedure including validation and prediction was done using Statgraphics
Centurion XV and Unscrambler 8.0 software.

148

PA-33
Standardless material identification
V. Riger. M. Hofmann, and B. Nensel
Helmut Fischer GmbH Institut fr Elektronik und Messtechnik, Industriestrae 21,
D 71069 Sindelfingen, Germany
A new technique has been developed to identify unknown samples or
materials utilizing only pre-calculated spectra. This provides a more universal
and flexible approach than the traditional methods based on measured spectra of
reference samples.
For practical analysis there are several advantages with the new method. No
inventory of a large base of standard reference materials is needed. The meaning
of material can be extended to a class of material which covers predefined
concentration ranges. Coated alloys and multi layered samples can be included
which are defined by related thickness ranges. For practical application, the class of
material has to be defined only by element concentration and/or thickness ranges
there are no other requirements. After having performed a theoretical calculation of
the spectra according to their class of material definition any measured spectrum
of an unknown sample can be specified as IN or OUT with respect to the
defined class of material. The respective data files which include all the necessary
information to identify an unknown material can be exported to another instrument
without any further setup and calibration.
This identification tool can be used for any application and is especially
helpful when otherwise no standards are available. We will present practical
examples for RoHS and precious metal analyses. The method will also assist the
user to identify the correct measurement application which can then be used to
make a full quantitative analysis.

149

PA-34
Micro distribution of biologically important metals in primary
invasive ductal carcinoma of breast
M.J.Farquharson1, A. Al-Ebraheem1, R.Leek2, A.L.Harris2, G. Falkenberg3,
R.Simon4, D.A.Bradley5 and K.Rickers3
Department of Radiography, City Community and Health Sciences, City
University, London, EC1V 0HB, UK.
2
Cancer Research UK, Oxford Cancer Centre, Molecular Oncology Laboratories,
University of Oxford, Weatherall Institute of Molecular Medicine, Oxford, UK
3
Hamburger Synchrotronstrahlungslabor at Deutsches Elektronen-Synchrotron,
DESY, Notkestr. 85, D-22603, Hamburg, Germany
4
ANKA Forschungszentrum Karlshruhe, Institut for Synchrotronstrahlung (ISS,)
Eggenstein, Germany
5
Department of Physics, University of Surrey, Guildford, Surrey, UK
1

A micro beam synchrotron x-ray fluorescence (SRXRF) technique was

used to determine the localisation of metals in primary invasive ductal carcinoma
of breast. The work was carried out at two facilities, namely the Hamburger
Synchrotronstrahlungslabor at Deutsches Elektronen-Synchrotron, DESY, Germany
and ANKA, Forschungszentrum, Karlsruhe, Germany. A number of samples were
examined which were formalin fixed tissues arranged as micro arrays of 1.0mm
diameter and 10m thickness. Maps of the elements Ca, Fe, Cu and Zn, which
are of physiological importance, are presented. The distribution of these metals
was obtained at approximately 18m spatial resolution at DESY and approximately
3m at ANKA. The distributions are compared with light transmission images of
adjacent sections that are H and E stained to reveal the location of the cancer cell
clusters. Correlations were found between these reference images and the elemental
distributions indicating an increase in all element concentrations in the tumour regions
of all samples, with the exception of Fe, which in some cases showed a reverse of
this trend. On average over all samples the percentage difference from the normal tissue
elemental concentrations are Ca 67%, Cu 64% and Zn 145%. Micro X-ray absorption
near edge structure (XANES) spectroscopy was used to estimate the oxidation
state of Cu in normal and tumour regions. Tumour regions were found to have a
higher fraction of Cu+ compared to the normal samples.

150

PA-35
Biological study using X-Ray microfluorescence images
I.Lima1,2, M.J.Anjos3, J.T.Assis2, T.U.Pantaleo4, V.M.Correa da Costa4,
M.L.Farias5, E.Sales1 and R.T.Lopes1
1

Nuclear Instrumentation Laboratory, Federal University of Rio de Janeiro, Brazil.

P.O.Box:68.509, Zip Code: 21941-97
2
Engineering and Energy Department, IPRJ, State University of Rio de Janeiro,
Brazil
3
Physics Institute, State University of Rio de Janeiro, Brazil.
4
Biophysic Institute, CCS, Federal University of Rio de Janeiro, Brazil
5
University Hospital, Federal University of Rio de Janeiro, Brazil.

The bone structures consist essentially of a protein and hydroxyapatite. Trace

elements are found in both mineral and organic phases, although their role in normal bone
function and in bone pathology is not fully established. In this context, the knowledge of major
and trace elements is very significant to elucidate some important questions that remain
unanswered or are controversial about bone alterations such as aging process.
Several kinds of imaging techniques can be useful to access morphology and
the minerals present in osteoporotic bones. In this work, Synchrotron Radiation by X-Ray
Microfluorescence was used as an X-Ray imaging technique to investigate bone structures.
Therefore, this research aims to improve the knowledge about some aspects of bone quality
and its relationship with bone strength.
The measurements were performed at the Brazilian Synchrotron Light National
Laboratory on the XRF beam line. This line is equipped with an HPGe detector with a
resolution of 150 eV at 5.9 keV, a white beam, and the sample holder is placed at 45o in
relation to the detector and the incident beam. The beam is focused by a fine conical capillary
which provides X-Ray microbeam of 20 m diameter. To perform the experiment, the samples
were placed in a mylar adhesive tape, positioned in the experimental set up. The spectra were
acquired in 10 s and 200 s to perform 2D images and single profiles respectively. No sample
preparation was required and the experiment was performed in vertebrae and femur bone
sites (in several positions) with 150 m of thickness approximately. It was also measured
NIST Standard Reference Material (bone ash and bone meal SRM 1400 and SRM 1486)
in order to evaluate our experimental method. The sample holder has complete translational
capacity and all the stages are fully remote controlled. The XRF images were acquired over
a range area equal to 0.87mm2 approximately which corresponds to a matrix equal to 30x30
points2 respectively.
The results showed that the elemental distributions in bone zones in microns order
were very helpful to understand those functions in such structures. Although Ca and P are
the main component of bone as hidroxyapatite, other elements, such as S, K, Cu, Zn and
strontium were also found in all the investigated bone sites. X-Ray microfluorescence images
and profiles by synchrotron radiation can be an efficient and a non destructive technique to
evaluate the distribution of minerals in bone samples and useful to provide information about
the differences found between vertebrae and femurs sites. Using this methodology we show
that the bone quality can and must be evaluating not only by the architecture of the bones but
also to take into account the concentration and the distribution of chemical elements which
have important contribution on bone strength, such as Sr and Zn, specially to demonstrate
alterations in bone morphology in the aging and osteoporosis processes.

151

PA-36
SR-XRF analysis of trace amounts of Pt in gold alloys
M. Radtke1, H. Riesemeier, I. Reiche2 and M.F. Guerra 2
1

Bundesanstalt fr Materialforschung und prfung (BAM), Richard-WillsttterStrae 11, 12489 Berlin, Germany
2
Centre de Recherche et de Restauration des Muses de France, UMR 171
CNRS, Palais du Louvre - 14, quai Franois Mitterrand, 75001 Paris, France

Pt provides important information on the origin and provenance of ancient

gold. Among the few analytical techniques available to non-invasively measure low
contents of Pt in gold [1], SR-XRF fulfils all the necessary requirements.
In our first attempt we used excitation energy at the PtL3-edge (11.564keV)
taking into account the resonant Raman scattering [2]. The MDL was estimated to
20ppm. In order to improve the MDL and avoid the difficult quantification process, we
made new developments of both the analytical SR-XRF set-up and the quantitative
calculation procedure with excitation energy at the PtK-edge [3]. The MDL was
estimated to 40-90ppm using the PtK1 line, but the unknown thickness of small
and thin gold items is a significant source of error for quantitative analysis.
The aim of this work is to present the most recent developments of the
determination of Pt with excitation energy at the PtL-edge and a Si SDD detector
accepting higher count rate. At the chosen energy of 11.58keV we could reach a
MDL of 3.1ppm.
[1] M.F. Guerra, Nucl. Instr. and Meth. B 226 (2004) 185.
[2] M.F Guerra, T. Calligaro, M. Radtke, I. Reiche, H. Riesemeier, Nucl. Instr. and
Meth. B 240 (2005) 505-511.
[3] M. F Guerra, M. Radtke, I. Reiche, H. Riesemeier, E. Strub, Nucl. Instr. and
Meth. (2008) in press

152

PA-37
Absolute determination of cross sections for resonant Raman
scattering on silicon carbide
M. Mller1, M.Kolbe1, B.Beckhoff1, K. Feldrapp2, S. Storm2, A.-D. Weber2
1 Physikalisch-Technische Bundesanstalt, Abbestr. 2-12, 10587 Berlin, Germany
2 SiCrystal AG, Gnther-Scharowsky-Str. 1, 91058 Erlangen, Germany
Reference-free total-reflection x-ray fluorescence analysis for the
quantification of surface contamination requires the accurate knowledge of all
experimental values as well as of the fundamental parameters involved [1]. Besides
the fundamental parameters of the contaminants also the parameters of the substrate
affect the result. To reduce the impact of tabulated data with unknown or estimated
relative uncertainties the resonant Raman scattering of X-rays in the vicinity of the K
absorption edge of silicon carbide has been studied. The investigation was carried
out at the plane grating monochromator beamline for undulator radiation of the PTB
laboratory at BESSY II in Berlin.
For the investigation a silicon carbide wafer was thinned to a thickness of
about 10 m to allow for transmission measurements to determine the absorption
correction factor for the fluorescence measurements. Cross sections were determined
absolutely for the energy range below the silicon K absorption edge of incident photons
with small relative uncertainties employing calibrated instrumentation avoiding any
reference samples. The experimentally determined values for this silicon compound
are compared to the values determined for pure silicon [2].
[1] B. Beckhoff, R. Fliegauf, M. Kolbe, M. Mller, J. Weser, G. Ulm, Anal. Chem., 79
(2007) 7873-7882.
[2] M. Mller, B. Beckhoff, G. Ulm, B. Kanngieer, Phys. Rev. A 74 (2006), 012702

153

PA-38
A study of low energy K X Ray satellites of Phosphorous and
its compounds
Koteswara Rao Veeranki1, M. V. R. Murti2, L. Mombasawala3, S. S. Raju1 and
B. Seetharami Reddy1
1

Department of Nuclear Physics, Andhra University, Visakhapatnam, India.

2
CSRE, Indian Institute of Technology, Bombay, India.
3
SAIF, Indian Institute of Technology, Bombay, India.

Low energy K X Ray spectra of Phosphorous, Magnesium Phosphate,

Potassium Phosphate, Zinc Phosphate and Cobalt Phosphate generated by photon
excitation are studied by a wave length dispersive spectrometer (Philips 2404) using
PET plane crystal. The energies of the observed low energy X -ray satellites are
measured. Comparing these energies with the Semi Empirical Auger - Electron
energies1, the X ray satellites have been identified as KLL RAE2 (Radiative Auger
Emission) Peaks. These lines are ascribed KL3L3, KL2L3, KL2L2, and KL1L2-3 transitions.
The integrated KLL RAE intensity is measured in phosphorous and its compounds
and analyzed for chemical effects. Abergs theoretical value of integrated KLL Relative
intensity of Phosphorus based on SCF (Self Consistent Field) calculations is in better
agreement with the experimental value compared to the Scofields3 theoretical value
based on Hartee Fock formalism.
[1] F. P. Larkins, Atomic Data and Nuclear Data tables 20, (1979) 311 387
[2] T. Aberg and J. Utriainen, Phys.Rev. 22, (1969) 1346 - 1348
[3] J. H. Scofield, Phys.Rev. A 9, (1974) 1041 1049

154

PA-39
A novel multi-purpose PIXE induced XRF chamber
D. Sokaras1, Ch. Zarkadas1,2, R. Fliegauf3, B. Beckhoff3 and A.G. Karydas1
Institute of Nuclear Physics, N.C.S.R. Demokritos, Aghia Paraskevi, 15310,
Athens, Greece
2
PANalytical B.V., 7600AA Almelo, The Netherlands
3
Physikalisch-Technische Bundesanstalt, Abbestrae 2-12, 10587 Berlin, Germany
1

The development and implementation of a multi-purpose scattering chamber

at the Demokritos Tandem 5 MV TN accelerator is presented. The set-up combines
effectively particle and photon interactions with matter and aims to fundamental and
applied research topics such as: Sub-keV X-ray fluorescence spectrometry, X-ray
Resonant Raman scattering [1], study of the PIXE continuum polarization properties
[2] and the successful treatment of interference problems that usually appear in
conventional XRF and PIXE techniques [3]. The PIXRF scattering chamber utilizing
multiple primary target sample rotatable holders and selectable absorber foils for
the modification of the primary exciting radiation allows the accurate and reproducible
production of particle-induced, almost monochromatic and background free X-ray
beams of discrete set of energies, enabling in a reliable manner complementary
PIXE-induced and (externally performed) SR-induced XRF studies of identical
samples. With the additional use of an ultrathin window X-ray detector (600 nm
polymer window) having a transmission of about 40% for carbon and oxygen
K-lines, low energy particle-induced X-rays can provide unique possibilities for X-ray
spectrometric studies in the low or sub-keV energy region.
A suitable integrated C++ software has been developed including appropriate
data bases to account for: i) the K-shell, L-subshell and M-subshell heavy ions
ionization cross sections (up to 5 MeV/amu) for all the elements of the periodic table
ii) K and L sub-shell fluorescence cross sections, iii) stopping power of heavy
ions in matter and iv) mass attenuation coefficients of X-rays in matter. By this way,
integrated simulations of the PIXE induced XRF intensities, can be carried out in
order the experimental parameters (heavy ion type, kinetic energy, primary target,
absorbers etc.) to be optimized.
First experimental results are presented and discussed revealing the
potential of the novel experimental apparatus.
[1] Ch. Zarkadas, A.G. Karydas, M. Mller, B. Beckhoff, Spectrochimica Acta Part B
61 (2006) 189195
[2] C. Potiriadis, A. G. Karydas, Ch. Zarkadas and A. Clouvas, X-ray Spectrom., 34
(2005), 335-340.

[3] M. F. Querra, T. Calligaro, M. Radtke, I. Reiche, H. Riesemeier,

Nucl. Instr. Meth. B 240 (2005) 505-511
155

PA-40
On the accuracy of L-shell ionization cross sections II. The
choice between experimental or thoretical
T. Papp1,2
Cambridge Scientific, 175 Elizabeth Street, Guelph, ON, N1E 2X5, Canada,
Institute of Nuclear Research of the Hungarian Academy of Sciences
Bem ter 18/c Debrecen, H-4021, Hungary

1
2

In the PIXE analytical technique the fundamental parameter approach is frequently

used. Therefore the physical quantities of excitation, decay and transport
parameters need to be included and knowledge of their accuracy is required.
However, the scatter of these experimental data is huge [1,2].
Beyond that a strange practice is used, where the data are averaged, outliers are
discarded and this average is considered. Basic statistics and simple logic dictate
that this method is related to human behavior. The proper method is to find and
eliminate the reason of the scatter or if this is not possible incorporate it into the
analysis. If we have ten data points with significantly larger scatter than the error
bars that are claimed then we cannot average to find the best value. Averaging
nine bad data with one good datum will generally result in a poor value. Therefore
good measurements are required.
An alternative is to use the theoretical data. However the data generated by
present theoretical approaches used in PIXE is not expected to be an accurate
representation and with the support of experimental data we will present that it is
inherently incapable of yielding the needed cross sections.
Beyond that it is worth to note that even these experimental data are biased by the
tendency to get good agreement with theory. There is a need for unbiased data,
and we will present some elements for consideration.
[1] A. Balsamo, N. De Cesare, F. Murolo, E. Perillo, G. Spadaccini, M. Vigilante, J.
Physics B.: At. Mol. Opt. Phys. 1999, 32, 5699.
[2] http://www.atomki.hu/ar2005/3_atom_mol/a07.pdf, published online
[3] T. Papp, J. L. Campbell and J. A. Maxwell Phys. Rev. A 48 (1993) 3062

156

PA-41
PIXE protocols for cluster analysis of archeological samples:
the funny filter case
M. Roumi and B. Nsouli
Accelerator Laboratory, Lebanese Atomic Energy Commission, National Council for
Scientific Research, Airport Road, P.O.Box: 11-8281, Beirut, Lebanon.
Ion Beam Analysis techniques were developed and utilized for applications
in the domain of archeology at the accelerator laboratory of the Lebanese Atomic
Energy Commission. In order to have accurate and relatively fast measurements for
analysis studies of archeological objects, mainly ceramics, different experimental
protocols were tested and established, using Proton Induced X-ray Emission
technique. The first experimental protocol was done using two runs at 1 MeV and 3
MeV. The second one was more advantageous since it is time consuming by using
just one run at 3 MeV with a pinhole filter as x-ray absorber. Hence, a classification
study based on the elemental composition and on multivariate statistical techniques
could be performed for provenance studies of archeological objects. The performed
protocols were applied and checked on standard reference materials such as DRN,
BEN from Geo-standard and SRM-679 brick clay from NIST.

157

PA-42
PIXE identification of fine and coarse particles of aerosol
samples from Beirut
M. Roumi1, B. Nsouli1 and N. Saliba2
Accelerator Laboratory, Lebanese Atomic Energy Commission, National Council
for Scientific Research, P.O. Box 11-8281, Beirut, Lebanon
2
Department of Chemistry, Faculty of Arts and Sciences, American University of
Beirut, Beirut, Lebanon

Beirut is a cross road for several meteorological phenomena during the

year, thus the transport of pollution over the different seasons and storm episodes
was studied, by simultaneous sampling of PM10 and PM2.5. The collection of fine
and coarse particles on Teflon filters was carried out once a month, for a period of
24 hours, during a whole year between February 2004 and January 2005, using
a dichotomous sampler. The characterization of the elemental content of the two
fraction mode, fine and coarse particles, were analyzed using proton induced X-ray
emission (PIXE). The use of 75 m of Kapton filter, as x-ray absorber, with a 3 MeV
proton beam delivered by the 1.7 MV Tandem-Pelletron accelerator of the LAEC
facility, allowed the simultaneous determination of Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe,
Ni, Cu, Zn and Pb. Furthermore, PIXE study and the calculation of the enrichment
factor showed the differentiation, of pollution sources, between anthropogenic versus
natural emissions. Finally, the results of PIXE analysis of the NIST SRM 2783 will
be showed.

158

PA-43
In-situ observation of chemical state change of sulfur
in solid targets during MeV-proton irradiation
T. Tada, H. Fukuda, J. Hasegawa and Y. Oguri
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology,
2-12-1-N1-14, Ookayama, Meguro-ku, Tokyo, 152-8550, Japan
Change of fine structures of the K X-ray spectra for sulfur compound
targets during MeV proton irradiation was observed in-situ using a high-resolution
X-ray spectrograph. Six standard samples of sulfur with different chemical states
(elemental sulfur, MoS2, Na2SO3, (NH4)2SO4, Na2SO4, and Na2S2O3) were prepared
for this measurement. The proton beam current and the beam spot diameter were
50-70 nA and 9 mm2, respectively.
We found that the sulfur K line energy for sulfite became higher with the
increase of the proton dose. After the irradiation of 90 C protons, the K energy
for sulfite was nearly equal to that for sulfate. This result indicates that the most of
the S4+ on the surface of the target has changed into S6+ through the irradiation. For
lower doses, we could determine the ratio of S6+ from the spectral shape. On the
other hand, no significant change was observed in the K peak for other compounds.
During the measurements, the loss of sulfur atoms was monitored by measuring the
K X-ray yield by a Si(Li) detector. The relation between beam current and the rate
of the chemical state change is also discussed.

159

PA-44
Approximate solution for the fraction of backscattered
electrons using invariant imbedding method.
Carlos Figueroa, Nicols Nieva, Silvia Perz Heluani
Laboratorio de Fsica del Slido, Departamento de Fsica,
Facultad de Ciencias Exactas y Tecnologa, Universidad Nacional de Tucumn.
Avenida Independencia 1800, San Miguel de Tucumn, Argentina.
Electron Probe Microanalysis (EPMA) is a widely used technique for material
characterization. Is based on detection of the characteristic X-ray radiation emited
by a sample when a electron beam, with energies ranges from 2 to 50 kev, impinges
on it. The beam-sample interaction generate backscattering electrons, secundary
electrons, absorbed electrons and a complex X-ray spectrum. During 50 years,
EPMA has been applied in order to obtain the chemical composition of samples
starting from analysis of microvolumes ( 1m3 ).
Quantitative analysis of solid samples with EPMA requires correction
procedures of the experimental data. Therefore, information about the physical
processes involves in the scattering, as much of inpinging electrons as X-ray photons,
is needed. Although these processes have been studied during many years, most of
correction procedures are based on empirical or semi-empirical aproximations.
In this work, an aproximated analytic method used for calculate the fraction of
backscattered electrons in EPMA, is reported. The fractions are calculated in function of the
initial energy of the electron beam and the atomic number Z of the target.
Starting from Invariant Embedding Method applied to a "states ladder model"
(used to represent the energy lost of the electrons in the sample [1,2]), the theoretical
expressions for the fraction of backscattered electrons are obtained. A previous
reported model was restricted to electron movements in an one-dimensional (1D)
space.
The current proposal is an improvement of the mentioned previous model.
By mean of a new aproximation method that simplify the calculations, theoretical
expressions for a 3D model are obtained[3]. In this work this new method is applied
to a 1D model, and comparisons with experimental data and the 3D model are made
and exposed.
[1] S. P. Heluani, C. Hoffmann, Nuclear Instrument and Method, B, 160, 235-242,
2000
[2] C. Figueroa, H. Brizuela, S. P. Heluani, Journal of Applied Physics, 99, 044909,
2006
[3] C. Figueroa, N. Nieva, S. P. Heluani. Physics B, 398, 2, 356-359, 2007.
160

PA-45
EPMA determination of modes of gold and silver occurrence in
lithochemical stream sediments exemplified by the Ducat goldsilver deposit in northeastern Russia
L.A. Pavlova and R.G. Kravtsova
Institute of Geochemistry, Siberian Branch, Russian Academy of Sciences,
Favorsky Str., 1, Irkutsk 664033
The EPMA technique has been elaborated to measure the composition of
stream sediments containing silver and gold. This technique made good use for
identification of the modes of gold and silver occurrence in loose sediments of lithochemical stream sediments.
In search of gold-silver deposits application of qualitative and quantitative
characteristics of ore elements at some deposits should be supplemented with
additional criteria to make prospecting more effective. We order to use the modes of
occurrence of mineralization indicator elements gold and silver as an additional
criterion for searching.
Dependence of silver and gold intensities on beam power densities was
chosen as the criterion for selecting optimum conditions of analysis. Stability of
sediments was determined. It found that the beam power densities >2.55 W*m2
are unacceptable for silver-containing samples. The quality of available results
complies with the applied geochemistry category of performance (category 2).
This technique is applicable in prospecting as the criteria for a perspective
evaluation of geochemical anomalies ascertained with litho-chemical stream
sediments.
The modes of silver and gold were studied in alluvial sediments of lithochemical stream sediments. The larger part of gold is available as micro-inclusions
and micro-impurities in the oxides and hydro-oxides of iron and manganese. It is
established that mineral and element compositions of primary ore of Dukat goldsilver deposit are very much similar to those of gold and silver-containing loose
sediments and minerals from litho-chemical streams of the same deposit.
This work was supported by the RFBR (Grant No 08-05-00272).

161

PA-46
Investigation of phase composition of metallurgical silicon by
EPMA
L. Suvorova1 and N. Nemchinova2
Institute of Geochemistry, Russian Academy of Sciences,
1A Favorsky Str., Irkutsk, Russia
2
Irkutsk State Technical University, 83, Lermontov Str., Irkutsk, Russia
1

Production of metallurgical silicon with insignificant impurities is important

for its application as the base material for solar elements.
The samples of metallurgical silicon obtained by traditional technology
contain some impurities, e.g. Fe 0.4, Al 0.3, Ca 0.4 wt. %. The goal of this study
was to define the element and phase compositions of inclusions for developing the
methods aimed at reducing abundances of impurities in silicon.
The investigation of metallurgical silicon samples by the electron microprobe
(Superprobe8200) defined fine inter-metallic silicon-containing inclusions (silicides)
and nonmetallic. The silicides are small-sized (2 -50 m) and occur on the boundaries
between silicon grains. Their composition is very heterogeneous, that is evident on
the inclusion images acquired in back-scattered electrons and X-Rays. The data
of quantitative analysis point out that silicides are composed of silicon, aluminium
and iron. The chemical composition of silicides is defined as adequate to the
following phases in metallurgical silicon: Al5Fe2, (Fe,Ti)Si(Al), FeSi2(Al) and AlFeSi.
The nonmetallic inclusions are round-shaped, their size reaches 300 m, and they
consist of CaSiO3, SiO2 and SiC. The data obtained agree with the results of x-ray
phase analysis and metallographic investigations.
The further purification of refined silicon provided multi-crystalline silicon,
received by directed crystallization. The investigation of multi-crystalline silicon
shows that it consists of pure silicon crystals with the thin fibers of silicides present
between silicon grains. These inclusions are very few; their size is smaller than that
in metallurgical silicon.
It has been eventually inferred that a single crystallization is not sufficient for
production of truly pure multi- crystalline silicon from refined metallurgical silicon.
The project was supported by grant MES RF RNP 2.1.2.2382

162

PA-47
X-Ray and electron emission during transporting of slow
energy electrons through glass capillary optics
V.P. Petukhov
D.V. Scobeltsin Institute of Nuclear Physics, MSU, 119991 Moscow, Russia
The transmission of ions through dielectric capillaries has attracted
considerable attention during recent years [1-3]. As a result of experimental and
theoretical studies performed, it was demonstrated that high transmission coefficient
ions through a dielectric channel is explained by electrification of channel walls
in the course of ions motion, followed by self-organization of a beamwall charge
system, i.e. a charge is generated, at which there are no more collisions of ions with
the wall and no more changes in the charge distribution. We believe, that it is of
interest to investigate the mechanism of transporting of electrons through glass
capillaries.
In this work we investigate the transmission of electrons with the energy
from 1 keV to 10 keV through the glass tube, polycapillaries and tapered glass
capillary. The experiment was conducted using a chamber designed for electron
and X-Ray spectroscopy measurements. Glass poly-capillaries were fabricated by
M.A. Kumakhov, Institute for Roentgen Optics.
The main results of the experiment are:
The transmission coefficient of electrons decreases with the increase of
incident electron beam current.
The transmission coefficient of electrons decreases with the increase of the
time of measurement.
Electron energy at the exit of glass tube differs by several percent from
energy of incident electrons, i.e. the most part of electrons moves without collisions
with the wall of the tube.
From the X-ray spectrum at the exit of the glass tube follows that the part of
the electrons ionize the atoms of the wall during collision with the walls.
The results of the measurements indicate that the transporting of the electrons
through the glass capillary is related with electrical charge-up and discharge on the
bulk and on the surface of the apillary due to incident electrons.
This work has been supported by INTAS Grant No. 06-1000012-8972
[1] S. Ninomiya, Y.Yamazaki, F.Koike, et. al., Phys. Rev. Lett. 78, (1997), 4557.
[2] Stolterfoht N., Bremer J.-H., Hoffmann V. et al. Phys.Rev.Lett. 88, (2002),
133201-1 4
[3] K A Vokhmyanina, L A Zhilyakov, A V Kostanovsky, et. al.. Phys. A: Math. Gen.
39 (2006) 47754779.
163

PA-48
X-ray detection system for PIXE measurements based on a SDD
coupled to polycapillary optics
R. Alberti1, A. Bjeoumikhov2, N. Grassi3, C. Guazzoni1, T. Klatka1, A. Longoni1,
A. Quattrone1
Dipartimento di Elettronica e Informazione, Politecnico di Milano and INFN,
Sezione di Milano, Via Golgi 40, 20133 Milano, Italy
2
IFG - Institute for Scientific Instruments GmbH, Rudower Chaussee 29/31,
12489 Berlin, Germany
3
Dipartimento di Fisica, Universit degli Studi di Firenze and INFN, Sezione di
Firenze, Via G. Sansone 1, 50019 Sesto Fiorentino, Firenze, Italy
1

Silicon Drift Detectors (SDDs) offer higher performance than conventional

silicon detectors traditionally used in X-ray spectroscopy applications, thanks to their
very low output capacitance (of the order of 100 fF) independent of the active area.
In order to fully exploit in PIXE the superior performance of SDDs especially
for the detection of low- and medium-energy X-rays, avoiding the negative effects of
backscattered particles, we developed a custom spectrometer based on a 10 mm2
chip with a thermoelectric Peltier cooler and home-designed front-end electronics,
coupled to a weakly focusing polycapillary lens. Thanks to the latter, a large collection
efficiency for X rays can be achieved, while backscattered particles are prevented
from reaching the detector.
This work describes the detector + lens assembly and reports the results of
first tests carried out at an external beam line of the LABEC laboratory in Florence.
Excellent energy resolution is achieved under real operating conditions in a PIXE
run (measured FWHM at 1 keV is 81 eV with a count-rate of 500 cps), and the line
shapes are also very good (FW1/10M over FWHM ratio is 2.1). These preliminary
tests also helped to point out some aspects worth to be investigated, in order to profit
fully from such a good performance of the spectrometer.

164

PA-49
Sim-IBA - computer software for simulation of PIXE and RBS
spectra and elemental mapping
I. Orli1 and M. Bogovac2
1

Department of Physics, University of Rijeka, Croatia,

2
Ruer Bokovi Institute, Zagreb, Croatia

A new expert system Sim-IBA is developed to provide simulation and semiquantitative analysis tool to ion beam community. One of the main features of this
program is to simulate PIXE and RBS spectra for any sample composition and
experimental conditions. The program also provides simulation of line spectra as
well as elemental maps of an arbitrary, user defined, 3D sample composition. The
expert system is based on previous work of one of the authors (1) but its functionality,
features and data base is now significantly upgraded. Through a modern and
functional GUI the program allows the user to define a wide variety of experimental
parameters, e.g. energy and species of incident ions (protons, deuterons and
helium), detection geometry, characteristics of detectors and filters for both PIXE
and RBS channels. User can define excitation geometry as well as 3D elemental
composition of the sample and simulate PIXE line spectra as well as elemental maps
on pixel by pixel basis. By using parameterization of the latest database the code
is very efficient and calculates elemental maps of a complex sample composition in
only several seconds. It is our belief that Sim-IBA is an excellent teaching tool for
students/researchers with no experience in PIXE/RBS techniques. Secondly, it is
of immense help in planning an experiment and choosing the optimal experimental
conditions for various analytical problems that PIXE analyst encounter in contacts
with various collaborators. Such expert system will give the user a possibility to run
a simulated experiment for an unknown sample and test various settings/scenarios
to achieve the optimal results without actually running the experiment. This could
potentially save a lot of expensive machine time that would otherwise have been
spent on trial and error experiments.
[1] Orli et. al, Nuclear Instruments and Methods in Physics Research B 150 (1999)
83-89

165

PA-50
A methodology based on thickness dependent sample
irradiation to evaluate the enhancement in K-shell ionization
cross sections due to vacancies in the projectile.
C. M. Romo-Krger
Institute of Basic Sciences, Catholic University of Maule, Casilla 617, Talca, Chile.
The interaction ion-atom is a physical phenomenon normally described by a
semi classical model of two particle collision. The Plane Wave Born Approximation
PWBA, and its derivative the ECPSSR model, have been good to describe collisions
in which projectiles are low mass and energetic. At relative low projectile velocities
and near symmetric collisions a very different quantum system is formed when the
collision partners approach, the named Molecular Orbital system. In this transitory
state, an orbital vacancy in the projectile can be transferred to the target atom by
coupling of electronic orbital states. Experimental ionization cross sections attained
with light ions impact and those for symmetric collisions present very different
tendencies, and it is impossible to relate them by means of a scaling law. The growth
observed in cross sections is attributed to 2p vacancies in the projectile transferred
to 1s orbitals in the target. The total ionization of a target atom have been expressed
as the sum of a direct ionization d by impact with the projectile plus an ionization S
due to the mechanism of transfer vacancies from the projectile during the Molecular
Orbital formation. A procedure is suggested here to evaluate the enhancement in
ionization cross sections due to orbital vacancies in the projectile transferred to the
target, consisting of the irradiation of a sequence of different thickness thin targets
to monitor the K shell X-rays produced. According to a rate equation and to the
production of K X-rays in target, it is expected to get a threshold thickness in which
the enhancement reaches a maximum.

166

Abstracts
Poster Session B

PB-1
Large area silicon drift detectors
A. Pahlke, T. Eggert, S. Pahlke, R. Sttter, F. Wiest
KETEK GmbH, Hofer Str. 3, 81737 Munich, Germany
Silicon Drift Detectors (SDDs) are commercially available for more than 10
years. They are widely used in XRF, TXRF, electron microprobe analysis systems
and synchrotron applications.
The big benefit of SDDs compared to other x-ray detectors as Si(Li)s or
pin-diodes is the spectroscopic performance principally being independent of the
sensitive area. As there is a growing demand for larger detector areas, KETEK has
developed SDDs with active areas up to 100 mm.
We will present spectroscopic measurements of SDDs with areas varying
from 10 to 100 mm. Energy resolution below 130 eV for the Manganese K line
and peak to background values of more than 10,000 will be shown for devices with
active areas of 100 mm when cooled down to -60C. Count rate dependency of the
energy resolution and the peak position is shown to be negligible up to count rates
of 100,000 counts per second.
Temperature dependent measurements of the energy resolution will be
shown for different detector areas. We will present improved cooling techniques for
KETEK VITUS modules which allow detector temperatures down to -50C at an
ambient temperature of +20C. Energy resolutions below 135 eV for 100 mm SDDs
and 130 eV for 30 mm devices at -50C are achieved.

169

PB-2
Enhance detection sensitivity of micro X-ray Fluorescence by
using advanced X-ray optic chain
N. Gao, Z. Chen, and I. Ponomarev
X-Ray Optical Systems, Inc., East Greenbush, NY, USA
Both polycapillary X-ray optics and doubly curved crystal (DCC) optics have
been widely used in X-ray analytical instruments and a variety of research applications.
A polycapillary optic is a broad-band optic that consists of up to millions of small
channels that are precisely curved to a designed profile to efficiently transmit X-rays
by multiple external total reflections off the inner surface of each individual capillary
channel. The optic collects a large solid angle of X-rays from a divergent X-ray
source and redirects them to either a parallel beam of a focused beam. A focusing
polycapillary optic can generate a focal spot less than 10m while delivering an
X-ray intensity equivalent to a pinhole collimator of millimeters in diameter, making it
an inevitable tool to use for many applications. A doubly curved crystal (DCC) optic,
on the other hand, is a diffractive X-ray optic that collects X-rays from a divergent
X-ray source and redirects a narrow band of them by diffraction to form a focused,
monochromatic beam. The two optic technologies have their own characteristics and
advantages, but also have their limitations. We will report in this paper the use of a
DCC-polycapillary optic chain to achieve a monochromatic beam with the focal spot
size less than 10m and the use of such configuration for micro X-ray fluorescence
applications. The performance will be compared with that of other technologies to
demonstrate the capability of the innovative approach in achieving higher detection
sensitivity, higher measurement precision and other analysis benefits.

170

PB-3
Ultratrace total reflection X-ray fluorescence (TXRF) analysis
of platinum group elements applying nickel sulfide melt
enrichment
H. Stosnach
Bruker AXS Microanalysis GmbH, Schwarzschildstrasse 12, D-12489 Berlin,
Germany
The analysis of platinum group elements (PGE) is of high importance in many
application fields. In most industrial applications, e.g. PGE for catalytic processes,
concentration ranges are in the high mg/kg up to wt.-% range. For these samples
common X-ray fluorescence (XRF) methods offer an adequate solution.
In other application fields, in which PGE are processed (mining/exploration,
medicine, pharmacy, automotive catalysts), element concentations are in the low
mg/kg or even g/kg range. Those samples require digestion procedures and
subsequent analysis by means of TXRF or atomic spectroscopy.
However, for many samples even a digestion is not sufficient, either the
accuracy of this procedure is insufficient or the concentrations of the PGE are in the
low g/kg or even ng/kg range.
In this presentation a procedure for the PGE enrichment by melting the
samples after addition of nickel sulfide is described. Measurement data derived by
TXRF analysis are compared with results from inductively coupled plasma mass
spectrometry (ICP-MS). On the basis of these measurements the benefits and
limitations of the TXRF method are evaluated.

171

PB-4
Improvements of the low-energy performance of a micro-focus
X-ray source for XRF analysis with the SEM
M. Procop1, V.-D. Hodoroaba1, A. Bjeoumikhov2, R. Wedell3 and A. Warrikhoff4
Bundesanstalt fr Materialforschung und prfung (BAM), D-12200 Berlin,
Germany
2
IfG Institute for Scientific Instruments GmbH, D-12489 Berlin, Germany
3
IAP Institut fr angewandte Photonik e. V., D- 12489 Berlin, Germany
4
rtw Rntgen-Technik Dr. Warrikhoff GmbH & Co. KG, D-15366 Neuenhagen b.
Berlin, Germany
1

XRF with a scanning electron microscope (SEM) is a valuable completion

of the analytical capabilities of SEMs [1]. A small and compact micro-focus X-ray
source such as iMOXS [2] is mounted to the microscope chamber, and the X-ray
spectra are monitored with the conventional EDS system.
Modern SEMs are characterized by large specimen chambers to enable
the implementation of several analytical methods like EBSD, FIB, WDS, etc. The
consequence of such a large specimen chamber is the large clearance between the
X-ray tube outside the chamber and the specimen inside. The distance between the
input focus of the X-ray optics with its position on the tube target and the output focus
on the specimen ranges between 30 and 40 cm.
Up to now the X-ray tubes used for the micro-focus X-ray sources have
thick beryllium windows. The poly-capillary optics has its transmission and gain
maximum at photon energies around 10 keV. They drop down in both low and high
energy ranges [3]. L-radiation from a Mo or Rh target will be strongly attenuated. The
excitation of fluorescence in the soft X-ray range becomes very ineffective.
A new micro-focus X-ray source was developed. It is characterised by
lower self-absorption in the tube target, thin beryllium windows and an X-ray optics
having a large distance between its foci and the maximum of transmission at about
5 keV. Thus K-line fluorescence of light elements becomes effectively excited by the
L-radiation from Mo or Rh targets. We have determined a detection limit of about 1
mass-% for sodium oxide in glass.
[1] M. Procop, V.-D. Hodoroaba, Microchim. Acta (2008) Online First.
[2] A. Bjeoumikhov et al., X-Ray Spectrom. 34 (2005) 493.
[3] A. Bjeoumikhov et al., X-Ray Spectrom. 32 (2003) 172.

172

PB-5
Development of the analyzer for thickness and trace elements in
multilayer using multi excitation sources
Y.Nose1,N.Kawada2,S.Maeo1,T.Utaka1,2 and K.Taniguchi1,2
1

Osaka Electro Communication Unversity (18-8 Hatsucho, Neyagawa, Osaka

572-8530, Japan)
2
Institute of X-ray Technologies Co. Ltd, (Dai-3 Maruzen-Bldg. 3-5-21,
Kigawahigashi, Yodogwa-ku, Osaka 532-0012, Japan)

The X-ray fluorescence (XRF) analysis is a very suitable technique for the
estimation of the thickness of layers in the plating and multilayer on the Si wafer[1].
Recently, it is required to analyze not only the thickness of layer but also trace
elements in the layer. Then, the WDXRF and EDXRF with some X-ray tubes were
put on the market. However, these analyzers are large size and expensive.
In this research, the table-top EDXRF analyzer has been developed for
measurement of the layer thickness at small area and trace element analysis in the
layer. For satisfaction of the analyzer performance, the background must be reduced
to improve the Lower Limit Detection (LLD). In addition, the X-ray source is selected
which has high excitation efficiency for wide range elements.
In this report, a multi targets X-ray tube is developed which has three target
materials, namely, Cr, W, and Rh, on the anode, To select a target, the area that is
bombarded by electron should be changed depending on the target materials by
different electron source in same X-ray tube. The operating power of the tube is set
to 50 watts (50 kV, 1 mA), and it is cooled by forced air convection. The diameter of
the focal spot is 50 m. The spot size on the sample is 50 m as minimum limited by
the collimator. The monochromatic X-ray beam is archived by selection of the filters.
The filters were set each three filters, on which between X-ray tube and sample as
primary filters, and between sample and detector as secondary filters. The Silicon
Drift Detector (SDD) with high P/B ratio is selected for the improvement of the LLD.
This analyzer has following advantages: (1) wide range elements can be
measured with high efficiency due to applied a multi targets X-ray tube, (2) the
LLD can be improved by quasi-monochromatic excitation source with selection of
the optimal filters, (3) the analytical accuracy of layer thickness can be improved
because matrix correction is easy by using quasi-monochromatic excitation source
and the fundamental parameter method is used, (4) it can be measured that not
only thickness information but also the elemental information of layer itself and trace
elements in the layer.
[1] S.Terada, IEEE International Symposium on Semiconductor Manufacturing
Conference Pro-ceedings(1999),365

173

PB-6
Short soft X-Ray sources
A. Lorusso1, V. Nassisi1 and M.V. Siciliano2
Department of physics, Laboratorio di Elettronica Applicata e Strumentazione
LEAS, University of Salento, INFN Lecce SS Lecce-Monteroni,C.P. 193,
73100Lecce-Italy
2
Department of Material Science, University of Salento, SS Lecce-Monteroni,C.P.
193, 73100Lecce INFN Lecce - Italy
1

It is demonstrated that laser-induced plasma is a very efficient generator of

soft X-ray that has a high interest for applications in lithograph, sequencing of DNA
and living cell studies [1]. In this work, a fast Faraday cup (FC) equipped by an X-ray
filter is utilised to diagnostic the X-rays. The plasma was generated by a KrF excimer
operating at 248 nm and 23 ns. The laser energies utilized were 40, 80 and 120 mJ
and the laser spot was approximately 0.01 cm2. The metal target utilised were made
of Cu, Si and Ta.
Fig. 1 shows the experimental apparatus. The X-rays, provided by the
laser-plasma, strikes the internal walls of the chamber and the FC collector and
electrons of different energy are emitted. The cup signals can be positive or negative
depending on bias polarity and electron energy. A collimator was placed in front of the
cup because the electron emission from the chamber walls does not favour a good
diagnostic of the X radiation. To characterize the X-rays, we suppressed the electron
emitted from the cup collector by polarising the cup at a trapping positive voltage.
The electron currents decrease as the trapping voltage increases. Measurements of
the X-rays energy were done by means of a filter of 0.2 m thin deposited on 1 m
C3H6. Comparing the X-rays percentage reduction with the attenuation coefficient of
the filter we calculated the X-rays energy. The X-rays energy was less than 200 eV.
The obtained results are comparable with the ones found by the FC.

Fig. 1: Experimental set-up. B: beam splitter; Ph: photodiode; FC: Faraday cup.
[1] T. Yorkey, J. Brase, J. Trebes, S. Lane, J. Gray, Proc. SPIE v. 1345 (1991) 255
259.
174

PB-7
Development of laboratory -XRF spectrometer
using multi monochromatic X-Ray sources
S. Maeo1, M. Krmer1, T.Utaka1,2 and K. Taniguchi1,2
Osaka Electro-Communication University
(18-8 Hatsucho, Neyagawa, Osaka 572-8530, Japan)
2
Institute of X-ray Technologies Co. Ltd,
(Dai-3 Maruzen-Bldg. 3-5-21, Kigawahigashi, Yodogwa-ku, Osaka 532-0012,
Japan)
1

X-ray fluorescence (XRF) analysis is a suitable technique for elemental

analysis in non-destructive measurement. Recently, small area analysis by using
the XRF technique has gained popularity. The synchrotron radiation source is
responsible for the increase in the popularity of -XRF analysis. However, most
people find it difficult to gain access to the synchrotron radiation facility. On the other
hand, the laboratory -XRF spectrometers with the capillary lens optics had been
developed[1]. The capillary lens can focused X-rays but it cannot monochromatize.
Then the background of measurement spectra are higher than using monochromatic
X-rays as excitation source.
In this study, a -XRF spectrometer has been developed for use in laboratories,
with which multi monochromatic X-rays as excitation sources. To enable the use of
this system, it is necessary to satisfy the following two conditions: (1) the excitation
source must be optional for efficient excitation of the sample and (2) the X-rays must
be focused. An X-ray tube with multi excitation sources has also been developed[2].
In this tube, there are three targets, namely, Cr, W, and Rh, on the anode, and
each target can be excited sequentially without changing focal spot position. An
Einzel lens is applied as the electron gun. The operating power of the tube is set
to 50 watts (50 kV, 1 mA), and it is cooled by forced air convection. The diameter
of the focal spot is 10 m. As the optics for focusing of X-rays, Johansson type
Doubly Curved Crystal (DCC) which is Si(111) crystal has been made. A DCC has
Johansson focusing geometry along horizontal direction and Von Hamos geometry
along vertical direction. Then the effective area of diffraction is almost all surface of
crystal. In addition, the focusing efficiency is quite good as compared with Johann
geometry. Therefore, the focus size becomes smaller and intensity gain becomes
higher.
A system composed of an X-ray tube and DCC optics is used to perform the
small particle analysis. In this report, some estimation results of the -XRF system
and capabilities of the system are discussed.
[1] D. A. Carpenter, X-Ray Spectrom., 18 (1989) 253-257.
[2] S. Maeo, T. Utaka, T. Kubota, K. Taniguchi, Adv. X-Ray Chem. Anal., Japan, 38
(2007) 165 - 174.
175

PB-8
Usability of industrial grade Si wafers for x-ray optical
instruments
R. Havlikova1, V. Semencova2, L. Sveda1,3, L. Pina1,2, A. Inneman2 and R.
Hudec4
CVUT, FJFI, KFE, V Holesovickach 2, CZ-18000 Praha 8
2
Reflex s.r.o., Novodvorska 994, CZ-14221 Praha 4
3
Elya Solutions s.r.o., Pobrezni 95/74, CZ-18600 Praha 8
4
AU AV CR, v.v.i., Fricova 298, CZ-25165 Ondrejov

Si wafers are produced by semiconductor industry in large amounts and with

very good quality. Due to their extremely low surface microroughness, other PSD
properties and low cost, Si wafers are of high interest as X-ray mirrors for laboratory
instruments and for X-ray space telescopes. The work summarizes the study of
industrial Si wafers done for the purpose up to now. It includes measurements
of wafer properties relevant to X-ray optics and to X-ray mirrors manufacturing
processes. Surface characterisation and multi instrument PSD analysis are of the
main concern. Experimental Si-wafers data is compared to typical properties of
optical glass currently used for the mirrors.

176

PB-9
Characterization of polycapillary halflenses in two directions
T. Wolff1,2, I. Mantouvalou2, W. Malzer2*, J. Nissen3, D. Berger3 and B.
Kanngieer2
BAM Federal Institute for Materials Research and Testing, Unter den Eichen 87,
12205 Berlin, Germany
2
Institute for Optics and Atomic Physics, Technische Universitt Berlin,
Hardenbergstrasse 36, 10623 Berlin, Germany,
3
ZELMI Zentraleinrichtung Elektronenmikroskopie, Technische Universitt Berlin,
Strasse des 17. Juni 135, 10623 Berlin, Germany
* current affiliation: Brucker AXS Microanalysis
1

Polycapillary halflenses are widely used to focus x-ray radiation onto a

small spot. Additionally they can reduce the field of view of a detector when placed
in front of one. In 3D micro X-ray fluorescence spectroscopy (3D Micro-XRF) with
synchrotron radiation two polycapillary halflenses are used in a confocal geometry.
Up to now characterization measurements have only been performed in the case of
the lens focusing parallel radiation. Assumptions have been made, that in the other
case, when isotropic radiation from a spot source is transported to a detector, the
intensity distribution in the focal plane is Gaussian, as well [1]. In this presentation,
we show for the first time measurements with an electron beam which confirm this
assumption.
With a polycapillary halflens placed in front of an EDX-detector of a SEM
it is possible to scan the sensitivity of the investigated optic in the focal plane.
Measurements have been performed at the ZELMI in Berlin. The Gaussian form
and symmetry of the sensitivity distribution have been verified, and the energy
dependence of the FWHM has been analysed. Additional measurements without the
lenses provide the possibility to determine the focal and the total spot transmission.
Furthermore the lenses have been characterized in the conventional focusing
direction by knife-edge-scans with synchrotron radiation at BESSY II in Berlin. In this
presentation the energy dependence of FWHM, focal and total spot transmission
are compared for the different experimental methods. We show, that the spot size in
the focal plane differs for the same lens, when used in the two different geometries.
[1] W. Malzer, B. Kanngieer, Spectrochim. Acta, Part B 2005, 60, 1334-1341.

177

PB-10
X-Ray capillary optics: status and perspective
Semfira Bjeoumikhova and Aniouar Bjeoumikhov
Institute for Scientific Instruments GmbH, Berlin
In this poster the principles of X-ray capillary optics are described and
different types of capillary optical elements are considered. Especially, the main
parameters of these optical elements such as intensity gain, focal spot size, beam
divergence and others, are discussed in detail and experimental results for these
parameters are presented. Also is analyzed further developments of capillary optics.
They are described some examples of applications of these optics.

178

PB-11
New applications of capillary optics for XRF and XRD
Aniouar Bjeoumikhov and Semfira Bjeoumikhova
Institute for Scientific Instruments GmbH, Berlin
The varios application examples in micro X-ray fluorescencs analysis for
determination of the two dimensional elemental distribution at sample surfaces
as well as depth profiling are given. Finally, the usefullness of capillary optics for
different diffractometric investigations is shown. Especially, examples for single
crystal, polycrystal and powder diffraktometry also with high lateral resolution and
real time diffraktometry are presented.

179

PB-12
Characterisation of the Multilayeroptic Astix 100
L. Luehl1, C. Seim1, T. Holz2, R. Dietsch2 and B. Kanngieer1
Institut fr Optik und Atomare Physik, Technische Universitt Berlin,
Hardenbergstr. 36, 10623 Berlin, Germany
2
AXO DRESDEN GmbH,Siegfried-Rdel-Strae 31, 01809 Heidenau, Germany
1

Monochromatic excitation for x-ray fluorescence analysis has several

advantages: it simplifies the quantification and, in some cases, it enhances the
sensitivity of a spectrometer. Furthermore, for Micro-XRF monochromatizing
properties have to be combined with focussing ones. The development of X-ray
optics with monochromatizing properties and local spot sizes below 50 m is very
interresting for Micro-XRF [1].
Therefor we investigated a modified Montel multilayer optic Astix 100
produced by AXO DRESDEN GmbH. These multilayer optics are produced for their
application in Micro-XRD, enlarging the anode spot size of the X-ray tube by a factor
of 3. We used this optic in the demagnifying geometry, for the reduction of the spot
size.
The multilayer optic was characterized by its spot size and its spot shape
produced and its throughput. Results will be shown and discussed in view for use in
Micro-XRF.
[1] B. Kanngieer, B. Beckhoff, J.Scheer, W. Swoboda, Advances in X-Ray Analysis,
Vol. 37 (1994) 535-544

180

PB-13
Monochromatic X-beam for micro-beam EDXRF
Z.W. Chen, D. Li, S. Kemtekar, and W. M. Gibson
X-ray Optical Systems, Inc., 15 Tech Valley Drive, East Greenbush, NY 12061,
USA
It is well known that a doubly curve crystal (DCC) optic can provide a
monochromatic micro beam from a point x-ray source based on Bragg reflection.
A compact x-ray source integrated with a focusing DCC optic, called X-beam, has
been developed and continues to evolve for monochromatic micro XRF applications.
In this paper, recent developments of DCC X-beams will be presented. Focusing
geometries, beam profiles and spot sizes will be discussed for various beam energies.
Each type of beam has a monochromatic energy of 5.4 keV, 8.0 keV, 17.5 keV or
22.2 keV. The beam spot size is in the range of 30m to 200m.
A DCC Mo K X-beam that provided a 70m monochromatic beam with
energy of 17.5 keV was used for energy-dispersive XRF applications. A silicon
drifted detector was used to record the fluorescent spectra. Elemental maps of
various samples at low level concentrations will be presented and discussed. Fe
and Cu maps of mouse brain tissue with Alzheimer Disease (AD) are illustrated.
This technique can be a valuable tool to assist AD clinical research.

181

PB-14
Comparative characterization of x-ray beams formed by
complicated waveguide-resonance compositions
V.K. Egorov1, E.V. Egorov1 and M.S. Afanasev2
1

IMT RAS, Chernogolovka, Moscow District, 142432 Russia

2
MIREA, Moscow, Russia

X-ray optics devices functioned on base of the waveguide-resonance

mechanism for X-ray flux propagation as opposited to conventional units destined
for the radiation fluxes formation is characterized by a number of indisputable
advantages. The devices form nanosize width beams of quasimonochromatic X-rays
with an enhanced radiation density. Moreover, these devices are distinguished by
very low attenuation of X-ray flux intensity in process of the radiation transportation
[1]. But the simplest device construction the planar X-ray waveguide-resonator
(PXWR) has some users imperfections. There are the noticeable angular divergence
(0.1) and the low integral intensity magnitude of its emergent beam. So, the
chief task of X-ray waveguide-resonance optics development is the attack on these
imperfections.
The work presents the space distribution intensity investigations for X-ray
quasimonochromatic component of beams formed by some specific design PXWRs.
Data of these investigations were compared with ones obtained for slit-cut beam
former systems and for planar monocapillars at the same conditions of X-ray source
function. On base of the set results we discuss more effective approaches and methods
for the waveguide-resonance structure modification. Some attention is devoted to
technological peculiarities description of PXWR preparation. Main directions for the
practical using of the elaborated waveguide-resonance constructions are assigned.
There are forecasted principle tendencies to X-ray nanophotonics development on
base of the planar waveguide-resonators.
[1] V.K. Egorov, E.V. Egorov. Spectrochimica Acta. B59 (2004) 1049-1069.

182

PB-15
The performance of picrofocus X-Ray tubes:
The influence of X- Ray tube- settings
C. Seim, L. Luehl and B. Kanngieer
Institut fr Optik und Atomare Physik, Technische Universitt Berlin, Hardenbergstr.
36, 10623 Berlin, Germany
Since microfocus x-ray tubes in combination with x- ray optics are more
and more used lately, the stability and reliability of their anode spot has received a
greater deal of importance.
This presentation shows the characterization of x-ray tubes by the use of two
different methods to determine spot size and spot shape at the anode. Depending on
the x-ray tubes settings the results can differ vastly.
For the first method a knife-edge of a thin foil was being moved horizontally
and vertically step by step through the x-ray beam. At each step a spectrum was
gathered by an energy dispersive detector. According to the German Industrial Norm
(DIN EN 12543-5) the second method consists of a lead sphere being placed in front
of the x-ray tube into the beam. The resulting image is captured by a CCD camera.
The two methods are being exemplified by testing a microfocus x-ray tube.
The differences and results between the two approaches are elaborated.
The results show clearly that it is inevitable to have a good characterization
of the x- ray tubes anode spots size in order to obtain a reliable experimental set up
for Micro- XRF Analysis.

183

PB-16
Discharge of meta-stable nuclei during muon capture and
realization of the high power monochromatic radiation source
A. Glushkov1,2, O. Khetselius2 and Yu. Dubrovskaya2
Odessa University, P.O.Box 24a, Odessa-9, 65009, South-East, Ukraine
Institute for Spectroscopy of Russian Academy of Sciences, Troitsk,142090,
Russia
1

The problem of creation of the high power monochromatic radiation source

is studied. The possible approach is based on the effect of discharge of meta-stable
nuclei during negative muon capture. A negative muon captured by a meta-stable
nucleus may accelerate the discharge of the latter by many orders of magnitude
[1,2]. For a certain relation between the energy range of the nuclear and muonic
levels the discharge may be followed by the ejection of a muon, which may then
participate in the discharge of the other nuclei. We present the results of calculating
(within QED energy approach [2]) characteristics for discharge of a nucleus with
emission of quantum and further muon conversion, which initiates this discharge.
The key features of the possible high power monochromatic radiation source are
analyzed.
[1] V.I.Gol'dansky, V.S.Letokhov,JETP 67 (1974) 513-518; L.N.Ivanov, V.S.
Letokhov
JETP 70 (1976) 19-28.
[2] A.Glushkov, L.N.Ivanov, Phys.Lett.A 170 (1992) 31-36; A. Glushkov etal, Recent
Advances in Theory of Phys. and Chem. Systems (Springer) 15 (2006) 301-318.

184

PB-17
Search of the optimal plasma parameters for X-ray lasing on the
basis of modeling the elementary processes in a collisionally
pumped plasma
O. Khetselius and A. Loboda
Odessa University, P.O.Box 24a, Odessa-9, 65009,Ukraine
In recent years the X-ray laser problem has stimulated a great number
of papers devoted to the development of theoretical methods for modeling the
elementary processes in collisionally pumped plasma. The problem of diagnostics
for the collisionally pumped plasma and search of the optimal plasma parameters of
X-ray lasing are studied. We present the uniform energy approach, formally based
on the QED for the calculation of electron collision strengths and rate coefficients
for electron-collision excitation. The electron collision excitation cross-sections and
rate coefficients for some Ne-like ions (Fe, Ba) are calculated. To test the results of
calculations we compare them with other authors calculations and with available
experimental data. The most effective ions and transitions for producing lasing in the
vacuum ultraviolet and soft X-ray region are found and analyzed.
[1] A.Glushkov etal, Int.J.Quant.Chem.104 (2005) 562-572; A.Glushkov, O.
Khetselius, etal, Recent Advances in Theory of Phys. and Chem. Systems (Springer)
15 (2006) 285-300

185

PB-18
Generation of ultra-short X-ray pulses in cluster system during
ionization by femto-second optical pulse
A. Glushkov1,2, O. Khetselius1, E. Gurnitskaya1 and A. Loboda1
Odessa University, P.O.Box 24a, Odessa-9, 65009, South-East, Ukraine
Institute for Spectroscopy of Russian Academy of Sciences, Troitsk,142090,
Russia
1

We present the results of modeling generation of the atto-second X-ray

pulses during ionization of atomic and cluster systems by femto-second optical laser
pulse. The concrete data are received for the cluster Ar10 response, the molecular
2D H2+ response for different inter nuclear distances (R=2.5, 3.5, 7.4, 16a.u.) with
smoothed Coulomb potential and atomic (H) response (spectral dependence) under
ionization of the system by femto-second optical pulse. Our calculation show that the
generation of the atto-second X-ray pulses in the cluster system is more effective
and profitable (as minimum the 2-3 orders) than in similar molecular atomic one.
The generation of the atto-second pulses in the molecular system is more profitable
too (as minimum the 1-2 orders) than in similar atomic one. The last achievements
in this field demonstrate a possibility of construction of the compact X-ray radiation
sources.
[1] A. Glushkov, et al, Int.J.Quant.Chem. 99 (2004) 889-895; 104 (2005) 562-572.

186

PB-19
New measurements and observations on aged NaI detectors
A. Tartari1,2,3, G. Di Domenico1,2, C. Bonifazzi4 and C. Baraldi1
Department of Physics University of Ferrara I44100 Ferrara Italy
2
National Institute of Nuclear Physics (INFN), Rome, Italy
3
CNISM, National Consortium of Material Sciences, Genova, Italy
4
Department of Biomedical Sciences - University of Ferrara Ferrara Italy
1

Although advanced high efficiency, high resolution low energy gamma ray
detectors are today available, sodium iodide scintillation counters i.e. NaI - are still
used in medical and technological applications [1, 2]. Despite to almost fifty years
of extensive investigations, a full description of phenomena originating spectrum
features including aging and damaging effects is difficult to find in the open literature.
In this work an experimental distribution resembling the K X ray fluorescence (K-XRF)
of iodine is found and proved to interfere with both the K-escape and XRF peaks
eventually allowed by when low energy incident photons are used. XRF investigations
with different equipments and photon transport simulations are carried out in order
to assess such unexpected distribution and to establish its nature. The hypothesis
of a thin dead layer near the front surface induced by aging or degradation of the
crystal is proved to explain the building up of such peaks. In addition, such peak
can be exploited as an internal reference to assess the dead layer thickness and
the relative loss of efficiency. Results by both experimental and simulation seem to
strongly support such conclusions.
[1] S. Steenstrup et al. X ray Spectrometry 29 (2000) 249-252
[2] A. Tartari et al. Radiation Physics and Chemistry61 (2001) 737-738

187

PB-20
X-Ray prism spectrometer for ultra-fast single pulse spectral
measurements
A.G. Touriyanski1, R.A. Khmelnitski1, M.A. Negodaev1, and T. Tschentscher2
1

P.N. Lebedev Physical Institute

2
European XFEL/DESY

Energy dispersive X-ray prism spectrometer (EDXPS) for ultra-fast

measurements and time-dependent investigations is proposed. A new compound
mosaic construction of a refracting prism provides energy dispersion up to a theoretical
limit. Physical requirements to a prism material, detection unit and processes of
heat dissipation at high power radiation loads are considered. Dispersive properties
of diamond and beryllium prisms were computer simulated. It was demonstrated
that expected parameters of the European X-ray free-electron laser (XFEL) ensure
EDXPS energy resolution of a few eV at E~10 keV. The technique provides unique
opportunities for single pulse x-ray absorption spectroscopy in the femtosecond time
domain.
Preliminary results of the EDXPS testing in laboratory conditions are
presented. An optically polished diamond prism was used as a dispersive element.
Broad band emission and absorption spectra were registered using scintillation
counters and high resolution CCD matrix.

188

PB-21
2-resolution in synchrotron micro-XRPD: instrumental
comparison at HASYLAB Beamline L
W. De Nolf1, J. Jaroszewicz1, R. Terzano2, O.C. Lind3, B. Salbu3, G.
Falkenberg4 and K. Janssens1
Department of Chemistry, University of Antwerp,Universiteitsplein 1, B-2610,
Wilrijk, Belgium
2
Dipartimento di Biologia e Chimica Agro-forestale ed Ambientale, Via Amendola
165/A, I-70126, University of Bari, Bari, Italy
3
Isotope Laboratory, Dep. of Plant- and Environmental Sci. , Norwegian University
of Life Sciences, P.O. Box 5003, N-1432 s, Norway
4
HASYLAB at DESY, Beamline L, Notkestraat 85, D-22603, Hamburg, Germany
1

The -XRPD (X-Ray Powder Diffraction) setup at HASYLAB Beamline L has

been utilized successfully for the investigation of several materials [1]. Two important
characteristics define the applicability of an XRPD setup: the detection limits (the
lowest abundance of a phase diffracting with an intensity above the background
noise) and the resolving power (the ability to distinguish reflections with a small
scattering angle difference). The detection limits are determined by the primary X-ray
beam intensity and the detector sensitivity. The resolving power can be expressed
by the Full-Width-at-Half-Maximum (FWHM) of the diffraction peaks as a function of
scattering angle 2. The contributions to the diffraction peak FWHM can be divided
in two groups:
defects

(a) sample induced broadening due to finite crystallite size, strain and

(b) instrumental broadening caused by the energy resolution E/E and

divergence of the primary X-ray beam, the point spread function (PSF) and number
of pixels of the CCD area detector collecting two-dimensional diffraction patterns
within a solid angle behind the sample.
At HASYLAB Beamline L two double multilayer monochromators (DMM) and
a double crystal monochromator (DCM) are available, covering a E/E range from
2 % to 0.02 %. A gain in energy resolution is obtained at the cost of a reduced X-ray
flux. Depending on the needs of the experiment, it is useful to employ the appropriate
balance between beam intensity and scattering angle resolution. Two case studies
are presented, illustrating this: a study about the chemical forms in which heavy
metals are present in polluted soil from the Val Basento district (Basilicata, Italy)
and the speciation of uranium in DU particles in soil collected at Ceja Mountain
(Kosovo).
[1] R. Terzano, M. Spagnuolo, B. Vekemans, W. De Nolf, K. Janssens, G.
Falkenberg, S. Fiore and P. Ruggiero, Environmental Science & Technology, 41
(2007) 6762-6769
189

PB-22
High performance read-out electronics for Silicon Drift
Detectors
R. Alberti, L. Bombelli, C. Fiorini, T. Frizzi, A. Gola, C. Guazzoni,
T. Klatka, A. Longoni1, G. Membretti
Politecnico di Milano, Dipartimento di Elettronica e Informazione, Piazza Leonardo
da Vinci, 20133 Milano, Italy and INFN sezione di Milano, via Celoria 16, 20133
Milano, Italy
Semiconductor Drift Detectors (SDD) have nowadays reached a leading
position as detectors for X-ray spectroscopy due to their outstanding performances
in terms of energy-resolution and detection-rate. These performances can
nevertheless be exploited at the best only with specifically and carefully designed
readout electronics. We discuss here the critical aspects of the readout process and
present the experimental results recently obtained with new circuits.
The SDDs performances are basically due to their very small output
capacitance. The integration of the input JFET of the preamplifier directly on the
detector maximizes the benefits of the low output capacitance [1]. The readout
electronics here presented has been designed for SDDs with integrated JFET.
A pulse-reset preamplifier, with embedded the integrated JFET, was designed
and tested. This solution allows keeping high values of the spectroscopic resolution
also at very high count-rates. The noise associated to the anode discharge current
can in fact be avoided. Moreover the gain stability is greatly improved by the feedback
configuration. A hybrid version of this preamplifier and a four channel integrated
CMOS (AMS 0.35 m) version will be presented.
A VLSI CMOS 8 channel readout circuit, designed for large-scale applications
[2], is also presented. Its composed of an analog and a digital section. The analog
section is based on charge preamplifiers with selectable shaping times, baseline
holder and peak stretcher. The digital section performs the signals management:
queuing of events, pileup rejection, multiplexing of the analog outputs. It also
provides a real time signal for timing purposes. The circuit is characterized by high
peak stability and good spectroscopic resolution.
In order to fully exploit the detection rate performance of SDDs coupled
with our readout electronics a novel 4 channels (extendible up to 48) acquisition
and processing unit has been designed [3]. The on-board histogramming capability
allows reaching count rates rate up to 1 Mcounts/s per channel.
[1] P.Lechner, S.Eckbauer, R.Hartmann, S.Krisch, D.Hauff, R.Richter, H.Soltau,
L.Struder, C.Fiorini, E.Gatti, A.Longoni, M.Sampietro, Nucl. Instr. and Meth., A 377,
346-351, 1996.
[2] T. Frizzi, L. Bombelli, C. Fiorini, A. Longon, 2006 IEEE Nuclear Science Symposium
Conference Record
[3] R.Alberti, S.Buzzetti, C.Fiorini, C.Guazzoni, T.Klatka, P.Lechner, A.Longoni,
L.Struder, IEEE Trans on Nucl. Sci. Volume 54, Issue 3, June 2007, 751-757.
190

PB-23
The advantages of digital adaptive filtering in fast pulse
processing
G. Georgiev and I.Peev
Institute for Nuclear Research and Nuclear Energy, Bulgarian Academy of
Sciences, 72 Tzarigradsko chaussee, Blvd., 1784 Sofia, BULGARIA
Improving the productivity and performance of XRF is of great importance in
determining elements in samples of various origin. The advantages of using adaptive
matched filtering in digital pulse processing for the purpose of energy dispersive
x-ray fluorescence analysis are demonstrated by comparing the instrumental
performance achieved with that of conventional analog processing and other digital
filtering methods. Due to the task complexity of matched filtering computation[1],
an application-specific digital pulse processor was designed, based on fast, state
of the art, field programmable gate arrays (FPGA). The performance of different
pulse processing techniques was evaluated for two different detector types: SiLi and
thermoelectrically cooled silicon drift detector (VITUS-SDD). The results clearly show
that digital adaptive matched filtering can be as twice faster, compared to analog
processing, without degrading the accuracy. It also has improved accuracy at same
processing time, compared to other digital filtering methods[2].
[1] G. Georgiev, I. Peev, EXRS-2006, Adaptive Matched Filtering Of XRF Detector
Signals.
[2] V. Radeka and N. Karlovac, Nucl. Instrum. Methods 52: 8692, 1967.

191

PB-24
Modelling the response function of an EDS with a silicon
detector
F. Scholze1 and M. Procop2
1

Physikalisch-Technische Bundesanstalt, Abbestr. 2-12 ,D-10587 Berlin, Germany

2
Bundesanstalt fr Materialforschung und prfung, D-12200 Berlin, Germany

A new physical model-based, analytical description of the response function

of an energy dispersive X-ray spectrometer with a silicon detector (Si(Li) or SDD) is
presented. It accounts for charge generation statistics, electronic noise, incomplete
charge collection that gives rise to peak tailing, the escape effect, the fluorescence
of the front contact or the dead layer, and hot photoelectrons that cause the shelf.
Only five free parameters are necessary to describe the response function for any
individual detector: the electronic noise, three parameters describing the shape of
the charge collection efficiency beneath the front contact [1], [2] and the thickness
of the front contact metal layer including any possible dead layer. The thickness
of the front contact layer can be determined from the spectral sensitivity curve,
the electronic noise from the line width or the zero-energy peak if available. The
parameters describing the charge collection efficiency beneath the front contact can
be obtained by fitting the model to a response function measured preferably close
above the silicon K-edge where tailing is most pronounced. Once determined, this
set of parameters can be used to calculate the response function for any photon
energy in the range from 0.1 to 30 keV.
A free computer program has been written in MATLAB. It enables the
determination of an optimal set for the five parameters by fitting a measured spectrum
for either purely monochromatic radiation or a K-series fluorescence spectrum from
a 3d metal. As the direct analytical computation is fast, a (m,n) response matrix can
be calculated to be used in an XRF quantisation program to convert the calculated
fluorescence intensities of n fluorescence lines of a multi-element specimen to an
m-channel spectrum to be directly compared to the measurement.
[1] S. Goto, Nucl. Instrum. Methods A, 333 (1993) 452 457.
[2] F. Scholze, M. Procop, X-Ray Spectrom. 30 (2001) 69 - 76

192

PB-25
Modular analytical X-Ray acquisition system (AXAS-M)
S. Pahlke, C. Dietzinger, T. Eggert, A. Pahlke, R. Sttter, F. Wiest
KETEK GmbH, Hofer Str. 3, 81737 Munich, Germany
The Analytical X-Ray Acquisition System (AXAS) is commercially available
for more than five years as a compact analogue signal processing tool including all
necessary power supplies, preamplifier and shaping amplifier in combination with a
KETEK Vitus Silicon Drift Detectors (SDD) in one housing.
The new modular Analytical X-Ray Acquisition System (AXAS-M) consists of
two parts M1 and M2. AXAS-M1 includes a thermal optimized and stabilized detector
head in combination with a reset type preamplifier and KETEK Vitus SDD with active
areas selectable from 10 to 100mm. Part M2 includes all necessary stabilized and
well-defined filtered power supplies for biasing the detector and for powering the
implemented thermoelectric cooler. Optional, signal processing either analogue
or digital can be implemented in the M2. The signal processing can be chosen by
either using an analogue shaping amplifier with an analogue-to-digital converter in
combination with a multichannel analyzer or a brand new digital pulse processor for
complete digital signal processing.
The big benefit of this unique system is that KETEK provides a complete
chain starting from the detector to the complete signal processing and the connection
to a host PC via USB interface. All parts are well optimized for operation with KETEK
Vitus SDDs to achieve best possible performance. In addition, thermal stability is
improved significantly by using a properly designed heat sink.
KETEK will present technical datasheets and spectroscopic results as
well as the complete system itself. The AXAS-M therefore represents a complete
spectroscopic system.

193

PB-26
Fast tomography for the study of time-dependent processes
I. Gomez-Morilla1, H. Rahn1, A. Waske1, J. Herzen2, S. Weise1 and S.
Odenbach1
1

Technische Universitt Dresden, Institut fr Strmungsmechanik, Lehrstuhl fr

Magnetofluiddynamik, 01062 Dresden, Germany
2
GKSS-Forschungszentrum, Max-Planck-Str. 1, 21502 Geesthacht, Germany

A new micro-computed tomography (CT) equipment was installed and

commissioned last year on the high-energy beamline HARWI II at Deutsches
Elektronen Synchrotron. In this new end-station, two different detectors can be used,
depending on the application. With one of them, high resolution analysis of static
objects can be performed. The second detector is a fast camera that enables the
acquisition of a whole tomogram in just a few seconds, in what is called process
microtomography (PCT). In contrast to conventional CT, where the time needed
to acquire a tomogram can take up to several hours, with PCT we can decrease the
scan time down to scales where the study of time-dependent processes is possible.
We will employ this technique to examine a number of dynamic samples, such as
liquid and multiphase flow in porous ceramics, and the propagation in the blood
vessels of ferrofluids acting as drug carriers for cancer treatment.
First tests have been performed in order to investigate the loss of spatial
resolution at reducing fast speeds. For this, a sequence of tomograms of a static
porous ceramic sample has been acquired with scan times ranging from 424 to 5
seconds. For comparison, the same sample has also been analysed with conventional
CT (scan time 90 minutes) and set as reference. The different fast tomograms have
been compared to the reference image, and the trade-off between resolution and
scan speed established. These conclusions, together with the planned experiments
for the next beam time at the synchrotron, will be presented.

194

PB-27
Tomography analysis of femoral bones from rats under
osteoporosis preventive treatments
I. Gomez-Morilla1, M.D. Ynsa2, J.C. Milln3, L.C. Alves4, H. Rahn1, S.
Odenbach1 and T. Pinheiro4
Technische Universitt Dresden, Institut fr Strmungsmechanik, Lehrstuhl fr
Magnetofluiddynamik, 01062 Dresden, Germany
2
Centro de Micro-Analisis de Materiales, Universidad Autonoma de Madrid, Spain
3
Departamento Terapeutica Medico-Quirurgica, Universidad de Extremadura,
Badajoz, Spain
4
Lab Feixes de Ioes, Instituto Tecnologico e Nuclear, Sacavem, Portugal
1

X-ray microtomography analysis has been performed to complement the

results achieved by nuclear microscopy in a study of femoral bones from rats under
osteoporosis preventive treatments. With nuclear microscopy, a change in the
concentration of certain elements suggested a change in bone density, but this was
not conclusive. With X-ray tomography, the changes in density may be correlated to
the changes in element distribution and concentration.
In order to study the influence of steroid supplementation on bone remodeling,
the distribution and concentration profiles of a number of elements within bone
samples were imaged by nuclear microscopy [1]. The relevance of trace elements in
bone structure and remodeling was shown. In particular, the depletion of Fe, Zn and
S could indicate a decrease in bone mass, as they are matrix constituents and/or
promoters of bone formation. With nuclear microscopy, this mass reduction could not
easily be identified, due to the fact that the mineral composition did not vary greatly.
To better evaluate the changes observed in the elemental composition of
the bone after treatment, the density should also be investigated. For this, the same
samples are being examined by X-ray tomography, a technique that permits the nondestructive examination of the inside of an object, getting as a result a 3D density
map. Any change between bone resorption by osteoclasts and bone formation by
osteoblasts causes an absolute reduction in the amount of bone in osteoporosis.
With X-ray microtomography, it is possible to image this loss of bone mass and to
correlate it to the previous results on elemental distribution. With these results, it is
possible to better weight the benefits of steroid supplementation for osteoporosis
treatment.
[1] M.D. Ynsa, F.J. Ager, L.C. Alves, M.A. Zubeldia, J.C. Millan, T. Pinheiro, Journal
of Microscopy, 224 (2006) 298 305.

195

PB-28
Ni mapping in Berkheya coddii by Micro-PIXE and NEXAFS
W.J. Przybylowicz1, T. Tyliszczak2, A. Barnabas1 and J. Mesjasz-Przybylowicz1
1

Materials Research Group, iThemba LABS, PO Box 722, Somerset West 7129,
South Africa
2
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley,
California 94720, USA

Near Edge X-ray Absorption Spectroscopy (NEXAFS) and scanning

transmission x-ray microscope (STXM), installed at 11.0.2 line of the Advanced Light
Source of Lawrence Berkeley National Laboratory, has been used for quantitative
elemental mapping in leaves of Berkheya coddii, Ni-hyperaccumulating plant from
South Africa. Specimens were prepared using cryofixation in high-pressure freezer
and freeze-substitution with diethyl ether, followed by sectioning with ultramicrotome.
Spectra and maps were processed using AXIS2000 software.
Comparative studies of the same specimens were performed with microPIXE and proton backscattering spectrometry (BS) using the nuclear microprobe
at Materials Research Group, iThemba LABS. Quantitative maps of Ni and other
elements as well as concentrations of elements from selected areas within maps
were obtained using GeoPIXE software. Thickness of specimens and composition of
major elements obtained from BS method were used for matrix corrections in PIXE
maps and spectra.
STXM offers excellent lateral resolution of the order of 30 nm. Available
energy range is 80 2100 eV with E/E > 7500. Ni mapping was performed using Ni
L3 absorption edge. Predictably, the requirement of x-ray transmission through the
specimen introduces strict limits on specimen thickness. This is a serious practical
limitation in multielemental analysis where various x-ray energies must be used.
Micro-PIXE has inferior lateral resolution (3 m x 3 m) but is much more
flexible as far as specimen thickness is concerned. Multielemental analysis and
easy quantification make it a method of choice for study of elemental distribution in
plants. However, STXM is needed for studies of the details of elemental distribution
at intracellular level, and chemical mapping.

196

PB-29
A compact 3D Micro-XRF laboratory spectrometer for
archeometric applications
M. Haschke1, D. Grtzsch1, A. Gnther1, I. Reiche 2, I. Mantouvalou 3, K. Lange3 and
B. Kanngieer3
IfG Institute for Scientific Instruments GmbH, Berlin, Germany
Laboratoire du Centre de recherche et de restauration des muses de France
(LC2RMF) UMR 171 CNRS Paris, Frankreich
3
Institut fr Optik und Atomare Physik, Technische Universitt Berlin, Berlin,
Deutschland
1

After having gained experience from the setup and applications of a 3D

Micro-XRF tabletop setup [1], a new compact 3D Micro-XRF laboratory spectrometer
was designed and developed for non-destructive investigations of cultural heritage
for the laboratory of the Center for research and restoration of French museums. For
the excitation a Rh micro focus x-ray tube is used while a SDD detector serves for
X-ray detection. The confocal setup is realized with a polycapillary mini-lens in the
excitation channel and a Poly-CCC in the detection channel forming a probing volume
with a FWHM between 33 m and 50 m depending on the searched element. The
specific feature of this setup is the measuring head with the solid mechanical fixation
of the lenses and the ease of its alignment with respect to the X-ray tube and the
detector. The lens in the excitation channel is completely fixed whereas a movement
of the Poly-CCC in the detection channel is only possible perpendicular to the beam
direction. This simplifies the adjustment of the confocal setup and minimizes the
danger of misalignment during sample change.
Several characterization measurements were carried out on this spectrometer
concerning the dependence of FWHM of the probing volume on energy and the
stability and warming up of the x-ray tube.
First investigations were carried out on paint layer dummies. Using the 3D
Micro-XRF laboratory spectrometer the course of several layers could be determined.
Further applications on archaeological and art objects are in progress.
[1] B. Kanngieer, W. Malzer, A. F. Rodriguez and I Reiche, Spectrochimica Acta
Part B, 2005, P 41-47

197

PB-30
Collimation of non-axial x-rays spectrum by means of steering
ferrofluid - way of reducing geometrical faults in x-ray-pictures
A. Dyszkiewicz1,2 , P. Poe 1, Jakub Zajdel 1 , D. Chachulski 1, B. Pawlus1,
Jan Szczegielniak2
Laboratory of Biotechnology 43-400 Cieszyn ul. Godzikw 2, Poland
Department of Biomedical Computer Systems, Institute of Informatics, Univ. of
Silesia
41 200 Sosnowiec ul. Bdziska 39, Poland
2
Affiliation of the second author (if different)
2
Technical University of Opole, Faculty of Physiotherapy, Poland
1

Issues relating to the incoherence of X-ray beams generated both by older

type X-ray tubes and newer, multi-focal tubes with a spinning anode, have been
presented in the paper. Collimators employing high-density metallic materials are
used for practical reasons to overcome difficulties with focusing X-rays. A wholly new
approach has been to use dynamic magnetorheological fluid, which serves both as
a spectrum filter and most likely also as a refractor, to change the parameters of the
diagnostic beam.
The objective was to find answers to the questions: (1) does the rotation of
the ferrofluid in the magnetic field influence the spectrum and geometry of the X-ray
beam? (2) does the presumptive change of the beams spectrum and geometry in
the ferrofluid reduce the geometrical deformations of the image as effectively as
when passing through a metal collimator?
Scope of work: performing a series of X-ray shots of a metal object and
recording their results on a "DIGORA" system matrix while maintaining a fixed
distance away from the X-ray tube.
Three series of measurements were carried out employing constant
parameters of time and emission: (1) NC no collimation; (2) MC through metal
collimators ; (3) DC through a dynamic collimator using 4 different volumes of
ferrofluid and a repeatable sequence of rotations.
The following were assessed: (1) R(m) Deformation (magnification) ratio of
the image for all the collimation techniques; R(ec) Effective collimation ratio; (c) A(e)
average energy per each 1mm2 .
Results: (1) changing the rpm of the collimator with ferrofluid, as in the case
of metal collimators, leads to a considerable fall in the magnification ratio of the
object's images; (2) The effective collimation ratio R(ec) has a significantly better
value in the ferrofluid than in the steel collimator; (3) The average energy A(e) in the
cross-sections of the collimators is higher in the case of the ferrofluid.

198

PB-31
X ray scattering tissue characterization in microbeams based
techniques
A. Tartari1,2,3, M. De Felici1,4, M. Gambaccini1,2, P. Querzoli5, C. Bonifazzi6 and R
Felici7
Department of Physics University of Ferrara I44100 Ferrara Italy
2
National Institute of Nuclear Physics (INFN), Rome, Italy
3
CNISM, National Consortium of Material Sciences, Genova, Italy
4
European Synchrotron Radiation Facility, Grenoble, France
5
Department of Experimental Medicine - University of Ferrara Ferrara Italy
6
Department of Biomedical Sciences - University of Ferrara Ferrara Italy
7
INFM/OGG c/o European Synchrotron Radiation Facility, Grenoble, France
1

High quality X ray scattering distribution were obtained from biological

samples at two typical intervals of the momentum transfer variable q=4 sin(/2)/
nm-1, i.e. 0.04 < q < 4.9 nm-1 (Small Angle X ray Scattering, the SAXS regime)
and 4.6 < q < 47.0 nm-1 (Wide Angle X ray Scattering, the WAXS regime). is the
scattering angle and the incident wavelenght. The measurements were performed
at the ID02 beam line of the ESRF-Grenoble, France and intact excided samples of
human skin, lung, white and grey cerebral matter were considered. The obtained
diffraction patterns - which found interest in technological applications other than
classical chemical structure investigations were investigated in terms of their
possible exploitation. Two techniques are particularly interested. First, pathological
signatures based on the spectrometry of scattered X ray both in wave (WDXRS) or
energy (EDXRD) dispersive modality [1]. Second, the X-ray micro-beam radiation
therapy (MRT), a preclinical radiotherapy technique based on the use of arrays of
X-ray microbeams with a mean energy in the hard X ray regime [2]. It is shown that the
inclusion of the measured scattering distribution in the photon transport calculations
induce not negligible effects in the dose deposited around the microbeams.
[1] SE Bohndiek et al. Phys Med Biol 53 (2008) 655-672
[2] M De Felici et al. Nucl Instrum Meth A580 (2007) 489-492

199

PB-32
Metals in aerosol particulate matter from the metropolitan zone
of the valley of Mexico
T. Martinez1, J. Lartigue1, G. Zarazua2, L. Carapio2, P. Avila-Perez2, S. Tejeda2.
Facultad de Qumica, Departamento de Qumica Inorgnica y Nuclear,
Universidad Nacional Autnoma de Mxico, Mxico, DF.04510, Mxico
2
National Institute of Nuclear Research. Ocoyoacac, Edo. de Mxico,
05045, Mxico.

The impact of metal pollution in the Metropolitan zone of the Valley of Mexico
was assesed by means of SEM-EDX (Scanning Electron Microscopy and Energy
Dispersive X-ray Microanalysis) of particulatte matter (Total Suspended Matter, TSP
and PM10) obtained with an automatic high volume sampler in an average flow
rate of 1.5 m3 min-1 for 24 hours in five monitoring stations of the National Network
System, covering the four cardinal directions and the center zone. One of the most
important group in which particles were classified was the metal group that acomplish
the criteria to have a transition metal in concentration 20%. Metals were observed
in all samples though with higher abundance, up to 46%, in Northwest (Tlanepantla)
and Southest (Cerro de la Estrella) monitoring stations, in both TSP and PM10.
Metals found were Ti, Cr, Mn, Ni, V, Sn, W, Co, Zr, La, Ce, Cu, Zn and Pb. Some of
them have soil as their common source but others have and anthropogenic origin
and some discussion about this subject its made.
[1] T. Martinez, J. Lartigue, P. Avila-Perez, L. Carapio, G. Zarazua, M. Navarrete,
S. Tejeda, L. Cabrera. J. of Radioanalytical and Nuclear Chemistry, 273 (3),
(2008)799-806.

200

PB-33
Identification of aerosol particle sources in semi-rural area of
Kwabenya, near Accra, Ghana
Innocent Joy Kwame Aboh1,4, Dag Henriksson1, Jens Laursen2, Magnus
Lundin1, Francis Gormon Ofosu4, Niels Pind3, Eva Selin Lindgren1 and Tomas
Wahnstrm1
1

School of Engineering, University College of Boras, SE-50190 Boras, Sweden

2
Department of Natural Sciences, University of Copenhagen, DK-1871
Frederiksberg C, Denmark
3
Department of Chemistry, University of Aarhus, DK-8000 Aarhus C, Denmark
4
National Nuclear Research Institute, Ghana Atomic Energy Commission, P. O. Box
LG80, Legon. Ghana
Aerosol particles from Kwabenya, near Accra, capital of Ghana, was sampled
using a Gent sampler. The particles were segregated into two size fractions fine
(PM2.5) and coarse (PM10-2.5) - and were collected on Nuclepore polycarbonate
membrane filters. EDXRF together with gravimetric and black carbon analysis (BC)
were used to determine elemental, BC and mass concentrations in the two particle
fractions. Principal component analysis (PCA) was applied to characterize possible
sources of the aerosol particulate matter.
Over 26 elements were identified in the aerosol samples; however not all of
them were used for the source assignments. The coarse particle fraction contained
over 80% of the mass. The results show that the fine particle fraction in the aerosol
has much higher contribution of black particles than the coarse particle fraction, a
finding which is typical of all industrial areas world-wide.
Six source profiles could be identified on the basis of element analysis.
There was very good agreement between the experimental particulate mass and the
particulate mass as modeled on the basis of the principle component analysis .

201

PB-34
Determination of elements in PM10 by EDXRF
in the air in 2006-2007 over Flanders, Belgium
Y.Makarovska1, A.Krata1, R.VanGrieken1, K. VanMeel1,
J. Vercauteren2 and E. Roekens,2
1

Micro and Trace Analysis Centre, Department of Chemistry, University of Antwerp,

Universiteitsplein 1, 2610 Antwerp, Belgium
2
Flemish Environment Agency, Kronenburgstraat 45, 2000 Antwerp, Belgium

Flanders is a densely populated region in the North of Belgium. Residents

of the region are exposed daily to ambient air pollution, arising mainly from industrial
and traffic activities and domestic heating. To better understand the high PM10
concentrations in the region the Flemish Environment Agency (VMM) carried out the
one year long Chemkar PM10 project from September 2006 to September 2007. Six
sampling sites in the region of Flanders were chosen, namely: Aarschot (background
site), Borgerhout (urban), Hasselt (suburban), Houtem (rural, about 10 km from the
North Sea), Mechelen (suburban site), Zelzate (industrial zone).
As part of the Chemkar project PM10 was collected on two types of filter
material every 6th day during 24 h with LVS automatic samplers at a flow rate of 2.3
m3/h. The PM collected on Teflon (PALL Teflo) filter material was analyzed by the
University of Antwerp (UA) with energy-dispersive X-ray fluorescence (EDXRF) and
the PM collected on quartz filter material was subjected to ion chromatography (IC)
analysis (also by UA).
The EDXRF spectrometer Epsilon 5 from PANalytical (Almelo, The
Netherlands) was used. The spectrometer has a powerful X-ray tube, 3D polarizing
geometry, up to 15 secondary targets and a high-resolution HPGe-detector. The
conditions for EDXRF determination of 22 elements (Al, Si, P, S, Cl, K, Ca, Ti, V, Cr,
Mn, Fe, Ni, Cu, Zn, As, Rh, Pd, Cd, Pt, Pb, Se) were optimized. Most of the detection
limits of elements were found within 1-5ng/m3 range. Relatively high concentrations
of some anthropogenic elements were detected. Soil fraction contribution in total
PM10, calculated on the basis of the EDXRF results was within the range of 6-14 %
depending from sampling location.
According to a comparison of IC and EDXRF results, all total Cl was found
in soluble form of Cl-. 74% of total S was SO42- for one sampling location, for other
sampling sites all total S was found in the form of SO42-.

202

PB-35
Study of the elemental concentration of air particulate matter by
EDXRF method collected in Poland.
L. Samek and M. Lankosz
AGH University of Science and Technology, Faculty of Physics and Applied
Computer Science, AL. Mickiewicza 30, 30-059 Krakow, Poland
The preliminary investigation of air particulate matter in Poland was
conducted. All the sample collecting took place in a small city placed 25 km S/E from
Warszawa in the Warszawa province, Poland. This city is a healthresort, all covered
with forests. The NILU Filter holder System was used to collect the particulate matter
on Nuclepore filters. The air particulate matter was divided into grainsize fractions.
The samples were measured on the EDXRF spectrometer. Elemental concentrations
were calculated using the AXIL program. Concentrations of particulate matter were
below admissible values. Coarse fraction (> 8 m) contained mainly soil derived
elements like Ca, Ti, Fe. Pb and Br were derived equally by all collected fractions.
Zn during the first two days of the campaign was mainly in coarse fraction but
afterwards it changed into fine fraction. The measurement in various seasons will
be continued.

203

PB-36
Analysis of urban and sub-urban fine particles (PM2.5)
collected in Ouagadougou, Burkina Faso
J. Boman1, J. Lindn2, S. Thorsson2, B. Holmer2, I. Eliasson2
University of Gothenburg, department of chemistry, Atmospheric science,
SE-412 96 Gteborg, Sweden
2
University of Gothenburg, department of earth science, urban climate group,
Box 460, SE-405 30 Gteborg, Sweden
1

Background measurements of CO, PM, NOx, VOC and O3 along with

meteorological parameters was performed at two sites in Ouagadougou, Burkina
Faso in December 2007. The aim was to determine the mass, black carbon (BC)
and elemental concentrations in fine particles (PM2.5) and their variations at the two
sites. Ouagadougou is located in the hot arid steppe climate of the Sahel region at
1220 N, 140 W. The weather situation in Ouagadougou during the field campaign
was dominated by high pressure with variable cloudiness and no precipitation.
Temperatures varied between 19 - 38 C and wind speeds show a diurnal pattern
with gusts of up to 6 m/s during daytime, while evenings and nights were generally
calmer ( 3 m/s) with more stable atmospheric conditions.
Cyclones were used at both sites to collect PM2.5. The inorganic analysis
was done using EDXRF spectroscopy. Cl, K, Ca, Ti, Mn, Fe, Cu, Zn, Br, Rb, Sr and
Pb were identified and quantified in the samples. The mass concentration of the
collected particles varied between 27 - 164 g/m3 while the BC varied between 1.3
and 8.2 g/m3. Iron attributed to half of the weight of the detected elements. Mean
concentrations of Br and Pb was higher at the sub-urban site. The concentration of
the other detected elements and the mass and BC content was higher in the urban
site compared to the sub-urban site. The similar mass variation at both sites can be
attributed to the soil dust present in the air most of the day. This was confirmed by
comparing the elemental content on the particle samples with the elements on an
analyzed soil sample.
The project was performed in collaboration with Directeur Diallo and his staff
at Direction de la Meteorologie Nationale (DMN) in Ouagadougou, Burkina Faso
whose help we acknowledge greatly. The project is financially supported by SIDA/
sarec.

204

PB-37
Elemental content of aerosol particles in an underground
tram station
J. Boman1, M. L. de Carvalho2, M. B. Alizadeh1, P. Rezaievar1 and A. Wagner1
1

University of Gothenburg, department of chemistry, Atmospheric science,

SE-412 96 Gteborg, Sweden
2

Department of Atomic Physics, University of Lisbon, Lisbon, Portugal

Particulate matter is an important air pollutant, especially in closed environ

ments like a tunnel. The aim of this study was to determine the mass, black carbon
and elemental concentrations of particulate matter of two size fractions at an
underground tram station in Hammarkullen, Gteborg, Sweden. Samples were
collected during June 2007 using a dichotomous virtual impactor separating the
sampled aerosol particles into coarse (aerodynamic diameter between 2.5 and 10
m) and fine fractions (below 2.5 m). To minimize the possible influence of waiting
passengers the platform for trams going towards the suburb Angered was chosen.
The elemental analysis of the samples, collected on Teflon filters, was carried out
using EDXRF spectroscopy resulting in concentrations of 13 elements in most of
the samples. Data reduction was done by Principal Component Analysis (PCA) to
identify possible sources for the elements in the particles.
Due to the tunnel environment the difference between the fine and coarse
particle fractions was not as large as under normal ambient conditions. Likewise
the influence of the local weather was not significant. Particle content from the
tram traffic as well as from natural sources were identified, with Fe being the major
element in both coarse and fine particles. Comparing the mass concentration of the
measured aerosol particles to the corresponding ambient concentration measured
at a monitoring station in downtown Gteborg shows a higher mass concentration
in the tunnel. In some days the mass concentration was over the daily ambient air
quality standard of 50 g/m3, but lower than the limits in the environmental work act,
5 mg/m3.
This project has been carried out in cooperation between University of
Gothenburg, Chalmers University of Technology, University of Lisbon, Gothenburg
Environmental Protection Agency and Gothenburg Traffic and Public transport
Authority. The kind support of all involved parts is highly appreciated.

205

PB-38
Trace elements in hourly ambient aerosol samples determined
with synchrotron XRF
M. Furger1, A. Richard1, N. Bukowiecki2, P. Lienemann2, D. Grolimund1, A.S.H.
Prvt1 and U. Baltensperger1
1

Paul Scherrer Institut, 5232 Villigen PSI, Switzerland

2
Empa, 8600 Dbendorf, Switzerland

Ambient aerosols were sampled with a rotating drum impactor (RDI) in

different places in Switzerland in the winter of 2005/2006. RDIs allow for a sizesegregated collection of particulate matter in the size ranges of 0.1 1 m, 1 2.5
m, and 2.5 10 m. With sampling time of one or two hours, relatively little mass
is deposited on the collecting substrate, a 1.8-m Mylar foil. For the analysis of trace
element concentrations, reasonable signal-to-noise and signal-to-background ratios
were achieved with synchrotron-XRF[1,2], which was performed at PSI's synchrotron
light source, SLS. However, the smaller size ranges typically exhibit an increasing
amount of carbonaceous material not accessible with synchrotron-XRF.
The results showed remarkable differences in sample composition for the
different size ranges. Zurich and Reiden, the sampling sites north of the Alps, show
similar elemental distributions in the smaller size ranges. In the largest size range,
Cl is conspicuous for Reiden, which is close to a freeway where road salt is regularly
applied in winter. The intermediate and smallest ranges are dominated by S and K.
South of the Alps, Cl is the dominant element in the largest size fraction, Fe in the
intermediate fraction, and S and K equal each other in the smallest size fraction.
[1] N. Bukowiecki et al., Environmental Science and Technology 39 (2005)
5754-5762
[2] N. Bukowiecki et al., Spectrochimica Acta Part B, in preparation (2008)

206

PB-39
PIXE and XRF analysis of Suspended Particulates in an Urban
Residential Area of Zagreb, Croatia.
S. Bamford1, 2, M. Jaki3, S. Fazini3, D. Wegrzynek1, 4, E. Chinea-Cano1, K.
ega5, I. Beslic5, A. Markowicz1, 4, and P. Wobrauschek2
International Atomic Energy Agency, IAEA Laboratories, A-2444 Seibersdorf,
Austria
2
Atominstitut der Oesterreichen Universitaeten, TUW, Vienna, Austria
3
Ruder Boskovic Institute, Zagreb, Croatia
4
Faculty of Physics and Applied Computer Science, AGH University of Science and
Technology, 30-059 Krakow, Poland
5
Institute for Medical Research and Occupational Health, Zagreb, Croatia
1

Knowledge of the elemental composition of airborne particulates is essential

to identify potentially toxic components, enable pollution source profiling and
apportionment, and augment the assessment of the effects of particulate matter
on health and welfare [1]. Nevertheless, no single analytical method is suitable
for measuring all chemical species of interest in airborne particulates. PIXE and
XRF techniques [2,3] were consequently employed in an optimized manner to
characterize a wide range of elements in suspended particulates collected from an
urban residential area in Zagreb, Croatia, during summer and winter seasons. The
PIXE quantitative technique, based on calibration done using micromatter standards,
showed enhanced sensitivity for low Z elements at 2 MeV proton energy with a mylar
filter of 24m, for air filter analysis. The XRF spectrometer was also optimized by
careful selection and combination of four secondary/polarizing excitation targets of
Ti, Co, Mo, and Al2O3 Barkla polarizer. Validation of the quantitative methods of both
techniques with the air filter standard SRM2783 gave good agreement in the results
for most of the elements. Consequently, by focusing on the inherent strengths of the
two respective techniques, the following elements were identified and quantified: Al,
Si, S, Cl, K, Ca, Cr, Mn, Fe, Cu, Zn, Br, and Pb. A comparison was carried out on the
elemental compositions of the suspended particulates in the different seasons, and
between the two techniques.
[1] W. Zhao, and P. Hopke, Atmospheric Environment, 38 (2004) 5901.
[2] USEPA, Compendium Method IO-3.6, Determination of Metals in Ambient
Particulate Matter using Proton Induced X-ray Emission (PIXE) Spectroscopy
EPA/625/R-96/010a, June 1999)
[3] USEPA, Compendium Method IO-3.3, Determination of Metals in Ambient
Particulate Matter using X-ray Fluorescence (XRF) Spectroscopy EPA/625/R96/010a, June 1999

207

PB-40
Seasonal variations in particulate mass concentrations and
elemental composition of urban aerosols in Zagreb, Croatia,
using ED(P)XRF analysis
S. Bamford1, 3, K. ega2, I. Beli2, R. Godec2, and P. Wobrauschek3
International Atomic Energy Agency, IAEA Laboratories, A-2444 Seibersdorf,
Austria
2
Institute for Medical Research and Occupational Health, Zagreb, Croatia
3
Atominstitut der Oesterreichen Universitaeten, TUW, Vienna, Austria

Significant efforts in time, instrumentation, expertise, and money are

required in aerosol sampling and data generation. It is therefore unfortunate to focus
mainly on mass concentration measurements in air pollution studies. Subsequent
and additional determination of the chemical composition of aerosol particles is
needful, and of interest in deriving maximum information from collected aerosols
[1]. Particle mass concentrations of suspended particulates in an urban residential
area in Zagreb, Croatia, have been determined using the Gent air sampler at an
average flow rate of 1 m3/h. Twenty four hour samples were collected during the
periods July September 2007, and December 2007 January 2008, and the mass
concentrations for coarse and fine particle fractions have been determined and
compared for the two seasons. This was followed by elemental composition analysis
using energy dispersive polarized x-ray fluorescence (ED(P)XRF) spectrometry, with
four secondary/polarizing excitation targets [2]. Also presented and compared, are
the elemental concentration results of the following identified elements: Al, Si, S, Cl,
K, Ca, Ti, Cr, Mn, Fe, Cu, Zn, Pb, and Br. This paper also discusses the seasonal
influences on the particulate and elemental concentration levels.
[1] R. Harrison, and J. Yin, The Science of the Total Environment, 249 (2000)
85-101.
[2] J. Heckel, M. Haschke, M. Brumme, and R. Schindler, J. Anal. Atom. Spectrom.
7, (1992) 281

208

PB-41
Analysis of methyl bromide ozone depleting substance
R. Moschochoritou1 and N. Kallithrakas-Kontos2
1

Laboratory of Physical Sciences, Akrotiri Lyceum, Akrotiri, GR-73100 Chania,

Greece
2
Technical University of Crete, Analytical and Environmental Chemistry Lab.,
University Campus, GR-73100 Chania, Greece

Methyl bromide (bromomethane, CH3Br) is a wide application fumigant (e.g.

in wood exporting; ISPM-15 regulation) and a soil sterilant. On the other hand methyl
bromide is in the list of the ozone depletion substances [1] (bromine is much more
dangerous for the ozone layer than chlorine).
During methyl bromide application as fumigant, it usually makes a thin layer
on the sterilized surface. This layer can stay for many days (or even months) and
its analysis is not easy with conventional methods of chemical analysis, especially
if a fast and on site method is needed. Energy Dispersive X-Ray Fluorescence
(EDXRF) cannot determine organic substances but it can easily analyze bromine.
If the sterilized substrate (blank sample) does not contain high bromine content,
bromine concentration can be attributed to methyl bromide. Analysis of thin layers
is a quite accurate task in XRF analysis, if a suitable thin standard calibration has
been used.
In the present work imported (from a non EU country) rubber samples that
had been processed by methyl bromide fumigant, were analyzed for residual bromine.
Radioisotope excitation and EDXRF analysis was used, with NIST and Micromatter
thin target calibration; calibration assurance was confirmed by IAEA Interlaboratory
test [2]. Blank rubber samples did not contain detectable bromine quantities, while
analyzed samples contain significant amounts (of the order of 10 g/cm2) of methyl
bromine; this amount was reduced as a function of time. The method can be easily
used with an XRF mobile system for in situ analyses.
[1] http://www.epa.gov/Ozone/ods.html

209

PB-42
Determination of trace metal concentrations in waters of
Nakivubo channel and Lake Victoria using Energy Dispersive
X-ray Fluorescence Analysis
B. B. Naziriwo1, 2, S. O. Wandiga2, M. J. G. Gatari3, O. V. Madadi2 and P. J.
Ssebuwufu1
Department of Chemistry, Makerere University, P .O. Box 7062,Kampala,
Uganda.
2
Department of Chemistry, University of Nairobi, P. O. Box 30197-00100, Nairobi,
Kenya.
3
Institute of Nuclear Science & Technology, University of Nairobi, P. O. Box
3019-00100, Nairobi, Kenya.
1

In an effort to understand the pollution levels in waters of Nakivubo channel

in Kampala, Uganda and Lake Victoria concentrations of Mn, Fe, Co, Cu, Zn and Pb
were determined using convectional EDXRF and TXRF analysis.
Water samples were collected with a 1-litre Van Don sampler (code, 1077)
and transferred into polyethylene containers that were stored in an ice cooled box.
Five samples were obtained at each sampling site and were all stored at -21 0C until
analysis. Filtration on cellulose filter gave a particulate deposit that was analyzed
for trace metals on a convectional EDXRF spectrometer. Pre-concentration and
evaporation at 50 0C were used for extraction of dissolved metal content that was
analyzed on TXRF. Samples of the unfiltered water were treated with HNO3 and H202
in a process for extracting total trace metal content that was subsequently prepared
and analyzed on TXRF. Spectra from the spectrometers were analyzed for the trace
elements of interest and elemental quantification was achieved using Quantitative
X-ray Analysis software from International Atomic Energy Agency.
The results showed high concentrations of particulate Fe and Mn, and
relatively low Zn upstream the Nakivubo Channel. These were lower in the Lake
Victoria waters. At the shores of Lake Victoria the dissolved Fe and Zn were higher
than in the channel. The concentrations of Fe, Mn and Zn in Lake Victoria were
below the USEPA maximum contamination limits of 0.3, 0.05 and 5 mg/L respectively.
However, Fe at the mouth of Nakivubo Channel was high and in general the quantified
total elemental concentrations increased upstream along the channel. This meant
increased water pollution input upstream and along the channel.
US Environmental Protection Agency (EPA), www.epa.gov/osw/ visited on 23rd
February 2008.
Morin et al. (2008). Environmental Pollution 151: 532-542
Acknowledgement:
The authors appreciate TWOWS financial support to Betty through Makerere
University, Uganda and University of Nairobi, Kenya. The assistance by IAEA and
IPPS, Uppsala University, Sweden to Institute of Nuclear Science & Technology
(INST) and the technical staff at INST.
210

PB-43
Analysis of major and trace elements content of mining waters
by means of wavelength dispersive X-ray fluorescence of dried
residues
O. Gonzalez-Fernandez and I. Queralt
Laboratory of X-ray Analytical Applications, Institute of Earth Sciences Jaume
Almera, CSIC, Sol Sabars, s/n 08028 Barcelona, Spain
Analysis of trace heavy metals and major elements in aqueous solutions is
becoming more important due to the increasing of environmental quality regulations.
XRF techniques have been widely employed for the study and assessment of
soil pollution. At many polluted sites, there are also concerns about heavy metal
contamination of ground and surface stream water. The major drawback to the use
of conventional XRF equipments (EDXRF and WDXRF) for water analysis raises
in the detection limits that ranges in the mgL-1 order. The common concentration
of many pollutants is at gL-1 levels. To solve this situation several specimen
preparation methodologies (precipitation, ion exchange, extraction and desiccation)
were proposed [1]-[2].
In this work, we use a conventional WDXRF instrumentation to evaluate the
content of a wide range of elements (20 different elements ranging from Na to Pb) in
heavy metals polluted waters.
Samples were prepared by drying on a Prolene film producing a thin layer.
Spectra were evaluated integrating the peak area instead of the commonly peak
net intensity used in WDXRF. The limit of detection and sensitivities were calculated
for all the elements using 3 different multielemental standard solutions. Limits of
detection were improved respect to other studies obtaining limits of detection ranging
from 0.005 to 0.1 mgL-1.
Several mine water samples were analyzed and the results from the
WDXRF method were compared with the results from Inductively Coupled Plasma
spectrometry methods (ICP-MS and ICP-OES). The WDXRF results show a good
agreement for the elements of Z>20 and some discrepancies in the elements with
Z=<20.
[1] Van Grieken, R., 1982, Preconcentration methods for the analysis of water by
X-ray spectrometric techniques. Analytica Chimica Acta. 143, 3-34.
[2] Anderson, E.C., Shumway, B., and Turner, C., 2000, Preparation and
characterization of dried residue calibration standards for use in microsample X-ray
analysis, 43, 456-464.

211

PB-44
XRF determination of metals in water using Polyurethane foams
N. Alov, R. Bulgachev and S. Dmitrienko
Lomonosov Moscow State University,
Department of Analytical Chemistry, 119992 Moscow, Russia
In this paper we propose a new high-performance technique of X-ray
fluorescence (XRF) determination of metals (iron, cobalt, manganese, lead, and
mercury) collected on polyurethane foam (PUF) discs using different chemical
reagents (KSCN, PAN, and dithizone) in drinking and natural water. Analysis of PUF
discs after the metal sorption from water was carried out by a portable wave-dispersive
X-ray fluorescence spectrometer Spectroscan (Spectron). The mechanisms of metal
sorption in the presence of KSCN, PAN and dithizone on PUF discs were studied
and the optimal conditions for metal sorption were found. The combined sorption and
XRF technique was checked using the method "added found" and it was proved to
give good results for determination of metal contents in water in the range of 10-2-10
g ml-1. The technique developed is very simple, cheap and rather quick, does not
demand complicated device and expensive chemicals and can be used for routine
and field analyses and monitoring research. It allows to carry out simultaneous
multielement analysis, does not need PUF discs to be colored and does not demand
all the solution impurities to be masked or removed. We used our new combined
sorption and XRF technique for determination of the contents of metals in drinking
water from different sources and manufacturers, in Moscow tape water, in natural
water from two Moscow rivers and several ponds, in winter and spring snow.

212

PB-45
WDXRS of minor and trace element contents in the soil of
moscow's park
D. Zaichick1, V. Zaichick2, S. Lyapunov3 and E. Schevchenko3
Moscow State Agricultural Academy, Moscow 127550, Russia
Medical Radiological Research Centre, Obninsk 249020, Russia
3
Geological Institute of Russian Academy of Sciences, Moscow 109017, Russia
1

Within recent years Moscow traffic increased greatly that made the ecological
situation of the capital much worse. The topsoil is a strong absorber of many chemical
elements keeping them in the surface, the most fertile layer. Thus, changes in the
chemical contents of surface soil layer reflect adequately environmental cumulative
alterations conditioned by the effect of both local and global factors. The aim of
the present study was to determine concentrations of some chemical elements in
topsoil samples of the Wooded Experimental Dacha (WED) belonged to the Moscow
Agricultural Academy (MAA) using wave dispersive X-ray fluorescent spectroscopy
(WDXRS). A simultaneous analysis of sub-samples of the CRM IAEA Soil-7 reference
material was used to estimate the method reproducibility and the accuracy of the
obtained results.
Contents of As, Ba, Br, Co, Cr, Cu, Fe, Mn, Mo, Nb, Ni, Pb, Rb, Sr, Th, Ti, V,
U, Y, Zn, and Zr were measured using ARF-6 Analyzer (Ag-, Mo-tube) and SPM-25
Quantometer (Rh-tube). Measurements of 100s duration were carried out twice. The
K1-lines were used to register intensities of characteristic X-ray of Ti, V, Cr, Mn,
Fe, Co, Ni, Cu, Zn, As, Br, Rb, Sr, Y, Zr, Nb, Mo, Ba and L1-lines - Pb, Th, and U.
The sample matrix effect was account by noncoherent scattered K-line of the X-ray
tube.
The total contents of all investigated chemical elements in the topsoil of WED of
MAA were in the range characteristic for norm or clean soil and do not exceed
Russian environmental quality standards. For example, mean concentration of Pb
equal 17.9 mg/kg (range 12.5-24.8 mg/kg) is under Russian environmental standard
limit (32 mg/kg) and more less than Pb level in park soil of many cities of West
Europe and North America.

213

PB-46
Application of a portable EDXRF spectrometer for in-situ
measurement of pollutants in over-bank sediments of Mati River
(Northern Albania)
N. Civici1 and A. Tashko2
1

Institute of Nuclear Physics, Rr. Qesarake, P.O.Box 85, Tirana, Albania

Faculty of Geology and Mining, Polytechnic University, Tirana, Albania

The recent interest in assessment of environmental pollution has created a

growing need for in-situ analysis of a variety of pollutants in samples of different kind.
Field portable EDXRF instruments offer great possibilities in this kind of activities.
The measuring head of the portable EDXRF spectrometer assembled at our
laboratory includes a Peltier-cooled Si-PIN X-ray detector (XR-100CR, AMPTEK INC.,
USA) and a Cd-109 disc source (740 MBq) mounted in an orthogonal geometry. The
spectrum acquisition system consists of the power supply and amplifier (PX2CR),
Pocket MCA 8000A and palmtop computer (HP200LX). The spectrometer allows
the multielement analysis of soil and sediment samples with acceptable analytical
parameters. The calculated detection limits vary from about 2500 ppm for K to about
25 ppm for Cu and up to about 5 ppm for the elements from Rb to Zr. The precision
for major elements is generally better than 5%, while for most of the minor and
trace analyzed elements its values are within 10%. Generally a good agreement
is observed between the measured and recommended concentrations of standard
reference materials (SRM).
Overbank sediments of the Mati River are contaminated due to former Cu
mining and metallurgical activities in the drainage basin. The concentrations of four
major and twelve trace elements are determined by the in situ measurements of
the different cross sections of overbank sediments. The results show that the main
pollutants are Cu, Zn, As and Se which as confirmed by Factor Analysis are related
with two main sources: copper metallurgy and copper ore processing plant. In the
same time the results permitted not only the evaluation of the contamination but
also the possibility to give an indication of the contamination history of the studied
sediments.

214

PB-47
Determination of Mo, Nb, Zr, Y, Sr, Rb, U, Th, Pb in different
rocks by X-ray fluorescence analysis
E.V. Khudonogova and T.Yu. Cherkashina
Institute of the Earths Crust, SB, RAS, Russia
Nowadays there are many techniques to determine Mo, Nb, Zr, Y, Sr, Rb, U, Th,
and Pb in different rocks [1, 2]. During last 17 years we have accumulated the practical
material on the application of XRF to the quantitative determination of contents of main
and trace (C, F, Sc, V, Cr, Co, Ni, Cu, Zn, Ga, As, Rb, Sr, Y, Zr, Nb, Mo, Ba, La, Ce,
Pb, Th, U, W,) elements [3]. With progress in new technologies of substance study
and development of analytical instruments of new generations the analytical studies
are necessary in order to improve the techniques already existed for the quantitative
determination of chemical compositions of different geological materials.
This report presents our technique for the quantitative determination of Mo,
Nb, Zr, Y, Sr, Rb, U, Th, and Pb contents in different rocks using the S4 PIONEER
automated X-ray spectrometer. The optimum parameters and measuring conditions
were chosen for each element determined. For the accurate determination of contents
of elements under analysis the contribution of foreign radiation to an experimental
intensity of analytical line has been taken into account: for MoK1 ZrK1, for ZrK1
SrK1, for YK1 RbK1, for NbK1 YK1, for UL1 RbK1, SrK1, for ThL1 RbK1.
To correct interelement effects the background standard method was used. When
calculating Mo, Nb, Zr, Sr contents the incoherently scattered characteristic radiation
of the X-ray tube anode was used as the standard. When calculating Y, Rb U, Th,
and Pb contents the radiation intensity was used as the standard that was measured
at the angular position 2 = 29. We successfully used this angular position before.
When calculating the calibration characteristics the certified reference materials
of rocks of different compositions were used. The ranges of determined contents were
as follows (in ppm): Mo 10-260, Nb 3-380, Zr 50-990, Y 5-130, Sr 5-3200,
Rb 11-1900, U 2-63, Th 2-130, and Pb 5-490. The metrological studies were
conducted to estimate the accuracy of results of analysis of elements determined.
The values of the relative root-mean-square deviation of determination errors do not
exceed the values of permissible root-mean-square deviations of the relative error of
results of analysis made by the methods of I-III categories of the classification.
The work was made under support of RFBR, grant No 07-05-01061.
[1] Revenko A.G. X-ray fluorescence analysis of natural materials. Novosibirsk:
Nauka. 1994. 264 p.
[2] Rammlmair D. et al. Geology, mining, metallurgy // Handbook of Practical X-Ray
Fluorescence Analysis. Springer, Berlin, Heidelberg, New York. 2006, Chapter 7.3.
P. 640-687.
[3] A.G. Revenko, E.V. Khudonogova, T.Yu. Cherkashina. Analitika i Kontrol. V. 10.
(2006). P. 71-79.
215

PB-48
Application of High-Energy Polarised-Beam EDXRF for the study
of metal burden in mining waste samples
E. Margu1,2, K.Van Meel3, R.Van Grieken3, C.Fonts1, M.Hidalgo1 and
I.Queralt2
Department of Chemistry, University of Girona, Campus Montilivi, 17071 Girona,
Spain.
2
Laboratory of X-Ray Analytical Applications, Institute of Earth Sciences "Jaume
Almera", CSIC, Sol Sabars s/n, 08028 Barcelona, Spain.
3
Department of Chemisrty, University of Antwerp, Universiteitsplein 1, 2610
Antwerp, Belgium.

Environmental metal pollution as a result of abandoned mining activities is an

acute problem nowadays. Although mineral resource extraction has been carried out
for centuries, until the last several decades, relatively little attention has been given
to minimise the metal dispersal around this areas coming from the indiscriminately
dumping of mining waste. As a consequence, one of the challenges facing society
today is the identification, evaluation and remediation of these old disused areas to
protect public health and environment quality. These studies are heavily depending
on observation and quantitative measurements of the amounts and distribution of
metals, leading to the necessity of appropriate analytical methodologies.
The work presented is based on the application of High-Energy Polarised
Beam EDXRF spectrometry (HE-P-EDXRF) for the study of metal burden in the
remains of different flotation ponds from an abandoned Pb-Zn mining area located in
the northern part of Spain. A typical feature of these kinds of spoils is the high heavy
metal content, mostly Pb and Zn (up to gkg-1), but also the presence of other minor
and trace metals associated with sulphide ores such as copper, iron, arsenic and
cadmium (up to mgkg-1) which are also of significance due to their high toxicity even
at low concentrations. Additionally, for each mining waste sample, four different size
fractions (<500m, <250m, <125m and <63m) were studied in order to assess
the relationship between metal distribution and grain-size particles. It was found
that lower size fraction contains higher metal concentrations that can dramatically
influence the reactivity and mobility of metals and thus, the environmental impact.

216

PB-49
The seasonal variation of the elemental composition of
particulate matter in Skopje, FYR of Macedonia
Borka Kovacevik1, Annemarie Wagner1, Johan Boman1, Jens Laursen2, and
Jan B. C. Pettersson1
Department of Chemistry, Atmospheric Science, University of Gothenburg,
SE-412 96 Gothenburg, Sweden
2
University of Copenhagen - Faculty of Life Sciences, Department of Natural
Sciences, Thorvaldsensvej 40, DK-1871 Frederiksberg C, Denmark
1

Aerosol samples were collected at an urban background site in Skopje,

FYR of Macedonia, during four measurement campaigns from December 2006
to October 2007. An impactor was used to collect aerosol particles in a PM2.5 size
fraction (total mass of particles with an equivalent aerodynamic diameter < 2.5
m), and the samples were analysed for particulate mass, black carbon (BC) and
seventeen elements (Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, Pb).
The 12 h average PM2.5 concentrations varied in the range 10-140 g m-3 with the
highest concentrations measured during wintertime pollution episodes and during
the summer period. A statistical analysis of the dataset by means of factor analysis
indicated large contributions to the aerosol from mineral dust (main observed tracers
Si, K, Ca, Mn, Fe, Br), combustion sources (BC, S, Ni and Cu) and traffic (Pb, Zn).
Combustions sources dominated during wintertime and were likely dominated by
biomass burning and industrial activities within the city area. Mineral dust was
observed throughout the year, but peaked during the unusually hot and dry summer
of 2007. It is concluded that Skopje suffers from serious air pollution due to central
and residential heating, the transport sector and industrial activities within the city.
Topography and meteorological conditions aggravate the problems, and make the
air quality comparable to the conditions in highly polluted mega-cities around the
world.

217

PB-50
Design and development of an Energy-Dispersive X-ray
Spectrometer: A tool for environmental research in Kenya
M.J. G. Gatari1 and Johan Boman2
University of Nairobi, College of Architecture & Engineering, Institute of Nuclear
Science & Technology, P. O. Box 30197-00100, Nairobi, Kenya.
2
Department of Chemistry, Atmospheric Science, Gteborg University, 412 96
Gteborg, Sweden

Contribution of scientific research to local and international journals from

Africa and indeed Kenya is weak in comparison to other regions. One of the main
problems is the non-availability of reliable and affordable analytical instrumentation.
Energy-Dispersive X-ray Fluorescence (EDXRF) analysis is a special analytical
technique for trace elements in that it is economical and easy to use. Its analytical
capacity has the advantage of having multi-elemental characteristics and satisfactory
speed. Convectional EDXRF analysis is used in identifying toxic trace elements in the
general environment, trace elements in airborne particles for source apportionment,
investigation of micronutrients in different ecosystems and agriculture practices
among other areas of scientific investigations.
A new EDXRF Spectrometer has been built and installed at the Institute of
Nuclear Science and Technology, College of Architecture and Engineering, University
of Nairobi. It is a new research tool that has improved local analytical detection limits
of heavy metals in environmental and air pollution samples. A Siemens type D x-ray
tube-stand was modified to facilitate x-ray irradiation of a Mo-secondary target. The
target is a glued disk that was cut from a 1 mm thick Mo plate of 99.99 % purity. The
fluoresced secondary x-rays propagate through three Ag collimators giving a near
monochromatic Mo characteristic x-rays for sample excitation. The disk holder was
designed to be easily removable, from the Al-measuring head, thus allowing the
flexibility of carrying out experiments using different secondary targets. Air samples
on Teflon filters and water samples on Cellulose filters were analyzed. The results
were better than those obtained in previous spectrometer setups. The detection limits
of trace elements improved by a factor of 10. The spectrometer is an extra facility for
direct analysis of trace elements in air and other environmental samples.
[1] W. W. Gibbs, Scientific American, 273 (1995) 76-83
[2] A. Markowicz, N. Haselberger, N. Dargle, A. Tajani, A. Tchantchane, V. Valkovic,
P. R. Danesi, Radioanalytical and Nuclear Chemistry, 206 (1996) 269-277
Acknowledgement
International Programme in the Physical Sciences, Uppsala University, Sweden,
funded the project.
218

Abstracts
Poster Session C

PC-1
XRD and EDS investigations of metal matrix composites and
syntactic foams
I. N. Orbulov1, . Nmeth1 and J. Dobrnszky2
Budapest University of Technology and Economics, Department of Materials
Science and Engineering, H1111, Goldmann tr 3, Budapest, Hungary
2
Research Group for Metals Technology of the Hungarian Academy of Sciences,
H1111, Goldmann tr 3, Budapest, Hungary
1

Unidirectionally reinforced metal matrix composite blocks (MMCs), containing

~60 vol% carbon fibers were made by pressure infiltration technique. Two types of
carbon fibers were applied; one had rather amorphous microstructure than other. X-ray
diffraction (XRD) measurements were done to determine the quantity of intermetallic
phase (Al4C3) in the interfacial zones. This is important because aluminium-carbide
has strong influence on mechanical properties. XRD measurements showed that
in carbon fiber reinforced metal matrix composites, which have higher quantity of
amorphous carbon phase higher quantity of Al4C3 was formed. The crystallinity
of carbon fibers was determined also by XRD method. When carbon fiber which
contained higher quantity of amorphous phase was used, 18 times higher amount
of Al4C3 produced.
Metal matrix syntactic foams filled with ceramic microballoons were produced
by vacuumpressure infiltration method. These cellular materials are closed cell
foams, but they can be classified as MMC also. In the case of syntactic foams porosity
which is the main property of these materials is generated by introducing hollow
spheres (microballoons) into the matrix. In the syntactic foams different reactions can
be happened between aluminum matrix and microballoons with high alumina and
silicon content. The morphology and microchemical composition were investigated
by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS)
analysis, to clarify the kinetics of interphase reactions and the timetemperature
dependence.
[1] S. Kleiner, F. A. Khalid, P. W. Ruch, S. Meier, O. Beffort, Scripta Materialia, 55
(2006) 291 294.
[2] K-C. Chang, K. Matsugi, G. Sasagi, O. Yanagisawa, JSME International Journal
Series A 48 (2005) 205 209.
[3] D. K. Balch, D. C. Duand, Acta Materialia 54 (2006) 1501 1511.

221

PC-2
X-Ray diffraction studies on crystallography of Martensite in two
Copper based shape memory alloys
O. Adiguzel
Firat University, Department of Physics, 23169 Elazig/Turkey
Shape memory effect is an unusually property exhibited by certain alloy
systems, and the behaviour of shape memory alloys is evaluated on the basis of
structural changes on the microscopic scale. The origin of shape memory effect is
closely related to the changes in internal crystalline structure of materials caused
by a phase transition, martensitic transition. This transition occurs on cooling from
high temperature; and microstructural changes in microscopic scale govern this
property.
Metastable beta-phases of noble metal copper based ternary alloys
transform martensitically from the ordered structures to the layered structures on
cooling from high temperatures. Martensitic transformations occur in a few steps
with the cooperative movement of atoms less than interatomic distances by means of
lattice invariant shears on a {110}-type plane of austenite matrix which is basal plane
or stacking plane of martensite. Product phase in this transition has the unusual
layered structures which consist of an array of close-packed planes with complicated
stacking sequences called as 3R, 9R or 18R martensites depending on the stacking
sequences on {110}- type planes of parent phase.
On the basis of austenite-martensite relation, it is experimentally determined
that the basal plane of 9R (or 18R) martensites originates from one of the {110} -type
planes of the parent phase, on which a homogenous shear occurs in two opposite
directions with martensite formation. Furthermore, another step is hexagonal
distortion of basal plane and at which atom sizes have important effect. The basal
plane becomes ideal hexagon or distorted hexagon, respectively dependent on the
equivalence or differences of atom sizes occupying the lattice sites.
Due to this distortion, the interplane distances of some plane pairs providing
a special relation between miller indices become equal or different, and differences
leads to disordering in martensite. In the present contribution, x-ray diffraction studies
have been carried out on two copper based ternary alloys, which have the following
alloy compositions in weight, respectively; Cu-26.1%Zn 4%Al and Cu-11%Al-6%Mn.
X-ray powder diffraction profiles have been taken several times after post-quench
heat treatments. These profiles reveal that peak locations of some diffracted planes
change with ageing, and one can say that these changes lead to the disordering in
crystal lattice of materials.

222

PC-3
X-ray study of composite materials based on montmorillonite
organoclay
G. Puchkovska1, T. Bezrodna1, A. Tolochko1, E. Kotelnikova2, N. Platonova2
Institute of Physics NAS Ukraine, 46 Nauki prosp., Kyiv 03022, Ukraine
St. Petersburg University, 7/9 Universitetskaya Quay, St. Petersburg 199034,
Russia
1

Nanocomposites based on organoclay nanoparticles in the polymer or

organic media draw much attention of researches due to their potential applications
for the development of information record and storage devices, photonic crystals,
opto-electronic equipment, etc. This work deals with the investigations of the
nanocomposites based on montmorillonite modified with cetyltrimethylammonium
bromide (CTAB) surfactant. The analysis of the results obtained by X-ray diffraction
(small and medium angle ranges), IRspectroscopy (400 4000 cm-1, at the
temperature range 100 400 K) and DSC methods is presented. The changes of the
montmorillonite interlayer distances in the dependence on the sample preparation
method, filler type and surrounding organic media are discussed. The nematic liquid
crystal, 4-pentyl-4-cyanobiphenyl (5CB) and glycol were used as fillers. The models
for the CTAB molecule arrangements in the montmorillonite galleries are proposed
and analyzed in the comparison way with other ionic surfactants containing longer
alkyl chains. The possible mechanisms of the interface interactions between the
solid particles and organic matrix are concluded from the IRspectroscopy study. The
phase transitions of bulk CTAB, CTAB-modified organoclay and the heterosystem of
5CB CTAB-modified organoclay are investigated in the temperature range 100
400 K by the IR-spectroscopy and DSC methods. The possibility of the CTAB rotator
phase display in the montmorillonite organoclay is demonstrated.

223

PC-4
Depth dependant nanolayer analysis of vertical sidewalls on
structured wafers
P. Hnicke1, B. Beckhoff1, M. Kolbe1, T. Conard2, S. List3 and H. Struyff2
1

Physikalisch-Technischen Bundesanstalt, Abbestr. 2-12, 10587 Berlin

2
IMEC, Kapeldreef 75, B-3001 Leuven, Belgium
3
Intel assignee at IMEC, Kapeldreef 75, B-3001 Leuven, Belgium

Complete cleans characterization plays an important role in todays

semiconductor fabrication. This term summarizes investigations necessary to
understand and improve cleaning processes, i.e. etch residue removal. Therefore,
depth profiles as well as the chemical speciation of certain contaminants gain useful
information.
Sidewall layers are of special interest but using most non-destructive
analytical techniques they are only accessible with difficulties, e.g. ARXPS[1].The
PTB developed an advanced alignment strategy to specify elemental depth profiling
in sidewall layers on structured wafers by X-ray fluorescence analysis (XRF) [2].
Therefore total-reflection XRF (TXRF) [3] and grazing incidence XRF (GIXRF)
techniques were combined employing monochromatized undulator radiation in the
soft X-ray energy range. The investigated structures consisted of silicon bars with
thicknesses in the m and the nm range. On each sidewall a silicon nitride layer
was deposited. Four different types regarding the bar thickness and density of these
structures were examined. The developed alignment procedure consists of three
main steps and allows for distinct excitation of sidewalls in the different structure
types in order to provide information about depth dependant sidewall contamination,
composition, layer thickness as well as chemical speciation. First results, obtained
on these samples, demonstrate the potential of this technique.
The development of this alignment procedure enables measurements for
cleans characterization and depth profiling on sidewall structures. The XRF methods
used provide an enhanced information depth compared to ARXPS. Hence, layer
systems with thicknesses of several 10 nm can be characterized.
However, there are requirements towards samples due to the size of the
beam footprint: the structures must be of comparable dimensions to the ones
presented here. Furthermore, it is necessary, that the structures are spread evenly
across this field because the technique is based on the simultaneous excitation of
multiple sidewalls.
[1] T. Conard, S. List, M. Claes, B. Beckhoff, Solid State Phen., 134 (2008)
281-284.
[2] B. Beckhoff, R. Fliegauf, P. Hnicke, M. Kolbe, M. Mller, B. Pollakowski, J.
Weser, G. Ulm, ECS Transactions, 11(3) (2007) 273-279.
[3] B. Beckhoff, R. Fliegauf, M. Kolbe, M. Mller, J. Weser, G. Ulm, Anal. Chem., 79
(2007) 7873-7882.
224

PC-5
Corrosion layers on steel and their XPS analysis
J. Petr1, M. Hubikov2, P.Sajdl1
1

Department of Power Engineering, Institute of Chemical Technology, Technick 5,

Prague 6, Czech Republic
2
Central Laboratories, Institute of Chemical Technology

This work is focused on the efficiency of corrosion inhibitors. Various types of

corrosion layers were created for testing corrosion inhibitors. Steel samples (Czech
Standard CSN 411373) were exposed to 6% FeCl3 solution (by ASTM G48-03) for 1,
3, 5 and 7 days. Prepared corrosion layers were analyzed by XPS method on ESCA.
Measured spectra describe surface conditions which are very important for following
measuring of inhibitors effectiveness. Surface properties markedly influence an
inhibitory activity.
The inhibitors used in this study were triethoxy-3-(2-imidazolin-1-yl)
propylsilane and T 440E, T 8529E (inhibitors used for industrial applications).
Inhibiting effects were studied by the electrochemical method of measuring
polarization curves (program Gamry instruments, software Framework 4/0). A steel
electrode with total surface area of 2,2cm2 was used as a working electrode and a
second one as a reference and counter electrode for all electrochemical tests. The
surface of the electrode was polished with 1500 silicon carbide paper and cleaned
with ethanol. The electrodes were exposed in aggressive medium (S2-, Cl-, pH 3),
simulating conditions in pipelines, with low concentration of oxygen. The measuring
cell was irrigated with Argon during the experiment.
Electrochemical data were used to calculate corrosion efficiency. The results
of measuring confirm a high efficiency of all corrosion inhibitors and usability as
effective corrosion protection in pipelines. These experiments, mainly results of XPS
analysis, are in order to know the effectiveness of these tested samples and to obtain
a better understanding of the corrosion protection processes.
Authors wish to thank Ministry of Education Czech Republic (Grant no.
604613 7304) for financial supports.

225

PC-6
XPS investigations of nanoscale Ti-O-N films on silicon
A. Styervoyedov1,2 and V. Farenik1,2
V.N. Karazin Kharkiv National University, Svobody sq. 4, 61077 Kharkiv, Ukraine
Scientific Centre of Physical Technologies, Svobody sq. 6, 61022 Kharkiv, Ukraine
1

High surface sensitivity and excellent elemental sensitivity make X-ray

photoelectron spectroscopy more and more popular because of growing interest
in investigation of ultra-thin films for nanotechnology applications. When the film
thickness doesnt exceed few nanometres, XPS allows to investigate film / substrate
interface and reactions, which occur there as the result of thermal or radiation
effects. Such investigations are essential in nanoelectronics where formation of
undesirable bonds on the interfaces strongly influences on electric characteristics
of obtained structures. The current work presents complex experimental study of
ultra-thin (~5 nm) Ti, TiN, TiO2 and TiNxOy films on silicon and Ti-O-N/Si interface with
angle-resolved X-ray photoelectron spectroscopy. The films were grown by ion beam
sputter deposition in controlled vacuum environment using cold cathode ion gun.
Titanium foil of 99.99% purity was sputtered by argon ions with the 5 keV energy and
15 A/cm2 ion current density [1]. After deposition samples were transported from
the preparation chamber to the analytical chamber without breaking vacuum. Highresolution XPS investigations were performed at the pressure of 510-10 mbar with
using of Mg-K X-ray radiation. The influence of substrate temperature during films
formation and post deposition annealing on elemental composition and chemical
state of obtained films and film/substrate interfaces were investigated.
[1] A. Styervoyedov, V. Farenik, Surface Science, 600 (2006), p. 37663769.

226

PC-7
Analysis of XPS spectra of metal oxides
on corrosion surface
M. Hubikov 1, P. Kuera, J. Petr, P. Sajdl
Institute of Chemical Technology Prague, Technick 5, 16628, Prague 6, Czech
Republic
Laboratory of Surface Analysis ESCA 1, Department of Power Engineering
Pitting and crevice corrosion are dangerous forms of localized corrosion.
They result from a failure of passive film. Well-known examples include weld zones,
surface deposits, rivets, and steam generator tubes.
Austenitic stainless steel 08CH18N10T was used for this study. The alloy
had a composition about 20 % Cr, 10 % Ni, min. 0,5 % Ti. An autoclave simulating
the secondary side of a steam generator was used at 300C and 10 MPa, water
solution, 100mg/l NaCl and pH 10. Crevice sample was formed under Teflon block.
Exposure samples showed different state and damage of surface. Samples were
investigated by metallographic and microscopic methods.
Metal oxide films were identified from X-ray photoelectron spectroscopy
(XPS) analysis. The XPS study was carried out using ESCAProbe P apparatus
(Omicron Nanotechnology Ltd.) equipped with Al K (1486.6 eV) X-ray source with
monochromator and hemispherical analyzer. The size of the analyzed area was
approximately 1 mm2. Ar ions (energy - 5 keV) were used for ion sputtering.
High resolution XPS spectra of metal surface where measured. The peak
positions and peak shape of Fe 2p spectra were used to estimate Fe2+/Fe3+ ratio on
metal surface. Peak positions of Fe 2p, Cr 2p and Ni 2p depend on ionic states and
determined chemical composition. The C 1s peaks of hydrocarbon were used for
calibration of spectra.
The surface of the sample was examined on passive region, near pits,
inside and outside crevice regions. Various compositions of metallic surfaces were
determined. The XPS spectra of the surfaces were found useful for understanding
the localized corrosion behavior.
Authors wish to thank Ministry of Education Czech Republic (Grant no. 604 613
7304) for financial supports.

227

PC-8
Eu L3 XANES investigations of the valence instability of
Eu4Pd29B8
U. Burkhardt, I. Veremchuk, R. Gumeniuk, A. Leithe-Jasper, Yu. Prots,
W.Schnelle and Yu. Grin
Max-Planck-Institute for Chemical Physics of Solids, Noethnitzer Str.40,
01187 Dresden, Germany
Intermetallic compounds containing Eu and other rare earth metals are
subject of both experimental and theoretical interest since the oxidation state of
these lanthanoides atoms can be influenced by chemical composition, temperature
and pressure. In intermetallic Eu compounds, this may result in structural phase
transitions as found for the mixed-valence phase Eu4P3 at 8 GPa [1] or a complete
change from valence state Eu2+ to Eu3+ between ambient pressure and 9 GPa in
EuNi2Ge2.[2]. Recently, the tendency to valence fluctuation observed experimentally
for the perovskite-like EuPd3Bx phase were confirmed by theoretical calculations [3]
and motivated us to investigate the valence stability of Eu in ternary phases of the
system Eu-Pd-B.
The temperature dependent XANES studies of the new phase Eu4Pd29B8
were recorded at the beamline A1 of Haslab at Desy. The spectra near the Eu L3
edge at T = 5 K and 85 K show one dominant maximum reflecting the contribution
of Eu with 4f6 (Eu3+) configuration. Additionally, both low-temperature spectra reveal
a shoulder on the rising edge of the white line that indicates a small contribution
of the 4f7 (Eu2+) state. This shoulder is significantly stronger in the spectra at room
temperature and shows the increasing contribution of the 4f7 (Eu2+) state at higher
temperature. The comparison of the spectra at different temperatures indicates that
the valence change of Eu takes place mainly in the temperature range 85 K < T
< 293 K, but a complete 4f6 (Eu3+) state is not reached down to T = 5 K. Magnetic
susceptibility measurement shows an upturn below 55 K and a broad maximum at
approx. 140 K. While the Curie law at lowest T (2 K < T < 40 K) corresponds to 7
% Eu2+ species, at highest T (400 K) the moment suggests the presence of nearly
50 % Eu2+ species.
[1] R. Cardoso-Gil, R. Niewa, M. Schmidt, M. Armbrster, M. Hanfland, K.
Klementiev and U. Schwarz, Z. Anorg. Allg. Chem. 629 (2003) 454 458.
[2] H.-J. Hesse, R. Lbbers, M. Winzenik, H. W. Neuling, and G. Wortmann, J.
Alloys Compd. 246 (1997) 220 231.
[3] C. Loison, A. Leithe-Jasper, and H. Rosner, Phys. Rev. B, 75 (2007) 205135.

228

PC-9
Chemical speciation of unknown uranium ore and mine tailings
particles with -XANES and -XRD methods
A. Alsecz1, J. Osn1, I. Saj2, S. Trk1, G. Falkenberg3 and K. Rickers3
KFKI Atomic Energy Research Institute, P.O. Box 49, H-1525 Budapest, Hungary
Chemical Researh Centre of the Hungarian Academy of Sciences, Pusztaszeri t
59-67, H-1025, Budapest, Hungary
3
Hamburger Synchrotronstrahlungslabor (HASYLAB) at Deutsches ElektronenSynchrotron (DESY), Notkestr. 85, 22607 Hamburg, Germany

1
2

Uranium as a necessary raw material for the nuclear fuel cycle is usually
extracted from uranium ore. There exists only one uranium ore deposit in Hungary
that is located in the south of the country at the foot of the Mecsek Mountains at
the western border of the city of Pcs. A wide variety of uranium minerals exist in
the Mecsek Mountains: uraninite, pitchblende, soddyite, autunite, liebigite, zippeite,
uranopilite and clarkeite. Recognition of uranium species in U-rich particles from
unknown uranium ore samples and unknown mine tailings particles was the aim of
the investigations described in this work. The particles came from the ore and the
mine tailings of the closed uranium mine.
Uranium particles were pre-selected with laboratory micro-XRF technique at
KFKI AEKI. Mineral composition of the particles and the oxidation state of uranium
in the particles was investigated at the micro-fluorescence beamline L at HASYLAB
(Germany) using -XRD and -XANES. For simultaneous -XRF and -XRD, the
energy of the synchrotron radiation was tuned to 21.0 keV. The diffraction images
were recorded using a MarCCD camera. For -XANES UO2, UO3 and U3O8 particles
were used as standards.
The chemical state of uranium in the mine tailings particles were 5080 %
in the less mobile U(IV) but many uranium minerals contain uranium in the U(VI)
form. For the investigation of the oxidation state of uranium -XANES is a very
efficient method. It can give us information one of the elements but sometimes this
information is not sufficient. Micro-XRD was used as a complementary method for
deriving the mineral composition of the particles, because many times uranium has
the same oxidation state in the particles and more information needed.

229

PC-10
Structural characterization of Sulfur vulcanized natural rubber
using X-ray Absorption Near-Edge Spectroscopy
W. Pattanasiriwisawa1, J. Siritapetawee2, O. Patarapaiboolchai3 and W.
Klysubun1
1

National Synchrotron Research Center, 111 University Avenue, Muang,

Nakhon Ratchasima 30000, Thailand
2
College of Medicine and Public Health, Ubon Rajathanee University,
85 Sathollmark Rd. Warinchamrap, Ubon Ratchathani 34190, Thailand
3
Department of Mechanical Engineering, Prince of Songkla University,
Had Yai, Songkla 90112, Thailand

X-ray absorption near-edge spectroscopy (XANES) is an advantage technique

based on synchrotron light application on chemical structure determination. At
presented here, the chemical structures of sulfur contained in the vulcanized natural
rubber (NR) by efficient vulcanization (EV), semi-EV, and conventional system
(CV), were studied using XANES at beamline-8 equipped with Si 111 double crystal
monochromator of the National Synchrotron Light Source Center (NSRC), Thailand.
All samples were controlled of the thickness of rubber sheet and the vulcanization
temperature. The XANES results have been illustrated the bonding of sulfur in the
CV, EV and semi-EV system of the NR vulcanization as polysulfidic, monosulfidic,
and both poly- and mono-sulfidic crosslinks, respectively.
[1] R. Chauvistre, J. Hormes, E. Hartmann, N. Etzenbach, R. Hosch and J. Hahn,
Chem. Phys., 223 (1997), 293-302.
[2] R. Chauvistre, J. Hormes, D. Bruck, K. Sommer and H.W. Engels, Kautschuk
Gummi Kunststoffe, 45(1992), 808-813.

230

PC-11
Structure peculiarities of catalytically active gold nanoparticles
by EXAFS and XANES spectroscopy
S.B. Erenburg1, N.V.Bausk1, S.V.Trubina1, B.L.Moroz2, A.V.Kalinkin2,
V.I.Bukhtiyarov2, S.G.Nikitenko3
1

Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Russia

2
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia,
3
DUBBLE-CRG & ESRF,Grenoble, France

It was shown recently that the Au particles of less than 5 nm in size

supported onto various metal oxides exhibit the extraordinary high catalytic activity
in some reactions.
A series of Au/Al2O3 and Au/carbon catalysts prepared by the different
procedures and differing in the mean Au particle diameter (d = 2-30 nm) was tested
in CO oxidation. Gold particles for the model samples prepared by the deposition
of metallic gold in UHV on Si(111) and Si(100) planes of single crystals. The AuLIII
XAFS spectra were measured at 12 K, 296 K at the BM26 beamline of the ESRF
(Grenoble, France) and at the VEPP-3 storage ring of the BINP (Novosibirsk,
Russia) [1].
In spite of variation in the d value, the XANES spectra indicate no visible
changes in electron states of Au and the absence of gold oxide species in all
samples. Interatomic Au-Au bond length (R) and firstshell Au-Au coordination
numbers (N) decrease and Debye-Waller factors increase from these samples to
the samples containing the smallest Au particles with the average number of Au
atoms equal to 100 - 200 atoms. The Debye-Waller factor for the most dispersed
catalysts measured at 12K is about three times higher than that for the bulk gold,
while this variation is only 10% at 296K. A gradual reduction of the Au-Au bond
length (0.002-0.003nm) and variations in other microstructural parameters of Au
nanoparticles are in line with an increase in their catalytic activity in CO oxidation.
[1] S.B.Erenburg, B.L.Moroz et al., Nucl. Instr. & Meth. Phys. Res.A, 575(2007)
105-108.

231

PC-12
EXAFS effects around K-edge in Lanthanum
M.A.Kareem1, Phanisree K.D. TImmaraju 2, N.V.Sitamahalakshmi2 and
K.PremaChand2
Dept. Of Physics, M.R.College, Vizianagaram (India),
Swami Jnanananda laboratories for Nuclear Research, Andhra University,
Waltair, Visakhapatnam-530003, India
1

Total photon cross-sections in Lanthanum were determined at nine energies

in the range of 30 keV-55 keV using secondary excitation method and deviations
were observed near the absorption edges. Gamma photons of energy 59.54
keV from 241Am radio active source were used to obtain characteristic X-rays of
various energies from rare earth oxides Nd2O3, Sm2O3, Gd2O3 and Dy2O3. K and
K X-rays thus obtained were used to determine photon cross-sections in La2O3.
The experiments were carried out by employing a modified narrow beam geometry
and a HpGe detector. The measured values of total photon cross-sections were
used to deduce elemental cross-sections in Lanthanum. The experimental values
were compared with those determined by other investigators1, 2, 3 in the above energy
range and also with theoretical values obtained by summing photo-electric crosssections of Scofield4, coherent scattering cross-sections of Hubbell and Overbo5 and
incoherent scattering cross-sections of Hubbell6 etal. Deviations from theory were
observed near the absorption edges. A deviation of about 23% was observed at an
energy 686 eV away from the edge which indicates the existence of EXAFS effects
around absorption edges.
[1] M. L. Mallikarjuna, S. B. Appaji Gowda, R. Gowda and T. K. Umesh Radiation
Physics and Chemistry, 65 (2002) 217-223
[2] J.H.McCrary, Elizabeth H Plassmann, J.M.Puckett, A.L.Conner and
G.W.Zimmermann, Physical Review 153 (1967) 307-312
[3] W.H. McMaster, N. Kerr Del Grande J.H. Mallett, J.H. Hubbell UCRL report No.
50174 (1969)
[4] J.H.Scofield, UCRL Report No. 51326 (1973) unpublished
[5] Hubbell, J.H. and Overbo, I, J.Phys. Chem. Ref. Data 8, (1979) 69-105.
[6] Hubbell, J.H., Veigele, W.M.J., Briggs, E.A., Brown, R.T., Cromer, D.T. and
Howerton, R.J., J.Phys. Chem. Ref. Data 4, (1975) 471-538.

232

PC-13
Environmental analyses by TXRF - NEXAFS and IRSpectroscopy:
Speciation of Bromine in organics andcharacterization of the
organic matrix
B. Beckhoff 1, O. Hahn2, M. Kolbe1, J. Weser1, M. Wilke3
Physikalisch-Technische Bundesanstalt, Abbestrae 2-12, 10587 Berlin, Germany
2
BAM Bundesanstalt fr Materialforschung und prfung, Unter den Eichen 78,
12205 Berlin, Germany
3
GeoForschungsZentrum Potsdam, Sektion 4.1,Telegrafenberg, 14473 Potsdam,
Germany

Reference-free total-reflection X-ray fluorescence analysis (TXRF) [1]

allows for the absolute determination of minute mass depositions on semiconductor
surfaces. The use of tunable synchrotron radiation enables the speciation of
compounds and functional groups by near-edge X-ray absorption (NEXAFS)
spectroscopy. When combining reference-free TXRF and NEXAFS, a spectroscopic
tool is formed capable to assess the bonding state of minor components in minute
amounts of organics without any prior chemical pre-treatment or sample preparation,
thus certainly preserving the chemical state of a trace component of interest: By a
simple mechanical abrasive technique just a few ng of flame retardants (FR) [2] were
deposited on a clean surface of a 200 mm silicon wafer. Initial results confirm the
theoretical prediction and demonstrate the potential of the TXRF-NEXAFS method
to successfully contribute to the elemental speciation, even of trace elements such
as Br in FR.
In a case study involving the speciation of Br in various FR samples,
Synchrotron-based IR spectroscopy in reflection mode was employed to characterize
the organic matrix. The study also serves to assess the potential of this methodological
coupling for the analysis of preparation-free deposition of nanoparticles such as
aerosols in the field of environmental science. Trace component analysis reveals its
importance in public control such as RoHS directive.
[1] B. Beckhoff, R. Fliegauf, M. Kolbe, M. Mller, J. Weser, G. Ulm, Anal. Chem. 79
(2007) 7873.
[2] S. Kemmlein, O. Hahn, O. Jann, Atmosph. Environm. 39-40 (2003) 5485.

233

PC-14
XAS on surfactant-based nanostructured V2O5 thin films:
monitoring short and long range order from mesophase residual
to crystalline network
A. Cremonesi1, G. Calestani1, G. Antonioli2, D. Bersani2, P. P. Lottici 2
1

GIAF Chemistry Department, University of Parma, Viale G. P. Usberti 17/A,

43100 Parma, Italy
2
Physics Department, University of Parma, Viale G. P. Usberti 7/A,
43100 Parma, Italy

X-ray Absorption Spectroscopy (XAS) has been employed to characterize

sol-gel derived surfactant-based nanostructured V2O5 thin films. The experimental
data have been collected in Total Electron Yield mode on the GILDA BM08 beamline
at ESRF, Grenoble, France.
In the XANES region, all samples show the characteristic pre-edge peak, with
intensities comparable to that found in the orthorhombic V2O5 reference, suggesting
an axial configuration very similar to the crystalline phase (ROA 1.58 , ROAlong
2.78 ). On the contrary, the near edge features depend on the different surfactant
used (Brij76, Tween-60 and Triton X-100), and show peculiar behavior suggesting
differences in the symmetry of the equatorial oxygen atoms.
EXAFS analysis has shown a low temperature crystallization of the
orthorhombic V2O5 phase. For all the annealing temperatures, even for samples
heated at 250 C, the VO5 unit is detectable showing that the short range order
is preserved even when the surfactants are present in the metal oxide network.
Ordered VO5 units are consistent with relatively low 2 values of the first shells
of oxygen around the absorbing V0 atom. Moreover, the possibility to extend the
R-region of the fit up to 4.2 shows the good crystalline quality of the synthesized
nanostructured thin films.
Slight discrepancies with the orthorhombic structure can be detected in the
shells of the apical long VO bond, linking adjacent vanadium oxide layers and on the
nearest vanadium neighbors, located at RV13 . The discrepancies are eliminated
by the thermal treatment, causing more order into the metal oxide framework. The
final products (i.e. the high temperature samples) show EXAFS experimental (k)
functions corresponding to those obtained in the commercial orthorhombic V2O5
powder.

234

PC-15
X-ray fluorescence determination of FeO/Fe2O3total ratio in rocks.
V.M.Chubarov1 and A.L.Finkelshtein2
Irkutsk State University, (126, Lermontov str., Irkutsk, Russia)
Institute of Geochemistry SB RAS (1a, Favorsky str., Irkutsk, Russia)
1

Determination of chemical states of iron as Fe2+ and Fe3+ in rocks is of

interest for geochemical, petrological and mineralogical research. Wet chemistry
is the main technique to determine bivalent Fe. In 70s it was reported that ratio
Fe2+/Fe3+ in minerals can be ascertained by EPMA using the ratio of the X-ray
intensities of L and L lines [1]. Accuracy of EPMA determination of (Fe2+/Fetotal )
in amphiboles ranges from 6 to 20% [2]. In paper [3] it was recommended to define
the chemical state of iron and some others elements using X-ray fluorescence with
lines of K-series. The advantage of X-ray fluorescence technique is a low cost of
preparation, as compared to wet chemistry.
In this work the possibility to estimate the ratio (FeO/Fetotal) in rocks using the
K and L series of the x-ray florescent spectrum is studied. Measurements were carried
out on a WDX Spectrometer S4 Pioneer (Bruker AXS). Accuracies of determination of
(FeO/Fetotal) with the ratio of K5/K1,3 and L/L were compared through the samples
of single mineral powdered fractions, e.g. garnet, pyroxene, ilmenite, amphibole and
magnetite. It was found that the K5/ K1,3 ratio as an analytical signal, is preferable
(using ratio L/L the correlation factor was less than 50%, with K5/ K1,3 it is over
80%).In the Table the relative standard deviations of FeO content determination for
46 reference standard materials of igneous rocks are shown for different range of
(FeO/Fetotal) and different ranges of FeO content.
Range of
FeO/Fetotal
>0.45
<0.45

Range of
FeO,%
0,5-5,0
5.0-20.0
0,20-5.0

Number of samples
16
19
11

Relative standard
deviation, %
16.17
5.51
12.59

The accuracy of wet chemistry varies from 5 to 15%. As evident from Table,
the X-ray fluorescence technique can ensure a comparable accuracy or a bit worse.
However the XRF is adavntageous as it is express and has low cost of preparation;
and it is can be used for routine analysis in geochemistry.
[1] A.L. Albee, A.A. Chodos, Amer. Miner., 55 (1970), 103-107.
[2] G.V. Legkova, V.G. Vojtkevich, O.P. Sharkin, Ukrainian Mineral. Journale, 4
(1982), (in Russian)
[3] M.N. Philippov, T.A, Kuprijanova, O.O Lyamina, Journal of Analytical Chemistry,
56 (2001), 817-824, (in Russian).

235

PC-16
X-ray tracing study of crystall spectrometers
for WDXRS application
T. Tadi, M. Jaki and Iva Boievi
Laboratory for Ion Beam Interactions,
Ruer Bokovi Institute, POB 1016, HR-10000 Zagreb, Croatia
Construction of wavelength-dispersive crystal X-ray spectrometer, used in
high resolution wavelength dispersion X-ray emission spectroscopy (WDXRS), may
result in geometrical aberrations, such are systematic X-ray line shifts and changes
of the X-ray line shape. Most of these aberrations can be reduced by a careful
design of a crystal spectrometer, maintaining efficiency of the spectrometer as high
as possible. Since experimental investigation of impact of WDX spectrometer design
on aberrations is difficult, a numerical X-ray tracing procedure has been applied for
this purpose, with output in the form of a 2-dimensional virtual X-ray intensity array
on the detector surface or in the form of virtual X-ray energy spectrum.

236

PC-17
Spectrum modelling and influence on chemical state analysis
using WDS-PIXE system
L. Mandi1, S. Fazini2, M. Jaki2, J. Dobrini1
1

Faculty of Engineering, University of Rijeka, Rijeka, Croatia

2
Ruer Bokovi Institute, Zagreb, Croatia

The Tandem accelerator facility of the Ruer Bokovi Institute is equipped
with high resolution wavelength dispersive spectrometer system (WDS) used for
chemical state analysis by PIXE method. In our recently performed analysis of
vanadium and titanium samples, the most important conclusions are derived from
relative intensities and energies of the K5 and K'' X-ray lines extracted from fitted
K spectra [1]. In some cases results of analysis are very sensitive on the fitting
procedures, especially on how they handle absorption K edge feature. In this work
we report the influence of fit models on analysis of spectra and final interpretation of
chemical states.
[1] S. Fazinic, M. Jaksic, L. Mandic and J. Dobrinic, Physical Review A 7406 (6),
2501 (2006).

237

PC-18
DLC layers on biocompatibile Ti alloys
V. Star1, R. Havel1, J. Kadlec2, K. Jurek3, V. Peina4 and J. Fencl5
Dept. of Mat. Engn., Fac. of Mech. Engn. of CTU in Prague, Karlovo nm. 13,
CZ-121 35 Prague 2, Czech Republic
2
SVM a.s., Bchovice near Prague, Czech Republic
3
Institute of Physics of AS CR, Prague, Czech Republic
4
Nuclear Physics Institute of AS CR, e near Prague, Czech Republic
5
Beznoska s.r.o., Kladno, Czech Republic

The principal materials for fabricating implants are usually metallic alloys,
which have suitable mechanical and corrosion properties. Titanium and its alloys
are widely used nowadays. In this work, we studied a thin layer appearing at the
surface of samples of Ti and Ti alloys during electroerosion, which produce the high
surface roughness suitable for good binding of material and tissue. The chemical
composition of the carbon-based gradient layer was inhomogenious and the depth
profiles of Ti, C and O in the layer were found by RBS. By Elastic Recoil Detection
Analyses method the hydrogen content was analyzed [1]. The first estimation of
layer thickness was about 0.5 m, but during repeated measurement we have found
it was inhomogeneous.
The layer thickness and composition was measured by both RBS method
and Electron Probe X-ray Microanalysis (EPMA) and evaluated by suitable software
[2]. Due to its high roughness, the reliability of ussual measurement by EPMA is low.
Thus, the modified method using P/B ratio instead of X-ray intensities [3] was used
for thickness and composition calculation. Simultaneously, the layer thickness was
measured directly in SEM from cross-section samples approximately at the points
of RBS and EPMA measurement. The results obtained by all the methods were in
reasonable agreement.
[1] V. Star, V. Peina, L. Bakov et al., Journal of Physics: Conference Series
IVC-17, Stockholm 2007 (in print).
[2] software SAMX StrataGem based on J.L. Pouchou, F. Pichoir, Scanning
12 (1990) 212-224.
[3] Sullivan L.A., Bush R.T., Soil Science 162 (1997) 749-757.

238

PC-19
Cement analysis for ASTM C114 by using bench-top WDXRF
K. Watanabe, H. Homma, Y. Kataoka, Y. Yamada, K. Kansai and H. Kohno
Rigaku Industrial Corporation (14-8 Akaoji-cho,Takatsuki, Osaka
569-1141, Japan)
A newly developed bench-top WDXRF (Supermini) was applied to cement
analysis for ASTM C114 qualification, which is a test method for chemical analysis of
hydraulic cement. The equipment is a compact sequential spectrometer measurable
from Fluorine to Uranium equipped with a new 200W Pd target X-ray tube and no
cooling water is required.
The evaluation for the ASTM C114 was performed for both fused bead
method and pressed powder pellet method. Empirical calibration curves for 13
components (CaO, SiO2, Al2O3, Fe2O3, SO3, MgO, K2O, TiO2, Na2O, P2O5, MnO,
Cl and ZnO) were created by using NIST SRMs for cement. By using the theoretical
alphas to correct for the matrix effect, accurate calibration curves could be obtained
in both fused beads and pressed pellets even for Na2O. The results of duplicate
sample analysis demonstrated the qualification for both of the differences between
duplicates and the differences between the averages of duplicates from certified
values. These results show that the spectrometer has adequate performance for
both powder and fused bead method for cement analysis within affordable measuring
time. This spectrometer can be used not only as backup system but also as master
equipment instead of high power XRF in cement analysis.

239

PC-20
XRF application in the early prostate cancer diagnosis
V. Zaichick1, T. Sviridova1 and S. Zaichick2
Medical Radiological Research Centre, Obninsk 249020, Russia
Northwestern University Department of Immunology and Microbiology, Chicago,
IL, USA
1

The method for prostate cancer diagnosis based on the measurement of

zinc concentration in prostatic fluid was previously reported by us1. It was found that
prostatic neoplasm resulted in sufficient about 25-fold decrease in zinc secretion in
comparison with the normal level. At the same time, no changes in the Zn content
were found for chronic prostatitis and adenoma as well. The EDXRF device with a
Si(Li) detector and 109Cd sources was particularly developed for precise determination
of zinc concentration in the drop of prostatic fluid with volume in 20 L only. The 10
min exposure made it possible to determine zinc in the most fluid specimens with a
relative uncertainty no more than 5%.
In present study only this test for prostate cancer screening of 598 men, Obninsk
residents, aged above 60 and without any pre-clinical manifestation of prostate
diseases was used. Expressed prostatic fluid was conventionally obtained by
digital rectal massage. The concentration under 100 mg/L was set as a limit for the
selection of cancer risk group counted in 34 subjects. All of them were invited to
the Department of Urology for more detailed examination under hospital conditions
including common clinical, X-ray, ultrasonography and biopsys morphology data.
The probability of cancer cases in the risk group formed on the basis of zinc secretion
results approached 30%. In the other words, the amount of wrongfully positive
conclusions about 70% were at least not worse than PSA-test (prostate specific
antigen test) data. However, the cost of EDXRF of Zn in prostatic fluid is much less
and the method do not need in pierce the vein.
[1] V. Zaichick, T. Sviridova, S. Zaichick, Int. Urol. Nephrol., 28 (1996) 687-694.

240

PC-21
The skin barrier function: a micro-PIXE study
M. Simon1, H. Seznec1, P. Barberet1, D. Bacqueville2, A. Mavon2 and P.
Moretto1
1

Centre dEtudes Nuclaires de Bordeaux-Gradignan, Universit Bordeaux 1,

IN2P3-CNRS, BP120, 33175 Gradignan Cedex, France
2
Institut de Recherche Pierre FABRE, Castanet Tolosan, France

Today, man is perpetually subjected to environmental exposures as sun,

natural, urban or industrial pollutions and societal exposures. Skin is the main
physiological barrier facing to these different stresses; however its response
mechanisms are still not well understood. So, skin models are necessary to understand
skin physiology and behaviour in normal conditions or under stress. Because of the
large natural inter-individual variability and of some difficulties in obtaining human
skin biopsies, we are working on the development and characterization of different
skin models such as reconstructed epidermis in vitro, native pig skin and human
keratinocyte cells. These models allow us to study the mechanisms involved in ion
homeostasis in correlation with structural organisation and biological responses. We
have undertaken the characterization of these models using a combination of original
analytical and imaging techniques like micro-PIXE, epifluorescence and confocal
microscopy. The aim is to evaluate the distribution of inorganic ions under normal or
stress conditions, the transepidermal penetration of external agents, together with
the cellular morphology to better understand the barrier function of the skin.

241

PC-22
Use of hydroxyapatite bone composites for the calibration of in
vivo EDXRF-based systems for bone strontium quantification
E. Da Silva1,2, C. Heirwegh3, A. Pejovi-Mili2 and D. V. Heyd1
Department of Chemistry & Biology, Ryerson University, Toronto, Ontario, Canada
M5B 2K3
2
Department of Physics, Ryerson University, Toronto, Ontario, Canada M5B 2K3
3
McMaster University, Medical Physics & Applied Radiation Science Unit, Hamilton,
Ontario, Canada L8S 4K1
1

Various metals, most notably lead and strontium, have been quantified in
vivo in human bone tissue using energy-dispersive X-ray fluorescence spectrometrybased systems. Calibration of these systems has tradiationally relied on the use of
plaster of Paris (PoP) phantoms that are doped with the element of interest and
calibration proceeds by the preparation of a standard calibration curve. For the in
vivo quantification of bone strontium, calibration using the PoP method presents
the significant challenge of strontium contamination (an inherent contaminate
to calcium) and the required corrections due to calibration via a sulfate and not
an apatite. This work presents the development and use of 'strontium-free' bone
composites for the calibration of the in vivo EDXRF system, which allows for
phantoms to be moulded easily into various geometries as needed, the purification
of reactants (CaCO3, Ca(OH)2 and CaHPO4) from strontium and the synthesis of
continous phase carbonated or non-carbonated hydroxyapatite. The composite can
be prepared easily and analytically with a short setting time and the setting liquid
adjusted as to incorporate biological amounts of sodium, potassium, magnesium
and other biologically relavant cations in the form of their respective hydroxides,
if required. The method of phantom preparation described in this study ultimately
results in a calibration curve for strontium with standards at concentrations that are
lower than expected human bone strontium concentrations as well as a near 0 ppm
phantom after purification of reactants using a 4,4'(5')-di-t-butylcyclohexano-18-crown-6
resin.

242

PC-23
Micro-PIXE and SEM study of endosseous implants surface and
the implant material release in the surrounding bone tissue
N. Uzunov1,6, C. Furlan2, S. Galassini3, G. B. Girardello4, P. Passi4, G. Moschini1,5,
A. Zadro4
INFN, National Laboratories of Legnaro, Italy
2
CUGAS, University of Padua, Italy
3
Department of Medicine and Public Health, University of Verona, Italy
4
Dental School, University of Padua, Italy
5
Department of Physics, University of Padua, Italy
6
Department of Natural Sciences, Shumen University, Bulgaria
1

Titanium and its alloys are unambiguously considered as a preferred material

for building bulk dental and orthopaedic implants. The debates about the implants
surface treatment in view of possible metal release and eventual subsequently caused
lateral effects however, are still opened. At present there is a number of developed
implant surface treatment techniques which are based either on the implant surfaces
roughening or appropriate implant surface coating in order to achieve a better
osseointegration and to gain a shorter healing time as a consequence.
To evaluate the rate of the roughening procedure (and hence the effectiveness
of bone anchorage) and to study the influence of the implant insertion on the
surrounding tissue we have conducted a surface analysis of some commercially
available dental implants. The tested implants have been made from a commercially
pure titanium, roughened using different procedures such as: sand blasting (SB) with
Al2O3, acid-etching, or a combination of both techniques. The titanium implants have
been inserted in the tibia of New Zealand rabbits and after some period of insertion
the animals have been sacrificed. A subject of interest has been also the implant
material deposits on the interleave surface between the implant and the bone, as
well as the implant material release in the surrounding bone tissue.
The study has been conducted using a microbeam-Particle-Induced X-ray
Emission (micro-PIXE) technique and Scanning Electron Microscopy (SEM) analysis.
The analyses were carried out using a proton microprobe set up of the 2 MeV Van
de Graaf accelerator beam line at the National Laboratories of Legnaro, INFN and
with the EDAX XRF-EDS of the University of Padua, (Italy). Maps of the elemental
distribution drawn for the specific regions of interests have been studied.
The analysis of the elemental maps drawn using micro-PIXE as well as
the analysis of the SEM images confirms the conclusions made in our previous
investigations indicates that Ti released into the peri-implant tissues appears mainly
as small-size debris. Analyses of the bone tissues in depth shows a presence of SB
debris eventually drifted the implants through the harvesian canals of the compact
bone structure.

243

PC-24
PIXE and PIGE assessment of in vivo elemental and physical
changes of a composite from a dental filling
Eugen A. Preoteasa1, Elena Preoteasa2, Daniel D.Marin,1 Dan Gurban1
and Adela Scafes1
1

National Institute for Physics and Nuclear Engineering, P.O. Box MG-6,
077125 Bucharest-Magurele, Romania
2
Helident Dental Surgery Ltd., 021575 Bucharest 2, Romania

Although successful in dentistry, composite fillings convey foreign elements

in organism, degrade chemically and mechanically, and favor secondary caries
formation. To reduce the latter, the new biomaterials release F and Ca2+ ions. We
analyzed by PIXE and PIGE such a composite removed surgically from an old dental
filling of a patients tooth and its elemental composition changes. The filling was
sectioned centrally, and its outer and inner surfaces were examined comparatively,
together with flat samples of the composites Ariston and Tetris Ceram (IvoclarVivadent, Liechtenstein), Valux Plus and F2000 (3M Dental, USA) and of five
Romanian products (Restacril). The specimens were irradiated at 45o with 3.0 MeV
protons and PIXE spectra were collected with a HP Ge detector. PIGE spectra were
recorded between 0 and 300 keV with the same detector at proton energies of 3.00,
3.20, 3.37 and 4.19 MeV.
The filling was identified as Tetric Ceram by similar concentrations of Ca,
Fe, Sr, Zr, Ba, Yb and Hf. However, Ba and Yb were partly lost, and Cl and K were
massively accumulated from saliva. PIGE showed an important decrease of F (110
and 197 keV) and the quasi-disappearance of Al (170.7 keV). The results suggest
the partial dissolution of composites particles of YbF3 and of Ba aluminofluorosilicate
glass, and to less extent of Ca fluorosilicate glass. The inner sections composition
was similar to the outer surfaces, pointing to the diffusion of Cl, K+ deep inward
and of F, Al3+, Yb3+, Ba2+ outward the filling. However, the ratio F(197)/F(110) was
lowered outside and unchanged inside, suggesting some matrix physical structure
alteration (non-uniformity) only at surface. Thus PIXE and PIGE showed that during
the in vivo use of a dental composite chemically similar changes occur at surface
and in bulk, but the surface is somewhat altered physically.

244

PC-25
Single detector PIGE and PIXE analysis of
dental composites
E.A. Preoteasa1, D.D. Marin1, D. Gurban1, A. Scafes1, M. Gugiu1, E. Preoteasa2
1

National Institute for Physics and Nuclear Engineering, P.O. Box MG-6, 077125
Bucharest-Magurele, Romania
2
Helident Dental Surgery Ltd., 021575 Bucharest 2, Romania

PIGE is widely used for analyzing light elements as a complementary method

to PIXE. In particular, fluorine is analyzed by the 110 and 197 keV radiation from the
19
F(p, p)19F reaction at energies around 3 MeV. Fluorine helps the maturation and
protection of teeth, and added in dental composites prevents secondary caries. We
examined the feasibility of detecting fluorine by PIGE together with heavier elements
by PIXE using protons and a single low energy HP Ge detector, a technique with the
advantage of simplicity, and we tested it on F-rich dental composites. Flat samples
of the composites Ariston and Tetric Ceram (Ivoclar-Vivadent, Liechtenstein), and
reference materials including Teflon, NaF and metallic Al were analyzed. The samples
were irradiated at 45o and at 3.0 MeV for PIXE, and for PIGE also at 3.20, 3.37 and
4.19 MeV, where the cross-section of F lines show maxima [1].
The composites evidenced mainly Ca, Zr, Ba, Yb and Hf by PIXE and F by
PIGE. In addition, their PIGE spectra collected between 0 and 300 keV showed a
line at ~171 keV, probably due to Al (170.68 keV). The PIGE detection limit for F was
of ~0.2% with 3.0 MeV protons and of ~50 ppm with 4.19 MeV protons. However
Al was best observed with 3.0 MeV protons. The cross-sections were material
dependent. In the composites, F and Al arise as YbF3, and Ca fluorosilicate glass and
Ba fluoroaluminosilicate glass, respectively. As shown by the lower Ba and Al/F ratio,
Ariston contained less of the latter glass than Tetric. The ratio F(198)/F(110) was
slightly different in the composites, suggesting granularity differences. The results
proved relevant for analyzing the dental composites, and encourage the techniques
further development.
[1] A. Caciolli et al, NIM B 249 (2006) 98-100.

245

PC-26
A study by XRF and XRD of fossilized dinosaur bones from
Spain
A. Brunetti 1,5, G. Piga 2 A. Santos Cubedo3, A. Malgosa2, S. Enzo4
Struttura Dipartimentale di Matematica e Fisica, Universit di Sassari, via Vienna
n. 2, I-07100 Sassari, Italy
2
Unitat de Antropologia Biologica, Departament de Biologia Animal, Biologia
Vegetal i Ecologia. Universitat Autonoma de Barcelona, E-08193 Bellaterra, Spain
3
Institut Catal de Paleontologia C/ Escola Industrial, 23, E-08201 Sabadell,
Barcelona, Spain
4
Dipartimento di Chimica, Universit di Sassari, via Vienna n. 2, I-07100 Sassari,
Italy
5
INFN, Sezione di Cagliari, Italy
1

We have addressed an XRF and XRD study on a collection of ca 30 Spanish

dinosaur bone specimens referred to an age time range from 70 to 220 millions
of years to investigate the fossilization in terms of physico-chemical properties.
The fluorescence data show that the apatite of bones is containing the calcium
and phosphorus elements and also strontium, which is expected for the case of
herbivores. Further elements found at a significant level are iron, manganese and
yttrium. The XRD patterns showed that a large fraction of the examined bones
maintain an apatite-like structure, with the secondary presence of the calcite and
quartz phases. In some cases we have also observed dolomite at varying level of
concentration. The lattice parameters of the apatite phase appear to be subjected
to changes on account of taphonomy and diagenetic processes involved. Also, the
average domain size of the apatite phase roughly increases as a function of the age,
with some noticeable outliers that deserve further discussion and interpretation.

246

PC-27
Elemental concentration in lead contaminated rat kidneys by
EDXRF analysis
D. Guimares1, J. P. Santos1, M. L. Carvalho2, V. Geraldes3, L. Silva-Carvalho3
and I. Rocha 3
Centro de Fsica Atmica da Universidade de Lisboa e Departamento de Fsica,
Faculdade de Cincias e Tecnologia, Universidade Nova de Lisboa, Monte da
Caparica, 2825-114 Caparica, Portugal.
2
Centro de Fsica Atmica da Universidade de Lisboa e Departamento de
Fsica,Faculdade de Cincias, Universidade de Lisboa, Av. Prof. Gama Pinto 2,
1649-003, Lisboa, Portugal
3
Instituto de Fisiologia, Faculdade de Medicina de Lisboa, Av. Prof. Egas Moniz,
1649-028 Lisboa, Instituto de Medicina Molecular, Lisboa, Portugal

There is a lack of knowledge about human and animal lead metabolism.

However, it is known that kidney show substantially higher lead concentrations than
other soft tissues, reflecting their importance in the lead excretation pathways [1]. It
has been also determined that lead and lead compounds are reasonably anticipated
to be human carcinogens based on limited evidence from studies in humans and
sufficient evidence from animal studies (kidney tissue among others) [2].
Due to the many metabolic interactions among the different elements, it is
important to study not only Pb, but also other elements which could be affected by
toxicokinetic alterations.
In this study we have determined Pb, K, Ca, Fe, Cu, Zn and Br concentrations
in exposed rat kidneys by Energy Dispersive X-ray Fluorescence (EDXRF) analysis
[3]. The analysed samples belong to a group of adult Wistar rats (n=3) exposed to
lead acetate since the fetal period and a control group (n=2) of the same sex and
age. The obtained results show a steady level in exposed and control group animals
for all detected elements except for Pb, where a strong increase was observed. All
samples were analysed without any chemical treatment.
[1] L. Gehardsson, V. Englyst, N. G. Lundstrm, S. Sandberg, F. Steinwall, Journal
of Trace Elements in Medicine and Biology, 9 (1995) 136 43.
[2] Agency for Toxic Substances and Diseases Registrys, US Department of Health
and Human Services (2005).
[3] P. J. Custdio, M. L. Carvalho, F. Nunes, S. Pedroso, A. Campos, Journal of
Trace Elements in Medicine and Biology, 19 (2005) 151 158.

247

PC-28
3D Micro-XRF under cryogenic conditions:
A pilot experiment for elemental imaging in biological
specimens
M. Pagels1, W. Malzer1,* G. Weseloh,2 L. Lhl,1 and B. Kanngieer1
1

Technische Universitt Berlin, Institut fr Optik und Atomare Physik,

Hardenbergstr. 36, 10623 Berlin, Germany
2
Universitt Heidelberg
* current affiliation: Bruker AXS Microanalysis GmbH

For micro-XRF investigations of sections of biological and biomedical

specimens it is mostly needed to section the samples physically with the risk to alter
the sample structure and the chemical composition. In contrast, the 3D micro-XRF
in combination with a cryo-fixation offers the possibility to scan arbitrary sites or
sections of water-rich biological specimens without the need to cut them physically.
To demonstrate the capabilities and prospects of this method a pilot experiment
was carried out at the Spot beamline of the synchrotron storage ring BESSY II.
The spatial distribution of the trace elements Ca, Fe, Zn and Cu across virtual cross
sections of the root of common duckweed was investigated with a resolution of
around 20 m and compared to a micrograph of a cross section of a root. Due to selfabsorption in the specimen algorithms for absorption-correction had to be developed
and were applied.
[1] B. Kanngieer, W. Malzer, M. Pagels, L. Lhl, G. Weseloh., Analytical and
Bioanalytical Chemistry, 89 (2007): 1171-1176

248

PC-29
EDXRF Analysis of Thaumatococcus Danielli in Osun State of
Nigeria
S.O. Olabanji1, G.A. Osinkolu1, D.A. Pelemo1, A.A. Abiona1 and A.T. Oladele2
1

Centre for Energy Research & Development (CERD), Obafemi Awolowo University
(OAU), Ile-Ife, Nigeria.
2
Department of Pharmacognosy, Faculty of Pharmacy, Obafemi Awolowo
University (OAU), Ile-Ife, Nigeria.

Thaumatococcus danielli {Marantaceae} (Benn.) Benth. [Miraculous berry]

is a multi-purpose perennial herb that is widely distributed in the tropical rainforest
areas of West Africa. The leaves are simple, broad with slender stems connected
underground to the perennial rhizomes. Farmers grow it in pockets within cocoa
(Theobroma cacao) and kola (Cola nitida) plantations in South western Nigeria,
Ghana and Cameroon. Propagation is mainly by rhizomes cuttings and occasionally
by the seed. T. danielli plays very important roles in the rural economy generating
income for the peasant farmers and traders. T. danielli is used mainly in three ways
by the people. The leaves are used in food wrapping because of its very good flavour
and its preservative ability; and roof thatching while the stem is locally used as straw
in weaving mats and in making baskets, bags, hats, hand fans and other artistic
works. Research has shown that the fruits of T.danielli contain low-calorie protein
named Thaumatin which is about 2000 times as sweet as sucrose. The stems also
can be processed to produce fibre industrially in addition to the industrial potential of
Thaumatin. Thaumatin have been implicated to be suitable sweetener for diabetes
patients. However, despite the great economic values, potentials and benefits of T.
danielli, there is hardly any data on its elemental compositions. This work therefore
presents the elemental composition of T. danielli plants parts (leaves, stems, fruits
(mesocarps), seeds and roots (rhizomes)) from six different towns in Osun State of
Nigeria using Energy-Dispersive X-ray Fluorescence (EDXRF) spectrometry, and
the EDXRF spectrometer facility at Centre for Energy Research and Development
(CERD), Obafemi Awolowo University, Ile-Ife, Nigeria supplied by AMPTEK INC.,
MA, USA. The results showed the detection of elements which include K, Ca, Fe,
Mn, Sr, Zn, Pb, Br, and Cl at various concentrations. These very important novel
results are presented and discussed.

249

PC-30
Why L:L=1:1 in spite that the quantum mechanical intensity
ratio is 2:1?
Jun Kawai, Ryosuke Shioi, Nobuharu Sasaki, Kenji Okada, Goro Kinugawa,
Shinsuke Kunimura, Takashi Yamamoto
Department of Materials Science and Engineering, Kyoto University
In a typical EDXRF (energy dispersive X-ray fluorescence) spectrum, where the
L intensity approximately equals to L (Fig.1). Sometimes we observe spectra
where L is slightly stronger than L, depending on atomic number or spectrometer
used. However, if you know quantum mechanics, after a tedious multiplet structure
calculations including the spin-orbit interaction, the intensity ratio is expressed as
L2:L1:L1 = 1:9:5. Since the observed L peak in EDXRF is composed of L1 + L2,
thus L:L = 10:5, or L should be one half the intensity of L. In the present paper,
we would like to show by experiments that the L to L intensity ratio of various
elements depends on (1) atomic number, (2) chemical state, (3) concentration, (4)
X-ray tube voltage as well as target (Rh, W, ) for XRF, (5) electron acceleration
potential for SEM, (6) EDX or WDX, (7) spectrometer resolution (slit used is fine or
coarse for WDX), (8) filter, (9) detector counting efficiency, (10) grain size for powder
or surface roughness for metal, and (11) solid or solution.

Fig.1 Spectrometer resolution

dependent intensity difference.

Fig.2 High resolution Bi L and

L measured by a double-crystal
spectrometer.

250

PC-31
New approach for measuring fluorescence yields
using tunable monochromatic radiation
Y. Mnesguen and M.-C. Lpy
CEA, LIST, Laboratoire National Henri Becquerel, Gif-sur-Yvette, F-91191, France
Most of the available experimental data concerning fluorescence yields
have been determined more than forty years ago [1], and for low Z elements, the
associated uncertainties are rather high. The lower Z, the lower K, and the larger
its associated uncertainty. For light elements, low K means that the de-excitation
process is preferentially done via an Auger transition, the X-ray photons being very
few. To overcome the relative inefficiency of the X-ray emission for light elements
resulting in large fluorescence yields uncertainties, Auger electrons counting should
give better results.
Today, available experimental facilities, like monochromatic radiation (tunable
X-ray source or synchrotron), improved semiconductor detectors should offer new
perspectives of experimental measurements.
New experimental approaches are proposed, using the SOLEX facility [2] that
produces a tunable monochromatic X-ray beam in the 1-20 keV range. SOLEX has
recently been equipped with a new rotation system, thus the same monochromatic
beam can be sent successively towards two different directions.
A first experiment reproduces a classical measurement system: the primary
beam intensity is determined using a reference detector and then the same beam
is sent under 45 incidence to the target whose fluorescence X-rays intensity is
measured using another detector.
In a second step, there is no need for monitoring the primary since both
the X-rays and Auger electrons are measured. However, acquiring a spectrum of
emitted electrons as for photons is a challenging task. Experimental conditions are
more demanding than for photons and detectors have to be carefully chosen. First
experimental results and perspectives will be given as this experimental arrangement
is conceived to be used on the metrology beam line of the SOLEIL synchrotron.
[1] W. Bambynek, B. Crasemann, R. W. Fink, H. U. Freund, H. Mark, C. D. Swift, R.
E. Price, P. Venugopala Rao, Reviews of Modern Physics, 44, 4 (1972) 716-813
[2] C. Bonnelle, P. Jonnard, J.-M. Andr, A. Avila, D. Laporte, H. Ringuenet, M.-C.
Lpy, J. Plagnard, L. Ferreux, J. C. Protas, Nuclear Instruments & Methods in Physics
Research A, 516 (2004) 594 601

251

PC-32
High-resolution X-ray analysis with multilayer gratings
P. Jonnard, K. Le Guen, J.-M. Andr
Laboratoire de Chimie Physique Matire et Rayonnement, Univ UPMC Paris 06,
CNRS UMR 7614, 11 rue Pierre et Marie Curie, F-75231, Paris Cedex 05, France
Periodic multilayers are nowadays widely used to perform x-ray analysis in
the soft x-ray range (photon energy lower than 1keV). However, they do not permit
to obtain high-resolution spectra like natural or synthetic crystals. Thus, multilayers
cannot manage some problems due to interferences between close x-ray lines.
It has been shown and demonstrated experimentally [1] that patterning a grating
within a multilayer structure leads to a diffractive optics having an improved resolving
power.
We illustrate in this communication the use of a multilayer grating in the CK
(around 280eV) and FeL (around 700eV) emission ranges. In the CK range, we
show that it is possible to separate the CK emission at the first diffraction order from
the OK emission at the second order. We also show by comparing CK spectra from
B4C and cellulose that the shape of the emission band is sensitive to the chemical
state of the carbon atom. In the FeL range, the improved spectral resolution enables
us to distinguish the FeL and L emissions (13eV spin-orbit coupling). By using
a sample made of a mix of LiF and an iron ore, we show that it is possible to easily
resolve the FeL and FK emissions. These examples demonstrate that an improved
x-ray analysis can be obtained with multilayer gratings when there is the need to
study samples having elements giving rise to close emission lines.
PANalytical is thanked for providing us with some analysed samples.
[1] R. Benbalagh, et al., Nucl. Instrum. Meth. Phys. Res. A541, 590 (2005).

252

PC-33
Post edge structure effects on mass attenuation coefficients
B. R. Kerur1, Sharanabasappa1, S. B. Kaginelli1 and Anilkumar S.2
1

Department of Physics, Gulbarga University, Gulbarga 585 106. India

2

Radiation Safety Systems Division, BARC, Mumbai - 400 085.India

The mass attenuation coefficient, [MAC], for any chemical compounds

is usually estimated from the sum of the weighted contributions of the constituent
elements, these contributions are additive and linear, a law known as Braggs additivity
law or the mixture rule is in common practice. The X-ray transmission, T, is defined
as T = I/I0, where I and I0 are the observed intensities with and without absorber.
This mixture rule ignores any changes in the atomic wave functions as a result of
the molecular, chemical and crystalline environment and validity of the mixture rule is
not well established in the soft and X-ray region and current methods of calculations
are inaccurate at photon energies near any absorption edge and that experimental
evidence of chemical effects is needed in particular close to absorption edges (Jackson
and Hawkes, 1981, Jackson 1982, Saloman et al. 1988). Experimental results were
presented by Deslattes (1969) Lakshminarayana et al. (1986), similarly, Kerur et al.
(1993, 1994) have thoroughly studied photon cross sections at or near absorption
edges and shown that deviations from the mixture rule occur as far as 1.2 keV above
the edge, and also some 42 eV below the edge for transition elements.
In the present investigation, chromium compounds with purity 99.99% were
chosen for the photon energy range from 5.895 to 14.439 keV to study the mixture
rule. The X-ray spectrometer consisted of a Canberra make HPGe X-ray detector
with a rated resolution of 200 eV at 5.898 keV and DSA-1000 stand alone system
were used for measurements, all parameters of the X-ray spectrometer were set
and the spectra was recorded and analyzed using Genie 2000 software. The longtime stability and linearity of the spectrometer were checked before data collection.
Radioisotopes 55Fe and 57Co were used and both are electron capture source give
their characteristic x-rays along with gamma rays, if present. The absorbers were
prepared by blotting paper method (Kerur et al., 1993) so as to cover the transmission
range 0.5T0.02. The incident spectrum and the transmitted spectrum was obtained
keeping the dummy and prepared blotting paper by gating the spectrometer at the
area under photo peak. For each absorber, two to three times were measured on
different area so as to cover whole area of the absorber. Finally, MAC was obtained
by a least-squares method. For each specimen, MAC was determined twothree
times to ensure a reproducibility within 2% for all samples. The measured values
are compared with theoretical calculations. The disagreement between experiment
and theory is larger than the experimental error when the incident photon energy
is close to the K shell absorption edge. Further away from the edge the agreement
between experiment and theory is within 3%. The breakdown of the mixture rule
close to K absorption edges is discussed. Acknowledgments: One of the authors
(BRK) is thankful to BRNS Office for providing the financial assistance to carry out
the research project.
253

PC-34
Some cases of mineralogical effect due to the presence of
crystals different from that one containing the fluorescent
element
J. Lartigue and A. Ramrez
Faculty of Chemistry, National University of Mxico, Ciudad Universitaria, D.F.
04510, Mxico
Accordingly to Tertian and Claisse1 the mineralogical effect can be associated
with variations in the fluorescence intensities of the order of 100% or more and
presents serious problems to the analyst. However, references to this effect in the
literature are very scarce. It is assumed to correspond to a diffraction phenomena
originated into the crystal that contains the fluorescent element. Chandler et al2
mention the possibility of a well-aligned Bragg back-reflection, increasing the count
rate of the upstream monitor detector, which was not quantified but ruled-out.
This paper describes some experiments by EDXRF where the mineralogical
effect was evident by self-diffraction, and others that could only be explained by
the influence of a crystal different than that one containing the fluorescent element.
Results of the last ones show increases in the intensity of the L(Pb) higher than
50% when 10% Al was added to the matrix and higher than 100% in the intensity
of K(Ca) with 10% K added. An analysis of the results is performed and the
necessary conditions are proposed for 3 possible cases: enhancement by selfdiffraction, enhancement by external diffraction and non-enhancement in spite of
crystals presence. The variables considered are: fluorescent wavelength, interplanar distance and the absorption coefficient.
[1] R. Tertian and F. Claisse, Principles of Quantitative X-Ray Analysis, Heyden &
Sons Ltd. (1982), p. 311.
[2] C.T. Chandler et al, Radiation Physics and Chemistry, 61 (2001), 347-350

254

PC-35
On population dynamics of the atomic ensembles in a
X-ray laser pulse: Optical bi-stability effect
O. Khetselius
Odessa University, P.O.Box 24a, Odessa-9, 65009, Ukraine
We consider the problem of interaction of the atomic ensembles with X-ray
radiation. The results of numeric calculation of population kinetics of resonant levels
for atoms in the X-ray laser pulse on the basis of the modified Bloch equations
are presented [1]. Cited equations describe an interaction between two-level atoms
ensemble and resonant radiation with an account of the atomic dipole-dipole
interaction. It has been found a strengthen possibility of manifestation of the internal
optical bi-stability effect special features in the temporary dynamics of populations for
the atomic resonant levels under adiabatic slow changing the acting field intensity.
The application of the cited effect in the nanoscience is discussed.
[1] O.Khetselius, Photoelectronics 17 (2007) 131-142; A.Glushkov, O. Khetselius, S.
Malinovskaya, Europ.Phys.Journ. in print (2008); Molec.Phys. in print (2008).

255

PC-36
Study of the performance of two x-ray spectrometers in different
matrix samples
S. Pessanha, M.L. Carvalho and A. Guilherme
Centro de Fsica Atmica da Universidade de Lisboa, Av. Prof. Gama Pinto, 2,
1649-003, Lisboa, Portugal.
The aim of this work is to compare the features of two X-ray fluorescence
spectrometers in order to evaluate their performances in different matrices.
Two non-commercial EDXRF spectrometers, a portable and a large dimension
with tri-axial geometry one were tested using reference materials regarding different
types of matrices.
Seven reference materials were analyzed, orchard leaves, (NBS-1571), clay
(ISE-954), fish flesh (MA-A-2), animal blood (IAEA-A-13), bone meal (NIST-1486),
70% copper alloy (BCR-691) and 22ct gold alloy (Fischer).
The obtained results showed significant differences in the response of the
two spectrometers for the different matrices.
Two case studies were also performed in order to appraise the performance
of the spectrometers: two Portuguese coins from the XVIIIth and XIXth centuries and
samples of animal tissues contaminated with lead.

256

PC-37
Construction and applications of the Cracow X-ray microprobe
J. Bielecki, S. Boek, J. Lekki, Z. Stachura and W.M. Kwiatek
The Henryk Niewodniczaski Institute of Nuclear Physics, Polish Academy of
Sciences (IFJ PAN) ul.Radzikowskiego 152, 31-342 Cracow, Poland
Since many years the IFJ PAN Institute in Cracow is using a nuclear
microprobe to investigations in the field of biophysics, geology and materials
science. Construction of an X-ray microprobe described in this presentation
extended this research to interactions with focused beam of X-ray radiation.
As a source of X-ray an open type X-ray tube Hamamatsu L9191 with
microfocusing down to about 1 m spot is used. As exchangeable targets the Ti,
Mo, Ag, and W were chosen. The microprobe will be used in the high resolution
computer microtomography (CMT), to trace elements concentration analysis
by XRF and TXRF methods, and to radiation biology studies by irradiation of
mammalian cells with targeted microfocused X-ray beam. In future also other
measuring methods like SAXS or micro-crystallography are foreseen. The tube is
emitting radiation into a cone of 1200. When the formed beam, focused or parallel,
is required, sets of elliptical or parabolic mirrors in the Kirkpatrick-Baez geometry
are used. Low energy beam of 4.5 keV (Ti-K) used for the cell irradiations facility is
focused by a pair of multi-layer mirrors produced by Rigaku (USA). Higher energies
of 17.5 keV and 22.2 keV (Mo-K and Ag-K) in a stand for the XRF and TXRF
measurements are focused with the total reflection mirrors produced by Xradia
(USA). Radiation of other energy ranges is used for the CMT only.
Details of the microprobe construction with special emphasis on the CMT
method, its hardware, software, and the first experimental results will be presented.

257

PC-38
Micro X-ray Fluorescence Spectrometer with Low Power Tube
for Light Element Analysis
S. Smolek, C. Streli, N. Zoeger, P. Wobrauschek and F. Meirer
Vienna University of Technology, Atominstitut, Stadionallee 2, 1020 Vienna, Austria
Micro X-ray Fluorescence (Micro-XRF) is a well established tool to determine
the spatial distribution of major, minor and trace elements in a sample. It is widely
used to investigate samples from different fields (biology, geology, life science,
etc.). The method is non-destructive, requires little sample preparation and allows
simultaneous multi-element detection.
Most available Micro-XRF spectrometers operate in air which does not allow
the analysis of low-Z elements (Z 14). To extend the analytical range down to light
elements (Z 6) a special micro-XRF spectrometer has been designed.
This system consists of an air cooled low power x-ray tube (50W) with
molybdenum anode and a thin (70m) exit window. An optional beam filter can be
inserted to reduce spectral background. The beam is focused onto the sample using
a polycapillary x-ray optics, offering a focal spot of about 30m FWHM. Characteristic
X-rays from the sample are detected by means of a Si(Li) detector with ultra thin
window. An optical microscope attached to a high resolution CCD camera is used
to control the measurement position. Sample positioning and scanning is performed
using a motorised xyz sample stage.
The new spectrometer offers improved excitation and detection conditions,
necessary for light element analysis. The thin window of the x-ray tube allows both,
the molybdenum L-lines and K-lines to sufficiently excite the sample over a wide
energy range. Detection of the low energetic characteristic radiation is possible due
to the ultra thin window of the detector. To eliminate absorption of the exciting and
fluorescent radiation in air the system operates under vacuum condition. Sample
scanning is automated and controlled by specialized computer software developed
for this spectrometer. Access to the spectrometer will be available for external users
through the transnational programme of a running EC project (ANNA, www.i3-anna.
org).
In this work the spectrometer design as well as first test measurements on
different samples, such as artificially created elemental patterns of light elements
and human bone will be presented.

258

PC-39
Portable TXRF spectrometer with a 40 kV X-ray tube
S. Kunimura and J. Kawai
Department of Materials Science and Engineering, Kyoto University
A portable TXRF spectrometer with a Rh X-ray tube was designed and
constructed. The size of the present spectrometer was similar to that of a portable
TXRF spectrometer with a W X-ray tube presented in the previous papers [1, 2]. A
maximum target voltage of the Rh X-ray tube was 40 kV, and it was four times as
high as that of the W X-ray tube. The present spectrometer extended the range of
detectable elements. Figure 1 shows (a) an XRF spectrum of 10 ng of As without
X-ray total reflection and TXRF spectra of (b) 10 ng of Sc, Cr, Co, Zn, As, Sr, and
Nb and (c) 10 ng of Pb that were measured by using the present spectrometer.
The spectral backgrounds in the spectra in Figure 1 (b, c) were lower than that in
the spectrum in Figure 1 (a). The Zn, As, and Sr K lines and Pb L line which the
previous spectrometer could not detect were detected as well as the Sc, Cr, and Co
K lines. It was difficult to detect 10 ng of Nb. Table 1 gives the detection limits for
Sc, Cr, Co, Zn, As, Sr, and Pb. The detection limits were sub nanograms to several
nanograms. The present spectrometer detected wide range of elements with trace
amounts.
Table 1. The detection limits for elements.

Element

Detection limit / ng

Sc

0.7

Cr

0.5

Co

0.8

Zn

1.0

As

1.6

Sr

6.3

Pb

3.3

Figure 1. Representative XRF spectra measured

by a portable TXRF spectrometer with a Rh X-ray
tube. (a) An XRF spectrum of 10 ng of As without
X-ray total reflection, and TXRF spectra of (b) 10
ng of Sc, Cr, Co, Zn, As, Sr, and Nb, and (c) 10
ng of Pb. The X-ray tube was operated at 25 kV
and 50 A.

[1] S. Kunimura and J. Kawai, Anal. Chem. 79, 2593 (2007).

[2] S. Kunimura and J. Kawai, Anal. Sci. 23, 1185 (2007).
259

PC-40
Tabletop spectrometer for Grazing Incidence XRF
N. Zoeger1, D. Ingerle1, C.Streli1, F. Meirer1, P. Wobrauschek1, G. Pepponi2
1

Vienna University of Technology, Atomic Institute of the Austrian Universities,

Stadionallee 2, A-1020 Vienna, Austria
2
Fondazione Bruno Kessler-irst, Via Sommarive 18, I-38050 Povo, Italy

Secondary ion mass spectrometry (SIMS) is routinely used for determining

profile shapes, junction depths, and doses of dopants in Si wafers. However, in case
of ultra shallow junctions (USJ) SIMS is going towards its intrinsic limits. Whereas
the depth resolution and quantification in the deeper regions are still sufficient with
SIMS, the native oxide-induced matrix effects are limiting factors for the technique if
dose and distribution in the first nanometres are required.
Therefore a more complete characterization of USJ, as demanded by
microelectronics technological nodes will require the application of different
complementary techniques such as Medium Energy Ion Scattering, Scanning
Transmission Electron Microscopy, Spectroscopic Ellipsometry as well as Grazing
Incidence X-ray Fluorescence Analysis (GIXRF). The development of the mentioned
techniques and the understanding of their complementariness for USJ analysis will
be the task of a research activity within the running EC project ANNA (European
Integrated Activity of Excellence and Networking for Nano and Micro- Electronics
Analysis). Within the frame of this activity the X-ray group of the Atomic Institute
develops GIXRF as a laboratory source driven tool for USJ analysis. The technique
relies on the measurement of fluorescence signals at various incidence angles of
the exciting X-ray beam. As the penetration of the primary X-rays becomes larger
as a function if increasing incidence angles, GIXRF provides information on the total
implanted dose in the substrate material. Since GIXRF is very sensitive in the first
few nanometres it delivers satisfactory results for sample depths where SIMS has
its drawbacks.
To successfully accomplish GIXRF analyses a tabletop measuring chamber
is currently under development.
In the present work the design as well as the current status of the prototype
will be presented. Hardware and software requirements to meet the demands of
depth profiling with GIXRF will be discussed. Moreover first results obtained on As
doped Si wafers will be presented.

260

PC-41
A new Grazing-Exit-XRF setup at HASYLAB beamline L
F. Meirer1, G. Pepponi2, C. Streli1, P. Wobrauschek1 and N. Zoeger1
1

Atominstitut, Vienna University of Technology, 1020 Wien, Austria.

2
ITC-irst, via Sommarive 18, 38050 Povo (Trento) Italy

Total reflection x-ray fluorescence analysis (TXRF) operates with the incident
beam impinging below the critical angle of total reflection on the surface of a flat
polished surface of reflector. The interference between incident and reflected beam
causes in case of microcrystalline samples an intensity increase of the fluorescence
signal by a factor (1+R) where R is the reflectivity numerically close to 1. The
additional effect due to the penetration depth in the nm region is a low background.
Both effects are leading to excellent detection limits in TXRF and are widely used
in ultra trace element analysis. Grazing incidence XRF (GI-XRF) uses the angle
dependent wavefield intensity in order to characterize the structure of layered
materials and the composition gradient of materials that are inhomogeneous along
the direction perpendicular to the surface. The inverse GI-XRF with the incident
beam perpendicular to the reflectors surface and collecting the fluorescence under
grazing angle can also be applied [1]. This mode of analysis was named grazing exit
X-ray fluorescence (GE-XRF) and is theoretically based on the reciprocity theorem
[2]. The interference in this case is not between primary and reflected beam but
among the superposition interference of the fluorescent waves emitted from the
sample and observed under the critical angle of total reflection crit.
A GE-XRF experiment was performed at HASYLAB beamline L using the
newly designed equipment from the Atominstitut Vienna X-ray group. The setup was
designed with the axis of rotation of the detector exactly in the plane of the reflector.
The experiments were performed with the aim to study XANES self-absorption
effects, which were observed previously in GI-XRF geometry.
A series of dried residues with different total amounts of arsenic masses on
quartz reflectors were investigated. Angle dependent measurements of the samples
were carried out by rotating the detector around the sample in the center of the
reflector. The experimental data and the theoretical curves showed good agreement.
The GE setup allows spatially resolved measurements of the sample. In order to
achieve measurements with higher lateral resolution a polycapillary half lens was
used to produce a focal spot of 40m in diameter. With this setup 2D-scans of the
samples have been performed and compared with data from confocal microscopy.
XANES measurements of the samples were performed and compared with data
gained for the same samples under GI conditions.
[1] T. Noma, A. Iida, K. Sakurai, Phys. Rev. B 48 (1993) 17524.
[2] R.S. Becker, J.A. Golovchenko, J.R. Patel, Phys. Rev. Lett. 50 (1983) 153.

261

PC-42
Influence of the sample morphology on Total Reflection X-Ray
Fluorescence Analysis
C. Horntrich1, F. Meirer1, C. Streli1, P. Kregsamer1, G. Pepponi2, N. Zoeger1,
P.Wobrauschek1
1

Vienna University of Technology, Atominstitut, Stadionallee 2, 1020 Vienna,

Austria
2
ITC-irst, via Sommarive 18, 38050 Povo (Trento) Italy

Total Reflection X-ray Fluorescence Analysis (TXRF) is a method for

qualitative and quantitative analysis of trace elements. In general TXRF is known
to allow for linear calibration typically using an internal standard for quantification
[1,2]. Absorption effects concerning exciting and detected radiation are usually
disregarded. This is justified because mostly small sample amounts are used. The
thin film approximation in particular assumes a very thin sample and therefore
differential absorption for photons with different energies can be ignored. Furthermore
the elements in the sample are assumed to be homogeneously distributed. Hence
the loss of the fluorescence signal due to absorption of the primary beam equally
affects all elements and quantification by using an internal standard is justified.
However, for higher total amounts of samples deviations from the linear relation
between fluorescence intensity and sample amount have been observed [3].
The topic of the presented work is an investigation of the parameters
influencing the absorption phenomenon. A simulation model was developed to
calculate the influence of the absorption effects. Samples with different total amounts
of arsenic have been prepared to determine the upper limit of sample mass where
the linear relation between fluorescence intensity and sample amount is no longer
guaranteed. It was found that the relation between fluorescence intensity and sample
amount is linear up to ~100ng Arsenic. The parameters necessary for the simulation
(sample dimensions and volume) were determined by analyses with a confocal white
light microscope. Even though the results of the simulations are not satisfying yet it
could be shown that the key parameters for the absorption effect are the density of
the investigated atom in the dried residues and the shape of the residue. Difficulties
for the simulation appeared due to the determination of the density of the arsenic
atoms in the sample. To improve the simulation model further investigations are
necessary.
[1] P. Wobrauschek, X-Ray Spectrometry 36 (2007) 289-300.
[2] R. Klockenkamper, Wiley-Interscience, New York, 1997.
[3] D. Hellin, J. Rip, S. Arnauts, S. De Gendt, P.W. Mertens, C. Vinckier,
Spectrochimica Acta Part B: Atomic Spectroscopy 59 (2004) 1149-1157.

262

PC-43
Micro TXRF Analyses of multiple residues on a flat substrate
K. Tsuji and S. Kawamata
Department of Applied Chemistry, Graduate School of Engineering, Osaka City
University, (3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan)
In the conventional total reflection x-ray fluorescence (TXRF), a large area
of the sample surface is analyzed because the primary x-rays irradiate a large area
of the surface. In the applications of TXRF analysis, the residue of a sample droplet
on the flat sample carrier is measured. In this case, the analyzed object is the small
residue itself. The x-ray fluorescence emitted from areas other than that of the residue
just produces background peaks. Therefore, it would be a good idea to analyze only
the micro region of the small residue, leading to trace elemental TXRF analysis [1].
In this work, TXRF of a micro-sized region has been attempted by using a simple
pinhole. Single pinhole with an inner diameter of 1 mm was attached to the top of
an energy dispersive x-ray detector. Standard solutions containing Fe, Cu, and Zn
were dropped on the specific positions on a flat substrate. Finally, multiple residues
were prepared on the single substrate plate. It was difficult to selectively measure
each residue by a conventional TXRF, because the primary X-rays irradiated the
whole surface of the substrate. The sample substrate was put on an XYZ stage
controlled by stepping motors and a computer; therefore, each residue could be
sequentially measured by micro-TXRF. In the case that each residue is prepared
on the different substrates one by one, we have to exchange and adjust the sample
substrate for every TXRF analyses of all samples. Our micro-TXRF method enables
the sequential rapid TXRF analyses of multiple residues on the substrate.
[1] K. Tsuji, M. Kawamata, Y. Nishida, K. Nakano, K. Sasaki, Micro Total Reflection
X-ray Fluorescence (Micro-TXRF) Analysis, X-ray Spectrom., 35, (2006) 375-378.

263

PC-44
X-ray Fluorecenece analysis using X-ray transparent thin films
for sample surpport
K. Tsuji, K. Nakano, K. Okubo and Y. Nishida
Department of Applied Chemistry, Graduate School of Engineering, Osaka City
University, (3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan)
We have studied XRF analysis by using X-ray transparent thin film for sample
support. Here, we will present XRF results obtained by two approaches.
(1) XRF sampling of the particles by adhesive tape
In some cases, it is difficult to take the sample of small particles on the
outer wall or the statues. We used a thin adhesive tape of 30 m in thickness. The
sampling efficiency was checked for the dried residue on the glass plate by ED-XRF
and TXRF methods. We confirmed that sampling the particles on the glass substrate
was possible by using the adhesive tape [1]. Finally, we took the particles on the
outer wall in the campus of the Osaka City University by the adhesive tape. The
particles on the tape were analyzed by ED-XRF and micro-XRF methods.
(2) Preconcentration in agar thin films
The natural polymer (agar) was used for sample preparation of trace XRF
analysis [2]. A 10 mL volume of the aqueous sample and 0.07 g of the dried agar
powder were mixed. The mixed solution was heated on a hot plate and was poured
into a hollow Teflon cup. After the solution was dried, the thin agar films (50 m in
thickness) containing trace metals were measured by EDS and WDS. The linear
calibration curves of several elements showed a good linearity. The lower limits of
detection (LLD) were 1.4 mg/mL for K, 0.26 mg/mL for Ca, 0.029 mg/mL for Mn,
0.11 mg/mL for Fe, 0.016 mg/mL for Ni, 0.030 mg/mL for Cu, 0.20 mg/mL for Cd,
and 0.066 mg/mL for Pb, respectively. The proposed preconcentration method was
applied to the several environmental waters.
[1] Y. Nishida, K. Tsuji, Adv. X-ray Chem. Anal. Japan, 39 (2008), in press.
[2] L.P. Eksperiandova, A.B. Blank, Y.N. Makarovskaya, X-ray Spectrum., 28 (1999)
24-26; 31 (2002) 259-263.

264

PC-45
Study of alteration of elemental contents In human whole blood
and Hemocomponents following irradiation injury by SR-TXRF
C.L. Mota1, N.G.V. Pinto1, C.J.G. Pinheiro1, D. Braz1, R.C. Barroso2,
A.S. Melo Junior3 and S. Moreira3
Nuclear Instrumentation Laboratory - COPPE \ UFRJ - Rio de Janeiro Brazil
University of Rio de Janeiro State, Physics Institute - Rio de Janeiro Brazil
3
State University of Campinas, School of Civil Engineering Campinas - Brazil
1

The total-reflection X-ray fluorescence using synchrotron radiation (SRTXRF) is a very well-suited analytical technique to study the trace element contents
in biomedical samples [1]. The aim of this study was to investigate the suitability
of measuring mineral and essential trace elements as a monitoring tool for the
diagnosis of alterations caused by irradiation procedures. Fresh blood specimens
were obtained from Dr. Eliel Figueiredo Laboratory, Rio de Janeiro. The samples
(n=956) were irradiated with doses from 2 to 3000 cGy using gamma radiation. After
irradiation process, all samples were lyophilized [2] to remove the water content and
then, they were submitted to the standard chemical digestion by adding nitric acid.
All the measurements were carried out at the X-Ray Fluorescence beamline at the
Brazilian Synchrotron Light Laboratory (LNLS), in Campinas. In the whole blood
samples, the data show a decrease in the concentration of K, Fe ( > 95%) and Zn
( > 90%) as the dose increases over the dose range. In blood formed elements
samples, there was a slight decrease of K level compared to the non-irradiated
samples ( > 95%) up to 20 cGy. In blood plasma samples, K levels increase up
to 4 cGy ( > 95%). However Fe levels ( > 90%) decrease for all dose range. The
statistical analysis showed that the variation found for the Ca levels is not significant
for the whole blood and hemocomponents samples. In this way, Ca levels were not
found sensitivite to the irradiation dose.
[1] J. M Jaklevic, F. S Goulding, IEEE Trans. Nucl. Sci., NS-19 (1990) 384-390.
[2] J.Moody, Philos. Trans.R. Soc., 305 (1982) 669-682.

265

PC-46
TXRF-NEXAFS study of carbon and nitrogen compounds in fine
particulate matter deposited on silicon wafers
J. Osn1, S. Trk1, B. Beckhoff2 and F. Reinhardt2
KFKI Atomic Energy Research Institute, P.O. Box 49, H-1525 Budapest, Hungary
Physikalisch-Technische Bundesanstalt, Abbestr. 2-12, D-10587 Berlin, Germany

1
2

The impact of carbon- and nitrogen containing fine aerosol particles on human
health and atmospheric chemistry is an important issue for several environmental
studies. Near edge X-ray absorption fine structure (NEXAFS) measurements in the
total-reflection X-ray fluorescence (TXRF) geometry offer non-destructive speciation
of the atmospherically important low-Z elements (C, N and O) in minute samples
collected by cascade impactors directly on the reflector surface.
Atmospheric particulate matter was collected at different urban and rural,
continental and marine locations using a 7-stage May impactor having aerodynamic
cut-off diameters of 1, 0.5 and 0.25 m for stages 5 to 7, respectively. The TXRFNEXAFS experiments were performed at the plane grating monochromator
beamline for undulator radiation in the laboratory of the Physikalisch-Technische
Bundesanstalt at the electron storage ring BESSY II. (NH4)2SO4, NaNO3, NH4NO3,
graphite and CaCO3 standard particles in the 0.25 to 2 m size range deposited on
silicon wafers were measured in identical conditions. Using a linear combination of
the TXRF-NEXAFS spectra recorded for the nitrogen standards, a semi-quantitative
ammonium/nitrate ratio was obtained.
The twofold effect of the increased traffic intensity on the aerosol composition
can be clearly seen on the carbon TXRF-NEXAFS spectra. In the smallest size
fraction (0.250.5 m), a higher concentration of primary carbonaceous particles
was observed. Higher traffic also increases resuspension of larger particles of
crustal erosion origin, with calcium carbonate as a major component in Hungary.
The ammonium to nitrate ratio shows a decreasing trend with increasing particle size
in the range of 0.25m to 2.0 m. The variation of nitrate-to-ammonium ratios could
be well explained with the air mass backward trajectories.
The above results were obtained from samples collected from much smaller
air volumes than usually used for filter sampling, supporting the applicability of TXRFNEXAFS in the characterization of particulate matter with high time resolution.

266

PC-47
Effect of ethanol intake during lactation on brain mineral status
of pup and young rats using X-ray total reflection spectrometry
L. A. Marins1, R.F. Barbosa1,2, E. F. O. de Jesus3, M. J. Anjos1,2, M. G. T. do Carmo3,
M. S. Rocha4, and R. T. Lopes1
Federal University of Rio de Janeiro/COPPE, Nuclear Instrumentation Laboratory,
P.O. Box: 68509, Zip Code: 21941-972, Rio de Janeiro, Brazil. Fax:; Tel: 55 21
2562-7311
2
University of Rio de Janeiro State, Physics Institute, RJ, Brazil
3
Federal University of Rio de Janeiro, Nutrition Institute, RJ, Brazil
4
Federal University of Rio de Janeiro, Department of Basics and Clinic Pharmacy,
RJ, Brazi
l
Nowadays alcohol consumption is one of the main problems of public health
in the world. The hippocampus is a brain structure very vulnerable to the oxidative
stress and, consequently it is more sensitive to the negative effects to alcohol
consumption. The present study cover the lactation period since this is the time,
which the growing-up and brain development is more intense than in prenatal period.
Therefore, this work determined the elemental concentrations in the hippocampus
of pups that received alcohol through the maternal milk, comparing their levels with
the control group and the recuperated one. Female Wistar rats (20 days old) were
separated into two groups: control group C.G and ethanol group E.G (n = 20) and
male Wistar rats (20 days and 90 days old) were separated in three groups: C.G (20
days old and 90 days old), E.G (20 days) and recuperated group R.G (90 days old
n = 28). The R.G received ethanol like the EG and then received commercial diet
such as the control group. The mineral contents were determined using X-Ray Total
Reflection Spectrometry with Synchrotron Radiation at the XRF beam line at Brazilian
Synchrotron Laboratory. This technique was very useful in this study, since it requires
small sample amount, which became possible to analyze the hippocampus of rats
(mass about 50 mg). The ethanol intoxication leads a decreased in K, Ca, Fe and
Cu levels only in the lactation period (20 days old) of female and male rats. These
findings suggested that the R.G has got to maintain the levels of these elements,
i.e., they reversed the changes caused by the ethanol intake. The ethanol absorption
in the lactation period of female pups (20 days old) lead an increase in P, S and Cl
levels, which occurs differently to male pups. Therefore, the ethanol leads to several
changes in the mineral concentration, which can affect the growing and development
of the brain.
1

267

PC-48
Depth profiling of Al-implanted Si by means of synchrotron
radiation based high resolution grazing emission x-ray
fluorescence
Y. Kayser1, J-Cl. Dousse1, J. Hoszowska1, W. Cao1, J.-L. Schenker1, M. Pajek2,
A. Kubala-Kukus2, P. Jagodzinski2, M. Kavcic3, J. Szlachetko4
Department of Physics, University of Fribourg, Chemin du Muse 3, CH-1700
Fribourg, Switzerland2Institute of Physics, Swietokrzyska Academy, Swietokrzyska
15 St., 25-406 Kielce, Poland
3
J. Stefan Institute, P.O. Box 3000, SI-1001 Ljubljana, Slovenia
4
European Synchrotron Radiation Facility, BP 220, F-38400 Grenoble, France
1

Progress in semiconductor microelectronic technology requires improved

diagnostic tools for the depth profiling of doping elements in semiconductor materials.
In this perspective, the high resolution grazing emission x-ray fluorescence (GEXRF)
technique combined with synchrotron radiation was tested in order to develop an
effective method for studying the depth profiles of Al-implanted in Si. This technique
has already proven its high detection sensitivity when being used for the detection
of low level concentrations of Al on Si surfaces [1] (see Fig. 1). The depth profiling
is achieved by measuring the dependence of the Al x-ray fluorescence intensity
on the grazing emission angle around the critical angle for Al-K radiation. This
dependence is uniquely related to the
studied concentration depth-profile.
We report on depth profiles of
Al-implanted Si at energies of 30, 50
respectively 100 keV implanted with a
dose of 1016 ions/cm2. Measurements were
performed at the ESRF ID21 beam line
by means of the Fribourg high-resolution
von Hamos x-ray spectrometer [2]. Since
the critical angle of Si is larger than that
of Al, the bulk Si x-ray fluorescence was
limited to a surface layer of only a few tens
of nanometers which resulted in a relative
increase of the Al x-ray fluorescence signal.
The background due to bulk Si was further Fig.1: High-resolution grazing emission
decreased by selecting the beam energy x-ray K fluorescence line from Al
below the K-absorption edge. Thus, the impurities in a Si wafer.
sensitivity and the quality of the Al depthprofile measurement were enhanced. By means of the described high resolution
GEXRF excited by synchrotron radiation the depth profiles can be determined
accurately and the effect of thermal processing (annealing, diffusion) on the
concentration profiles can be evinced.
[1] A. Kubala-Kukus et al. ,XXV International Conference on Photonic, Electronic, and Atomic
Collisions (ICPEAC),25-31 July 2007, Freiburg, Germany, Book of Abstracts p. We048.
[2] J. Hoszowska et al., Nucl. Instr. Meth. Phys. Res., A 376 (1996) 129-138.

268

PC-49
Determination of trace metals in bottled commercial drinking
water using TXRF in Nairobi, Kenya
M. J. G. Gatari, D. M. Maina, S. Bartilol and S. M. Gaita
Institute of Nuclear Science and Technology, University of Nairobi, P. O. Box
30197-00100, Nairobi, Kenya
Heavy metals in drinking water can be a hazard to human health depending
on their concentration. Health concerns within the Kenyan population have been
increasing and a larger population is drinking commercial bottled water as opposed
to tap water or direct from rivers.
Samples of bottled water were purchased from shops in Nairobi Central
district, slums and city outskirts (rural). From each bottle 10 l portions were pipetted
and carefully dropped on TXRF sample carriers. The carriers were thoroughly precleaned with HNO3, HCL and distilled water. Three portion replicates from each bottle
were left to dry overnight at 25 0C in a vacuumed oven. They were then analysed on
the Vienna TXRF module under x-rays from a Phillip X-ray tube that was powered by
a model 710H Siemens high voltage generator.
The obtained spectra were analysed and concentrations of the elements
of interest quantified using QXAS software from IAEA. Analytical calibration was
achieved by preparing standard solutions of Ti, Cu, Zn and Pb and obtaining
spectra the same way and under the same spectrometer setup. Most of the harmful
elements that were analysed were below detection limits (DL). Cu and Mn were seen
in spectra of portions from slum and rural. Investigation of concentration values,
50 % of DL for below DL concentrations, of the analysed elements showed a high
standard deviation of K and Ca in upmarket bottled water and low in those from
the slums and rural. However Ti, Fe, Zn and Pb had similar deviations in all shops.
The high variability in this preliminary work needs further investigation for it may
be a precursor of high contamination if measured against the allowed maximum
contaminant levels by USEPA.
[1] United States Environmental Protection Agency (USEPA). Water on tap, pp23;
book pp23 on www.epa.gov/ visited on 20th February 2008.
Acknowledgement:
The work was possible due to the assistance of International Atomic Energy
Agency (IAEA) and International Science Programs (ISP), Uppsala University,
Sweden to University of Nairobi, Institute of Nuclear Science & Technology.

269

PC-50
On-Line X-Ray Fluorescence analysis of Iron-ore mixtures on a
conveyor belt
N. Alov1, A. Volkov1, A. Sokolov2, E. Ishmetyev3 and A. Usherov3
Lomonosov Moscow State University,
Department of Analytical Chemistry, 119992 Moscow, Russia
2
Bruker Baltic, LV-1005 Riga, Latvia
3
ZAO KonsOM SKS, 455044 Magnitogorsk, Russia
1

In ferrous metallurgy it is very essential to determine the composition of

iron-ore mixtures used in sinter production on-line above the conveyer belt. In this
paper we propose for the first time to apply energy-dispersive X-ray fluorescence
analysis (EDXRF) for on-line quantitative determination of Fe and CaO in iron-ore
mixtures. We used an EDXRF spectrometer Con-X 02 (Bruker Baltic) mounted by
an original suspension bracket directly above the conveyer belt of the agglofactory at
the Magnitogorsk iron and steel works, Russia. To minimize the influence of changes
in the distance between material and spectrometer on the X-ray fluorescence
spectra the analysis geometry is chosen when the X-ray tube primary radiation cone
is situated inside the collection cone of the detector. For the element composition
calculation we used software based on the fundamental parameters method. This
program accounts for the distance to the measured material, the lump size, unknown
and changing amounts of elements unseen by the spectrometer. We obtained a
standard deviation of 1.0% for Fe and 0.6% for CaO. The accuracy of EDXRF was
verified by more than 70 comparisons with chemical analysis measurements.

270

PC-51
The application of standardless material Identification for the
analysis of precious metal alloys and RoHS samples
B. Nensel, V. Riger, M. Hofmann, and S. Dill
Helmut Fischer GmbH Institut fr Elektronik und Messtechnik, Industriestrae 21,
D 71069 Sindelfingen, Germany
The Standardless Material Identification is a useful tool in many
applications when samples of unknown material or structure are investigated. The
user will get automatically the type of material and in a further step the quantitative
analysis with best calculation and calibration routine is performed. For this
standardless method no large base of standard reference materials is needed. The
base for the different classes of materials is calculated theoretically by defining the
ranges of concentrations or coating thickness of the materials. This method is more
flexible and easier to use compared to methods based on reference materials.
Two applications are presented in more detail:
1.
Analysis of precious metals. Many different types of alloys are
used in jewellery, dental and technical applications. It is often even not known, if
the material is coated or not. The Standardless Material Identification will find the
correct material to perform the analysis with the required high accuracy for the Au,
Pt or Pd content.
2.
Analysis according to the RoHS directive. RoHS causes the
necessity to analyse trace elements in electrical and electronic equipment, which
consists of a large amount of different materials. In particular many different types
of coatings like Sn, Ag, Au are used. For good trace analysis the knowledge of the
matrix is a precondition. With the Standardless Material Identification the different
types of coatings, metals or polymers that are used in electrical and electronic
equipment are identified.

271

PC-52
Quality improvement of FP quantification for thickness and
composition of alloy layers by XRF methods
E.Blokhina1, X. Dreiigacker2, W. Klck1,.
1

Rntgenanalytik Messtechnik GmbH, 65232 Taunusstein, Germany;

2
Enayati GmbH, 75217 Birkenfeld, Germany

Precision of FP quantifications is defined by the accuracy of instrumental

parameters as well as by atomic data and modelling of the physical processes. In order
to improve results for thickness and composition of metallic layers we tested a bulk
and layer based recalibration routine using independently characterized samples.
Alloy layers such as Pd-Ni and Zn-Ni are often used in industrial surface
coatings, and are therefore excellent examples for FP quantification testing.
We selected alloy layer standards for thickness and composition in the range of
Pd70-100 and Zn80-95. Three specific alloy samples were chosen as standards for
Pd-Ni alloy composition, and were analyzed with independent methods. Thicknesses
ranged from about 1 m to 10 m for Pd-Ni layers. Among the Zn-Ni layers two layer
samples were checked independently and thicknesses of all Zn-Ni samples ranged
from 2-35 m.
Results of the original FP calculations of alloy layer systems were not
always satisfying (see table 1). The amount of Ni in Zn-Ni alloys was too variable
and thicknesses were systematically underestimated. In the case of the Pd-Ni alloy
layers, deviations from the given values could be as high as 10%, but differ apparently
among different instrument parameter sets.
After recalibration using independent standards these deviations for all the
Pd-Ni layer standards were less than 1% relative for composition and thickness.
In case of the Zn-Ni samples the calibrated results showed a somewhat higher
variability, which seems to be related to the production process.
This approach, using independently characterized bulk and layer standards
and calibrating thickness and composition separately, seems to be very helpful for
analyses of alloy layers because in many cases compositions of these layers are
less well known compared to their thickness.
Table 1: Comparison of FP and recalibrated results measured on two different
x-ray systems
Pd-Ni alloy layers
Standards

certified

1
2
3
4
5
6

1.16 m
4.95 m
9.55 m
70 % Pd
80 % Pd
90 % Pd

Instrument 1
FP calculated
0.91m
3.95 m
7.64 m
68.4 % Pd
78.5 % Pd
90.4 % Pd

recalibrated
1.15 m
4.96 m
9.55 m
70.48 % Pd
79.85 % Pd
90.41 % Pd

272

Instrument 2
FP calculated
1.15 m
4.87 m
9.43 m
69.13 % Pd
79.96 % Pd
91.16 % Pd

recalibrated
1.16 m
4.93 m
9.57 m
70.00 % Pd
79.98 % Pd
90.01 % Pd

PC-53
Development and characterization of new polymeric reference
materials with the aid of XRF, LA-ICP-MS and Sy-XRF
C. Simons1, C. Mans1, S. Hanning1, A. Janen1, D. Alber2, M. Radtke3,
U. Reinholz3 and M. Kreyenschmidt1
1

University of Applied Sciences Mnster, Department of Chemical Engineering;

Advanced Analytical Chemistry, Stegerwaldstr. 39, 48565 Steinfurt, Germany
2 Hahn-Meitner-Institut, Department SF6, Glienicker Strasse 100,
14109 Berlin, Germany
3
Bundesanstalt fr Materialforschung und -prfung (BAM), Fachgruppe I.3
Richard-Willsttter-Strae 11, 12489 Berlin, Germany

Polymers are essential materials in our modern society. Due to their use in
numerous fields of application, polymer materials are subjected to a series of
restrictions and regulations regarding the presence and concentrations of a number
of additives and fillers.
The use of solid sampling techniques such as X-ray fluorescence spectroscopy
(XRF) and mass spectroscopy with inductively coupled plasma and laser ablation
(LA-ICP-MS) for the elemental analysis in plastics becomes more and more
popular. As both techniques are strongly matrix dependent, the use of matrix
matched and highly characterized reference materials is the favorable method for
calibration.
A set of 10 different materials based on acrylonitrile-butadiene-styrene terpolymer
(ABS) was produced by a specially developed extrusion process at University of
Applied Sciences Mnster containing different amounts of Br, Cd, Cr, Hg and Pb.
[1]
The resulting granulates were formed to solid discs using injection molding. The
exact elemental concentrations were determined by neutron activation analysis
(NAA) at the Hahn-Meitner-Institute Berlin for Br, Cd, Cr and Hg. The concentration
of Pb was determined by ICP-MS after acid digestion.
The determination of macroscopic homogeneity was carried out by measurements
with the aid of XRF. Therefore 18 samples per batch were measured as granulates
in standard liquid cups and the results were compared. All materials showed good
macroscopic homogeneity.
Determination of micro homogeneity was preliminarily carried out with the aid
of synchrotron micro XRF spectroscopy (Sy-XRF) for one batch at the BESSY.
The results were compared with measurements carried out by LA-ICP-MS. The
investigated material showed highly satisfying homogeneity for all elements.
The materials were successfully used for the calibration of XRF and LA-ICP-MS
measurements. They are therefore considered as candidate materials for the
certification by the Federal Institute for Materials Research and Testing (BAM).
[1] C. Mans, S. Hanning, C. Simons, A. Wegner, A. Janssen, M. Kreyenschmidt,
Spectrochimica Acta 62B (2007) 116-122.

273

PC-54
Delay of ruthenium escape in the presence of some fission
product elements
N. Vr, L. Matus, M. Kunstr, J. Osn, Z. Hzer
KFKI Atomic Energy Research Institute, P.O. Box 49, H-1525 Budapest, Hungary
The RUSET (RUthenium SEparate Effect Test) experimental program was
launched in order to understand the main phenomena in connection with escape of
Ru from spent fuel at severe accident processes with air ingress. In separate effect
tests Ru oxidation rate and content of Ru in escaping air flow have been studied.
The results showed that Ru evaporates in form of RuO3 and RuO4 and the amount of
RuO4 in the outlet air was in the range of 10-6 bar, far above the value that would be
expected from equilibrium. It was also observed that other fission products and UO2
influenced the concentration of RuO4 in the ambient temperature escaping gas and
caused a time delay in appearance of its maximum values.
The main objectives of the last test series were identification of those fission
products which play role in this time delay. Above the high temperature solid state
reactions in the reaction chamber presumably reactions in the decreasing temperature
outlet area delayed the release of Ru in the escaping cooled down air.
To understand these latter chemical reactions and the thermo chromatographic
effects, quartz rods with 2 mm diameter were placed into the decreasing temperature
outlet tube. The outer surface of quartz rods was investigated by micro-beam X-ray
fluorescence (-XRF) in order to determine the axial distribution of the inactive
simulated fission elements deposited along the sampler rods with acceptable
resolution.
The measurements were performed using a silver-anode fine-focus X-ray
tube. The beam was focused to 80 m (FWHM) by means of a polycapillary minilens
(IfG, Germany). The samples were fixed to a computer-controlled sample stage
vertically and were moved in front of the capillary in vertical direction. The scanning
results showed that MoO3 and TeO2 deposited together in temperature range between
600 and 300C, while the Cs deposition occurred between 800 and 300C.

274

PC-55
Total Reflection X-ray Fluorescence (TXRF): A future routine
analysis tool in structural biology?
G. Wellenreuther1, U.E.A. Fittschen2, M. Achard1, M. Salomone Stagni1,
A. Faust1, X. Kreplin1 and W. Meyer-Klaucke1
EMBL c/o DESY, Notkestr. 85, Building 25A, 22603 Hamburg, Germany.
Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg,
Germany
1

Metal ions are essential for the function of biological systems, about 30% of all
proteins require metals. They are involved in many crucial biological processes such
as respiration, metabolism, photosynthesis, cell division, muscle contraction, oxygen
transport, neurotransmission, and gene regulation. Knowing the metal content of a
protein therefore directly translates into new knowledge.
We have evaluated the applicability of total-reflection X-ray fluorescence (TXRF) and
synchrotron-based TXRF (SR-TXRF) to quantify the concentration of trace elements
in protein samples. TXRF is well suited to study protein samples since it allows
the quick quantification of all relevant elements using a comparable small sample
volume. Neither crystals nor high protein concentrations are required, allowing
measurements at various stages of a research project.
For a correct quantification of protein-bound metals the concentration of trace elements
in the pure buffer has to be determined also. To ensure a correct quantification matrix
effects have to be taken into account; ideally both protein and buffer should form a
thin film during drying. Therefore we studied the influence of different reflector types
on the drying properties of buffer and protein samples with spatial resolved XRF[1].
In addition, we developed a standard to be used for elemental analysis in structural
biology which allows quantifying and correcting any matrix effects present.
Possible applications of TXRF as presented on the poster include:
- Determination of metal occupancy
- Searching for contaminants
- Loading experiments
[1]
G. Wellenreuther, U.E.A. Fittschen, M.E.S. Achard, A. Faust, X. Kreplin,
W. Meyer-Klaucke, Spectrochimica Acta Part B: Atomic Spectroscopy (submitted)
(2007).

275

276

Author Index

Abe T.
Abiona A. A.
Achard M.
Adiguzel O.
Afanasev M. S.
Aggarwal S. K.
Agnese P.
Alber D.
Alberti R.
Al-Ebraheem A.
Alford T.
Aliane A.
Alizadeh M. B.
Almansour A.
Alov N.
Al-Saad Z.
Alsecz A.
Alshehne J.
Alves L. C.
Amokrane A.
Andr J. M.
Andreasson B. P.
Andri V.
Angeyo H. K.
Anglos D.
Anilkumar S.
Anjos M. J.
Antonioli G.
Aquilanti G.
Arafat A.
Aron I.
Argyropoulos V.
Arikan P.
Assis J. T.
Avila-Perez P.
Azar M.
Baake O.
Baba Y.
Bacescu D.
Bacqueville D.
Badro J.
Bez M. I.
Baldonedo J. L.

O11-2
PC29
PC55
PC2
PB14
O7-4, O14-6
O5-9
PC53
O3-4, PA48,
PB22
PA34
PA31
O5-9
PB37
O1-6
PB44, PC50
O1-6
PC9
O1-6
PB27
O12-3
O10-2, PC32
O8-4
PA10
PA32
O1-6
PC33
O1-10, O6-4,
PA35, PC47
PC14
O8-1
O1-6
O7-8, O8-2
O1-6
O1-7
PA35
PB32
O1-6
O7-2
O5-10
O3-4
PC21
I9
PA1
PA1

Balogh Z.
Baltensperger U.
Bamford S.
Banas D.
Bani Hani M.
Baraldi C.
Barberet P.
Barbosa R. F.
Bargheer M.
Barkan S.
Barnabas A.
Barroso R. C.
Bartilol S.
Baumberg J. J.
Bausk N. V.
Beckhoff B.

O7-7
O9-6, PB38
PB39, PB40
O14-5
O1-6
PB19
PC21
PC47
O5-13
O5-3
PB28
PC45
PC49
O7-3
O8-6, PC11
O2-1, O3-3,
O3-5,
O3-6, O7-2,
O8-5,
O10-1, O14-1,
O14-2, PA28,
PA37, PA39,
PC4, PC13,
PC46
Beke D. L.
O7-7
Belozerova O.Y.
O4-6
Berger D.
PB9
Bersani D.
PC14
Bersani M.
O14-2
Berset M.
O12-1
Beli I.
PB39, PB40
Bezrodna T.
PC3
Bielecki J.
PC37
Bielewski M.
O13-6
Bjeoumikhov A.
PA48, PB4,
PB10, PB11
Bjeoumikhova S.
PB10, PB11
Blokihina E.
PC52
Boeykens S.
O7-6, PA20
Bogdanovi-Radovi O13-2
I.
Bogovac M.
O4-4, O13-2,
PA49
Boman J.
PB36, PB37,
PB49, PB50
279

Bombelli l.
Bonifazzi C.
Bonizzoni L.
Brcsk E.
Bosnjak M.
Bostedt C.
Boek S.
Boievi I.
Bradley D. A.
Bras W.
Braun S.
Braz D.
Brenker F.
Brenker F. E.
Brennan S.
Brocklesby W. S.
Broekaert J.
Brunetti A.
Buar K.
Bhler B.
Bukhtiyarov V. I.
Bukowiecki N.
Bulgachev R.
Burkhardt U.
Butcher T. J.
Butorin S. M.
Buzanich G.
Caglio S.
Calestani G.
Calusi S.
Calza C.
Cao W.
Carapio L.
Carvalho M. L.
Chachulski D.
Chapman R. T.
Chau C. F.
Chen Z.
Chen Z. W.
Cherkashin E.
Cherkashina T. Y.
Cherkashina T. Yu.
Chinea-Cano E.

PB22
PB19, PB31
PA4, PA17
O14-3
PA7
O3-2
PC37
PA13, PC16
PA34
O8-3
O8-5
PC45
O2-6
O13-1
O5-3
O7-3
O3-1
PC26
O10-4
O1-1
PC11
O9-6, PB38
PB44
PC8
O7-3
O8-7
PA11
PA3, PA4, PA21
PC14
O4-3
O1-10, PA6
O12-1, O14-5,
PC48
PB32
O1-4, PC27,
PC36
PB30
O7-3
O7-3
O5-5, PB2
PB13
PA26
O9-5
PA26, PB47
I6, PA11, PB39

Chol M.
Chu B.
Chubarov V. M.
Civici N.
Clar M.
Coe S.
Cohen D. D
Collins A. L.
Colombo E.
Conrad T.
Correa da Costa
V. M.
Costa M.
Cosyns P.
Cox D.
Cremonesi A.
Cserhti C.
Csik A.
upi S.
Czyzycki M
Da Silva E.
Dabagov S. B.
de Carvalho M. L.
De Cooman W.
De Felici M.
De Groot Frank
M. F.
de Jesus E. F. O.
de la Paz F.
De Moro F.
De Nolf W.
de Panfilis S.
De Pappe P.
De Samber B.
de Schamphelaere
K.
Degrigny C.
Delmotte F.
Desnica V.
Dhara S.
Di Domenico G.
Dietsch R.
280

O2-2
O9-3
PC15
PB46
O1-9
O4-8
I4
O9-4
O4-3
PC4
PA35
O1-4
PA21
O4-5
PC14
O7-7
O7-7
PA10
O13-6
O11-3, PA5,
PC22
O12-4
PB37
O9-4
PB31
I8
PC47
PA16
O5-9
O6-1, O9-2,
O13-1, PA2,
PB21
O8-1
O5-7
O6-2
O6-2
O1-6
O10-2
PA7, PA8, PA9
O7-4, O14-6
PB19
PA27, PB12

Dietzinger C.
Dik J.
Dill S.
Dmitrienko S.
do Carmo M. G. T.
Dobrnszky J.
Dobrini J.
Dousse J. -Cl.
Drbohlav I.
Dreiigacker X.
Dubrovskaya Yu.
Duliska-Litewka J.
Dvurechenskii A. V.
Dyszkiewicz A.
Eggert T.
Egorov E. V.
Egorov V. K.
Elam W. T.
Eliasson I.
Elkin D.
Ender B.
Ensinger W.
Enzo S.
Erdlyi Z.
Erdogan H.
Erenburg S. B.
Ertugrul M.
Esposito A.
Evans C.
Evans R. J.
Evens R.
Fabbri B.
Fainer N.
Falkenberg G.
Farenik V.
Farias M. L.
Farnell S.
Farquharson M. J.
Faust A.
Fazini S.
Feldrapp K.

PB25
O1-2, PA2
PC51
PB44
PC47
PC1
PC17
I5, O12-1, O14-5,
PC48
O4-7
PC52
PB16
O11-4
O8-6
PB30
O5-1, PB1, PB25
PB14
PB14
I10
PB36
PA20
O1-7
O7-2
PC26
O7-7
O12-6
O8-6, PC11
O12-6
O1-5
PA5
O5-4
O6-2
PA12
O7-2
O3-1, O6-2,
O14-3, PA27,
PA34, PB21, PC9
PC6
PA35
O6-1
PA34
PC55
O13-2, PA7, PA8,
PA9, PB39, PC17
PA37

Felici R.
Fencl J.
Feng L.
Fennane K.
Fernandez J. E.
Figueroa C.
Finkelshtein A. L.
Fiorini C.
Fittschen U.
Fittschen U. E. A.
Fliegauf R.
Fonts C.
Fraenkel B. S.
Fraser G.
Frey J. G.
Frieh Ch.
Frizzi T.
Froud C. A.
Fujii M.
Fujii Y.
Fukuda H.
Fukuda N.
Furger M.
Furlan C.
Gaita S. M.
Galassini S.
Galli A.
Gambaccini M.
Gao N.
Garca M. J.
Garcia-Moreno R.
Garnir H.-P.
Garraffo S.
Gasse A.
Gatari M. J. G.
Gawlitza P.
Gayo M. D.
Gazulla M. F.
Gedeon O.
Georgiev G.
Geraldes V.
Gerlach M.
Giakoumaki A.

281

PB31
PC18
O5-3
O12-1
O12-5
PA44
PC15
PB22
O3-1, PA27
PC55
O10-1, O14-1,
PA39
O7-1, PB48
O10-6
O3-3
O7-3
I6
PB22
O7-3
O11-1
O1-3
PA43
O11-2
O9-6, PB38
PC23
PC49
PC23
PA4, PA17
PB31
O5-5, PB2
PA1
O1-9
O1-9
O1-5
O5-9
PB42, PB50,
PC49
O8-5
PA1
O10-5
O4-7
PB23
PC27
PA28
O1-6

Giannoulaki M.
Gianoncelli A.
Gibson W. M.
Girardello G. B.
Giubertoni D.
Giudice A. L.
Giuntini L.
Glatzel P.
Gligor M.
Gluevi S.
Glushkov A.
Godec R.
Gola A.
Golfomitsou S.
Gmez M. P.
Gomez-Morilla I.
Gonzalez-Fernandez
O.
Gormon Ofosu F.
Goro Kinugawa
Granin M.
Grant-Jacob J.
Grassi N.
Griesser M.
Grime G.
Grin Yu.
Grlj N.
Grolimund D.
Groma V.
Grtzsch D.
Gualtieri S.
Guazzoni C.
Guerra M. F.
Gugiu M.
Guilherme A.
Guimares D.
Gumeniuk R.
Gnther A.
Guoxia Li
Gurban D.
Gurnitskaya E.
Haddad N.
Hahn O.
Handa S.

O1-6
O3-4
PB13
PC23
O14-2
O4-3
O4-3
O10-4
PA12
O1-3
PB16, PB18
PB40
PB22
O1-6
O10-5
PB26, PB27
PB43
PB33
PC30
PA26
O7-3
PA48
PA11
O4-8
PC8
O4-1
O9-6, PB38
O14-3
PB29
PA12
PA48, PB22
I1, PA18, PA36
PC25
PC36
PC27
PC8
O5-13, PB29
PA15
PC24, PC25
PB18
O1-6
O6-3, PA22,
PA25, PC13
I13, O11-1

Hanna D. C.
Hanning S.
Hanzer H.
Hardouin A.
Harris A. L.
Harris J.
Hartmann R.
Hartwig M.
Haschke M.
Hasegawa J.
Hatzistavros V.
Havel R.
Havlikova R.
Heirwegh C.
Helinski M.
Heluani S. P.
Henriksson D.
Herzen J.
Heyd D. V.
Hidalgo M.
Hocquet F-P.
Hodoroaba V. - D.
Hoenicke P.
Hoffmann P.
Hofmann M.
Hokura A.
Holmer B.
Holz T.
Homma H.
Homma Y.
Hnicke P.
Horntrich C.
Hoszowska J.
Hzer Z.
Hubikov M.
Hudec R.
Hwang H.
Ingerle D.
Inneman A.
Ishii H.
Ishikawa T.
Ishmetyev E.
282

O7-3
PC53
PA11
O10-2
PA34
O13-1
O3-2
O1-9
O5-13, PB29
PA43
O14-4
PC18
PB8
PC22
I6
PA44
PB33
PB26
O11-3, PA5,
PC22
O7-1, PB48
O1-9
O5-12, PB4
O14-2
O7-2
PC51, PA33
O1-3, O5-10,
O11-2
PB36
PB12
O10-3, PC19
O5-10
PC4
PC42
O12-1, O14-5,
PC48
PC54
PC5, PC7
PB8
O2-2
PC40
PB8
O5-3
I13, O11-1
PC50

Jach T.
Jacobs P.
Jagodzinski P.
Jaki M.
Janousch M.
Janen A.
Janssen C.
Janssens K.

Jaroszewicz J.
Jeynes C.
Jonnard P.
Jovanovi D.
Jun Kawai
Jurado-Roldn A. M.
Jurek K.
Kadlec J.
Kaginelli S. B.
Kalinkin A. V.
Kallithrakas-Kontos
N.
Kalman Z. H.
Kanngieer B.

Kansai K.
Kantarelou V.
Kareem M. A.
Karydas A. G.
Kasap R.
Kataoka Y.
Kato K.
Kato N.
Kaui V.

I10, O5-11
O9-4
PC48
O13-2, PA13,
PB39, PC16,
PC17
O8-4
PC53
O6-2
O1-2, O6-1,
O9-2,
O13-1, PA2,
PA21, PB21
O6-1, O9-2, PA2,
PB21
O4-5, O4-8
O10-2, PC32
PA10
PC30
PA19
O4-7, PC18
PC18
PC33
PC11
O14-4, PB41
O10-6
O2-5, O3-5,
O4-1,
O4-2, O6-3,
O10-1,PA22,
PA25, PB9,
PB12, PB15,
PB29, PC28
PC19
O1-6, PA24
PC12
O1-6, O4-1,
O4-2, PA24,
PA28, PA39
O1-7
O10-3, PC19
O1-3
PA23
O7-8

Kaulich B.
Kavi M.
Kawada N.
Kawai J.
Kawamata S.
Kayser Y.
Kemtekar S.
Kenji Okada
Kerur B. R.
Khetselius O.
Khmelnitski R. A.
Khudonogova E. V.
Kimura T.
Kitajima N.
Klaassen L.
Klatka T.
Klein A.
Klck W.
Klysubun W.
Kodre A.
Kohno H.
Kolbe M.

Kosinova M.
Kotelnikova E.
Koudryashov V. I.
Kovacevik B.
Krmer M.
Krata A.
Kravtsova R. G.
Kregsamer P.
Kreplin X.
Kreyenschmidt M.
Kriznar A.
Krsti D.
Krumrey M.
Kubala - Kukus A.
Kuera P.
Kump P.
283

O3-4
O10-4, O12-1,
O14-5, PC48
PB5
O12-2, PC39
PC43
O12-1, O14-5,
PC48
PB13
PC30
PC33
PB16, PB17,
PB18, PC35
PB20
O9-5, PB47
I13, O11-1
O11-2
O6-1, PA2
O3-4, PA48,
PB22
O7-2
PC52
PC10
O8-2
O10-3, PC19
O3-3, O3-6,
O14-1, O14-2,
PA28, PA37,
PC4, PC13
O7-2
PC3
O5-6
PB49
PB7
PB34
PA45
PC42
PC55
PC53
PA16
PA13
O3-3
O14-5, PC48
PC7
O8-2

Kunimura S.
Kunstr M.
Kurdab A.
Kwame Aboh I. J.
Kwiatek W. M.
Laboury D.
Laidler P. M.
Lange K.
Langer G. A.
Lankosz M.
Lartigue J.
Laursen J.
Le Guen K.
Leek R.
Leithe-Jasper A.
Lekki J.
Lpy M. - C.
Leterme K.
Levicheva E. N.
Li D.
Li Q.
Li Y.
Lienemann P.
Lima I.
Lin Cheng
Lin J. -F.
Lind O. C.
Lindn J.
List S.
Liu Y.
Loboda A.
Loginova I. Y.
Longoni A
Lopes R. T.
Lorusso A.
Lottici P. P.
Lovreni Mikeli I.
Luehl L.
Lhl L.
Luli S.
Lundin M.
Luo L.

PC39
PC54
O1-6
PB33
O11-4, PC37
O1-9
O11-4
PB29
O7-7
O13-6, PB35
PB32, PC34
PB33, PB49
O10-2, PC32
PA34
PC8
PC37
O5-8, PC31
O1-9
O11-5
PB13
O5-10
O9-3
O9-6, PB38
PA35
PA15
I9
O9-2, PB21
PB36
PC4
O9-3
PB17, PB18
O11-5
O3-4, PA48,
PB22
O1-10, O6-4,
PA6, PA35, PC47
O7-5, PB6
PC14
PB44
PB12, PB15
O2-5, PA22,
PC28
PB44
PB33
O9-3

Lyapunov S.
Mackowiak W.
Madadi O. V.
Maeo S.
Mahfoud L.
Maina D. M.
Makarovska Y.
Malcolm C. A.
Malgosa A.
Malzer W.
Mandi L.
Manfredotti C.
Mangala M.
Mans C.
Manso M.
Mansurov V. G.
Mantero A.
Mantler M.
Mantouvalou I.
Marcello A.
Marchal A.
Margu E.
Marin D. D.
Marins L. A.
Markowicz A.
Martinez S.
Martinez T.
Masschaele B.
Massi M.
Mathis F.
Mathis W.
Mathon O.
Matsuyama S.
Matus L.
Mavon A.
Maxwell J.A.
Mayer J.
Meijer G. I.

284

PB45
O5-13
PB42
PB5, PB7
O1-6
PC49
O9-4, PB34
I6
PC26
I2, O2-5, O4-2,
O6-3, PA22,
PA25, PB9, PC28
PC17
O4-3
PA32
PC53
O1-4
O8-6
O3-3
O2-1, O3-3
O2-5, O6-3,
PA22, PA25,
PB9, PB29
O3-4
O1-9
O7-1, PB48
PC24, PC25
PC47
I6, O13-6, PA11,
PB39
PA8, PA9
PB32
O6-2
O4-3
O1-9
O5-13
O8-1
I13, O11-1
PC54
PC21
O2-3
PA31
O8-4

Meirer F.

O3-1, O13-3,
O14-3, PC38,
PC40, PC41,
PC42
Melcher M.
O1-1
Melo Junior A. S.
PC45
Membretti G.
PB22
Mnesguen Y.
PC31
Mesjasz-Przybylowicz PB28
J.
Meyer-Klaucke W.
PC55
Miheli A.
O10-4
Mikeli L.
PB44
Milazzo M.
PA17
Milln J. C.
PB27
Mills B.
O7-3
Mimura H.
I13, O11-1
Misra N. L.
O14-6, O7-4
Mombasawala L.
PA38
Moreira S.
PC45
Moretto P.
PC21
Moretto Ph.
I11
Mori R. A.
O10-4
Moroz A. P.
O5-6
Moroz B. L.
PC11
Moschini G.
PC23
Moschochoritou R.
PB41
Mostaert F.
O9-4
Mota C. L.
PC45
Mudronja D.
PA7, PA13
Mueller M.
O14-2
Mller M.
O3-5, O10-1,
O14-1, PA37
Muoz M. V.
PA16
Murti M. V. R.
PA38
Muss U.
O1-1
Mustapha O. A.
PA32
Nakai I.
O1-3, O5-10,
O11-2, PA23
Nakano K.
PC44
Nakayama S.
O5-10
Nassisi V.
O7-5, PB6
Naziriwo B. B.
PB42
Neemer M.
O8-2
Negodaev M. A.
PB20

Nemchinova N.
Nmeth .
Nensel B.
Nieva N.
Nikiforov A. I.
Nikitenko S.
Nikitenko S. G.
Nikitenko S. G.
Nishida Y
Nishino Y.
Nissen J.
Nobuharu Sasaki
Nose Y.
Nourreddine A.
Novak Tuar N.
Nsouli B.
Nys K.
Odenbach S.
Oesker F.
Oguri Y.
Okubo K.
Okuneva G. N.
Olabanji S. O.
Oladele A. T.
Oliveira D. F.
Ono Y.
Orbulov I. N.
Ordua M.
Oreanin V.
Orli I.
Osn J.
Osinkolu G. A.
Ouziane S.
Owens A.
Pagels M.
Pahlke A.
Pahlke S.
Pajek M.
Pantaleo T. U.
Papp A. T.
Papp T.
Pappalardo G.
Pappalardo L.
285

PA46
PC1
PA33, PC51
PA44
O8-6
O8-3
O8-6
PC11
O13-5, PC44
I13, O11-1
PB9
PC30
PB5
O12-3
O7-8
PA41, PA42
PA21
PB26, PB27
O5-13
PA43
PC44
O11-5
PC29
PC29
PA6
O5-10
PC1
O10-5
PB44
PA49
O14-3, PC9,
PC46, PC54
PC29
O12-3
O3-3
O2-5, PA22,
PC28
O5-1, PB1, PB25
O5-1, PB1, PB25
O14-5, PC48
PA35
O2-3
O2-3
O1-5
O1-5

Passi P.
Pastuovi .
Patarapaiboolchai O.
Pattanasiriwisawa
W.
Pavlova L. A.
Pawlus B.
Peacock A.
Pedreira A.
Peev I.
Pejovi-Mili A.
Pelemo D. A.
Pelicon P.
Pepponi G.
Pereira G. R.
Prez C. A.
Perez R. D.
Peina V.
Pessanha S.
Petr J.
Pettersson J. B. C.
Petukhov V. P.
Phanisree K. D.
Timmaraju
Pia M.-G.
Pianetta P.
Pietsch U.
Piga G.
Pigot C.
Pina L.
Pind N.
Pinheiro C. J. G.
Pinheiro T.
Pinto N. G. V.
Pisternick T.
Plagnard J.
Platonova N.
Podgrczyk M.
Poldi G.
Poe P.
Pollakowski B.
Ponomarev I.

PC23
PA8, PA9, PA7
PC10
PA14, PC10

Praeger M.
Pratesi G.
PremaChand K.
Preoteasa E.
Preoteasa E. A.
Prvt A. S. H.
Procop M.

PA45
PB30
O3-3
O1-10, PA6
PB23
O11-3, PA5,
PC22
PC29
O4-1
O3-1, O14-2,
PC40, PC41,
PC42
O6-4
O6-4, O13-4
O13-4
PC18
PC36
PC5, PC7
PB49
PA47
PC12
O3-3
O5-3
O3-2
PC26
O5-9
PB8
PB33
PC45
PB27
PC45
O13-1
O5-8
PC3
O11-4
PA3, PA4
PB30
O3-5, O7-2, O8-5
O5-5, PB2

O7-3
O4-3
PC12
PC24, PC25
PC24, PC25
O9-6, PB38
O5-12, PB4,
PB24
Prots Yu.
PC8
Przybylowicz W. J.
PB28
Puchkovska G.
PC3
Pujol J.
PA19
Pullan D.
O3-3
Quattrone A.
PA48
Queralt I.
O7-1, PA19,
PB43, PB48
Querzoli P.
PB31
Raakka S.
O1-9
Rabin I.
O6-3
Radthe M.
PC53, PA36
Rahn H.
PB26, PB27
Raino A.
O7-5
Raju S. S.
PA38
Ramrez A.
PC34
Ramrez-Castellanos PA1
J.
Rammlamir D.
O9-1
Ravet-Krill M. F.
O10-2
Regvar M.
O8-2
Reiche I.
PA36, PB29
Reinhardt F.
O3-5, O8-5,
PC46
Reinholz U.
PC53
Respaldiza M. A.
PA16
Revenko A.G.
O1-8
Rezaievar P.
PB37
Ribot H.
O5-9
Richard A.
O9-6, PB38
Rickers K.
O1-2, O6-2,
PA34,
PC9
Riesemeier H.
PA36
Ritchie N.
O5-11
Rizzo F.
O1-5
Ro C.-U.
O2-2

286

Robinson M.
Rocha H. S.
Rocha I.
Rocha M. S.
Rodrigo M.
Roekens E.
Rogers E. T. F.
Rohde M.
Roje V.
Romano F. P.
Romo-Krger C. M.
Rongwu Li
Riger V.
Roumi M.
Rousseau R. M.
Rubi M.
Rubio M.
Rueff J. -P.
Ryosuke Shioi
Sajdl P.
Saj I.
Salbu B.
Sales E.
Saliba N.
Salome M.
Salomone Stagni M.
Samek L:
Snchez H. J.
Sandborg A.
Sandhu B. S.
Sanjay Kumar S.
Sano Y.
Santos Cubedo A.
Santos J. P.
Sasaki N.
Sasamori S.
atovi D.
Sauvageot J. - L.
Saveliev V. D.
Scafes A.
Schalm O.
Schaumann I.
Scheibner A.
Schenker J.-L.

PA5
O6-4, PA6
PC27
PC47
O10-5
PB34
O7-3
O5-2
PB44
O1-5
PA50
PA15
PA33, PC51
PA41, PA42
O2-4, PA29
PB44
O13-4
I9
PC30
PC5, PC7
PC9
O9-2, PB21
PA35
PA42
O14-5
PC55
PB35
O13-4
I10
O12-7
O7-4
I13, O11-1
PC26
PC27
O12-2
O13-3
PA8, PA9
O5-9
O5-3
PC24, PC25
PA21
O2-5
O9-1
O12-1, PC48

Schevchenko E.
Schmitz S.
Schnelle W.
Scholze F.
Schoonjans T.
Schreiner M.
Schtz R.
Scot V.
Scoullar P. A. B.
Seetharami Reddy
B.
ega K.
Seim C.
Selin Lindgren E.
Semencova V.
enyurt S. Y.
Serebryakov A. S.
Seznec H.
Sharanabasappa
Shimura M.
Shindo Y.
Shinsuke Kunimura
Shunnaq M.S.
Siciliano M. V.
Silva-Carvalho L.
Silversmit G.
Simon R.

PB45
O2-6
PC8
PB24
O2-6, O6-2,
O13-1
O1-1
O4-1
O12-5
O5-4
PA38

PB39, PB40
PB12, PB15
PB33
PB8
O1-7
O5-6
PC21
PC33
O11-1
PA23
PC30
O1-6
PB6
PC27
O2-6, O6-2, O8-3
I6, O13-6, PA27,
PA34, PC21
Simons C.
PC53
Singh B.
O12-7
Siritapetawee J.
PC10
Sitamahalakshami N. PC12
V.
Skaric K.
PA7
Skukan N.
O13-2
Smolek S.
O13-3, PC38
Sokaras D.
O1-6, O4-1,
O4-2, PA24,
PA28, PA39
Sokolov A.
PC50
Somphon W.
PA14
Srilomsak S.
PA14
Ssebuwufu P. J.
PB42
287

Stachura Z.
Star V.
Stebbings S. L.
Stojanovi M.
Storm S.
Stosnach H
Sttter R.
Straub U.
Streib K.
Streli C.

Strivay D.
Strder L.
Struyff H.
Styervoyedov A.
Sulyaeva V.
Susini J.
Suvorova L.
Sveda L.
Sviridova T.
Szczegielniak J.
Szeflinski V.
Szlachetko J.
Szlachetko M.
Szymanski A.
Tada T.
Tadi T.
Takahashi M.
Takashi Yamamoto
Tamasaku K.
Tanaka K.
Taniguchi K.
Tanthanuch W.
Tantrakarn K.
Tapp T.
Tartari A.
Tashko A.
Tejeda S.
Terada Y.
Terborg R.
Terzano R.

PC37
PC18
O7-3
PA10
PA37
PB3
O5-1, PB1, PB25
O8-4
PA31
I6, O3-1, O13-3,
O14-2, O14-3,
PA11, PC38,
PC40, PC41,
PC42
O1-9
O3-2
PC4
PC6
O7-2
O14-5
PA46
PB8
PC20
PB30
O5-9
O12-1, O14-5,
PC48
O12-1
O13-1
PA43
PC16
O5-3
PC30
I13, O11-1
O5-10
PB5, PB7
PA14
O1-3
PA40
PB19, PB31
PB46
PB32
O11-2
O5-2
PB21

Thorsson S.
Tolochko A.
Trk S.
Toropov V. Y.
Toumert I.
Touriyanski A. G.
Tretner F.
Trojek T.
Trubina S. V.
Trunova V.
Trunova V. A.
Tschentscher T.
Tsuji K.
Tucoulou R.
Tull C. R.
Tyliszczak T.
Uhlir K.
Ullom J.
Ulm G.
Usherov A.
Utaka T.
Uzunov N.
Valek L.
Van der Linden V.
Van der Loeff L.
Van der Snickt G.
Van Elslande E.
Van Grieken R.
Van Hoorebeke L.
Van Meel K.
Van Vaerenbergh P.
Vandenabeele P.
Vank G.
Vanlierde E.
Varga I.
Varvara S.
Vzquez C.
Veeranki K. R.
Vega M.

288

PB36
PC3
O14-3, PC9,
PC46
O5-6
O12-3
PB20
O5-13
PA30
O8-6, PC11
O7-2
O11-5
PB20
O13-5, PC43,
PC44
O13-1
O5-3
PB28
PA11
O5-11
O3-3, O3-5,
O8-5,
O14-1
PC50
PB5, PB7
PC23
PA8, PA9
PA21
O1-2, PA2
O1-2, O6-1, PA2
O1-9
O7-1, O9-4,
PB34, PB48
O6-2
O7-1, O9-4,
PB34, PB48
O8-1
O1-9
I9
O9-4
O14-6
PA12
O7-6, PA20
PA38
PA16

Vekemans B.

O2-6, O6-2,
O8-3,
O13-1
Velardi L.
O7-5
Vr N.
PC54
Vercauteren J.
PB34
Veremchuk I.
PC8
Vidal L.
PA1
Vila F.
I10
Vincze L.
O2-6, O6-2,
O8-3,
O13-1
Virgili V.
PA18
Vitobello M. L.
PA18
Vittone E.
O4-3
Vogel-Miku K.
O8-2
Vogt C.
O2-5
Volkov A.
PC50
von Bohlen A.
I14
Wagner A.
PB37, PB49
Wahnstm T.
PB33
Wandiga S. O.
PB42
Wang X.
O9-3
Warrikhoff A.
PB4
Waske A.
PB26
Watanabe K.
PC19
Webb M.
O4-5, O4-8
Weber A. -D.
PA37
Wedell R.
PB4
Wegrzynek D.
I6, O13-6, PA11,
PA30, PB39
Weise S.
PB26
Weissbach D.
PA27
Weitkamp T.
I6
Wellenreuther G.
PC55
Welter E.
O11-4
Wepukhulu G. W. W. PA32
Weseloh G.
PC28
Weser J.
O14-1, PC13
Wiest F.
O5-1, PB1, PB25
Wilke M.
PC13
Wittenberg A.
O9-1

Wobrauschek P.

Wolff T.
Xunliang Ding
Yabashi M.
Yamada Y.
Yamauchi K.
Ynsa M. D.
Yumoto H.
Zadro A.
Zaichick D.
Zaichick S.
Zaichick V.
Zaitz M.A.
Zajdel J.
Zaray Gy.
Zarazua G.
Zarkadas C.
Zarkadas Ch.
Zhuravlev K. S.
Ziegler E.
itnik M.
Zoeger N.
Zumaquero E.
Zvereva V. V.

289

I6, O3-1, O13-3,

O14-3, PA11,
PB39, PB40,
PC38, PC40,
PC41, PC42
O6-3, PA22,
PA25,
PB9
PA15
I13, O11-1
O10-3, PC19
I13, O11-1
PB27
I13, O11-1
PC23
PB45
PC20
PB45, PC20
O3-1
PB30
O3-1
PB32
PA28
O1-6, PA39
O8-6
O8-1
O4-1, O10-4
I6, O13-3, O14-2,
PC38, PC40,
PC41, PC42
O10-5
O11-5

290