EFFECTS OF BLAST FURNACE SLAG ON CHLORIDE PERMEABILITY OF CONCRETE
First examination of slag inclusions in medieval armours by confocal SR-m-XRF and LA-ICP-MS
Transcript of First examination of slag inclusions in medieval armours by confocal SR-m-XRF and LA-ICP-MS
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First examination of slag inclusions in medieval armours by confocalSR-m-XRF and LA-ICP-MS†‡xS. Leroy,*ab R. Simon,c L. Bertrand,b A. Williams,d E. Foya and Ph. Dillmanna
Received 15th December 2010, Accepted 28th February 2011
DOI: 10.1039/c0ja00261e
To elucidate the origin of armours supposed to be from Lombardy according to art-historians, the very
small Slag Inclusions entrapped in the metallic matrix were analysed on the samples taken on armours.
This paper presents the analytical protocol, based on the coupling of LA-ICP-MS and confocal SR-m-
XRF (confocal Micro-X-ray fluorescence under Synchrotron Radiation) developed to obtain trace
element information from this kind of inclusion. Confocal SR-m-XRF has been applied to inclusions of
ancient iron artefacts for the first time. The reliability and reproducibility of the procedure developed
for the trace elements quantifying have been checked by a comparison of the results obtained by LA-
ICP-MS and by confocal SR-m-XRF. Our first results allow us to draw some preliminary observations
on the origin of the samples.
Introduction
During the Middle Ages, manganese-rich iron ores of areas like
Lombardy (Italy) were intensively exploited to produce steel in
bloomeries.1 The bloomery process took place in shaft furnaces
in which ores and charcoal were heated below the iron melting
temperature. Thus, a part of the slag coming from the non-
reduced part of the ore remains entrapped in the metal in the
form of microscopic non-metallic Slag Inclusions (hereafter,
SI).2,3 Manganese-rich iron ores were recognised as important in
the Middle Ages and were a significant factor in the growth of the
armour manufacturing industry of Milan and Brescia. These
armours were extensively exported all over Europe4,5 as can be
shown by the marks that they bear. There are nevertheless many
more examples of armour, Italian in form, but bearing no mark,
to be found in museums all over Europe. These have frequently
been ascribed to a Milan or Brescia production on stylistic
grounds, but could well have been copies. Determining that such
armours were or not made from Lombard ore may help to solve
the question of their origins.
aSIS2M LAPA UMR3299, CEA/CNRS et IRAMAT LMC UMR5060CNRS, CEA Saclay, Gif-sur-Yvette, France. E-mail: [email protected], UPS3352 CNRS, Synchrotron SOLEIL, BP 48, Saint-Aubin, Gif-sur-Yvette, FrancecKarlsruhe Research Center, Institut f€ur Synchrotronstrahlung,Eggenstein-Leopoldshafen, D-76344, GermanydThe Wallace Collection, London, W1U 3BN, England
† This article is part of a themed issue highlighting the latest research inthe area of synchrotron radiation in art and archaeometry.
‡ This work is in memoriam to Joseph Salomon.
x Electronic supplementary information (ESI) available. See DOI:10.1039/c0ja00261e
1078 | J. Anal. At. Spectrom., 2011, 26, 1078–1087
Stylistic information on a putative provenance can be backed
by the advanced analysis of the SI entrapped in the metal of the
armours.6–9 Indeed, SI carry the chemical signature of the iron
ore initially used. Identifying the geographical provenance of
iron artefacts may therefore be possible based on the study of
appropriate major and trace elements.10–14 Desaulty13 developed
a methodology to follow the chemical signature from a given iron
ore into the SI in the artefacts in order to test this hypothesis. (1)
By selecting the trace elements that are not significantly
contaminated by the lining or the charcoal during the bloomery
process and which segregate almost totally into the slag and
therefore in the SI (i.e. lithophilic elements). For populations of
slag samples formed from the same initial iron ore, concentra-
tions of these elements will retain a constant ratio.10,13,14 (2) By
analysing a large number of ore and slag samples from the tested
iron-production area in question to define its chemical signature.
(3) By comparing the concentration ratios of the elements of
Fig. 1 (a) Morion W.C. A144, (b) specimen taken on the morion and (c)
SI trapped in the metallic matrix of the sample.
This journal is ª The Royal Society of Chemistry 2011
-IC
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interest to test the compatibilities between the chemical signa-
tures of this area and any artefact of unidentified origin. To
validate the chemical signature compatibility, all elemental ratios
have to be the same. By contrast, only one incompatible ratio is
considered sufficient to exclude the area of supposed origin.
ICP-MS coupled with Laser Ablation (LA-ICP-MS) is an
analytical tool well-suited to quantify trace elements with low
detection limits (below ppm levels) in the SI. Nevertheless, the
quantitative analyses of SI smaller than 50 mm, as they can be
found in armours (Fig. 1), are a real challenge with this technique
because of very low count rates of the elements under
interest.10,11,13,14 Moreover, a specific requirement for the analysis
of the armour samples is the preservation of their integrity.
Consequently, this work aims at testing confocal micro-X-ray
fluorescence analysis (m-XRF) to non-destructively investigate
samples at the micrometre length scale.15 Up to now, confocal
XRF analysis has been mainly carried out on materials included
in the sample16 or on stratified materials17 with unknown
composition. Malzer and Kanngiesser17 described the modelling
of the probing volume, and Mantouvalou et al.18 developed a
calibration procedure for stratified materials, introducing a new
quantification scheme by constructing an algorithm for a full
quantification of the depth profile.
We aimed here at testing the potentiality of the coupling of
LA-ICP-MS and confocal m-XRF under Synchrotron Radiation
(SR) to analyse very small slag inclusions in historical armours
attributed to a Lombard provenance from stylistic consider-
ations. These first results will then be compared to the chemical
signature of slags and ores coming from Lombardy and dis-
cussed.
mple
s(S
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Cr
Rb
Sr
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81
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96
72
45
Samples
Samples from Lombardy
We characterised the Lombard production area by collecting and
analysing, in collaboration with archaeologists, ores from the
Lombard iron rich deposits that were exploited during the
Fig. 2 Location of the iron mines and archaeological sites sampled in
Lombardy. Ta
ble
1C
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elem
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(wt%
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race
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Al
Si
PK
Mn
Fe
Ti
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Ver
reB
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61
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.00
23
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2.1
99
73
3
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Table 2 Description of the armour samples entrusted by the Wallace Collection,21,22 the number of smelting SI selected for trace element analyses andthe average weighted composition in MnO (noted MnO* following Dillmann and L’H�eritier3 procedure)
Armourreference
Part of thearmour Description
Number of SI analysedfor trace elements
Average weighted compositionin MnO* in SI (wt%)
W.C. A143 Morion Embossed decoration. Described as‘‘Milan about 1575–1590’’
27 4.83
W.C. A144 Morion Embossed decoration. Described as‘‘Milan or Brescia about 1600–1610’’
15 7.21
W.C. A235 Gorget Decorated with some bands ofetching. Described as ‘‘NorthItalian about 1600’’
12 8.11
W.C. A180 Helmet ‘‘Savoyard’’ type. Described as‘‘North Italian about 1635’’
2 6.94
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medieval times as well as ores and slags from two archaeological
sites (Fig. 2).14
The trace elemental compositions of samples from different
medieval iron-making areas that exploited Mn-rich ores (Lom-
bardy in Italy; the Ari�ege, the Montagne Noire, the Dauphin�e in
France; Andorra) were studied in Leroy.14 Contrary to the other
Fig. 3 Schematic sketch of the confocal setup for m-XRF analysis of a SI
in metal at the FLUO beamline at ANKA.
Fig. 4 Experimental determination of the sampling volume depth value for
a function of some of the detected K-line energies for two experiments. Value
values with a curve governed by the 1/E proportionality due to the photon tra
attenuation length of elements in the energy range 12–17 keV in a fayalitic m
1080 | J. Anal. At. Spectrom., 2011, 26, 1078–1087
areas, Lombard ores are characterized by high Sr and Ba levels
(>100 ppm).14,19 These elements should therefore not be signifi-
cantly altered during the ore smelting as it can happen for other
systems.13,14 Thus, they will be considered here in addition to
other elements used for provenance studies to verify the
compatibility with the Lombard area investigated. Moreover,
chemical analyses revealed that the Lombard samples differ
from samples from the other tested iron-making areas by
considering ratios of specific trace elements (e.g. Sr/Y, Ba/Sr,
Y/Yb).14
Reference samples
First, homogeneous glasses synthesized in our laboratory
(VerreB) or at the University of Fribourg (TIZ0033) (courtesy of
Serneels20) were used as references. In addition, large SI (Incl1) in
which trace elemental contents were already determined by
LA-ICP-MS analyses were used. Their composition is close to
that of the SI to be analysed, especially considering the high iron
contents (Table 1).
Armours
Samples of armours were entrusted by the Wallace Collection
(London) (Table 2). By following the procedure proposed by
Dillmann and L’H�eritier,3 we first selected the SI coming from
an excitation energy of 22 keV. Graphical representation of dFWHM as
s for missing elements were obtained by interpolation between the fitted
nsport in channels of the polycapillary.16 Values in the table describe the
atrix (7.8 g cm�3).
This journal is ª The Royal Society of Chemistry 2011
Fig. 5 SEM micrographs of two SI and confocal SR-m-XRF elemental maps associated. (Top) Mn distribution at the sample surface when the Cr filter
was not used. (Down) Distribution of the sum of K-lines intensities IMn-Ka + ICr-Kb and the ratio of K-lines intensities (IMn-Ka + ICr-Kb)/ICr-Ka at the
sample surface when the Cr filter was used.
Fig. 7 Confocal SR-m-XRF spectrum obtained on a SI at 10 mm in depth be
Fig. 6 Themanganese intensity profile of the most intense pixel on each
map as a function of the position in depth. The diamonds depict the
intensities measured for Mn-Ka lines in a SI. The intensity increases from
the right to the left, when the microvolume moves along the Z axis by 5
mm steps from outside the sample into the SI and decreases again due to
absorption or finite size of the SI. The axial distance of the sample
describes the position of the sample holder on the Z axis (see Fig. 3).
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the smelting. To identify them, the ratios of compounds that are
not reduced (noted NRC for Non-Reduced Compounds; mainly
%Al2O3/%SiO2, %K2O/%CaO, %MgO/%Al2O3) were plotted on
bivariate scatters. It has been shown that the SI coming from the
smelting phase tend to show a linear distribution whereas the SI
from additives present different NRC ratios. After discrimina-
tion of inclusions not coming from the smelting, an average
weighted major element content taking into account the area of
each SI was expressed per artefact. This average weighted
content is noted with an * symbol following the element (or
oxide) name. Then, only armour containing SI with a major
element composition compatible with that of the Lombard
samples from the area investigated were selected for the present
study (in particular their high content in MnO* was checked, see
Table 2). Lastly, it was checked whether the armour samples
were products of the bloomery process. Detailed procedure and
results can be found in Leroy.14
low the surface. Excitation energy ¼ 22 keV. Acquisition time ¼ 3600 s.
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Fig. 8 Schematic of the instrumental arrangement at a given energy for:
(top) the present confocal setup; (down) the situation simulated for the
quantification. Vx ¼ probing volume. The comparison highlights
a difference between the excitation and detection geometries.
Fig. 9 Linear correction coefficient as a function of the energy calculated at
VerreB. Table: average values of Coefcorr calculated from the three reference
Fig. 10 Standard deviation in % between the reference value and the one
measured by confocal SR-mXRF with the calibration procedure at
various depths for several reference samples and SI in armours W.C.
A143 and W.C. A235. Each point: one measurement. The various anal-
ysis depths underline the variability of the relative error functions of the
depth. Parentheses: no. of the SI.
1082 | J. Anal. At. Spectrom., 2011, 26, 1078–1087
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Experimental section
LA-ICP-MS
A Perkin-Elmer Elan 6000 instrument in conjunction with
a Nd:YAG laser operating at 266 nm was used. The international
geostandard used for calibration was BCR2. The operating
conditions for the ICP-MS coupled to the laser sampler were as
follows: dwell time, 10 ms; sweeps per reading, 1; readings per
various depths below the surface in reference samples Incl1, TIZ0033 and
samples at each depth below the surface.
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replicate, 200; replicates, 1; flow rate for plasma gas, 15 L min�1;
flow rate for auxiliary gas, 1 L min�1; flow rate for carrier gas,
0.96 L min�1.10
The duration of the ablation was fixed at 30 s by carrying out
concentration depth profiles. The shape of the concentration
profiles allows us to observe the start of the ablation of the
metallic matrix below the SI. Note that the minimal width of the
Table 3 Results on the trace element composition in the armour samples obtppm. Empty cell ¼ contents below quantification limit. Hatched cell ¼ nonelements to define the chemical signature
This journal is ª The Royal Society of Chemistry 2011
ablation crater which was possible to reach was 30 micrometres.
As a consequence, only the biggest SI (>30 mm) found in armour
could be analysed with this method. In addition, the speed of the
laser penetration in the SI and the low quantity of matter
sampled by the laser limited the number of trace elements that
can be quantified (limit of quantification ¼ 3 times the detection
limit10).
ained by coupling confocal SR-m-XRF and LA-ICP-MS. All values are in-detected or non-quantified elements. Elements in bold ¼ suitable trace
J. Anal. At. Spectrom., 2011, 26, 1078–1087 | 1083
Fig. 11 Comparison between the Sr/Y ratio defining the Lombard
signature (pale gray) and that of the SI in armour W.C. A180 (hatched
gray).
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Confocal SR-m-XRF
Experimental conditions. For SI smaller than 30 mm, trace
element contents were determined by confocal SR-m-XRF on the
FLUO beamline at ANKA (Karlsruhe).23 A planar polymer
Compound Refractive Lens (KIT-IMT) was used to focus the
beam (spot size of 7.5 � 2.8 mm2). The confocal setup was con-
structed by mounting a polycapillary-half lens (XOS�, USA) in
front of the energy dispersive fluorescence detector (Vortex�Silicon Multicathode Detector, SII, USA). The sample was
translated through the beam by means of a sample holder with
two rotational and three translational stages. An excitation
energy of 22 keV was selected, thanks to a multilayer mono-
chromator (1.5% bandwidth, 27 nm period, W/Si). This energy
was a compromise between the detection of trace elements of
interest and the maintenance of an acceptable photon flux. A 20
mm filter of Cr was placed when necessary between the poly-
capillary and the detector window to absorb a part of the
photons emitted by the iron present in the SI.
In confocal setup, the probing volume of analysis is defined by
the intersection of the exciting beam and the energy-dependent
polycapillary focus (see Fig. 3).24 As the detection-side
polycapillary accepts an energy-dependent section from the
incoming beam path, the dimensions of this micro-volume
analysed vary according to the detected energy within the
investigated SI.16,25,26
To characterize these dimensions in our work, we followed the
procedure detailed by Janssens et al.25 By scanning foils (<10 mm)
of different elements with negligible self-absorption or a free
Standing thin Foil SF1 (stack of thin films of Mo, Pb, Cu, Fe, La,
and Pd on 8 mm Ultralene Foil, AXO, Germany)27 through the
micro-volume of analysis in the horizontal plane (Z axis shown
in Fig. 3), we estimated the energy-dependent depth resolution
(dFWHM) of the setup to range from 26 mm to 30 mm at 5.9 keV
(Mn-Ka) and from 12 mm to 17 mm in the energy range 13–17
keV (Fig. 4). The use of the confocal setup is limited only by
radiation self-absorption effects in the sample. The main type of
SI in armours is fayalitic-rich ((Fe, Mn)2SiO4, d ¼ 7.8 g cm�3).
Thus, the attenuation lengths of given elements in a fayalitic
matrix (Fig. 4) determine the maximum depths from which the
elements can be detected.
Data acquisition. For the measurements, we will define as ‘‘the
surface of the sample’’ the sample position for which the
probing volume of analysis starts to penetrate the sample and
XRF signal starts to be detected. Around each SI, an elemental
map of the Mn-Ka line was performed at several depths below
the surface by 5 mm steps to locate the SI. When the Cr filter
was used, the Cr-Kb could overlap the Mn-Ka. We therefore
plotted the map from the intensities ratio to more easily locate
the SI (Fig. 5):
IðCr filterÞ ¼ICr-Kb þ IMn-Ka
ICr-Ka
The ideal 3D position was determined from the maximum of
the Mn signal intensity which is a compromise between the signal
intensity and the fact that the micro-volume of analysis does not
probe the iron matrix (Fig. 6). Finally, a XRF spectrum is
collected at this position during 3600 s (Fig. 7).
1084 | J. Anal. At. Spectrom., 2011, 26, 1078–1087
Calibration. In our work, the probed SI are exposed on top so
that no matrix layer is covering the SI. Consequently, the system
is different from those developed in previous studies.16,24,25 Here,
only self-absorption within the SI needs to be taken into
account. Moreover, the emission energy of the Fe-Ka emission is
lower than the K-edge absorption energies of the Mn (that will
be used as an internal standard, see below), Rb, Sr, Y and Zr so
that secondary fluorescence can be neglected for these elements.
The major element composition in each SI is known14 and can be
used to define the matrix. Therefore, we performed a quantifi-
cation of the trace elements using the conventional method of
the internal standard without taking into account the poly-
capillary in the detection channel in a first step. The internal
standard selected is Mn because its detection is easy in the
experimental conditions and its concentration is known in all
SI.14 Nevertheless, the probing volume considered by this
conventional method of quantification is not the same than the
real one defined by the confocal setup (Fig. 8). Consequently, we
approximated a linear correction coefficient (Coefcorr) by the
following equation:
Coefcorr¼calculated concentration ðppmÞ
known reference concentration ðppmÞ
This Coefcorr was evaluated by means of the reference samples at
different depths and for energies corresponding to the emission
lines of the four considered lithophilic trace elements (Fig. 9).
For the three reference samples, the Coefcorr resulting values are
consistent with each other at the same depth thus allowing the
determination of an average Coefcorr value.
Results and discussion
LA-ICP-MS vs. confocal SR-m-XRF
Results on SI in armours and reference glasses that were analysed
using confocal SR-m-XRF and LA-ICP-MS were compared. The
values of the standard deviation between results of both methods
show a statistical spread lower than 20% except for one analysis
(28%) (Fig. 10). The error generated for measurements carried out
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Fig. 12 Comparison between the adequate trace element ratios defining the Lombard signature (pale gray) and those of the SI in armour W.C. A235
(hatched gray) for the Sr/Y, Nb/Cs, Ba/La, Y/La, Nb/U, Sr/Ba ratios.
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at the surface of the SI is higher compared to other positions. This
is mainly due to the fact that the micro-volume of analysis is not
totally in the sample. Consequently, the obtained signal-to-noise
ratio is low. In the following, no measurement will be performed at
this location, thus the relative standard deviation will be consid-
ered as lower than 20%.
Fig. 13 Comparison between the trace element ratios defining the Lombard
gray) and W.C. A144 (black) for the Sr/Ba and Yb/Y ratios.
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Provenance of the armour samples
The results on the armour samples (Table 3) only yield a limited
number of quantified trace elements. Among these elements only
those that are not altered during the smelting can be used.13,14
Thus, the possible ratios for comparing to the chemical signature
signature (pale gray) and those of the SI in armours W.C. A143 (hatched
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of the tested production area examined are limited. Validation of
a Lombard provenance for the armour samples could therefore
not be undertaken. By contrast, if only one of the examined
ratios does not fit with the production area signature, the
exclusion is possible.13 In the following cases, these ratios are
considered for each armour.
For W.C. A180, only the Sr/Y ratio can be considered since
only Sr and Y are non-polluted elements. The Sr/Y values are
compatible with the ones measured in ores and slags from
Lombardy (Fig. 11) but only one ratio is not sufficient to validate
a provenance. Thus, these results remain inconclusive and the
investigation must be continued with other element.
For W.C. A235, a larger number of trace elements could be
quantified permitting the comparison of more ratios. All the
possible ratios examined are in the domain of the tested
Lombard area. Thus, it was not possible to exclude such
a provenance as shown, for example, for 6 ratios in Fig. 12.
On the contrary, for W.C. A143 and W.C. A144, some of the
ratios obtained seem to be incompatible with the Lombard area
investigated (Fig. 13).
(a) For W.C. A143, the Yb/Y ratio values clearly differ from
the Lombard values. These results are corroborated for a larger
number of SI by the Sr/Ba ratio. Thus, we tend to exclude
a Lombard provenance for this object.
(b) For W.C. A144, the Yb/Y ratio is clearly different.
Unfortunately only one inclusion was analysed. Thus, the
Lombard origin of this armour needs to be questioned but
complementary analyses would be necessary to confirm this
result.
Conclusion
To the best of our knowledge, the analysis of very tiny slag
inclusions in such important artefacts as armours had never been
the object of thorough studies. These first experiments confirm
the difficulty of a quantitative approach with such small inclu-
sions (i.e. <40 mm) and the necessity to implement complemen-
tary methods. The main innovation of the analytical protocol
developed here lies in the use of both LA-ICP-MS and confocal
SR-m-XRF for the quantification of trace elements. The use of
LA-ICP-MS is constrained by the limited ablated volume, which
is a main disadvantage of this analytical method for our work;
the use of confocal SR-m-XRF is limited by the limited number of
elements under interest reached using conventional excitation
energies (i.e. around 20 keV). In the future, this limitation might
be corrected by working at lower energy and especially under the
Fe absorption edge to detect the L-lines of elements like barium
which is of great interest in this study. Nevertheless, this
approach in energy dispersive mode will always be limited by the
excitation of major elements as Si, K or Ca which Ka emission
energies are close to the elements of interest. Another solution
might be crossing the important energy gap to reach the excita-
tion of K emission lines for elements of interest. Then, control-
ling the analytical volume will be a real challenge. Nevertheless,
the development of new 2D detectors for fluorescence, combined
with micro-focused beam may be a solution.
Despite these important limitations, these first experiments
bring us interesting information for at least one supposedly
Lombard morion: W.C. A143. Despite its having been decorated
1086 | J. Anal. At. Spectrom., 2011, 26, 1078–1087
in an Italian fashion, its chemical signature is not compatible
with that of the Lombard area investigated and might have been
made elsewhere in Italy, where the iron ore is manganese-rich. It
might also have been sold under a false Italian provenance, as the
latter was regarded as a pledge of quality. It may thus have been
a counterfeit.
Acknowledgements
This work was supported by the I3 Project IA-SFS (Integrating
Activity on Synchrotron and Free Electron Laser Science). The
financial support of the ISS, Karlsruhe, David Batchelor and the
staff of ANKA for assistance are gratefully acknowledged. We
thank Delphine Neff (LAPA-SIS2M, CEA, Saclay), Serge
Cohen (IPANEMA, SOLEIL Synchrotron, Saclay) and Marie-
Pierre Coustures (Traces, Toulouse) for their help in analyzing
the armour samples and Ina Reiche (C2RMF, Paris) for intro-
ducing to us the confocal XRF. Marco Tizzoni (University of
Bergame) and Vincent Serneels (University of Fribourg) are
acknowledged for providing us Lombard samples and references.
Part of the work was funded by the research program ACEUR
ANR05JCJC-0164 of the French Agence Nationale de la
Recherche. The IPANEMA platform is jointly developed by
CNRS, MNHN, the French Ministry of Culture and Commu-
nication and SOLEIL and benefits from a CPER grant (MESR,
R�egion Ile-de-France28).
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