First examination of slag inclusions in medieval armours by confocal SR-m-XRF and LA-ICP-MS

10
First examination of slag inclusions in medieval armours by confocal SR-m-XRF and LA-ICP-MS†‡x S. Leroy, * ab R. Simon, c L. Bertrand, b A. Williams, d E. Foy a and Ph. Dillmann a 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 Europe 4,5 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. 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 Desaulty 13 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. a SIS2M LAPA UMR3299, CEA/CNRS et IRAMAT LMC UMR5060 CNRS, CEA Saclay, Gif-sur-Yvette, France. E-mail: stephanie.leroy@ cea.fr b IPANEMA, UPS3352 CNRS, Synchrotron SOLEIL, BP 48, Saint- Aubin, Gif-sur-Yvette, France c Karlsruhe Research Center, Institut f ur Synchrotronstrahlung, Eggenstein-Leopoldshafen, D-76344, Germany d The Wallace Collection, London, W1U 3BN, England † This article is part of a themed issue highlighting the latest research in the 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 This journal is ª The Royal Society of Chemistry 2011 Dynamic Article Links C < JAAS Cite this: J. Anal. At. Spectrom., 2011, 26, 1078 www.rsc.org/jaas PAPER Published on 22 March 2011. Downloaded by CEA Saclay on 24/03/2014 08:19:29. View Article Online / Journal Homepage / Table of Contents for this issue

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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

P-M

S)

Zr

Ba

Ce

Nb

Cs

La

Nd

Sm

Eu

Tb

Yb

Hf

Ta

Th

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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.

m

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Sr

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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

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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.

J. Anal. At. Spectrom., 2011, 26, 1078–1087 | 1081

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

This journal is ª The Royal Society of Chemistry 2011

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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