Microchemical Journal 126 (2016) 423430

Contents lists available at ScienceDirect

Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Combined X-ray diffraction and uorescence analysis in the cultural

heritage eld
Luca Lutterotti a, Federica DellAmore b, Diego E. Angelucci b, Francesco Carrer c, Stefano Gialanella a,
a
b
c

Dipartimento di Ingegneria Industriale, Universit di Trento, via Sommarive 9, 38123 Povo, Trento, Italy
Dipartimento di Lettere e Filosoa, Universit di Trento, via T. Gar, 38122, Trento, Italy
McCord Centre for Historic and Cultural Landscape, School of History, Classics and Archaeology, Newcastle University, Queen Victoria Rd, Newcastle upon Tyne, NE1 7RU, UK

a r t i c l e

i n f o

Article history:
Received 18 August 2015
Received in revised form 16 December 2015
Accepted 20 December 2015
Available online 28 December 2015
Keywords:
X-ray diffraction
X-ray uorescence
Rietveld method
Combined analysis
Non-destructive testing
Bronze alloys

a b s t r a c t
X-ray diffraction (XRD) and X-ray uorescence (XRF) techniques are broadly used for materials characterisation.
In some respects, they can be regarded as complementary, as long as the rst is mostly used to get phase (crystallographic) information and the second to evaluate chemical composition of the analysed samples. In this paper
we present a combined approach for the acquisition and integrated analysis of XRD and XRF data. A novel laboratory instrument has been developed to perform XRD and XRF measurements simultaneously, using the same
radiation source and two detectors collecting the diffraction and uorescence patterns in a scanning mode. A
combined Rietveld based renement of both XRD and XRF data is then performed to obtain phase and chemical
compositions. As a eld test of the proposed approach, we analysed some archaeological nds from an alpine pastoral enclosure in Val Por (Val di Sole, Trentino, Italy). The different features of the analysed archaeological specimens provide indications on the wide applicability range of the proposed approach, that may therefore result
particularly useful and effective in materials analysis, including those pertaining to the archaeological and cultural heritage elds.
2015 Published by Elsevier B.V.

1. Introduction
X-ray diffraction (XRD) and uorescence (XRF) techniques, originally
developed for materials science and engineering research, are also widely
used to obtain primary material information in the cultural and archaeological heritage elds [1,2]. In some respects, these techniques are
complementary, since the rst one is mostly used to get phase (crystallographic) information and the second chemical composition of the
analysed samples. Of course, a close relationship is there between the
two material properties and data from XRD and XRF can be in principle
interactively used to improve the reliability of phase and chemical quantitative analyses. In fact, several literature studies report on the use of
these techniques to attain a better understanding in specic material issues. XRD and XRF data can be acquired either separately, using different
instruments [1,36], possibly in association with other techniques [1,7] or
with a single integrated equipment [812]. This latter approach is particularly interesting from two standpoints. First of all, experimental data
come from substantially the same material volume. Moreover, the integration of the two techniques in one single instrument is denitely interesting for portable equipment and, thereby, in situ measurements.
Selected papers presented at TECHNART 2015 Conference, Catania (Italy), April 27
30, 2015.
Corresponding author.
E-mail address: stefano.gialanella@unitn.it (S. Gialanella).

http://dx.doi.org/10.1016/j.microc.2015.12.031
0026-265X/ 2015 Published by Elsevier B.V.

The chemical composition evaluated from XRF can be used as a

guideline in the search for the most appropriate phases present in the
XRD pattern and to obtain their concentrations. Once chemical and crystallographic qualitative compositions have been settled, a quantication, using a Rietveld like renement, can be performed.
In our approach, we merge together XRD and XRF, both as concerns
data acquisition as well as the computing step in order to attain an effective and more reliable analysis. A laboratory instrument has been developed on purpose. It is capable to perform the two measurements using
the same radiation source (Mo with a microfocus, in the present study)
and two detectors, collecting the diffraction and uorescence patterns
in scanning mode (several XRF spectra are actually collected at different
beam incident angles).
A combined Rietveld renement, involving the simultaneous tting
of XRD and XRF data using a single global model, is then performed to
obtain phase quantication and chemical analysis using the MAUD software [13,14]. The XRD spectrum is modelled using the crystallographic
phases with their variable composition to evaluate the concentrations of
each single element, also of those that are not directly revealed by the
XRF instrument. Since tests are conducted in air, X-ray photons with energy below the Si K-alpha cannot be detected. An important information
inferred from the phase composition in the model is the actual absorption coefcient of the material, that permits to evaluate the free mean
path for X-ray photons of different energies inside the material and to
automatically correct, for the so-called matrix effect, the XRF data.

424

L. Lutterotti et al. / Microchemical Journal 126 (2016) 423430

The whole data analysis procedure needs rst the identication of all
the principal crystallographic phases present in the analysed material.
Therefore, all crystallographic parameters of the identied phases are
required to carry out the analyses described in the present paper.
Minor phases and chemical impurities can be added successively to
ameliorate the XRD and XRF pattern tting.
To test the investigation protocol, a set of measurements has been
conducted on some archaeological samples from an alpine pastoral enclosure in Val Por (Val di Sole, Trentino, Italy) [15,16].

resolving in-depth chemical in-homogeneity or concentration

gradients.
An interesting feature of this instrument, particularly for archaeological and cultural heritage studies, is its exibility as concerns sample
mount. Samples with relatively complex geometries and shape can be
properly located in the optimal test position using a manual platform
with micrometric displacement control. The straight beam at zero position is used to adjust the sample height until its spot dimension is cut in
half as recorded on a CMOS high resolution 2D detector (pixel size:
20 20 m2).

2. Combined X-ray diffraction and uorescence methodology

2.2. The data tting model
2.1. The experimental set-up
To combine the XRD and XRF analyses and to get full benets from
this synergic approach, specic instrumentation and relevant data acquisition and treatment have been developed.
A single X-ray source is used for diffraction and uorescence: as
specied previously, this is a prerequisite to have both XRF and XRD signals coming from substantially the same interaction volume. Actually,
an additional benet comes not only from the use of the same X-ray
source but also from the fact that by collecting XRD and XRF data at
the same time, by changing the incident angle during the diffraction
scan, different depths in the material are sampled at each position acquired by the XRF solid state detector. In this way, immediate information on the possible stratigraphy of the analysed material is obtained.
Fig. 1 is showing the INEL Equinox 3500 instrument developed and
tested in the present study to perform simultaneous XRD and XRF
acquisitions.
The diffraction pattern is recorded by an Xpad 2D detector operated
in a scanning mode. At each scanning step an image is collected and all
images are merged together to obtain a complete diffraction image, in
some respect similar to images that were recorded with an old fashion
Debye-Scherrer camera. The diffraction pattern is obtained by integrating the nal image along the reection circles. During the scanning, the
XRF detector (Amptek X123 solid state detector) records the uorescence pattern, remaining at a xed position close to the sample. Since
for each 2, comparatively small, step there is not a big change in penetration depth on the incident beam, every XRF spectrum is acquired
over a certain 2 range, thus minimising the total number of spectra collected. Typically, one XRF spectrum is collected each 1 in 2. Incidentally, collecting XRF data at different incident beam angles may help

Fig. 1. INEL Equinox 3500 diffractometer modied with a 2D XRD detector working in
scanning mode and a X123 Amptek detector to collect the X-ray uorescence spectra. The
source is a Mo microsource operated at 40 kV and 1 mA. The sample holder is horizontal
and xed during the scanning. XRF detector is xed. The large space below the sample
holder permits the non-destructive analysis even of large samples.

The main element that qualies the novelty of our experimental

method is the combined analysis of the XRD and XRF data. With the
term combined XRDXRF analysis it is generally meant to analyse
each set of data, either XRD or XRF, separately and using the information
of each technique to support the analysis of the other. As a further step,
results are merged together and cross-checked. This is indeed an improvement over just using solely one technique. However, we can better
exploit the synergies and specic features of the two techniques by using
for both data sets a combined Rietveld-like t. We have developed this
new methodology [17] and implemented it in the Rietveld software
MAUD [13,14]. To t simultaneously XRD and XRF data, a generalized
model, in which the sample is assumed to be composed of one or more
layers, is used. Each layer contains a specic composition of crystallographic phases each one with its own chemical composition. The phase
composition of each layer, the relevant composition of each phase and
the distribution of the phases within each layer are modelled in order to
reproduce the XRD pattern. The elemental composition of each layer
and the associated matrix effects are used to simulate the XRF spectra collected at different angles of the incident beam. If the sample is homogeneous from the surface inward, the main changes in the XRF spectra are
mostly due to the absorption path of the excited uorescence photons
travelling outward in the material, affected only by the change in the incident beam glancing angle. Setting the right balance between the diffraction and uorescence patterns in the least squares tting is very
important indeed. XRF spectra generally display a better signal to noise
ration and, since several spectra are acquired for each XRD pattern, this
ensures a signicant statistical reliability. In the least squares renement
strategy, it is a good practice to increase the weight of the diffraction pattern contribution in order to establish a rst qualitative estimation of the
phase content. Once the main phases have been identied, modelling can
shift to a more balanced situation, in which XRD and XRF data have comparable statistical weights. At this stage, with higher accuracy and precision, the elemental composition in each phase can be rened.
XRD is less sensitive than XRF to elemental composition changes.
Therefore, by adding the XRF tting to the diffraction analysis results in
a better chemical sensitivity of this latter. In this regard, it is interesting
to highlight a further benecial effect of the combined approach. The experimental apparatus just described operates in air and this limits to silicon the lightest element whose XRF lines can be detected. However,
thanks to the combination with XRD, even lighter, than silicon, elements
can be detected in the XRD patterns of the crystallographic phases of
which they are components. All details on the adopted model and relevant relations used for the mathematical description of the method can
be found in [17].
In Fig. 2a) and b) an example of the XRD and XRF combined tting is
displayed for sample ID 1083, described in the following (Fig. 3).
For a complete characterisation of the samples selected to validate
the proposed combined approach, scanning electron microscopy
(SEM) observations and energy dispersive X-ray spectroscopy (EDXS)
analyses were also conducted. For the SEM observations a lowvacuum (LV) mode was adopted, so that no conductive coating was necessary to render the samples observable. In fact, they were either covered with reaction products and/or traces of the burial ground or

L. Lutterotti et al. / Microchemical Journal 126 (2016) 423430

425

Fig. 2. XRD and XRF combined tting for sample ID 1083. In a) the Rietveld t plot is shown for the diffraction part and in b) the corresponding t for the XRF is reported. In both plots dots
correspond to experimental values and the line the calculated pattern. The phases and elemental composition obtained by the t are reported in Table 1.

consolidated, after the cleaning, and protected with a layer of Paraloid

B72. EDX spectra were acquired from selected regions with a twofold
aim. Provide additional data useful to complete the picture emerging
from the XRDXRF combined approach and to validate the relevant results, as concerns particularly the indirect quantication of those elements, from Si downward, whose characteristic lines cannot be
detects with the XRFXRD instrument. Moreover, EDXS analyses provided specic information on inclusions and minority phases, potentially interesting for the archaeological and functional assessment of the
artefacts considered in the study.
The experimental protocol adopted in the present study turns out to
be fully non-destructive for the analysed archaeological samples.
3. Validation of the combined XRDXRF approach: characterisation
of archaeological artefacts results
To test the efciency and applicability of the combined XRDXRF approach to materials characterisation, we report herewith also on its

application to the archaeometric investigation of a few artefacts (see

Fig. 3), selected among those excavated at the site codenamed
MZ005S, located in Val Por, near the hamlet of Ortis (Mezzana, Val
di Sole, Trentino Province, Italy). The site is at 2257 m a.s.l., and its
main remaining structures are a large compound enclosure for animal
stabling and a small stone hut. On the basis of these indications, it
seems likely that this place had been used for sheep and cattle mountain
pasture during summer. However, no conclusive denition of the site
function and frequentation has been established as yet, notwithstanding the archaeological investigations carried out under the project
ALPES (Alpine Landscapes: Pastoralism and Environment of Val di
Sole) of the University of Trento in collaboration with the Ofce of Archaeological Heritage Superintendence for Cultural Heritage of Trento.
In fact, although there is clear evidence of the occupation of the site in
the early Modern (15th17th centuries) and in protohistoric times
[15,16], still many open issues are standing, as concerns origin and function of the many artefacts the site has provided. Therefore, we
proceeded with materials analysis on these samples, so to have solid

426

L. Lutterotti et al. / Microchemical Journal 126 (2016) 423430

Fig. 3. The investigated archaeological samples. Macrographs of the archaeological artefacts considered in the present study (see Table 1 for sample description). All archaeometric
investigations have been conducted on the face/side of the specimen appearing in the relevant picture. a) ID 1122; b) ID 1123; c) ID 1124; d) ID 1125; e) ID 1083; f) RR29.

evidences in the perspective of further systematic investigations of the

many artefacts found in the site in view of a reliable archaeological interpretation and contextualisation.

In Table 1 the results of the XRD and XRF are summarised. All tests
were conducted in a fully non-destructive way, just mounting each artefact in the experimental apparatus.

L. Lutterotti et al. / Microchemical Journal 126 (2016) 423430

427

Table 1
Results of the combined XRDXRF analysis on the archaeological samples (Fig. 3).
Sample

Overall composition (wt.%)

Crystallographic phases

Description

ID 1112

Cu: 52.89, Sn: 42.9, Pb: 0.701,

Fe: 1.7, Zn: 0.12, K: 1.2, Ti: 0.1,
Mn: 0.08, Ca: 0.005, Ni: 0.16, Sb: 0.15
Si: 37.83, O: 30.79, Al: 15.58, Fe: 10.75,
K: 1.51, P: 2.29, Ca: 0.6, Ba: 0.22, Ti: 0.23
Others (b 0.1 tot.): Pb, Cu, Mn, Zn, Sr,
Zr, Rb, S, Cr, Co, Ni, Br
Pb: 86.2, S: 0.06, O: 7.0, C: 4.8, Cd: 1.02,
Ag: 0.3, Fe: 0.2, Ca: 0.4

-CuSn (N99 wt.%)

Fragmentary artefact composed of bronze sheet with little rivets

on both sides; the fragment was probably a part of a decoration
item.
Undetermined ferrous object, with irregular platy shape;
possible slag or smelting waste by-product.

ID 1113

ID 1124

ID 1125

ID 1083
border

Si: 37.31, O: 30.36, Al: 15.36, Fe: 11.34,

K: 1.22, P: 3.06, Ca: 0.5,
Ba: 0.18, Ti: 0.2
Others (b 0.1 tot.): Pb, Cu, Mn, Zn, Sr, Zr,
Rb, S, Cr, Co, Ni, Br
Ag: 52.77, Cu: 39.6, Pb: 0.92, O: 6.16,
Fe: 0.41, Zn: 0.08, Bi: 0.06

ID 1083
center

Ag: 30.6, Cu: 49.95, Pb: 2.46, O: 11.11,

Fe: 7.61, Zn: 0.12, Ca: 1.75

RR 29

Cu: 23.73, O: 20.76, Sn: 18.8, Pb: 11.39,

Ca: 11.11, Si: 5.4, Fe: 2.97,
C: 2.2, Zn: 1.58, As: 0.45, Ni: 0.14,
Ag: 0.41, K: 0.76, Mn: 0.11

Aluminosilicate glass (N99 )

Cerussite Pb3(CO3)2 (91.7)

Massicot PbO (2.2)
Pb(CdAg)-alloy (4.2)
Galena PbS (0.4)
Calcite CaCO3 (1.1)
Magnetite Fe3O4 (0.3)
Ematite Fe2O3 (0.1)
Aluminosilicate glass (N 99)

Undetermined sub-triangular-shaped object.

Silver alloy (52.52)

Cu2O (37.01)
AgO (1.51)
FeO (0.55)
CuO (8.41)
Silver alloy (73.05)
Cu2O (11.30)
AgO (11.25)
CuO (4.43)
Tin rich silica glass (SiCaCuSn)
(65.4)
Cu(Zn)-alloy (9.1)
Calcite (17.9)
FeO (1.2)
Ca2Fe9O13 (6.1)
Ca3Zn (0.2)

Venetian coin, 16th century (attributed).

3.1. Sample ID 1112

The XRD results indicate that the -CuSn bronze is by far the majority phase present in this object. Actually, -CuSn, strictly speaking is not
an equilibrium phase at room temperature [18], although the sluggish
phase decomposition occurring at temperature below 350 C is generally capable to stabilise down to room temperature the higher temperature phase. Delta phase is generally regarded as comparatively brittle
and for this reason hot working is usually required. On the surface of
the sample a patination layer is present. Its colour suggests that one of
the majority phases may be malachite [19]. The lack of this phase in
the XRD pattern provides an indirect indication of the sampling depth
of our analysis, with a main interaction volume falling deeper than
50 m from the sample surface. For this same reason, the chemical composition obtained from XRF is to be mostly referred to the bulk composition of the bronze alloy.

3.2. Sample ID 1113 and ID 1125

Both samples display an amorphous structure and similar chemical
composition. The aluminosilicate glass has been modelled using the
method reported in [20]. Only a couple of small crystalline peaks are visible over the amorphous bumps that did not allow a reliable identication
of the relevant phase(s). This crystalline contribution was estimated not
to exceed 1%. Oxygen is mostly concentrated in the glass structure and
the estimation of its concentration comes from the oxide concentrations
obtained from the cation experimentally measured concentrations. The
aluminium content in the glass can be inferred by the pseudo-cell value
used in analysis that affects the position of the rst bump at low angle.
A more precise quantication was available from the EDXS analysis and
was used to correct the glass modelling.

Drop-shaped undetermined ferrous object; possible slag or

smelting waste by-product.

Undetermined metal object, composed of a sub-pyramidal-shaped

bronze core partly coated by a thick ferrous-like concretion;
possible smelting waste by-product.

Another common feature of these samples is the general external aspect, in terms of colouring, surface roughness, most likely featuring the
presence of residuals of the burial ground. From the methodological
point of view, these samples afford an excellent opportunity to assess
phase and chemical compositions even in case light elements are significantly present and their quantication is not supported by the presence
of well crystallised structures. Notwithstanding these limitations, silicon, aluminium and iron oxides result to be the main components of
both specimens. These results have been conrmed by the EDXS analyses that provided also additional information, interesting for the archaeological attribution of the material samples (see below).
3.3. Sample ID 1124
Lead is the majority element in this sample and several lead based
compounds have been identied. The core part of the fragment is
made of metallic lead, in which a little amount of cadmium and silver
are dissolved. The thick outer layer is mainly made of white lead
(PbCO3, cerussite) with lower contributions from lead (II) sulde (galena) and lead oxide (PbO-massicot). Small amounts of calcite (CaCO3),
magnetite (Fe3O4) and hematite (Fe2O3), mostly close to the surface,
complete the picture of the phase composition of this fragment.
3.4. Sample ID 1083
This coin features on both sides, although to a different extent, a
thick corrosion layer, that partially covers the central part of the nd.
The main crystallographic phase in both regions is an fcc silver alloy
that coexists with copper oxides: CuO (tenorite) and Cu2O (cuprite)
(see Fig. 2a) and b)). The equilibrium AgCu binary phase diagram
[21] features a limited solid state solubility and this involves the presence of a mixture of silver and copper rich solid solutions. From the

428

L. Lutterotti et al. / Microchemical Journal 126 (2016) 423430

XRD data, no traces of this latter have been detected: a preferential oxidation of the copper rich phase of the original two phase alloy has occurred, leading to the formation of copper oxides, that are usually
reported as constituent phases of patination layer in CuSn alloys [22].
3.5. Sample RR 29
This sample, that on eye inspection appeared to be made of a bronze
material, was actually tested with the deliberate intention to verify
whether its composition is compatible with that of the ID 1112 sample.
The high concentration of lead and the additional presence of iron, differentiate clearly one sample from the other, providing also indication
on a fully different extraction approach, as proved by the concentration
of As in the RR29 specimen. This element, fully missing in the ID 1112
material, will certainly address further investigations on mining and extraction technologies, in potential association with the development of
trading and commercial routes.

The combined XRDXRF analysis shows a high content of a glass

phase rich in Sn (Fig. 4, Table 1). The Rietveld glass modelling method
reported in [20] allows us to quantify the amorphous structure. Calcite
is also present and it is homogeneously distributed inside the material,
as proved by the trend of the uorescence Ca k-lines at the increasing
incident beam angle (see Fig. 4c, arrowed lines). Iron oxide and
calcium-iron oxide are also present, again well distributed inside the
sample matrix. The oxygen concentration, as for other samples, is estimated from the stoichiometry of the oxide and carbonate phases detected and quantied from the XRD data. To conrm the presence and
relevant concentration of the glassy phase, an additional XRD measurement has been made on purpose, using a monochromatic Cu source to
lower the background avoiding the Pb uorescence and the Bremsstrahlung not cut by the Zr lter in the Mo instrument. This pattern
was also used to identify some of the minority phases, that were
added to the combined XRDXRF renement. Fig. 4ad show the combined tting for this sample, using also the Cu radiation pattern to

Fig. 4. Combined analysis t for sample RR29: in a) the XRD (Mo radiation) Rietveld t part is shown, in b) the XRF spectrum tting part, both collected simultaneously. In c) a 2D plot is
reported for the XRF tting with all the experimental spectra in the bottom and the calculated ones in the top part; the incident beam angle increases from bottom to top in each
corresponding part; the plot in b) corresponds to the summation of all experimental and calculated spectra reported in c); a similar decrease of all uorescence lines intensities is
visible here indicating the sample homogeneity. In d) the XRD Rietveld t (Cu monochromatic radiation) is reported as rened in combination with the XRD and XRF data reported in
a), b) and c); the metallic glass bump is well visible in this pattern.

L. Lutterotti et al. / Microchemical Journal 126 (2016) 423430

429

Fig. 4 (continued).

improve the sensitivity on the glass amount. The homogeneous distribution of all phases and composition is visible from the comparable
smooth decrease of all uorescence lines in Fig. 4c well reproduced by
the calculation (apart the Mo diffraction lines and Compton scattering
between 16.5 and 21 keV, that have not been completely modelled
but excluded from the renement see Fig. 4b).
4. Tentative archaeological interpretation
Although the main focus of the work was to assess the possibilities
afforded by the proposed combined XRDXRF approach described in
the former paragraphs, the results obtained from the characterisation
of the archaeological nds (Fig. 3) still deserve a few comments,
concerning possible historical and archaeological implications.
The general feeling is that the site from which these artefacts have
been excavated was exploited, probably over quite a wide time interval,
for different metallurgical activities. The main indication that in the site
metals and related materials were not just used but also produced and

manufactured is based on the retrieval of specimens ID 1113 and ID

1125. Composition and glassy structure suggest that these specimens
are most probably smelting (primary) slags [23]. Both these samples
are rich in iron, whose concentration gets even higher in the inner
parts, that could be accessed through surface fractures with EDXS analyses. However, the high concentration of iron alone is not providing a
conclusive indication that actually these materials came from the extraction of this metal, since iron compounds, like fayalite, are commonly
found in copper smelting slags too [23]. However, the presence of lead
and tin based inclusions observed on the surface of both specimens
(Fig. 5), even assuming they are occasionally trapped on the surface of
the analysed specimens, represents an indirect proof of the complex
metallurgical activity at the site over the time.
The other two bronze items (ID 1112 and RR29) would be coherent
with this interpretation, although a deeper comparison with similar
contexts and bibliographic data is absolutely needed.
Although quite a small and altered fragment, sample ID 1124 exhibits a peculiar layered structure that may suggest it is a remaining

430

L. Lutterotti et al. / Microchemical Journal 126 (2016) 423430

phases, like carbonates and oxides, containing elements falling outside

the sensitivity range of XRF; the limitation of the search match to only
those crystallographic reference cards containing elements detected
by XRF are just two aspects that show immediately the interesting features of the proposed approach.
Better phase and chemical composition can be obtained since they
rely on a unique model complying with both crystallographic and spectroscopic data. The model building can be identied as a critical aspect
of the proposed approach.
As concerns the archaeological conclusions of the case study presented herewith, the structural and analytical results provide interesting indications, on which further analyses and, most importantly,
literature comparisons are on-going at the present time.
References

Fig. 5. SEM micrographs showing inclusion found on the surface of the: a) ID 1113 tin
based; b) ID 1125 lead based. Chemical determinations by EDXS.

piece of an enamelled lead alloy object, featuring an inner layer of metal

sheet with a ceramic coating on both surfaces. Lead carbonate
(cerrussite) is most probably the main original component of the coating, whereas the other phases have formed as a result of alteration processes in the burial environment. Any additional hypothesis would
denitely require a widening of the eld of the presently available
information.
To conclude a few comments of the ID 1083 specimen, for which the
situation is quite well established! On the basis of the analytical results
and in agreement with typological data, this coin was probably minted
in Venice under the Doge Girolamo Priuli (14861567 and he was Doge
of Venice from 1559 until 1567)). The AgCu alloy is named mixture
alloy and therefore the coin can be named mixture coin (moneta di
mistura). The relative percentages of the two main elements, Ag and
Cu are important as concerns both time attribution and authentication.
In the present study, the retrieval of the coin can be taken as a proxy for
one of the many frequentation events of the site.
5. Conclusions
In this paper a combined XRDXRF methodology for the nondestructive characterisation of Cultural Heritage samples has been
presented.
The method has been implemented through the design and development of a suitable experimental apparatus featuring a single X-ray
source a two detectors for XRD and XRF respectively.
The simultaneous acquisition of XRD and XRF data is coupled with
the integrated and interactive analyses of the experimental pattern
and spectrum.
The combination of two sets of data increases remarkably the analytical and structural investigation capabilities of the two techniques, as
compared to their separated use. The detection of crystallographic

[1] E. Pantos, W. Kockelmann, L.C. Chapon, L. Lutterotti, S.L. Bennet, M.J. Tobin,
J.F.W. Mosselmans, T. Pradell, N. Salvado, S. Buti, S. Garner, A.J.N.W. Prag, Neutron and X-ray characterisation of the metallurgical properties of a 7th century
BC Corinthian-type bronze helmet, Nucl. Inst. Methods Phys. Res. B 239 (2005)
1626.
[2] Y. Xie, L. Lutterotti, H.-R. Wenk, F. Kovacs, Texture analysis of ancient coins with TOF
neutron diffraction, J. Mater. Sci. 39 (2004) 33293337.
[3] J. Schnenberger, T. Momose, B. Wagner, W.H. Leong, V.R. Tarnawski, Canadian eld
soils I. Mineral composition by XRD/XRF measurements, Int. J. Thermophys. 33
(2012) 342362.
[4] V.R. Tarnawski, M.L. McCombie, W.H. Leong, B. Wagner, T. Momose, J.
Schnenberger, Canadian eld soils II. Modeling of quartz occurrence, Int. J.
Thermophys. 33 (2012) 843863.
[5] G. Piga, G. Solinas, Giuliana, T.J.U. Thompson, A. Brunetti, A. Malgosa, S. Enzo, Is X-ray
diffraction able to distinguish between animal and human bones? J. Archaeol. Sci. 40
(2013) 778785.
[6] G. Piga, A. Brunetti, B. Lasio, L. Malfatti, Luca, A. Galobart, Angel, F.M. Dalla Vecchia,
M. Fabio, S. Enzo, New insights about the presence of celestite into fossil bones from
Moli del Bar 1 site (Isona i Conca Della, Lleida, Spain), Appl. Phys. A Mater. Sci. Process. 118 (2015) 487496.
[7] L.V. de Voorde, J. Van Pevenage, K. De Langhe, R. DeWolf, B. Vekemans, L. Vincze, P.
Vandenabeele, M.P.J. Martens, Non-destructive in situ study of Mad Meg by Pieter
Bruegel the Elder using mobile X-ray uorescence, X-ray diffraction and Raman
spectrometers, Spectrochim. Acta B 97 (2014) 16.
[8] D. Vaniman, D. Bish, G. Guthrie, S. Chipera, D. Blake, S.A. Collins, S.T. Elliott, P.
Sarrazin, Process monitoring and control with CHEMIN, a miniaturized CCD-based
instrument for simultaneous XRD/XRF analysis, Proc. SPIE Int. Soc. Opt. Eng. (October 1999).
[9] A. Duran, J.L. Perez-Rodriguez, T. Espejo, M.L. Franquelo, J. Castaing, P. Walter, Characterization of illuminated manuscripts by laboratory-made portable XRD and
micro-XRD systems, Anal. Bioanal. Chem. 395 (2009) 19972004.
[10] L. Beck, H. Rousseliere, J. Castaing, A. Duran, M. Lebon, B. Moignard, F. Plassard, First
use of portable system coupling X-ray diffraction and X-ray uorescence for in-situ
analysis of prehistoric rock art, Talanta 129 (2014) 459464.
[11] A. Mendoza Cuevas, F. Bernardini, A. Gianoncelli, C. Tuniz, Energy dispersive X-ray
diffraction and uorescence portable system for cultural heritage applications, XRay Spectrom. 44 (2015) 105115.
[12] L.V. de Voorde, B. Vekemans, E. Verhaeven, P. Tack, R. De Wolf, J. Garrevoet, P.
Vandenabeele, L. Vincze, Analytical characterization of a new mobile X-ray uorescence and X-ray diffraction instrument combined with a pigment identication case
study, Spectrochim. Acta B 110 (2015) 1419.
[13] L. Lutterotti, S. Matthies, H.-R. Wenk, A.S. Schultz, J.W. Richardson, Combined texture and structure analysis of deformed limestone from time-of-ight neutron diffraction spectra, J. Appl. Phys. 81 (1997) 594600.
[14] L. Lutterotti, Total pattern tting for the combined size-strain-stress-texture determination in thin lm diffraction, Nucl. Inst. Methods Phys. Res. B 268 (2010)
334340.
[15] F. Carrer, D.E. Angelucci, Debates de Arqueologa Medieval, 3 2013, pp. 149165.
[16] Paesaggi pastorali d'alta quota in Val di Sole (Trento), in: D.E. Angelucci, F. Carrer
(Eds.),Le ricerche del progetto ALPES 20102014. Dipartimento di Lettere e
Filosoa, Universit di Trento, Trento, (2015) complete volume (in Italian), 2015.
[17] L. Lutterotti, G. Pepponi, 2016 (in preparation).
[18] D. Li, P. Frank, S. Furtauer, D. Cupid, H. Flandorfer, The CuSn phase diagram part II:
new thermodynamic assessment, Intermetallics 34 (2013) 148158.
[19] D.A. Scott, Copper and Bronze in Art: Corrosion, Colorants, Conservation, Getty Publ.,
2002
[20] L. Lutterotti, R. Ceccato, R. Dal Maschio, E. Pagani, Quantitative analysis of silicate
glass in ceramic materials by the Rietveld method, Mater. Sci. Forum 278 (1998)
8792.
[21] ASM Handbook Volume 03: Alloy Phase Diagram, ASM International, 1992.
[22] L. Robbiola, J.M. Blengino, C. Fiaud, Morphology and mechanisms of formation of
natural patinas on archaeological CuSn alloys, Corros. Sci. 40 (1998) 20832111.
[23] R.F. Tylecote, A History of Metallurgy, 2nd ed. Maney publ, London, UK, 1992.