Journal of Archaeological Science: Reports 23 (2019) 396–405

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Journal of Archaeological Science: Reports

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Characterization of building materials by means of spectral remote sensing: T

The example of Carcassonne's defensive wall (Aude, France)
⁎
C. Sciutoa, , D. Alliosb, R. Bendoulac, A. Cocouald, M.-E. Gardele, P. Geladif, A. Gobrechtc,
N. Gorrettac, N. Guermeurb, S. Jayc, J. Linderholma, M. Thyrelf
a
MAL- Environmental Archaeology Laboratory, Umeå University, Sweden
b
LAHM University of Rennes 2, France
c
ITAP, Irstea, Montepllier Sup Agro, Université de Montpellier, IRSTEA, France
d
W3DS, Rennes, France
e
Amicale Laïque de Carcassonne, France
f
SLU- Swedish university of Agricultural Sciences, Umeå, Sweden

A R T I C LE I N FO A B S T R A C T

Keywords: Geological and archaeological analysis of stone masonries in standing structures helps reveal information about
Hyperspectral imaging use of natural resources. At the same time, the study of historical materials is useful for conservators and cultural
Portable NIR heritage management. Geochemical and petrographic analysis of building material types is usually done through
ED-XRF destructive analysis on a few selected samples and can be problematic due to the costs of operations and the size
Multivariate statistics
of buildings themselves. This paper demonstrates that the combination of hyperspectral imaging portable Near
Provenance of building materials
Buildings archaeology
Infrared (NIR) spectroscopy and Energy Dispersive X-ray Fluorescence (ED-XRF) spectroscopy can be useful for
Historical monuments analysing types of raw materials used in distinct construction phases of the inner defensive wall in the citadel of
Carcassonne (Aude, France). Stratigraphic analysis of the architecture, short-range spectral remote sensing and
portable ED-XRF measurements were combined in an interdisciplinary approach to classify sandstone elements.
The experimental protocol for in situ non-destructive analysis and classification of the masonry types allows the
investigation of the monument in a diachronic perspective, collecting information to delineate raw materials
varieties and their use or re-use through time.

1. Introduction
1.1. A global project
In this paper, we explore the possibilities of a close range applica-
tion of hyperspectral image-based instruments, coupled with portable
NIR probe and ED-XRF, to record and compare chemical signatures of
stone elements in historical buildings. The combination of spectral
features and elemental analysis is valuable to distinguish sandstone
types according to their composition and mineral components. Our
interdisciplinary approach to the study of constructions involves the
indirect chemical characterization of stone elements associated to the
stratigraphic analysis of standing structures in order to delineate the
story of a monument contextualised in the surrounding landscape. The
association of raw material types and phases of construction helps in
unravelling details of stone supply dynamics and organization of labour
on the working site.
Our case study is the inner defensive wall in the citadel of
Carcassonne, situated in the Aude region in Southern France (Fig. 1a), a
site registered with Unesco World Heritage Monuments since 1997. A
great deal has been written about Carcassonne, and scholars have been
investigating its iconic military architecture since the XIX century. The
earliest historical and archaeological studies concerning the citadel and
its walls were published by Jean-Pierre Cros-Mayrevieille (1846, 1850,
1896) and Viollet-le-Duc (1878), commissioned in 1850 to restore the
entire fortress. The remarkable monographs of Viollet-le-Duc and Jo-
seph Poux (1923) were later followed by studies focusing on specific
issues (Bekker-Nielsen, 2008; Foudrin, 2001; Fourdrin, 2002; Héliot,
1966; Rancoule, 1979; Salamagne, 1999). A global study of the archi-
tecture, merging historical, archaeological and scientific data, was
missing until 2014, when a Collective Research Project (Projet Collectif
de Recherche – PCR, led by Marie-Élise Gardel et Nicolas Faucherre) was
initiated with the ambition of compiling the existing data and com-
pleting the investigation of the citadel urban space, with a particular

⁎
Corresponding author at: Umeå universitet, Miljöarkeologiska laboratoriet, 901 87 Umeå, Sweden.
E-mail address: claudia.sciuto@umu.se (C. Sciuto).

https://doi.org/10.1016/j.jasrep.2018.10.030
Received 10 July 2018; Received in revised form 22 October 2018; Accepted 28 October 2018
2352-409X/ © 2018 Elsevier Ltd. All rights reserved.
C. Sciuto et al. Journal of Archaeological Science: Reports 23 (2019) 396–405

Fig. 1. a) Localization of the site; b) Plan of the citadel ramparts, the towers are numbered according to the plan by Cros-Mayrevieille (1850), the areas indicted with
a square on the inner wall are the ones sampled for analyses.

focus on the military architecture. The international project was carried
out in collaboration with several institutions and lasted until 2016. The
work of different research teams was integrated in preliminary reports
(Allios et al., 2016; Faucherre et al., 2016) constituting the basis for
future research. The interdisciplinary study included documentation of
the standing structures as well as collection of archive documents and
characterization of the building materials provenance. This extended
examination of the big architectural complex brought a new and
broader perspective on the monument as an assemblage of material
elements and inscribed meanings, as a single but multifaceted historical

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object.
1.2. Archaeology of building materials as archaeology of natural resources
Archaeology of freestanding structures relies on the stratigraphic
observation of walls, with identification of macro and micro phases of
construction, restoration and repair. Archaeology of architectures is a
well-established discipline with a long tradition of studies, initiated at
the end of the XIX century (Davies, 1987, Ferris, 1989, Morriss and
Betty, 2000, Schuller, 2002). Scholars have made important contribu-
tions to the subject from the 70ies onwards, focusing on the strati-
graphic analysis of structures and characterization of building materials
(Bessac et al., 1999; Boato, 2008; Boto-Varela et al., 2012; Brogiolo,
1996; Brogiolo and Cagnana, 2012; Cagnana and Mannoni, 2000;
D'Ulizia, 2005; Mannoni, 1976; Mannoni, 1984; Mannoni, 1990;
Mannoni and Boato, 2002; Parron-Kontis and Reveyron, 2005;
Reveyron, 2002).
Archaeology of architecture is also archaeology of building mate-
rials and, as such, is committed to documenting trails of stone, from a
historical and geographical perspective, including the result of raw
materials transformation and assemblage, from the quarry, to the
construction site, to the eventual reuse or abandon (Edensor, 2011).
Determination of building materials types and provenance is crucial to
understand the network of exchanges existing between a construction
site and the surrounding territory. In fact, an anthropic landscape is
continuously transformed through exploitation of geological materials:
blocks extracted from quarries are transported and implemented in new
structures, leaving behind carved empty spaces.
On the other side, documentation of stone technology and archi-
tectural solutions helps determining organization of labour on the
construction site. Generally, important construction campaigns rely on
the usage of regular blocks mostly extracted from one single quarry and
dressed by teams of expert stonemasons, while smaller interventions
can be achieved by non-professional workers using diverse materials.
A broad interdisciplinary approach to historical monuments, en-
compassing the study of materials and resources, has been shown to be
fruitful to understand diachronic organization of supply sites and de-
velopment of construction techniques (Blary et al., 2008; Gély and
Lorenz, 2011). If different construction styles in masonries can be
pinpointed by an attentive stratigraphic documentation of standing
structures, implementing the geochemical description of stone types is
more challenging.
Characterization of building materials is mostly conducted through
petrographic observation of the rock types, often combined with che-
mical analysis operated on selected samples (Colao et al., 2010; Dreesen
and Dusar, 2004; Götze et al., 2007; Michalski et al., 2002).
Nevertheless, a close observation of stone modules and collection of
samples for destructive analysis is not always possible. A solution can
be found by combining the archaeological protocol for the study of
standing structures with non-destructive analytical methods, with the
intent of screening large datasets of materials and achieve a fast geo-
chemical characterization.
In order to study portions of masonry, we combined portable non-
destructive techniques such as a MicroNIR probe and a portable ED-XRF
together with hyperspectral imaging on vertical structures. Spectral
remote sensing is well known to scholars as a tool for survey and
identification of archaeological features in multispectral-hyperspectral
aerial images (Cavalli et al., 2007; Grøn et al., 2011; Kurz et al., 2011;
Masini and Soldovieri, 2017; Parcak, 2009; Traviglia, 2006). Spectral
imaging has also been shown to be crucial for mapping geological
outcrops at different scales and is applied for mineral explorations and
characterization of quarry walls (Goetz et al., 1983; Greenberger et al.,
2015; Gupta, 2013; Kruse, 2012). Considering the flexibility of Near
Infrared Spectroscopy instruments and portable ED-XRF, we decided to
test a protocol integrating both imaging and point measurements, to
better describe the variability of materials in the masonries.
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Journal of Archaeological Science: Reports 23 (2019) 396–405
2. Materials and methods
2.1. “La cité”
This study focuses on the inner of two concentric circles of fortified
walls enveloping the citadel of Carcassonne. The composite architecture
is constituted of a series of towers and curtain walls, revealing several
distinct construction phases. While the inner rampart is composed of
overlapped wall patches, a result of construction and restoration cam-
paigns from late Antiquity until the present, the outer wall was mostly
built during the 13th century and completed in a shorter time span. The
history of the town is embodied in its defensive system: built, partially
destroyed, re-built and restored over centuries. The first construction
phase of the inner wall of the Roman colony Julia Carcaso, already part
of the province of Gallia Narbonensis, dates back to late antiquity,
during the political troubles of the 3rd century AD (Gardel et al., 2003;
Gardel and Enjalbert, 2015; Gardel et al., 2017; Heijmans, 2006;
Passelac, 2001). Stretches of this ancient fortification are characterised
by small elements on regular beds, 9–10 cm height, intermediated by
bricks. Bricks in the masonry have been dated by paleomagnetism to
the mid-3rd century (Report: Lanos P. Mourges C., 1996, Report, PHL-
1996-2, Carcassonne, Enceinte intérieure de la Citée, tour effondrée prés du
Grand-Burlas, 1 lot de briques: 11069-B, CNRS, UMR 153.). The con-
struction was probably reinforced in the 5th century against the re-
curring incursions of the Visigoths and later, when Carcassonne became
part of the Visigothic domains. In the 8th century, after being occupied
by the Umayyads forces for few years, the town was conquered by the
Carolingian and ruled by emissaries of the emperor. At the end of the
9th century Carcassonne and surroundings were controlled by the
Trincavel family, in this period of feudal prosperity both the cathedral
of Saint Nazaire and the count's castle were built and the wall repaired
from damages caused by centuries of war (Bruand, 1973; Bruand, 1982;
Gardel, 2001; Héliot, 1966; Salamagne, 1999). During the 12th century
the Cathar heresy spread in the southern regions of the kingdom of
France until 1208, year in which Pope Innocent III called the Albigeans
crusade in order to eradicate it. In 1209 Carcassonne was sieged by the
crusaders lead by Simon de Monfort, and when the army finally entered
the city a substantial part of the suburbs and defensive walls was de-
stroyed. A last attempt of the Trincavel family, few years later, to re-
claim the citadel led to various battles and another siege that left the
walls profoundly damaged. In 1240 Carcassonne finally became part of
the domain of the king of France and the King Louis IX (Saint Louis)
ordered the renovation of the defensive system and the construction of
a second rampart around the existing one. The construction project was
completed years later, under the reigns of Philippe III and Philippe IV.
From the 15th century onwards, the citadel was gradually abandoned
and the few inhabitants moved down by the river in the faubourg built
after 1240. The citadel was kept under the jurisdiction of the ministry of
the armed forces until the 19th century when architects such as Prosper
Mérimée (1835) and Gabriel Cros-Mayrevieille (1850) started showing
interest in the monument and its preservation. In 1853 the big re-
storation campaign was approved and financed on the project of Eu-
gene Viollet-le-Duc, who made of it a manifesto of his theory of ar-
chitectural restoration (Viollet-le-Duc, 1878).
The analysis of written documents in the archives and previous
archaeological and historical research has shown that the defensive
walls of Carcassonne are the result of a long series of construction and
transformation events. Discontinuous patches of masonry are re-
cognizable and can be ascribed to historical events and major inter-
ventions on the building. A few macro phases characterised by dis-
tinctive construction styles can be mapped on the vertical surfaces, but
a large part of the history of the citadel is still unknown and the close
reading of this incredible artefact still hides surprises. During the two
years research project, the documentation of style and typology of
various stretches of masonry was combined with the systematic mea-
surement of single stone elements' dimensions on the whole perimeter
C. Sciuto et al. Journal of Archaeological Science: Reports 23 (2019) 396–405

Table 1
Characterization and chronology of various masonry types, modified from Faucherre et al., 2016.
Phase Chronology (centuries) Blocks height Description
(cm)

1 ?–3rd – Not a recognizable masonry but architectural elements still in place referring to constructions standing on the walls layout
before the construction itself
2a 3rd 4–11 Regular beds of small stone units sometimes alternated with beds of bricks.
2b 3rd 35–58 Big blocks, probably re-used from an earlier monument. Irregular bedding
3 9th–10th 4–8 Similar to 2 but more irregular, mostly built with grey sandstone
4 11th–12th 10–15 Regular beddings, slightly rectangular stone elements, traces of chisel
5 13th–14th 16–30 Considerable intervention of reconstructions ordered by the kings of France. “Bossage” masonry used in towers and curtains
walls, in less exposed areas blocks with traces of chisel and axe.
6 15th–18th Period of abandonment, few sporadic reparation
7 19th 8–35 Restoration campaigns on Viollet-le-Duc's project. Imitation of masonries 2a and 5 (“pseudo-bossage”). The blocks are
dressed in a more regular way. Grey sandstone with traces of saw and bush hammer.
8 20th–21th 20–22 Various and irregular restorations

of the inner rampart, while the geochemical characterization of stone
materials was conducted on four sampled spots in order to test the
combination of the analytical techniques and evaluate the results
(Fig. 1b).
As shown in Table 1, we propose eight macro phases that can be
dated by association to historical events or construction campaigns
reported directly or indirectly in the written sources.
determination of specific dynamics of degradation remains problematic
and should be addressed with specific studies aimed at monuments
preservation (Fitzner et al., 2003; Jiménez-González et al., 2008; Götze
and Siedel, 2004; Griffin et al., 1991; Rihosek et al., 2016; Siedel, 2010;
Siedel and Siegesmund, 2014).
2.3. Analytical methods

Considering the geological peculiarity of the stone elements used for

2.2. Building materials and geology of the Aude valley
the construction and the considerable dimension of the monument, it
was necessary to elaborate a sampling strategy comprehensive of dif-
Carcassonne is situated in the Aude region, in the valley between
ferent issues. Although on one hand the fact of working with one par-
the mountain ranges of the Massif Central and the Pyrenees. The plain,
ticular stone type, sandstone, reduced the difficulty of dealing with very
of alluvial origins, is characterised by sedimentary bedrock, mostly
different minerals and textures, on the other hand the natural varia-
sandstone. The various layers of sand and calcitic binder forming the
bility of the sedimentary rock made it difficult to establish a regular
sandstone of the Aude valley originated from both mountain regions,
sampling strategy. In order to take into account the unique character-
resulting in a mixed composition of quarzitic and volcanic aggregates.
istics of the sandstone, depositional layers and post-depositional fea-
The citadel is placed on the top of a hill incorporating a thick layer of
tures, it was necessary to elaborate a flexible sampling strategy that
compacted sandstone called “molasse de Carcassonne” covered by a bed
could be adapted to the morphology of the wall, allowing for a larger
of more etherometric elements with sandstone boulders (Berger et al.,
screening and reliable classification.
1993; Bilotte and Capera, 1990). The materials used for the construc-
In order to gather a large dataset and evaluate the reliability of
tion of the inner wall reflect the geological nature of the area, with
different methods, we decided to combine three non-destructive and
sandstone being the predominant raw material used in all phases. In the
portable techniques:
archive documents, there is no mention of particular supply sites or of
batches of stones purchased or traded for building the wall. Viollet-le-
- Near Infrared portable probe, MicroNIR from JDSU (908–1676 nm,
Duc, in his first report about the conservation of the historical monu-
pixel to pixel interval 6.2 nm) with a sensor positioned between two
ments of Carcassonne, in 1844, observes that the poor state of the
integrated tungsten lamps measuring a surface of 5 by 5 mm. The
monument was partly due to the bad quality of the stone used for the
Micro probe is connected to a tablet and can be used for collecting
construction (Poux 1923, Vol III/2, pp. 449). The landscape around
point measurements. Data acquisition time is a few seconds for each
Carcassonne has been deeply transformed by urban development and
measurement. The instrument was calibrated using a white re-
extraction activities causing the obliterations of most ancient quarrying
ference (Spectralon) and spectra were recorded as absorbance scale.
sites. In this circumstance, supply sites are not clearly identifiable (and
- Hyperspectral Imaging system. NEO HySpex-320m-e (Norsk Elektro
this could be the case, unfortunately, of numerous other ancient
Optikk, Skedsmokorse, Norway), linescan push broom camera with
monuments), nevertheless, a systematic survey of sandstone outcrops
256 × 320 HgCdTe sensor and a PGP filter. The camera records
and their analysis through the same combination of methods, could
wavelenghts from 1000 nm to 2500 nm in 256 channels. The in-
help finding raw materials provenience and help shed a light on the
strument was mounted on a rail and moved horizontally through a
process of transformation of the territory. Even though the supply sites
computer-controlled stepping motor. The distance between the
are not easily identifiable, the observation of raw materials used in the
target and the camera was set to 1 m so that the scanned width was
construction reveals the presence of different sandstone types with
about 25 cm and the size of each pixel 408 × 261 μm. Scans of
peculiar characteristics. Specific geological features distinguish a few
larger portions of the wall were obtained juxtaposing several image
macroscopic raw materials groups: colours of sandstones vary from grey
bands, while the height of the instrument was controlled by moving
to yellow with features created by soil development processes in the
the rail up and down with a pulley system. For each location of
original sand deposits, such as clay lumps (fine grained and greyish
interest, the acquired stripes have been concatenated in a hyper-
coloured) or red stains (due to the accumulation of iron oxides). The
spectral image approximately measuring one square metre.
building materials also display marks caused by atmospheric agents.
Reflectance images were obtained by scaling the hyperspectral
The stone blocks display various erosion patterns such as alveolar
images using a white reference (Spectralon, Labsphere) held on the
weathering, differential erosion of the beddings and scaling due to wet-
target and recorded for each image. The resulting images were
dry expansion of clay minerals. This large-scale deterioration of
converted to absorbance scale (−log10).
building materials is visible across the entire citadel and cannot be
- Portable X-ray fluorescence spectrometer. A battery-driven Thermo
ascribed to a specific sandstone type or construction phase. The

399
C. Sciuto et al.
Scientific Niton XL3t ED-XRF analyser was used for collecting
spectra on the surface of each analysed element in the masonry. The
instrument was used for complementing the MicroNIR measure-
ments, it was supplied with a 50 kV X-ray tube, an Ag target, and a
Si-PIN detector with a resolution of 175 eV at Mn Kα (5.895 keV).
The recordings were divided into 15 s intervals where three different
filter and tube settings were employed. The light filter mode, de-
signed for measuring light elements (for example Si and P), applied
no filter and a tube voltage of 6.2 kV. Low and main filter modes
were set with tube voltages of 20 and 40 kV respectively. ED-XRF
spectra were collected in 0.015 keV intervals (bins) from 0 to
60 keV, resulting in spectra composed by 4000 data points.
Combined measurements were conducted on four sampled portions
of the wall, chosen in order to include a wide selection of different
materials and construction phases (Fig. 1b). The documentation was
carried out directly in the field using tablets, marking down the ana-
lysed masonry elements and the position of hyperspectral images on
rectified orthophotos (Fig. 2).
In total, four portions of the inner wall were analysed (Fig. 1), and a
composite database comprehensive of images and point measurements
was collected (Table 2).
The sampling strategy was aimed at overlapping the measurements
as much as possible in order to compare the different datasets. While
one hyperspectral image includes several stone elements close to each
other and measures the entire external surface, point measurements
performed with the MicroNIR probe or with the ED-XRF had to be ac-
cumulated in different spots for each module. Five measurements for
each stone module were collected with the MicroNIR in random posi-
tion while the XRF readings were repeated three times. All the masonry
elements analysed with the portable XRF have mirror measurements
conducted with the MicroNIR probe. All stone types/phases scanned
with the hyperspectral camera have also been analysed with MicroNIR/
XRF, most of the times the measurements are overlapped on the same
modules.
The three methods deliver information about different qualities of
Table 2
List of measurements collected with the different instruments on sampled
portions of the rampart.
Portion Number of Number of Micro NIR Number of XRF (point
hyperspectral (point measurements) measurements)
images
1 3 65 39
2 4 30 24
3 2 10 6
4 2 30 18
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Journal of Archaeological Science: Reports 23 (2019) 396–405
Fig. 2. Documentation of sampling strategy in
the sector between the towers 47 and 48 (Area 1
in Fig. 1a). On the rectified ortophoto of the wall,
the rectangles indicate the hyperspectral images.
The single masonry elements measured with ED-
XRF and MicroNIR are illustrated as well as the
macro phases of construction of the monument.
materials. Both the Hyperspectral camera and the MicroNIR probe
collect spectral features relative to the vibration of molecules in the
Near Infrared band of the electromagnetic spectrum. NIR spectra are
comprehensive of a large range of information about the materials,
grain size, mineral composition, presence of water. ED-XRF spectro-
meter was used for elemental analysis. In Fig. 3 spectra recorded with
the three instruments are compared for two masonry elements (R1 and
R2) located in the zone 4 and both belonging to the Phase 5 (13th–14th
century). Spectra recorded with the hyperspectral camera (Fig. 3a)
show peaks related to the presence of clay minerals in the sandstone, in
particular illite (Bowitz and Ehling, 2008). NIR spectra collected with
the portable probe, five per stone, show a vertical shift for each curve
due to the variation of grain size in the measured spot while XRF
spectra display a consistent presence of Ca, Fe and Sr.
3. Calculation
The large number of different variables contained in spectral data
was modelled applying multivariate statistics. Exploratory analysis in
archaeological datasets by the means of multivariate statistics is
common and carried out in different contexts (Baxter, 2003), particu-
larly to achieve a certain degree of simplification of large datasets. Each
stone element was categorised according to chronology (Table 1,
Fig. 2), defined through the stratigraphic observations conducted on the
whole inner wall (Faucherre et al., 2016). The single datasets, created
with each analytical instrument, were explored through principal
component analysis (PCA) in order to reduce variability in the in-
formation and identifying clusters of materials with the same mineral/
elemental composition. The local models allowed evaluation of the
produced datasets, identifying eventual outliers due to scattering effect.
The hyperspectral images were processed through two consecutive
steps of multivariate modelling. The spectral bands below 1000 nm
were removed because they were very noisy and pre-processing algo-
rithms were applied, such as mean centring and Standard Normal
Variate (SNV) correction to reduce spectral noise and eliminate scat-
tering effects or interference. A PCA was then conducted on the images,
calculating a scatter plot of the pixels according to their spectral value
(Fig. 4a–b). The clustering was mostly influenced by vibration of mo-
lecules of AlOH and OH in the combination bands region as shown in
the loading line vectors plot (Fig. 4c). Different sandstone types could
be distinguished due to size and mineralogy of grains and the presence
of clay minerals (Bowitz and Ehling, 2008). The PCA components value,
in this case t[1], can also be visualized as colour composite on the
original image (Fig. 4a).
The hyperspectral images so created show the variability of texture
and composition for entire portions of masonry. It is possible to dis-
tinguish clearly each block of sandstone from the mortar binder and
C. Sciuto et al.
Fig. 3. NIR and XRF spectra compared for two different stone modules (R1 and R2, Zone 4, Phase 5); a) Hyperspectral camera, reflectance spectra (peaks identi-
fication refers to the work done on sandstone by Bowitz and Ehling, 2008) b) MicroNIR probe absorbance spectra c) ED_XRF spectra.
highlight the variations within single stone elements. In order to obtain
a dataset comprehensive of data from all images, the spectral in-
formation was averaged at the stone level. Through this procedure, it
was possible to obtain a spectral signature for each stone module, re-
ducing markedly the size of the dataset without losing too much in-
formation about variability on the surface of materials.
A new PCA model was then calculated on the averaged dataset, the
construction phases recorded for each element were added as catego-
rical attributes to the spectral values and visualized as shape/grayscale
code in the scatter plot (Fig. 5).
The measurements collected with the MicroNIR were pre-processed
in the same way. Spectra were mean centred and the SNV correction
was applied. The PCA model was then calculated on the data matrix
choosing the same shape/grayscale code according to the construction
phase (Fig. 6).
XRF spectra were reduced by removing bins with low, or no, signals
resulting in light, low and main filter sizes of 0–2.8 keV, 2.8–7.0 keV
and 7.0–19.0 keV, respectively. The data were then normalized, di-
viding each spectral value (counts/s) by the corresponding X-ray tube
current value obtained from the instrument parameter file. A PCA was
calculated by pre-processing the data matrix with Pareto scaling to
reduce the relevance of large values in the model still preserving the
general data structure (Fig. 7).
4. Discussion
The PCA model of the averaged values from hyperspectral images
shows distinct patterns. The first three components are relevant to
highlight clusters relative to the presence of certain minerals in the
sandstone (Fig. 5, see loading lines for this PCA in the supplementary
materials, Fig.5b). In particular, spectral features associated to the
presence of clay minerals, vibration of AlOH and OH, are useful vari-
able to discriminate among the masonry elements (Bowitz and Ehling,
2008). The cluster distribution corresponds to the variability of the raw
materials used in the construction that can be interpreted according to
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Journal of Archaeological Science: Reports 23 (2019) 396–405
chronological and stratigraphic references. Illitic sandstones are used
for the phase 1 and 4, Kaolinitic ones for the phase 2 and part of phase
5. The masonry elements considered to be dated within phase 2 (3rd
century) seem to have different provenience (Fig. 5). Two types can be
distinguished a green-grey glauconitic sandstone and a yellow illitic
one.
Similar trends can be observed in the model created from the
MicroNIR measurements. The spectral signatures obtained with this
instrument are less informative, as the bands measured cover only the
interval between 1000 nm and 1700 nm. The spectra collected with this
probe are more informative about the physical characteristics of the
objects, grain size and shape, together with vibration signals of OH and
H2O molecules in the first and second overtone. In the model (Fig. 6),
we can observe clustering patterns comparable to the ones observed in
the hyperspectral data.
The ED-XRF measurements display relevant concentrations of Ca
and Fe with Sr and Si (see Fig. 7; the loading histograms with the
mentioned peaks can be found in the supplementary materials, Fig. 7b).
Near Infrared spectroscopy and X-Ray fluorescence spectroscopy are
techniques targeted to the analysis of different characteristics in ma-
terials. If XRF can be used to estimate the presence of defined chemical
elements, NIR measurements result in spectra that are the sum of mo-
lecular vibrations and therefore are comprehensive of physical in-
formation such as texture or humidity (water content). In order to as-
sociate the information potential of these techniques, it was decided to
combine measurements obtained with the two hand-held probes:
MicroNIR and XRF. Two data matrices on the same measured samples
were merged using an O2PLS model (orthogonal projection to latent
structures; Trygg, 2002), the XRF spectra were pre-processed through
Pareto scaling and coupled with second-derivative NIR spectra. The
resulting model (Fig. 8), calculated for the measurements performed on
the zone 1 (Fig. 2), shows variability both for XRF and NIR data. After
combining the spectral information, the patterns observed in the local
models are enhanced.
As observed from the spectra collected with the different methods,
Fig. 4. PCA on a hyperspectral image of the
citadel wall taken with the hyperspectral
camera (NEO HySpex-320m-e). The chron-
ology of the masonry is uncertain (Phase 2
or 3). a) Colour composite picture, the as-
signed RGB value is determined by the
spectral information; b) Scatter plot showing
the distribution of image pixels in a multi-
variate space, clusters are visible; c) Loading
line for the first two components showing
pics relevant for the classification and re-
lated to the presence of clay minerals in the
sandstone.
C. Sciuto et al. Journal of Archaeological Science: Reports 23 (2019) 396–405

Fig. 5. PCA model of spectra averaged from the hyperspectral image, every point indicates a different masonry element (one point, one stone), phases of construction
is indicated as shape/grayscale code.

Fig. 6. PCA model of MicroNIR measurements for the analysed masonry elements in all the four areas, each point indicates one recording, five measurements have
been collected for each stone, the construction phase is indicated as shape/grayscale code.

402
C. Sciuto et al.
Fig. 7. PCA model of the XRF measurements on the analysed masonry elements in all the four areas, every point represents one recording, three measurements have
been collected for each stone; the construction phase is indicated as shape/grayscale code.
Fig. 8. O2PLS model combining ED-XRF and MicroNIR spectra of single ma-
sonry elements analysed in the zone 1 (Fig. 2). Score plot in which every point
corresponds to one measurement, the construction phase is indicated as shape/
grayscale code.
different types of sandstone have been used in the construction. This
evidence could suggest a variability of raw materials supply, from
distinct quarrying sites located in the area. The rock types can be dis-
tinguished according to elemental composition and presence of precise
minerals. Integration of analytical data and stratigraphic observations
reveal a more complex scenario of materials usage and organization of
the working site. Blocks made of different raw materials are included in
patches of wall that present homogeneous formal characteristics (in
terms of size of stones and joints). The explanation for this analytical
evidence could be found in the organization of the supply strategy and
403
Journal of Archaeological Science: Reports 23 (2019) 396–405
the procedure of construction. During the several phases of construc-
tion, some elements could have been reused from older structures
standing in the area; this could be the case for the glauconitic green
sandstone blocks used as foundation for the Late Antiquity towers
(Phase 2, 2b). The distinct composition and origin of reused elements
would be the explanation for the clustering detected in the models,
showing a substantial difference between the big blocks and the smaller
elements on regular beds characterising the third century construction.
While the first ones were reused, the latter were probably quarried on
purpose and coming from a different source. We could therefore assume
that distinct supply strategies of stone materials could coexist on the
construction site, and batches of raw materials could come from dif-
ferent sites (quarries or older constructions) and be dressed directly by
stonemasons on the workshop before being fixed onto the building.
Another interesting case is one of the stone elements dated to con-
struction phase 4 (13th century). The blocks belonging to this group
seem to have a quite homogeneous mineralogical composition, and the
13th century segments of the wall were built according to a regular
scheme. This regularity in the masonry is to be attributed to the fact
that the reconstruction of the wall dated after the last siege was per-
formed after a direct order from the king. Royal engineers travelled to
Carcassonne accompanied by stonemasons, or recruiting local workers,
to supervise the construction. We can imagine that for such a big op-
eration and economic investment the material supply must have been
more regular, probably with batches of stone shipped from one big
quarrying site selected for the purpose. Such a scenario would explain
the homogeneity in the composition of the materials dated to the 13th
century.
5. Conclusion
The instruments used for the study provided interesting results and
granted good accuracy. Probes such as portable NIR and portable ED-
XRF allow collection of fast point measurements and can be carried by
C. Sciuto et al.
one person. The recordings can be multiplied to guarantee a good
coverage of samples, and the data matrices can be statistically merged
to enhance the information. The combination of MicroNIR and ED-XRF
can be used as a screening method for classification of lithic materials in
various field situations but does not guarantee a very detailed miner-
alogical characterization. The imaging system is less portable but re-
sults in a more complex datasets, encompassing chemical information
and its spatial variability, highlighting the complexity of the materials'
surfaces. The imaging system can be moved around an object, but have
height limits. Considering this issue, we envisage associating the NEO
HySpex camera with drone imaging in order to reach higher portions of
the building.
The spectra extracted for each stone element have been shown
useful for detecting clay minerals while configuration of absorption
bands display grain size and shape, XRF spectra contained information
about elemental composition of the masonry. The data collected were
suitable for distinguishing different types of sandstone used in the
construction, comparing and combining distinct datasets, by means of
multivariate statistics. Different types of sandstone could be associated
with the observed chronological phases to shed light on diachronic
variability of raw materials usage in the construction.
This study is preliminary and provides a first test of the application
of non-destructive spectral techniques for characterization of building
materials in-situ. The results described are promising and will be fur-
ther implemented with a screening of sandstone outcrops available in
the plain to identify possible supply sources. Moreover, the analysis will
be performed on larger stretches of masonry and other monuments of
the citadel in order to delineate large scale dynamics of building ma-
terials supply and organization of labour in the working site. If the
study of archive documents and historical records gives us clues about
why and when the military architecture was built and restored, the
materials tell us how the construction was erected. A close examination
of stones and their characteristics helps us to shed light on the stories of
unrecalled quarrymen, stonemasons and their craft, building a wall that
nowadays represents an iconic monument in southern France.
Acknowledgements
Thanks to the anonymous reviewers for helping us in improving this
article through their positive comments.
Thanks to the Marcus and Amalia Wallenberg Foundation, Sweden,
(grant number MAW 2012.0136) for financially supporting the project.
To Daniel Moura and Constance Mallard for their help during the
data acquisition campaign.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.jasrep.2018.10.030.
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