Appl. Phys.

A (2017) 123:215
DOI 10.1007/s00339-017-0844-2

S.S. Annunziata Church (LAquila, Italy) unveiled bynon-

andmicro-destructive testing techniques
StefanoSfarra1,2 EleniCheilakou3 PanagiotisTheodorakeas3 DomenicaPaoletti1
MariaKoui3

Received: 2 September 2016 / Accepted: 9 February 2017

Springer-Verlag Berlin Heidelberg 2017

Abstract The present research work explores the poten-
tial of an integrated inspection methodology, combining
Non-destructive testing and micro-destructive analytical
techniques, for both the structural assessment of the S.S.
Annunziata Church located in Roio Colle (LAquila, Italy)
and the characterization of its wall paintings pigments.
The study started by applying passive thermal imaging for
the structural monitoring of the church before and after
the application of a consolidation treatment, while active
thermal imaging was further used for assessing this con-
solidation procedure. After the earthquake of 2009, which
seriously damaged the city of LAquila and its surround-
ings, part of the internal plaster fell off revealing the pres-
ence of an ancient mural painting that was subsequently
* Panagiotis Theodorakeas
pantheod@mail.ntua.gr
Stefano Sfarra
stefano.sfarra@univaq.it
Eleni Cheilakou
elenheil@mail.ntua.gr
Domenica Paoletti
domenica.paoletti@univaq.it
Maria Koui
markoue@chemeng.ntua.gr
investigated by means of a combined analytical approach
involving portable VISNIR fiber optics diffuse reflec-
tance spectroscopy (FORS) and laboratory methods, such
as environmental scanning electron microscopy (ESEM)
coupled with energy dispersive X-ray analysis (EDX), and
attenuated total reflectance-fourier transform infrared spec-
troscopy (ATR-FTIR). The results obtained from the ther-
mographic analysis provided information concerning the
two different constrictive phases of the Church, enabled
the assessment of the consolidation treatment, and contrib-
uted to the detection of localized problems mainly related
to the rising damp phenomenon and to biological attack. In
addition, the results obtained from the combined analyti-
cal approach allowed the identification of the wall painting
pigments (red and yellow ochre, green earth, and smalt)
and provided information on the binding media and the
painting technique possibly applied by the artist. From the
results of the present study, it is possible to conclude that
the joint use of the above stated methods into an integrated
methodology can produce the complete set of useful infor-
mation required for the planning of the Churchs restoration
phase.
1Introduction

1
Las.E.R. Laboratory, Department ofIndustrial The present work is centered on a series of non-destructive
andInformation Engineering andEconomics (DIIIE), inspections which started in 2000 and ended in June 2015.
University ofLAquila, Piazzale E. Pontieri no. 1, Loc.
This started as a routine inspection on the cultural heritage
Monteluco di Roio, 67100Laquila, Italy
2
of the city, conducted by the Las.E.R. Lab. of University
Tomsk Polytechnic University, Lenin Av., 30, Tomsk634050,
of LAquila (Italy), and it was concluded as a collaborative
Russia
3
project along with the NDT Lab of National Technical Uni-
NDT Laboratory, Department ofMaterials Science
versity of Athens (Greece). In this long-term survey, pas-
andEngineering, School ofChemical Engineering, National
Technical University ofAthens, Iroon Polytechniou no. 9, sive infrared thermography was primarily used to inspect
Zografou Campus, 15780Athens, Greece the faade and the internal walls of the S.S. Annunziata

13
Vol.:(0123456789)
 215 Page 2 of 12
Church, built in 1178 [1]. The present thermographic study
focused on the monitoring of the most important phases of
the faade restoration process (i.e., cleaning and consolida-
tion), while the results obtained in time acted as a valuable
scientific contribution for the planning of the preservation
policies of the building. To that direction, the inspection
of the interior walls by means of passive thermal imaging
confirmed the historical supposition inherent to two differ-
ent constructive steps of the structure, separated by the bel-
fry. A first clue for the re-adaptation of the internal walls
was verified after the 2009 earthquake that caused the par-
tial fall of the most recent decorative plaster layer, revealing
the presence of a previously built fresco layer. The above
observation was correlated with the historic incidents of
plague spreading in the Abruzzo region in 1464, 1484,
and 1486, and in the city of LAquila in 1478. More spe-
cifically, the local community, taking into account health
safety necessities, decided to cover the original decorative
paintings with a new mortar layer that was subsequently
repainted. On the other hand, information about the wall
texture, at least for a small part, has been retrieved using
active infrared thermography (IRT) and data elaboration by
advanced thermographic signal processing [2].
In addition to the thermographic survey, the nature of
the ancient pigments has been characterized by means of a
combined analytical approach involving portable VISNIR
fiber optics diffuse reflectance spectroscopy (FORS) and
laboratory methods, such as environmental scanning elec-
tron microscopy (ESEM) coupled with energy dispersive
X-ray analysis (EDX), and attenuated total reflectance-
fourier transform infrared spectroscopy (ATR-FTIR) [3].
The latter techniques are considered a benchmark to the
materials characterization coming from the cultural herit-
age field [46]. In particular, an extensive investigation of
the mural paintings was initially carried out with the use
of FORS technique, where in-situ measurements were per-
formed on multiple spots of almost all painted areas (red,
yellow, orange, green, and blue), with the aim of identify-
ing the pigments through the comparative analysis of the
acquired diffuse reflectance spectra with suitable spectral
databases. Since only very limited sampling of the origi-
nal paint layers was permitted, the results obtained from
the FORS analysis acted as a valuable guideline for the
subsequent targeted sampling procedures, only from areas
highlighted by FORS as uncertain cases which needed to
be further investigated by more sophisticated techniques.
Therefore, a total of three micro-samples were removed
from distinct locations, where green and blue pigments
were located, and were examined by means of the common
methods of ESEM-EDX and ATR-FTIR for the chemical
elemental composition analysis and the characterization of
their molecular structure. The laboratory results confirmed
previous identifications of pigments and yielded further
13
S.Sfarra et al.
information on the binding media, possibly used by the
artist, which was not available from the FORS analysis, as
well as on the painting techniques employed together with
the degradations that took place as a function of time.
The main aim of this research was the investigation
for the complementary evaluation of an integrated testing
procedure that combines the application of thermographic
non-destructive testing (NDT) for the structural assessment
of the inspected cultural heritage building and the applica-
tion of an analytical methodology for the mural paintings
pigments characterization. In this way, the complete set of
information necessary for the planning of the restoration
processes can be produced.
2Main information oftheS.S. Annunziata
Church
The Church, having a rectangular structure and one nave,
was built with stone walls with typical Romanesque crafts-
manship and other remaining materials from the Roman
and early medieval ages. The date of consecration (1182)
has been passed down by an epigraph engraved on a com-
memorative stone fixed within a wall. Inside the Church,
two ogival recesses contain paintings dated between the
15th and 16th century, while below the left recess, an
Annunciation icon appeared after the 2009 earthquake.
The consolidation process of the stone walls started in
2011 with the aid of a low pressure pumping system, inject-
ing mortar inside the walls. The consolidation mortar used
consisted of a Rurewall B1 type by Ruredil binder, a
pozzolanic hydraulic binder with a low salt content. The
selection of the above binder type was made considering
its chemical composition that excludes the possibility of
the mortars chemical reaction with salts (sulphates, car-
bonates, nitrates, chlorides, etc), usually presented in the
walls of ancient buildings. As stated above, the mortar was
applied by pumping it from the external faade of the wall
up to its internal surface. In some cases, when the grout re-
emerged on the internal surface of the wall, the pumping
system was stopped and the restorers proceeded with clean-
ing it. For the clarity of the readers regarding the injection
procedure, they may consult the video uploaded on [7],
where the holes in which the above-mentioned mortar was
injected are shown at the 5 min. In addition, a schematic
presentation showing the injection points on the wall is
illustrated in Fig.1.
Figure 2 summarizes the evolution of the state of the
faade from 2000, through 2007, and arriving at 2015,
respectively. Comparing the three images, it is obvious that
the structure suffered from biological attacks, presented
by the black strains, in 2000, while a surface area lacking
mortar between the stones (surrounded by a dark dotted
S.S. Annunziata Church (LAquila, Italy) unveiled bynon- andmicro-destructive testing Page 3 of 12 215

Fig.1Points on the external wall from which the consolidation mor-

tar was injected into the ancient structure

Fig.3S.S. Annunziata Church: thermogram recorded on June 17th,

2000

Fig.2S.S. Annunziata Church: photographs taken on June 17th,

2000 (left), June 17th, 2007 (middle) and June 17th, 2015 (right)

rectangle) was observed in 2015. The red dotted oval indi-

cates a part of the faade above the rose window, where the
stones seem to have been placed irregularly contrary to the
rest of the stone masonry.

3Description ofnon andmicrodestructive

testing techniques, results, anddiscussion

3.1Thermographic survey

The different thermograms captured during this long-

term survey are reported in Figs.3, 4, and 5. In particu-
lar, three thermographic images recorded in 2000, 2007,
and 2015, respectively, were collected on the same day of
the year (17th of June) and at the same time (9:30a.m.), Fig.4S.S. Annunziata Church: thermogram recorded on June 17th,
with the only difference between them owning to the year 2007
of their recording. This was performed to ensure that the
structure had received approximately the same amount
of solar energy prior to each thermographic record- above conditions enabled the relative comparison of the
ing, which was also confirmed through the monitor- three thermal images. They are also presented using the
ing of the climatic conditions in each individual survey same temperature scale for an easier interpretation of the
that were found to be quite similar. In other words, the detected thermal inhomogeneities.

13
 215 Page 4 of 12
Fig.5S.S. Annunziata Church: thermograms recorded on June 17th,
2015 (faade and right wall)
By observing the respective thermograms, the influence
of the biological attack can be detected from the record-
ing of the increased temperatures on some areas of the
faade. The presence of black mount colonies (Fig.2) indi-
cates moisture as well. Thus, considering the early time of
inspection along with the low heat exchange coefficient of
water, the zones of increased temperature can be correlated
with the bio-deteriorated regions.
It is also very interesting to note how the thermal
imprint, which is surrounded by the dotted line, the lunette
and the main door, follows the same trend (i.e., an incre-
mental gradient of the surface temperature starting from its
lower part) both in Fig. 3 and Fig. 4, ending at the same
point, where the yellow line of Fig. 2 is marked to (see
the bottom left part). In the latter figure, the border line,
indeed, separates the black (dirty) stones from the white
(clean) stones. Nevertheless, the thermogram of Fig.4 also
presents the above-discussed surface temperature gradient,
despite the fact that this was recorded after the application
of the cleaning intervention on the faade. Thus, the above
observation can be possibly correlated with the rising damp
effect, as a result of the comparative assessment of the dif-
ferent thermographs captured over time.
Moreover, interesting results can be seen in Figs. 6
and 7, where the thermal behavior of the interior left and
Fig.6S.S. Annunziata Church: thermogram (top) and photograph
(bottom) taken on June 15th, 2007 inherent to the left internal wall
13
S.Sfarra et al.
Fig.7S.S. Annunziata Church: thermogram (top) and photograph
(bottom) taken on June 15th, 2007 inherent to the internal right wall
right lateral walls was examined. In particular, the ther-
mograms inside the white oval (Fig. 7) reveal a layer of
sub-superficial stones beneath the plaster surface. It is
interesting that these thermal imprints can be detected
only in this part of the lateral wall, i.e., on the right
side. It is also interesting to note that, at the time when
the thermograms were recorded, the sun did not directly
irradiate the right side. On the other hand, at the lowest
part of the respective external wall (Fig. 5), a high-tem-
perature reading appeared, possibly due to the presence
of moisture.
Screening from inside, it was also confirmed that the
lowest part of the wall was affected by moisture coming
from the ground, while the middle part of the wall had a
higher temperature, receiving slightly greater solar radia-
tion, and similarly the upper part accumulated the greatest
amount of sun heat during the day. Despite the different
temperature distributions on the wall, it is possible to say
that the thermograms outside of the oval (Fig.7) have two
layers of plaster, i.e., the old one that was revealed after the
earthquake and the new one that covered the old fresco. On
the contrary, the images inside the oval only reveal the new
plaster applied directly on the stone masonry; therefore,
the detection of the sub-superficial stones was possible.
Instead, the inspection of the left lateral wall (Fig. 6) did
not reveal the presence of the stone masonry; therefore, the
realization of an older sub-superficial plaster as appears in
Fig.7 is highly probable.
The latter supposition, as well as the particular thermal
imprint surrounded by a white dotted oval in Fig.6, urged
the competent authorities to remove the external plaster at
least on that part. The result was impressive as an unknown
ogival arch was brought to light (Fig. 8) along with an
ancient fresco beneath the new plaster layer, as described
above.
S.S. Annunziata Church (LAquila, Italy) unveiled bynon- andmicro-destructive testing
Fig.8S.S. Annunziata Church: a buried ogival arch built on the
internal left wall
In addition to the above-discussed measurements, the
last part of the thermographic survey was dedicated to the
application of active infrared thermography (hot air stimu-
lation). By this testing configuration, an area on the internal
right wall occupying a space of 1 m2 (see the white rec-
tangleFig. 7) was inspected aiming to the retrieval of
information regarding the consolidation intervention, previ-
ously applied to structure. In the tested area (presented also
in Fig.9), the external plaster had fallen off after the 2009
earthquake, revealing a part of the ancient fresco. Through
the forced convection, the mural painting was heated for
8 min from a distance of 2.25 m, while for the recording
of both the heating up and cooling down phases, a frame
rate equal to 0.0835Hz was used. The cooling down phase
recording lasted 17 min. The elaboration of the raw data
was performed through the aid of pulsed phase thermog-
raphy [8] (PPT) and principal component thermography
Fig.9S.S. Annunziata Church: the inspected part and the PPT and
PCT results linked to a hot air stimulation
Page 5 of 12 215
(PCT) techniques [9], selected on the basis of previous
experience in this matter [10].
As can be seen from the results of Fig. 9, PCT analy-
sis revealed some regions of interest (ROI), indicated by
arrows, that were further confirmed by the PPT technique.
These ROIs can be possibly attributed to the presence of
the material injected into the wall during the consolidation
process. The red arrows indicate a consolidated area (i.e.
injected mortar) that is presented in all the three processed
images. On the other hand, the yellow arrow is not reported
in the PPT result at the frequency equal to 0.48Hz, indicat-
ing that this consolidated area is undetectable in this case.
Nevertheless, it can be detected from the phase image at the
frequency of 0.16 Hz. The latter observation verifies that
the injected mortar, in the zone indicated by the yellow
arrow, penetrated deeper (considering that it was injected
from the external surface) contrary to the result of the con-
solidate area indicated by the red arrow. Here, it shall be
stated that no sign was visualized to the naked eye on the
surface of the ancient mural painting.
3.2Insitu FORS andlaboratory analytical procedures
Along with the thermographic survey, the main pigments
of the oldest fresco were analyzed in-situ by means of
FORS technique. The measurements were performed on
multiple spots of almost all color impressions (red, yellow,
orange, green, and pale blue) appearing on the wall paint-
ings (indicative measurement areas are shown in Figs.10,
11, marked with arrows), using a portable Ocean Optics,
USB4000-VISNIR FORS to perform a reflectance spec-
tral analysis of the pigments. The instrument features a
high-performance 3648-element linear CCD-array detector,
installed with a multi-bandpass order-sorting filter to cover
Fig.10S.S. Annunziata Church: part of wall painting indicating rep-
resentative spots of in-situ measurements
13
 215 Page 6 of 12
Fig.11S.S. Annunziata Church: part of wall painting indicating rep-
resentative spots of in-situ measurements and the sampling areas
the 3501000nm wavelength range, and a 25m entrance
slit for optical resolution to 1.5 nm. It is equipped with a
QR400-7-VIS/NIR reflection bifurcated probe providing
illumination and detection of diffused light from the same
direction, an HL-2000 tungsten-halogen light source and
an RPH-1 reflection probe holder enabling the positioning
of the QR400-7 under an angle of 45 for measuring dif-
fuse reflection in order not to include specular reflectance.
A locking setscrew is also included in the RPH-1 device to
mount the probe into position, which was used to maintain
a constant working distance of 10 mm between the probe
tip and the surface being analyzed during all the reflection
measurements. Diffuse reflectance spectra were referenced
against WS-1 Standard and guaranteed reflective at 98% or
more in the spectral range investigated. Spectral data treat-
ment was performed with the SpectraSuite software add-on
for Origin.
In addition, totally three micro-samples were collected
from selected painted areas appearing pale blue, dark
greyblue, and light green colorations. The exact prov-
enance of each sample is indicated in Fig. 11 (see dotted
arrows), while a brief description of their characteristics
is reported in Table 1. All micro-samples were examined
under an FEI Quanta 200 ESEM, coupled with an EDX, for
the microstructure investigation and the chemical elemental
analysis of the pigments. ESEM imaging parameters were
Table1Description of micro-samples collected from painted areas
of the S.S. Annunziata Church
Sample no. Color impression Location
Sample 1 Pale blue Indicated in Fig.11
Sample 2 Dark greyblue
Sample 3 Light green
13
S.Sfarra et al.
selected as follows: 30kV accelerating voltage, magnifica-
tions up to 3000 and dwell time of 5 s for each single
image. The surface elemental composition was determined
by EDX detector using: spot analysis locally at different
selected spots of interest, and surface analysis (mapping)
on the whole image. The Quanta 200 ESEM system can
provide high resolution images without requiring any sam-
pling pretreatment (carbon or gold coating), thus enabling
to leave the samples intact for further analysis.
For the characterization of the pigments molecular
structure, the above micro-samples were further analyzed
using a ThermoScientific Nicolet 6700 FTIR, equipped
with an ATR accessory. Transmission FTIR spectra were
recorded in the mid-IR spectral region 4000400 cm1,
at a resolution of 4 cm1 and by collecting 120 co-added
scans for each spectrum. The approximate collection time
was about 1 min. Data processing was carried out using
the OMNIC 7.1 Software. The great advantage of the ATR
technique utilized is that minimum amount of sample is
required without involving any preparation (i.e., KBr pel-
letization), enabling thus to obtain high-quality IR spectra
of the samples very quickly.
3.2.1Red color impressions: identification ofred pigments
The diffuse reflectance spectra obtained from the in-situ
FORS measurements on the red color impressions of the
wall paintings are presented in Fig. 12. In the same fig-
ure, two spectra collected from pure hematite pigment and
pure red ochre pigment containing hematite as the major
Fig.12S.S. Annunziata Church: diffuse reflectance spectra acquired
from the red color impressions of the wall paintings. The spectra of
reference hematite and red ochre pigments are also demonstrated for
comparative purposes
S.S. Annunziata Church (LAquila, Italy) unveiled bynon- andmicro-destructive testing
component, which served as the reference spectra, are also
added for comparative purposes.
From the comparative spectral analysis of Fig. 12, all
spectra corresponding to the in-situ measurements present
a similar trend with the reference pigment curves and are
differentiated in their reflectance intensity.
More specifically, the curves present a typical S shape
and they are characterized by a sharp positive slope at the
wavelengths between 550 and 600nm and a maximum near
740 nm. The aforementioned spectral features are charac-
teristic for red ochre with the form of hematite. Moreover,
all spectra present two absorption bands, a strong one in the
bluegreen region (near 490nm) and a weaker one in the
near-infrared region (near 850nm) that are also attributed
to hematite [1113]. The above results verify that the pig-
ment used by the artist for the production of the wall paint-
ings red color impressions was red ochre with the form of
hematite [Fe2O3].
3.2.2Yellow color impressions: identification ofyellow
pigments
Figure 13 demonstrates the diffuse reflectance spectra
obtained from the in-situ FORS measurements on the yel-
low color impressions along with a reference spectrum col-
lected from pure yellow ochre pigment containing goethite
as the major component.
From the comparative spectral analysis, it is observed
that the curves corresponding to the in-situ measure-
ments present a typical S shape and are characterized by a
sharp positive slope between 500 and 550nm and a broad
Fig.13S.S. Annunziata Church: diffuse reflectance spectra acquired
from the yellow color impressions of the wall paintings. The spec-
trum of reference yellow ochre (goethite) pigment is also demon-
strated for comparative purposes
Page 7 of 12 215
absorption band (minimum) near 640nm, coinciding with
the reference yellow ochre spectral features. In addition, all
spectra present a shoulder between 450 and 480nm and a
broad absorption band at 910 nm which are attributed to
goethite [1113].
The aforementioned findings confirm the utilization of
yellow ochre pigment with the form of goethite [FeO(OH)]
for the production of the yellow color impressions.
3.2.3Orange (ceramic) color impressions
The diffuse reflectance spectra obtained from the in-situ
FORS measurements on the orange color impressions of
the wall paintings (Fig.14) show features halfway between
the spectra of red ochre (hematite) and yellow ochre (goe-
thite). The above results suggest the possible mixing of red
and yellow ochre for the production of the ceramic-orange
colorations [14].
3.2.4Green color impressions: identification ofgreen
pigments
Figure 15 demonstrates the diffuse reflectance spectra
obtained from the in-situ FORS measurements on the
light green color impressions along with a reference spec-
trum collected from a pure green earth pigment. From the
comparative spectral analysis, we can observe that the
in-situ curves are characterized by a reflectance maxi-
mum at max560 nm which lie between two minima
(absorption maxima) about 500 and 750 nm, presenting
also a secondary broad maximum in the near-IR (around
850 nm) and a shoulder about 480 nm. The above spec-
tral features are characteristic for green earth and are also
Fig.14S.S. Annunziata Church: diffuse reflectance spectra acquired
from the orange (ceramic) color impressions of the wall paintings
13
 215 Page 8 of 12 S.Sfarra et al.

most likely in the form of glauconite [(K, Na)[(Fe3+, Al,

Mg)2](Si, Al)4, O10(OH)2].
The EDX chemical elemental analysis results of the
green micro-sample reported in Table2 revealed the pres-
ence of high Ca and Si concentrations along with lower Mg
and Fe contents, suggesting the presence of calcium com-
pounds, possibly calcium carbonate (CaCO3) coming from
the plaster substrate, and that the green pigment used was
green earth.
The above hypothesis concerning the presence of cal-
cium carbonate was confirmed by the results obtained
from the ATR-FTIR spectroscopic analysis of the sample
demonstrated in Fig. 16. Strong characteristic signature
bands of C aCO3 were recorded at about 1400 cm1 aris-
Fig.15S.S. Annunziata Church: diffuse reflectance spectra acquired ing from the 3CO3= asymmetric stretching vibrations of
from the green color impressions of the wall paintings. The spectrum
of reference green earth pigment is also demonstrated for comparative
calcium carbonate, as well as in the regions of 870 and
purposes 710 cm1 that can be assigned to the 2CO3=asymmet-
ric out-of-plane and 4CO3=symmetric in-plane bending
vibration modes, respectively. The above bands indicate
Table2EDX elemental analysis of the micro-samples collected that the calcium carbonate has the form of calcite structure
from painted areas of the S.S. Annunziata Church (Wt%) in the samples. Besides the first-order internal modes, the
El. Sample 1 with Sample 2 with dark Sample 3 with light 1+4 combination mode was also observed at 1795cm1.
pale blue color greyblue color green color (map- The 1CO3=stretching vibration gives rise to a very strong
(spot) (mapping) ping) Raman band at about 1090 cm1 which is normally inac-
C 10.42 37.50 13.19 tive in IR [16]. The presence of calcite could suggest the
O 38.95 34.30 53.17 employment of either a fresco technique, in which alkali-
Na 0.57 0.66 nd resistant pigments (mainly earthy such as red and yellow
Mg 0.59 0.49 0.52 ochre and green earth) mixed with water or limewater were
Al 0.98 0.36 nd applied to the still-wet plaster layer, where they would
Si 22.35 13.55 26.37 adhere to the surface through carbonation of the hydrated
Bi nd 1.82 nd lime, or a fresco-secco technique executed on dry plaster
S 0.38 nd nd and using lime as a binder.
K 7.51 0.44 nd The presence of green earth is evident in the obtained
Ca 8.98 6.60 6.61 ATR-FTIR spectrum of the green sample (Fig. 16) by the
Mn 1.05 nd nd strong absorption band recorded at about 1010cm1. This
Fe 2.63 0.89 0.23 is characteristic of aluminosilicate compounds arising from
Co 1.23 1.20 nd the SiOAl stretching vibrations modes and thus verify-
Ni 0.59 0.61 nd ing the EDX results. The above findings are in accordance
As 1.13 1.58 nd with the results obtained from the in-situ FORS analysis of
Pb 2.63 nd nd the green color impressions described above.
Total 100.00 100.00 100.00 The ATR-FTIR spectra of celadonite [K[(Al, F e3+),
2+
(Fe , Mg)](Si3, Si4)O10(OH)2] are characterized by a group
of four well-resolved bands in the region 1110950 cm1
consistent with the reference pigment spectral features arising from the in-plane SiO stretching modes (usu-
[11, 12]. A broadening and shifting of the reflectance ally occurring at 955, 970, and 1075 cm1) and the SiO
maximum towards higher wavelengths is observed in the stretching vibrations perpendicular to the S iO4 tetrahedral
in-situ curves possibly due to the aging of the pigment. sheet (at about 1110 cm1), suggesting a quite crystalline
The above could also indicate the possible presence of order. In the ATR-FTIR spectrum of Fig.16, the fine struc-
glauconite, whose spectra usually shows a maximum in ture of the SiO band characteristic of celadonite is sub-
higher wavelengths (about 570 nm) compared with that stituted by the broad and intense SiOAl absorption band
of celadonite (usually occurring at about 540 nm) [15]. centered near 1010cm1 leaving a weak shoulder at about
The above results indicate that the green color impres- 1100cm1, which are more consistent with the IR spectral
sions could be attributed to the utilization of green earth features of glauconite.

13
S.S. Annunziata Church (LAquila, Italy) unveiled bynon- andmicro-destructive testing Page 9 of 12 215

Fig.16S.S. Annunziata
Church: ATR-FTIR spectrum of
Sample 3 (light green color)

The above behavior could be explained by the decreas-

ing of symmetry (more distorted structure) in the tetrahe-
dral silicate layers, taking into account that the shape of the
principal SiO band is particularly sensitive to even small
differences of Al3+-for-Si4+ substitutions in the SiO4 tet-
rahedra. The bands observed at about 790 and 750 cm1
could be related to the OH bending vibrations involving
octahedral ions, while the band near 640 cm1 could be
assigned to AlO vibration modes. A sequence (triplet)
of bands normally occurs below 500 cm1 in both miner-
als (usually found near 440, 460, and 490cm1) related to
the SiOR3+ vibrations, and it is well known that they are
very sensitive to the variations of ions with an octahedral
coordination in such structures, particularly of Fe3+ [17,
18].
In addition, in the region between 1700 and 1600cm1,
the ATR-FTIR spectrum of the sample showed a very weak Fig.17S.S. Annunziata Church: diffuse reflectance spectra acquired
and broad absorption band with a peak centered at about from the pale blue color impressions of the wall paintings
1640 cm1 that could be related to the so-called Amide I
band arising from the NHCO vibrations of the peptide
group of proteins [19]. One of many possibilities could blue pigments in Italy between the 15th and 18th centuries.
be the attribution of the above band to the use of a protein Smalt is a cobalt containing potash silicate glass and its ref-
binding medium, which along with the identification of erence FORS spectrum is given in Fig.18 [22].
calcite may suggest the application of a fresco-secco wall From the comparative spectral analysis between Figs.17
painting technique. and 18, it is observed that the in-situ curves approach
the shape of the reference smalt spectrum. However, the
3.2.5Blue color impressions: identification ofblue intense reflectance maximum centered near 470nm, which
pigments is characteristic for blue smalt, seems to be weaker in the
in-situ measurements curves. This could be attributed to
The diffuse reflectance spectra obtained from the in-situ the well-established degradation phenomenon of smalt usu-
measurements on both the pale blue and the pale blue with ally occurring in paintings that result in the discoloration of
grey hue color impressions of the wall paintings are pre- the pigment leaving a faded bluegrey hue on the painted
sented in Fig. 17. The spectra show an absorption band areas [2325], ascertained also by the macroscopic obser-
in the 550650 nm range, which is structured in three vations. However, another hypothesis that could be made to
sub-bands at about 535, 590, and 650 nm (reflectance explain the above spectral behavior concerns the fact that
maxima centered at about 470, 570, and 625nm), and are smalt, according to historical sources, was available in dif-
also characterized by a sharp increase in reflectance inten- ferent grades, varying in shades from strong blue to pale
sity at wavelengths between 650 and 700 nm. The above grey [26].
spectral features could be attributed to the pigment smalt Nevertheless, smalt can be revealed by FORS even in
[20, 21] that is referred to as one of the most widely used low concentration, since the very intense absorption bands

13
 215 Page 10 of 12
Fig.18S.S. Annunziata Church: reference smalt spectrum (available
from IFAC FORS database at http://fors.ifac.cnr.it/)
of Co(II) ions are easily detected. The above-mentioned
findings suggest that the pale blue coloration may be
assigned either to the presence of smalt suffering from dis-
coloration as a result of its degradation, or to the deliberate
selection and use of a weak colored variety of smalt by the
artist.
The EDX chemical elemental analysis results of the blue
micro-samples (Figs. 19, 20; Table 2) revealed the pres-
ence of high Ca concentrations suggesting the presence of
calcium compounds, possibly calcium carbonate (CaCO3)
coming from the plaster substrate. The determination of
high Si content as the major component of the samples
along with the lower amounts of K and Co indicate the
presence of blue pigment smalt, thus verifying the in-situ
FORS analysis results described above.
Smalt is a potassium silicate glass strongly colored by
cobalt (Co2+) ions mostly found in tetrahedral coordination.
In addition to silica, potassium, and cobalt, historic smalt
Fig.19S.S. Annunziata Church: EDX spectrum of Sample 1 with
pale blue color (spot)
13
S.Sfarra et al.
Fig.20S.S. Annunziata Church: EDX spectrum of Sample 2 with
dark greyblue color (mapping)
also contains other elements associated with the silica
source, such as Al and Fe, or with the cobalt ore used to
manufacture the blue glass pigment, such as As, Ni, and Bi.
These are often present at levels equal to or greater than
cobalt, and were identified in the examined samples. The
above impurities reflect the geographical location of the
mineral deposit and their composition can vary signifi-
cantly due to the use of different recipes, but also according
to the origin of the raw materials and the way in which they
were processed prior to manufacturing of the pigment.
Furthermore, the decreased percentage of K and the
increased Ca levels observed in all EDX spot and mapping
analyses results could be related to the smalt discolora-
tion phenomena. The Pb content identified on the pale blue
sample may be attributed to the presence of white lead that
was possibly mixed with smalt to obtain a higher stability
of the pigment and prevent discoloration to a degree.
Finally, the high C levels identified on the dark
greyblue sample allow us to assume that over the lime-
based plaster, a primary, dark covering, thin layer made
from carbon black was employed. In this case, the blue
pigment exhibits crystalline grains in a variety of sizes in
hues from deep blue to greyish blue. This is a traditional
technique that was used for centuries in murals of the
Paleologan and Cretan styles and has also been reported
in medieval wall paintings from Italy [23, 25]. The upper
blue layer is hardly preserved due to the smalt deteriora-
tion mentioned above that leads to the detachment of the
smalt grains from the paintings and the widespread loss of
the pigment, and therefore, only the dark grey underpaint
is visible. The above can be a hypothesis, since we do not
have other evidences or observations.
The presence of the blue pigment smalt was identi-
fied with ATR-FTIR spectroscopy (Fig. 21) through the
absorption bands observed at about 1080, 780 cm1 and
690, 460 cm1 that are typical of silicate compounds and
could be assigned to stretching and bending vibrations of
the SiO groups, respectively. The bands present at 1030
S.S. Annunziata Church (LAquila, Italy) unveiled bynon- andmicro-destructive testing
Fig.21S.S. Annunziata
Church: ATR-FTIR spectrum
of Sample 2 (dark greyblue
color)
and 795cm1 may be attributed to the vibrations of alumi-
nosilicate compounds in the glass pigment, and the band at
525cm1 could be assigned to SiO bending vibrations, as
well [2325].
In addition, similar to the examined light green micro-
sample described above, the presence of calcite was iden-
tified in the dark greyblue sample by the characteris-
tic signature bands of CaCO3 (at about 1400, 870, and
710cm1). The assignment of the weak band observed near
1650cm1 to Amide I vibration suggesting that the use of a
protein organic medium could be one of many possibilities,
as well. The above allow us to assume that a fresco-secco
wall painting technique was employed combining limewa-
ter and protein binder.
Finally, based on relative research studies dealing
with the investigation of smalt loss on wall paintings
[25], the authors assumed that the discoloration of smalt
may be possibly attributed to a weakening of the protein
binder, which may undergo oxidative, chemical, and bio-
chemical processes from the environment, humidity, and
microorganisms.
4Conclusions
From the results of the present study, it is possible to affirm
that the joint use of chemical and physical NDT analyses
is highly recommended when an answer to structural and
artistic ambiguities is needed. The methodology explained
herein demonstrates that a periodical monitoring over the
years and/or the application of complementary inspection
methods can contribute to the accurate documentation of
the historical site, helping the work of both the art histo-
rians and the restorers [2731]. The acquisition and inter-
pretation of different informative contents may enhance
the effective decision-making, minimizing the restoration
costs; thus, the above-presented integrated methodology
can also be considered as a smart procedure.
In particular, infrared thermography can contribute
in solving complex cases inherent to buried frescoes, as
Page 11 of 12 215
well as to clarify the activity status of the rising damp
effect, or monitor in retrospect the consolidation process.
In addition, the combined analytical approach
employed in this paper for the characterization of the
wall paintings pigments showed that a deep understand-
ing of the chromatic palette can be obtained through the
use in sequence of the discussed complementary meth-
ods, contributing significantly towards the planning of
the most appropriate conservationrestoration treatments
on mural paintings. Portable FORS technique confirmed
its wide potential as a valuable non-invasive tool for the
in-situ identification of pigments that enables a rapid pre-
liminary investigation of the wall paintings in an effective
manner, thus minimizing the need for subsequent sam-
pling procedures and application of more sophisticated
laboratory methods. Only areas highlighted by FORS
us uncertain cases were further analyzed by means of
ESEM-EDX and ATR-FTIR techniques, which allowed to
verify the previous identifications of pigments as well as
to derive further information on the binding media and
the painting techniques possibly used by the artist. The
analytical approach could be advantageously comple-
mented by cross-sectional analysis of paint samples to
provide information on the painting stratigraphy and reli-
able identification of the executive technique.
Acknowledgements The authors are grateful to Mr. Giovanni
Pasqualoni of the University of LAquila for the valuable assistance
during the IRT inspections. The authors want also to thank the
continuous support of the Soprintendenza per i Beni Ambientali,
Architettonici, Artistici e Storici per lAbruzzo (Italy), as well as Mr.
Antonio Mignemi (restorer) for the kind help during the sample tak-
ing procedure. Finally, the authors are also in debt with Agnese Anna
Aureli (a mother-tongue English professor) for her valuable com-
ments on the English language.
Compliance with ethical standards
Conflict of interest The authors declare that they have no conflict
of interest.
13
 215 Page 12 of 12 S.Sfarra et al.

References technologies. In Proc. of the 8th International Symposium on the

Conservation of Monuments in the Mediterranean Basin, Patras,
Greece, 2010, Vol.2, pp.131141
1. D. Paoletti, D. Ambrosini, S. Sfarra, F. Bisegna, J. Cult. Herit.
17. R. Newman J. Am. Inst. Conserv. 19, 4262 (1979)
14, 116121 (2013)
18. F. Ospitali, D. Bersani, G. Di Lonardo, P.P. Lottici, J. Raman
2. X.P.V. Maldague, Theory and practice of infrared technology
Spectrosc. 39, 10661073 (2008)
for nondestructive testing, 1stedn. (Wiley, New York, 2001), pp.
19. T. Theophanides, J.F. Angiboust, M. Manfait, in Spectroscopic
1704
and Structural Studies of Biomaterials. I. Proteins, ed. by Twar-
3. G. Artioli, Scientific methods and cultural heritagean intro-
dowski (Sigma Press, Wilmslow 1988), pp.312
duction to the application of materials science to archaeom-
20. M. Aceto, A. Agostino, G. Fenoglio, A. Idone, M. Gulmini, M.
etry and conservation science (Oxford University Press, Oxford,
Picollo, P. Ricciardi, J.K. Delaney, J. Anal. Methods (2014).
2010), pp.1560
doi:10.1039/c3ay41904e
4. K. erifaki, H. Bke, S. Yalin, B. Ipekolu, Mater. Charact. 60,
21. M. Picollo, M. Bacci, A. Casini, F. Lotti, S. Porcinai, B. Radi-
303311 (2009)
cati, L. Stefani, in Optical Sensors and Microsystems: New Con-
5. F. Sandrolini, E. Franzoni, Mater. Charact. 61, 97104 (2010)
cept, Materials, Technologies, ed by Martellucci et al (Kluwer
6. P. Ropret, R. Zoubek, A. Sever kapin, P. Bujovec, Mater. Char-
Academic/Plenum Publishers, New York, 2000), pp.259265
act. 58, 11481159 (2007)
22. Fiber Optics Reflectance Spectra (FORS) of Pictorial Materi-
7. Video of the Chiesa S.S. Annunziata a Colle di Roio, uploaded
als in the 2701700 nm range. Database, http://fors.ifac.cnr.it/.
by Struttura del Vice Commissario Delegato per la tutela dei
Accessed 21 June 2016.
beni culturaliIng. Luciano Marchetti, https://www.youtube.
23. S. Daniilia, E. Minopoulou, S.K. Andrikopoulos, A. Tsakalof, K.
com/watch?v=QMYDZ1mUiiU. Accessed 21 June 2016
Bairachtari, J. Archaeol. Sci. 35, 24742485 (2008)
8. X. Maldague, S. Marinetti, J. Appl. Phys. 79, 26942698 (1996)
24. S. Daniilia, E. Minopoulou, Appl. Phys. A- Mater. Sci. Proc. 96,
9. N. Rajic, Compos. Struct. 58, 521528 (2002)
701711 (2009)
10. S. Sfarra, C. Ibarra-Castanedo, D. Ambrosini, D. Paoletti, A.
25. L. Robinet, M. Spring, S. Pages-Camagna, Anal. Methods

Bendada, X. Maldague, Arab. J. Sci. Eng. 39, 34613480 (2014)
(2013). doi:10.1039/c3ay40906f
11. E. Cheilakou, M. Kartsonaki, M. Koui, P. Callet, Int. J. Micro-
26. L. Robinet, M. Spring, S. Pages-Camagna, Investigation of the
struct. Mater. Properties 4, 112127 (2009)
loss of color in smalt on degradation in paintings using multiple
12. E. Cheilakou, M. Troullinos, M. Koui, J. Archaeol. Sci. 41, 541
spectroscopic analytical techniques, In Proc. of the 16th ICOM-
555 (2014)
CC triennial conference, Lisbon, Portugal, 2011
13. E. Cheilakou, V. Dritsa, A. Saint, P. Theodorakeas, M. Koui, K.
27. F. Toschi, A. Paladini, F. Colosi, P. Cafarelli, V. Valentini, M.
Kostanti, A. Christopoulou, Non-invasive identification of pig-
Falconieri, S. Gagliardi, P. Santoro, Appl. Surf. Sci. 284, 291
ments on Mycenaean wall paintings (14th12th Century BC)
296 (2013)
from the archaeological sites of Mycenae and Tiryns, Pelopon-
28. M. Sawczak, A. Kamiska, G. Rabczuk, M. Ferretti, R. Jendrze-
nese. In Proc. of the 9th International Symposium on the Con-
jewski, G. liwiski, Appl. Surf. Sci 255(10), 55425545 (2009)
servation of Monuments in the Mediterranean Basin, Ankara,
29. S. Sfarra, C. Ibarra-Castanedo, M. Tortora, L. Arrizza, G. Ceri-
Turkey, 2014 (in press)
chelli, I Nardi, X. Maldague, J. Cult. Herit. 18, 229241 (2016)
14. M. Elias, C. Chartier, G. Prvot, H. Garay, C. Vignaud, Mater.
30. S. Sfarra, C. Ibarra-Castanedo, S. Ridolfi, G. Cerichelli, D.

Sci. and Eng. B 127, 7080 (2006)
Ambrosini, D. Paoletti, X. Maldague, Appl. Phys. A- Mater. Sci.
15. L.M. Moretto, E.F. Orsega, G.A. Mazzocchin, J. Cult. Herit. 12,
Proc. 115, 10411056 (2014)
384391 (2011)
31. M. Tortora, S. Sfarra, M. Chiarini, V. Daniele, G. Taglieri, G.
16. T. Theophanides, J. Anastasopoulou, Monument damage from
Cerichelli, Appl. Surf. Sci. 387, 971985 (2016)
environmental pollution of ancient marbles using spectroscopic

13