Heritage 02 00080 v3 PDF

heritage
Article
The Effect of Fire on Building Materials: The
Case-Study of the Varnakova Monastery Cells
in Central Greece
Ekaterini T. Delegou 1, *, Maria Apostolopoulou 1 , Ioanna Ntoutsi 1 , Marina Thoma 1 ,
Vasileios Keramidas 1 , Christos Papatrechas 2 , George Economou 2 and Antonia Moropoulou 1, *
1 Laboratory of Materials Science & Engineering, School of Chemical Engineering, National Technical
University of Athens (NTUA), 9 Iroon Polytechniou Str., Zografou Campus, 15780 Athens, Greece;
mairi_apostol@hotmail.com (M.A.); ioanna_ntoutsi@yahoo.gr (I.N.); marina_tho@hotmail.com (M.T.);
bkeramidas@hotmail.gr (V.K.)
2 Institute of Geology and Mineral Exploration (I.G.M.E.), Mineralogy and Petrology Department,
1 Spyrou Loui, Acharnes, 13677 Eastern Attica, Greece; papatrechas@windowslive.com (C.P.);
georgeoik7@gmail.com (G.E.)
* Correspondence: edelegou@central.ntua.gr (E.T.D.); amoropul@central.ntua.gr (A.M.);
Tel.: +30-2107-723-075 (E.T.D.); +30-2107-723-276 (A.M.)

Received: 21 February 2019; Accepted: 17 April 2019; Published: 20 April 2019
Abstract: The evaluation of the fire impact on building materials is of great scientific and
socio-economic importance since fire can result in materials’ chemical and mechanical alterations,
which leads to structural stability problems of historical and/or modern construction. This highly
increases the cost of rehabilitation interventions. The case study of the Byzantine Monastery of
Panagia (Virgin Mary) Varnakova is an example of the fire effect on both historical and newer stone
masonries. The Varnakova Monastery is a typical 19th century monastic complex and, during its
long history, it has undergone multiple reconstructions after major catastrophic events that have
taken place due to its strategic geographical position and its financial and spiritual significance for
the region. The last big-scale renovation of the Monastery was conducted between the years 1992 to
2014. However, in January 2017, a devastating fire destroyed the largest part of the monastic cells’
quarter. In this work, a diagnostic study of the different construction phases’ materials comprising
the masonries of the monastery cells in their present state is presented. The examination of a series
of samples through analytical techniques, such as optical microscopy, X-ray diffraction, thermal
analysis, and total immersion tests, along with the use of non-destructive techniques in situ, such as
Infra Red Thermography, Digital Microscopy, and Schmidt Hammer Rebound tests, shed light on
the preservation state and on the decay of the diverse building materials. In addition, the impact
of the fire on their properties was investigated. The results reveal the diversity of the materials
used in the historical masonries throughout the centuries, while the combination of analytical and
non-destructive techniques demonstrates the damages induced by the fire.
Keywords: stone; mortar; masonry; fire; NDT; IRT; SHR; microscopy; petrography; XRD; TG/DTA
1. Introduction
In recent years, more research has focused on the effect of high temperatures on building
materials [1–16]. The development of high temperatures affects the various characteristics of a material.
Petrographic, mineralogical, chemical, physical, and mechanical properties may alter, depending on
the temperatures developed, the characteristics of the material, the timeframe of the high temperature
event, and the manner of cooling. The assessment of the effect of high temperatures on the building
Heritage 2019, 2, 1233–1259; doi:10.3390/heritage2020080 www.mdpi.com/journal/heritage

Heritage 2019, 2 1234
materials of a structure, especially after a catastrophic event, such as a fire, is crucial in order to evaluate
the safety level of its damaged state and plan appropriate repair measures [10]. This assessment is
even more important in the case of monumental structures, where the historic building materials are
“precious” and should, if possible, be replaced to the minimum extent.
The effect of high temperature on a building material is a complex mechanism and various
material properties must be examined in order to obtain a holistic view of a fire effect. Visual inspection
provides useful information regarding the effect of a fire event, since many damages and decay
patterns are macroscopically manifested, including cracking, surface crazing, deflection, delamination,
color changes, and smoke damage [12,13,15,16].
Petrographic analysis assists not only in the characterization of a stone type, which reveals
composition, texture, binder type, and micro-morphology, but in the evaluation of the effect of
high temperature as well, by examining the alterations observed in these characteristics [2,4–7,10].
A temperature increase induces inter-granular and intra-granular effects on a material while
inter-granular effects are connected to the development of microcracks within the matrix of the material
and are usually the result of different characteristics of the material’s constituents. Intra-granular
effects manifest through the development of microcracks within the grains themselves [1]. Inherent
anisotropy of materials is an example of degradation in the case of thermal loads. For example,
inherent anisotropy of calcite grains, when heated, is considered to be the main agent for marble
and limestones disintegration [11,13]. Mineralogical analysis reveals the alteration of mineralogical
compounds. Thus, the absence or decrease of a compound after the fire event is indicative that the fire
reached a temperature at which the compound’s structure irreversibly collapses and/or is transformed
into an amorphous compound that is no longer detectable [2]. Chemical analysis can reveal alterations
in the composition of the material, which is also connected to transformations that take place during
the fire effect. These alterations include oxidation, dehydration, de-hydroxylation, calcination, and
other processes [6,14]. These processes may infer matrix alterations of a building material and/or
color changes, such as reddening (e.g., when ferrous minerals are included in the material). Thus,
for example, the clay and iron oxides-hydroxides content within a stone or aggregates of a mortar may
be a determinant for a series of transformations induced by heat [16].
Microstructural analysis is of paramount importance since the alteration of microstructural
characteristics affects other properties, such as the behavior of a material under hygro-thermic loads
and compressive strength [1–7,9]. Porosity usually increases when a material is subjected to high
temperatures [1,3], while density decreases due to material loss and compound decomposition,
dehydroxilation, and dehydration processes. Mechanical characteristics are crucial to structural
stability. Compressive strength usually decreases due to the development of microcracks and/or the
increase of porosity [8,9].
The effect of fire and the consequent alterations induced to a material’s characteristics is clearly
dependent on the material itself. In the case of stones, each lithotype presents a different behavior to
fire-attack, depending on pertrographic characteristics, chemical composition, porosity, anisotropy of its
components, etc. For example, granites are more prone to crack when thermally shocked, in comparison
with other softer stones [5]. In quartz-rich sandstones, due to the open porosity they exhibit, as well
as due to their calcitic matrix (which undergoes a parallel calcining process), micro-strains due to
quartz expansion (when it is transformed from α→β at ~575 ◦ C), are absorbed by the matrix [1]. Thus,
knowledge of the type of stone and parallel evaluation of alterations studied in related research and
practice can assist in predicting the alterations induced in a certain lithotype in the event of a fire [12].
In terms of physico-mechanical and structural stability of the monument, it is crucial to assess the
impact of fire damage. In an extent to the above discussion, the indirect consequences to the whole
masonry need to be taken under consideration, during a diagnostic study. Another important aspect to
be explored is the variability of the fire impact parameters on the different lithotypes and parts of the
masonry depending on the diverse temperatures, duration of the event, or other synergic factors (e.g.,
precedent defaults of a masonry block or an isolated stone). Mortars, depending on the mortar type,
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may be more
diffusivity andorhigh
less resistant to a fire event.
incombustibility. For example,
However, the decreaseconcrete
in itspresents low thermal
load-bearing capabilitydiffusivity
and its
and high incombustibility. However, the decrease in its load-bearing capability
“explosive spalling” due to the fire action may compromise these assets, especially when the fire and its “explosive
spalling” dueexceeds
temperature to the fire action
300°C may Taking
[15,16]. compromise these assets,
into account all theespecially
above, the when
fire the fire temperature
impact needs to be
exceeds 300 ◦ C [15,16]. Taking into account all the above, the fire impact needs to be addressed initially
addressed initially in terms of building materials. However, it aims to a holistic perspective by
in terms of
studying thebuilding
structurematerials. However, it aims to a holistic perspective by studying the structure as
as a whole.
a whole.
Within the above framework, this study is an attempt to investigate the effect of the 2017 fire
eventWithin
on thethe above framework,
Varnakova Monastery this study ismaterials
building an attempt to investigate
and the masonriesthe effect of the 2017 Hereby,
they comprise. fire eventthe
on
the Varnakova
preliminary Monastery
results building materials
of a diagnostic and the an
study through masonries they comprise. Hereby,
in situ non-destructive testingthe
and preliminary
an in-lab
results of a diagnostic study through an in situ non-destructive testing and an in-lab
application of analytical techniques on selected samples are presented, which aim to understand the application of
analytical techniques on selected samples are presented, which aim to understand the
effect of the fire on the different lithotypes and mortars comprising the masonries of this historic effect of the fire
on the different lithotypes and mortars comprising the masonries of this historic structure.
structure.
2. Materials
2. Materialsand
andMethods
Methods
2.1. The Varnakova Monastery

2.1. The Varnakova Monastery
The Byzantine Monastery of Panagia (Virgin Mary) Varnakova is located on a mountainous
The Byzantine Monastery of Panagia (Virgin Mary) Varnakova is located on a mountainous
landscape of Southwest Central Greece, at an altitude of 800 m (Figure 1a). Its general structure follows
landscape of Southwest Central Greece, at an altitude of 800 m (Figure 1a). Its general structure
the typical 19th century of a monastic complex with an almost-rectangular courtyard and a church
follows the typical 19th century of a monastic complex with an almost-rectangular courtyard and a
(catholicon) in the center (Figure 1b, topographic depiction: Figure 1c) [17]. The evolution of the
church (catholicon) in the center (Figure 1b, topographic depiction: Figure1c) [17]. The evolution of
architectural phases of the catholicon until the 13th century is reflected in the Ch. Bouras drawing
the architectural phases of the catholicon until the 13th century is reflected in the Ch. Bouras drawing
(Figure 1d) [18].
(Figure 1d) [18].
Figure 1.(a) A general photo of the Varnakova Monastery before the 2017 fire. Arrows and dotted
Figure 1. (a) A general photo of the Varnakova Monastery before the 2017 fire. Arrows and dotted lines
lines indicate the cells’ section and the catholicon. (b) A general photo of the Varnakova Monastery
indicate the cells’ section and the catholicon. (b) A general photo of the Varnakova Monastery after the
after
fire –the fire dotted
yellow – yellow dotted
lines linesthe
indicate indicate the burnt
burnt cells’ area. cells’
(c) A area.(c) A topographical
topographical depiction ofdepiction of the
the complex by
complex by Rural and Survey Engineer S. Zacharopoulos[19].(d) The ground plan
Rural and Survey Engineer S. Zacharopoulos [19]. (d) The ground plan of Ch. Bouras depicting the of Ch. Bouras
depicting the four phases
four architectural architectural
of the phases of the
catholicon catholicon
between between
the 11th the 11
and 13th
th and 13th centuries [18].
centuries [18].
The first church was founded in 1077 AD by Saint Arsenios Varnakovitis. During the 11th and
12 century, it was decorated with wall paintings and on-floor marble mosaics, while the extended
th
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church was founded in 1077 AD by Saint Arsenios Varnakovitis. During the 11th and4
12th century, it was decorated with wall paintings and on-floor marble mosaics, while the extended
renovation
renovation of of 1148–1151
1148–1151 waswas fostered
fosteredbybythe
theByzantine
Byzantineemperors
emperorsofofthetheComnenian
Comnenian Dynasty,
Dynasty, some
some of
of whom
whom were
were buried
buried beneath
beneath the monastery,
the monastery, as referred
as referred by A. by A. Orlandos
Orlandos in his
in his 1922 1922[20].
study studyThe[20]. The
church,
church,
as it wasasatitthe
was at of
time theOrlandos’s
time of Orlandos’s
inspection,inspection,
is referred is
toreferred to as a three-aisled
as a three-aisled basilica withbasilica with
a narthex anda
narthex and a main altar [21].
a main altar [21].
The monastery was almost completely destroyed in 1826, as it served as refuge and base during
The monastery was almost completely destroyed in 1826, as it served as refuge and base during
the Greek War of Independence (1821–1830) against the Ottoman Empire. The reconstruction works
the Greek War of Independence (1821–1830) against the Ottoman Empire. The reconstruction works
commenced soon after the liberation, in 1831, according to the plans made by the architect Andreas
commenced soon after the liberation, in 1831, according to the plans made by the architect Andreas
Gasparis Kalandros, an army lieutenant, and were completed by three Epirot masons by 1838. This
Gasparis Kalandros, an army lieutenant, and were completed by three Epirot masons by 1838. This is
is also the year of the construction of the wooden temple of the catholicon. A. Orlandos uses the term
also the year of the construction of the wooden temple of the catholicon. A. Orlandos uses the term
“hammered limestones” to describe the chosen building material used in this construction phase
“hammered limestones” to describe the chosen building material used in this construction phase [17,21].
[17,21].
Between the years 1992–2014, the monastery was extensively renovated. On 29 January 2017,
Between the years 1992–2014, the monastery was extensively renovated. On 29 January 2017, a
a devastating fire started due to a boiler explosion destroyed the largest part of the monastic cells’
devastating fire started due to a boiler explosion destroyed the largest part of the monastic cells’
quarter [22]. Thus today, the monastery cells are in a state of collapse and in need of major restoration
quarter [22]. Thus today, the monastery cells are in a state of collapse and in need of major restoration
and rebuilding (Figure 2).
and rebuilding (Figure2).
Figure 2. Depiction of the Monastery cells in its present state after the fire, which indicates the
Figure 2. Depiction of the Monastery cells in its present state after the fire, which indicates the external,
external, the intermediate, and the internal masonry. The church, as indicated, is to the east.
the intermediate, and the internal masonry. The church, as indicated, is to the east.
2.2. Visual
Visual Inspection
Inspection
The external (Figure
(Figure 2,
2, Figure
Figure 3a)
3a) and
andthe
theintermediate
intermediatemasonry
masonry(Figure
(Figure2,2,Figure
Figure3d,e)
3d, and Figure
of the cells’
3e) of the
quarter cells’ to
belong quarter belong to
the 1831–1838 the 1831–1838
construction construction
phase, referred tophase, referred
as historic to as historic
masonries. masonries.
It should be noted
It should
that, bethe
during noted that, duringconstruction
aforementioned the aforementioned
phase, theconstruction
intermediatephase,
masonry thewas,
intermediate
in fact, themasonry
masonry
was, in fact, the
surrounding the masonry surrounding
internal courtyard andthe internal
directly courtyard
facing and directly
the Church. facing masonries
The historical the Church. of The
this
historical
phase were masonries
constructed of this
usingphase were lithotypes:
two main constructeda)using two main
a grey-beige lithotypes:
limestone, a) aoccasionally
which grey-beige
limestone,
appears withwhichblackoccasionally appears
veins and b) with black
sandstones veins and
of greenish b) sandstones
to brownish shade.ofIngreenish to brownish
some areas, a black
shade.
compact Instone
somehas areas,
alsoabeen
blacksporadically
compact stone has
used. Atalso been
certain sporadically
areas used. At certain
of the intermediate masonry,areas of the
relatively
intermediate masonry,
recent repointing seemsrelatively recentplace.
to have taken repointing seems to have taken place.
The internal masonry (Figure 2, Figure 3c, and Figure 3f), which faces the courtyard and the
church today, was added during the major reconstruction that took place after 1992. This aims to
improve residential functionality. This new restoration masonry, which is referred to as new
masonry, was raised on an already existing base (19th century construction phase). The building stone
used for the construction of the interior masonry was a freshly-quarried grey-beige limestone, which
greatly resembles the limestone used in the 19th century construction phase masonries.
and Figure 3e). Its building materials present several damages and stone decay patterns such as color
change, spalling, and flaking (Figure 4a). The western façade of this masonry (interior of domestic
cells) was covered in plaster including remnants that still remain.
iii) Finally, the new masonry was strongly affected by the fire on its western façade (the one facing
Heritage 2019, 2 1237
the cells corridor). However, its eastern façade (the one facing the courtyard) seems to be unaffected
(Figure 3f, Figure 4b).
Figure 3. Different areas of the cells quarter: (a) the exterior of the external wall (historic masonry),
(b) the plastered interior façade of the external wall presenting severe damages from the fire (historic
masonry), (c) the lower part of the internal wall facing the courtyard (new masonry raised on a historic
base), (d) the historic intermediate masonry,(e) detail from the fire-affected intermediate masonry,
base), (d) the historic intermediate masonry, (e) detail from the fire-affected intermediate masonry, and
and (f) the new masonry of the cells’ quarter: its exterior façade seems intact after the fire, while its
(f) the new masonry of the cells’ quarter: its exterior façade seems intact after the fire, while its interior
interior has suffered fire damage.
has suffered fire damage.
The internal masonry (Figure 2, Figure 3c,f), which faces the courtyard and the church today, was
added during the major reconstruction that took place after 1992. This aims to improve residential
functionality. This new restoration masonry, which is referred to as new masonry, was raised on an
already existing base (19th century construction phase). The building stone used for the construction
of the interior masonry was a freshly-quarried grey-beige limestone, which greatly resembles the
limestone used in the 19th century construction phase masonries.
The visual inspection of the fire-exposed masonries allowed for the following observations:
i. The exterior façade of the external masonry (Figure 3a), which faces to the west, does not
present any apparent damage from the fire. The interior plastered facade (Figure 3b) has clearly
been affected, which displays blackened areas from the smoke produced during the fire, while
partial plaster detachments can be noticed. Unfortunately, the total destruction of the wooden
floors restricted access to these areas during this preliminary study.
ii. The historic intermediate masonry seems to have been severely affected by the fire (Figure 3d,e).
Its building materials present several damages and stone decay patterns such as color change,
spalling, and flaking (Figure 4a). The western façade of this masonry (interior of domestic cells)
was covered in plaster including remnants that still remain.
iii. Finally, the new masonry was strongly affected by the fire on its western façade (the one facing
the cells corridor). However, its eastern façade (the one facing the courtyard) seems to be
unaffected (Figure 3f, Figure 4b).
base), (d) the historic intermediate masonry,(e) detail from the fire-affected intermediate masonry,
Heritage
and (f) 2the new masonry of the cells’ quarter: its exterior façade seems intact after the fire, while its 1238
2019,
interior has suffered fire damage.
Figure 4. (a) Collapse of building materials from the upper part of the intermediate masonry.
(b) Discolorations and scaling of the beige-grey limestone on the interior (western) façade of the
new masonry.
2.3. Investigation Techniques and Methodology

A variety of techniques were used in the current study, which aim to evaluate the preservation
state of the masonries and their building materials comprising them, after the effect of fire. Due to the
different exposure of the building materials to the fire event, it was possible to select samples with a
varying degree of fire damage, which is affected and not affected. This facilitated the evaluation of the
fire effect on the examined building materials.
Analytical techniques were applied in the lab after sampling and were used in order to characterize
the building materials and diagnose their decay due to the fire effect. Optical microscopy (OM) was
employed for the petrographic characterization of the stone samples, using a ZEISS-AXIOSKOP 40
microscope, while a ProgRes-C14PLUS camera and ProgRes Capture Pro2.1 software were used for
taking and editing microphotographs of the samples. Digital Microscopy (DM, i-scope, Moritex) was
applied to examine the morphology and texture of the mortars under investigation. X-Ray Diffraction
(XRD), using an Advanced D8 Diffractometer by Bruker, was applied for the identification of the
crystalline compounds of selected stone and mortar samples, which aim to ascertain the mineralogical
transformations due to the fire. Simultaneous Differential Thermal and Thermogravimetric Analysis
(DTA/TG, Regulus 2500, Netzsch) was implemented on selected stone and mortar samples for the
qualitative and quantitative determination of their compounds. The analyses were carried out at
30–1000 ◦ C temperature range with a heating rate of 10 ◦ C/min in a nitrogen atmosphere. Selected
stone and mortar samples also underwent total water immersion tests [23], which aim to estimate the
porosity accessible to water by total immersion for each sample, their water absorption capacity and
apparent density, and, consequently, the alterations of these characteristics due to the fire effect.
In addition to the analytical techniques, non destructive techniques (NDTs) were applied in situ.
In particular, Schmidt hammer rebound tests (SHR) were conducted on several building stones from
various areas of the cell masonries in order to evaluate surface hardness of the various lithotypes [24–26]
as well as its modification due to the fire effect. A Proceq N-type hammer (impact energy: 2.207 N m)
was used, which followed the operation guidelines [27]. An average of 10 impacts was performed on
each of the examined building elements. All tests were performed with the hammer held perpendicular
to the examined surface. For the statistical elaboration of the results, both the mean value (Rm) and the
median value (RM) were calculated, while, in order to compare the dispersion of the measurements,
the coefficient of variation (COV) was also estimated.
Infra-Red Thermography (IRT, B200, FLIR) was used to evaluate the preservation state of the
masonry as a whole, by investigating representative areas [28–30]. The passive approach implemented
aimed to reveal any temperature gradations of the different building materials consisting of the
masonry after the fire effect.
Heritage 2019, 2 1239

The methodological approach followed in this study is schematically represented in Figure 5.
The evaluation was conducted on two levels: building elements scale and masonry scale. The evaluation
in its current condition (fire-affected). The evaluation on building material scale assists in the
on material level is necessary in order to succeed in the evaluation on the masonry level, since the
interpretation of the IRT results and, consequently, in the assessment of the overall preservation state
individual materials comprise and, therefore, affect the overall performance of the masonry.
of the masonry as a whole.
Figure 5. Diagram summarizing the methodological approach followed in this study.

Figure 5. Diagram summarizing the methodological approach followed in this study.
3. Results and Discussion

The evaluation on building materials scale was conducted both in lab and in situ. The in
lab evaluation aimed to reveal petrography and texture characteristics of the various building
3.1. Characterization
materials, of the Building
their mineralogical Materials composition, and physical characteristics, such as porosity,
and chemical
bulk density, and water uptake. In the present study, OM, DM, XRD, TG/DTA, and total water
3.1.1. Investigation of the Building Stones
immersion tests were conducted in lab for the previously mentioned purposes. The in situ evaluation
The stone
on building samplesscale,
materials selected for in-lab
aimed examination
to estimate are described
their surface in the
hardness, following
using SHR. table (Table
All the above1).
The stone samples
measurements werewere collected
applied on both from fire affected
fire-affected andand seemingly
seemingly unaffected
unaffected stone areas of thein
elements masonry.
order to
achieve a comparison of their properties’ modification because of the fire event. In situ non destructive
testing by IRT wasTable
used1.Description of the selected
as a tool in order stonethe
to evaluate samples from thestate
preservation cells’ of
quarter.
the masonry (masonry
scale) in
Stone its current condition (fire-affected). The evaluation on building material scale assists in the
interpretation
Sample of the IRT results and, consequently, in theDescription
Sample assessment of the overall preservation state
of theCode
masonry as a whole.
Sandstone of green hue. Collected from intermediate historic masonry, which is
3. Results and Discussion
V1 seemingly unaffected by the fire area (based on visual inspection). Second most
abundant stone type used in the monument.
3.1. Characterization of the Building Materials
Sandstone sample, collected from intermediate historic masonry, from a fire-
V2
3.1.1. Investigation of the Building Stones affected area of the masonry.
The stone samplesCompact
selected black stoneexamination
for in-lab collected from
are adescribed
severely fire-affected areatable
in the following of the(Table 1).
V5
intermediate masonry.
The stone samples were collected from fire affected and seemingly unaffected areas of the masonry.
Grey-beige limestone from the new masonry (internal wall), which is a seemingly
V6
unaffected by the fire area.
V7 Grey-beige limestone from the historic intermediate masonry, affected by the fire.
V8 Grey-beige limestone from the new masonry (internal wall), affected by the fire.
Limestone, with two distinct zones, one black and one grey-beige, the later similar
V9
to V7, unaffected by the fire (based on visual inspection).
Limestone, with two distinct zones (beige-gray and black), severely affected by
V10
fire.
Petrographic Examination of the Lithotypes

Heritage 2019, 2 1240
Table 1. Description of the selected stone samples from the cells’ quarter.
Stone Sample Code Sample Description

Sandstone of green hue. Collected from intermediate historic masonry, which is seemingly unaffected by the
V1
fire area (based on visual inspection). Second most abundant stone type used in the monument.
V2 Sandstone sample, collected from intermediate historic masonry, from a fire-affected area of the masonry.
V5 Compact black stone collected from a severely fire-affected area of the intermediate masonry.
V6 Grey-beige limestone from the new masonry (internal wall), which is a seemingly unaffected by the fire area.
V7 Grey-beige limestone from the historic intermediate masonry, affected by the fire.
V8 Grey-beige limestone from the new masonry (internal wall), affected by the fire.
Limestone, with two distinct zones, one black and one grey-beige, the later similar to V7, unaffected by the
V9
fire (based on visual inspection).
V10 Limestone, with two distinct zones (beige-gray and black), severely affected by fire.
Petrographic Examination of the Lithotypes

The petrographic examination was performed on selected samples from different areas of the
historic and new masonries. Samples were collected from fire affected and non-affected masonry
areas based on visual inspection, which aim to trace the heating impact on the mineralogical and
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characteristics of the different lithotypes. 8
One of the Themain building

petrographic stones used
examination in the historic
was performed masonries
on selected of 1831
samples from (second
different areas most
of the abundant
stone typehistoric
used and in the
new masonries. Samples were collected from fire affected and non-affected masonry and lithic
monument) is a clastic calcite sandstone consisting of crystalline
areas based
fragments. The sandstone on visual sample
inspection,V1which
wasaim nottoaffected
trace the heating
by theimpact on the mineralogical
fire, based on the visual andinspection
micro-structural characteristics of the different lithotypes.
(Figure 6a). According to the petrographic examination (Figure 6b), the crystalline fragments include
One of the main building stones used in the historic masonries of 1831 (second most abundant
quartz SiOstone
2 , feldspars
type used[albite
in the (NaAlSi
monument) 3 Ois8 ),a and
clasticmicrocline (KAlSi
calcite sandstone 3 O8 )], calcite
consisting CaCOand
of crystalline 3 , muscovite
lithic folia
[indicativefragments.
formula:TheKAl 2 (AlSi3sample
sandstone O10 )(F,OH)
V1 was2 ], notand grains
affected of iron
by the and zirconium
fire, based on the visual oxides/hydroxides.
inspection
(Figure6a).consists
The lithic fraction According oftoquartzite,
the petrographic examination
limestone, slate,(Figure 6b), the crystalline
serpentine, fragments include
and sub-volcanic rock fragments.
quartz SiO2, feldspars [albite (NaAlSi3O8), and microcline (KAlSi3O8)], calcite CaCO3, muscovite folia
The cementing material of the clasts is of sparitic calcite nature. V2 is a sandstone sample of a
[indicative formula: KAl2(AlSi3O10)(F,OH)2], and grains of iron and zirconium oxides/hydroxides. The
fire-affected
lithicarea of consists
fraction the historic masonry
of quartzite, limestone,(Figure 6c). Theand
slate, serpentine, petrographic
sub-volcanic rockresults depict
fragments. The oxidation
phenomena of iron-containing minerals. This is macroscopically manifested by
cementing material of the clasts is of sparitic calcite nature. V2 is a sandstone sample of a fire-affected the reddening of
the sample.area of the historic masonry (Figure 6c). The petrographic results depict oxidation phenomena of
iron-containing minerals. This is macroscopically manifested by the reddening of the sample.
Figure 6. (a) Photograph of sandstone sample V1. (b) The crystalline and lithic fragments of the
(a) Photograph
Figure 6. sandstone of sandstone
are observed. sample
The cementing V1.
material is of(b) The crystalline
a sparitic calcite natureand lithic
(crossed fragments
Nicols). (c) of the
sandstonePhotograph
are observed. The sample
of sandstone cementing
V2. (d) material is of a sparitic
Oxidation phenomena of iron calcite
compoundsnature (crossed
into the stone Nicols).
mass (crossed
(c) Photograph Nicols). sample V2. (d) Oxidation phenomena of iron compounds into the stone
of sandstone
mass (crossed Nicols).
A compact black stone detected on some areas of the historic masonry is a chert (Figure7a,
sample V5). This stone type is sporadically detected in the historic masonries. It was collected from a
severely fire-affected area of the intermediate masonry. The stone consists of several zones. In
Figure7b, three zones are discerned downwards: a) the upper fossiliferous limestone comprising
sparitic fossils (mostly foraminiferal species) bound to a micritic mass, b) the intermediate zone of
large rhomboid dolomite [CaMg(CO3)2] crystals,and c) the chert zone consisting of amorphous
siliceous material and scattered dolomite crystals. Likewise, in Figure 7c, there is an additional zone
where intense diffusion of iron hydroxides is distinguished (dark brown area, Figure 7c). This
Heritage 2019, 2 1241
A compact black stone detected on some areas of the historic masonry is a chert (Figure 7a, sample
V5). This stone type is sporadically detected in the historic masonries. It was collected from a severely
fire-affected area of the intermediate masonry. The stone consists of several zones. In Figure 7b,
three zones are discerned downwards: a) the upper fossiliferous limestone comprising sparitic fossils
(mostly foraminiferal species) bound to a micritic mass, b) the intermediate zone of large rhomboid
dolomite [CaMg(CO3 )2 ] crystals, and c) the chert zone consisting of amorphous siliceous material and
scattered dolomite crystals. Likewise, in Figure 7c, there is an additional zone where intense diffusion
of iron hydroxides
Heritage2019, 2 FORis distinguished
PEER REVIEW (dark brown area, Figure 7c). This phenomenon is evident 9in the
Heritage2019,
fossiliferous 2 FOR PEERzone
limestone REVIEW
(Figure 7f). The chert zone is depicted in Figure 7d–e where joints9filled
with Figure
carbonate7d–7e where joints
material filled with
and super carbonateiron
fine-grained material and
pyrite super fine-grained
crystals iron pyrite crystals
are observed.
Figure
are 7d–7e where joints filled with carbonate material and super fine-grained iron pyrite crystals
observed.
are observed.
Figure 7. (a) Photograph of sample V5. (b,c) The stone constitutes of three to four zones (crossed
Figure 7. (a) Photograph
Figure 7.(d)(a)The
Photograph
of sample
of is
V5. V5.
sample
(b,c)(b,c)
TheThe
stone constitutes of three
stone
to four zones (crossed Nicols).
Nicols). chert zone traversed by joints filled constitutes of three
with carbonate to four
content, zones
while (crossed
super fine-
(d) The chert zone
Nicols). iron
(d) The is traversed
chert by joints filled with carbonate content, while super fine-grained
super fine- iron
grained pyrite is, zone
also, is traversed
observed by joints
(crossed filled (e)
Nicols). with carbonate
The content,
chert zone while
consists of amorphous
pyrite is, also,
grained observed
iron pyrite (crossed
is, also, Nicols).
observed (e) The
(crossed chert
Nicols).zone
(e) consists
The chertof amorphous
zone consists
siliceous material and scattered iron pyrite crystals, (metallographic microscope, incident light). (f)ofsiliceous
amorphousmaterial
and scattered
siliceous iron pyrite
material and crystals,
scattered (metallographic
iron pyrite crystals,microscope,
(metallographicincident light).
microscope,
The fossiliferous limestone zone. The orange hue is attributed to the diffusion of iron hydroxides (f) The
incident fossiliferous
light). (f)
limestone
The zone. The
fossiliferous
(parallel Nicols). orange
limestone hue is
zone. attributed
The orange to the
hue diffusion
is of
attributed iron
to thehydroxides
diffusion of(parallel
iron Nicols).
hydroxides
(parallel Nicols).
The Thelimestone used
limestone in inthe
used thenew newmasonry
masonry (internal wall,1992
(internal wall, 1992 reconstruction)
reconstruction) is a is a grey-beige
grey-beige
The
biomicritic limestone used in the new masonry (internal wall, 1992 reconstruction) is
biomicritic limestone (sample V6, visually fire non-affected, Figure 8a). The matrix of the stonestone
limestone (sample V6, visually fire non-affected, Figure 8a). The matrix a
of grey-beige
the is of is of
biomicritic
micritic
micritic texture, limestone
texture, while
while (sample
traces
traces ofofV6, visually
fossilsand
fossils fire
andspariticnon-affected, Figure
sparitic foraminiferal
foraminiferalspecies8a).
speciesThe matrix
areare
detectedof the
inside
detected stone is ofstone
the stone
inside the
micritic
mass.mass.
A greattexture,
A great
numberwhile
number traces
of of of
joints,
joints, fossils and
filledwith
filled sparitic
withsecondary foraminiferal
secondary calcite, species
calcite,traverse
traverse are
thethe detected
stone mass
stone inside
(Figure
mass the stone
8b). 8b).
(Figure
mass. A great number of joints, filled with secondary calcite, traverse the stone mass (Figure 8b).
Figure 8. (a) Photograph of limestone sample V6. (b) Grey-beige micritic fossiliferous limestone: the
Figure of
matrix 8. (a)
thePhotograph of limestone
stone is ofofmicritic sample
texture, V6.
whileV6. (b) of
traces Grey-beige
fossils andmicritic fossiliferous
sparitic foraminiferallimestone: are
the
Figure 8. (a) Photograph limestone sample (b) Grey-beige micritic fossiliferousspecies
limestone: the
matrix of the stone is of micritic texture, while traces of fossils and sparitic foraminiferal
detected inside the stone mass. A great number of joints, filled with secondary calcite, traverse the species are
matrix of the stone is of micritic texture, while traces of fossils and sparitic foraminiferal species are
detected inside the stone
stone mass (parallel Nicols). mass. A great number of joints, filled with secondary calcite, traverse the
detected
stoneinside the stone
mass (parallel mass. A great number of joints, filled with secondary calcite, traverse the
Nicols).
stoneThe
mass
new(parallel
masonryNicols).
is comprised solely of the grey-beige biomicritic limestone (V6). Sample V8
The new
was also masonry
collected fromisthe
comprised solely from
new masonry of thean
grey-beige
area highlybiomicritic
affected limestone
by the fire(V6). Sample
(Figure 9a), V8
as
was also collected
indicated, from the
not only from thelocation
new masonry from an
of the sample, area
but fromhighly affected
its pinkish hueby as the
well.fire (Figure
This 9a), as
is confirmed
indicated,
by not only fromasthe
optical microscopy, V8location
presentsofsimilar
the sample, but from its
characteristics to pinkish hue(Figure
sample V6 as well.9b).
ThisHowever,
is confirmed
the
by optical microscopy, as V8 presents similar characteristics to sample V6 (Figure 9b).
effect of the fire is evident through the widening and rupture of the joints filled with secondaryHowever, the
effect of the fire is evident through the widening and rupture of the joints filled with secondary
Heritage 2019, 2 1242
The new masonry is comprised solely of the grey-beige biomicritic limestone (V6). Sample V8 was
also collected from the new masonry from an area highly affected by the fire (Figure 9a), as indicated,
not only from the location of the sample, but from its pinkish hue as well. This is confirmed by optical
Heritage2019, 2 FOR PEER
Heritage2019, PEER REVIEW
REVIEW 10
microscopy,2 FORas V8 presents similar characteristics to sample V6 (Figure 9b). However, the effect of the 10
fire is evident
calcite, which through
is an thecommonly
an effect
effect widening and rupture
observed inof the joints filled
limestones whenwith secondary
exposed calcite,
to extreme
extreme which is an
temperatures
calcite, which is commonly observed in limestones when exposed to temperatures
effect
(Figure commonly
9c). observed in limestones when exposed to extreme temperatures (Figure 9c).
(Figure 9c).
Figure 9.
Figure 9. (a)
(a) Photograph
Photograph of of fire-effected
fire-effected limestone
limestone sample
sample V8.
V8. (b)
(b) Grey-beige
Grey-beige micritic
micritic fossiliferous
fossiliferous
Figure 9. (a) Photograph of fire-effected limestone sample V8. (b) Grey-beige micritic fossiliferous
limestone:
limestone: the matrix of the stone is of micritic texture, while traces of fossils and sparitic foraminiferal
limestone: the
the matrix
matrix of
of the
the stone
stone isisof
ofmicritic
micritictexture,
texture, while
while traces
traces of
offossils
fossilsand
andsparitic
foraminiferal
species are
species are detected
detected inside
inside thethe stone
stone mass.
mass. A A great
great number
number of of joints,
joints, filled
filled with
with secondary
secondary calcite,
calcite,
species are detected inside the stone mass. A great number of joints, filled with secondary calcite, traverse
traverse
traverse the stone mass (parallel Nicols). (c) Joint rupture with a width range of 15–18μm (crossed
the stonethe
massstone mass Nicols).
(parallel (parallel(c)Nicols). (c) Jointwith
Joint rupture rupture with
a width a width
range range
of 15–18 µmof(crossed
15–18μm (crossed
Nicols).
Nicols).
Nicols).
One of the main construction materials of the historic masonry is a grey-beige micritic fossiliferous
One of the
the main construction
construction materials
materials ofof the
the historic
historic masonry
masonry is is aa grey-beige
grey-beige micritic
micritic
limestone.of
One Samplemain
V7 was collected from a severely damaged area of the intermediate masonry, which
fossiliferous limestone.
fossiliferous limestone. Sample
Sample V7 waswas collected from
from aa severely
severely damaged
damaged area
area of
of the
the intermediate
intermediate
was clearly affected by the fire V7
(Figure collected
10a). This damaged historical stone, as expected, presents
masonry,
masonry, which
which was
was clearly
clearly affected
affected by
by the
the fire
fire (Figure
(Figure 10a).
10a). This
This damaged
damaged historical
historical stone, as
stone, as
similar petrographic characteristics to the damaged limestone collected from the new masonry (V8),
expected,
expected, presents
presents similar petrographic
similar petrographic characteristics
characteristics to the
to the damaged limestone collected from the
which confirms macroscopic observations. Joint ruptures are damaged limestone
also evident. However,collected from thea
they present
new
new masonry (V8), which confirms macroscopic observations. Joint ruptures are also evident.
largermasonry (V8), which
width, ranging from 35confirms
µm to 65macroscopic observations. Joint ruptures are also evident.
µm (Figure 10b,c).
However, they present a larger width, ranging from 35μm to 65μm (Figure 10b,
However, they present a larger width, ranging from 35μm to 65μm (Figure 10b, Figure 10c). Figure 10c).
Figure 10. (a)

Figure (a) Photograph of of fire-effected limestone
limestone sample
sample V7.V7. (b) Grey-beige
Grey-beige micritic fossiliferous
fossiliferous
Figure 10.
10. (a) Photograph
Photograph of fire-effected
fire-effected limestone sample V7. (b)
(b) Grey-beige micritic
limestone: the
limestone: the matrix
the matrix of
matrix of the
of the stone
the stone
stone isis of
isof micritic
ofmicritic texture,
micritictexture, while
texture, while traces
while traces
traces ofof fossils
offossils and
fossilsand sparitic
andsparitic foraminiferal
foraminiferal
species are
species aredetected
are detectedinside
detected inside
inside the
thethe stone
stone
stone mass.
mass.
mass. A great
A
A great great number
number
number of joints,
of
of joints, joints, filled
filled
filled with with secondary
with
secondary secondary calcite,
calcite,
calcite, traverse
traverse
traverse
the the
stonethe stone
stone
mass mass (crossed
mass
(crossed (crossed (c)
Nicols). Nicols).
Nicols). (c) Joint
(c) Jointwith
Joint rupture rupture
rupture withrange
with
a width aa width
width range
range
of 35 ofµm
to 65of 35 (crossed
35 to 65μm
to 65μm Nicols).
(crossed
(crossed
Nicols).
Nicols).
In both fire-affected samples of the grey-beige fossiliferous limestone (V8 from new masonry,
In both
In
V7 from both fire-affected
fire-affected
historic masonry), samples
samples of the
of
stylolites the grey-beigewhile
are grey-beige
detected, fossiliferous
fossiliferous limestone
limestone
iron hydroxides and(V8clay
(V8 from
from new masonry,
new
minerals masonry,
seem to
V7
V7
havefrom
from historic
historic
intruded masonry),
masonry),
into their mass. stylolites
stylolites are detected,
are detected,
In parallel, while iron hydroxides
while mentioned,
as previously iron hydroxides and
both and clay minerals
clay present
samples seem
mineralsa seem to
to
distinct
have intruded
have
pinkishintruded into
color. into their
The their mass.
visualmass. In parallel,
In
reddening parallel,
of theasasstone
previously
previously mentioned,
mentioned,
is attributed both
to theboth samples
samples
oxidation present
ferrous aaminerals
ofpresent distinct
distinct
pinkish
pinkish color.
and the color. The
The of
diffusion visual
visual reddening
ironreddening
hydroxides of the
of due stone
the stone is attributed
to theishigh
attributed to the oxidation
to the oxidation
temperatures developed of ferrous
of ferrous minerals
duringminerals and
and
the burning
the diffusion
the
eventdiffusion
(Figureofof iron
9b,iron hydroxides
hydroxides
Figure due to
due to the
10b,c). Generally, thethehigh
high temperatures
temperatures
reddening developed
developed
of limestones dueduring
during the
to thethe burningofevent
burning
oxidation event
iron
(Figure
(Figure
compounds 9b, Figure
9b, Figure 10b,
begins10b, and Figure
and Figure
at 250–300 ◦ 10c).
C, 10c).
but may Generally,
Generally, the reddening
the reddening
not be evident before ofof limestones
◦
thelimestones
400 C when due
duetheto the
to the oxidation
oxidation
color change
of iron
of iron compounds
becomes compounds
more intense begins
begins at 250–300
at
[10,31]. 250–300 °C, but
°C, but may
This discoloration may not as
not
serves be an
be evident
evident before
before
indication the
of the
the 400400 °C
°C when
minimum when the color
the color
temperature
changereached
change
range becomes
becomes morethe
more
during intense
intense [10,31].
fire in[10,31].
this area. This discoloration
This discoloration serves
serves as as an
an indication
indication of of the
the minimum
minimum
temperature range reached during the fire
temperature range reached during the fire in this area. in this area.
Sample V9
Sample V9 waswas collected
collected fromfrom the the historic
historic intermediate
intermediate masonry,
masonry, and and visual
visual inspection
inspection
indicated that
indicated that it
it was
was not
not affected
affected byby the
the fire.
fire. Macroscopically,
Macroscopically, the the lithotype
lithotype presents
presents twotwo distinct
distinct
zones of different coloration (black and grey-beige, Figure11a). The matrix of
zones of different coloration (black and grey-beige, Figure11a). The matrix of the stone is of micritic the stone is of micritic
texture, while
texture, while traces
traces ofof fossils
fossils and
and sparitic
foraminiferal species
species are
are detected
detected inside
inside the
the stone
stone mass.
mass. A A
great number of joints, filled with secondary calcite, traverse the stone mass
great number of joints, filled with secondary calcite, traverse the stone mass (Figure 11b). The grey- (Figure 11b). The grey-
Heritage 2019, 2 1243
Sample V9 was collected from the historic intermediate masonry, and visual inspection indicated
that it was not affected by the fire. Macroscopically, the lithotype presents two distinct zones of different
coloration (black and grey-beige, Figure 11a). The matrix of the stone is of micritic texture, while traces
of fossils and sparitic foraminiferal species are detected inside the stone mass. A great number of joints,
filled with secondary
Heritage2019, calcite, traverse the stone mass (Figure 11b). The grey-beige biomicritic limestone
2 FOR PEER REVIEW 11
is accompanied by laminae of a black-grey fossiliferous limestone comprising foraminiferal species
comprising foraminiferal
of sparitic texture bound to species of sparitic
a micritic texture bound
mass. Oxidized grainstoofaferrous
micriticminerals
mass. Oxidized
are, also,grains of
detected
comprising foraminiferal species of sparitic texture bound to a micritic mass. Oxidized grains of
ferrous
(Figure minerals
11c). are, also, detected (Figure 11c).
ferrous minerals are, also, detected (Figure 11c).
Figure 11. (a) Photograph of limestone sample V9 where two zones are distinct. (b) On the left, the
grey-beige micritic fossiliferous limestone zone and, on the right, the grey-black fossiliferous
Figure 11. (a)
(a) Photograph
Photograph of
of limestone
limestone sample
sample V9 where two zones are distinct.
distinct. (b) On the left, the
Figure 11.
limestone zone, (parallel Nicols). (c) Grains of V9
ironwhere two
oxides zones
close to are
the interface(b)
of On
the the
twoleft, the
zones
grey-beige
grey-beige micritic
limestone zone
zone and, and,
on on
the the
right, right,
the the
grey-blackgrey-black fossiliferous
(parallel Nicols).
limestone zone,
zone, (parallel (parallel
Nicols). Nicols).of(c)
(c) Grains Grains
iron oxidesofclose
irontooxides close toofthe
the interface the interface
two zonesof(parallel
the twoNicols).
zones
(parallel Nicols).
Based on visual inspection, a fire-affected sample of the above-described lithotype from the
Based on visual inspection, a fire-affected sample of the above-described lithotype from the
historic intermediate masonry was, also, examined (Figure 12, Sample V10). The visual reddening of
Based
historic on visual masonry
intermediate inspection,
was,a also,
fire-affected
examined sample of 12,
(Figure theSample
above-described lithotype
V10). The visual from the
reddening of
the stone is attributed to the oxidation of ferrous minerals and the diffusion of iron hydroxides due
historic
the stoneintermediate
is attributedmasonry was, also,
to the oxidation examined
of ferrous (Figureand
minerals 12,the
Sample V10).ofThe
diffusion ironvisual reddening
hydroxides due of
to
to the high temperatures developed during the burning event (Figures12 a, 12b, and 12c), as also
the stone is attributed to the oxidation of ferrous minerals and the diffusion of iron
the high temperatures developed during the burning event (Figure 12a–c), as also noticed in samples hydroxides due
noticed in samples V8 and V7. The capillary rupture observed in the stone mass constitutes a micro-
to the
V8 andhigh temperatures
V7. The developed
capillary rupture duringinthe
observed theburning event
stone mass (Figures12a micro-structural
constitutes a, 12b, and 12c), change,
as also
structural change, as an additional result of the fire impact on the beige-grey limestone zone. The
noticed in samples
as an additional V8 and
result V7.
of the The
fire capillary
impact rupture
on the observed
beige-grey in the zone.
limestone stone mass constituteslimestone
The black-grey a micro-
black-grey limestone zone does not present any significant difference from the V9 sample, which was
structural
zone does not present any significant difference from the V9 sample, which was not affected by the The
change, as an additional result of the fire impact on the beige-grey limestone zone. fire.
not affected by the fire.
black-grey limestone zone does not present any significant difference from the V9 sample, which was
not affected by the fire.
Figure 12. (a) Photograph of fire-affected limestone sample V10. (b) The capillary rupture of some μm
Figure 12. (a) Photograph of fire-affected limestone sample V10. (b) The capillary rupture of some µm
width observed in the stone mass constitutes a micro-structural change. The orange hue is due to the
width
Figureobserved in the stone
12. (a) Photograph of mass constitutes
fire-affected a micro-structural
limestone sample V10. change. The orange
(b) The capillary hue is
rupture ofdue to μm
some the
diffusion of iron hydroxides and infers the visually observed reddening of the stone (parallel Nicols).
diffusion
width of ironin
observed hydroxides and infers
the stone mass the visually
constitutes observed reddening
a micro-structural of the
change. The stone hue
orange (parallel
is dueNicols).
to the
(c) Oxidation of iron compounds due to the high temperature during the fire (parallel Nicols).
(c) Oxidation
diffusion of iron
of iron compounds
hydroxides due tothe
and infers thevisually
high temperature during theoffire
observed reddening the(parallel Nicols).Nicols).
stone (parallel
(c) Oxidation of iron compounds due to the high temperature during the fire (parallel Nicols).
Mineralogical Examination of the lithotypes through X-ray Diffraction
Mineralogical Examination
Mineralogical of the
examination
examination lithotypes
was
was conductedthrough
conductedonly onX-ray
only Diffraction
on samples
samples of theofmain
the building
main building
stones ofstones of
historic
historic
and new and new masonries,
masonries, sandstone
sandstone samples samples
V1, V1,limestone
V2, and V2, and limestone
samples samples V6, V7,Theand V8. The
Mineralogical examination was conducted only on samples of V6,
theV7, and
main V8.
building lithotypes
stones of
lithotypes
were were pulverized
pulverized and studiedand studied
through through
X-ray X-rayThe
diffraction. diffraction.
results The
are results are in
summarized summarized
Table in
2. The
historic and new masonries, sandstone samples V1, V2, and limestone samples V6, V7, and V8.
TableRegarding
2.
lithotypes were the green sandstone,
pulverized boththrough
and studied unaffected anddiffraction.
X-ray affected samples (V1 and
The results areV2, respectively)
summarized in
Regarding
present similar the green sandstone,
mineralogical both unaffected
composition, with quartz and
as affected
the samples
principal (V1 and V2,
mineralogical respectively)
component and
Table 2.
present
calcite, similarmuscovite,
albite, mineralogical composition, with quartz as the principal mineralogical component
sampleand
Regarding the greenand chlorite both
sandstone, as accessory mineralogical
unaffected and affectedcomponents.
samples (V1 However,
and V2, in V1,
respectively)
calcite, albite, muscovite, and chlorite as accessory mineralogical components. However, in sample
present similar mineralogical composition, with quartz as the principal mineralogical component and
V1, microcline is detected, while, in sample V2, it is not detected. This is in accordance to other studies
calcite, albite, muscovite, and chlorite as accessory mineralogical components. However, in sample
that have demonstrated that microcline does decrease as the temperature of the stone increases [32].
V1, microcline is detected, while, in sample V2, it is not detected. This is in accordance to other studies
Regarding the beige-grey limestone, the only lithotype used in the new masonry and the most
dominant in the historic ones, no alterations are noticed in relation to mineralogical composition
Heritage 2019, 2 1244
microcline is detected, while, in sample V2, it is not detected. This is in accordance to other studies
Table 2. XRD analysis of stone samples.
Sample Code Mineralogical Composition (XRD Analysis)

Principal mineralogical components Accessory mineralogical components
V1 Quartz calcite, albite, microcline, muscovite, chlorite
V2 Quartz calcite, albite, muscovite, and chlorite
V6 Calcite quartz
V7 Calcite quartz
V8 Calcite quartz
dominant in the historic ones, no alterations are noticed in relation to mineralogical composition
between the unaffected (V6) and the affected by the fire samples, from both the new (V8) and the
historic masonry (V7). Thus, the beige-gray limestone presents calcite as its principal mineralogical
component and quartz as an accessory.
Compositional analysis of stone samples through simultaneous thermal analysis (TG/DTA)

The previously mentioned stone samples (V1, V2, V6-V8) were also examined through
simultaneous thermal analysis, which aim to reveal modifications in their chemical composition
due to the fire. The results are presented in Table 3, which report the mass loss (%) measured in specific
temperature ranges.
Table 3. TG results of stone samples.
Mass Loss (%) per Temperature Range (◦ C)

Stone Sample Code
<120 ◦ C 120–200 ◦ C 200–600 ◦ C >600 ◦ C
V1 0.20 0.04 1.19 5.44
V2 1.11 0.13 1.04 1.64
V6 0.14 0.03 0.23 39.30
V7 0.17 0.02 0.36 38.99
V8 0.12 0.01 0.16 38.92
The unaffected sandstone sample V1 presents distinct differences in relation to the affected ones by
the fire sandstone sample V2. In particular, sample V2 presents a higher amount of physically bound
water in comparison to V1 (increased mass loss in temperature range 30–120 ◦ C), which indicates a
modification in the microstructure that increases water uptake from the environment after the effect of
the fire. In addition, the mass loss above 600 ◦ C, which is connected to the decomposition of carbonate
compounds, is also distinctly different. The affected sample V2 presents a much lower carbonate
content indicating that the calcite binding material of the matrix of the sandstone was reduced due
to the fire, which confirms OM observations. It should be noted that, in the DTA curve, the distinct
endothermic peak connected to quartz transition from α→β is noticed at ~575 ◦ C. Although the
carbonate compounds’ decomposition endothermic peak is clear in the unaffected sample (~770 ◦ C),
it is not discernable in the fire-affected sample V2.
The beige-grey limestone of the historic and new masonries (V6-V8) seems to be unaffected by the
fire in relation to its chemical composition. All samples present similar mass losses in all temperature
ranges, which is independent of the fire effect. This confirms XRD results as well. The decomposition
temperature of the carbonate compounds was detected above 800 ◦ C.
Total Immersion Results on Stone Lithotypes

Total immersion was conducted on the stone samples, which aim to evaluate their porosity (%)
accessible to water through total immersion. Water Absorption Capacity (WAC%) was calculated,
Heritage 2019, 2 1245
while the apparent density of the samples was calculated as well. The results are summarized in
Table 4.
Table 4. Total water immersion tests results – stones.
Stone Sample Code Porosity (%) Bulk Density (g/cm3 ) W.A.C. (%)
V1 3.7 2.4 1.5
V2 6.1 2.2 2.8
V6 2.6 2.3 1.1
V7 2.9 2.1 1.4
V8 2.1 2.3 0.9
The characteristics of the unaffected and fire-affected sandstone samples display diverse values,
which confirm a visual inspection observation regarding their state. In particular, the affected sample,
V2, presented a higher porosity (~6% in relation to 3.7%), which indicates the creation of pores and
micro-cracks. This alteration is consistent with the different mass loss values demonstrated by TG
measurements in temperatures above 600 ◦ C. Bulk density is slightly decreased from 2.4 g/cm3 to
2.2 g/cm3 due to the porosity increase and transformation, which take place on a mineralogical and
chemical level. The water absorption capacity of the sandstone increases after the fire-event, as expected.
The later statement is also evident through the higher mass loss detected for the affected stone through
TG attributed to physically bound water (mass loss <120 ◦ C).
The beige-grey limestone, on the other hand, seems not to be affected in relation to its physical
characteristics, which is also noticed in the mineralogical and thermal analysis results. Porosity of the
unaffected limestone (V6) and the fire-affected one (V8), from the new masonry, is very close (2.6% and
2.1%, respectively). Bulk density values are identical (2.3 g/cm3 ), while water absorption capacity of
the affected and non-affected samples are also extremely close (1.1%, 0.9%). The fire-affected limestone
sample from the historic intermediate masonry (V7) also presents similar values to the previously
mentioned samples, as expected since they are of the same lithotype. Its slightly higher porosity (2.9%)
could be attributed to ageing processes in addition to the fire effect. The same is true for the slightly
lower bulk density that it exhibits (2.1 g/cm3 ) in relation to the new masonry fire-affected limestone
V8 (2.3 g/cm3 ), as well as the slightly higher water absorption capacity it presents (1.4% in relation
to 0.9%).
3.1.2. Investigation of the Mortars

Mortar samples were collected from both the historic intermediate masonry and the new masonry.
The mortar samples’ description, along with characteristic digital microscopy images depicting their
surface texture, are presented in Table 5.
for the slightly lower bulk density that it exhibits (2.1 g/cm ) in relation to the new masonry fire-
affected limestone V8 (2.3g/cm3), as well as the slightly higher water absorption capacity it presents
(1.4% in relation to 0.9%).
3.1.2. Investigation of the Mortars

Mortar samples were collected from both the historic intermediate masonry and the new
Heritage 2019, 2 masonry. The mortar samples’ description, along with characteristic digital microscopy images 1246
depicting their surface texture, are presented in Table5.
Table 5.Description of the selected mortar samples from the cells’ quarter.
Table 5. Description of the selected mortar samples from the cells’ quarter.
Mortar
Sample Description DM Image
Sample Code
Mortar Sample Code Sample Description DM Image
Structural soft mortar of clay texture

Heritage2019, 2 FOR PEERand
REVIEW 14
Structural soft mortar ofhue
light-orange claywith blackened
texture and
light-orange external
hue with surface
blackeneddue to thesurface
external smokedue
Vm1 Heritage2019, 2 FOR PEER REVIEW
Vm1to the smoke deposition-upper part of the historical 14
deposition-upper part of the historical
intermediate
Heritage2019, 2 FOR PEER REVIEW masonry (above 2 m). 14
intermediate masonry (above 2m).
Joint mortar of cementitious texture

from a severely fire-affected area from
Vm2 the middle part of the new masonry
Joint mortar of cementitious texture from a severely
(~1.5m).
Vm2 fire-affected area from the middle part of the new
masonry (~1.5 m).

and dark-orange
Structural hue from
soft mortar of claythetexture
upper
Vm3 part
and of the historical
dark-orange intermediate
hue from the upper
Structural soft mortar of2m).
clay texture
Vm3 part ofmasonry (above
the historical intermediate
and dark-orange
Structural softmasonry
mortar hue
clayfrom
of(abovetexturethe upper
Structural soft mortar clayand
of 2m). texture
Vm3 Vm3dark-orange part of the
hue from thehistorical
upper partintermediate
of the historical
and dark-orange
intermediate masonry hue from
(above 2 the upper
m).
masonry (above 2m).
Vm3 part of the historical intermediate
masonry (above 2m).

and yellow soft
Structural hue mortar
from the ofupper part of
clay texture
Vm4 theyellow
and historical
hue intermediate
from the masonry
upper parthue
of
Structural soft mortar of
Structural clay
soft textureofand
mortar yellow
Vm4 from the upper
the historical (above 2m). clay
intermediate
texture
masonry
Vm4 part of the historical intermediate
and yellow
masonry
hue from2 the
(above m).
upper part of
Structural (above
soft mortar2m).
of clay texture
Vm4 the historical intermediate masonry
and yellow hue from the upper part of
(above 2m).
(above 2m).

Structuraland
soft yellow hue
mortar of
Structural from
clay
soft the
texture
mortar upper
ofand parthue
yellow
clay textureof
Vm5 Vm5 from theand
theyellow
upper historical
hueintermediate
part of the masonry
historical intermediate
from the upper part of
masonry
Structural (above
soft 22m).
mortar
(above m).
of clay texture
Vm52 FOR PEERthe
Heritage2019, historical
REVIEW intermediate masonry 15
Structural (above
soft 2m).
mortar of clay texture
Heritage2019,
Vm52 FOR PEERthe
REVIEW
historical intermediate masonry 15
(above 2m).
(above 2m).
In-depth mortar of mixed

In-depthcementitious
In-depth
mortar of mixedand clay of
mortar texture
cementitiousmixed from
and claya
Vm6 texture fromseverely fire-affected
a severely
cementitious area
fire-affected
and clay areaatatthe
texture thelower
lower
from a
Vm6
partIn-depth
part of the historical mortar masonry
intermediate
of the historical of mixed(<1 m).
intermediate
severely fire-affected area at the lower
Vm6 cementitious and clay
masonry texture from a
(<1m).
partIn-depth
of the historical
mortar intermediate
of mixed
Vm6 masonry (<1m).
cementitious and clay texture from a
part of the historical intermediate
Vm6 masonry (<1m).
part of the historical intermediate
Joint mortarmasonry (<1m). texture
of cementitious
from a severely fire-affected area with
Joint mortar of cementitious
Joint texture from atexture
mortar of cementitious severely
fire-affected blackened
areaawith externalexternal
blackened surface due todue
from severely fire-affectedsurface
area with
Vm7 Vm7 to smokesmoke deposition
deposition - lower
- lower part part
of the of the
historical
intermediate
blackened
masonry
external surfacearea
(same sampling
duewith
to
historical intermediate masonry (same
Vm7 smoke deposition
Vm6, <1 m)- lower part of the
sampling area with Vm6, <1m)

(above 2m).
(above 2m).
blackened external surface due to
Vm7 smoke deposition - lower part of the
blackened external surface due to
Heritage 2019, 2 Vm7 smoke deposition - lower part of the 1247
Table 5. Cont.
Mortar Sample Code Sample Description DM Image

Structuraland
soft yellow hue
mortar of from
clay the upper part of
texture
(above 2m).and yellow hue
Vm8 Vm8 from the upper
the historical intermediate
part of the masonry
masonry (above
(above 22m).
m).

and
Joint mortar of pinkish hue texture
cementitious from aandseverely fire-
pinkish hue
Vm9 Vm9from a severely
affected area at the
fire-affected arealower part of
at the lower theof
part
andthepinkish
new
hue
masonry
from a severely
(<1 (<1m).
m).
fire-
new masonry
Vm9 affected area at the lower part of the
new masonry (<1m).
3.1.3. Mineralogical Examination

3.1.3. Mineralogicalof the Mortar
Examination of theSamples through
Mortar Samples throughX-Ray Diffraction
X-Ray Diffraction
3.1.3.XRD results areExamination

Mineralogical presented in Table
of the 6Mortar
and show that the
Samples principal
through mineralogical
X-Ray Diffractioncomponent phase
XRD results are ofpresented in Table
the clay textured mortars6(Vm1,
and Vm3,show that
Vm4, the
Vm5, principal
and mineralogical
Vm8) is quartz. The previously component
mentioned phase
XRD results are presented in Table 6 and show that the principal mineralogical component phase
samples
of the clay textured mortars all display an
(Vm1,mortars adequate
Vm3,(Vm1,
Vm4, presence
Vm5, of calcite and muscovite. Chlorite is also detected in
of the clay textured Vm3, Vm4,andVm5, Vm8) isisquartz.
and Vm8) The
quartz. The previously
previously mentioned
mentioned
samples Vm4, Vm5, and Vm8, while microcline is detected in Vm5 and Vm8. In Vm5, the presence
samples all display an adequate
samples presence
all display of
an adequate calcite and
presence muscovite.
of calcite Chlorite
and muscovite. is
Chlorite also detected
is also in samples
detected in
of microcline is increased. Albite is detected with a high presence in samples Vm1 and Vm5 and with
samples Vm4, Vm5, and Vm8, while microcline is detected in Vm5 and Vm8. In Vm5, the presence
Vm4, Vm5, and Vm8,aofwhile microcline
lower presence is
in sample detected
Vm3. in Vm5 and Vm8. In Vm5, the presence
microcline is increased. Albite is detected with a high presence in samples Vm1 and Vm5 and with
of microcline
is increased. Albite aislower
detected with
presence in a Vm3.
sample high presence in samples Vm1 and Vm5 and with a lower
presence in sample Vm3.
Table 6. XRD analysis of mortars’ samples.
Sample Code Mineralogical Composition (XRD Analysis)

Principal mineralogical components Accessory mineralogical components
Vm1 Quartz Calcite, albite, muscovite
Vm2 Calcite Quartz, albite
Vm3 Quartz Calcite, muscovite, albite
Vm4 Quartz Calcite, muscovite, chlorite
Vm5 Quartz Microcline, albite, calcite, muscovite, chlorite,
Vm6 Quartz, calcite Muscovite
Vm7 Calcite, quartz albite
Vm8 Quartz calcite, muscovite, microcline, chlorite
Vm9 Calcite, quartz -
Samples Vm2, Vm6, Vm7, and Vm9 are fire-affected mortars of a cementitious texture.
Vm2 presents calcite as a principal mineralogical component and quartz and albite as accessory
minerals. Vm6, which is of a mixed clay-cementitious texture, presents quartz and calcite as the
main mineralogical components, while muscovite is also present. Vm7 presents calcite and quartz as
principal mineralogical components, and albite is also detected. Vm 9 from the new masonry and an
area that was severely affected by the fire presents only calcite and quartz as mineralogical components,
with no secondary accessory minerals. It is thus evident, that all cementitious textured mortars present
a high amount of calcite in relation to other minerals. Contrary to the cementitious textured mortars,
the clayey textured mortars present quartz as principal mineralogical component, except for Vm6,
which presents both quartz and calcite in high abundance, thus confirming to a certain extent the DM
microscopy results regarding this sample’s mixed texture (Table 5).
3.1.4. Compositional Analysis of Mortar Samples through Simultaneous Thermal Analysis (TG/DTA)
Thermal analysis results are presented in Table 7, where the weight loss percentages per
temperature range are presented. Each temperature range corresponds to different processes: (i) the
Heritage 2019, 2 1248
mass loss observed in the <120 ◦ C temperature range is due to the loss of physically bound water
(H2 OPBW ), (ii) the mass loss detected in the range 120–200 ◦ C is attributed to the loss of the crystalline
water of salts (e.g., gypsum), (iii) the mass loss observed in the temperature range 200–600 ◦ C is
attributed to chemically-bound water (H2 0SWB ) (e.g., dehydroxylation of clay minerals, dehydration
of aluminosilicates, or calcium aluminosilicate phases etc.), (iv) the mass loss detected in the range
>600 ◦ C is attributed to the decomposition of carbonates and consequent CO2 loss [33]. The inverse
hydraulicity index is calculated as the ratio CO2 /H2 0SWB and is widely used in order to evaluate
the hydraulicity of a mortar (lower inverse hydraulicity indexes are indicative of more hydraulic
mortars) [34].
Table 7. TG results of mortars’ samples.
Mass Loss (%) per Temperature Range (◦ C)

Mortar Sample Code CO2 /H2 OCBW
<120 ◦ C 120–200 ◦ C 200–600 ◦ C >600 ◦ C
Vm1 1.17 0.44 4.02 7.96 1.98
Vm2 0.54 0.22 1.49 20.19 13.55
Vm3 1.00 0.25 2.84 8.32 2.93
Vm4 1.17 0.45 4.32 8.41 1.95
Vm5 1.23 0.43 3.81 7.33 1.92
Vm6 1.23 0.27 3.31 14.45 4.37
Vm7 1.37 0.51 2.99 20.93 7.00
Vm8 1.28 0.47 4.04 6.62 1.64
Vm9 1.50 0.62 3.11 18.57 5.97
All samples present mass losses attributed to physically bound water between 1% and 1.5%, except
for the cementitious textured mortar Vm2, which presents 0.54%. They also present low mass losses
in the temperature range of 120 to 200 ◦ C, which indicates extremely low percentages of crystalline
water bound to hygroscopic salts. Chemically bound water presents dispersion among the mortar
samples ranging from 1.49% to 3.11% for the cementitious-textured mortars, and 2.84% to 4.32% for the
clayey textured mortars. Sample Vm6, which is of a mixed texture, presents a chemically-bound water
percentage higher than the cementitious-textured mortars and within the range of the clayey textured
mortars. All cementitious-textured mortars present relatively high mass losses attributed to the loss
of CO2 due to the decomposition of carbonate materials (ranging from 18.57% to 20.93%), while all
clayey textured mortars present lower mass losses in the previously mentioned range (ranging from
6.62% to 8.41%). Sample Vm6, of a mixed texture, presents a CO2 mass loss value intermediate of the
cementitious and clayey textured mortars. The mass loss values attributed to CO2 loss also indicate
the siliceous and mixed carbonate and siliceous nature of the aggregates of all mortars investigated.
However, the CO2 /H2 OCBW ratio is used to determine whether a mortar is of hydraulic nature.
In the present study, it is used, in addition to the mass loss attributed to the decomposition of
carbonates above 600 ◦ C, to discriminate clay mortars from cement mortars aimed to ascertain their
nature (Figure 13). It is clear that the “clayey” mortars (Vm1, Vm3, Vm4, Vm5 and Vm8) are all
grouped in a very tight area, while the “cement textured” mortars are also grouped, but with a wider
distribution. The mixed-textured sample, Vm6, falls between the two groups, in closer vicinity to the
cement textured mortars. The thermal analysis results indicate that there are two types of mortar in the
masonry, namely clay mortars and cement-based mortars. The thermal analysis results, in combination
with the mineralogical analysis, indicate relatively high carbonation of the cement-based mortars,
especially in the case of Vm2, which was located in the middle part of the new masonry.
Heritage 2019, 2 1249
Figure 13. Correlation of CO2 and the CO2 /H2 OCBW ratio. The clay mortar group and cement-based
Figure 13. Correlation of CO2 and the CO2/H2OCBW ratio. The clay mortar group and cement-based
mortar group are indicated.
mortar group are indicated.
3.1.5. Total Immersion Results on Mortar Samples
3.1.5. Total Immersion Results on Mortar Samples
Total water immersion tests were conducted on selected mortar samples. Since it was not
possible to water
Total immersion
conduct tests were on
these measurements conducted
all mortaron selected
samples, mortar
due samples.
to their Since
poor state it was not
of preservation
possible to conduct
and consequent these measurements
dissolution on all mortar samples,
in water, measurements due
were only to their poor
conducted on state of preservation
samples Vm2, Vm9
and consequent dissolution in water, measurements were only conducted on samples Vm2,
(cement-based mortars), and sample Vm4 (clay mortar). The results are summarized in the following Vm9
(cement-based
table (Table 8). mortars), and sample Vm4 (clay mortar). The results are summarized in the following
table (Table 8).
Table 8. Total water immersion tests results – mortars.
Table 8. Total water immersion tests results – mortars.
Mortar Sample Code Porosity (%) Bulk Density (g/cm3 ) W.A.C. (%)
Mortar Sample
Vm2 17.00 1.45 14.33
Code Vm4 Porosity (%) Bulk Density (g/cm3) W.A.C. (%)
31.18 1.63 25.38
Vm2 Vm9 22.00 1.34 17.15
17.00 1.45 14.33
Vm4 31.18 the highest porosity accessible
1.63
The clay mortar (V4) presents to water (31.18%),25.38as expected for
a mortarVm9 of this category. The cement mortars present relatively
22.00 1.34 high porosity values 17.15of 17% and
22% The
for samples Vm2(V4)
clay mortar andpresents
Vm9, respectively.
the highestHowever, this is distinctly
porosity accessible to water lower than the
(31.18%), clay mortar.
as expected for
aTheir porosity
mortar of thisvalues, in addition
category. The cement to thermal
mortarsanalysis results,
present confirm
relatively highaporosity
high level of carbonation,
values of 17% and which
22%
is probably
for samples dueVm2toandtheVm9,
fire effect and the consequent
respectively. However, thismicrostructure alteration.
is distinctly lower Theclay
than the water absorption
mortar. Their
capacity values,
porosity of the clay mortar is
in addition to the highest
thermal among
analysis the examined
results, confirm asamples (25.38%),
high level while thewhich
of carbonation, cementis
mortars present similar values (14.33% and 17.15%). Regarding bulk density,
probably due to the fire effect and the consequent microstructure alteration. The water absorption the cement mortars
Vm2 andof
capacity Vm9
the present values
clay mortar is very low foramong
the highest cementthemortars,
examined which is clearly
samples due to their
(25.38%), whilepoor state of
the cement
preservation (1.45similar3
g/cm and 1.34(14.33% 3
g/cm ) because of theRegarding
fire effect. This
mortars present values and 17.15%). bulkresult can the
density, alsocement
be attributed
mortarsto
a mixed cement-lime composition of the cement-based mortars (which present
Vm2 and Vm9 present values very low for cement mortars, which is clearly due to their poor state of lower bulk densities
than cement (1.45
preservation mortars)
g/cmwithout
3and 1.34diminishing
g/cm3) because theofdestructive roleThis
the fire effect. of the firecan
result event.
also Vm 4, which to
be attributed is
3
athe clay cement-lime
mixed mortar examined, presents
composition of athe
bulk density of 1.63g/cm
cement-based . This present
mortars (which is an intermediate
lower bulk value for
densities
historic mortars.
than cement mortars) without diminishing the destructive role of the fire event. Vm 4, which is the
clay mortar examined, presents a bulk density of 1.63g/cm3. This is an intermediate value for historic
3.2. SHR Results
mortars.
AREA 1 (Figure 14) is the area left of the entrance to the Monastery and is mainly comprised of
the beige-grey limestone and the sandstone. The results from the SHR measurements are presented in
3.2. SHR Results

Heritage 2019, 2 1250
AREA 1 (Figure 14) is the area left of the entrance to the Monastery and is mainly comprised of
the beige-grey limestone and the sandstone. The results from the SHR measurements are presented
Table 9. As already mentioned, this part of the masonry belongs to the historical phase of 1831-1838
in Table 9. As already mentioned, this part of the masonry belongs to the historical phase of 1831-
and is seemingly unaffected by the fire. The highest Rebound value corresponds to the black chert,
1838 and is seemingly unaffected by the fire. The highest Rebound value corresponds to the black
which is found as an inclusion inside the limestone in this area. The grey-beige limestone presents
chert, which is found as an inclusion inside the limestone in this area. The grey-beige limestone
higher surface hardness index values than the sandstone examined.
presents higher surface hardness index values than the sandstone examined.
Figure 14. AREA 1: The exterior of the external masonry, on the left of the entrance to the monastic
Figure 14. AREA 1: The exterior of the external masonry, on the left of the entrance to the monastic
cells quarter (historic
cells quarter (historic masonry,
masonry, western
western façade).
façade). Bullets
Bullets and
and numbering
numbering indicate
indicate where
where the
the SHR
SHR
measurements were performed.
measurements were performed.
Table
Table 9. SHR values
9.SHR values from
from the
the AREA
AREA 11 (see
(see Figure
Figure 14).
AREA
AREA 11
Type of Lithotype
Type of Lithotype Rm Rm RmedianRmedian COV% COV%
1.1.Beige - grey
Beige - grey limestone
limestone 51.04 ± 1.97 50.00 ±50.00
51.04 ± 1.97 1.25 ± 1.25 7.6 7.6
2. 2.
Sandstone
Sandstone 43.96 ± 3.14
43.96 ± 3.14 44.00 ± 2.25
44.00 ± 2.25 7.14 7.14
3.3.Black
Black chert inclusion
chert inclusion 56.92 ± 4.72
56.92 ± 4.72 58.50 ±58.50 5.3 ± 5.3 8.30 8.30
4. Beige - grey limestone
4.Beige
4a. Black- calcite
grey limestone
vein 47.58 ± 14.20 42.75 ± 7.75 29.84
4b. 4a. Black calcite
Beige-grey vein
limestone 47.58 ± 14.20 49.50 ±42.75
50.08 ± 5.22 3.50 ± 7.75 10.4229.84
4b. Beige-grey limestone 50.08 ± 5.22 49.50 ± 3.50 10.42
The
The eastern façade of the intermediate historic masonry (AREA 2) was investigated after
eastern façade of the intermediate historic masonry (AREA 2) was investigated after being
being
divided
divided perper height
height in intwo
twoareas:
areas:below
below5050cm cmandandabove
above1 1meter (Figure15a
m (Figures 15aand
and15b).
15b). This
This area
area was
was
completely
completely affected by the fire burning and presents the most intense deterioration patterns, such as
affected by the fire burning and presents the most intense deterioration patterns, such as
extreme scalingof
extreme scaling ofthe
thebeige-grey
beige-greylimestone
limestone andand exfoliation
exfoliation of the
of the sandstones.
sandstones. TheThe
blackblack
chertchert
was was
also
also examined
examined (Figure(Figure 15a, sub-area
15a, sub-area 2). latter
2). This This latter
type oftype of stone
stone seemsseems macroscopically
macroscopically less affected
less affected by the
by the fire, but presents a SHR value decrease close to 50% compared to the
fire, but presents a SHR value decrease close to 50% compared to the value from the fire unaffected value from the fire
unaffected
masonry (Figuremasonry (Figure1,14—AREA
14—AREA sub-area 3).1,Insub-area 3). the
both zones, In beige-grey
both zones, the beige-grey
limestone presentslimestone
the lower
presents the lower Rebound values compared to the green sandstone,
Rebound values compared to the green sandstone, which indicates a higher deterioration level which indicates a higher
due to
deterioration level due
the fire event (Table 10). to the fire event (Table 10).
The lower value for the sandstone, from all examined areas, was recorded in the intermediate
Heritage 2019,
masonry 2
(Figure 15c, sub-area 6), in an area severely affected by the fire. This higher alteration of 1251
the
sandstone surface in this area may indicate a higher exposure of this part of the masonry at the fire.
Figure 15.
Figure AREA 2:
15. AREA 2: Intermediate
Intermediatemasonry
masonryof of the
the cells
cells quarter
quarter (historic
(historic wall,
wall, eastern
eastern façade).
façade). Bullets
Bullets
and numbering
and numbering indicate
indicate the
the areas
areas where
where the
the SHR
SHRmeasurements
measurements werewere performed:
performed: (a)
(a)Three
Threesub-areas
sub-areas
examined below 50 cm. (b) Two sub-areas examined above 1 m. (c) The examined
examined below 50 cm. (b) Two sub-areas examined above 1 m. (c) The examined fire affected fire affected
sandstone. Bullets and numbering indicate where the SHR measurements were
sandstone. Bullets and numbering indicate where the SHR measurements were performed. performed.
Table 10. SHR values from the AREA 2 (see Figure 15).
Table 10.SHR values from the AREA 2 (see Figure 15).
AREA 2- Under 50 cm Height
AREA 2- Under 50 cm Height
Type of Lithotype Rm Rmedian COV%
Type of Lithotype Rm Rmedian COV%
1.1.Sandstone
Sandstone 42.14 ± 2.67 ± 2.67
42.14 42.00 ±42.00
3.00 ± 3.00 6.34 6.34
2. Black chert 30.00 ± 3.96 30.50 ± 4.50 13.19
2.Black chert
3. Beige-grey limestone
30.00 ± 3.96
15.79 ± 1.95
30.50 ± 4.50 12.38
16.25 ± 2.00
13.19
3. Beige-grey limestone 15.79 ± 1.95 16.25 ± 2.00 12.38
AREA 2 –above 1 m height
AREA 2 –above 1m height
17.14 ± 1.52 17.00 ± 1.10
4. 4. Beige-grey limestone
Beige-grey limestone 17.14 ± 1.52 17.00 ± 1.10 8.87 8.87
5. Sandstone 36.87 ± 2.54 36.90 ± 2.5 6.88
5. Sandstone 36.87 ± 2.54 36.90 ± 2.5 6.88
Sub-Area 6
Sub-Area 6
6.6.Sandstone
Sandstone 25.83 ± 5.29 ± 5.29
25.83 28.00 ±28.00
6.00 ± 6.00 20.46 20.46
The plastered
The lower value south-western
for the sandstone,façadefromof the intermediate
all examined masonry
areas, (AREAin3)the
was recorded had also been
intermediate
impacted
masonry (Figure 15c, sub-area 6), in an area severely affected by the fire. This higher alteration3.5
by the fire (Figure 16). The three-layer plaster has a total width that varies from of cm
the
(thicker
sandstonelayer in theinwestern
surface this areaside)
may to 2 cm (thinner
indicate a higherlayer on the
exposure of southern side).
this part of The SHRattests
the masonry the were
fire.
performed in both south-western
The plastered sides of the stone blocks
façade of the(west and south
intermediate sides) and
masonry (AREAafter
3) the
hadfull
alsoremoval of the
been impacted
overlying
by the fireplaster.
(Figure The
16). overall results are
The three-layer presented
plaster in Table
has a total width11. During
that variesthe
from procedure, the higher
3.5 cm (thicker layer
Rebound valuesside)
in the western weretomeasured
2 cm (thinnerat the points
layer of the
on the stone that
southern were
side). Thecovered
SHR testsby were
the thicker
performedplasterin
layer on the western stone side. This may indicate an increased protective function
both sides of the stone blocks (west and south sides) and after the full removal of the overlying plaster. of the thicker
plaster layerresults
The overall on thearemasonry.
presentedTheinreduction
Table 11. in the SHR
During the index for the
procedure, thebeige-grey limestone
higher Rebound is lower
values were
compared to the eastern façade of the intermediate masonry, which was un-plastered,
measured at the points of the stone that were covered by the thicker plaster layer on the western stone since it used
to be the
side. external
This wall ofan
may indicate theincreased
cells’ rooms (see Table
protective 10). of the thicker plaster layer on the masonry.
function
The reduction in the SHR index for the beige-grey limestone is lower compared to the eastern façade of
the intermediate masonry, which was un-plastered, since it used to be the external wall of the cells’
rooms (see Table 10).
Heritage 2019, 2 1252
Figure 16. AREA 3: South-Western façade of the intermediate masonry. The area was examined after
Figure 16. AREA 3: South-Western façade of the intermediate masonry. The area was examined
the plaster’s removal. (a) South façade of the intermediate masonry. (b) Western façade of the
after the plaster’s removal. (a) South façade of the intermediate masonry. (b) Western façade of the
intermediate
intermediate masonry.
masonry. Numbering
Numbering indicates
indicates the
the corner-stones
corner-stones examined
examined by
by SHR
SHR from
from south
south to
to west.
west.
Table 11.
Table SHRvalues
11.SHR valuesfrom
fromAREA
AREA33(see
(seeFigure
Figure16).
16).
AREA3
AREA3
TypeTypeof ofLithotype
Lithotype Rm Rm Rmedian RmedianCOV% COV%
1. Sandstone
1. Sandstone 47.35
47.35 ± 1.33 ± 1.33 47.00 ± 0.85 47.00 ± 0.85 2.82 2.82
2. Sandstone
2. Sandstone 34.57 ± 4.0234.50 ± 4.5034.50 ± 4.5011.64
34.57 ± 4.02 11.64
3. Beige- grey
3. Beige- limestone
grey limestone 42.5 ± 5.6242.5 ± 5.62 43.00 ± 5.2543.00 ± 5.2513.22 13.22
4. Beige-grey limestone
4. Beige-grey limestone 46.16 ± 4.69
46.16 ± 4.69 44.50 ± 5.30 44.50 ± 5.30 10.17 10.17
In order to further estimate the fire impact on the grey compact limestone, a wall pillar from the
new masonry
In order to (northern façade, from
further estimate interior
the fire impact to on
exterior)
the grey was examined
compact (Figure a2 wall
limestone, and Figure 3f). the
pillar from
new This part of
masonry the masonry
(northern façade, was
fromconstructed
interior tobetween
exterior)the wasyears 1992 to(Figures
examined 2014. The 2 and2017’s
3f). fire event
left intact the of
This part exterior façadewas
the masonry of the masonrybetween
constructed (easternthe façade,
years the
1992one facing
to 2014. Thethe2017’s
courtyard) while
fire event left
intense
intact thefireexterior
effects façade
are observed at the interior
of the masonry (eastern (western)
façade, thefaçade,
one such
facingasthediscoloration,
courtyard) while scaling, and
intense
detachments.
fire effects are The area under
observed at the examination,
interior (western)depicted
façade,in such
Figureas 17, was divided
discoloration, into zones
scaling, for the SHR
and detachments.
measurements to be carried out. a) a fire-affected zone (FAZ), according
The area under examination, depicted in Figure 17, was divided into zones for the SHR measurements to visual inspection with a
total
to belength
carriedofout.
approximately 8 cm,zone
a) a fire-affected where a burnt
(FAZ), front, facing
according to visualwest (interior with
inspection façade), andlength
a total a burnt of
zone, facing north,
approximately 8 cm,are whereevident.
a burntb)front,
A potentially
facing west fire unaffected
(interior zone
façade), and(FUZ),
a burntwhich
zone, wasfacingfurther
north,
examined
are evident. bothb)inAthe middle and
potentially fire in the outer zone
unaffected side of each stone
(FUZ), whichblock, and c) an
was further in-between
examined bothzone of
in the
~10 cm length.
middle and in theTheouter
total side
width of thestone
of each wall block,
is 51 cm,
andwhile
c) an the SHR measurements
in-between zone of ~10 cm were conducted
length. in
The total
awidth
height of of
thesixwall
stone arrays
is 51 (total height
cm, while the SHR around 60 cm). The
measurements were results are presented
conducted in a height in Table
of six 12. A
stone
progressive
arrays (totaldecline
height in the Rebound
around 60 cm). values is observed.
The results The most
are presented affected
in Table 12. area i.e. the FAZ
A progressive burnt in
decline front
the
presents
Reboundan approximate
values is observed. loss The
of SHR
mosthardness valuei.e.
affected area of the
52%–58%
FAZ burnt compared to the macroscopically
front presents an approximate
perceived
loss of SHR sound zones.value
hardness The SHR values ofcompared
of 52%–58% the beige-greyto thelimestone, which are
macroscopically visually sound
perceived perceived as
zones.
fire
The unaffected
SHR valueszones,of the are similar limestone,
beige-grey to the oneswhichreceived from theperceived
are visually fire unaffected AREA 1 (Figure
as fire unaffected zones, 14,
are
Table
similar 9).to the ones received from the fire unaffected AREA 1 (Figure 14, Table 9).
Heritage 2019, 2 1253
Figure 17. AREA 4: New masonry (Northern façade). The pillar is built from the beige-grey limestone.
Figure 17. AREA 4: New masonry (Northern façade). The pillar is built from the beige-grey limestone.
The
The examined areas by
examined areas by SHR
SHR are
are labeled.
labeled.
Table
Table 12. SHR values
12.SHR values from
from the
the AREA
AREA 44 (see
(see Figure
Figure 17).
AREA
AREA 44
TypeofofFire-Affected
Type Fire-Affected Zone
Zone Rm Rm Rmedian
Rmedian COV%
COV%
Fire Affected Zone(FAZ)
Fire Affected Zone (FAZ)
FAZ burnt front 23.86 ± 1.95 23.50 ± 2.50 8.18
FAZ burnt front 23.86 ± 1.95 23.50 ± 2.50 8.18
FAZ burnt
FAZ burnt zonezone 32.57 32.57
± 1.99 ± 1.99 33.5033.50
± 2.50± 2.50 6.10 6.10
Zone between FAZ & FUZ 48.93±3.67 48.50 ± 3.10 7.5
Zone between FAZ & FUZ 48.93±3.67 48.50 ± 3.10 7.5
Fire Unaffected Zone (FUZ)
Fire Unaffected Zone (FUZ)
FUZ middle side 50.25 ± 4.80 49.50 ± 5.50 9.5
FUZ
FUZmiddle
outerside
side ± 4.80 ± 3.38
50.25 57.14 ± 5.50± 4.00
49.5056.00 9.5 5.91
FUZ outer side 57.14 ± 3.38 56.00 ± 4.00 5.91
3.3. IRT Inspection

3.3. IRT Inspection
IRT investigation took place on several parts of the new and the historical masonry, and some
IRT investigation
characteristic results aretook place on
presented several parts of the new and the historical masonry, and some
below.
characteristic results are presented below.
The higher masonry part of the new masonry (above 1m) presents lower temperature readings
The higher
compared to the masonry part ofpart,
lower masonry the new masonry
as well (above 1m) presents
as an intermediate lowerdistribution
temperature temperaturewidth
readings
of 3
compared to the lower masonry part, as well as an intermediate temperature
°C (from 23 °C to 27 °C), (Figure 18a–18d). Regarding the lower masonry part, the lower stone distribution widthzoneof
◦
3 C (from ◦ ◦
23 Ctemperatures
to 27 C), (Figure 18a–d).
presents higher (Figures 18cRegarding the lower
and 18d, zone undermasonry part,line)
the dotted the lower stonetozone
compared the
presents higher temperatures (Figure 18c,d, zone under the dotted line) compared to the
upper zone (Figure 18c, 18d, zone above the dotted line), as well as a tighter temperature distribution upper zone
(Figureof18c,d,
width zone 26
2 °C (from above
°C tothe
28dotted line), as
°C), whereas well
the as azone
upper tighter temperature
displays distribution
a temperature width of
distribution 2 ◦C
width
(from ◦ C to 28 ◦ C), whereas the upper zone displays a temperature distribution width of 4 ◦ C (from
of 4 °C26(from 23.5 °C to 27.5°C).
◦
23.5 ItCcan
to 27.5 ◦ C).
be assumed by the 2 IRT images’ co-evaluation that the new masonry presents different
temperature zones height-wise. In particular, lower masonry parts display higher temperature
readings compared to the upper masonry parts. This indicates a difference of the fire effect on the
new masonry stone blocks, according to their height and position, even though a precise pattern is
not demonstrated.
Heritage 2019, 2 1254
Figure 18. (a) Photo of the examined area 1 on the new masonry (higher masonry part). (b)
Figure 18. (a) Photo of the examined area 1 on the new masonry (higher masonry part).
Thermography of area 1. (c) Photo of the examined area 2 on the new masonry (lower masonry part-
(b) Thermography of area 1. (c) Photo of the examined area 2 on the new masonry (lower masonry
area 2 is below area 1). (d) Thermography of area 2.
part-area 2 is below area 1). (d) Thermography of area 2.
IRT investigation
It can be assumedofbythe theintermediate
2 IRT images’ historical masonry
co-evaluation shows
that the newtemperature
masonry variations among
presents different
the Figure 18.
different (a) types
stone Photo examined
of the examined
(Figures area
19a 1and
on 19b),
the new
whichmasonry
are (higher masonry
attributed to the part). (b)
different degree
temperature zones height-wise. In particular, lower masonry parts display higher temperature readings
of Thermography
the surface of area 1.
detachment/scaling(c) Photo of
due tothe examined
theindicates area
fire effect. 2 on the new
The intermediate masonry (lower
historical masonry part-
compared to the upper masonry parts. This a difference of the fire effect onmasonry presents
the new masonry
astonearea
wide 2 is below area
temperature 1). (d) Thermography
distribution width of of °C
4.5 area(from
2. 22.5 °C to 27 °C).
blocks, according to their height and position, even though a precise pattern is not demonstrated.
IRT investigation of the intermediate historical masonry shows temperature variations among
IRT investigation of the intermediate historical masonry shows temperature variations among
the different stone types examined (Figure 19a,b), which are attributed to the different degree of the
the different stone types examined (Figures 19a and 19b), which are attributed to the different degree
surface detachment/scaling due to the fire effect. The intermediate historical masonry presents a wide
of the surface detachment/scaling due◦to the fire effect. The intermediate historical masonry presents
temperature distribution width of 4.5 C (from 22.5 ◦ C to 27 ◦ C).
a wide temperature distribution width of 4.5 °C (from 22.5 °C to 27 °C).
Figure 19. (a) Photo of the examined area 3 of the intermediate historical masonry. (b) Thermography
of area 3.
The application of IRT at higher historic masonry parts (above 2m) display lower temperature
readings compared to the lower masonry parts (Figure 20).The wooden element in the middle of the
Figure
IRT image 19.
19. (a)
(a) Photo
Figurepresents of
of the
the examined
temperatures
Photo area
up to
examined 33 of
of the
25.5°C,
area intermediate
while
the historical
the masonry
intermediate parts
historical masonry. (b)
(b) Thermography
above and
masonry. below it reach up
Thermography
of
to 26.8 area
of °C. 3.
areaThe
3. temperature distribution width of the masonry, except the wooden element, is about
4.5 °C. Thus, it is demonstrated that the historic masonry holds a similar pattern with the new one,
as farThe
as itapplication of IRT at higher
concerns temperature historic masonry
distribution. The upperparts (above
masonry 2m)display
parts displaylower
lowertemperatures
temperature
readings compared to the
when compared to the lower parts. lower masonry parts (Figure 20).The wooden element in the middle of the
IRT image presents temperatures up to 25.5°C, while the masonry parts above and below it reach up
to 26.8 °C. The temperature distribution width of the masonry, except the wooden element, is about
4.5 °C. Thus, it is demonstrated that the historic masonry holds a similar pattern with the new one,
Heritage 2019, 2 1255
The application of IRT at higher historic masonry parts (above 2 m) display lower temperature
readings compared to the lower masonry parts (Figure 20). The wooden element in the middle of the
IRT image presents temperatures up to 25.5 ◦ C, while the masonry parts above and below it reach up
to 26.8 ◦ C. The temperature distribution width of the masonry, except the wooden element, is about
4.5 ◦ C. Thus, it is demonstrated that the historic masonry holds a similar pattern with the new one,
Heritage2019,
Heritage2019, 22 FOR
FOR PEER
PEER REVIEW
REVIEW 23
23
as far as it concerns temperature distribution. The upper masonry parts display lower temperatures
when compared to the lower parts.
Figure
Figure 20.
20. (a)
(a) Photo
Photo of
of the
the examined
examined area
area 44 of
of the
the intermediate
intermediate historical
historical masonry.
masonry. (b)
(b) Thermography
Thermography
Figure
of 20. (a) Photo of the examined area 4 of the intermediate historical masonry. (b) Thermography
of area
area 4.
4.
of area 4.
Furthermore,
Furthermore, IRT investigation
IRTinvestigation
investigation of the
the historical
of historical
intermediate masonry
masonry surfaces that
that are
Furthermore, IRT of the intermediate masonry surfaces surfaces
that are blackenedare
blackened
blackened from
from the
the fire,
fire, records
records these
these areas
areas with
with higher
higher temperature
temperature readings
readings (Figure
(Figure 21);
21); a
a result
result in
in
from the fire, records these areas with higher temperature readings (Figure 21); a result in accordance
accordance
accordance with the IRT examination of the respective areas of the new masonry. Temperature
with the IRTwith the IRT of
examination examination of areas
the respective the respective
of the newareas of the
masonry. new masonry.
Temperature Temperature
distribution width
distribution
distribution width
width of
of the
the blackened
blackened
◦ surface
surface ◦ is
is 22 °C
°C (from
(from
◦ 23.5
23.5 °C
°C to
to 25.5
25.5 °C),
°C), whereas
whereas the
the rest
rest of
of the
the
of the blackened surface is 2 C (from 23.5 C to 25.5 C), whereas the rest of the masonry area under
masonry
masonry area
area under
under investigation
investigation holds
holds aa temperature
temperature distribution
distribution
◦ width
width
◦ of
of 3
3
◦ °C
°C (from
(from 22
22 °C
°C to
to 25
25
investigation holds a temperature distribution width of 3 C (from 22 C to 25 C).
°C).
°C).
Figure
Figure 21.
21. (a)
(a) Photo
(a) Photo of
Photo of the
of the examined
the examined area
examined area 55 of
of the
the intermediate
intermediate historical
historical masonry.(b)
(b) Thermography
masonry.(b)
masonry. Thermography
Thermography
of area 5.
of area 5.
4. Conclusions
4. Conclusions
Conclusions
During this preliminary
During this preliminary study,
preliminary study,the
study, thecharacterization
the characterizationofof
characterization ofthe
thedifferent
the different
different lithotypes
lithotypes
lithotypes and
and
andmortars
mortars
mortarsused in
used
used
the
in
in thedifferent architectural
the different
different architectural phases of
architectural phases Varnakova
phases of Monastery
of Varnakova took
Varnakova Monastery place.
Monastery took The petrographic
took place.
place. The examination
The petrographic
petrographic
examination proved to be an indispensable tool for characterization and the fire impactthe
proved to
examination be an indispensable
proved to be an tool for characterization
indispensable tool for and the fire
characterization impact
and assessment
the fire on
impact different
assessment
assessment
lithotypes
on the of
differentthe historic
lithotypes structure.
of the The
historic main building
structure. The stones
main of the
building historic
stones masonries
of the
on the different lithotypes of the historic structure. The main building stones of the historic masonries are a
historic beige-grey
masonries
fosilliferrous
are
are aa beige-grey
beige-grey biomicritic limestone,
fosilliferrous
fosilliferrous as well
biomicritic
biomicritic as a clastic
limestone,
limestone, as calcite
as well
well as aasandstone,
as clastic
clastic calcite consisting
calcite sandstone,
sandstone,of crystalline
consisting
consisting
of
of crystalline and lithic fragments. Other stones are also sporadically detected, such as a black chert
crystalline and lithic fragments. Other stones are also sporadically detected, such as a black chert
and
and aa black
black fossiliferous
fossiliferous limestone,
limestone, which
which appears
appears as as laminae
laminae of of the
the beige-grey
beige-grey fosilliferrous
fosilliferrous
biomicritic
biomicritic limestone.
limestone.
Regarding
Regarding the the main
main building
building stones,
stones, the
the petrographic
petrographic examination
examination of of the
the fire-affected
fire-affected sandstone
sandstone
shows
shows oxidation
oxidation phenomena
phenomena of of iron-containing
iron-containing minerals
minerals due
due toto the
the fire,
fire, which
which isis macroscopically
macroscopically
Heritage 2019, 2 1256
and lithic fragments. Other stones are also sporadically detected, such as a black chert and a black
fossiliferous limestone, which appears as laminae of the beige-grey fosilliferrous biomicritic limestone.
Regarding the main building stones, the petrographic examination of the fire-affected sandstone
shows oxidation phenomena of iron-containing minerals due to the fire, which is macroscopically
manifested by the reddening of the sample. While the fire-affected beige-grey limestone presents a
pinkish hue macroscopically, due to the effect of the fire, the fire-effect is also evident through the
widening and rupture of the joints filled with secondary calcite. The latter is more intense in the case
of the limestone collected from the historical masonry.
Both XRD and thermal analysis measurements indicated distinct alterations of the sandstone due
to the effect of fire. The microcline peak detected in the unaffected sample is not discerned in the
fire-affected sample, while the calcite content also decreased. Physical properties of the sandstone
are also altered. The effect of fire has increased porosity, decreased bulk density, and increased water
absorption capacity. SHR values conducted in situ on a large number of sandstone building elements,
both affected and unaffected, showed a decrease of surface hardness, as expected, in accordance with
the degree of the fire exposure.
On the other hand, the limestone samples do not present distinct differences in their mineralogical,
chemical, or physical properties due to the fire effect. However, the SHR evaluation reveals that,
although relatively stable in the terms mentioned above, the effect of fire and the rupturing of the
limestone’s joints filled with secondary calcite are quantitatively evident in the decreased SHR values
and, therefore, the decreased surface hardness. Further research is necessary in order to ascertain
whether the mechanical strength values and especially compressive strength has also decreased, as
expected. This highlights the need for further sampling to obtain samples of adequate geometry and
dimensions in order to accomplish mechanical strength measurements. Such a sampling campaign
requires further authorization, as the Monastery is a listed historical monument and is under a strict
sampling legislation.
The mortars selected from the new masonry are classified as cement-based mortars, a fact which
is anticipated in a recently constructed masonry. The thermal analysis and microstructure evaluation
results demonstrate that these mortars are highly carbonated due to the fire effect. The mortars selected
from the intermediate historical masonry belong to two categories: clay mortars and cement-based
mortars. All structural mortars belong to the clay mortars category, while the final joint mortars
belong to the cement-based category, which demonstrate that recent repointing had taken place using
a cement-based mortar, prior to the fire event. Digital microscopy observations regarding the texture
of the mortars proved to be a useful tool for an initial classification.
IRT inspection of the masonries as a whole, demonstrates that the historic masonry presents
relatively high temperature variations, due to the presence of diverse lithotypes, as well as the different
degree of the fire effect. Similar fluctuation of temperatures is observed for the new masonry as well,
despite the fact that it is entirely built from one lithotype (namely the grey-beige limestone) and can be
attributed to the fire event.
Both historical and new masonries present different temperature zones with their upper parts
being cooler than the lower ones. This is an indication of the different effect of the fire per height.
However, even though the fire effect seems to depend on position, height, and lithotype, no clear
pattern is displayed.
Blackened surfaces, in both the historical and new masonries, present higher temperatures,
which indicate differences in the thermo-hygric behavior of the masonry in these areas, due to soot
accumulation from the fire, as well as a possible stronger fire damaging effect.
It is evident from the IRT results that the historical masonry presents wider temperature distribution
width in comparison to the new masonry. However, the recorded temperature readings of the historical
masonry are lower in comparison to the ones of the new masonry. These differences are attributed to
the differentiated development of the fire event, as well as to the fire’s different effect on the historical
masonry, due to the variety of building materials comprising it.
Heritage 2019, 2 1257
The results of the present study provide information regarding the characterization of the
building materials of the Varnakova cell’s quarter and diagnosis of their decay due to the fire event.
The techniques implemented have proven valuable for evaluating the present state of the masonries.
These results can serve as a basis for further investigation, which are necessary in order to plan
appropriate restoration and conservation strategies for the rehabilitation of the cells’ quarter in terms
of sustainability.
Author Contributions: E.T.D. offered the methodology about materials characterization and nondestructive
testing, and supervised the in situ investigation and sampling, all related measurements, and the overall writing of
the paper. M.A. participated in the in situ investigation and sampling, as well as implemented and supervised the
investigation related to thermal analysis measurements. Elaborated total water immersion tests and conducted
writing and editing of the paper. I.N. conducted the writing of the original draft, elaborated the SHR measurements,
and performed the DM measurements. M.T. assisted in the in situ investigation and sampling and implemented
the investigation of the building materials. V.K. implemented the investigation of the building materials and
performed the total water immersion tests. C.P. and G.E. implemented and supervised the microscopy and
mineralogical measurements. A.M. was responsible for the scientific administration and scientific supervision of
the research team, the scientific conceptualization and visualization of the project and research conducted.
Funding: This research received no external funding.
Acknowledgments: The authors would like to thank the Abbess and the Sisterhood of the Varnakova Monastery,
as well as Ch. Alexopoulou, Civil Engineer, and S. Fidani, for inviting Professor Moropoulou and the NTUA
team to undertake the diagnostic study of the Church and the Cells. In addition, the authors would like to
acknowledge the Central Greece Regional unit, the Governor of Central Greece, K. Bakoyannis, the Regional
Councilor, P. Aravantinou, as well as the General Directorate of Antiquities and Cultural Heritage of the Ministry
of Culture and Sports of the Hellenic Republic and the Ephorate of Antiquities of Phocis, A. Psalti, for their
fruitful cooperation. Lastly, the authors would like to thank NTUA Associate Professor Ch. Mouzakis for the
interdisciplinary cooperation, which we anticipate to continue through a Program Agreement with the Ministry
of Culture and Sports and the Central Greece Region. This research was orally presented in its initial form at
the 1st International Conference TMM_CH: Transdisciplinary Multispectral Modeling and Cooperation for the
Preservation of Cultural Heritage, held on 10–13 October 2018 at the Eugenides Foundation Athens, Greece
under the title “The effect of fire on building materials: the case-study of the Varnakova monastery cells in
Central Greece” by I. Ntoutsi, E. T. Delegou, M. Thoma, M. Apostolopoulou, Ch. Papatrechas, G. Economou,
and A. Moropoulou. It has since then been modified and elaborated with further results and interpretations.
Lastly, we would like to thank the anonymous reviewers for their valuable suggestions and comments during the
manuscript’s revision process.
Conflicts of Interest: The authors declare no conflict of interest.
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© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
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Heritage 2019, 2, 1233–1259; doi:10.3390/heritage2020080 www.mdpi.com/journal/heritage

2.1. The Varnakova Monastery

2.3. Investigation Techniques and Methodology

Heritage2019, 2 FOR PEER REVIEW 7

Figure 5. Diagram summarizing the methodological approach followed in this study.

3. Results and Discussion

Petrographic Examination of the Lithotypes

Stone Sample Code Sample Description

Petrographic Examination of the Lithotypes

One of the Themain building

Figure 10. (a)

Table 2. XRD analysis of stone samples.

Sample Code Mineralogical Composition (XRD Analysis)

Compositional analysis of stone samples through simultaneous thermal analysis (TG/DTA)

Table 3. TG results of stone samples.

Mass Loss (%) per Temperature Range (◦ C)

Total Immersion Results on Stone Lithotypes

Table 4. Total water immersion tests results – stones.

3.1.2. Investigation of the Mortars

3.1.2. Investigation of the Mortars

Structural soft mortar of clay texture

Joint mortar of cementitious texture

Structural soft mortar of clay texture

Structural soft mortar of clay texture

Structural soft mortar of clay texture

In-depth mortar of mixed

Structural soft mortar of clay texture

Structural soft mortar of clay texture

Joint mortar of cementitious texture

3.1.3. Mineralogical Examination

3.1.3.XRD results areExamination

Table 6. XRD analysis of mortars’ samples.

Sample Code Mineralogical Composition (XRD Analysis)

Table 7. TG results of mortars’ samples.

Mass Loss (%) per Temperature Range (◦ C)

3.2. SHR Results

Heritage2019, 2 FOR PEER REVIEW 21

3.3. IRT Inspection

Heritage2019, 2 FOR PEER REVIEW 22

Heritage2019, 2 FOR PEER REVIEW 22

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