Construction and Building Materials 96 (2015) 442–460

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Characterisation of ancient mortars from the S. Niccolò archaeological

complex in Montieri (Tuscany – Italy)
Nicoletta Chiarelli a,⇑, Domenico Miriello b, Giovanna Bianchi c, Giuseppe Fichera c, Marco Giamello a,
Isabella Turbanti Memmi a
a
Department of Physical Sciences, Earth and Environment, University of Siena, Italy
b
Department of Biology, Ecology and Earth Sciences, University of Calabria, Italy
c
Department of Historical Sciences and Cultural Heritage, University of Siena, Italy

h i g h l i g h t s

 The study of the mortars allowed us to identify 5 principal building phases.

 Metallurgic slags, cocciopesto and glasses are visible in the mortar aggregate.
 The metallurgic slags give to the binder a greater hydraulicity.
 Argentiferous minerals are present in the aggregate of some mortars.

a r t i c l e i n f o a b s t r a c t

Article history: The object of the present work is the archaeometric study of the mortars from the S. Niccolò archaeolog-
Received 10 March 2015 ical site in Montieri (Tuscany – Italy). The petrographic, mineralogical and chemical characterisation of
Received in revised form 17 July 2015 the samples was obtained by the use of multi-analytical techniques (OM, XRD, SEM–EDS, XRF). The
Accepted 5 August 2015
knowledge of the constitutive materials allowed us to understand the different production technologies
and highlighted the use of materials with hydraulic behaviour, such as metallurgical slags and coc-
ciopesto. The compositional analogies and differences among the samples contributed to the reconstruc-
Keywords:
tion of the building phases, favouring the reading of the history and the evolution of the site over time.
Archaeometry
OM
Ó 2015 Elsevier Ltd. All rights reserved.
XRD
SEM–EDS
XRF
Lime
Lump
Slag

1. Introduction
Mortars have been employed for the edification of historical
monuments since the ancient times. They can be defined as artifi-
cial stone materials, consisting of a mixture of inorganic or organic
binders, aggregate, water and inorganic or organic additives. The
proportions of the previous single components should give suitable
workability and appropriate physical, mechanical and aesthetic
characteristics to the finished product [1]. Today, a great number
of researches focus the attention on the study of historical mortars,
as source material of important information in archaeological, con-
servative and scientific fields [2–12]. The investigation about the
⇑ Corresponding author.
E-mail address: chiarelli_nicoletta@alice.it (N. Chiarelli).
nature and the provenance of the raw materials, the productive
technologies, the change of the production practices (lime burning,
mortar mixing), the building phases and the dating of the builds
are interesting data in historical and archaeological contexts, in
order to reconstruct the economic and political scene of the coun-
tries. The compatible materials for restoration can be planned
through the study of the original compositions and the deep
knowledge of the deterioration processes. Furthermore the chem-
ical, physical and mechanical processes in the mortars, such as
the burning of the binder, hydration, carbonation and production
of the hydraulic phases, are analysed for a better understanding
of the behaviour and potentiality of these materials.
The present work is focussed on the study of ancient mortars
coming from the Canonica of S. Niccolò, a medieval archaeological
site, located in the Colline Metallifere area (Tuscany)

http://dx.doi.org/10.1016/j.conbuildmat.2015.08.023
0950-0618/Ó 2015 Elsevier Ltd. All rights reserved.
 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460 443

Fig. 1. Location of the archaeological site, (a) map, (b) aerial photo and (c) wall rests of the church.

Fig. 2. Sampling, (a) location of the samples on the map, (b) macrophotography of the mortar MM1 and (c, d) sampling of the mortar MM19 and MM1.

(Fig. 1a and b). The development of the site is closely related to the
near centre of Montieri (Grosseto), founded for the control and
exploitation of the mines in the district.
The aim of the study is the compositional characterization of
the mortar samples, extensively taken from the wall remains of
the archaeological site. For this purpose a multi-analytical
approach is necessary, by using different analytical techniques:
the petrographic study in thin section of the samples by optical
microscopy (OM); the mineralogical analysis by X-ray diffraction
(XRD); micro-chemical investigations by scanning electron micro-
scope (SEM–EDS) and bulk chemical analysis by X-ray fluorescence
(XRF). The combination of this methodology with archaeological
studies provides useful data to understand different aspects linked
to the production technology of the mortars, the provenance of the
444 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460

Table 1
Sampling data of the bedding mortars (MM: Montieri Mortar). d.g.l.: distance from the ground level, d.r.e.: distance from the right edge, d.l.e.: distance from the left edge, U.S.:
stratigraphic unit, n.d.: not determined.

Location Stratification Adherence

Area d.g.l. (cm) d.r.e. (cm) d.l.e. (cm)
MM1 Area 1000 – 2nd building – foundation wall southeast apse 17 92 – – Poor
MM2 Area 1000 – 2nd building – southeast apse 58 130 – – Poor
MM3 Area 1000 – 2nd building – southeast apse 86 152 – – Poor
MM4 Area 1000 – 2nd building – northeast apse 50 60 – – Good
MM5 Area 1000 – 2nd building – north apse 39 – 26 – Good
MM6 Area 1000 – 2nd building – jamb of the north entrance 42 4 – 2 layer Good
MM7 Area 1000 – 2nd building – jamb of the north entrance 32 0 – – Good
MM8 Area 1000 – 2nd building – north apse 30 57 – – Poor
MM9 Area 1000 – 2nd building – northwest apse 54 160 – – Good
MM10 Area 1000 – 2nd building – jamb of the south entrance 101 12 – – Very poor
MM11 Area 1000 – 2nd building – southeast apse 82 73 – – Good
MM12 Area 1000 – 2nd building – south apse 85 15 – – n.d.
MM13 Area 1000 – 2nd building – south apse 100 60 – – n.d.
MM14 Area 1000 – 1st building – U.S. 302 35 – 120 – Good
MM15 Area 1000 – 1st building – U.S. 203 110 – 190 – Poor
MM16 Area 1000 – 1st building – foundation wall U.S. 206 80 – 197 – Poor
MM17 Area 1000 – 1st building – semicircular wall 80 125 – – Poor
MM18 Area 1000 – 1st building – semicircular wall 67 160 – – Poor
MM19 Area 2000 – U.S. 1003 58 160 – – Good
MM20 Area 2000 – U.S. 1003 13 65 – – Good
MM21 Area 2000 – U.S. 1003 24 60 – – Good
MM22 Area 2000 – U.S. 1001 50 – 120 – Moderate
MM23 Area 2000 – U.S. 1006 110 – 230 – Poor
MM24 area 2000 - U.S. 803 30 230 – – Good
MM25 Area 2000 – U.S. 801 65 260 – – Good
MM26 Area 2000 – foundation wall U.S. 1106 17 – 398 – Poor
MM27 Area 2000 – U.S. 1105 35 – 468 – Moderate
MM28 Area 2000 – U.S. 1101 100 – 636 – Good
MM29 Area 2000 20 – 25 – Poor
MM30 Area 1000 – 1st building 20 – 230 – Moderate
MM31 Area 4000 – U.S. 601 40 – 60 – Moderate
MM32 Area 4000 – U.S. 402 90 – 193 – Good
MM33 Area 4000 90 – 100 – Good
MM34 Area 4000 – U.S. 502 95 – 270 – Good
MM35 Outer wall of boundary – foundation wall U.S. 907 26 330 – – Good
MM36 Outer wall of boundary – U.S. 906 100 295 – – Moderate
MM37 Outer wall of boundary – U.S. 901 120 – 75 – Good
MM38 Area 4000 50 – 150 – Good
MM39 Area 9000 – jamb of entrance 0 0 – – n.d.
MM40 Area 9000 – jamb of entrance – U.S. 1205 75 0 – – Good
MM41 Area 9000 50 – 50 – Poor
MM42 Area 1000 – 1st building – floor level U.S. 302–303 21 145 – – Good
MM43 Area 1000–1st building 0 – 0 – Good
MM44 Area 1000 – 1st building – foundation wall U.S. 102 70 – 140 – Poor
MM45 Area 1000 – 1st building – U.S. 101 80 0 – – Moderate
MM46 Area 1000–1st building 42 – 320 – Poor
MM47 Area 1000 – 2nd building – foundation wall southwest apse 25 – 90 – Poor
MM48 Area 1000 – 2nd building – floor level southwest apse 45 – 85 2 layer Good
MM49 Area 1000–2nd building – southwest apse 100 – 270 – Good
MM50 Area 1000–2nd building – jamb of the southwest entrance 50 250 – – Good
MM51 Area 1000 – 2nd building – southwest apse 48 248 – – n.d.
MM52 Area 1000 – 2nd building – foundation wall northeast apse 60 120 – – n.d.
MM53 area 1000–2nd building – northeast apse 90 270 – – Poor
MM54 Area 1000–2nd building – northeast apse 100 180 – – Poor

raw materials and the identification of the different building
phases, in order to understand the growth and changes of the site
in time. This approach becomes an useful tool, that can be used in
other archaeological sites to solve archaeometric problems regard-
ing ancient mortars and plasters.
1.1. Historical context and results of archaeological investigations
The Colline Metallifere is an area with some of the richest silver
deposits in Europe. Underground veins of minerals were mined to
get raw materials, silver and copper, for the production of coins,
from the early medieval period. The main political figures involved
in mining these resources were members of important aristocratic
families, monasteries of European standing and bishops.
The richness of this evidence stimulated the interest of the
archaeologist of the University of Siena and since the mid-80s,
the ‘Progetto Colline Metallifere’ was launched. Connected to this
is a large number of research projects, one of the main aims of
which is to study relations between settlements and mineral
resources, with particular reference to settlement dynamics and
the dynamics of controlling the cycle of production in the medieval
period. As of 2007, there began a large-scale project in the munic-
ipality of Montieri, including excavations at the Canonica [13,14].
The site is a few kilometres away from Montieri. The modern
town corresponds to a small inhabited site whose size is not very
different from the original medieval castle, first mentioned in
1133. Montieri was one of the main centres of silver production.
The castle had links with the Bishop of Volterra, who, since the
 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460 445

Fig. 3. Photomicrographs of the mortar aggregates, (a) shale in sample MM54, (b) charcoal in sample MM11, (c) metallurgic slag in sample MM29, (d) glass in sample MM29,
(e) opaque euhedral minerals in sample MM30, (f) iron oxides in sample MM27, (g) melilites in the metallurgic slag of the sample MM39 and (h) calcite in sample MM5.

end of the 12th century, set up a mint inside it, to produce
Volterra’s coinage. The castle of Montieri stands at the foot of a hill
with many mines in it. On the northern slopes of the hill, there also
stood the site which we excavated. In the documents, this site was
linked to the Bishop of Volterra and in the 1133 document it was
called La Canonica dedicated to San Niccolò. The complex is com-
posed of a church with six radiating conchs (Fig. 1c), located inside
an enclosure that contained a central, open space with two long
buildings, and a smaller construction, along its sides. Outside the
enclosure there is a group of other structures, sited in relation to
a further open space.
The stratigraphy found so far bears witness to a settlement
sequence spanning a long period of time [15]: initial occupation
of the terraced site probably in the period between the 9th and
10th centuries; in the first half of 11th century the layout of the
buildings at La Canonica comprised a church with six apses, with
a small adjacent space containing a privileged burial. The peculiar
shape of the church is likely to reflect the significance that this
building must have had for the people who commissioned it.
Indeed, as yet no parallels have been found in Italy, except for
buildings dating to Late Antiquity. The objective of these opera-
tions would seem to have been the creation of an important centre
of worship that was immediately venerated by local residents. This
led to the formation of an area of lay burials arranged around the
church between the 11th and 13th centuries. Excavation of less
than a third of these burial areas, inside and outside the enclosure,
has already brought to light more than 300 individuals belonging
to the lay society of Montieri. The Bishop of Volterra’s objective
446 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460
Fig. 4. Photomicrographs of the mortar aggregates, (a) sandstone in sample MM40, (b) rhyolite in sample MM7, (c) quartzite in sample MM7 and (d) cocciopesto in sample
MM7.
was to combine control and management of mining resources with
religious and social control over the Montieri community. This cer-
tainly strengthened the status of the Bishop himself, within the
various dialectics of economic control of the local area on the part
of the newly-formed local seigneurships.
In the 12th century two long buildings and a stone enclosure
were built. During the 12th century, and especially in the first dec-
ades of the 13th century, variations were made to the existing sys-
tem of structures, and it was only at the end of 14th century that a
new, residential building was added to the original structures. This
was the last major intervention before final abandonment of the
site, which occurred just before the 15th century.
2. Sampling and analytical techniques
A total of 54 mortar samples were taken from the buildings of
the archaeological site at the area 1000, area 2000, area 3000, area
4000 and area 9000 (Fig. 2; Table 1). The particularly interesting
sampling was the area 1000, including the church (area 1000 –
2nd building) and its annex (area 1000 – 1st building).
Petrographic, mineralogical and chemical characterisation required
a multi-analytical approach. After a preliminary macroscopic anal-
ysis, the thin sections were observed with a polarised light optical
microscope Leica DMRX (Figs. 3 and 4; Tables 2 and 3).
Mineralogical composition was determined by a Bragg–Brentano
Philips X’ Pert PRO PW 3040 X-ray diffractometer (XRD), equipped
with a X’ Celerator PW 3015 detector. The instrument works on Cu
Ka radiation, at 40 kV and 40 mA, and the diffraction data were col-
lected in the range 3–60° 2h, step size of 0.02°, step time 58.42 s.
The diffractograms were interpreted by using X’Pert High Score
software (Fig. 5; Table 4). Textural and micro-chemical analysis of
the binder (size <1/16), lumps, some minerals and lithic fragments
in the aggregate were performed through a Philips XL30 FEI Quanta
200 electron scanning microscope (SEM), equipped with an EDAX Si
(Li detector) (Figs. 6 and 7; Tables 5–7). The chemical analysis of the
major (CaO, MgO, MnO, Fe2O3, P2O5, K2O, SiO2, Na2O, TiO2, Al2O3)
and trace elements (Ni, Cu, Zn, Co, Cr, Pb, Ba, Sr, Rb, Nb, Y, Zr, V)
on mortar pressed powders were carried out by a Philips MagiX
X-ray fluorescence spectrometer (XRF), operating on Rh Ka tubes
(Figs. 8 and 9; Tables 8 and 9). At the last, some variables were pro-
cessed by a statistical discriminant analysis, using the software IBM
SPSS STATISTICS 21.00.
3. Results and discussion
3.1. Macroscopic analysis
The majority of the samples show light grey colour, main size
class of the sand [16] and poor cohesion [17] (Fig. 2b). Lime lumps,
coal fragments, straw, metallurgic slags and cocciopesto (fragments
of pottery) were observed. Primary and secondary porosity, musk
and biological patinas are often visible on the surface [18]. The
mortars of the foundation walls are composed by a very poorly
cohesive greyish-brown clay binder.
3.2. Microscopic description on the thin section
The microscopic analysis of the thin section under the polarised
light optical microscope allowed us to describe the main features
of each sample (Tables 2 and 3). The comparison between the sam-
ples let us to distinguish the following groups.
3.2.1. 1st Group (MM2, MM3, MM6, MM9, MM11, MM12, MM13,
MM17, MM48_I, MM49, MM53, MM54)
The mortars come from the six apses of the church. The poorly
sorted aggregate has a main size of 450 lm (medium sand) [16],
low sphericity and high roundness. It is mainly composed of shale
(Fig. 3a), phyllites, sandstones, siltstones, limestones, quartzites
Table 2
Petrographic features of the mortar aggregate on thin sections. CS: coarse sand, MS: medium sand, FS: fine sand, PS: poorly sorted, LS: low sphericity, WR: well-rounded, SR: sub-rounded, SA: sub-angular, A: angular; R: random, P:
preferential, H: homogeneous, I: inhomogeneous. Bt: biotite, Cal: calcite, Ms: muscovite, Opm: opaque mineral, Or: orthoclase, Opx: orthopyroxene, Pl: plagioclase, Qtz: quartz (abbreviations according to Refs. [20,21]).

Aggregate
Size (lm) Sorting Sphericity Roundness Orientation Distribution Mineralogical Rock fragments Artificial stone Other
phases material
Max. Min. Mean
MM1 4800 5 160 PS LS A-WR R I Qtz, Cal, Opm, Shale, phyllite, sandstone, siltstone, limestone, Cocciopesto, Metallurgic slag, charcoal,
FS Ms, Bt, Or volcanic rock, marble, quartzite reused mortar limestone partially burnt
MM2 7000 10 450 PS LS WR R H Qtz, Cal, Ms, Shale, phyllite, sandstone, siltstone, limestone, - Charcoal, limestone partially
MS Opm flint, quartzite burnt
MM3 5000 10 450 PS LS WR R H Qtz, Cal, Pl, Ms, Shale, phyllite, sandstone, siltstone, limestone, – Charcoal
MS Opm quartzite
MM4 2400 10 250 PS LS A-WR R I Qtz, Cal, Pl, Opm Sandstone, shale, phyllite, siltstone, limestone, Cocciopesto Charcoal
MS quartzite
MM5 2500 10 650 PS LS A-WR R H Cal, Qtz, Or, Ms, Limestone, marble, shale, phyllite, sandstone, – Metallurgic slag, charcoal
CS Bt, Opm volcanic rock, siltstone, quartzite

N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460

MM6 8000 10 450 PS LS WR R H Qtz, Cal, Ms, Shale, phyllite, sandstone, siltstone, limestone, – Charcoal
MS Opm quartzite
MM7 2880 10 650 PS LS A-WR R H Cal, Qtz, Or, Ms, Shale, phyllite, sandstone, limestone, marble, Cocciopesto Metallurgic slag, charcoal
CS Bt, Opm volcanic rock, quartzite, flint
MM8 640 10 250 PS LS WR R I Qtz, Opm Shale, sandstone – –
MS
MM9 3000 10 450 PS LS WR R H Qtz, Cal, Pl, Ms, Shale, phyllite, sandstone, siltstone, limestone, – Charcoal
MS Bt, Opm quartzite, marble
MM10 1920 10 250 PS LS A-WR R H Qtz, Opm, Cal, Quartzite, sandstone, shale, limestone – Glass
MS Ms
MM11 4560 10 450 PS LS WR R H Qtz, Cal, Or, Pl, Shale, phyllite, sandstone, siltstone, limestone, – Charcoal
MS Ms, Opm quartzite
MM12 4000 10 450 PS LS WR R H Qtz, Cal, Opm Shale, phyllite, sandstone, siltstone, limestone, – Charcoal, limestone partially
MS quartzite burnt
MM13 5500 10 450 PS LS WR R H Qtz, Cal, Pl, Ms, Shale, phyllite, sandstone, siltstone, limestone, – Charcoal
MS Opm flint, quartzite
MM14 1300 5 160 PS LS A-WR R I Qtz, Cal, Opm, Shale, phyllite, limestone, sandstone, volcanic Reused mortar Metallurgic slag, charcoal,
FS Ms, Bt rock, quartzite limestone partially burnt
MM15 5000 5 160 PS LS A-WR R I Qtz, Cal, Opm, Shale, sandstone, limestone, siltstone, phyllite Cocciopesto Metallurgic slag, charcoal
FS Ms, Pl, Opx
MM16a 2960 5 160 PS LS WR R I Ms, Bt, Qtz Sandstone, phyllite, shale, quartzite – –
FS
MM16b 3500 5 160 PS LS A-WR R I Qtz, Cal, Opm, Shale, phyllite, limestone, sandstone, siltstone, Cocciopesto Metallurgic slag, charcoal
FS Ms, Or, Bt quartzite
MM17a 3200 5 160 PS LS WR R I Ms, Bt, Qtz, Cal, Phyllite, siltstone, sandstone, shale, limestone – Charcoal
FS Opm
MM17b 5000 10 450 PS LS WR R H Qtz, Cal, Ms, Bt, Shale, phyllite, sandstone, siltstone, limestone, – Charcoal
MS Opm quartzite
MM18 3120 5 160 PS LS WR R I Ms, Bt, Qtz, Cal, Phyllite, shale, sandstone, limestone, quartzite – Charcoal
FS Opm
MM19 4700 5 250 PS LS A R H Qtz, Cal, Opm, Sandstone, quartzite, shale, limestone, Cocciopesto Charcoal
MS Ms siltstone, phyllite
MM20 3400 5 250 PS LS A R H Qtz, Cal, Opm, Sandstone, quartzite, limestone, shale, Cocciopesto Charcoal
MS Or, Pl, Bt phyllite, siltstone
MM21 7000 5 250 PS LS A R H Qtz, Cal, Opm, Sandstone, quartzite, limestone, shale, Cocciopesto Charcoal
MS Or phyllite, siltstone
MM22 2800 5 250 PS LS A R H Qtz, Cal, Opm, Sandstone, quartzite, limestone, shale, Cocciopesto Charcoal
MS Or, Pl, Ms, Bt phyllite, siltstone
MM23 6000 10 400 PS LS WR R H Qtz, Cal, Ms, Bt, Sandstone, shale, phyllite, siltstone, limestone Reused mortar Charcoal, limestone partially
MS Opm burnt, metallurgic salg

(continued on next page)

447
 448
Table 2 (continued)

Aggregate
Size (lm) Sorting Sphericity Roundness Orientation Distribution Mineralogical Rock fragments Artificial stone Other
phases material
Max. Min. Mean
MM24 5000 5 250 PS LS A R H Qtz, Opm, Cal, Sandstone, quartzite, shale, phyllite, Cocciopesto Charcoal
MS Or, Pl, Ms, Bt limestone, siltstone, marble
MM25 3200 5 250 PS LS A R H Qtz, Opm, Cal, Sandstone, quartzite, phyllite, shale, siltstone, – –
MS Or, Pl, Ms limestone
MM26a 3000 5 250 PS LS A R H Qtz, Opm, Cal, Quartzite, shale, phyllite – –
MS Ms, Bt, Or
MM26b 2400 5 250 PS LS A R H Qtz, Opm, Cal, Sandstone, quartzite, phyllite, shale, siltstone, – Charcoal
MS Or, Pl, Ms, Bt limestone
MM27 2000 5 250 PS LS A R H Qtz, Opm, Cal, Sandstone, quartzite, shale, limestone Cocciopesto –
MS Or, Pl, Ms, Bt
MM28 2200 5 250 PS LS A R H Qtz, Cal, Opm, Sandstone, quartzite, phyllite, shale, limestone Cocciopesto Charcoal
MS Or, Pl, Ms, Bt

N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460

MM29a 2300 5 160 PS LS A-WR R I Cal, Opm, Qtz, Shale, phyllite, limestone, sandstone, marble – Metallurgic slag, charcoal,
FS Ms, Or, Bt glass
MM29b 4960 5 160 PS LS WR R I Ms, Bt, Qtz Phyllite, shale, sandstone – –
FS
MM30 2050 5 160 PS LS A-WR R I Cal, Opm, Qtz, Shale, phyllite, sandstone, siltstone, limestone, Cocciopesto Metallurgic slag, charcoal
FS Ms, Bt quartzite
MM31 4000 10 400 PS LS WR R H Qtz, Cal, Ms, Bt, Shale, phyllite, sandstone, siltstone, limestone Reused mortar Charcoal, limestone partially
MS Opm burnt
MM32 4000 10 400 PS LS WR R H Qtz, Cal, Ms, Bt, Shale, phyllite, sandstone, limestone Reused mortar Charcoal, limestone partially
MS Opm burnt
MM33 8000 5 250 PS LS A R H Qtz, Opm, Cal, Quartzite, sandstone, shale, phyllite, siltstone Cocciopesto Charcoal
MS Or, Ms
MM34 5000 10 400 PS LS WR R H Qtz, Cal, Ms, Bt, Shale, phyllite, sandstone, limestone Reused mortar Charcoal, limestone partially
MS Opm burnt
MM35 4000 5 250 PS LS A R I Qtz, Opm, Cal, Sandstone, quartzite, shale, phyllite, siltstone, – Charcoal
MS Or limestone
MM36 7000 5 250 PS LS A R I Qtz, Opm, Cal, Sandstone, quartzite, shale, phyllite, siltstone Cocciopesto Charcoal
MS Or, Pl, Ms, Bt
MM37 8000 10 400 PS LS WR R H Qtz, Cal, Ms, Shale, phyllite, sandstone, limestone, siltstone Reused mortar Charcoal, limestone partially
MS Opm burnt
MM38 11000 10 400 PS LS WR R H Qtz, Cal, Ms, Shale, phyllite, limestone, sandstone, siltstone Reused mortar Charcoal, limestone partially
MS Opm burnt
MM39 5000 10 650 PS LS A-WR R H Qtz, Cal, Opm, Shale, phyllite, limestone, sandstone, siltstone, Cocciopesto Metallurgic slag, charcoal
CS Or, Bt volcanic rock
MM40 2800 10 651 PS LS A-WR R H Qtz, Cal, Opm, Shale, phyllite, limestone, siltstone, marble, Cocciopesto Metallurgic slag, charcoal
CS Or, Ms, Bt flint
MM41 3280 5 160 PS LS WR R I Ms, Bt, Qtz, Or Sandstone, shale, phyllite, quartzite – Charcoal
FS
MM42_I 1840 10 400 PS LS WR R I Qtz, Opm, Bt, Sandstone, shale, phyllite, siltstone, limestone, – Charcoal
MS Cal quartzite
MM42_II 1040 5 160 PS LS A-WR R H Cal, Opm, Qtz Shale, phyllite, sandstone, siltstone – Charcoal
FS
MM43 8000 5 160 PS LS A-WR R I Qtz, Cal, Opm, Sandstone, phyllite, shale, limestone, siltstone Reused mortar Metallurgic slag, charcoal,
FS Ms, Mc limestone partially burnt
MM44a 5000 10 450 PS LS WR R I Ms, Bt, Qtz, Cal, Sandstone, shale, phyllite, siltstone, limestone – Charcoal
MS Opm, Or
MM44b_I 2680 5 160 PS LS A-WR R I Cal, Qtz, Opm, Phyllite, shale, sandstone, siltstone, marble, – Metallurgic slag, charcoal
FS Ms, Bt limestone
MM44b_II 2480 5 160 PS LS WR R I Qtz, Cal, Ms, Phyllite, shale, sandstone, limestone – –
FS Opm
 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460 449

and flints. A few monocrystalline phases, such as quartz, calcite,

Charcoal, limestone partially muscovite, opaque minerals, plagioclase, orthoclase and biotite,

Charcoal, limestone partially

Charcoal, limestone partially

coal fragments (Fig. 3b) and traces of limestone partially burnt
Metallurgic slag, charcoal,
Metallurgic slag, charcoal

Metallurgic slag, charcoal

limestone partially burnt

were identified. The aggregate amount, as assessed by visual esti-

mation, is about 30% [19]. The binder shows a homogeneous
greyish-brown colour and cryptocrystalline aspect; some lime
lumps can be observed. The porosity is prevalently of secondary
type and the main size of the pores is 200–250 lm.
Charcoal

Charcoal

Charcoal
burnt

burnt

burnt
3.2.2. 2nd Group (MM1, MM14, MM15, MM16b, MM29a, MM30,
MM42_II, MM43, MM44b_I, MM45, MM46)
The mortars mainly belong to the annex of the church (area
Cocciopesto

1000 – 1st building). Many monocrystalline phases such as calcite,

quartz, euhedral opaque minerals, muscovite and lesser amounts
of orthoclase, biotite, plagioclase, microcline and orthopyroxene
–

were identified. Shales, sandstones, limestones, phyllites, silt-

Phyllite, shale, limestone, sandstone, quartzite
Sandstone, phyllite, shale, limestone, siltstone,

Shale, phyllite, sandstone, siltstone, limestone

Shale, phyllite, sandstone, siltstone, limestone

Shale, phyllite, sandstone, siltstone, limestone

Shale, phyllite, sandstone, siltstone, limestone

Shale, phyllite, sandstone, siltstone, limestone

stones, rhyolites, biomicrites, quartzites, metallurgical slags

(Fig. 3c), coal, limestones partially burned, some reused mortars
Shale, phyllite, volcanic rock, limestone

and rare glasses (Fig. 3d) were also recognised. The main size is
about 160 lm (fine sand) [16] and the quantity of the aggregate
is 40%. The porosity has a main size of about 120–200 lm and it
was evaluated at 15%.
Phyllite, shale, sandstone

3.2.3. 3rd Group (MM19, MM20, MM21, MM22, MM24, MM25,

MM26b, MM27, MM28, MM33, MM35, MM36)
The samples were taken from the productive area (area 2000)
and from the outer wall bounding the complex. The poorly sorted
quartzite

aggregate is mainly composed of quartz, sandstones and quart-

zites. The angular clasts show a main size of 250 lm (medium
sand) [16]. Monocrystalline phases essentially are quartz, calcite,
Ms, Bt, Qtz, Cal,

opaque minerals (Fig. 3e), iron oxides with growth structure

Qtz, Pl, Ms, Bt,
Cal, Qtz, Opm,

Cal, Qtz, Opm,

Cal, Qtz, Opm,

Qtz, Cal, Opm

Qtz, Cal, Ms,

Qtz, Cal, Ms,

(Fig. 3f), orthoclase, plagioclase, muscovite and biotite. In order

Qtz, Ms, Bt,
Ms, Or, Bt

of abundance, sandstones, quartzites, shales, limestones, siltstones,

Ms, Or

Opm

Opm

Opm

Opm

phyllites, fragments of pottery (cocciopesto) and coal can be

Ms

Pl

observed. The aggregate was estimated at 50%.

A further discrimination in the group arose between the mortar
foundations (MM24, MM26b, MM27) and the samples of the outer
wall (MM33, MM35, MM36). The first ones manifest an inhomoge-
neous binder and a higher aggregate amount, of about 50–55%; the
H

H
I

second ones show a lower quantity of aggregate, of about 40%.

3.2.4. 4th Group (MM23, MM31, MM32, MM34, MM37, MM38)

The mortars come from the square building (area 4000). A great
R

R
P

number of partially burnt limestone and reused mortars were

detected. The composition of the reused mortars was similar to
A-WR

A-WR

A-WR

that of the adjacent productive area (3rd group). Other lithic frag-
WR

WR

WR

WR

WR

WR

ments are shales, phyllites, sandstones, limestones, siltstones,

quartzites, few metallurgic slags and coal. The aggregate amount
was evaluated at 35% and the porosity, of primary and secondary
type, is about 15%.
LS

LS

LS

LS

LS

LS

LS

LS

LS

3.2.5. 5th Group (MM5, MM7, MM39, MM40, MM50)

The samples were taken from the north and south-west
PS

PS

PS

PS

PS

PS

PS

PS

PS

entrances of the church and from the area 9000. The aggregate dis-
plays a mean size of 650 lm (coarse sand) [16], medium–low
451
160

160

450

450

650

160

450
600
MS

MS

MS

MS
CS

CS
FS

FS

FS

sphericity and it is visually estimated at 35%. Several metallurgical

slags are visible. Although the slags mainly have an opaque appear-
10

10

10

10

10

10
5

ance in transmitted light, it was possible to recognise melilite crys-

tals (Fig. 3g) and iron oxides, sometimes showing dendritic shape.
10000
1920

2240
1600

2200
4000

5000

6000

9000

Monocrystalline phases such as calcite (Fig. 3h), quartz, euhedral

opaque minerals, muscovite, biotite and orthoclase compose the
aggregate. Lithic fragments mainly consist of shales, sandstones
MM48_I
MM45

MM46

MM49

MM51

MM52

MM53

MM54
MM50

(Fig. 4a), limestones, siltstones, phyllites, rhyolites (Fig. 4b), marble

and quartzite (Fig. 4c); cocciopesto (Fig. 4d) and coal are also pre-
sent. The primary and secondary porosity was valued at 15%.
450 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460

Table 3
Main characteristics of the binder and porosity on thin sections and percentage amount of aggregate, binder and porosity by visual estimation. H: homogeneous, I:
inhomogeneous, n.d.: not determined.

Binder Porosity % by visual estimation [16]

Colour Crystallinity Size (lm) Tipology Distribution Aggregate Binder (size < 1/ Porosity
16 mm)
Max. Min.
MM1 Pale Brown- Cryptocrystalline 4000 10 Primary and I 40 45 15
grayish secondary
MM2 Gray-brownish Cryptocrystalline 3200 10 Primary and I 30 50 20
secondary
MM3 Gray-brownish Cryptocrystalline 1680 10 Primary and I 30 55 15
secondary
MM4 Gray-brownish Cryptocrystalline 4800 10 Primary and I 25 55 20
secondary
MM5 Brown-grayish Cryptocrystalline 8000 10 Primary and I 35 50 15
secondary
MM6 Gray-brownish Cryptocrystalline 4800 10 Secondary I 30 50 20
MM7 Brown-grayish Cryptocrystalline 7000 10 Primary and I 35 50 15
secondary
MM8 Dark gray Cryptocrystalline 1760 10 Primary and I 3 82 15
secondary
MM9 Gray-brownish Cryptocrystalline 3200 10 Secondary I 30 50 20
MM10 Brown Cryptocrystalline 3200 10 Primary H 40 53 7
MM11 Gray-brownish Cryptocrystalline 4400 10 Secondary I 30 50 20
MM12 Gray-brownish Cryptocrystalline 2900 10 Secondary I 30 50 20
MM13 Gray-brownish Cryptocrystalline 2600 10 Secondary I 30 50 20
MM14 Brown Cryptocrystalline 1700 10 Secondary I 40 40 20
MM15 Brown-grayish Cryptocrystalline 2500 10 Secondary I 40 40 20
MM16a Red-Brownish – 1040 10 Secondary I 30 50 20
MM16b Brown Cryptocrystalline 1800 10 Secondary I 40 45 15
MM17a Red-Brownish – 1360 10 Secondary I n.d. n.d. n.d.
MM17b Gray-brownish Cryptocrystalline 1500 10 Secondary I 30 50 20
MM18 Red-Brownish – 1120 10 Secondary I 35 50 15
MM19 Pale brown Cryptocrystalline 6900 10 Primary and H 50 43 7
secondary
MM20 Pale brown Cryptocrystalline 1200 10 Primary and H 45 48 7
secondary
MM21 Brown-grayish Cryptocrystalline 1080 10 Primary and H 50 40 10
secondary
MM22 Pale brown Cryptocrystalline 1200 10 Primary and H 50 40 10
secondary
MM23 Brown Cryptocrystalline 1600 10 Primary and I 35 50 15
secondary
MM24 Pale brown Cryptocrystalline 1600 10 Secondary I 50 35 15
MM25 Gray-brownish Cryptocrystalline 2800 10 Primary and H 50 40 10
secondary
MM26a Brown Cryptocrystalline 1600 10 Secondary I n.d. n.d. n.d.
MM26b Pale brown Cryptocrystalline 1680 10 Secondary I 50 30 20
MM27 Pale brown Cryptocrystalline 3100 10 Secondary I 50 35 15
MM28 Pale brown Cryptocrystalline 2200 10 Primary and I 50 40 10
secondary
MM29a Brown-grayish Cryptocrystalline 1300 10 Secondary I 40 35 25
MM29b Red-Brownish – 1440 10 Secondary I 30 50 20
MM30 Brown Cryptocrystalline 1000 10 Secondary I 40 40 20
MM31 Brown Cryptocrystalline 1900 10 Secondary I 35 50 15
MM32 Brown Cryptocrystalline 2200 10 Secondary I 35 50 15
MM33 Pale brown Cryptocrystalline 3000 10 Primary and I 40 40 20
secondary
MM34 Brown Cryptocrystalline 2400 10 Secondary I 35 50 15
MM35 Pale brown Cryptocrystalline 3200 10 Primary and I 40 45 15
secondary
MM36 Gray-brownish Cryptocrystalline 2000 10 Secondary I 40 40 20
MM37 Brown Cryptocrystalline 4000 10 Primary and I 35 50 15
secondary
MM38 Brown Cryptocrystalline 3200 10 Secondary I 35 50 15
MM39 Gray-brownish Cryptocrystalline 1840 10 Primary and H 35 55 10
secondary
MM40 Gray-brownish Cryptocrystalline 2600 10 Primary and I 35 50 15
secondary
MM41 Red-Brownish – 1356 10 Secondary I 30 50 20
MM42_I Gray-brownish Cryptocrystalline 3040 10 Primary and I 30 45 25
secondary
MM42_II Gray-brownish Cryptocrystalline 640 10 Primary and I 40 45 15
secondary
MM43 Gray-brownish Cryptocrystalline 2320 10 Secondary I 40 45 15
MM44a Gray-brownish Variable from micritic to 880 10 Secondary I 40 40 20
microcrystalline
 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460 451

Table 3 (continued)

Binder Porosity % by visual estimation [16]

Colour Crystallinity Size (lm) Tipology Distribution Aggregate Binder (size < 1/ Porosity
16 mm)
Max. Min.
MM44b_I Gray Cryptocrystalline 1000 10 Secondary I 40 40 20
MM44b_II Brown Variable from micritic to 1560 10 Secondary I 40 40 20
microcrystalline
MM45 Gray-brownish Cryptocrystalline 4800 10 Primary and I 40 50 10
secondary
MM46 Gray-brownish Cryptocrystalline 1120 10 Primary and I 40 45 15
secondary
MM48_I Gray-brownish Cryptocrystalline 800 10 Primary and H 30 55 15
secondary
MM49 Gray-brownish Cryptocrystalline 2400 10 Primary and H 35 50 15
secondary
MM50 Gray-brownish Cryptocrystalline 4000 10 Primary and I 35 45 20
secondary
MM51 Gray-brownish Cryptocrystalline 2400 10 Primary and I 50 35 15
secondary
MM52 Red-Brownish – 1440 10 Secondary I 30 50 20
MM53 Gray-brownish Cryptocrystalline 2240 10 Secondary I 30 50 20
MM54 Gray-brownish Cryptocrystalline 8000 10 Secondary I 31 51 20

Fig. 5. Diffractogram of the sample MM7, Ak: akermanite, Cal: calcite, Chl: chlorite, Mgt: magnetite, Ms: muscovite, Qtz: quartz, Wus: wustite.

The mortars sampled from the foundation wall of the whole
complex (MM16a, MM17a, MM18, MM29b, MM41, MM44b_II,
MM47, MM52) are characterised by a clay binder. Among these
samples, only in MM17a and MM18 were some lumps of lime
identified. Other samples (MM4, MM8, MM10 and MM42_I,
MM44a, MM51) showing different characteristics were not
included in the groupings.
hydrothermal deposits, in association with sulfides. In other sam-
ples, a small percentage of magnesite (MM21, MM45), dolomite
(MM50), pyroxene (MM51), fluorite (MM61) and clay minerals,
such as kaolinite (MM23) and vermiculite (MM62), was found.
Moreover, a detailed study was performed by microcapillary
XRD analysis on the opaque minerals in thin sections. The main
opaque phases consist of magnetite and goethite.

3.3. XRD analysis 3.4. SEM–EDS analysis

The main mineralogical phases detected by XRPD analysis were
calcite, quartz, muscovite, clinochlore and albite (Table 4). In the
samples of the 2nd and 5th groups, containing metallurgic slags,
melilites (hardystonite, akermanite and gehlenite) and iron oxides
(hematite, wustite and magnetite) were determined (Fig. 5).
Very low amounts of smithsonite (ZnCO3) and proustite
(Ag3AsS3) were also revealed in the samples MM15, MM16,
MM36 and MM40. Smithsonite is commonly present as a product
of oxidation in zinc deposits. Proustite is a secondary product in
The chemical composition of the binder was determined by
SEM–EDS microanalysis. For each sample three spots were col-
lected on a homogeneous area of the lumps and binder. A total of
153 analyses were performed on the binder and 149 on the lime
lumps. The data were elaborated in order to obtain the average
hydraulicity index for every sample. Tables 5 and 6, obtained by
statistical treatment of the data, show the maximum, minimum
and average values of the chemical elements and of the hydraulic-
ity indexes for each groups, with the relative error, standard
452 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460

Table 4
Mineralogical composition of mortars by X-ray powder diffraction; the number of stars is proportional to the phase abundancy. Ab: albite, Cal: calcite, Chl: chlorite, Hem:
hematite, Mgt: magnetite, Mel: melilite, Ms: muscovite, Qtz: quartz, Rt: rutile, Wus: wustite (abbreviations according to Refs. [20,21]).

Cal Qtz Chl Ms Ab Mel Mgt Wus Hem Rt

*** *** ** * *
MM1
*** *** ** * *
MM2
*** *** ** ** *
MM3
*** *** ** **
MM4
*** *** * ** * * **
MM5
*** *** ** ** *
MM6_I
*** *** * ** *
MM6_II
*** *** ** * ** * **
MM7
*** *** ** **
MM8
*** *** ** ** *
MM9
*** *** ** *
MM10
*** *** ** * *
MM11
*** *** ** ** *
MM12
*** *** ** ** *
MM13
*** *** * * **
MM14
*** *** * * *
MM15
*** *** ** * * *
MM16
*** *** ** ** *
MM17
*** *** ** ** *
MM18
*** *** ** ** *
MM19
*** *** * *
MM20
*** *** * **
MM21
*** *** * **
MM22
*** *** ** **
MM23
*** *** * **
MM24
*** *** * **
MM25
*** *** * ** *
MM26
*** *** * * *
MM27
*** *** * ** *
MM28
*** ** ** *
MM29
*** *** * * *
MM30
*** ** * *
MM31
*** ** * * *
MM32
*** *** * *
MM33
*** *** ** *
MM34
*** *** * ** *
MM35
*** *** * **
MM36
*** ** * * *
MM37
*** *** ** **
MM38
*** *** ** ** *
MM39
*** *** * * **
MM40
*** ** ** *
MM41
*** *** ** * * *
MM42
** *** ** ** *
MM43
*** ** * * * *
MM44
*** *** * ** *
MM45
*** *** * **
MM46
*** *** ** **
MM47
*** ** ** * *
MM48_I
*** *** ** *
MM48_II
*** *** ** ** *
MM49
*** *** * * *
MM50
*** *** ** ** **
MM51
*** ** ** **
MM52
*** *** ** ** *
MM53
*** *** ** ** *
MM54

deviation and variance. In the mortar samples of the 1st, 2nd, 3rd
and 4th groups the lumps are composed by aerial lime and the bin-
der shows weak hydraulicity [22]. In the mortars of the 5th group
the lumps have weak hydraulicity and the binder is moderately
hydraulic. The metallurgic slags and cocciopesto in the aggregate
probably induced the highest hydraulicity of these ones. The bin-
der in the samples MM10 and MM59 is eminently hydraulic and
this is due to the presence of artificial glasses in the first case
and of the great number of slags in the second one.
Another interesting observation concerns the presence of the
lead peaks in the binder and lumps microanalysis spectrums of
the 2nd and 5th groups. This can indicate the partial migration of
this element from the slags into the surrounding area (Fig. 6).
The composition of some metallurgic slags was studied by
SEM–EDS microanalysis, confirming the presence of melilite, previ-
ously identified by optical microscopy and XRPD (Fig. 7a).
Dendritic phases such as wustite or spinels (Fig. 7b), feldspathoids
(Fig. 7c) and metal-bearing grains (Fig. 7d and e) were also
detected (Table 6). The grains are constituted by lead, alloy, such
as Cu–Sb and As–Pb–Sb, and copper sulfides. The morphological
and chemical microanalysis was also carried out on the opaque
minerals, previously studied by XRD microcapillary, to verify their
 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460
Fig. 6. SEM–EDS microanalysis of binder and lumps, (a) Back Scattered Electrons (BSE) image of lump and the corresponding SEM–EDS spectrum in the sample MM5, (b) BSE
image of an area of the sample MM5 containing a metallurgic slag (indicated by the white arrow) and (c) map of the lead distribution.
composition (Fig. 7f). Furthermore particular polycrystalline
argentiferous pyrite was detected in MM24 and MM48_II samples
(Fig. 7g and h).
3.5. XRF analysis
The chemical composition of the major (CaO, MgO, MnO, Fe2O3,
P2O5, K2O, SiO2, Na2O, TiO2, Al2O3) and the trace elements (Ni, Cu,
Zn, Co, Cr, Pb, Ba, Sr, Rb, Nb, Y, Zr, V) was obtained by XRF analysis
(Tables 8 and 9). Among the major elements, in the foundation
samples, the values of Fe, Si, Al and Ti are higher than in the other
samples, due to the presence of a clay binder (Fig. 8a). The mortars
containing metallurgic slags have the highest amount of Fe, Mg
and Na, among the major elements, and Cu, Zn and Pb as traces
(Fig. 8b).
4. Reconstruction of the building phases
Recent archaeometric researches showed how the study of the
mortar composition can be of fundamental importance for the
analysis of the masonry structures in ancient monuments, support-
ing the archaeological investigation in the reconstruction of the
building phases [23–25]. In particular, the analysis of the mortars
provides much information about the production technology. The
workers operating in different historical periods probably pro-
duced building materials with different technological characteris-
tics. The differences could be due to the type of the sand, the
choice of limestone for the production of the binder, the addition
of other natural or artificial materials (for example materials with
hydraulic properties) and the processing. Sometimes, even within
the same construction phase, differences can arise because of dif-
ferent or variable proportions between the binder and the
aggregate.
453
In our case, the petrographic analysis on the thin sections high-
lighted some important compositional differences between the
mortars, allowing us to make a preliminary grouping. Subsequent
analysis led us to investigate the mineralogical (XRD) and chemical
(SEM–EDS, XRF) composition, deepening and increasing the avail-
able data.
A statistical discriminant analysis was performed using as vari-
ables the petrographic groups and the chemical data of the major
elements. The groups are clearly identifiable in the graphic of the
main functions (Fig. 9). The overlap of the 1st and 4th groups is
the consequence of the very similar composition of the sand in
the mortars.
Petrographic, mineralogical and chemical investigations
allowed us to highlight the compositional differences among the
samples, favouring the reading of the construction steps of the site
and supporting the archaeological interpretation. The 5 groups
identified correspond to many construction phases (Fig. 10), listed
below.
4.1. 1st Phase (1st group)
In the first half of the XI century the building of the church took
place. The mortar reveals similar characteristics in all the six apses
that compose the edifice. The presence of the same mortar was
traced in the semicircular wall remains inside the annex building
(area 1000 – 1st building), probably contemporary with the
church. The traces of walls in the area 2000, currently under fur-
ther archaeological analyses, are probably also ascribed to the 1st
phase.
4.2. 2nd Phase (2nd group)
The building annexed to the church was erected in a consecu-
tive step. Traces of the 1st group mortars were found in the foun-
dations of the edifice and traces of the 2nd group mortars are
454 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460

Fig. 7. BSE images, (a) metallurgic slag composed by melilite (Mel) and wustite (Wus) in sample MM1, (b, c) zoned spinels (Spl), Ni–Cu–Zn alloy and leucite in the slag of
sample MM23, (d) composite metal-bearing grain with pure antimony (Sb) and Sb–Cu metal alloy in the slag of the sample MM7, (e) composite metal-bearing grain with pure
lead (Pb) and Sb–Cu metal alloy in slag of the sample MM15, (f) iron oxide with structure of growth in sample MM20 and (g, h) argentiferous pyrite (Py).
 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460 455

Table 5
Statistical data of SEM–EDS microanalysis calculated on the binder for each mortar group. H.I.: hydraulicity index, b.l.d.: below detection limit.

SiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2 O5 Cl2O PbO2 SO3 ZnO H.I.
1st Group Average 6.70 2.48 0.83 0.22 1.14 86.75 0.83 0.42 0.65 b.d.l. b.d.l. b.d.l. b.d.l. 0.12
Standard deviation 2.42 0.57 0.44 0.46 0.60 3.86 0.23 0.20 0.50 – – – – 0.04
Variance 5.87 0.33 0.19 0.21 0.36 14.93 0.05 0.04 0.25 – – – – 0.00
Minimum 2.04 1.27 b.d.l. b.d.l. 0.02 80.36 0.38 0.17 b.d.l. – – – – 0.04
Maximun 11.14 3.47 1.37 1.24 2.18 93.93 1.03 0.76 1.19 – – – – 0.19
2nd Group Average 5.83 2.66 1.20 b.d.l. 1.61 82.06 1.42 0.45 1.05 0.01 3.71 b.d.l. b.d.l. 0.12
Standard deviation 1.02 0.51 0.35 – 0.31 1.73 0.55 0.18 0.53 0.04 2.02 – – 0.02
Variance 1.03 0.26 0.12 – 0.10 3.00 0.30 0.03 0.28 0.00 4.07 – – 0.00
Minimum 3.89 2.05 0.63 – 1.34 77.43 0.70 b.d.l. b.d.l. b.d.l. 1.03 – – 0.08
Maximun 7.29 3.82 1.91 – 2.48 83.76 2.30 0.72 1.69 0.13 6.85 – – 0.14
3rd Group Average 5.99 2.51 1.97 0.27 2.03 84.21 1.06 0.36 0.57 0.02 0.63 0.27 0.09 0.12
Standard deviation 2.26 0.63 1.50 0.45 1.34 5.06 0.43 0.26 0.56 0.06 0.87 0.41 0.29 0.05
Variance 5.09 0.39 2.25 0.20 1.78 25.56 0.18 0.07 0.31 0.00 0.75 0.17 0.08 0.00
Minimum 2.51 1.52 0.61 b.d.l. 0.79 73.88 0.46 b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. 0.05
Maximun 11.04 3.68 5.23 1.23 6.00 90.48 2.00 0.67 1.53 0.21 2.28 1.26 1.00 0.22
4th Group Average 7.68 2.89 1.26 b.d.l. 1.18 85.86 0.77 0.12 0.16 b.d.l. b.d.l. 0.08 b.d.l. 0.14
Standard deviation 0.91 0.87 0.17 – 0.42 2.38 0.36 0.15 0.37 – – 0.13 – 0.02
Variance 0.83 0.76 0.03 – 0.18 5.67 0.13 0.02 0.13 – – 0.02 – 0.00
Minimum 6.63 1.24 1.03 – 0.25 83.12 b.d.l. b.d.l. b.d.l. – – b.d.l. – 0.10
Maximun 9.09 3.94 1.45 – 1.43 89.91 1.17 0.37 0.98 – – 0.34 – 0.16
5th Group Average 10.59 4.45 1.21 b.d.l. 6.76 71.23 1.64 0.31 0.91 0.07 2.82 b.d.l. b.d.l. 0.22
Standard deviation 5.90 1.03 0.28 – 2.52 9.95 0.52 0.17 0.58 0.14 1.21 – – 0.12
Variance 34.84 1.06 0.08 – 6.34 98.92 0.27 0.03 0.34 0.02 1.46 – – 0.02
Minimum 6.85 2.94 0.97 – 4.55 52.01 1.25 b.d.l. b.d.l. b.d.l. 1.72 – – 0.13
Maximun 22.34 5.94 1.73 – 11.52 79.02 2.60 0.48 1.77 0.36 4.75 – – 0.46

Table 6
Statistical data of SEM–EDS microanalysis calculated on the lumps for each mortar group. H.I.: hydraulicity index, b.l.d.: below detection limit.

SiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5 Cl2O PbO2 SO3 H.I.
1st Group Average 3.34 1.48 0.64 0.21 1.03 91.40 0.87 0.29 0.75 b.d.l. b.d.l. b.d.l. 0.06
Standard deviation 1.16 0.55 0.16 0.45 0.45 2.38 0.18 0.14 0.57 – – – 0.02
Variance 1.35 0.31 0.03 0.20 0.20 5.64 0.03 0.02 0.33 – – – 0.00
Minimum 1.18 0.67 0.44 b.d.l. 0.18 87.61 0.59 0.08 b.d.l. – – – 0.03
Maximun 5.01 2.34 1.01 1.24 1.51 94.99 1.14 0.54 1.38 – – – 0.09
2nd Group Average 2.93 1.49 0.79 b.d.l. 1.70 87.84 1.40 0.29 0.94 0.05 2.58 b.d.l. 0.06
Standard deviation 1.44 0.65 0.29 – 0.55 3.93 0.68 0.16 0.62 0.14 1.40 – 0.03
Variance 2.08 0.43 0.08 – 0.31 15.42 0.46 0.03 0.38 0.02 1.97 – 0.00
Minimum 1.18 0.72 0.47 – 0.83 82.76 0.39 b.d.l. b.d.l. b.d.l. 0.76 – 0.03
Maximun 5.19 2.58 1.36 – 2.74 94.67 2.55 0.47 1.69 0.47 5.52 – 0.10
3rd Group Average 2.87 1.27 0.90 b.d.l. 1.72 90.50 1.10 0.12 0.58 0.13 0.51 0.31 0.06
Standard deviation 1.48 0.44 0.25 – 0.68 3.05 0.44 0.16 0.65 0.24 0.66 0.56 0.02
Variance 2.20 0.20 0.06 – 0.47 9.28 0.19 0.03 0.42 0.06 0.43 0.32 0.00
Minimum 1.22 0.87 0.49 – 0.47 85.41 0.39 b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. 0.03
Maximun 5.60 2.44 1.21 – 3.20 95.15 1.91 0.40 1.55 0.81 1.88 1.55 0.09
4th Group Average 3.11 1.26 0.82 b.d.l. 1.30 92.64 0.55 0.04 0.19 0.01 b.d.l. 0.09 0.06
Standard deviation 0.62 0.27 0.13 – 0.71 1.60 0.16 0.06 0.43 0.01 – 0.13 0.01
Variance 0.39 0.07 0.02 – 0.50 2.56 0.02 0.00 0.18 0.00 – 0.02 0.00
Minimum 1.91 0.85 0.59 – 0.71 90.22 0.38 b.d.l. b.d.l. b.d.l. – b.d.l. 0.04
Maximun 3.91 1.61 1.01 – 2.81 95.26 0.85 0.14 1.15 0.04 – 0.30 0.07
5th Group Average 8.10 2.68 0.71 b.d.l. 5.24 78.36 1.22 0.25 0.76 0.04 2.65 b.d.l. 0.14
Standard deviation 1.52 0.49 0.27 – 0.98 3.52 0.40 0.05 0.50 0.07 0.60 – 0.02
Variance 2.30 0.24 0.07 – 0.96 12.36 0.16 0.00 0.25 0.01 0.36 – 0.00
Minimum 5.79 2.06 0.42 – 3.73 73.43 0.62 0.18 b.d.l. b.d.l. 2.15 – 0.11
Maximun 9.86 3.35 1.00 – 6.30 83.37 1.72 0.31 1.36 0.17 3.65 – 0.17

present in the foundations of the south-east apse of the church. In
this phase, the presence of slags in the aggregate is widespread.
4.3. 3rd Phase (3rd group)
The 3rd phase coincides with the expansion of the productive
area and the construction of a boundary wall. The composition of
the mortar looks very different compared to the previous walls,
mostly for what concerns the type of aggregate, mainly composed
by quartz. This feature should indicate the change of the place for
the supply of sand.
4.4. 4th Phase (4th group)
In the XIII century a quadrangular building (area 4000) was
erected. The posteriority of the building is suggested both by
456 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460

Table 7
SEM–EDS analyses of the pyrometallurgic phases in the slags (MM_S: Montieri Mortar_Slag); the chemical formula was recalculated to 7 oxygens for melilite and to 6 oxygens for
leucite.

Melilites Leucite
MM1a_S1_1 MM7a_S1 _1 MM7b_S2_1 MM7b_S2_2 MM23_S1_3 MM23_S1_4
SiO2 35.54 36.14 31.79 28.43 56.83 56.99
TiO2 – – – – – –
MgO 3.39 3.34 2.34 2.69 – –
Al2O3 10.98 12.67 17.98 11.46 22.79 22.12
FeO 7.66 7.00 5.07 16.86 1.35 1.87
MnO – – – – – –
CaO 38.24 32.88 35.78 31.45 – –
Na2O 3.62 3.43 2.50 3.41 0.33 0.82
K2O 0.57 0.39 – – 18.70 18.21
ZnO – 4.14 4.54 5.70 – –
Si 1.69 1.72 1.51 1.35 2.04 2.05
Ti – – – – – –
Mg 0.24 0.24 0.17 0.19 – –
Al 0.62 0.71 1.01 0.64 0.96 0.94
Fe 0.31 0.28 0.20 0.67 0.04 0.06
Mn – – – – – –
Ca 1.95 1.67 1.82 1.60 – –
Na 0.33 0.32 0.23 0.31 0.02 0.06
K 0.03 0.02 – – 0.86 0.83
Zn – 0.15 0.16 0.20 – –

Table 8
Chemical composition of mortars by XRF analysis: the major elements are expressed in oxides wt%. L.O.I.: loss on ignition.

wt% SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P 2 O5 L.O.I.
MM1 32.51 0.34 8.41 5.60 0.19 2.94 25.04 0.58 1.05 0.14 23.21
MM2 33.39 0.33 9.67 4.15 0.10 1.67 24.70 0.30 1.16 0.07 24.47
MM3 36.19 0.34 9.81 4.33 0.08 1.93 22.79 0.32 1.18 0.08 22.95
MM4 19.61 0.21 5.91 2.96 0.12 1.66 41.95 0.13 0.59 0.08 26.77
MM5 27.29 0.30 7.27 6.58 0.26 7.82 25.98 0.39 0.84 0.13 23.14
MM6_I 41.30 0.42 11.74 4.66 0.09 1.77 19.58 0.42 1.50 0.10 18.42
MM6_II 32.27 0.30 7.32 8.48 0.14 2.23 24.17 0.21 1.02 0.08 23.80
MM7 32.26 0.38 8.40 9.06 0.42 6.37 22.98 0.53 0.91 0.16 18.52
MM8 15.37 0.17 4.97 2.32 0.09 2.72 37.15 0.09 0.46 0.08 36.58
MM9 34.08 0.37 10.55 4.27 0.09 1.81 23.36 0.30 1.26 0.07 23.86
MM10 43.83 0.23 6.41 3.04 0.26 2.68 22.44 0.32 0.95 0.09 19.75
MM11 35.11 0.35 9.94 4.40 0.09 1.72 23.23 0.30 1.13 0.08 23.66
MM12 31.27 0.30 9.40 3.89 0.09 1.82 25.88 0.26 1.10 0.06 25.93
MM13 33.68 0.32 9.65 4.00 0.09 1.86 24.58 0.29 1.15 0.06 24.32
MM14 22.13 0.28 7.19 5.02 0.19 2.20 32.85 0.25 0.89 0.15 28.85
MM15 28.69 0.38 8.21 8.12 0.30 2.93 26.20 0.66 1.16 0.15 23.21
MM16 30.62 0.33 7.98 8.32 0.27 2.89 25.24 0.74 1.12 0.37 22.11
MM17 49.04 0.65 15.21 7.10 0.21 2.22 9.34 0.45 2.44 0.28 13.05
MM18 55.10 0.76 17.04 7.45 0.24 2.26 4.19 0.50 3.08 0.19 9.19
MM19 42.77 0.19 5.77 2.81 0.19 1.68 24.86 0.12 0.98 0.15 20.47
MM20 45.88 0.20 6.08 3.41 0.19 1.48 22.61 0.15 1.03 0.10 18.86
MM21 54.49 0.19 5.83 2.92 0.22 1.14 18.33 0.23 1.04 0.10 15.50
MM22 44.59 0.20 5.88 3.64 0.23 1.52 24.04 0.22 1.07 0.12 18.50
MM23 28.83 0.31 8.94 3.87 0.13 2.07 28.11 0.22 1.03 0.10 26.38
MM24 48.12 0.20 6.10 3.21 0.22 1.38 21.82 0.19 1.12 0.16 17.49
MM25 44.93 0.17 5.53 4.60 0.20 1.36 23.39 0.17 0.96 0.15 18.55
MM26 47.25 0.29 8.26 4.09 0.33 1.49 18.78 0.21 1.44 0.48 17.38
MM27 57.51 0.28 7.91 4.25 0.30 2.09 13.29 0.23 1.47 0.30 12.36
MM28 58.23 0.26 7.72 4.19 0.16 1.30 13.49 0.24 1.53 0.16 12.72
MM29 56.05 0.86 18.28 8.31 0.22 2.26 2.33 0.38 3.32 0.23 7.78
MM30 27.31 0.31 7.86 4.42 0.15 2.42 28.92 0.35 1.01 0.13 27.12
MM31 13.94 0.13 4.32 1.65 0.06 1.40 42.44 0.05 0.31 0.06 35.65
MM32 22.37 0.25 6.48 4.46 0.14 2.33 33.77 0.16 0.79 0.12 29.12
MM33 37.36 0.21 6.41 3.53 0.15 2.03 26.40 0.14 0.89 0.12 22.76
MM34 34.45 0.26 7.30 3.37 0.11 2.03 26.03 0.15 0.87 0.14 25.30
MM35 51.19 0.22 6.43 3.82 0.21 1.28 19.12 0.16 1.14 0.24 16.20
MM36 51.37 0.21 6.39 3.74 0.19 1.56 18.31 0.17 1.23 0.18 16.66
 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460 457

Table 8 (continued)

wt% SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P 2 O5 L.O.I.
MM37 26.20 0.25 6.99 3.15 0.12 2.05 31.76 0.17 0.74 0.11 28.45
MM38 25.41 0.26 7.52 3.76 0.13 2.18 30.98 0.17 0.82 0.10 28.67
MM39 34.57 0.46 10.17 8.61 0.36 3.90 21.90 0.50 1.27 0.33 17.93
MM40 36.21 0.45 9.91 9.70 0.47 5.01 19.68 0.63 1.26 0.26 16.42
MM41 58.15 0.88 18.00 7.77 0.26 2.21 0.65 0.41 3.35 0.26 8.04
MM42 32.35 0.37 9.65 4.59 0.14 2.40 24.40 0.40 1.35 0.18 24.18
MM43 32.16 0.41 9.99 5.70 0.19 3.42 23.68 0.52 1.41 0.30 22.22
MM44 34.97 0.41 10.17 9.58 0.30 2.41 21.16 0.40 1.38 0.20 19.02
MM45 28.37 0.34 8.23 6.44 0.25 2.46 26.64 0.68 1.04 0.18 25.36
MM46 24.65 0.32 8.10 4.01 0.15 2.90 30.05 0.18 1.21 0.12 28.31
MM47 47.88 0.61 14.65 7.67 0.35 1.89 10.19 0.42 2.24 0.12 13.98
MM48_I 21.27 0.20 6.14 2.32 0.08 2.76 34.25 0.12 0.67 0.10 32.10
MM48_II 21.21 0.12 3.91 1.67 0.07 4.62 35.66 0.07 0.41 0.06 32.21
MM49 34.78 0.35 10.31 4.22 0.11 1.86 23.16 0.28 1.22 0.06 23.65
MM50 37.48 0.40 8.75 8.80 0.37 8.33 16.83 0.71 1.04 0.17 17.12
MM51 46.75 0.60 14.88 7.01 0.12 2.22 12.21 0.59 2.18 0.11 13.33
MM52 59.09 0.94 17.77 7.54 0.32 2.01 1.00 0.36 3.34 0.31 7.32
MM53 47.01 0.44 11.99 4.79 0.15 1.63 15.29 0.41 1.70 0.09 16.50
MM54 34.87 0.42 11.51 5.07 0.15 1.89 22.07 0.31 1.46 0.07 22.17

Fig. 8. Elaboration of the chemical data, (a) Al2O3 vs Fe2O3 diagram, and (b) Pb vs Cu diagram.

4.5. 5th Phase (5th group)

Finally, a subsequent reconstruction by bricks of the entrances

can be observed. The mortars, light in colour, contain many frag-
ments of metallurgic slags of high dimensions.

5. Conclusions

Nowadays the archaeological research more and more needs

Fig. 9. Discriminant analysis, Function 1 vs Function 2 diagram, obtained by using
the petrographic groups and chemical data as variables.
stratigraphic relationships and the presence of reused mortars sim-
ilar to those of the adjacent production area (3rd group). The lime-
stones partially burnt in the mortar aggregates reveal a regress of
the technical execution.
the contribution of archaeometry, most of all when the study
objects are the construction materials (natural stones, mortars,
plasters, bricks, etc.). The study of this kind of materials can pro-
vide several useful information for reconstructing the history of
an archaeological site and in this context the multi-disciplinary
and multi-analytical approach is fundamental. The study we per-
formed allowed us to determine the petrographic, mineralogical
and chemical composition of the mortar samples coming from
the St. Niccolò ecclesiastical complex in Montieri. In particular,
the petrographic description revealed the analogies and differences
among the samples, enabling the identification of 5 typologies of
mortars. The mineralogical and chemical data confirmed the differ-
ences, clearly identifiable in the graph of statistical discriminant
analysis (Fig. 9). The integration of the archaeological and
458 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460

Table 9
Trace element compositions of mortars by XRF analysis, expressed in ppm. L.O.I.: loss on ignition, b.d.l.: below detection limit.

Ni Cu Zn Co Cr Pb Ba Sr Rb Nb Y Zr V
MM1 46 2503 10,539 11 62 17136 b.d.l. 107 3782 9 9 64 53
MM2 31 46 71 12 48 60 227 145 65 11 8 71 58
MM3 33 40 66 8 53 34 229 98 61 12 7 64 59
MM4 26 285 1684 6 24 1720 86 118 405 9 7 36 28
MM5 46 2868 8822 8 60 12094 b.d.l. 141 2667 8 11 54 52
MM6_I 36 101 179 11 62 2878 258 144 690 11 8 89 73
MM6_II 31 1050 2291 11 51 4707 b.d.l. 124 1050 24 5 31 59
MM7 55 4779 12,893 12 77 12186 b.d.l. 210 2688 10 12 65 68
MM8 20 429 554 4 26 2461 137 96 566 8 5 34 26
MM9 33 56 81 11 57 56 197 132 68 11 7 59 65
MM10 31 1253 6483 9 37 7780 b.d.l. 46 1725 8 12 40 55
MM11 32 48 70 12 52 49 226 119 65 11 7 60 61
MM12 33 65 66 10 47 65 240 118 65 11 7 56 54
MM13 33 40 60 11 47 36 209 132 60 11 8 57 54
MM14 34 1646 3608 8 41 14768 30 110 3263 9 8 52 43
MM15 72 2660 15,736 14 62 16893 b.d.l. 92 3729 10 9 64 60
MM16 44 3375 14,348 9 57 29061 b.d.l. 85 6385 8 9 61 51
MM17 65 113 343 21 119 249 391 124 167 15 11 114 123
MM18 76 109 302 26 151 132 463 89 170 16 12 131 151
MM19 23 608 1574 10 29 2859 92 108 662 7 8 36 46
MM20 20 740 2000 9 27 3486 59 101 795 6 9 35 43
MM21 20 746 5609 12 31 3408 b.d.l. 65 777 6 8 29 41
MM22 22 773 2814 10 31 4283 4 79 969 7 11 34 45
MM23 36 125 314 8 48 837 226 290 236 11 10 68 51
MM24 20 1257 1872 10 29 6945 2 90 1543 6 12 37 40
MM25 20 1552 2800 12 25 4971 5 80 1110 6 10 26 35
MM26 36 484 1451 17 50 2605 124 427 625 9 13 79 63
MM27 32 963 2758 14 42 3960 62 86 908 7 11 44 57
MM28 21 844 4341 10 41 3447 b.d.l. 55 796 7 10 38 62
MM29 91 300 1724 30 183 1131 466 55 392 17 10 151 179
MM30 34 1590 4281 6 48 20029 51 142 4415 9 8 62 49
MM31 15 59 97 2 22 258 155 292 80 5 7 39 20
MM32 27 298 1318 6 40 2352 158 384 555 10 10 65 39
MM33 28 413 1170 10 34 2564 156 244 600 7 9 48 36
MM34 30 221 528 8 47 1076 173 384 281 9 11 72 47
MM35 24 801 2130 11 34 3512 67 81 803 6 9 35 46
MM36 20 1187 2396 9 35 4140 47 105 942 6 9 39 51
MM37 24 123 384 9 38 802 176 327 217 10 11 62 37
MM38 34 135 324 8 43 562 178 486 170 10 12 81 42
MM39 70 4576 10,154 13 91 14749 102 113 3264 12 12 69 83
MM40 73 5383 13,584 12 91 12511 57 263 2764 10 15 76 103
MM41 86 68 215 25 182 118 444 65 186 16 14 160 183
MM42 39 887 3965 11 59 12234 160 138 2729 11 7 71 54
MM43 63 1961 4753 13 83 15649 141 76 3473 11 10 78 67
MM44 58 6419 7006 12 82 21182 89 132 4669 9 10 70 72
MM45 49 3988 16,259 9 54 18544 b.d.l. 200 4087 9 10 66 57
MM46 30 329 2252 9 44 1480 157 92 376 12 8 62 42
MM47 62 68 149 22 102 74 409 94 117 14 11 96 119
MM48_I 20 134 300 4 32 1241 164 251 307 9 6 48 31
MM48_II 15 169 464 4 18 1197 94 213 284 5 6 32 23
MM49 37 40 67 10 55 36 227 106 63 10 7 56 60
MM50 64 4200 15,204 11 80 12198 8 171 2691 9 13 64 72
MM51 61 346 1139 15 94 3496 381 160 855 14 13 101 108
MM52 76 50 160 31 176 47 526 56 183 18 10 101 181
MM53 40 109 1188 15 68 86 223 97 93 12 9 101 88
MM54 44 59 100 13 66 95 251 142 92 13 9 101 79

archaeometric data leads to the recognition of the 5 major building
phases (Fig. 10). The 1st phase coincides with the construction of
the church, in the first half of the XI century. Between the late XI
and early XII century other edifices were erected. The building
technique seems to change over time: in the annex to the church
it was possible to identify the presence of metallurgical slags and
cocciopesto in the aggregate of the mortars. The slags are indicative
of metallurgical processes that took place in this period in an area
characterised by abundant mineral resources. Both slags and coc-
ciopesto give hydraulic properties to the binder. In addition to the
use of artificial materials in the aggregate, the variability of the
aggregate-binder proportion and of the aggregate typologies, par-
ticularly evident in the area 2000, testify to the changes of the pro-
duction technologies. The square building (area 4000) was
probably built in the XIII century. In this building, the mortars
reveal the worst executive technique, due to the presence of
numerous limestones partially burnt, reused mortars and the high-
est porosity.
The analysis of some metallurgical slags, consisting of poly-
metallic grains of Cu, Pb, Sb and As, suggest the exploitation of
mixed sulphide mineralisations [26,27]. Furthermore, the identifi-
cation of argentiferous pyrite testifies to the mineral wealth of the
place, in which the historical documents attest to the extraction of
silver for the production of coins.
The characterisation of mortar samples is the starting point for
the study of provenance of the raw materials, the object of a future
work. Furthermore, the knowledge of the original materials can be
useful for the reproduction of mortars highly compatible, for the
 N. Chiarelli et al. / Construction and Building Materials 96 (2015) 442–460 459

Fig. 10. Location of the samples belonging to different phases of construction: a symbol corresponds to each phase.

proper restoration and the long-term conservation of the archaeo-
logical site [28,29], using mixing optimisation methods on compo-
sitional chemical data [30–33].
Acknowledgements
The authors would like to thank the Superintendence for
Archaeological Heritage of Tuscany and the Medieval Archaeology
group of Siena University, for allowing us the sampling of mortars
from the archaeological site, and Andrea Scala and the laboratory
technicians of Physical, Earth and Environmental Sciences
Department, for their contribution during sampling and analysis.
The authors also thank the Science for Conservation of Cultural
Heritage PhD course of Florence University for funding the
research.
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