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Journal of Archaeological Science 38 (2011) 794e804

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Journal of Archaeological Science

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Characterisation of archaeological mortars and plasters from kyme (Turkey)

Domenico Miriello a,*, Andrea Bloise a, Gino M. Crisci a, Carmine Apollaro a, Antonio La Marca b

aDepartment of Earth Sciences, University of Calabria, 87036 Arcavacata di Rende (CS), ItalybDepartment of Archaeology and History of Arts, University of Calabria, 87036 Arcavacata di Rende (CS), Italy

a r t i c l e i n f o

Article history:Received 16 July 2010Received in revised form5 November 2010Accepted 10 November 2010

Keywords:AnatoliaMortarPlasterLime lumpBinderAggregateCocciopestoXRFSEM-EDSXRPD

* Corresponding author. Dipartimento di ScienzeCalabria, Via P. Bucci Cubo 12 B, 87036 Arcavacata di

E-mail address: miriello@unical.it (D. Miriello).

0305-4403/$ e see front matter � 2010 Elsevier Ltd.doi:10.1016/j.jas.2010.11.002

a b s t r a c t

The present study focuses on the compositional characterisation of Roman, proto-Byzantine and Medi-eval mortars, sampled in the archaeological site of Kyme (Turkey), an Aeolian city, founded in the middleof the XI century BC by Greek populations. The mortars were studied through elemental (SEM-EDS, XRF),mineralogical (XRPD, De Astis calcimeter) and petrographic (polarised optical microscopy) analysis. Thecomparison between the samples allowed us to emphasise compositional differences within mortars ofthe same historical period.

In particular, we detected the prevalent use of cocciopesto, which was used as a pozzolanic additive tocreate hydraulic mortars in the Roman and Byzantine period. The cocciopesto was used to improve thetechnological properties of an initially slaked lime. Furthermore, compositional similarities allowed us toattribute an unknown sample to the Roman period. Our study also pointed out the fact that the lowerquality mortars belonged to the Medieval period. As a matter of fact, the most friable sample belonging tothe Middle Ages turned out to be a mixture of clay, lime and volcanic sand.

� 2010 Elsevier Ltd. All rights reserved.

1. Introduction

Along theWestern coast of Turkey, 6 km from themodern city ofAlia�ga, between two hills, we find the ruins of the ancient city ofKyme (Fig. 1). Opposite the city lie the ruins of an ancient port, fromwhich an impressive quay is still visible, few centimetres below thewater level (Lagona, 1993, 2006, 1999; Esposito et al., 2003).

Kyme, the major city of the Aeolia was founded in the middle ofthe XI century by populations coming from the North of Greece. InVIII century BC, its inhabitants practiced seaborne trade and agri-culture was at the basis of its economy (Mele, 1979). It was themother country of several other cities, such as Side and Cuma in theSouth of Italy.

An outstanding port, in the archaic age, Kyme must haveundergone a period of economical floridity, partly deduced fromhistorical literature, and still reflected in the archaeological ruins(Lagona, 2004; La Marca, 2006; Scatozza Höricht, 2007). During theclassical age, Kyme had a strategic political position among theAegean cities. It was head of the Aeolic League, and subsequently it

della Terra, Università dellaRende (CS), Italy.

All rights reserved.

became part of the Athenian League. Alexander the Great dedicateda bronze candlestick to the city of Kyme in Apollo’s temple. Duringthe Hellenistic age, the city was renovated by building someimportant monuments, such as the theatre, impressive walls in theplain between the two hills (La Marca, 2006, 2007), residentialblocks on the Southern hill (Frasca, 2007), as well as the enlarge-ment of the quay (Esposito et al., 2003).

During the Imperial age, the earthquakes of AD 17 and 94 causedserious damage to the city, but Kyme managed to maintain a pres-tigious position, as pointed out by literary sources, some inscrip-tions and monuments come to light during the excavations (Honle,1967; Engelmann, 1976; Manganaro, 2000, 2004).

Archaeological evidence has proven that in late Roman age andin the early Byzantine age (VeVI centuries), Kyme occupied a widearea, and that it was abandoned during the VII century. In XIIeXIIIcenturies, life was centred around the port and the castle built indefence of the port (Fig. 1b) (Patitucci, 2001; Parapetti, 2004).

At the present time, the excavations of the Italian archaeologicalmission are the continuation Salaç’s ones, whose studies werepublished by his pupils (AA.VV, 1974, 1980).

However, despite the archaeological importance of Kyme, thereare few archaeometric studies on this city (Ciminale, 2003).

The present study,which is part of awider project, aims to supplythe first compositional data on the mortars of the archaeological

Fig. 1. (a) Location of Kyme; (b) Ruins of the Kyme castle; (c) Roman Agora of Kyme.

Fig. 2. Sampling of the mortars: (a) Sample M1 on random stone - “unknown historical period”; (b) Sample M2 on Proto-Byzantine floor “VeVII century AD”; (c) Sample M3 on thewall of the Medieval castle " XIIeXIII century AD; (d) Sample M4 on Proto-Byzantine floor “VeVII century AD”; (e) Sample M5 on Proto-Byzantine floor “VeVII century AD”; (f)Sample M6 on the floor of the theatre orchestra “Roman-Imperial period”; (g) Sample M7 under the marble slab on balteus in the theatre “Roman-Imperial period”; (h) Sample M8under the marble slab on balteus in the theatre “Roman-Imperial period”; (i) Sample Kmo is a plaster of the house in the Roman residential block (South hill) “Roman-Imperialperiod”.

D. Miriello et al. / Journal of Archaeological Science 38 (2011) 794e804 795

D. Miriello et al. / Journal of Archaeological Science 38 (2011) 794e804796

area of Kyme, and to highlight the chemical, petrographic andmineralogical differences between the Roman, Proto-Byzantine andMedieval mortars. Turkish Roman, Proto-Byzantine and Medievalmortars have been studied by several authors. These studies havehighlighted the complexity, in all historical periods, of themixtures,to which marble powder, volcanic tuff and cocciopesto were addedas aggregates (Güleç and Tulun, 1997; Bakolas et al., 1998; Degryseet al., 2002; Moropoulou et al., 2002; Böke et al., 2004, 2008;Özkaya and Böke, 2009; Binici et al., 2010).

The data we collected will be inserted into a database, aiming tocollect compositional information on all the stone materials ofKyme. Naturally, the choice of mortars as a first step of our study isnot casual. As a mixture of lime, sand and water, mortars reflect thebuilding technology of the civilisation. Thus, mortars may supply uswith important information on local raw materials used to makethem, and on the constructive history of a monument (Franziniet al., 2000; Moropoulou et al., 2000, 2003; Crisci et al., 2004;Miriello and Crisci, 2006; Riccardi et al., 2007; Carò et al., 2008;Barba et al., 2009; Miriello et al., 2010a, 2010b; Villaseñor andGraham, 2010; Sanjurjo-Sánchez et al., 2010).

2. Sampling and analytical techniques

In the following section we will refer to a “mortar” as a genericmixture of lime, aggregates andwater used todenote joiningmaterialbetween building stones; while the word “plaster” refers to mixtureof lime, aggregates and water, used to finish the surface of a wall.

One plaster and eight mortars were sampled from the archaeo-logical area of Kyme (Fig. 2). The sampleM1was taken froma randomstone, thus itshistorical-spatial location isuncertain (Fig. 2a). SamplesM2, M4 and M5 were taken from a proto-Byzantine floor in a Medi-eval castle (Fig. 2b,d and e). SampleM3was taken from thewall of the

Table 1Chemical composition of major and minor elements of the mortars by XRF analysis (L.O

Major elements

Wt% SiO2 TiO2 Al2O3 Fe2O3 MnO MgO

M1 40.65 0.50 9.01 2.63 0.08 1.85M2 43.80 0.45 8.63 2.28 0.09 1.78M3 53.03 0.41 9.59 2.39 0.10 2.41M4 50.05 0.44 10.11 2.11 0.03 2.09M5 41.35 0.38 7.90 1.86 0.10 1.37M6 42.46 0.46 9.09 2.50 0.09 1.90M7 30.60 0.37 6.80 1.67 0.07 1.72M8 38.63 0.51 9.34 2.86 0.08 2.15Kmo 5.32 0.04 0.83 0.15 0.03 0.42

Trace elements

ppm Ni Cr V La Ce CoM1 41 72 69 6 45 9M2 30 58 62 14 44 5M3 39 90 59 13 49 5M4 11 19 61 31 65 3M5 32 48 59 10 39 6M6 42 76 70 17 45 8M7 29 43 62 n.d. 33 4M8 43 75 85 5 49 10Kmo 4 n.d. 16 n.d. 5 n.d.

ppm Zn Rb Pb

M1 82 83 35M2 69 103 42M3 93 132 120M4 170 127 54M5 143 95 63M6 76 78 71M7 104 55 146M8 80 75 182Kmo 97 17 24

medieval castle.Whereas, themortarM6was sampled from the floorof the orchestra of the Roman theatre (Fig. 2f). Samples M7 and M8were taken from beneath the marble slabs covering the “balteus” ofthe theatre (Fig. 2g, h). The last sample, Kmo (Fig. 2i), belongs toa plaster (Frasca, 2007) brought to life during the excavations ina house in the Roman residential block (South hill).

The samples were studied in thin section by polarised lightmicroscopy with a Zeiss petrographic microscope, and analysed byXRF (X-Ray Fluorescence) on pressed pellets to determine thechemical composition of major (SiO2, TiO2, Al2O3, Fe2O3, MnO,MgO,CaO, Na2O, K2O, P2O5) and minor (Ni, Cr, V, La, Ce, Co, Ba, Nb, Y, Sr,Zr, Cu, Zn, Rb, Pb) elements, on a Bruker S8 Tiger WD X-ray fluo-rescence spectrometer. Chemical elements were analysed witha rhodium tube with 4 kW intensity, using 4 g of sample. Analyticalresults are listed in Table 1.

The binder (size<1/16 mm) of the samples, volcanic aggregatesand lime lumps (Bakolas et al., 1995; Barba et al., 2009) were alsoanalysed on polished thin sections to determine major chemicalcomposition by SEM-EDS (Scanning Electron Microscopy withEnergyDispersiveX-ray Spectroscopy)microanalysis (Tables2, 3) onaFEIQuanta200 instrument, equippedwithanEDAXSi (Li detector).To better point out the similarities and the geochemical differencesof the binder of the mortars, we calculated the hydraulicity index(H.I.) in agreement with Bonyton (1966). H.I. is defined asSiO2 þ Al2O3 þ Fe2O3/CaO þ MgO ratio. The hydraulicity indexcalculated by SEM-EDS analysis of the binder may be slightly over-estimated because of the presence of non-reactive silica. Therefore,the hydraulicity indexwas only used to compare the composition ofthe binder between the mortars and not as an absolute measure.

The mineralogical composition of the samples (Table 4) wasstudied using a Bruker D8 Advance XRD Diffractometer operating at40 kV and 40 mA, Cu Ka radiation monochromated with a graphite

.I.: loss on ignition).

CaO Na2O K2O P2O5 L.O.I. Sum

23.22 0.37 1.93 0.53 19.22 100.0022.87 1.05 2.22 0.40 16.43 100.0013.06 0.68 2.41 1.27 14.65 100.0016.74 1.20 2.62 0.20 14.41 100.0024.74 0.53 2.22 0.82 18.72 100.0021.36 0.40 2.01 0.28 19.46 100.0030.67 0.27 1.16 0.19 26.47 100.0023.00 0.31 1.91 0.31 20.89 100.0050.67 0.08 0.25 0.22 41.98 100.00

Ba Nb Y Sr Zr Cu666 12 28 421 146 20459 12 27 445 141 25526 15 23 451 149 39750 13 23 489 191 11522 12 28 425 126 21524 13 27 385 144 14388 9 26 423 115 17542 11 29 395 133 2031 5 5 400 26 9

Table 2SEM-EDS microanalysis of the binder and lime lumps in mortars (M_L: analysis of the lump; M_B: analysis of the binder; H.I.: hydraulicity index).

Wt% SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5 Sum H.I.

M1_L1 1.20 n.d. 0.82 0.63 0.45 1.66 92.53 0.89 0.09 1.73 100.00 0.03M1_B1 9.66 0.15 4.01 1.13 0.46 1.43 80.29 1.39 n.d. 1.49 100.01 0.18M1_B2 13.34 n.d. 4.90 0.53 n.d. 1.33 75.71 1.39 1.59 1.22 100.01 0.24M1_B3 10.67 n.d. 4.20 1.88 n.d. 1.33 79.27 1.27 0.18 1.19 99.99 0.21M2_L1 0.68 0.27 0.41 0.22 0.20 1.16 95.82 0.20 0.24 0.79 100.00 0.01M2_L2 1.96 0.00 1.69 0.44 0.00 2.24 90.61 1.59 0.27 1.19 100.00 0.04M2_L3 1.58 0.28 1.23 0.70 0.24 2.09 90.72 1.25 0.25 1.65 100.00 0.04M2_B1 6.79 0.13 1.67 0.65 0.56 0.87 87.46 0.44 0.29 1.13 100.00 0.10M2_B2 7.50 0.00 2.81 n.d. 0.00 2.09 83.20 2.00 0.34 2.06 100.00 0.12M2_B3 12.32 0.10 3.43 0.59 0.19 1.87 77.60 1.60 0.49 1.81 100.00 0.21M3_B1 62.13 0.34 13.67 4.15 n.d. 3.37 11.41 0.71 1.84 2.38 100.00 5.41M3_B2 61.76 0.46 13.88 4.54 n.d. 3.75 8.11 0.94 1.98 4.58 100.00 6.76M3_B3 61.58 1.09 10.63 4.77 0.36 2.49 11.47 0.58 2.03 5.00 100.00 5.51M3_L1 12.43 n.d. 1.42 0.64 0.38 2.24 80.39 1.27 0.21 1.02 100.00 0.18M4_L1 3.47 0.09 1.51 0.35 0.09 1.10 91.52 1.09 n.d. 0.77 99.99 0.06M4_L2 5.94 0.08 2.18 0.42 0.18 1.49 87.83 1.07 n.d. 0.81 100.00 0.10M4_B1 8.64 n.d. 2.86 0.93 0.21 1.73 83.59 1.02 n.d. 1.02 100.00 0.15M4_B2 8.26 0.08 2.43 0.79 0.41 1.41 83.72 1.19 0.47 1.24 100.00 0.13M4_B3 5.30 n.d. 1.98 0.56 0.12 1.61 88.15 1.24 n.d. 1.03 99.99 0.09M5_L1 1.04 0.12 0.58 0.62 0.48 0.89 94.57 0.40 0.21 1.09 100.00 0.02M5_L2 2.97 0.11 1.56 0.48 0.30 2.00 88.90 1.43 0.34 1.90 99.99 0.06M5_B1 6.56 n.d. 2.04 n.d. n.d. 1.65 86.21 1.20 0.35 1.98 99.99 0.10M5_B2 6.38 n.d. 2.06 0.36 0.13 1.37 86.72 1.25 n.d. 1.74 100.01 0.10M5_B3 7.19 n.d. 1.84 0.11 n.d. 0.82 88.05 0.58 0.41 0.99 99.99 0.10M6_L1 6.23 n.d. 3.05 n.d. n.d. 2.44 84.07 1.97 n.d. 2.24 100.00 0.11M6_L2 7.57 n.d. 2.72 0.26 n.d. 1.24 86.02 0.84 0.46 0.89 100.00 0.12M6_B1 12.22 n.d. 3.49 0.40 n.d. 1.42 80.24 0.77 0.58 0.88 100.00 0.20M6_B2 15.11 0.17 4.38 0.73 0.24 1.69 74.95 1.04 0.81 0.87 99.99 0.26M6_B3 12.77 n.d. 4.11 0.28 n.d. 1.56 78.60 0.98 0.67 1.03 100.00 0.21M7_B1 9.75 0.18 3.10 0.80 0.20 1.97 81.33 1.23 0.38 1.07 100.01 0.16M7_B5 3.81 n.d. 1.78 0.49 0.41 1.57 89.22 1.25 0.32 1.15 100.00 0.07M7_L1 2.57 n.d. 1.07 0.59 n.d. 1.24 93.56 0.11 n.d. 0.85 99.99 0.04M7_L2 1.98 0.23 1.07 0.81 0.32 1.07 92.44 0.63 0.32 1.13 100.00 0.04M8_L1 2.18 n.d. 1.03 0.35 n.d. 0.67 94.07 0.28 0.37 1.04 99.99 0.04M8_L2 1.25 n.d. 1.11 0.31 0.29 1.17 93.41 0.62 0.23 1.63 100.02 0.03M8_B1 10.22 0.32 3.73 0.92 0.18 1.78 79.96 1.30 0.54 1.05 100.00 0.18M8_B2 2.71 0.18 1.22 0.41 0.26 1.39 90.63 1.39 0.50 1.32 100.01 0.05Kmo_B1 2.09 0.20 0.63 0.74 0.30 0.56 93.47 0.69 0.36 0.95 99.99 0.04Kmo_B2 1.53 0.56 0.61 0.39 0.17 0.99 93.54 0.96 0.24 1.01 100.00 0.03Kmo_B3 3.10 0.20 1.64 0.37 0.31 1.89 89.27 1.69 0.29 1.24 100.00 0.06

D. Miriello et al. / Journal of Archaeological Science 38 (2011) 794e804 797

samplemonochromator. Scans were collected on powder samples inthe range 3e60� 2q using a step interval of 0.02� 2q, with a step-counting time of 3 s. The EVA software programme (DIFFRACplusEVA) was used to identify the mineral phases in each X-ray powderspectrum, by comparing experimental peaks with 2005 PDF2

Table 3SEM-EDS microanalysis of volcanic aggregates in mortars (M_V: microcrystalline fragme

Wt% SiO2 TiO2 Al2O3 Fe2O3 MnO

M1_V1 61.81 0.51 21.70 1.05 n.d.M1_V2 76.90 0.15 12.72 0.27 0.06M2_Pu_1 76.66 0.28 13.96 0.21 0.04M2_Pu_2 76.41 0.10 13.83 0.12 0.05M2_V2 76.71 0.22 12.63 0.43 n.d.M3_V1 61.03 0.85 19.02 5.14 0.15M3_V2 70.69 0.32 16.01 0.91 0.04M3_Pu_2 76.60 0.28 13.33 0.19 0.07M4_V1 60.33 0.88 18.46 5.24 n.d.M4_V3 69.11 0.47 16.69 1.04 n.d.M4_V4 69.96 0.33 15.70 1.78 0.05M5_V2 61.94 0.67 17.96 3.46 0.09M5_V3 62.41 0.34 21.35 0.89 0.07M6_V1 64.80 1.01 17.66 2.92 0.08M6_V2 63.75 0.71 16.47 3.70 0.11M6_V3 76.03 0.29 12.53 0.16 n.d.M7_V1 65.43 0.57 16.82 2.80 0.17M8_Pu_1 84.78 0.28 5.95 0.99 0.18

reference patterns. The semi-quantitativemineralogical compositionof each mineralogical phase detected in the XRPD spectrum wascalculated with the EVA support programme, which compares thearea and intensity of two diffraction peaks, each diagnostic of onemineral component of the mixture. Because of the flattened

nts; M_Pu: pumice fragment).

MgO CaO Na2O K2O P2O5 Sum

0.90 5.79 4.43 3.29 0.52 100.000.74 0.95 3.39 4.78 0.05 100.011.66 2.24 1.79 2.85 0.30 100.001.60 2.21 1.92 3.57 0.18 100.000.94 0.96 2.98 4.84 0.29 100.002.31 5.28 3.45 2.41 0.37 100.010.74 2.60 4.18 4.21 0.29 99.991.00 2.93 1.09 4.29 0.23 100.012.80 3.02 5.01 3.73 0.53 100.001.22 3.72 4.06 3.50 0.19 100.001.20 2.09 3.74 4.58 0.57 100.002.81 4.83 4.32 3.45 0.46 99.990.91 5.92 4.57 3.04 0.50 100.001.42 4.38 4.03 2.97 0.73 100.002.30 3.76 3.98 4.55 0.65 99.980.82 0.41 2.21 7.35 0.20 100.002.41 6.07 1.64 3.42 0.68 100.014.30 1.45 0.94 1.02 0.11 100.00

Table 4Semi-quantitative mineralogical composition of mortars in order of decreasingrelative abundance (as detected by XRPD, SEM-EDS and optical microscopy) andCaCO3 content by De Astis calcimeter; Act: actinolite, Ab: albite, An: anorthite,Cal: calcite, Chl: chlorite, Gt: goethite, He: Heulandite, Mnt: montmorillonite,Ms: muscovite, Qtz: quartz, Vat: vaterite.

by XRPD analysis by De Astis calcimeter

maxemin CaCO3(%)

M1 Cal, An, Qtz, Ms, Act, Gt 27.93M2 Cal, An, Qtz, Gt, Ms, He, Act 23.79M3 Cal, An, Qtz, Gt, Ms, He, Chl, Act, Mnt 17.83M4 Cal, An, Qtz, Gt, Ms, Act, Vat 20.29M5 Cal, An, Qtz, He, Gt, Ms, Act 30.77M6 Cal, An, Qtz, Gt, Ms, Vat 26.98M7 Cal, An, Qtz, Gt, Vat, Chl, Ms 43.85M8 Cal, An, Qtz, Vat, Gt, Ms, Chl 28.70Kmo Cal, Ab 82.52

nerals,Pl:plagioc

lase,Q

tz:qu

artz,M

.S.:mod

eratelysorted

,W.S:wellsorted

,*:present.

larize

dscop

y

alog

ical

phases

aggreg

ate

Coc

ciop

esto

Roc

kfrag

men

ts(supportedby

SEM-EDSan

alysis)

Sorting

Other

z,Ms,Om,A

mp,C

al*

Trachiandesites,rhyo

lites

M.S.

e

z,Ms,Om,A

mp

*Rhyo

lites

M.S.

e

z,Ms,Cal,O

m,A

mp

eAndesites,rhyo

lites,

phyllades

(traces)

M.S.

Charco

alfrag

men

ts

z,Ms,Cal,

Bt,Om

eTrachiandesites,d

acites,

rhyo

lites,q

uartzites

(traces)

W.S.

e

z,Ms,Amp,B

t,Om

*Trachiandesites

M.S.

Traces

ofmicrofossils

(ech

inoidsp

ines)

z,Ms,Om,A

mp

*Trachyd

acites,d

acites

M.S.

z,Cal,B

t,Ms,Om

*Dacites

M.S.

e

z,Ms,Om

*Rhyo

lites,p

hyllades

(traces)

W.S.

Reu

sedmortar

frag

men

tsl,Qtz

emarbles

(traces),

phyllades

(traces)

n.d.

Marblepow

der

D. Miriello et al. / Journal of Archaeological Science 38 (2011) 794e804798

morphology of crystals (e.g., muscovite), a problem of preferredorientation may have occurred during collection of powder XRPDdata, and may contribute to variations in the relative intensities ofsome XRPD peaks.

A semi-quantitative estimate of the aggregate/binder ratio andmacroporosity (Table 5) was obtained by comparing the thinsections observed by optical microscopy with charts to aid visualestimation of modal proportions of minerals in rocks (Ricci Lucchi,1980; Myron Best, 2003).

The calcium carbonate content was determined by De Astiscalcimeter (Table 4).

Table

5Pe

trog

raphic

featureson

thin

sectionsof

mortars.A

mp:am

phibole,

Bt:biotite,

Cal:calcite,

Ms:

muscov

ite,

Om:op

aquemi

Bypolarized

microscop

ysemi-qu

antitative

visu

alestimation

(Ricci

Lucchi,19

80;Myron

Best,20

03)

bypolarized

microscop

y

Bypo

micro

Mea

nag

greg

ate

size

(mm)

Max

.agg

rega

tesize

(mm)

Agg

rega

te(size>

1/16

mm)(%)

Binder

(size<

1/16

mm)(%)

Macroporosity

(size>

1/16

mm)(%)

Miner

ofthe

M1

1.0

6.0

2573

2Pl,Q

tM2

1.3

6.6

3563

2Pl,Q

tM3

0.4

4.2

2078

2Pl,Q

t

M4

0.6

6.2

2561

14Pl,Q

tAmp,

M5

0.7

4.6

2065

15Pl,Q

t

M6

0.8

6.3

2869

3Pl,Q

tM7

1.4

5.2

1583

2Pl,Q

tM8

0.7

5.8

3067

3Pl,Q

t

Kmo

0.1

1.2

181

18Cal,P

3. Results and discussion

3.1. Petrographic and mineralogical analysis

From a macroscopic point of view, it is possible to detect fewdifferences among samples. The most important difference is thepossibility of observing - with the naked eye - (in samples M1, M2,M5, M6, M7, M8), the presence of cocciopesto (Zendri et al., 2004),which makes the mortars turn to a pinkish colour. On the contrary,samples M3, M4 and Kmo, without any cocciopesto, have a greyishcolour. Macroscopically, most samples show a coarse sand Went-worth size class (Wentworth, 1922); whereas the sample Kmo hasa fine sand aspect (Wentworth, 1922). Most of the samples havea high cohesion and they only break under strong pressure of thehands, except for sample M3 which is highly friable.

Observation under polarised optical microscopy and imagesacquired by flatbed scanner (Fig. 3aei) allowed us to highlight thedifferences between the mortars. Apart from sample Kmo, which isalmost lacking aggregates (Fig. 3i), the other samples have an aggre-gate of more than 15% (Table 5 and Fig. 4b). The mean size of theaggregates varies from0.1mmof sampleKmoto1.3mmof sampleM2(Table 5 and Fig. 4a);whereas itsmaximumsize varies from1.2mmofsample Kmo to 6.6mmof sampleM2.Most samples havemoderatelysorted aggregates (Folk,1974; Jerramet al.,1996). Only sampleM4andM8 have well sorted aggregates (Folk, 1974; Jerram et al., 1996). In allmortars, a low sphericity and a subangular roundness prevail in theclastsof theaggregate (Powers,1953). Inall samples themodalcontentof the binder exceeds the oneof the aggregates (Table 5 and Fig. 4b). Inparticular, as concerns the aggregate/binder ratio, it is possible tosubdivide the sample into three groups. The first group (samples M1,M2, M4, M6, M8) includes samples with an aggregate/binder ratio of1/2; the second group (samples M3, M5) includes samples with anaggregate/binder ratio of 1/3; whereas the third group with only onesample (M7) has an aggregate/binder ratio of approximately 1/7.

Fig. 3. Comparison between flatbed scanner images of mortars under crossed polars (a) Sample M1; (b) Sample M2; (c) Sample M5, (d) Sample M6; (e) Sample M7; (f) Sample M8;(g) Sample M3; (h) Sample M4; (i) Sample Kmo.

Fig. 4. (a) Max. and mean aggregate size of the mortars; (b) semi-quantitative visual estimation of aggregate, binder and macroporosity (Ricci Lucchi, 1980; Myron Best, 2003).

D. Miriello et al. / Journal of Archaeological Science 38 (2011) 794e804 799

Fig. 5. Microphotographs of mortar aggregate and binder under crossed polars. (a) Calcite in aggregate of the sample M1; (b) Charcoal fragment in the sample M3; (c) Lime lumpwith dissolution porosity in the sample M4; (d) Recrystallizations of calcite binder in the sample M4; (e) Echinoid spine in the sample M5; (f) Reused mortar fragment in the sampleM8; (g) Marble powder fragment in the sample Kmo; (h) Pumice in the sample M8; (i) Trachiandesite and quartzite fragments in the sample M4.

D. Miriello et al. / Journal of Archaeological Science 38 (2011) 794e804800

Themacroporosity has a low variability, varying in almost all thesamples from 2 to 3% approximately, except for samples M4, M5and Kmo, in which porosity varies from 14 to 18% approximately(Fig. 4b and Table 5). In these samples we may observe numeroussecondary pores due to binder dissolution phenomena.

Observations in thin section confirmed that samples M1, M2,M5, M6, M7 and M8 have aggregates, which are prevalently madeof cocciopesto, combined with monomineralic crystalline phasesand volcanic rock fragments. In sample M8 only we may observerare metamorphic rock fragments (phyllades).

It is possible to detect plagioclase, quartz, muscovite and opaqueminerals in all sample, except sample Kmo, in which only calcite,plagioclase and quartz traces were detected (Table 5). The amphi-bole is found only in samplesM1,M2, M3,M4,M5 andM6;whereasbiotite is present only in samples M4, M5 and M7. Traces of calcitebelonging to the aggregate are revealed only in samples M1(Fig. 5a), M3,M4, M7 and Kmo. The calcite present in sample Kmo isdue to the presence of marble powder deliberately added to themixture (Fig. 5g). In sample M3, it is possible to detect charcoalfragments (Fig. 5b), deriving from vegetable residual combustionproducts used in limekilns.

In all samples, it is possible to find lime lumps (Bakolas et al.,1995; Barba et al., 2009) of size varying from 40 to 1000 mm,

many of which undergo dissolution phenomena which increasesecondary porosity in the mortars (Fig. 5c).

In all samples the binder has a criptocrystalline aspect, exceptfor sample M4, where we may observe recrystallizationphenomena (Fig. 5d) which make the binder microcrystalline.

Sample M5 presents a particular feature, since it is the onlysample presenting rare traces of bioclasts, classifiable as Echinoidspines (Fig. 5e).

SampleM8 also has some peculiarities since - in its aggregate - itis possible to trace reused mortar fragments (Fig. 5f), which, mostprobably, come from detritis of old walls used as aggregatematerialin the mixture.

As concerns the rock fragments present in the aggregates, it ispossible to find traces of metamorphic rocks, mainly phyllades, insamplesM4, M8 and Kmo. Traces of quartzite may only be observedin sample M4 (Fig. 5i). However, fragments of volcanic rock withporphyritic texture (Fig. 5i) may be found in most of the samples,with a lower concentration than cocciopesto. Volcanic aggregateswith pumiceous (Fig. 5h) texture (Myron Best, 2003) are found onlyin samples M2, M3 and M8.

SEM-EDS microanalysis allowed us to classify volcanic aggre-gates in detail, by using the TAS diagram (LeMaitre et al., 1989). Thediagram in Fig. 6 shows that all rock fragments have a SiO2 content

Fig. 6. Classification of volcanic aggregates by TAS diagram (Le Maitre et al., 1989).

D. Miriello et al. / Journal of Archaeological Science 38 (2011) 794e804 801

higher than 60%. Their composition varies from trachiandesites toryolites. The pumice fragments have the lowest content of alkali.This is due to a more intense alkali leaching in pumices rather thanin other volcanic rocks.

The XRPD analysis supplied us with more detailed informationon the mineralogical composition of the samples, allowing us toidentify other mineralogical phases, in addition to the mineralsrecognised by polarised optical microscopy (Table 4).

In all samples, except Kmo, we detected the presence ofgoethite. Traces of chlorite were found in samples M3, M7 and M8;whereas vaterite was found in samples M4, M6, M7 and M8.

The presence of montmorillonite, a clay mineral, in sample M3only, makes the sample more friable than other samples.

The presence of heulandite in samples M2, M3 and M5 is ofgreat interest. Heulandite is a common mineral in post-volcanicenvironments and belongs to the heulanditeeclinoptilolite zeolitegroup (Comodi et al., 2001). Scientific literature points out that theclosest presence of this mineral to Kyme is in the area of Bigadiçborate deposits, located approximately 120 km North-East of Kyme(Gündogdu et al., 1996; Helvaci and Alonso, 2000). However, wecannot exclude that it is possible to find heulandite in areas closerto Kyme that still have not been studied. Future studies on Kymemay use heulandite as an index mineral to accurately identify theprovenance of the aggregates used in the preparation of mortars.

3.2. Chemical analysis of the mortars and their binder

Analogies and compositional differences of mortars may bepointed out by using binary chemical diagrams obtained throughXRF analysis of mortars. Fig. 7a, representing the TiO2/Fe2O3 vsSiO2/CaO diagram, differentiates the samples with a higher SiO2/

Fig. 7. Chemical composition of Kyme mortars. (a) TiO2/Fe

CaO ratio (samples M3, M4) from the ones with a lower SiO2/CaOratio (samples Kmo, M7).

The same figure shows a group of more homogeneous samples(M1, M2, M5, M6 and M8) in the centre of the diagram (Fig. 7a).

These geochemical differences may be explained by referring tothe mineralogical and petrographic features of the samples.Samples M3 and M4 with a higher SiO2 content, are also thesamples with the lowest CaCO3 content (Table 4); whereas samplesKmo and M7 have the highest CaCO3 content (Table 4).

For samples Kmo and M7 the higher CaCO3 content is ascribedto the aggregate/binder ratio, which is the lowest (Table 5).

As concerns samples M1, M2, M5, M6 and M8, the chemicalhomogeneousness corresponds to a petrographic homogeneousnessin samplesM1 andM6, which are very similar both in the aggregate/binder ratio and in theirmineralogical andpetrographic composition,but also in samples M2 and M5. Samples M2 and M5 can be consid-ered very similar, except for unimportant differences in the aggregateof M5, which is the only sample to have traces of bioclasts and biotitein its aggregate. M8 is the only sample to present reused mortarfragments.

Also the graph in Fig. 7b shows that samples M3 and M4 are theones that differ from others, showing the highest Zr/Y ratio. Thisbehaviour could also be due to the fact that M3 and M4 do not havecocciopesto in their aggregate, but only fragments of natural rock.Samples Kmo and M7 have the lowest Ba/Sr ratio (Fig. 7b); becauseof the high quantity of binder, they are poorer in trace elements(Table 1). The graph in Fig. 7b points out that samples M1 and M6are rather close to each other, thus confirming their petrographichomogeneity.

The study of the binder through SEM-EDS microanalysis wascarried out - within each sample - by comparing the chemicalcomposition of the lime lumps with the composition of the binder.

The presence of the lime lumps in the mortars has to be seekedin the properties of the slaked lime (calcium hydroxide), but also inthe water/lime ratio. An insufficient seasoning of the calciumhydroxide can produce a lime with low plasticity; the latter,combinedwith a lowwater/lime ratio, makes theworkability of themixture between lime and aggregate difficult. These circumstancescan lead to the formation of nodules of slaked lime that becomecalcium carbonate nodules (lime lumps) (Bakolas et al., 1995)because of the carbonation process. The lime lumps have the samechemical composition of the raw materials (Barba et al., 2009), thisis why the comparison between lime lumps and binder within thesame samplemay supply uswith useful information on the binder’sdegree of hydraulicity.

The chemical parameter used in this comparison is thehydraulicity index (Bonyton, 1966).

The graph in Fig. 8a, referring to sample M1, shows that thebinder’s mean hydraulicity index is 0.21; whereas the lime lump’s

2O3 vs SiO2/CaO diagram; (b) Ba/Sr vs Zr/Y diagram.

Fig. 8. SiO2 þ Al2O3 þ FeO2O3 vs CaO þ MgO diagrams of binder (white circle) and lime lumps (black circle) in the mortars by SEM-EDS analysis. (a) Sample M1; (b) Sample M2; (c)Sample M3; (d) Sample M4; (e) Sample M5; (f) Sample M6; (g) Sample M7; (h) Sample M8; (i) Sample Kmo.

D. Miriello et al. / Journal of Archaeological Science 38 (2011) 794e804802

mean hydraulicity index is 0.03. This is due to the initial use ofslaked lime, that mixed with cocciopesto has undergone anincrease of SiO2, Al2O3 and Fe2O3 content due to the probableformation of CeSeH phases (Taylor, 1997; Hodgkinson and Hughes,1999; Qing et al., 2006). A similar behaviour is present in samplesM2 (Fig. 8b) and M6 (Fig. 8f), where the hydraulicity index of thebinder is very similar to the one in sample M1.

Themigration of SiO2, Al2O3 and Fe2O3 from the cocciopesto to thebindermay also be seen in samples M5 (Fig. 8e), M7 (Fig. 8g) andM8(Fig. 8h), though the former is less intense than the remainingsamples containing cocciopesto. Sample M4 (Fig. 8d) does not havecocciopesto and the slight increase of the binder’s hydraulicity indexis due to the presence - in the aggregate of volcanic aggregates (tra-chiandesites, dacites, rhyolites) with low pozzolanic features.

Sample M3 seemingly shows a very high hydraulicity index inthe binder, of approximately 5.89 (Fig. 8c); this anomaly may beexplained by the petrographic and mineralogical features of thesample itself. As we have already pointed out, sampleM3 has a highfriability and a binder content of 78% approximately (Table 5).Furthermore, in sample M3, we detected montmorillonite, as wellas the lowest content of calcite (Table 4). This data seems tocontradict the high quantity of binder in the sample itself. A plau-sible explanation of the observations presented may be given by

the addition of clay to the mixture of sample M3, as well as smallquantities of lime.

Therefore, the anomalous hydraulicity index (Fig. 8c) is not dueto the formation of CeSeH phases in the binder, but to the highcontent of SiO2, Al2O3 and Fe2O3 which are present in clay.

Lime lumps were not detected in sample Kmo (Fig. 8i), so theSEM-EDS analysis was only carried out on the binder, which ismade of slaked lime.

It is important to underline that, despite evidence of migrationphenomena of SiO2, Al2O3 and Fe2O3 from the cocciopesto to thebinder, CeSeH phases were not detected in the samples throughXRPD analysis. Probably th CeSeH phases in the binder are predom-inantly like a gel with low crystallinity (Taylor, 1997; Hodgkinson andHughes, 1999), which cannot be detected by XRPD analysis.

4. Conclusions

The heterogeneity and variability of mortars always makes itdifficult to obtain perfectly comparable results, even when differentanalytical techniques are used. However, in order to recognize groupsof compositionally homogeneous mortars, according to our experi-ence, the petrographic and chemical methods must take precedenceover all other criteria. As a matter of fact, small differences in the

D. Miriello et al. / Journal of Archaeological Science 38 (2011) 794e804 803

semi-quantitative mineralogical composition andmacroporosity canbe explained by the different decay of the samples.

The study showed that samples M1 and M6 are chemically andpetrographically similar. The exact historical provenance of sampleM6, belonging to the Roman-Imperial period, allows us to givesample M1 the same collocation, because of their compositionalanalogy. As regards the mortars sampled on the proto-Byzantinefloor, M2 and M5 samples (Fig. 2b, e), are both cocciopesto mortars.They are compositionally similar, while sample M4, another mortarsampled from the proto-Byzantine floor (Fig. 2d), has no coccio-pesto. These differences may be due to maintenance work carriedout on the pavement by different workers, but this remains onlya hypothesis to be confirmed in future studies.

Another important result concerns M3 sample. Among all themortars,M3 (sampled on thewall of theMedieval castle) is definitelythe samplewith the worst technological features. As a matter of fact,the sample, which is particularly friable, is made of a mixture of clay,lime and aggregate; thus denoting a loss of technological knowledgecompared to the mortars prepared in previous historical periods.

Marble powder artificially added to the mixture was found insample Kmo. This procedure was particularly appreciated by Romanworkers, who wanted the plaster to have a marble brightness(Vitruvius Pollio, 1990).

As concerns provenance studies, heulandite and echinoid spinetraces found in some sample (Tables 4 and 5), may be used in thefuture to determine the provenance of the aggregate. Provenancestudies will be extended to probable limestone caves used for thepreparation of the lime, by comparing the composition of limelumps present in mortars to the composition of geological samples(Barba et al., 2009).

It is useful to point out how, among the Romanmortars that havebeen studied within the archaeological site, no mortars made only ofnatural pozzolanas have been found. As a matter of fact, the Romansused to abundantly use “pozzolanas” in mixtures (Degryse et al.,2002; Miriello et al., 2010a), mainly in bedding mortars. This prac-tice could be justified by the difficulty offinding “natural pozzolanas”in the area, rather than cocciopesto. This hypothesis, however, needsto be verified in future studies mainly focusing on the provenance ofraw materials used to prepare mortars. Moreover, the Romans inKyme have used inert material coming from old constructions, as anaggregate in the new mortars. This has been proven because of thepresence of reused mortar fragments in sample M8.

Regards the typology of lime, the analysis of the binder pointedout that natural slaked lime was used in Kyme, but, to increase theperformance of the mortars, the lime was made hydraulic by add-ing cocciopesto to the mixture.

Thanks to the present study, the first compositional data con-cerning the mortars in the archaeological area of Kyme wereproduced. The compositional data we have so far obtained may beused to reproduce highly compatible mortars to be used in futurerestaurations.

Acknowledgements

The authors would like to thank Franco Russo and AdelaideMastandrea for their support in bioclasts recognition. We also wishto thank Rossella Pace for her advice on references. We also wish tothank the Editor and anonymous Reviewers for their helpfulcomments which helped in the revision of this manuscript.

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