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Journal of Archaeological Science 38 (2011) 794e804

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Journal of Archaeological Science


journal homepage: http://www.elsevier.com/locate/jas

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
a b

Department of Earth Sciences, University of Calabria, 87036 Arcavacata di Rende (CS), Italy Department 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 2010 Received in revised form 5 November 2010 Accepted 10 November 2010 Keywords: Anatolia Mortar Plaster Lime lump Binder Aggregate Cocciopesto XRF SEM-EDS XRPD

a b s t r a c t
The present study focuses on the compositional characterisation of Roman, proto-Byzantine and Medieval mortars, sampled in the archaeological site of Kyme (Turkey), an Aeolian city, founded in the middle of 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. The comparison between the samples allowed us to emphasise compositional differences within mortars of the same historical period. In particular, we detected the prevalent use of cocciopesto, which was used as a pozzolanic additive to create hydraulic mortars in the Roman and Byzantine period. The cocciopesto was used to improve the technological properties of an initially slaked lime. Furthermore, compositional similarities allowed us to attribute an unknown sample to the Roman period. Our study also pointed out the fact that the lower quality mortars belonged to the Medieval period. As a matter of fact, the most friable sample belonging to the Middle Ages turned out to be a mixture of clay, lime and volcanic sand. 2010 Elsevier Ltd. All rights reserved.

1. Introduction Along the Western coast of Turkey, 6 km from the modern city of  Aliaga, between two hills, we nd the ruins of the ancient city of Kyme (Fig. 1). Opposite the city lie the ruins of an ancient port, from which an impressive quay is still visible, few centimetres below the water level (Lagona, 1993, 2006, 1999; Esposito et al., 2003). Kyme, the major city of the Aeolia was founded in the middle of the XI century by populations coming from the North of Greece. In VIII century BC, its inhabitants practiced seaborne trade and agriculture was at the basis of its economy (Mele, 1979). It was the mother country of several other cities, such as Side and Cuma in the South of Italy. An outstanding port, in the archaic age, Kyme must have undergone a period of economical oridity, partly deduced from historical literature, and still reected in the archaeological ruins (Lagona, 2004; La Marca, 2006; Scatozza Hricht, 2007). During the classical age, Kyme had a strategic political position among the Aegean cities. It was head of the Aeolic League, and subsequently it

* Corresponding author. Dipartimento di Scienze della Terra, Universit della Calabria, Via P. Bucci Cubo 12 B, 87036 Arcavacata di Rende (CS), Italy. E-mail address: miriello@unical.it (D. Miriello). 0305-4403/$ e see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.jas.2010.11.002

became part of the Athenian League. Alexander the Great dedicated a bronze candlestick to the city of Kyme in Apollos temple. During the Hellenistic age, the city was renovated by building some important monuments, such as the theatre, impressive walls in the plain between the two hills (La Marca, 2006, 2007), residential blocks on the Southern hill (Frasca, 2007), as well as the enlargement of the quay (Esposito et al., 2003). During the Imperial age, the earthquakes of AD 17 and 94 caused serious damage to the city, but Kyme managed to maintain a prestigious position, as pointed out by literary sources, some inscriptions and monuments come to light during the excavations (Honle, 1967; Engelmann, 1976; Manganaro, 2000, 2004). Archaeological evidence has proven that in late Roman age and in the early Byzantine age (VeVI centuries), Kyme occupied a wide area, and that it was abandoned during the VII century. In XIIeXIII centuries, life was centred around the port and the castle built in defence of the port (Fig. 1b) (Patitucci, 2001; Parapetti, 2004). At the present time, the excavations of the Italian archaeological mission are the continuation Salas ones, whose studies were published by his pupils (AA.VV, 1974, 1980). However, despite the archaeological importance of Kyme, there are few archaeometric studies on this city (Ciminale, 2003). The present study, which is part of a wider project, aims to supply the rst compositional data on the mortars of the archaeological

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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 oor VeVII century AD; (c) Sample M3 on the wall of the Medieval castle " XIIeXIII century AD; (d) Sample M4 on Proto-Byzantine oor VeVII century AD; (e) Sample M5 on Proto-Byzantine oor VeVII century AD; (f) Sample M6 on the oor of the theatre orchestra Roman-Imperial period; (g) Sample M7 under the marble slab on balteus in the theatre Roman-Imperial period; (h) Sample M8 under 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-Imperial period.

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area of Kyme, and to highlight the chemical, petrographic and mineralogical differences between the Roman, Proto-Byzantine and Medieval mortars. Turkish Roman, Proto-Byzantine and Medieval mortars have been studied by several authors. These studies have highlighted the complexity, in all historical periods, of the mixtures, to which marble powder, volcanic tuff and cocciopesto were added as aggregates (Gle and Tulun, 1997; Bakolas et al., 1998; Degryse et al., 2002; Moropoulou et al., 2002; Bke et al., 2004, 2008; zkaya and Bke, 2009; Binici et al., 2010). The data we collected will be inserted into a database, aiming to collect compositional information on all the stone materials of Kyme. Naturally, the choice of mortars as a rst step of our study is not casual. As a mixture of lime, sand and water, mortars reect the building technology of the civilisation. Thus, mortars may supply us with important information on local raw materials used to make them, and on the constructive history of a monument (Franzini et al., 2000; Moropoulou et al., 2000, 2003; Crisci et al., 2004; Miriello and Crisci, 2006; Riccardi et al., 2007; Car et al., 2008; Barba et al., 2009; Miriello et al., 2010a, 2010b; Villaseor and Graham, 2010; Sanjurjo-Snchez et al., 2010). 2. Sampling and analytical techniques In the following section we will refer to a mortar as a generic mixture of lime, aggregates and water used to denote joining material between building stones; while the word plaster refers to mixture of lime, aggregates and water, used to nish the surface of a wall. One plaster and eight mortars were sampled from the archaeological area of Kyme (Fig. 2). The sample M1 was taken from a random stone, thus its historical-spatial location is uncertain (Fig. 2a). Samples M2, M4 and M5 were taken from a proto-Byzantine oor in a Medieval castle (Fig. 2b,d and e). Sample M3 was taken from the wall of the

medieval castle. Whereas, the mortar M6 was sampled from the oor of the orchestra of the Roman theatre (Fig. 2f). Samples M7 and M8 were taken from beneath the marble slabs covering the balteus of the theatre (Fig. 2g, h). The last sample, Kmo (Fig. 2i), belongs to a plaster (Frasca, 2007) brought to life during the excavations in a house in the Roman residential block (South hill). The samples were studied in thin section by polarised light microscopy with a Zeiss petrographic microscope, and analysed by XRF (X-Ray Fluorescence) on pressed pellets to determine the chemical 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 uorescence spectrometer. Chemical elements were analysed with a rhodium tube with 4 kW intensity, using 4 g of sample. Analytical results are listed in Table 1. The binder (size<1/16 mm) of the samples, volcanic aggregates and lime lumps (Bakolas et al., 1995; Barba et al., 2009) were also analysed on polished thin sections to determine major chemical composition by SEM-EDS (Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy) microanalysis (Tables 2, 3) on a FEI Quanta 200 instrument, equipped with an EDAX Si (Li detector). To better point out the similarities and the geochemical differences of the binder of the mortars, we calculated the hydraulicity index (H.I.) in agreement with Bonyton (1966). H.I. is dened as SiO2 Al2O3 Fe2O3/CaO MgO ratio. The hydraulicity index calculated by SEM-EDS analysis of the binder may be slightly overestimated because of the presence of non-reactive silica. Therefore, the hydraulicity index was only used to compare the composition of the binder between the mortars and not as an absolute measure. The mineralogical composition of the samples (Table 4) was studied using a Bruker D8 Advance XRD Diffractometer operating at 40 kV and 40 mA, Cu Ka radiation monochromated with a graphite

Table 1 Chemical composition of major and minor elements of the mortars by XRF analysis (L.O.I.: loss on ignition). Major elements Wt% M1 M2 M3 M4 M5 M6 M7 M8 Kmo SiO2 40.65 43.80 53.03 50.05 41.35 42.46 30.60 38.63 5.32 TiO2 0.50 0.45 0.41 0.44 0.38 0.46 0.37 0.51 0.04 Al2O3 9.01 8.63 9.59 10.11 7.90 9.09 6.80 9.34 0.83 Fe2O3 2.63 2.28 2.39 2.11 1.86 2.50 1.67 2.86 0.15 MnO 0.08 0.09 0.10 0.03 0.10 0.09 0.07 0.08 0.03 MgO 1.85 1.78 2.41 2.09 1.37 1.90 1.72 2.15 0.42 CaO 23.22 22.87 13.06 16.74 24.74 21.36 30.67 23.00 50.67 Na2O 0.37 1.05 0.68 1.20 0.53 0.40 0.27 0.31 0.08 K2O 1.93 2.22 2.41 2.62 2.22 2.01 1.16 1.91 0.25 P2O5 0.53 0.40 1.27 0.20 0.82 0.28 0.19 0.31 0.22 L.O.I. 19.22 16.43 14.65 14.41 18.72 19.46 26.47 20.89 41.98 Sum 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

Trace elements ppm M1 M2 M3 M4 M5 M6 M7 M8 Kmo ppm M1 M2 M3 M4 M5 M6 M7 M8 Kmo Ni 41 30 39 11 32 42 29 43 4 Zn 82 69 93 170 143 76 104 80 97 Cr 72 58 90 19 48 76 43 75 n.d. Rb 83 103 132 127 95 78 55 75 17 V 69 62 59 61 59 70 62 85 16 Pb 35 42 120 54 63 71 146 182 24 La 6 14 13 31 10 17 n.d. 5 n.d. Ce 45 44 49 65 39 45 33 49 5 Co 9 5 5 3 6 8 4 10 n.d. Ba 666 459 526 750 522 524 388 542 31 Nb 12 12 15 13 12 13 9 11 5 Y 28 27 23 23 28 27 26 29 5 Sr 421 445 451 489 425 385 423 395 400 Zr 146 141 149 191 126 144 115 133 26 Cu 20 25 39 11 21 14 17 20 9

D. Miriello et al. / Journal of Archaeological Science 38 (2011) 794e804 Table 2 SEM-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% M1_L1 M1_B1 M1_B2 M1_B3 M2_L1 M2_L2 M2_L3 M2_B1 M2_B2 M2_B3 M3_B1 M3_B2 M3_B3 M3_L1 M4_L1 M4_L2 M4_B1 M4_B2 M4_B3 M5_L1 M5_L2 M5_B1 M5_B2 M5_B3 M6_L1 M6_L2 M6_B1 M6_B2 M6_B3 M7_B1 M7_B5 M7_L1 M7_L2 M8_L1 M8_L2 M8_B1 M8_B2 Kmo_B1 Kmo_B2 Kmo_B3 SiO2 1.20 9.66 13.34 10.67 0.68 1.96 1.58 6.79 7.50 12.32 62.13 61.76 61.58 12.43 3.47 5.94 8.64 8.26 5.30 1.04 2.97 6.56 6.38 7.19 6.23 7.57 12.22 15.11 12.77 9.75 3.81 2.57 1.98 2.18 1.25 10.22 2.71 2.09 1.53 3.10 TiO2 n.d. 0.15 n.d. n.d. 0.27 0.00 0.28 0.13 0.00 0.10 0.34 0.46 1.09 n.d. 0.09 0.08 n.d. 0.08 n.d. 0.12 0.11 n.d. n.d. n.d. n.d. n.d. n.d. 0.17 n.d. 0.18 n.d. n.d. 0.23 n.d. n.d. 0.32 0.18 0.20 0.56 0.20 Al2O3 0.82 4.01 4.90 4.20 0.41 1.69 1.23 1.67 2.81 3.43 13.67 13.88 10.63 1.42 1.51 2.18 2.86 2.43 1.98 0.58 1.56 2.04 2.06 1.84 3.05 2.72 3.49 4.38 4.11 3.10 1.78 1.07 1.07 1.03 1.11 3.73 1.22 0.63 0.61 1.64 Fe2O3 0.63 1.13 0.53 1.88 0.22 0.44 0.70 0.65 n.d. 0.59 4.15 4.54 4.77 0.64 0.35 0.42 0.93 0.79 0.56 0.62 0.48 n.d. 0.36 0.11 n.d. 0.26 0.40 0.73 0.28 0.80 0.49 0.59 0.81 0.35 0.31 0.92 0.41 0.74 0.39 0.37 MnO 0.45 0.46 n.d. n.d. 0.20 0.00 0.24 0.56 0.00 0.19 n.d. n.d. 0.36 0.38 0.09 0.18 0.21 0.41 0.12 0.48 0.30 n.d. 0.13 n.d. n.d. n.d. n.d. 0.24 n.d. 0.20 0.41 n.d. 0.32 n.d. 0.29 0.18 0.26 0.30 0.17 0.31 MgO 1.66 1.43 1.33 1.33 1.16 2.24 2.09 0.87 2.09 1.87 3.37 3.75 2.49 2.24 1.10 1.49 1.73 1.41 1.61 0.89 2.00 1.65 1.37 0.82 2.44 1.24 1.42 1.69 1.56 1.97 1.57 1.24 1.07 0.67 1.17 1.78 1.39 0.56 0.99 1.89 CaO 92.53 80.29 75.71 79.27 95.82 90.61 90.72 87.46 83.20 77.60 11.41 8.11 11.47 80.39 91.52 87.83 83.59 83.72 88.15 94.57 88.90 86.21 86.72 88.05 84.07 86.02 80.24 74.95 78.60 81.33 89.22 93.56 92.44 94.07 93.41 79.96 90.63 93.47 93.54 89.27 Na2O 0.89 1.39 1.39 1.27 0.20 1.59 1.25 0.44 2.00 1.60 0.71 0.94 0.58 1.27 1.09 1.07 1.02 1.19 1.24 0.40 1.43 1.20 1.25 0.58 1.97 0.84 0.77 1.04 0.98 1.23 1.25 0.11 0.63 0.28 0.62 1.30 1.39 0.69 0.96 1.69 K2O 0.09 n.d. 1.59 0.18 0.24 0.27 0.25 0.29 0.34 0.49 1.84 1.98 2.03 0.21 n.d. n.d. n.d. 0.47 n.d. 0.21 0.34 0.35 n.d. 0.41 n.d. 0.46 0.58 0.81 0.67 0.38 0.32 n.d. 0.32 0.37 0.23 0.54 0.50 0.36 0.24 0.29 P2O5 1.73 1.49 1.22 1.19 0.79 1.19 1.65 1.13 2.06 1.81 2.38 4.58 5.00 1.02 0.77 0.81 1.02 1.24 1.03 1.09 1.90 1.98 1.74 0.99 2.24 0.89 0.88 0.87 1.03 1.07 1.15 0.85 1.13 1.04 1.63 1.05 1.32 0.95 1.01 1.24 Sum 100.00 100.01 100.01 99.99 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 99.99 100.00 100.00 100.00 99.99 100.00 99.99 99.99 100.01 99.99 100.00 100.00 100.00 99.99 100.00 100.01 100.00 99.99 100.00 99.99 100.02 100.00 100.01 99.99 100.00 100.00

797

H.I. 0.03 0.18 0.24 0.21 0.01 0.04 0.04 0.10 0.12 0.21 5.41 6.76 5.51 0.18 0.06 0.10 0.15 0.13 0.09 0.02 0.06 0.10 0.10 0.10 0.11 0.12 0.20 0.26 0.21 0.16 0.07 0.04 0.04 0.04 0.03 0.18 0.05 0.04 0.03 0.06

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

reference patterns. The semi-quantitative mineralogical composition of each mineralogical phase detected in the XRPD spectrum was calculated with the EVA support programme, which compares the area and intensity of two diffraction peaks, each diagnostic of one mineral component of the mixture. Because of the attened

Table 3 SEM-EDS microanalysis of volcanic aggregates in mortars (M_V: microcrystalline fragments; M_Pu: pumice fragment). Wt% M1_V1 M1_V2 M2_Pu_1 M2_Pu_2 M2_V2 M3_V1 M3_V2 M3_Pu_2 M4_V1 M4_V3 M4_V4 M5_V2 M5_V3 M6_V1 M6_V2 M6_V3 M7_V1 M8_Pu_1 SiO2 61.81 76.90 76.66 76.41 76.71 61.03 70.69 76.60 60.33 69.11 69.96 61.94 62.41 64.80 63.75 76.03 65.43 84.78 TiO2 0.51 0.15 0.28 0.10 0.22 0.85 0.32 0.28 0.88 0.47 0.33 0.67 0.34 1.01 0.71 0.29 0.57 0.28 Al2O3 21.70 12.72 13.96 13.83 12.63 19.02 16.01 13.33 18.46 16.69 15.70 17.96 21.35 17.66 16.47 12.53 16.82 5.95 Fe2O3 1.05 0.27 0.21 0.12 0.43 5.14 0.91 0.19 5.24 1.04 1.78 3.46 0.89 2.92 3.70 0.16 2.80 0.99 MnO n.d. 0.06 0.04 0.05 n.d. 0.15 0.04 0.07 n.d. n.d. 0.05 0.09 0.07 0.08 0.11 n.d. 0.17 0.18 MgO 0.90 0.74 1.66 1.60 0.94 2.31 0.74 1.00 2.80 1.22 1.20 2.81 0.91 1.42 2.30 0.82 2.41 4.30 CaO 5.79 0.95 2.24 2.21 0.96 5.28 2.60 2.93 3.02 3.72 2.09 4.83 5.92 4.38 3.76 0.41 6.07 1.45 Na2O 4.43 3.39 1.79 1.92 2.98 3.45 4.18 1.09 5.01 4.06 3.74 4.32 4.57 4.03 3.98 2.21 1.64 0.94 K2O 3.29 4.78 2.85 3.57 4.84 2.41 4.21 4.29 3.73 3.50 4.58 3.45 3.04 2.97 4.55 7.35 3.42 1.02 P2O5 0.52 0.05 0.30 0.18 0.29 0.37 0.29 0.23 0.53 0.19 0.57 0.46 0.50 0.73 0.65 0.20 0.68 0.11 Sum 100.00 100.01 100.00 100.00 100.00 100.01 99.99 100.01 100.00 100.00 100.00 99.99 100.00 100.00 99.98 100.00 100.01 100.00

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e e Charcoal fragments

Traces of microfossils (echinoid spines) M.S.

Table 5 Petrographic features on thin sections of mortars. Amp: amphibole, Bt: biotite, Cal: calcite, Ms: muscovite, Om: opaque minerals, Pl: plagioclase, Qtz: quartz, M.S.: moderately sorted, W.S: well sorted, *: present.

Trachydacites, dacites Dacites Rhyolites, phyllades (traces) Pl, Qtz, Ms, Om, Amp Pl, Qtz, Cal, Bt, Ms, Om Pl, Qtz, Ms, Om 3 2 3 69 83 67 28 15 30 6.3 5.2 5.8 0.8 1.4 0.7 M6 M7 M8 * * *

Trachiandesites, rhyolites Rhyolites Andesites, rhyolites, phyllades (traces) Trachiandesites, dacites, rhyolites, quartzites (traces) Trachiandesites

Rock fragments (supported by SEM-EDS analysis)

Pl, Qtz, Ms, Om, Amp, Cal Pl, Qtz, Ms, Om, Amp Pl, Qtz, Ms, Cal, Om, Amp

Pl, Qtz, Ms, Cal, Amp, Bt, Om Pl, Qtz, Ms, Amp, Bt, Om

Mineralogical phases of the aggregate

By polarized microscopy

3.1. Petrographic and mineralogical analysis From a macroscopic point of view, it is possible to detect few differences among samples. The most important difference is the possibility 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 greyish colour. Macroscopically, most samples show a coarse sand Wentworth size class (Wentworth, 1922); whereas the sample Kmo has a ne sand aspect (Wentworth, 1922). Most of the samples have a high cohesion and they only break under strong pressure of the hands, except for sample M3 which is highly friable. Observation under polarised optical microscopy and images acquired by atbed scanner (Fig. 3aei) allowed us to highlight the differences between the mortars. Apart from sample Kmo, which is almost lacking aggregates (Fig. 3i), the other samples have an aggregate of more than 15% (Table 5 and Fig. 4b). The mean size of the aggregates varies from 0.1 mm of sample Kmo to 1.3 mm of sample M2 (Table 5 and Fig. 4a); whereas its maximum size varies from 1.2 mm of sample Kmo to 6.6 mm of sample M2. Most samples have moderately sorted aggregates (Folk,1974; Jerram et al.,1996). Only sample M4 and M8 have well sorted aggregates (Folk, 1974; Jerram et al., 1996). In all mortars, a low sphericity and a subangular roundness prevail in the clasts of the aggregate (Powers,1953). In all samples the modal content of the binder exceeds the one of the aggregates (Table 5 and Fig. 4b). In particular, as concerns the aggregate/binder ratio, it is possible to subdivide the sample into three groups. The rst group (samples M1, M2, M4, M6, M8) includes samples with an aggregate/binder ratio of 1/2; the second group (samples M3, M5) includes samples with an aggregate/binder ratio of 1/3; whereas the third group with only one sample (M7) has an aggregate/binder ratio of approximately 1/7.

Macroporosity (size > 1/16 mm) (%)

3. Results and discussion

2 2 2

14

15

semi-quantitative visual estimation (Ricci Lucchi, 1980; Myron Best, 2003) by polarized microscopy

Binder (size < 1/16 mm) (%)

73 63 78

61

65

Aggregate (size>1/16 mm) (%)

25 35 20

25

20

Max. aggregate size (mm)

6.0 6.6 4.2

6.2

4.6

By polarized microscopy

Mean aggregate size (mm)

1.0 1.3 0.4

0.6

0.7

Kmo

M1 M2 M3

M4

M5

0.1

1.2

81

18

Cal, Pl, Qtz

morphology of crystals (e.g., muscovite), a problem of preferred orientation may have occurred during collection of powder XRPD data, and may contribute to variations in the relative intensities of some XRPD peaks. A semi-quantitative estimate of the aggregate/binder ratio and macroporosity (Table 5) was obtained by comparing the thin sections observed by optical microscopy with charts to aid visual estimation of modal proportions of minerals in rocks (Ricci Lucchi, 1980; Myron Best, 2003). The calcium carbonate content was determined by De Astis calcimeter (Table 4).

Cocciopesto

* * e

marbles (traces), phyllades (traces)

M1 M2 M3 M4 M5 M6 M7 M8 Kmo

Cal, Cal, Cal, Cal, Cal, Cal, Cal, Cal, Cal,

An, An, An, An, An, An, An, An, Ab

Qtz, Qtz, Qtz, Qtz, Qtz, Qtz, Qtz, Qtz,

Ms, Act, Gt Gt, Ms, He, Act Gt, Ms, He, Chl, Act, Mnt Gt, Ms, Act, Vat He, Gt, Ms, Act Gt, Ms, Vat Gt, Vat, Chl, Ms Vat, Gt, Ms, Chl

27.93 23.79 17.83 20.29 30.77 26.98 43.85 28.70 82.52

Sorting

maxemin

CaCO3(%)

W.S.

by XRPD analysis

by De Astis calcimeter

M.S. M.S. W.S.

M.S. M.S. M.S.

n.d.

e Reused mortar fragments Marble powder

Other

Table 4 Semi-quantitative mineralogical composition of mortars in order of decreasing relative abundance (as detected by XRPD, SEM-EDS and optical microscopy) and CaCO3 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.

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Fig. 3. Comparison between atbed 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).

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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 lump with 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 sample M8; (g) Marble powder fragment in the sample Kmo; (h) Pumice in the sample M8; (i) Trachiandesite and quartzite fragments in the sample M4.

The macroporosity has a low variability, varying in almost all the samples from 2 to 3% approximately, except for samples M4, M5 and Kmo, in which porosity varies from 14 to 18% approximately (Fig. 4b and Table 5). In these samples we may observe numerous secondary pores due to binder dissolution phenomena. Observations in thin section conrmed that samples M1, M2, M5, M6, M7 and M8 have aggregates, which are prevalently made of cocciopesto, combined with monomineralic crystalline phases and volcanic rock fragments. In sample M8 only we may observe rare metamorphic rock fragments (phyllades). It is possible to detect plagioclase, quartz, muscovite and opaque minerals in all sample, except sample Kmo, in which only calcite, plagioclase and quartz traces were detected (Table 5). The amphibole is found only in samples M1, M2, M3, M4, M5 and M6; whereas biotite is present only in samples M4, M5 and M7. Traces of calcite belonging to the aggregate are revealed only in samples M1 (Fig. 5a), M3, M4, M7 and Kmo. The calcite present in sample Kmo is due to the presence of marble powder deliberately added to the mixture (Fig. 5g). In sample M3, it is possible to detect charcoal fragments (Fig. 5b), deriving from vegetable residual combustion products used in limekilns. In all samples, it is possible to nd 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 increase secondary porosity in the mortars (Fig. 5c). In all samples the binder has a criptocrystalline aspect, except for sample M4, where we may observe recrystallization phenomena (Fig. 5d) which make the binder microcrystalline. Sample M5 presents a particular feature, since it is the only sample presenting rare traces of bioclasts, classiable as Echinoid spines (Fig. 5e). Sample M8 also has some peculiarities since - in its aggregate - it is possible to trace reused mortar fragments (Fig. 5f), which, most probably, come from detritis of old walls used as aggregate material in the mixture. As concerns the rock fragments present in the aggregates, it is possible to nd traces of metamorphic rocks, mainly phyllades, in samples M4, M8 and Kmo. Traces of quartzite may only be observed in sample M4 (Fig. 5i). However, fragments of volcanic rock with porphyritic texture (Fig. 5i) may be found in most of the samples, with a lower concentration than cocciopesto. Volcanic aggregates with pumiceous (Fig. 5h) texture (Myron Best, 2003) are found only in samples M2, M3 and M8. SEM-EDS microanalysis allowed us to classify volcanic aggregates in detail, by using the TAS diagram (Le Maitre et al., 1989). The diagram in Fig. 6 shows that all rock fragments have a SiO2 content

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

higher than 60%. Their composition varies from trachiandesites to ryolites. The pumice fragments have the lowest content of alkali. This is due to a more intense alkali leaching in pumices rather than in other volcanic rocks. The XRPD analysis supplied us with more detailed information on the mineralogical composition of the samples, allowing us to identify other mineralogical phases, in addition to the minerals recognised by polarised optical microscopy (Table 4). In all samples, except Kmo, we detected the presence of goethite. 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 M3 only, makes the sample more friable than other samples. The presence of heulandite in samples M2, M3 and M5 is of great interest. Heulandite is a common mineral in post-volcanic environments and belongs to the heulanditeeclinoptilolite zeolite group (Comodi et al., 2001). Scientic literature points out that the closest presence of this mineral to Kyme is in the area of Bigadi borate deposits, located approximately 120 km North-East of Kyme (Gndogdu et al., 1996; Helvaci and Alonso, 2000). However, we cannot exclude that it is possible to nd heulandite in areas closer to Kyme that still have not been studied. Future studies on Kyme may use heulandite as an index mineral to accurately identify the provenance 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 be pointed out by using binary chemical diagrams obtained through XRF analysis of mortars. Fig. 7a, representing the TiO2/Fe2O3 vs SiO2/CaO diagram, differentiates the samples with a higher SiO2/

CaO ratio (samples M3, M4) from the ones with a lower SiO2/CaO ratio (samples Kmo, M7). The same gure 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 to the mineralogical and petrographic features of the samples. Samples M3 and M4 with a higher SiO2 content, are also the samples with the lowest CaCO3 content (Table 4); whereas samples Kmo and M7 have the highest CaCO3 content (Table 4). For samples Kmo and M7 the higher CaCO3 content is ascribed to the aggregate/binder ratio, which is the lowest (Table 5). As concerns samples M1, M2, M5, M6 and M8, the chemical homogeneousness corresponds to a petrographic homogeneousness in samples M1 and M6, which are very similar both in the aggregate/ binder ratio and in their mineralogical and petrographic composition, but also in samples M2 and M5. Samples M2 and M5 can be considered very similar, except for unimportant differences in the aggregate of M5, which is the only sample to have traces of bioclasts and biotite in its aggregate. M8 is the only sample to present reused mortar fragments. Also the graph in Fig. 7b shows that samples M3 and M4 are the ones that differ from others, showing the highest Zr/Y ratio. This behaviour could also be due to the fact that M3 and M4 do not have cocciopesto in their aggregate, but only fragments of natural rock. Samples Kmo and M7 have the lowest Ba/Sr ratio (Fig. 7b); because of the high quantity of binder, they are poorer in trace elements (Table 1). The graph in Fig. 7b points out that samples M1 and M6 are rather close to each other, thus conrming their petrographic homogeneity. The study of the binder through SEM-EDS microanalysis was carried out - within each sample - by comparing the chemical composition of the lime lumps with the composition of the binder. The presence of the lime lumps in the mortars has to be seeked in the properties of the slaked lime (calcium hydroxide), but also in the water/lime ratio. An insufcient seasoning of the calcium hydroxide can produce a lime with low plasticity; the latter, combined with a low water/lime ratio, makes the workability of the mixture between lime and aggregate difcult. These circumstances can lead to the formation of nodules of slaked lime that become calcium carbonate nodules (lime lumps) (Bakolas et al., 1995) because of the carbonation process. The lime lumps have the same chemical composition of the raw materials (Barba et al., 2009), this is why the comparison between lime lumps and binder within the same sample may supply us with useful information on the binders degree of hydraulicity. The chemical parameter used in this comparison is the hydraulicity index (Bonyton, 1966). The graph in Fig. 8a, referring to sample M1, shows that the binders mean hydraulicity index is 0.21; whereas the lime lumps

Fig. 7. Chemical composition of Kyme mortars. (a) TiO2/Fe2O3 vs SiO2/CaO diagram; (b) Ba/Sr vs Zr/Y diagram.

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Fig. 8. SiO2 Al2O3 FeO2O3 vs CaO 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.

mean hydraulicity index is 0.03. This is due to the initial use of slaked lime, that mixed with cocciopesto has undergone an increase of SiO2, Al2O3 and Fe2O3 content due to the probable formation of CeSeH phases (Taylor, 1997; Hodgkinson and Hughes, 1999; Qing et al., 2006). A similar behaviour is present in samples M2 (Fig. 8b) and M6 (Fig. 8f), where the hydraulicity index of the binder is very similar to the one in sample M1. The migration of SiO2, Al2O3 and Fe2O3 from the cocciopesto to the binder may also be seen in samples M5 (Fig. 8e), M7 (Fig. 8g) and M8 (Fig. 8h), though the former is less intense than the remaining samples containing cocciopesto. Sample M4 (Fig. 8d) does not have cocciopesto and the slight increase of the binders hydraulicity index is due to the presence - in the aggregate of volcanic aggregates (trachiandesites, dacites, rhyolites) with low pozzolanic features. Sample M3 seemingly shows a very high hydraulicity index in the binder, of approximately 5.89 (Fig. 8c); this anomaly may be explained by the petrographic and mineralogical features of the sample itself. As we have already pointed out, sample M3 has a high friability and a binder content of 78% approximately (Table 5). Furthermore, in sample M3, we detected montmorillonite, as well as the lowest content of calcite (Table 4). This data seems to contradict the high quantity of binder in the sample itself. A plausible explanation of the observations presented may be given by

the addition of clay to the mixture of sample M3, as well as small quantities of lime. Therefore, the anomalous hydraulicity index (Fig. 8c) is not due to the formation of CeSeH phases in the binder, but to the high content of SiO2, Al2O3 and Fe2O3 which are present in clay. Lime lumps were not detected in sample Kmo (Fig. 8i), so the SEM-EDS analysis was only carried out on the binder, which is made of slaked lime. It is important to underline that, despite evidence of migration phenomena of SiO2, Al2O3 and Fe2O3 from the cocciopesto to the binder, CeSeH phases were not detected in the samples through XRPD analysis. Probably th CeSeH phases in the binder are predominantly like a gel with low crystallinity (Taylor, 1997; Hodgkinson and Hughes, 1999), which cannot be detected by XRPD analysis. 4. Conclusions The heterogeneity and variability of mortars always makes it difcult to obtain perfectly comparable results, even when different analytical techniques are used. However, in order to recognize groups of compositionally homogeneous mortars, according to our experience, the petrographic and chemical methods must take precedence over all other criteria. As a matter of fact, small differences in the

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semi-quantitative mineralogical composition and macroporosity can be explained by the different decay of the samples. The study showed that samples M1 and M6 are chemically and petrographically similar. The exact historical provenance of sample M6, belonging to the Roman-Imperial period, allows us to give sample M1 the same collocation, because of their compositional analogy. As regards the mortars sampled on the proto-Byzantine oor, M2 and M5 samples (Fig. 2b, e), are both cocciopesto mortars. They are compositionally similar, while sample M4, another mortar sampled from the proto-Byzantine oor (Fig. 2d), has no cocciopesto. These differences may be due to maintenance work carried out on the pavement by different workers, but this remains only a hypothesis to be conrmed in future studies. Another important result concerns M3 sample. Among all the mortars, M3 (sampled on the wall of the Medieval castle) is denitely the sample with 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 knowledge compared to the mortars prepared in previous historical periods. Marble powder articially added to the mixture was found in sample Kmo. This procedure was particularly appreciated by Roman workers, who wanted the plaster to have a marble brightness (Vitruvius Pollio, 1990). As concerns provenance studies, heulandite and echinoid spine traces found in some sample (Tables 4 and 5), may be used in the future to determine the provenance of the aggregate. Provenance studies will be extended to probable limestone caves used for the preparation of the lime, by comparing the composition of lime lumps present in mortars to the composition of geological samples (Barba et al., 2009). It is useful to point out how, among the Roman mortars that have been studied within the archaeological site, no mortars made only of natural pozzolanas have been found. As a matter of fact, the Romans used to abundantly use pozzolanas in mixtures (Degryse et al., 2002; Miriello et al., 2010a), mainly in bedding mortars. This practice could be justied by the difculty of nding natural pozzolanas in the area, rather than cocciopesto. This hypothesis, however, needs to be veried in future studies mainly focusing on the provenance of raw materials used to prepare mortars. Moreover, the Romans in Kyme have used inert material coming from old constructions, as an aggregate in the new mortars. This has been proven because of the presence of reused mortar fragments in sample M8. Regards the typology of lime, the analysis of the binder pointed out that natural slaked lime was used in Kyme, but, to increase the performance of the mortars, the lime was made hydraulic by adding cocciopesto to the mixture. Thanks to the present study, the rst compositional data concerning the mortars in the archaeological area of Kyme were produced. The compositional data we have so far obtained may be used to reproduce highly compatible mortars to be used in future restaurations.

Acknowledgements The authors would like to thank Franco Russo and Adelaide Mastandrea for their support in bioclasts recognition. We also wish to thank Rossella Pace for her advice on references. We also wish to thank the Editor and anonymous Reviewers for their helpful comments which helped in the revision of this manuscript.

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