On the potential of microbeam analyses in study of the ceramics, slip and paint of Late Bronze Age White Slip II ware: An example from the Canaanite site Tel Esur

Applied Clay Science 168 (2019) 324–339

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Research paper

On the potential of microbeam analyses in study of the ceramics, slip and paint of Late Bronze Age White Slip II ware: An example from the Canaanite site Tel Esur

T

Golan Shalvia, Shlomo Shovalb,c, , Shay Bara,d, Ayelet Gilboaa,d ⁎

a

Department of Archaeology, University of Haifa, 199 Aba Khoushy Ave, Mount Carmel, Haifa 31905, Israel Earth Sciences, Geology Group, Department of Natural Sciences, The Open University of Israel, The Dorothy de Rothschild Campus, 1 University Road, Raanana 43537, Israel c The Freddy and Nadine Herrmann Institute of Earth Sciences, The Hebrew University of Jerusalem, Edmund J. Safra Campus, Jerusalem 91904, Israel d The Zinman Institute of Archaeology, University of Haifa, 199 Aba Khoushy Ave, Mount Carmel, Haifa 31905, Israel b

ARTICLE INFO

ABSTRACT

Keywords: Black decoration Cypriot pottery EPMA, pXRF, LA-ICP-MS and FT-IR Manganese black technique Pigment analysis, Raw materials Umber ore White slip layer

Microbeam Analyses using EPMA, pXRF, LA-ICP-MS and FT-IR were conducted in this study of Late Bronze Age (LBA) White Slip II ware (WS-ware) imports at the Canaanite site Tel Esur (Tel Esur WS). The WS-ware is typically decorated with black-brown geometric patterns painted over a white slip layer. The study of the WSware provides useful information and a multi-analytical database regarding the composition, ceramic technology, raw materials, origin and cultural issues. The results demonstrate that the LBA potters select raw materials suitable for production of ceramics, slip and paint. The ceramic-body of the WS-ware was made of raw material that has been an appropriate selection to produce a hard and thin-walled vessel. For accentuating the black decoration over the dark reddish-grey ceramic-body, the latter was covered with white slip layer. The black decoration was made of ferromanganese-based pigment, which allows black decoration through firing of the vessels at an oxidizing atmosphere. The raw materials for the production of the ceramics, slip and paint were selected from Cypriot red basaltic clay of weathered basalt province, white hydrothermal clay of altered basalt zone and umber ore, respectively. The Tel Esur White Slip II ware is proved analytically to be imported from Cyprus.

1. Introduction 1.1. Tel Esur and imported WS II ware Tel Esur (Tell el Assawir) is situated in the Northern Sharon part of the Coastal plain in Israel (Shalvi, 2016; for location map see Shalvi et al., 2019). It is a small, five-acre site, containing fewer than two acres inhabited during the Late Bronze Age (LBA). The site seems to have been a rural settlement, lying at the western entrance to the Nahal ʻIron (Wadi ʻAra) mountain pass, which was constituted part of the historical Via Maris, leading from Egypt to Mesopotamia. The excavations in Tel Esur yielded several LBA contexts over three seasons (2010–12; Bar, 2016; Shalvi, 2016). The most significant remains from the LBA were found in the northern part of the site, Area B1. A well-preserved domestic building, was exposed in Stratum B1–2 with rooms containing, a rich restorable assemblage of pottery mainly

Canaanite, dated to the end of LB IB and the beginning of the LB IIB (circa 1400–1350 BCE) was exposed. The Canaanite pottery includes plain and painted vessels for household use as well as many large jars for storage (Shalvi et al., 2019). Imported LBA pottery was found as well, chiefly WS II ware and some Base Ring and Monochrome pottery. The WS-ware studied here is a ceramic family typified by blackbrown geometric patterns painted over a white slip layer which covers a dark ceramic-body (Popham, 1972; Eriksson, 2007). WS-ware vessels are predominantly hemispherical bowls termed ‘milk bowls’ (Karageorghis, 2001; Maeir, 2004), which have a plain rim and a wishbone shaped handle. The WS-ware comprises jugs, juglets and tankards (Beck et al., 2004). WS-ware was manufactured in great numbers during the LBA in Cyprus and uncovered at Cypriot archaeology sites and in tombs. During the 14th and 13th centuries BCE, a significant amount of WS-ware was exported from Cyprus to the Levant (Knapp and Cherry, 1994; Artzy, 2001; Hatcher, 2002; Grave et al.,

⁎ Corresponding author at: Earth Sciences, Geology Group, Department of Natural Sciences, The Open University of Israel, The Dorothy de Rothschild Campus, 1 University Road, Raanana 43537, Israel. E-mail address: [email protected] (S. Shoval).

https://doi.org/10.1016/j.clay.2018.11.019 Received 6 August 2018; Received in revised form 15 November 2018; Accepted 23 November 2018 0169-1317/ © 2018 Elsevier B.V. All rights reserved.

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2014; Yasur-Landau et al., 2014), among them Canaanite sites including Tel Esur (Tel Esur WS; Shalvi et al., 2019). Previous archaeometric studies of WS-ware were preformed mostly at Cypriot sites. Chemical and mineralogical composition of this ware from several of these sites has been documented (Courtois and Velde, 1981; Aloupi et al., 2001a; Aloupi et al., 2001b; Todd and Pilides, 2001). This ware have been further classified, on the basis of fabrics, techniques, typology and decorations, as WS I, WS II and as formative Proto WS (Maguire, 2012; Aloupi-Siotis and Lekka, 2017). The raw materials used for WS-ware manufacturing at the Cypriot sites have been investigated in previous studies (Gomez et al., 1995, 2002; Gomez and Doherty, 2000; Dikomitou, 2007; Renson et al., 2011, 2013). 1.2. Aims of the study In this study, we examined the potential of detailed Microbeam Analyses by EPMA, pXRF, LA-ICP-MS and FT-IR methods in study of the ceramics, slip and paint of the LBA WS-ware imported to the Canaanite site Tel Esur. EPMA-WDS elemental mapping and FT-IR spectral analysis by second derivatives are utilize for the first time in the study of WS-ware. A multi-analytical database regarding the composition, ceramic technology, raw materials, origin and cultural issues of the Tel Esur WS is constructed. For provenance study, a comparison is done with several comparable Cypriot raw materials that may have been used for the production. The current study is carried out in the framework of a wider, comprehensive research of paint-decorated Bronze and Iron Age pottery in the eastern Mediterranean (Shoval and Gilboa, 2016; Shoval, 2018). We are particularly interested in the way in which painted pottery and pigment technology may shed light on Cypro-Canaanite interconnections. 2. Experimental design and methods 2.1. The WS II ware analysed In all, thirteen documented Tel Esur WS-ware sherds were analysed. Photographs of the studied pottery sherds appear in Fig. 1. Since the Esur-130 sample was taken from a relatively well-preserved vessel with a complete profile and was found in a good context, it will serve as a representative sample of the WS-ware. The ceramics, slip and paint of the WS-ware was analysed ‘as is’ (as they were fired in the LBA).

Fig. 1. Photographs of the analysed Tel Esur WS-ware sherds. The last item is typological illustration of the sample Esur-130.

2.2. Comparable Cypriot raw materials There had been an import of WS-ware from Cyprus to Canaanite sites during the LBA (Artzy, 2001; Yasur-Landau et al., 2014). Therefore, a comparison is done between the composition of the ceramics, slip and paint of the Tel Esur WS and that of several comparable Cypriot raw materials that may have been used for the production. Samples of the Cypriot raw materials were collected in the Skouriotissa region (Keith et al., 2016), which had been settled during the LBA (Georgiou, 2014). Comparable Cypriot raw material for production of the ceramicbody of the WS-ware was collected from red basaltic clay of weathered basalt province (Renson et al., 2013). This clay was formed by Upper Cretaceous seafloor weathering of the Turonian Sheeted Dykes complex and the Pillow Lavas Fm. of the Troodos Ophiolite (Gillis and Robinson, 1985). Comparable Cypriot raw material for production of the white slip layer of the WS-ware was collected from white hydrothermal clay of altered basalt zone (Gomez and Doherty, 2000). This clay was formed by Upper Cretaceous hydrothermally leached alteration and argillization of Turonian Pillow Lavas Fm. of the Troodos Ophiolite (Gillis and Robinson, 1985). Comparable Cypriot raw material for production of the black decoration was collected from Cyprus umber ore. The umber ore is found in pelagic sediments of the Perapedi Fm. which was the first deposition over the ophiolite pillow basalts

(Robertson and Hudson, 1974). The umber enrichment with iron and manganese was a result of hydrothermal activity of hot solutions (Constantinou and Govett, 1972; Robertson and Hudson, 1973; Robertson, 1975). The comparable Cypriot raw materials were fired in an electric kiln at 800 °C for 6 h in order to simulate their compositions after ceramic firing. In our laboratory, we use firing in temperature of 800 °C for the preparation of spectral standards of minerals which are used as references for the FT-IR analysis of ceramics (Shoval, 2017). WS-ware has been fired during their LBA production at least at 800 °C (Aloupi et al., 2001b). The spectral standards of fired-smectite, poorly-crystalline silica mineral (e.g. opaline silica) and crystalline quartz used as references for the FT-IR analysis are described in our presentations of previous works (data in Shoval et al., 1991; Fabbri et al., 2014; Shoval, 2017). 2.3. Analysis methods Microbeam Analyses refer to any microanalytical methods used for compositional analyses, as defined by the Microbeam Analysis Society (MAS). The methods applied in this work were EPMA (SEM, WDS and EDS), pXRF, LA-ICP-MS and FT-IR. For the detailed experimental 325

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Table 1 EPMA-EDS analysis results of the major elements (oxides, in mass%) in the ceramic-body (C) and the slip layer (S) of the Tel Esur WS. Ceramic-body

Esur-4C

Esur-11C

Esur-20C

Esur-31C

Esur-32C

Esur-130C

Esur-200C

Esur-202C

Esur-204C

Esur-205C

Esur-209C

Esur-212C

Esur-213C

SiO2% TiO2% Al2O3% Fe2O3% MnO% MgO% CaO% Na2O% K2O% P2O5% SO3% Total % Al2O3/SiO2

54.47 0.58 16.90 10.35 0.22 6.94 5.25 2.99 1.24 0.33 0.03 99.30 0.31

54.27 0.68 21.52 9.58 0.20 6.84 4.50 0.93 0.71 0.07 0.05 99.35 0.40

53.17 1.18 25.88 5.17 0.19 4.52 6.25 2.09 0.50 0.37 0.19 99.51 0.49

52.03 0.64 24.21 8.90 0.35 5.46 5.80 1.25 0.82 0.22 nd 99.68 0.47

53.14 0.88 19.49 12.99 0.23 6.21 3.17 3.03 0.66 0.17 nd 99.97 0.37

53.17 0.05 21.24 10.26 0.00 8.83 2.24 3.12 0.46 0.27 0.37 100.01 0.40

56.59 0.81 19.74 7.96 0.18 3.98 6.51 1.62 1.18 0.39 0.11 99.07 0.35

54.26 1.42 19.95 7.41 0.19 4.11 9.51 1.07 0.87 0.17 0.18 99.14 0.37

51.78 0.65 23.18 10.44 0.19 5.86 4.92 1.67 0.51 0.19 0.19 99.58 0.45

53.44 1.02 18.60 10.87 0.18 5.38 6.45 2.26 0.87 0.18 0.24 99.49 0.35

45.49 10.13 19.62 6.91 0.00 4.00 7.74 4.10 0.77 0.00 1.25 100.01 0.43

52.42 0.06 26.47 8.47 0.00 5.03 2.10 4.45 0.16 0.75 0.09 100.00 0.50

53.19 2.57 21.39 8.24 0.30 7.67 4.31 1.39 0.54 0.24 0.16 100.00 0.40

Slip layer

Esur-4S

Esur-11S

Esur-20S

Esur-31S

Esur-32S

Esur-130S

Esur—200S

Esur-202S

Esur-204S

Esur-205S

Esur-209S

Esur-212S

Esur-213S

SiO2% TiO2% Al2O3% Fe2O3% MnO% MgO% CaO% Na2O% K2O% P2O5% SO3% Total % Al2O3/SiO2

55.87 0.66 23.04 5.41 0.13 6.25 3.83 0.50 2.04 1.95 0.31 99.99 0.41

52.41 1.58 23.49 4.08 0.14 6.55 6.02 0.5 3.00 1.18 0.24 99.19 0.45

48.91 1.31 29.39 2.20 0.08 11.57 2.57 0.68 1.82 1.02 0.45 100.00 0.60

53.98 1.67 23.79 4.96 0.11 6.74 2.31 0.77 1.89 3.03 0.75 100.00 0.44

61.08 0.94 19.32 4.74 0.36 5.78 4.19 0.40 1.94 1.02 0.24 100.01 0.32

49.22 0.45 24.98 4.64 0.50 8.55 5.96 0.44 1.68 0.00 3.58 100.00 0.51

49.70 0.65 19.60 2.71 0.66 9.25 2.95 2.78 3.66 1.30 6.74 100.00 0.39

45.24 5.10 27.53 2.74 0.00 10.39 2.80 1.38 2.12 1.62 1.09 100.01 0.61

48.41 0.70 26.70 4.21 0.00 9.75 5.60 0.65 2.34 1.45 0.19 100.00 0.55

50.47 0.22 27.38 3.29 0.00 7.79 3.55 2.61 1.98 0.71 2.01 100.01 0.54

43.11 0.89 28.31 3.50 0.05 10.85 8.59 1.67 1.26 0.56 0.14 98.93 0.66

48.52 2.45 27.49 3.25 0.16 13.65 1.43 0.64 1.13 0.44 0.83 99.99 0.57

47.26 0.46 26.22 3.67 0.28 9.23 8.36 0.28 2.13 0.99 0.42 99.30 0.55

protocol see references to our works quoted below for each analysis method. Electron probe micro-analyser (EPMA) method was performed using high-resolution JEOL SuperProbe JXA- 8230 EPMA apparatus equipped with SEM and four WDS spectrometers for microanalyses. This apparatus provides scanning electron-microscopy (SEM) images, wavelength-dispersive X-ray spectroscopy (WDS) elemental maps and energy-dispersive X-ray spectroscopy (EDS) analysis. The data was processed with a Phi-Rho-Z (PRZ) correction procedure. Beam conditions were set to 15 keV and 15–40 nA. Silicate and oxide standards (SPI 53 minerals) were used as a reference set for calibration,. The WDS maps were obtained using an interval of X: 0.50, Y: 0.50 μm and length of X: 200.0, Y: 150.0 μm. The EPMA analyses were conducted on polished cross sectioning of the ceramic-body and on external surfaces of the black decoration and the slip layer. For the ceramic-body, the specimens were mounted in cold-setting epoxy resin, and then were grounded and polished using standard sample preparation procedures. Since the painted decoration and the slip layer are thin, they could not be polished, and the scan was performed on their external surfaces (Shoval, 2018). To achieve good conductivity, the surfaces of the specimens were carbon coated with graphite under vacuum. Portable X-ray fluorescence spectroscopy (pXRF) analysis was performed with a handheld Bruker Tracer III–V XRF spectrometer (pXRF). This apparatus is equipped with a SiPIN detector and excitation source of X-ray tube Rh target standard. It is operated by Bruker HH Programs (S1 pXRF) software. For general analysis, the parameters employed were 40 kV, 9 mA for a 60 s live time count under vacuum. Analysing under vacuum conditions allows an accurate detection of the light elements Al, Si, S and P. The instrument is calibrated with internal apparatus standards (alloy with precious metals). The concentrations of the elements were calculated using the software designed by Rowe et al. (2012). Elemental detection is based on the locations and intensities of the individual main Ka1 peaks in the XRF spectra.

The pXRF analysis was conducted by targeting the beam on cross sectioning of the ceramic-body and on external surfaces of the black decoration and the slip layer of the pottery sherd (Shoval and Gilboa, 2016). The detected area by the pXRF apparatus is ca. 4 mm in diameter. The ceramic-body was analysed on freshly-cut sections, eliminating as much as possible measurement of the coarse particles (temper) within the ceramic. The paint decoration was analysed on thicker and best preserved pigment segments, eliminating as much as possible measurement of the ceramic-body substrate. Several measurements were performed for each specimen. We present the results with the highest detection counts. Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis was conducted with an ICP-MS AGILENT Technologies 7500 CX series ORS quadrupole mass spectrometer designed for high-precision measurements of elemental concentration. The laser ablation was carried out with a New-Wave UP-193FX ArF Excimer Laser Ablation (LA) system emitting 15 ns-long pulses at a wavelength of 193 nm. For calibration, a SRM NIST 610 international glass reference set (designated for geological studies) was used and mounted adjacent to the specimens in the ablation cell. The concentrations of the elements were calculated using the SILLS software package (Guillong et al., 2008). The LA-ICP-MS analysis was conducted by targeting the laser ablation on fresh cross sectioning of the ceramic-body and on external surfaces of the slip layer and the black decoration (Shoval and Paz, 2015; Shoval, 2018). The specimens were positioned in a New-Wave sealed ablation cell (60 cm3 round cell) equipped with an inlet nozzle. The cell was constantly flushed with 0.8 L/min helium gas that carried the ablated gases into the ICP-MS. The analysed area was controlled through apparatus screen (Wallis and Kamenov, 2013). Two measuring techniques were applied for each specimen: Line Analysis (LA, 1100 μm long × 100 μm laser spot measured at 36 μm/s) and Spot Analysis (SA, 100 μm-diameter laser spot, at a short time laser ablation). We employed intensive laser ablation (5.04 J cm − 2) for analysing the 326

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Table 2 pXRF analysis results of the major elements (oxides, in mass%) in the ceramic-body (C), the slip layer (S) and the black decoration (B) of the Tel Esur WS (a separate section for each). For comparison sake, the composition of the comparable Cypriot raw materials: red basaltic clay, white hydrothermal clay and umber ore appear in the last 2 columns of each section. For each specimen the result is normalized to 100%. Ceramic-body

Esur-4C Esur-11C Esur-20C Esur-31C Esur-32C Esur130C

Esur200C

Esur202C

Esur204C

Esur205C

Esur209C

Esur212C

Esur213C

Red basaltic clay

Red basaltic clay

SiO2 + Al2O3% TiO2% Fe2O3% MnO % CaO % K2O % P2O5% SO3% Trace elements (sum, %)

68.4 0.4 25.2 0.0 3.1 0.9 0.4 1.2 0.4

75.8 0.4 17.3 0.1 3.6 1.1 0.3 1.2 0.2

72.2 0.4 17.2 0.2 7.0 0.8 0.2 1.5 0.5

78.0 0.6 13.7 0.0 3.6 1.0 0.9 1.8 0.4

67.4 0.4 24.9 0.1 4.2 1.1 0.2 1.3 0.4

73.8 0.5 19.3 0.1 3.3 0.9 0.3 1.4 0.4

74.8 0.7 16.3 0.1 4.4 0.7 0.9 1.7 0.4

79.4 0.5 12.7 0.0 3.7 1.0 0.8 1.5 0.4

72.6 0.4 17.4 0.1 4.7 1.8 0.6 2.0 0.4

69.5 0.4 19.9 0.1 5.3 1.7 0.6 2.1 0.4

Slip layer

Esur-4S Esur-11S Esur-20S Esur-31S Esur-32S Esur130S

Esur200S

Esur202S

Esur204S

Esur205S

Esur209S

Esur212S

Esur213S

White hydrothermal clay

White hydrothermal clay

SiO2 + Al2O3% TiO2% Fe2O3% MnO % CaO % K2O % P2O5% SO3% Trace elements (sum, %)

82.8 0.6 8.9 0.1 3.3 2.0 0.4 1.5 0.4

85.3 0.4 6.9 0.1 1.2 1.3 0.8 3.8 0.2

85.4 0.5 7.1 0.0 1.2 3.0 0.9 1.5 0.4

84.1 0.7 7.1 0.1 1.8 3.7 0.7 1.4 0.4

86.7 0.6 5.8 0.0 1.6 2.8 0.8 1.3 0.4

87.0 0.5 6.7 0.0 1.2 2.4 0.7 1.1 0.4

89.1 0.6 5.2 0.0 0.9 2.2 0.7 1.1 0.2

89.2 0.8 5.0 0.0 1.0 2.0 0.6 1.0 0.4

87.5 0.9 5.3 0.0 1.9 2.1 0.7 1.2 0.4

83.4 0.4 11.0 0.2 0.8 0.3 0.6 3.0 0.3

83.1 0.5 10.8 0.1 0.9 0.3 0.7 3.3 0.3

73.7 0.3 19.0 0.1 4.0 0.8 0.3 1.4 0.4

63.5 0.5 28.5 0.1 4.0 0.9 0.3 1.8 0.4

81.0 0.6 10.0 0.1 3.5 2.7 0.3 1.6 0.2

82.7 0.8 8.9 0.0 2.3 2.3 0.6 1.9 0.5

60.2 0.6 26.5 0.1 7.4 1.6 0.3 3.0 0.3

83.4 0.5 9.4 0.1 2.1 2.2 0.4 1.6 0.3

64.2 0.6 27.1 0.1 4.1 0.8 0.4 2.2 0.5

89.3 0.7 4.6 0.0 1.0 2.1 0.7 1.2 0.4

67.1 0.4 26.7 0.1 3.2 0.6 0.2 1.3 0.4

Black decoration

Esur-4B

Esur-11B

Esur-20B Esur-31B

Esur-3B

Esur130B

Esur200B

Esur202B

Esur204B

Esur205B

Esur209B

Esur212B

Esur213B

Umber ore

Umber ore

SiO2 + Al2O3% TiO2% Fe2O3% MnO % CaO % K2O % P2O5% SO3% Trace elements (sum, %)

62.5 0.4 22.2 6.7 4.0 2.1 0.3 1.5 0.3

64.8 0.5 22.8 4.8 2.5 2.2 0.4 1.6 0.4

59.6 0.6 25.4 7.5 2.5 1.8 0.4 1.7 0.5

53.8 0.5 26.8 10.9 3.6 1.4 0.4 2.2 0.4

41.1 0.4 29.8 11.4 6.5 0.9 0.4 9.3 0.2

65.2 0.5 23.8 2.6 2.7 2.3 0.4 2.0 0.5

70.7 0.7 19.5 1.1 2.9 2.9 0.3 1.6 0.3

56.9 0.4 29.2 6.6 2.9 2.0 0.4 1.3 0.3

72.1 0.5 18.6 2.1 2.6 2.2 0.3 1.3 0.3

53.9 0.3 23.8 14.2 4.3 0.9 0.3 1.8 0.5

67.4 0.6 24.2 2.7 1.5 1.7 0.6 1.1 0.2

56.6 0.7 30.3 7.3 1.8 1.5 0.6 1.0 0.2

44.7 0.3 23.8 23.2 5.3 0.4 0.5 1.5 0.3

52.8 0.2 19.8 19.4 4.8 0.3 0.3 2.1 0.3

59.0 0.5 23.6 8.0 4.3 2.1 0.3 1.8 0.4

ceramic-body and the slip layer; and reduced laser intensity (30%, 0.63 J cm − 2 in the line analysis and 70%; 2.88 J cm − 2 in the spot analysis) for analysing of the painted decoration in order to limit the penetration of the ablation from the thin pigment layers into the substrate. Fourier-transform infrared spectroscopy (FT-IR) method was employed using a Jasco FT-IR spectrometer (Series 4000). This apparatus is operated by Spectra Manager software. Accumulations time of 60 s was used for spectra collection. Samples were extracted separately from the ceramic-body, the slip layer and the decoration pigment of each sherd (Shoval, 2018). For the analysis, 1 mg of powdered sample was ground in an agate mortar, mixed with 150 mg KBr and pressed into a disk. GRAMS/AI 32 software package of the ThermoScientific Corporation was used for the spectral analysis. Second derivatives of the spectra were calculated by using a derivative “gap” function of the GRAMS software (Shoval and Paz, 2015).

detection (Table 3). 3.1. EPMA analyses The EPMA method allows microprobe analysis of ancient ceramics (Ionescu et al., 2011; Panighello et al., 2012; Ionescu and Hoeck, 2016; Ashkenazi et al., 2017) and of painted pottery (Shoval, 2018). This method was applied here for SEM imaging, WDS elemental mapping and EDS detection through a direct analysis of the specimens. 3.1.1. EPMA-SEM images The EPMA-SEM method generates microstructural images of the pottery fabric (Tschegg et al., 2008, 2009) and of the painted pigments (Shoval, 2018). Fig. 2 illustrates the EPMA-SEM images scanned on the ceramic, slip and paint of sample Esur-130. Two types of SEM images are presented in the figure: secondary electron (SEI) and backscattered (COMPO) images. The former shows the microstructures of the scanned specimen (Fig. 2a, c, e) while the latter contrasts components consisting of light metals against those consisting of heavier metals (Fig. 2b, d, f). In the backscattered images, the areas assigned a darker shade of grey represent materials composed of light metals while the lighter areas represent materials composed of heavier metals. The ceramic-body is characterised by a platy microstructure of the fired-clay (Fig. 2a). Some porosity microstructure might occur as a result of the sintering during the firing process. The backscattered image

3. Results The results of EPMA-WDS (Figs. 3–5), EPMA-EDS (Table 1) and pXRF (Table 2) presents the concentrations of the major elements only (oxides) in mass% and these results are larger than the limit of detection. The results of LA-ICP-MS include also the concentrations of the trace elements in ppm (Table 3). Here, we use the symbol < to report when the concentration of an individual element is below its limit of 327

Esur-4B

LA 42.39 0.26 9.47 22.28 13.33 4.54 3.83 0.49 0.80 1.71 0.91 100.01

784.9 < 153.8 44.3 229.3 779.3 875.0 32.6 86.8 576.1 29.3 70.1 5.3 999.4 < 10.7 3.0 0.22

Black decoration

Operation SiO2% TiO2% Al2O3% Fe2O3% MnO% MgO% CaO% Na2O% K2O% P2O5% SO3% Total %

V ppm Cr ppm Co ppm Ni ppm Cu ppm Zn ppm Ga ppm Rb ppm Sr ppm Y ppm Zr ppm Nb ppm Ba ppm Pb ppm U ppm Al2O3/ SiO2

328

763.8 < 122.3 74.4 352.3 1075.7 935.9 18.5 < 47.3 486.7 40.3 37.1 9.6 868.5 30.7 4.0 0.19

SA 41.17 0.27 7.84 26.08 12.26 3.95 3.26 0.42 0.73 2.62 1.41 100.01

Esur-4B

215.6 < 230.7 67.5 < 203.3 < 978.7 < 298.4 83.6 254.6 < 507.0 16.9 48.8 29.6 1385.5 76.9 < 3.9 0.18

LA 62.21 0.46 11.22 9.41 1.84 1.74 6.61 0.77 1.05 3.40 1.29 100.00

Esur-11B

244.3 93.0 127.2 572.9 658.4 1070.0 62.0 95.1 273.5 32.1 130.6 18.2 5575.8 119.8 3.6 0.26

SA 53.29 0.88 14.05 6.54 9.41 2.13 6.87 0.35 0.81 4.56 1.12 100.01

Esur-11B

1031.3 < 66.9 81.2 337.7 1034.8 527.4 26.57 53.8 251.1 62.5 51.8 < 2.9 547.6 10.3 4.3 0.18

LA 43.04 0.26 7.96 24.53 11.81 3.31 3.07 0.95 0.78 2.44 1.83 99.98

Esur-31B

942.5 98.1 99.4 631.3 1015.7 342.6 11.3 23.8 223.4 52.8 63.8 6.3 363.6 5.6 3.1 0.17

SA 37.87 0.22 6.27 25.11 15.58 2.97 5.81 0.78 0.61 3.57 1.21 100.00

Esur-31B

474.3 < 69.5 66.1 239.6 443.8 651.8 17.9 27.1 < 237.0 17.1 34.7 3.1 602.2 43.1 < 1.4 0.42

LA 46.40 0.16 19.34 14.37 6.96 6.33 2.90 1.11 0.70 0.71 1.04 100.02

Esur-130B

715.2 < 62.5 137.9 571.7 1459.2 664.5 15.5 < 23.6 203.3 25.2 51.9 8.6 631.7 51.1 3.6 0.24

SA 41.68 0.23 9.90 26.64 10.90 3.71 2.80 0.91 0.78 0.95 1.48 99.98

Esur-130B

199.1 225.1 106.7 348.3 643.3 1478.3 55.4 308.7 620.2 36.3 140.1 30.6 3344.7 59.4 6.0 0.25

LA 52.31 0.52 13.31 8.03 1.44 2.48 9.96 1.00 1.07 8.65 1.23 100.00

Esur-204B

221.7 143.7 63.4 430.7 797.4 1390.0 58.8 91.2 258.7 17.7 57.0 14.5 1018.5 35.0 3.4 0.21

SA 51.79 0.38 10.91 16.82 6.61 3.31 4.92 0.49 0.93 2.82 1.03 100.01

Esur-204B

208.0 232.8 65.0 217.6 1411.6 1227.0 28.5 145.2 < 431.6 7.15 46.2 10.5 1146.3 56.3 < 3.3 0.18

La 56.57 0.30 10.15 12.38 4.92 3.51 6.30 1.57 1.07 2.12 1.12 100.01

Esur-209B

534.9 106.0 70.3 177.7 1242.9 372.4 15.6 19.6 231.6 37.4 67.9 4.3 312.9 55.7 1.4 0.29

SA 47.75 0.22 13.82 15.33 7.45 8.82 1.25 1.57 0.60 1.28 1.92 100.01

Esur-209B

349.5 112.6 35.1 89.9 56.5 64.9 21.5 14.5 64.9 11.5 38.8 5.5 82.1 4.2 0.5 0.39

LA 55.97 0.55 21.77 10.30 0.14 5.97 3.70 1.07 0.48 0.04 0.01 100.00

Esur-130C

215.3 119.9 29.6 70.9 59.4 54.7 20.0 12.5 64.6 11.2 37.5 5.5 89.0 3.9 0.5 0.39

SA 56.74 0.39 22.35 8.30 0.12 5.47 4.20 1.93 0.47 0.02 0.01 100.00

Esur-130C

36.5 < 117.5 14.2 159.6 < 59.7 < 58.9 8.6 7.6 62.9 4.5 8.8 < 3.3 67.7 < 4.1 < 1.9 0.55

LA 53.49 0.06 29.19 0.94 0.79 11.58 1.51 0.13 1.29 0.25 0.79 100.02

Esur-130S

49.9 139.7 23.6 169.9 78.9 42.5 11.0 11.4 44.2 7.6 57.7 1.3 57.5 4.8 0.4 0.48

SA 54.97 0.18 26.49 1.53 0.08 13.15 1.14 0.15 1.54 0.71 0.07 100.01

Esur-130S

Table 3 LA-ICP-MS analysis results of the major elements (oxides, in mass%) and trace elements (in ppm) of the black decoration (B) of the selected Tel Esur WS. For comparison sake, the compositions of the ceramic-body (C) and the slip layer (S) of sample Esur-130 appear in the last four columns. (LA = line analysis; SA = spot analysis).

G. Shalvi et al.

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Fig. 2. EPMA-SEM images of sample Esur-130 scanned on specimens of the (a, b) ceramic-body; (c, d) the slip layer; and (e, f) the black decoration layer in. a, c and e are secondary electron images and b, d, f are backscatter images.

of the ceramic-body (Fig. 2b) displays darker grey shaded areas indicating light-metal components (Si and Al; see below). The white slip layer has a granular microstructure (Fig. 2c). The backscattered images of the slip layer (Fig. 2d) also displays a dark grey shade representing light metal composition (Mg, Si and Al; see below). The black decoration is composed of small pigment particles (Fig. 2e) coating on the WS substrate. The whiter patches of the pigment particles observed in the backscattered images of the black decoration (Fig. 2f) represent a composition of heavier metals (Fe and Mn; see below). The decoration pigment particles may reach a size of 10 μm.

components in the scanned areas. The detection is also affected by the presences of fragmented and porous microstructures (Fig. 2). The elemental maps of the ceramic-body and the slip layer (Figs. 3–4) display high concentrations of SiO2 and Al2O3, attesting to the composition of the fired-clay ceramic in the specimens. The patches with higher SiO2 content reflect an additional contribution from an accessory silica mineral, in addition to that of the fired-clay. The elemental maps of the ceramic-body illustrate pronounced concentrations of Fe2O3, small amounts of CaO and traces of MnO. Those of the slip layer show smaller concentrations of Fe2O3 and higher amounts of MgO compared with the ceramic-body. The elemental maps of the black decoration (Fig. 5) illustrate prominent concentrations of Fe2O3 and MnO, attesting its ferromanganese-based composition.

3.1.2. EPMA-WDS elemental maps EPMA-WDS elemental maps present visually the distribution pattern of the detected elements and their degree of homogeneity in the scanned specimens (Panighello et al., 2012). Figs. 3–5 illustrate the EPMA-WDS elemental maps scanned from the ceramic, slip and paint of sample Esur-130. The colour tones in each map represent the concentration range of the detected element as determined according to the colour scale. The elemental maps of the ceramics, slip and paint (Figs. 3–5) reveal non-homogeneous distribution patterns of the detected elements, which reflect compositional variations of the

3.1.3. EPMA-EDS analysis The EPMA-EDS method provides chemical analysis of ancient ceramics (Ionescu and Hoeck, 2016) and painted pigments (Shoval, 2018). This method discerns the concentrations of major elements. Table 1 presents results of the EPMA-EDS analysis of the major elements in the ceramic-body and the slip layer of the Tel Esur WS. The results confirm that both specimens are rich in SiO2 and Al2O3. The ceramic329

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Fig. 3. EPMA-WDS elemental maps (oxides; colour scale in mass%) scanned from the ceramic-body of sample Esur-130: (a) SiO2; (b) Al2O3; (c) Fe2O3; (d) MnO; (e) CaO; and (f) MgO.

body is richer in Fe2O3 and poorer in MgO than the slip layer. The low concentrations of CaO in both specimens reflect a composition poor in calcite (Fabbri et al., 2014).

less accurate elemental concentrations than EPMA-EDS and LA-ICP-MS analyses. Results of the pXRF analysis of the major elements in the ceramicbody, the slip layer and the black decoration are presented in Table 2, for all the examined Tel Esur WS samples. The table presents also the composition of the comparable Cypriot raw materials: red basaltic clay, white hydrothermal clay and umber ore. As there is a significant overlapping between the peaks of Al and Si in the pXRF spectra of ceramics, we present in Table 2 the sum of the two concentrations, SiO2 + Al2O3 instead of each individual one. Furthermore, due to some analytical limitations of the pXRF method (Liritzis and Zacharias, 2011; Hunt and Speakman, 2015), Table 2 presents the sum of the trace elements concentrations, instead of each one individually. The results in Table 2 demonstrate that the ceramic-body is rich in SiO2 and Al2O3 and contains some Fe2O3 and traces of MnO. Concentrations of Fe2O3 in the slip layer are smaller compared to the ceramic body, and this layer is poor in MnO.

3.2. pXRF analysis The PXRF analysis allows chemical analysis of ancient ceramics (Goren et al., 2011; Speakman et al., 2011; Hunt and Speakman, 2015; Holmqvist, 2016) and of painted pottery (Aloupi et al., 2000; Aloupi et al., 2001a; Aloupi et al., 2001b; Shoval and Gilboa, 2016; AloupiSiotis and Lekka, 2017). This method is often utilized for provenance studies of ceramic vessels (Hein et al., 2004; Maritan et al., 2013). The pXRF discerns the concentration of most of the major elements as well as some of the trace elements through a direct analysis of the specimens. The pXRF proved to be an inexpensive, rapid and non-destructive method, which can be used on a large scale (Goren et al., 2011; Ferguson et al., 2015). However, this method has some analytical limitations (Hunt and Speakman, 2015). It does not detect several “light” major elements such as C and O, and often Na and Mg as well. As for the detection of the elements Al, Si, S and P, the analysis has to be performed under vacuum conditions. Thus, the pXRF method delivers

3.3. LA-ICP-MS analysis LA-ICP-MS analysis provides high-resolution and high-accuracy 330

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Fig. 4. EPMA-WDS elemental maps (oxides; colour scale in mass%) scanned from the white slip layer on sample Esur-130: (a) SiO2; (b) Al2O3; (c) Fe2O3; (d) MnO; (e) CaO; and (f) MgO.

quantitative chemical analysis of ancient ceramics (Golitko and Dussubieux, 2016) and of painted pottery (Speakman and Neff, 2002; Neff, 2003; Porter and Speakman, 2008; Shoval, 2018). The combination of ICP with LA discerns the concentrations of all major elements and the detectable trace elements (Porat et al., 1991) through a direct analysis of the specimens (Speakman and Neff, 2005; Neff, 2012). The LA-ICP-MS analysis was applied here for the selected Tel Esur WS in order to confirm the pXRF results and to detect the concentration of trace elements. Results of the LA-ICP-MS analysis of the black decoration for the selected Tel Esur WS samples are presented in Table 3. The table presents also the composition of the ceramic-body and the slip layer in sample Esur-130. The black pigment contains prominent concentrations of Fe2O3 and MnO and significant concentrations (in ppm) of the trace elements Cu, Zn, Ni, Co and V. Results of the LA-ICP-MS analysis of the comparable Cyprus umber ore from the Skouriotissa region are presents in Table 4. The umber ore is typified by pronounced concentrations of Fe2O3 and MnO, it is rich in SiO2 and poor in Al2O3 and CaO.

3.4. FT-IR spectroscopy analysis FT-IR spectroscopy provides mineralogical fingerprints of ancient ceramics (Shoval, 2003, 2017; Weiner, 2010) and of painted pottery (Sabbatini et al., 2000; Van Der Weerd et al., 2004; Centeno et al., 2012). This method is often applied for provenance studies (Maritan et al., 2005; Shoval et al., 2006) and for deducing firing conditions of pottery (Maritan et al., 2006). The major advantage of FT-IR spectroscopy is its ability to identify the composition of both crystalline minerals as well as the pseudo-amorphous phases of the fired-clay ceramic (Shoval, 2017), while amorphous phases are unsuccessfully detected by XRD (X-ray diffraction) method, because they lack distinct peaks in the diffractogram (Shoval et al., 2011). FT-IR spectral analysis by second derivatives further improves the identification of different minerals and minor phases in the ceramic (De Benedetto et al., 2002; Shoval and Paz, 2015). Fig. 6 illustrates FT-IR spectra and spectral analysis by second derivatives performed for the ceramic-body of the samples Esur-130 and Esur-202 as well as for the slip layer and the black decoration of the sample Esur-130. The phases detected in these specimens (Fig. 6) are 331

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Fig. 5. EPMA-WDS elemental maps (oxides; colour scale in mass%) scanned from the black decoration layer on sample Esur-130: (a) SiO2; (b) Al2O3; (c) Fe2O3; (d) MnO; (e) CaO; and (f) MgO.

of the stronger band doublet at 778 and 978 cm−1, and by the stronger band at 694 cm−1. Fig. 6 illustrates two major spectral patterns of ceramic body. The first spectral pattern (Fig. 6a) shows band components characteristic to fired-clay (compare with Fig. 7d) and silica mineral (compare with Fig. 7e). The location of the fired-clay band around 1041 cm−1 is characteristic to fired-smectite (Shoval and Paz, 2015). This composition is compatible with that of the fired red basaltic clay (Fig. 7a). Firedclay phase (FC in Fig. 6a) is formed when firing of clay to ceramic; fired-smectite (Fig. 7d) is formed by firing of smectitic clay (Shoval et al., 2011; Shoval and Paz, 2015). The second spectral pattern of the ceramic-body (Fig. 6b) is dominated by bands of silica mineral (compare with Fig. 7e), which has lower degree of crystallinity than that of crystalline quartz (Fig. 7f; Shoval et al., 1991). Some metakaolinite may also present (Shoval, 2017). The slip layer shows bands of fired-clay and silica mineral (Fig. 6c), which are compatible with that of the white hydrothermal clay (Fig. 7b). The decoration pigment (Fig. 6d) shows bands of ferromanganese mineral (Elderfield and Glasby, 1973) and silica mineral which are compatible with that of the fired umber ore (Fig. 7c). The weak CO3 bands in all these spectral types demonstrate calcite-poor compositions (Fabbri et al., 2014).

fired-clay (FC; Shoval, 2017), poorly-crystalline silica mineral (SM; Shoval et al., 1991) and calcite (C; Fabbri et al., 2014; Shoval, 2017). The ceramic-body contained also iron oxide (IO; Shoval, 2017); and the black decoration – some ferromanganese mineral (FM; Elderfield and Glasby, 1973; Shoval, 2017). For the identification of the mineral composition we use the reference spectral standards presented in Fig. 7, which are described in our presentations of previous works. Fig. 7 illustrates FT-IR spectra and spectral analysis by second derivatives of several Cypriot comparable Cypriot raw materials that may have been used for the production of the ceramics, slip and paint of the WS-ware. They are respectively red basaltic clay, white hydrothermal and umber ore (Fig. 7a–c), all from the Skouriotissa region. Before the analysis these raw materials were fired at 800 °C in order to simulate their compositions after ceramic firing. Spectra of respective reference materials: fired-smectite, poorly-crystalline silica mineral (e.g. opaline silica) and crystalline quartz are also presented (Fig. 7d–f). The crystalline quartz (Fig. 7f) can be distinguished from the poorly-crystalline silica mineral (e.g. opaline silica Fig. 7e) by the appearance of the main band at 1084 cm−1 (instead of about 1095–1105 cm−1 in poorly-crystalline silica mineral; Shoval et al., 1991), by the prominent diagnostic band at 1170 cm−1 with a shoulder at 1145 cm−1, by the deep splitting 332

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Table 4 LA-ICP-MS analysis results of the major elements (oxides, in mass%) and of the trace elements (in ppm) of the comparable Cyprus umber ore pigment (CU) from the Skouriotissa region. (LA = line analysis and SA = spot analysis). Umber ore

CU-1

CU-1

CU-2

CU-2

CU-3

CU-3

CU-4

CU-4

Operation SiO2% TiO2% Al2O3% Fe2O3% MnO% MgO% CaO% Na2O% K2O% P2O5% SO3% Total %

LA 55.36 0.17 5.05 22.52 12.81 1.27 1.13 0.64 0.62 0.42 0.40 100.39

SA 53.28 0.14 3.90 23.80 15.10 1.10 0.83 0.67 0.66 0.52 < 0.20 100.00

LA 54.86 0.18 5.26 22.97 12.57 1.28 1.19 0.62 0.63 0.45 0.50 100.51

SA 56.27 0.18 5.77 21.82 11.54 1.35 1.27 0.63 0.71 0.46 0.50 100.50

LA 47.96 0.17 4.84 27.96 15.06 1.23 1.12 0.60 0.63 0.42 0.50 100.49

SA 47.63 0.18 4.54 25.92 17.64 1.12 1.22 0.61 0.69 0.46 0.50 100.51

LA 50.01 0.17 5.04 27.28 13.61 1.17 1.10 0.60 0.61 0.42 0.50 100.51

SA 53.16 0.15 5.04 24.94 12.16 1.21 1.25 0.63 0.63 0.82 0.50 100.49

V ppm Cr ppm Co ppm Ni ppm Cu ppm Zn ppm Ga ppm Rb ppm Sr ppm Y ppm Zr ppm Nb ppm Ba ppm Pb ppm U ppm Al2O3/ SiO2

1083.0 22.2 169.1 443.9 2024.5 681.3 88.2 31.8 3266.0 72.7 94.3 5.2 2974.4 326.2 2.3 0.09

1155.4 24.7 166.0 547.3 2430.7 1049.2 75.1 47.7 2478.4 51.0 71.5 5.1 2785.6 388.4 2.9 0.07

1068.9 21.5 163.8 422.8 1987.5 648.7 89.2 32.9 3308.4 79.1 98.2 5.5 2990.7 315.0 2.3 0.10

1047.3 28.4 201.7 421.7 1929.6 765.1 77.3 35.4 2919.5 80.5 95.7 4.7 2862.4 277.7 1.9 0.10

1176.7 70.0 189.3 508.5 2362.1 743.1 94.2 32.5 4204.3 81.3 108.8 6.2 3344.0 412.8 2.8 0.10

1108.0 25.5 227.3 466.3 2249.4 835.0 112.6 34.5 5779.2 78.1 99.2 6.7 4135.0 534.3 3.2 0.09

1161.8 22.0 163.8 492.6 2235.6 746.8 89.2 35.3 3895.9 81.7 111.1 6.1 3205.7 395.9 2.6 0.1

1132.5 28.3 146.8 443.4 1999.6 649.5 72.4 30.0 3263.8 81.4 92.8 4.4 2301.3 291.0 1.4 0.09

Fig. 6. FT-IR spectra (SP) and spectral analysis by second derivatives (SD) of: (a, b) the ceramic-body of the samples Esur-130 and Esur-202, (c) the slip layer and (d) the black decoration of the sample Esur-130. The assigned bands are fired-clay (FC), poorly-crystalline silica mineral (SM), iron oxide (IO), ferromanganese mineral (FM) and calcite (C).

4. Discussion

trends. However, there were some differences between results obtained by the EMPA-EDS (Table 1) and the LA-ICP-MS (Table 3) for an individual specimen. This might be caused for several reasons: the applying of these different analysing methods, inhomogeneity of the object analysed, different locations on the object targeted by each apparatus, different sizes of the scanned area and different penetration depths of the analysis. Although, the similar trends, in our pXRF analysis (Table 2) larger amounts of Fe2O3 are detected, compared to the EPMA-EDS and LA-ICP-MS analyses, which indicates that the pXRF

4.1. Composition of the painted pottery The application of Microbeam Analyses using EPMA, pXRF, LA-ICPMS and FT-IR methods in the study of the Tel Esur WS provides useful information and served to construct a multi-analytical database regarding their composition, ceramic technology, raw materials, origin and cultural issues. Results by the different methods display similar 333

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Fig. 7. FT-IR spectra (SP) and spectral analysis by second derivatives (SD) of several Cypriot comparable Cypriot raw materials that may have been used for the production of the ceramics, slip and paint of the WS-ware. They are respectively (a) red basaltic clay, (b) white hydrothermal clay and (c) umber ore, all from the Skouriotissa region. Before the analysis these raw materials were fired at 800 °C. In addition spectra of respective reference materials: (d) fired-smectite, (e) poorlycrystalline silica mineral (e.g. opaline silica) and (f) crystalline quartz. The assigned bands are fired-clay (FC) fired-smectite (FS), silica mineral (SM), iron oxide (IO), ferromanganese mineral (FM) and calcite (C). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

method is less accurate in detection of elemental concentrations, in particular for Fe2O3. Diagrams compare the pXRF analysis of several elements are illustrated in Fig. 8, for the compositions of the ceramic-body, the slip layer and the black decoration of the Tel Esur WS. The diagrams emphasise that three different raw materials with different compositions were selected for the production of the ceramics, slip and paint of the Tel Esur WS. Thus demonstrates that the EBA potters had knowledge of raw

materials and manufacturing technologies, enabling them to choose the suitable ones according to advantageous for WS-ware manufacture. 4.2. Raw material utilized for the ceramic-body The ceramic-body of the WS-ware was made of raw material that has been an appropriate selection to produce a hard and thin-walled vessel (Fig. 1). In the WS-ware found at Cypriot sites the ceramic-body

Fig. 8. The diagrams compare the pXRF analyses results of several elements (oxides, in mass%) in the compositions of the ceramic-body, the slip layer and the black decoration of the Tel Esur WS (data in Table 2): (a) CaO versus SiO2 + Al2O3; and (b) MnO versus Fe2O3. 334

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was manufactured from basaltic clay (Renson et al., 2013). Smectitic raw material derived from weathering of leucocratic gabbro (Gomez et al., 1995) was utilized in the production centre of WS II ware at the Sanidha in the eastern Troodos foothills region (Todd, 2000; Todd and Pilides, 2001). The analyses of the ceramic body of the Tel-Esur WS (Figs. 3, 6a; Tables 1–2) indicate production from red smectitic clay raw material, rich in silica and in iron oxide and poor in calcite. This composition accords the utilization of Cypriot red basaltic clay of weathered basalt province (Table 2, Fig. 7a). The utilizing of basaltic clay for production of the ceramic body of WS-ware from Cypriot sites was reported by Renson et al., 2013. This supports the observation that Cypriot WS-ware was imported to Canaanite sites during the LBA (Artzy, 2001; YasurLandau et al., 2014). The utilizing of red basaltic clay rich in smectite and iron oxide allows higher degree of sintering when firing (Shoval and Beck, 2005), which is required for hard and thin-walled ceramic ware. The iron oxide in the clay gives the ceramic-body its reddish-grey colour. The low concentration of calcite in the raw material enables production of high quality dense ceramic, while calcareous clay would have caused formation of porous ceramic. The type of the clay mineral used for ceramic production can be determined from the ratio Al2O3/SiO2 (Shoval and Paz, 2015). A smectitic raw material yields an approximate ratio of 0.36 while kaolinitic clay yields a different ratio around 0.90. The ratio found in the ceramic-body of the Tel Esur WS ranges between 0.31 and 0.50 (Table 1) in accord with the use of smectitic clay rich material. Nevertheless, some SiO2 may be contributed by the silica mineral found in the ceramic body (SiO2 in Fig. 3). The FT-IR spectral analysis by second derivatives performed on the ceramic-body of the Tel Esur WS revealed two different major spectral patterns of the ceramic-body, indicating two different raw materials used. The first spectral pattern (Fig. 6a) was obtained for specimens Esur-4, 32, 205 and 130. This spectral pattern contains bands of firedclay and silica mineral (FC and AM in Fig. 6a). The second spectral pattern of the ceramic-body (Fig. 6b) was obtained for the specimens Esur-11, 20, 31, 200, 204, 209, 212, 213 and 202. This spectral pattern is dominated by bands of silica mineral (SM in Fig. 6b). The locations of the main band of the fired-clay around 1038 cm−1 and of the silica mineral around 1091 cm−1 are respectively characteristic to firedsmectite (Fig. 7d, Shoval, 2017) and poorly-crystalline silica mineral (Fig. 7e, Shoval et al., 1991) possibly with some metakaolinite (Shoval, 2017). In both spectral patterns (Fig. 6a, b), the presence of poorly-crystalline silica mineral (compare to Fig. 7e) and the absence of crystalline quartz here (compare to Fig. 7f) is in accord with the use of basaltic clay, like that of Cyprus. Indeed, crystalline quartz does not appear in the composition of the precursor basaltic rocks. In addition, the calcitepoor composition of the ceramic-body (Fig. 6a, b) rules out production from the calcite-rich sediments of the circum-Troodos sedimentary succession. In contrast to the Cypriot basaltic clay, the raw materials indigenous to the Tel Esur region are rich in crystalline quartz grains (Shalvi et al., 2019), contradicting local production of the Tel Esur WS. Fig. 9 compares the EPMA-EDS analysis results of several elements in the ceramic-body of the Tel Esur WS (data in Table 1) to these in WSware found at Cypriot sites (data in Aloupi et al., 2001a). The figure demonstrates that the concentrations in the ceramic-body are mostly contained within the value ranges of the WS-ware from Cypriot sites. This is one of several observations supporting a Cypriot origin for the Tel Esur WS.

sites white hydrothermal clay of altered basalt zone was utilized (Gomez and Doherty, 2000). Three types of slip layer compositions, designated A, B and C and typified respectively by fired kaolinite, by smectite and by mica clay, were reported by Aloupi et al. (2001a). The analyses of the slip layer of the Tel-Esur WS (Figs. 4, 6c; Tables 1–2) indicate production from pale smectitic clay raw material, rich in silica and in magnesium oxide, and poor in calcite. This composition accords the utilization of Cypriot white hydrothermal clay of altered basalt zone (Table 2, Fig. 7b). The utilizing of white hydrothermal clay for production of the ceramic body of WS-ware from Cypriot sites was reported by Gomez and Doherty (2000). The pale colour of the slip layer, a result of the poor iron oxide content, allows the white covering of the vessels. The FT-IR spectroscopy of the slip layer (Fig. 6c) shows bands of fired-clay. The location of the main fired-clay band at around 1042 cm−1 (FC in Fig. 6c) is characteristic to fired-smectite (Fig. 7d, Shoval, 2017). The range of the Al2O3/SiO2 ratio between 0.32 and 0.66 in the slip layer of the Tel Esur WS (Table 1) confirms a smectitic composition of the raw material. Nevertheless, some SiO2 may be contributed by the silica mineral found in the ceramic body (SiO2 in Fig. 4). The concentrations of MgO in the slip layer (Table 1) reveal the utilization of Mg-bearing smectitic clay. Indeed, before firing, smectitic clay is identified by the FT-IR spectroscopy in the composition of the comparable Cypriot white hydrothermal clay. Some poorly-crystalline silica mineral (Fig. 7e, Shoval et al., 1991) is also present in the white slip material (SM in Fig. 6c). The absence of crystalline quartz in the slip layer (Compare to Fig. 7f) accords the utilization of basaltic clay. Fig. 9 illustrates diagrams compare the EPMA-EDS analysis results of several elements in the slip layer of the Tel Esur WS (data in Table 1) to those of WS-ware found at Cypriot sites (data in Aloupi et al., 2001a). The figure demonstrates that the concentrations in the Tel Esur WS are mostly contained within the value ranges of the WS ware at Cypriot sites. This is one of several observations supporting a Cypriot origin for the Tel Esur WS. 4.4. Raw material utilized for the black decoration Two major painting techniques were used in Cyprus were used for decoration of painted pottery, the iron reduction technique and the manganese black technique (Aloupi et al., 2000; Aloupi et al., 2001a; Aloupi-Siotis and Lekka, 2017). By the iron reduction technique, the black decoration is obtained by applying a black ferrous iron mineral, which requires firing in a reduction atmosphere. By the manganese black technique the black decoration is obtained by applying a manganese-based pigment. In WS-ware found at Cypriot sites, the shift from the first technique to the second occurred during the LBA and the Proto Cypro-Geometric Age (Aloupi-Siotis and Lekka, 2017). The Cypriot source for manganese-based pigment was the umber ore (Shoval and Gilboa, 2016). By firing, the umber ore turns a rich black-brown known as burnt umber (Barnett et al., 2006). This ore is found in pelagic sediments over the ophiolite pillow basalts (Robertson and Hudson, 1974). The analyses of the black decoration of the Tel-Esur WS (Figs. 5, 6d; Tables 2–3) indicate production from ferromanganese pigment consisting of Fe2O3 and MnO. This composition accords the utilization of ferromanganese Cyprus umber ore for this propose (Table 4, Fig. 7c). The utilization of Cyprus umber ore for black decoration of WS-ware from Cypriot sites was reported by Aloupi et al., 2000, Aloupi et al., 2001a and Aloupi-Siotis and Lekka, 2017). The ferromanganese pigment reveals the utilization of manganese black technique for the painting, which allows black decoration through firing of the vessels in an oxidizing atmosphere (Shoval and Gilboa, 2016; Shoval, 2018). Fig. 10 illustrates diagrams compare the LA-ICP-MS analyses of several elements in the black decoration of the Tel Esur WS to those in the comparative Cyprus umber ore. The figure illustrates that the

4.3. Raw material utilized for the slip layer For accentuating the black decoration over the dark reddish-grey ceramic-body of the WS-ware, the latter was covered with white slip layer. For the production of the slip layer of WS-ware found at Cypriot 335

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Fig. 9. The diagrams compare the EPMA-EDS analysis results of several elements (oxides, in mass%) in the ceramic-body and in the slip layer of the Tel Esur WS (data in Table 1) to those of WS-ware found at Cypriot sites (data in Aloupi et al., 2001a): (a) SiO2 versus Al2O3; (b) MgO versus Fe2O3; (c) CaO versus Fe2O3; and (d) Na2O versus K2O.

composition of the decoration pigment of the Tel Esur WS is generally in accord with that of the Cyprus umber ore. Both pigments contain pronounced concentrations of MnO and Fe2O3 and significant concentrations of Cu, Zn, Ni, Co and V (Tables 3–4). The FT-IR spectral analysis of the decoration pigment of the Tel Esur WS (Fig. 6d) also resembles that of the Cyprus umber ore (Fig. 7c). Both contain ferromanganese mineral and poorly-crystalline silica mineral as confirmed by the FT-IR spectroscopy (FM and SM in these Figs.). Indeed, the Cyprus umber contains opaline silica of pelagic origin (Robertson and Hudson, 1974; Robertson, 1975), which is poorly-crystalline silica mineral. The identification of umber ore in the black decoration of the Tel Esur WS supports a Cypriot origin for the Tel Esur WS. Analysis of the black decoration reveals higher concentrations of SiO2 and Al2O3 with respect to that in the comparable Cyprus umber ore (Fig. 10a). The low content of Al2O3 in the raw umber reveals that clay is almost absent. This is an indication that the raw umber ore was mixed with some clay during preparation of the pigment for the painting. The clay might have been added in order to stabilize the black pigment on the pottery surface by sintering the clay during the firing. In Fig. 10 the element concentrations in the black decoration fall generally within the concentration ranges in the raw umber ore and the slip layer. This seems to be the result of the mixing the raw umber ore with some clay in preparing the pigment for the painting. The adding of clay resulted in a higher alumina content of the painted pigment with respect to the raw umber ore (Fig. 10a). Indeed, the FT-IR spectroscopy confirms presence of fired-clay in the black pigment (FC in Fig. 6d), and the almost absent of clay from the comparable Cyprus umber ore (Fig. 7c). The dilution of the raw manganese pigment with clay seems to be the reason for the reduced concentration of MnO in the black pigments (Tables 2–3).

5. Summary 1. The application of Microbeam Analyses using EPMA, pXRF, LA-ICPMS and FT-IR methods in the study of the Tel Esur WS provides useful information and served to construct a multi-analytical database regarding their composition, ceramic technology, raw materials, origin and cultural issues. 2. The analyses of the ceramic body of the Tel-Esur WS indicate production from Cypriot red basaltic clay of weathered basalt province. The utilizing of red basaltic clay rich in smectite and iron oxide allows a higher degree of sintering when firing, which is required for hard and thin-walled ceramic ware. 3. The analyses of the slip layer of this ware indicate production from Cypriot white hydrothermal clay of altered basalt zone. The pale colour of the slip layer, a result of the poor iron oxide content, allows the white covering of the vessels. 4. The analyses of the black decoration of this ware indicate production from ferromanganese Cyprus umber ore. The ferromanganese pigment reveals the utilization of manganese black technique for the painting, which allows black decoration through firing of the vessels in an oxidizing atmosphere. 5. In summary, three different raw materials were selected by the LBA potters for producing of the ceramics, slip and paint of the Tel Esur WS, each particularly suited to its purpose. This demonstrates the high skill of LBA potters, their familiarity with raw materials and their experience with manufacturing technologies. 6. The compositions of the ceramics, slip and paint of the Tel Esur WS was found similar to those of the WS II ware found at Cypriot sites thus proving analytically that the Tel Esur was imported from Cyprus. 336

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Fig. 10. The diagrams compare the LA-ICP-MS analyses results of several elements (oxides, in mass%) in the black decoration of the Tel Esur WS (data in Table 3) to those in the comparative Cyprus umber ore (data in Table 4): (a) SiO2 versus Al2O3; (b) MnO versus Fe2O3; and (c) MgO versus CaO, as well as (d) Zn versus Cu; (e) Cr versus V; and (f) Ni versus Co, (ppm). The concentrations of these elements in the ceramic-body and the slip layer of sample Esur-130 are also illustrated.

7. The current study an integral part of a wider, comprehensive research project about Bronze and Iron Age paint-decorated pottery in the eastern Mediterranean, designed to facilitate further comparative studies of paint-decorated pottery in the Levant and resulting cultural inferences.

gratitude. Part of this work was carried out while Shlomo Shoval was spending his sabbatical at the Institute of Earth Sciences at the Hebrew University of Jerusalem (HU). He expresses his appreciation for Oded Navon (HU) for his collaboration. The EPMA, pXRF and LA-ICP-MS analyses were conducted at the institute's facilities. The authors are grateful to Omri Dvir (HU) and Yael Levenson (HU) for operating the EPMA and the LA-ICP-MS laboratories and performing the analyses as well as for helpful discussions. We thank Yigal Erel (HU) for the permission to use the XRF apparatus. We are indebted to Costas Xenophontos (Cyprus Geological Survey, Department in Nicosia) for providing the umber ore. We thank Dana Harari of the Open University and Yaron Katzir of the Ben Gurion University for their help and the helpful discussions and to Judith Lempert for the effort that went into her editing. Lastly, we acknowledge the contribution of three anonymous readers to the clarity of the paper.

Acknowledgements The study was carried out within the framework of Golan Shalvi's MA Thesis at the Department of Archaeology, University of Haifa. We carried out this study in the framework of a wider, comprehensive research of paint-decorated Bronze and Iron Age pottery in the eastern Mediterranean supported by the Israel Science Foundation (grant no. 209/14, awarded to Ayelet Gilboa and Shlomo Shoval) and the Research Funds of the Open University of Israel (grants nos. 37179 and 31016, awarded to Shlomo Shoval). We acknowledge these grants with 337

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