Pigments on Late Bronze Age painted Canaanite pottery at Tel Esur: New insights into Canaanite–Cypriot technological interaction

Journal of Archaeological Science: Reports 30 (2020) 102212

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Pigments on Late Bronze Age painted Canaanite pottery at Tel Esur: New insights into Canaanite–Cypriot technological interaction

T

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

a

Department of Archaeology, The Zinman Institute 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, Israel1 b

ARTICLE INFO

ABSTRACT

Keywords: Black and red decorations Ceramic and pigment analyses Cypro-Canaanite liaisons Iron and manganese ores pXRF, LA-ICP-MS and EPMA Technology transfer Trade in pigments

The ceramics and pigments of Late Bronze Age (LBA) painted Canaanite pottery were studied using ceramic petrography and three microbeam methods: pXRF, LA-ICP-MS and EPMA. The analyses focused on specimens from Tel Esur in Israel’s northeastern Sharon Plain, which has yielded a well-preserved assemblage of the 15th/ 14th centuries BCE. We studied painted jars, biconical jugs and a bowl decorated with black, red or two-colored geometric patterns. The petrographic analysis revealed that the majority of the painted vessels were produced on the southern Levantine coastal plain. The microbeam analyses demonstrated the use of ferromanganese and ferric-iron pigments for the black and the red decorations respectively. The adoption of the manganese-based technique in Canaanite workshops seems to be an early LBA technological progress, which facilitated the production of black decoration while firing vessels in an oxidizing atmosphere; it explains the sharp increase in the production of two-colored Canaanite pottery during that period. Ferromanganese ore sources for the black pigment are rare in Canaan and absent from its coast; this required importation of raw ore from external sources. The analogous use of the manganese-based technique for black decoration on Cypriot wares suggests that both pigments and technology were transferred from Cyprus to Canaan, highlighting a ‘new’ aspect in the multifaceted Cypro-Canaanite liaisons of this period.

1. Introductions 1.1. Aims of the study The present paper forms part of a wider, comprehensive research we are conducting on paint-decorated Bronze and Iron Age pottery in the Eastern Mediterranean (Shalvi et al., 2019b; Shoval, 2018; Shoval and Gilboa, 2016). We submit that the analysis of the pigments in the painted designs on pottery and associated technologies may reveal hitherto unknown facets of cross-Mediterranean interactions, especially in the Canaanite–Cypriot sphere. By presenting our results fully, the paper is also meant to facilitate further comparative studies of paintdecorated pottery in the Mediterranean and beyond and ensuing cultural inferences. With very few exceptions, analytical studies of pigments on Iron Age, Bronze Age, or earlier ceramics in the East Mediterranean are astonishingly scarce (e.g. Aloupi et al., 2000, 2001a, 2001b; Aloupi-

Siotis and Lekka, 2017; Porter and Speakman, 2008). In the present study we performed, for the first time, detailed compositional analysis of an assemblage of Bronze Age painted pottery from Canaan. We chose a recently-excavated assemblage from Tel Esur, dating circa 1400–1350 BCE (Stratum 2; Shalvi et al., 2019a), the period in which trade between the Levant and Cyprus was at its apex. We applied ceramic petrography and microbeam methods to the ceramic body of the vessels and to their black and red painted decoration. The results were inter alia compared with those emanating from a previous study dealing with Cypriot White Slip II ware imports (‘Milk Bowls’) found at the same site and stratum (Shalvi et al., 2019b). The comparison between the two pottery groups enables the observation of similarities and dissimilarities between the black decorations between them and concomitantly to elucidate whether similar decoration technologies and pigment ore sources are in evidence.

Corresponding author at: The Open University of Israel, Raanana, Israel. E-mail address: [email protected] (S. Shoval). 1 Visiting scientist. ⁎

https://doi.org/10.1016/j.jasrep.2020.102212 Received 26 August 2019; Received in revised form 24 December 2019; Accepted 11 January 2020 2352-409X/ © 2020 Elsevier Ltd. All rights reserved.

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Fig. 1. Location map of Tel Esur and other LBA sites in the Levant. The background is a Digital Shaded Relief Map of Israel, the western margins of Jordan, and southern Lebanon by John K. Hall and Rani Calvo, The Geological Survey of Israel.

1.2. Tel Esur and its Late Bronze Age pottery

pottery, the building must have been functional in the late LBA IB and early LBA IIA, circa 1400–1350 BCE. The ceramic assemblage found in the structure is very well preserved, lay mostly in primary deposits and was restorable. It consists of objects primarily of local Canaanite forms, some Egyptianizing vessels, and several imported standard Late Cypriot II pottery such as White Slip, Base Ring, etc., which were, however, very fragmentary (Shalvi et al., 2019a). Beyond the painted pottery on which we focus here, the Canaanite assemblage consisted, of course, also of many plain vessels.

Tel Esur (Arabic Tell el-Assawir) is located on the Mediterranean coastal plain of Israel, about 12 km (7.4 miles) from the seashore (Fig. 1). It is a small, about seven-acre site, of which less than a half of it was inhabited during the LBA. In that period its seems to have been a rural settlement, situated at the western entrance to the Nahal ʻIron (Wadi ʻAra) pass, which constituted part of the historical Via Maris leading from Egypt to Syria and Mesopotamia. The most significant LBA remains were excavated in Area B1, on the northern part of the site. Here, in Stratum 2, this period is represented by an unusually wellpreserved domestic building (Bar, 2016; Shalvi, 2016). Judging from its 2

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Table 1 List of the pottery studied (for details see Shalvi et al., 2019a). (c = ceramic body; b = black pigment; r = red pigment). Sample No.

Vessel/shape (type)

Locus

Basket

Context

Analyzed segments

Esur-5 Esur-6 Esur-8 Esur-10 Esur-14 Esur-21 Esur-22 Esur-25 Esur-26 Esur-52 Esur-59 Esur-68 Esur-78 Esur-95 Esur-103 Esur-104 Esur-106 Esur-115 Esur-116 Esur-126 Esur-149 Esur-151 Esur-210

Biconical Jug Jar Bowl Biconical Jug? Jar? Biconical Jug? Jar? Jar Jar Biconical Jug? Jar? Jar Jug, Biconical (JB1) Jug, Biconical (JB1) Jug, Biconical (JB2) Storage Jar (SJ3b) Storage Jar (SJB3) Storage Jar (SJ3) Storage Jar (SJ6) Storage Jar (SJ3a) Storage Jar (SJ3a), ibex motif Storage Jar (SJ3a) Jug, General (JG4) Storage Jar (SJ2), slip Storage Jar (SJ3a), slip Jar

62229 62283 62271 62245 62255 62233 52222 42210 62229 42219 42226 42219 42225 42223 52222 42219 62233 62246 62270 52221 42210 42219 42219

622517/2 622639/10 622529/3 622663 622380/2/9 622629 522186 422356 622556/1 422283 422176 422283 422134 422277 522186 422283 622629 622514–622361 622459 522142 422334 422127 422280

Area 300 Yard 3 Yard 3 Area 46 Area 55 Room 33 Room 22 Yard 1 Area 300 Yard 1 Room 26 Yard 1 Room 25 Room 22 Room 22 Yard 1 Room 33 Area 46 Room 70 Room 21 Yard 1 Yard 1 Yard 1

c, c, c, c, c, c, c, c, c, c, c, c, c, c, c, c, c, c, c, c, c, c, c,

b, b b b b b, b, b b, b. r b, b, b b, r b, b, b, b b b, b,

r

r r r r r r r r r r r r

“dry” chemical analyses of the ceramic body and the pigments. For the detailed experimental protocol see also our previous works (Shalvi et al., 2019b; Shoval, 2018; Shoval and Gilboa, 2016; Shoval and Paz, 2015). Firstly, we used pXRF in order to establish the basic chemical composition of the ceramic body and the pigments of the decoration of all specimens. The pXRF method is a cheap, rapid, and non-destructive, it is usually available to archaeologists and can be used on a large scale (Ferguson et al., 2015; Goren et al., 2011; Pappalardo, et al., 2010); thus here it was employed for all specimens. This method is used for analyzing a number of major and trace elements composing the ceramic body (Frahm and Doonan, 2013; Holmqvist, 2016; Speakman et al., 2011) as well as the pigments of the paints on the pottery (Aloupi et al., 2000, 2001a, 2001b; Aloupi-Siotis and Lekka, 2017; Attaelmanan and Yousif, 2012; Shalvi et al., 2019b; Shoval and Gilboa, 2016). One of the reasons we applied this method to the ceramic body of the vessels was to assess the possible effects of the composition of the latter on the analysis of the pigments overlying it (such as regarding the contribution of manganese, for which see below). However, the method does have some analytical limitations (Hunt and Speakman, 2015; Liritzis and Zacharias, 2011); it is less accurate in identifying elemental concentrations than the EPMA-EDS, LA-ICP-MS and Neutron Activation Analysis (Maritan et al., 2013; Pérez-Arantegui et al., 2008; Porat et al., 1991; Wallis and Kamenov, 2013). The pXRF method does not detect several “light” major elements such as C and O, nor, in most instances, Na and Mg. For the detection of the elements Al, Si, S and P, the analysis is performed under vacuum conditions. For the analysis we used a handheld Bruker Tracer III-V XRF spectrometer. 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). The area detected by the pXRF apparatus is circa 4 mm in diameter. Because of the above-mentioned limitations of pXRF and in order to validate the analytical results and to detect trace elements, we analyzed seven fragments on which the pigments were well preserved using LAICP-MS (Table 5) and five using EPMA-SEM (Table 7). These methods, however, are expensive, not always available to archaeologists and destructive. Therefore, we could not apply these costly methods to the entire corpus under investigation (Table 1). The LA-ICP-MS method is used for high-resolution and high-accuracy quantitative chemical analysis of major and the trace elements

2. Materials and methods 2.1. The painted Canaanite pottery Twenty-three painted Canaanite specimens from Tel Esur were investigated: 13 complete or semi-complete vessels and 10 diagnostic pottery fragments (Table 1; Figs. 2, 3). The analyzed components included 23 ceramic body samples, 21 black-paint segments and 15 red ones. The vessels analyzed comprise mainly jars and biconical jugs, which are the most frequently-decorated vessels at the site, and a sole painted bowl. Most specimens are typically decorated with black, red or are two-colored, with simple geometric patterns over the ceramic body or a white slip layer. Only one vessel bore an ibex design, probably part of an ibex-and palm-tree motif, very typical to LBA Canaan (Figs. 2, 3; sample 115). The analyzed segments from the ceramic body, the black decoration and the red decoration of each pottery sample are marked with the prefix c, b and r, respectively (e.g. Esur-115b refers to a specimen from the black decoration on jar Esur-115). 2.2. Methods and protocol of analyses The painted Canaanite pottery was studied using ceramic-petrography and microbeam methods. As a first step, to lay the foundation for this study, thin sections from 13 painted Canaanite vessels were optically analyzed by ceramic-petrography in order to ascertain their supposed southern Levantine origin. Petrography is arguably the most commonly used method for defining the ceramic fabric and coarse particles in archaeological ceramics and consequently trace the vessels’ locale of manufacture (Di Caprio, 2017; Fabrizi et al., 2019; Goren, 1991, 2000; Maggetti, 1982, 1994; Quinn, 2013; Shoval et al., 2006). The thin sections were optically analyzed under a BX51-P Olympus polarizing microscope equipped with a camera (e.g., Shoval et al., 2006). Since we were only interested in establishing the southern Levantine origin of the vessels, especially vs. Cyprus, we deemed the petrographic method sufficient suffices (Gilboa and Goren 2015). Following the petrographic examination, we performed microbeam analyses. This term refers to any microanalytical method used for compositional analyses, as defined by the Microbeam Analysis Society (MAS). Here, we used Portable X-Ray Fluorescence Spectroscopy (pXRF), Laser-Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Electron Probe Micro-Analysis (EPMA), to undertake 3

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Fig. 2. Complete vessels studied.

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Fig. 3. Photographs of potsherds studied.

(Cochrane and Neff, 2006; Golitko and Dussubieux, 2016; Giussani et al., 2009; Neff, 2012; Resano et al., 2010; Robertson et al., 2002; Speakman and Neff, 2005). This is suitable for analyzing the pigments of the paint on the pottery (Neff, 2003; Porter and Speakman, 2008; Shalvi et al., 2019b; Shoval, 2018; Speakman and Neff, 2002). For the LA-ICP-MS analysis we used an ICP-MS AGILENT Technologies 7500 CX

series ORS quadrupole mass spectrometer designed for high-accuracy measurement of elemental concentrations. The laser ablation was carried out with a New-Wave UP-193FX ArF Excimer Laser Ablation (LA) system. 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 5

6

Southern coastal plain, southern Shephelah Western Galilee coast, west of the kurkar ridges South Lebanon coast Calcite-bearing clay with carbonate particles, or loess soil Calcareous-clay alluvium poor in quartz grains and silt, with kurkar particles from northern ridges Slightly calcareous alluvium, poor in quartz grains and silt, with kurkar particles from northern ridges Esur-106, Esur151 Esur-52

E

Poor in quartz grains from sand, rich in quartz silt, occasionally iron concretions Poor in quartz grains from sand, kurkar particles, calcareous algae, fragments of carbonate rocks, iron concentrates Poor in quartz grains from sand, small kurkar particles, fragments of carbonate rocks, other fragments B-1

B-2

Rich in quartz grains from sand, kurkar particles, calcareous algae, occasionally iron concentrates

A-1b

Esur-68, Esur-95, Esur-103 Esur-59 Esur-104 Esur-149 Esur-78, Esur-126 Esur-116

A-2b

Calcareous brown-gray clay, rich in quartz silt Calcareous brown-gray clay, rich in quartz silt Slightly calcareous yellowish clay, poor in quartz silt

Sharon or Carmel coast, west of the kurkar ridges

Calcareous-clay alluvium with quartz grains and silt, without fragments of carbonate rocks Calcareous-clay alluvium rich in quartz grains and silt, with kurkar particles Calcareous Brown-grey clay, rich in quartz silt Calcareous dark brown clay, rich in quartz silt

Southeast part of the Sharon coastal plain Northeast part of the Sharon coastal plain Calcareous-clay alluvium containing quartz grains and silt, with fragments of carbonate rocks Calcareous-clay alluvium rich in quartz grains and silt, with fragments of carbonate rocks A-1a

Particles

Esur-115

2 A comprehensive technological and provenance analysis by means of petrography has been carried out on all the complete LBA Canaanite vessels of Tel Esur (N=69). The presentation of this entire study is beyond our scope here and at present we discuss only results that are directly relevant to this paper.

Petro-graphic Group

Tables 3, 4 present the pXRF analysis of the major elements in the ceramic body, black and red decorations of all specimens analyzed. The detection of the elements by this method is based on the locations and intensities of the main individual Ka1 peaks in the XRF spectra. Because there is significant overlap between the broad peaks of Al and Si in pXRF spectra of ceramics, calculations of the accurate concentrations of these elements individually are limited. On the other hand, it is possible to calculate the sum of the Si and Al concentrations from their combined broad peak in the pXRF spectra. Therefore, in Tables 3, 4 the sum of SiO2 + Al2O3 is presented. Furthermore, due to some analytical limitations of the pXRF method (Hunt and Speakman, 2015; Liritzis and Zacharias, 2011), we present the sum of the trace elements concentrations, rather than individual results. The pXRF results demonstrate that the ceramic body of all vessels is rich in SiO2 + Al2O3, and some Fe2O3, but poor in MnO. The black pigments exhibit conspicuous concentrations of Fe2O3 and MnO and the red pigment is rich in Fe2O3 but poor in MnO.

Pottery

Table 2 Ceramic-petrography data for the painted Canaanite vessels from Tel Esur.

3.2. The pXRF analysis

Rich in quartz grains from sand, iron concretions, foraminifera

Matrix

As mentioned, 13 specimens underwent petrographic analysis and divided into petrographic groups (Table 2). Fig. 4 presents photomicrographs of their thin sections. The major coarse particles are quartz grains and, in some of the groups, fragments of carbonate rocks and aeolianite rock (locally termed kurkar). The ceramic matrix is calcareous and contains some quartz silt. Based on the nature of the coarse particles and the properties of the ceramic matrix, four major geographic origins were identified along the coastal plain of Israel and Lebanon (A, B-1, B-2 and E; Table 2 and see below, Section 4).2

A-2a

3.1. Ceramic petrography

Calcareous dark brown clay, rich in quartz silt Calcareous Brown-gray clay, rich in quartz grains, containing silt

3. Results

Quartz grains from sand, fragments of carbonate rocks, occasionally iron concentrates Rich in quartz grains from sand, coarse fragments of carbonate rocks occasionally containing foraminifera fossils

Raw material

Presumed origin

were calculated using the SILLS software package (Guillong et al., 2008). In order to verify the analytical results produced by the abovementioned methods, we applied EPMA for the ceramic material and pigments of five specimens. The EPMA system provides SEM (Scanning Electron-Microscopy) images, WDS (Wavelength Dispersive Spectroscopy) elemental maps, as well as EDS (Energy-Dispersive X-ray Spectroscopy) analyses (Tschegg et al., 2009). This allows analysis of the ceramic material (Ionescu et al., 2011) as well as of the decoration pigments (Ashkenazi et al., 2017; Rosado et al., 2018; Shalvi et al., 2019b; Shoval, 2018). The SEM images provide microstructural analysis of the scanned area (Tschegg et al., 2008); the WDS elemental maps present visually the distribution patterns of the detected elements in the scanned specimens (Panighello et al., 2012) and the EDS provides chemical analysis and primarily discerns the concentrations of major elements in the analyzed specimens (Ionescu and Hoeck, 2016). This, however, is a very expensive method; it operates slowly (usually two to six hours per analysis of only up to four elements each time) and is destructive when analyzing pottery. The EPMA analysis was performed using a high-resolution JEOL SuperProbe JXA-8230 EPMA apparatus equipped with SEM and four WDS spectrometers for microanalysis. The data were processed with a Phi-Rho-Z (PRZ) correction procedure (Ashkenazi et al., 2017). Silicate and oxide standards (SPI 53 minerals) were used as a reference set for calibration.

West Sharon-Carmel coast

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Fig. 4. Ceramic-petrography photomicrographs of thin sections analyzed from 13 painted Canaanite vessels from Tel Esur (cross-polarized light). Major coarse particles are quartz grains (Qu), fragments of carbonate rocks (CR) and kurkar (Ku) and some iron concretions (IC), calcareous algae (CA) and foraminifera (Fo).

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Table 3 Major elements (oxides; in mass %) in the ceramic body (c), the black (b) and red (r) pigments of complete Canaanite vessels as shown by pXRF analysis (for each specimen the data are normalized to 100%). Ceramic body

Esur-52c

Esur-59c

Esur-68c

Esur-78c

Esur-95c

Esur103c

Esur104c

Esur106c

Esur115c

Esur116c

Esur126c

Esur149c

Esur151c

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

70.7 0.3 1.7 1.6 8.6 0.9 0.1 15.6 0.5

64.2 0.3 1.8 2.3 19.9 0.7 0.1 10.4 0.3

61.9 0.0 2.3 2.5 23.4 0.8 0.1 8.8 0.2

52.0 0.0 2.2 1.4 37.5 0.5 0.0 6.1 0.3

64.3 0.0 1.9 1.3 26.1 0.5 0.0 5.6 0.3

60.5 0.2 2.0 1.3 29.9 0.5 0.0 5.2 0.4

55.0 0.1 3.0 1.0 36.2 0.3 0.0 3.9 0.5

58.8 0.2 2.4 2.1 27.1 0.6 0.0 8.4 0.4

67.5 0.3 2.4 2.0 14.7 0.9 0.1 11.6 0.5

63.4 0.2 1.7 1.6 19.9 0.9 0.1 11.9 0.3

58.1 0.2 2.2 1.6 29.1 0.6 0.1 7.7 0.4

70.2 0.3 1.6 1.2 18.8 0.6 0.0 7.1 0.2

55.8 0.2 2.6 1.4 31.0 0.7 0.1 8.0 0.2

Black decoration

Esur-52b

–

Esur-68b

Esur-78b

Esur-95b

Esur103b

–

Esur106b

Esur115b

Esur116b

Esur126b

Esur149b

Esur151b

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

58.4 0.3 2.2 2.0 7.5 0.9 0.8 27.3 0.6

58.0 0.4 3.4 2.0 11.3 0.9 4.5 18.9 0.6

59.3 0.3 2.4 2.2 7.6 0.9 8.1 18.5 0.7

52.2 0.8 1.9 2.4 3.1 1.1 2.0 35.9 0.6

56.4 0.3 2.6 1.4 8.6 0.8 10.5 19.0 0.4

58.8 0.2 3.1 2.7 12.9 0.8 1.8 19.2 0.5

57.6 0.3 1.9 2.7 13.8 0.8 4.4 17.9 0.6

59.9 0.1 3.0 2.3 15.0 0.7 4.3 14.1 0.6

60.3 0.2 2.2 2.4 16.6 0.8 2.3 14.9 0.3

60.5 0.2 3.1 2.0 13.2 0.8 2.6 16.9 0.7

52.7 0.7 3.5 2.0 4.7 1.1 2.4 32.4 0.5

Red decoration

Esur-52r

Esur-59r

Esur-68r

Esur-78r

–

Esur103r

Esur104r

Esur106r

Esur115r

Esur116r

–

–

Esur151r

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

63.6 0.1 2.5 2.4 10.9 0.9 0.5 18.6 0.5

58.5 0.1 3.8 2.1 16.4 0.8 0.4 17.2 0.7

62.0 0.4 3.1 2.0 11.2 0.9 0.5 19.5 0.4

63.1 0.4 2.7 2.4 8.9 1.0 0.6 20.4 0.5

62.0 0.4 3.1 2.0 11.2 0.9 0.5 19.5 0.4

65.2 0.2 3.0 1.5 13.8 0.7 0.4 14.7 0.5

55.7 0.2 3.0 3.3 14.9 0.8 0.4 21.3 0.4

53.6 0.3 2.2 3.2 14.0 0.7 0.4 25.1 0.5

61.9 0.3 2.8 2.6 12.6 1.0 0.5 17.8 0.5

3.3. The LA-ICP-MS analysis

57.6 0.7 2.9 1.9 4.1 1.0 0.6 30.7 0.5

those consisting of heavier metals (Fig. 5b, d and f). In the COMPO images, darker shades of gray were understood to represent materials made of lighter metals, while the lighter regions represent materials made of heavier metals. The ceramic body is characterized by a pseudo-platy microstructure, indicative of the firing of the raw clay (Fig. 5a, see Shoval et al., 2011). The backscattered electron image of the ceramic body (Fig. 5b) displays darker gray-shaded areas, indicating light metals (Si and Al; see below). The black and red pigments consist of small particles (Fig. 5c and 5e). The backscattered electron images of these pigments (Fig. 5d and 5f) display lighter-shaded areas, indicating heavier metals (Fe and Mn; see below).

Table 5 presents the results of the LA-ICP-MS analysis of the major and trace elements in the black pigment on seven vessels. Each analysis was performed in situ using two measurement techniques: Line Analysis (LA) and Spot Analysis (SA; Shoval, 2018). Certain differences in the results obtained by the two techniques are related to the different scanned areas targeted by them and the heterogeneity in the thickness of the pigment layers. The analysis supports the pXRF results of the major elements and also identified the trace element concentrations. In order to try to source the ore(s) utilized for the black pigment, LA-ICP-MS analysis was also conducted for comparative manganese ores from the Aravah valley in the Southern Levant: Timna in southern Israel and Faynan in southern Jordan, which are the major manganese (and copper) sources of the region, and for manganese umber ore from Cyprus. The compositions of these ores are presented in Table 6. The results are compared with those published by Dill et al. (2013), who studied Mn mineralization in the Middle East.

3.4.2. The EPMA-WDS elemental maps Figs. 6–8 illustrate the EPMA-WDS elemental maps scanned from the ceramic body of sample Esur-106; the black decoration on Esur-115; and the red decoration on sample Esur-103, respectively. The elemental maps correspond to the SEM images of these segments (Fig. 5). The color tones in each map represent the concentration range of the detected elements as determined by the color scale. The elemental maps reveal non-homogeneous distribution patterns of the detected elements, reflecting compositional variations of the components in the scanned areas. The elemental maps of the ceramic body (Fig. 6) display high concentrations of SiO2 and Al2O3 (Fig. 6a, b), indicative of clay composition (Shalvi et al., 2019b; Shoval, 2018). The patches with higher SiO2 content reflect contributions from accessory quartz particles in the ceramic matrix (Fig. 6a). Certain concentrations of Fe2O3 and traces of MnO were also observed in the ceramic body (Fig. 6c, d). The content of

3.4. The EPMA analyses 3.4.1. The EPMA-SEM images Fig. 5 presents the EPMA-SEM images scanned from the ceramic body of sample Esur-106 (Fig. 5a, b; the black decoration on sample Esur-115 (Fig. 5c, d); and the red decoration on sample Esur-103 (Fig. 5e, f). Two types of SEM images are shown in the figure: secondary electron images (SEI) and backscattered electron images (COMPO). The former shows the microstructures of the scanned specimen (Fig. 5a, c and e). The latter contrasts components consisting of light metals and 8

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Table 4 Major elements (oxides; in mass %) in the ceramic body (c), the black (b) and red (r) pigments of the painted pottery fragments as shown by pXRF analysis (for each specimen the data are normalized to 100%). Ceramic body

Esur-5c

Esur-6c

Esur-8c

Esur-10c

Esur-14c

Esur-21c

Esur-22c

Esur-25c

Esur-26c

Esur-210c

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

55 0.1 2.0 1.2 34.8 0.5 0.0 5.9 0.5

64.7 0.4 1.8 1.7 21.6 0.6 0.0 8.8 0.4

67.7 0.4 1.8 1.8 15.9 0.9 0.1 10.9 0.5

60.2 0.3 2.0 1.5 26.7 0.6 0.1 8.2 0.4

57.2 0.2 2.6 1.3 31.4 0.5 0.0 6.5 0.3

71.4 0.3 1.7 2.4 11.3 0.8 0.1 11.6 0.4

59.7 0.2 2.2 1.3 29.9 0.5 0.0 5.8 0.4

59.7 0.2 2.5 1.8 22.6 0.9 0.1 11.7 0.5

56.2 0.2 2.5 1.5 25.9 0.8 0.2 12.3 0.4

65.2 0.7 2.6 1.8 21.9 0.7 0.0 6.8 0.3

Black decoration

Esur-5b

Esur-6b

Esur-8b

Esur-10b

Esur-14b

Esur-21b

Esur-22b

Esur-25b

Esur-26b

Esur-210b

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

49.2 0.2 2.4 1.9 27.1 0.9 2.7 15.1 0.5

53.8 0.2 2.0 2.0 14.9 0.8 6.8 18.9 0.6

66.6 0.2 1.8 2.4 8.5 0.9 2.1 17.1 0.4

56.4 0.3 2.4 1.9 17.4 0.8 3.9 16.4 0.5

52.6 0.2 2.4 2.1 25.7 0.9 1.7 14.1 0.3

59.7 0.4 2.8 2.2 8.1 0.7 7.2 18.3 0.6

62.2 0.3 2.3 2.6 11.1 0.9 3.8 16.4 0.4

58.6 0.2 2.3 1.6 9.1 1.0 3.9 22.7 0.6

60.1 0.4 3.0 1.7 15.2 0.8 1.8 16.4 0.6

64.4 0.2 1.8 1.9 7.2 0.8 3.3 20.1 0.3

Red decoration

Esur-5r

–

–

–

–

Esur-21r

Esur-22r

–

Esur-26r

Esur-210r

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

59.2 0.2 3.3 2.8 14.5 1.2 0.6 17.8 0.4

53.7 0.2 2.7 2.7 16.3 0.7 0.4 22.9 0.4

61.4 0.2 2.3 2.5 15.7 0.8 0.4 16.3 0.4

59.6 0.2 2.2 1.6 16.9 0.9 0.4 17.8 0.4

54.3 0.3 2.6 2.1 7.6 0.9 0.4 31.2 0.6

Table 5 LA-ICP-MS analyses (major elements in mass %, trace elements in ppm) of the black pigment (b) in selected painted Canaanite vessels. The symbol < indicates that the concentration of an individual element is below its limit of detection. LA = line analysis; SA = spot analysis. Sample No. Operation

Esur-6b LA

SA

Esur-25b LA

SA

Esur-52b LA

SA

Esur-103b LA

SA

Esur-106b LA

SA

Esur-115b LA SA

Esur-210b LA SA

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

50.5 0.5 7.1 9.9 9.6 1.3 9.2 0.9 1.1 7.3 2.6 100 378 < 193 997 664 < 603 1709 122 268 996 17 47 < 12 7356 91 <5

51.1 1.3 8.8 15 12.4 1.3 7.1 0.5 0.7 1.5 0.3 100 639 260 2203 1065 104 1258 82 40 320 38 126 39 6202 66 3

42.3 1 10.5 14.5 11.8 2.1 11.2 0.5 0.9 4.6 0.6 100 527 231 2168 1272 254 4695 175 72 573 67 124 26 19,689 205 6

43.2 1 10.9 15.1 12.6 2.4 10.5 0 1 3.2 0.1 100 551 229 2050 1132 312 4294 165 76 559 68 120 22 22,785 198 5

56.5 0.8 16.5 11.6 0.7 2.4 3.7 2 1 3.4 1.4 100 389 396 121 315 < 173 802 90 243 < 240 17 52 16 5240 141 <3

58.9 0.8 16.2 10.7 1 4.2 4.3 0.3 1.1 1.4 1.1 100 370 331 215 280 255 1304 104 297 5538 36 78 28 14,406 116 3

48.2 0.3 7.3 11.3 5.7 1.1 9.2 1.1 1.1 14.1 0.6 100 584 336 1714 837 < 465 1850 267 162 766 45 32 13 24,982 127 < 7.2

44.3 0.9 12.6 13.5 8 1.3 9.7 1 0.8 7.1 0.8 100 561 182 1942 867 < 133 2375 188 53 694 74 146 21 14,935 59 10

42.3 0.9 13 18.8 10.5 1.8 9.2 0.6 1 1.6 0.3 100 772 173 2116 903 121 1069 108 75 518 99 180 29 10,461 115 6

67.3 0.2 4.8 8 3.4 1.3 9.1 0.8 0.5 1.9 2.7 100 136 283 660 301 < 458 1189 58 < 80 559 12 19 33 5879 125 5

47.2 0.9 11.8 12.6 6.3 1.4 16.7 0.7 0.4 1.8 0.2 100 422 185 1091 699 329 1839 76 47 391 53 147 23 6837 81 5

63.4 1 8.4 16 4.1 1.1 3.5 0.4 0.6 0.9 0.6 100 1097 258 538 483 < 223 1557 59 80 262 50 154 75 5708 200 14

9

44.8 0.8 11.1 16.4 7.5 1.6 14.7 0.6 0.3 1.9 0.3 100 480 227 1247 888 411 2953 70 57 327 56 112 24 7204 109 8

58.6 1 8.7 19.9 4.4 1.5 3.2 0.4 0.7 1.3 0.3 100 858 457 598 600 < 128 2120 47 106 235 34 140 65 6389 295 19

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Table 6 LA-ICP-MS analysis (major elements, oxides in mass %; trace elements in ppm) of comparative manganese ores from Timna in southern Israel and Faynan in Jordan (LA = line analysis and SA = spot analysis). The results are compared with those published by Dill et al. (2013). Sample

Mn-ore Timna (concretion)

Mn-ore Timna (concretion)

Mn-ore Faynan (concretion)

Mn-ore Faynan (concretion)

Mn ore (Dill et al., 2013)

Mn ore (Dill et al., 2013)

Operation

LA

SA

LA

SA

Mean

Max

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

31.8 0.5 12.9 4.8 43.5 1.1 0.8 0.2 3.8 0.3 0.3 100 233 35 270 96 68,966 3173 984 113 1850 67 129 30 72,677 37,518 62

19.3 1.1 10.3 5.8 58.6 0.6 0.6 0.2 2.8 0.3 0.4 100 271 23 332 123 69,466 4292 1556 61 2724 117 188 61 108,463 43,380 66

7.4 0.3 4.4 1.9 72.3 0.9 1.7 9.3 1.5 0.1 0.2 100 155 62 1008 108 20,614 1013 1510 35 3747 42 46 5 105,641 39,395 34

5.3 0.2 4.4 2.2 79.6 1 1.7 3.6 1.7 0.1 0.2 100 170 68 1062 135 23,323 1284 1755 45 3728 46 53 6 120,247 50,936 36

13.15 0.12 2.71 2.86 46.25 2.22 5.21 0.15 0.85 0.13 – 73.65 106 24 633 83 21,763 1227 – – 956 25 72 – 64,914 4698 24

27.76 0.26 5.10 9.11 68.22 12.08 18.97 0.24 2.68 0.32 – 144.74 294 81 940 167 29,070 1807 – – 2083 29 120 – 112,700 10,710 41

CaO (Fig. 6e) reflects the presence of fine calcite within the ceramic material (Fabbri et al., 2014; Shoval, 2003). The elemental maps of the black decoration (Fig. 7) illustrate prominent concentrations of Fe2O3 and MnO, indicative of the ferromanganese composition. The nonhomogeneous distribution patterns of the detected elements in the maps reflect the granular microstructure of the pigment grains. The elemental maps of the red decoration (Fig. 8) show higher concentrations of Fe2O3 and only traces of MnO in comparison with those of the black decoration.

Group A (N = 9) is characterized by a significant amount of quartz grains within the ceramic matrix, which point to raw material rich in quartz grains from Israel’s Sharon plain (Fig. 1). In Group A-1, the quartz grains are combined with coarse fragments of carbonate rocks (Group A-1a), part of the latter containing foraminifera fossils (Groups A-1b). This indicates an origin on the northeastern Sharon, but closer to the hill country to the east where these rocks are exposed. In Group A-2 the absence of coarse fragments of carbonate rocks within the ceramic matrix (Group A-2a) and the combination of quartz grains with coarse kurkar particles that also comprise quartz grains (Group A-2b) point to raw materials from the western Sharon or the Carmel coast just north of the Sharon plain (for the latter group, west of the coastal kurkar ridges, see Gvirtzman et al., 1998). In Group B1 (N = 1), the ceramic matrix is poor in quartz grains deriving from sand and rich in quartz silt. The combination with calcitebearing clay or with loess soil indicates production on the southern coastal plain or in the Israel’s southern Shephelah region (Fig. 1). The ceramic matrix of Group B-2 (N = 2) is also poor in quartz sand and silt, but includes coarse kurkar particles with fauna fossils, indicating raw material from the northern coastal region of Israel, the western Galilee coast (Fig. 1). The single vessel of Group E is composed of slightly calcareous yellowish matrix, poor in quartz grains and silt, but with kurkar particles from the northern coastal ridges, which characterizes production on the southern Lebanon coast (Fig. 1; Gilboa and Goren, 2015). In conclusion, petrography demonstrates that the ‘painted Canaanite vessels’ we examined were indeed made in Canaan, the majority on the southern Levantine coastal plain, several in vicinity of Tel Esur on the northeastern Sharon coastal plain. One vessels is from the southern Lebanon coast.

3.4.3. The EPMA-EDS analysis Table 7 presents results of the EPMA-EDS analysis of the major elements (presented as oxides) in the ceramic body, the black decoration and the red decoration on selected painted Canaanite pottery vessels. The analysis confirms the results observed by the other analytical methods. 4. Discussion 4.1. The origin of the painted Canaanite pottery Four main groups for the painted vessels were identified by the petrographic analysis – A, B1, B2 and E3 (Table 2; Fig. 4). These groups contain quartz grains in the ceramic matrix, a composition characteristic for ceramic production from raw materials of the southern Levantine coastal plain (Fig. 1; Gilboa and Goren, 2015), in which the quartz grains were derived from quartz sand. The presence of fine calcite within the ceramic matrix reflects an origin from calcareous raw materials. In this region, calcareous raw materials typify clay alluvia, river beds, certain soils and marshland sediments (Gvirtzman et al., 1998). 3 The group designations correspond to those in the forthcoming full petrographic report. Groups C and D there are not represented in the present paper.

10

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Fig. 5. EPMA-SEM secondary electron images (a, c, e) and backscattered electron images (b, d, f), scanned from specimens of the ceramic body of sample Esur-106 (a, b), the black decoration of sample Esur-115B (c, d) and the red decoration of sample Esur-103 (e, f).

4.2. The compositions of the painted Canaanite pottery and the decorations on it

these elements in different vessels (Fig. 9a) reflect variations in the compositions of the raw materials utilized (Table 2). The black decoration contains Fe2O3 and MnO (Fig. 9b), elements which characterize ferromanganese pigments (Shalvi et al., 2019b; Shoval and Gilboa, 2016). The red decoration contains Fe2O3 with only trace amounts of MnO (Fig. 9b), which typifies ferric-iron pigment (Sabbatini et al., 2000; Shoval, 2018). The variable distributions of these oxides in the black decoration of different vessels reflect some variations in the composition of the raw pigments as well as the preservation of the pigments that remained on the pottery. In each sample, the highest concentrations of these oxides were detected on the thickest and most consecutive painted segments and where the painted pigments have been better preserved. For each of the three different segments, similar trends for the concentrations of elements can be observed between the pXRF analyses (Tables 3, 4) and those obtained by LA-ICP-MS (Table 5) and by the

Fig. 9 compares the results of the pXRF analysis for selected elements (oxides) in the ceramic body, the black decoration and the red decoration of all the sampled Canaanite pottery. The figure shows three different compositions for these different segments. Although, as mentioned, the pXRF method has some analytical limitations with respect to LA-ICP-MS and EMPA-EDS, it is still insightful. It shows that the ceramic body is rich in SiO2 + Al2O3 and also contains CaO (Fig. 9a). These elements characterize calcareous ceramics composed of fired clay and fine calcite (Fabbri et al., 2014). The use of calcareous raw material allows for lower firing temperatures (Shoval, 2003). The calcareous ceramics also allow the painted decorations to stand out against the lighter ceramic substrate (see Fig. 3), thus eliminating the need to use light slips for this purpose (Shoval, 2018). The varying distributions of 11

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Fig. 6. EPMA-WDS elemental maps (oxides; color scale in mass %) scanned from the ceramic body on sample Esur-106C (corresponding to the SEM images in Fig. 5a, b): (a) SiO2; (b) Al2O3; (c) Fe2O3; (d) MnO; (e) CaO; and (f) MgO.

EMPA-EDS (Table 7). Variations in the results of the different methods may be due to several reasons: the accuracy of each analytical method; inhomogeneity of the object being analyzed; different locations on the object targeted by each apparatus; different sizes of the scanned area; and different penetration depths of the analyses. The pXRF analysis tends to detect larger concentrations of Fe2O3 compared to those in the EPMA-EDS and LA-ICP-MS analyses, owing to the lower accuracy of the former analysis in the detection of iron. Finally, the analysis also confirmed that the composition of the ceramic body does not affect in any meaningful way the results of analyses of the black decoration.

with ferrous-iron pigments (Aloupi et al., 2001a; Jones, 1986). The period between ~1625–1050 BCE was a transitional one, in which both techniques were used. The present study demonstrates that ferromanganese pigments consisting of Fe2O3 and MnO (Tables 3–5, 7; Fig. 9b) were used for the black decoration on Canaanite pottery. The adoption of the manganesebased technique in the Canaanite workshops seems to have been an LBA technological progress, which facilitated the production of black decoration while firing vessels in an oxidizing atmosphere (Schweizer and Rinuy, 1982; Uda et al., 1999), whereas the use of ferrous-iron pigments required firing in a reducing atmosphere (Maggetti and Schwab, 1982). Furthermore, on two-colored pottery, the combination of a ferromanganese pigment for black and a ferric-iron pigment for red enabled the production of two-colored decorations simultaneously under a single firing in an oxidizing atmosphere (Shoval, 2018). In this way, the difficulties of firing twice, which were required to produce a twocolored effect by the alternative ferrous-iron technique, were eliminated (Maggetti and Schwab, 1982). This may be the reason for the sharp increase in the production of two-colored Canaanite pottery during the LBA (Bonfil, 2003; Choi, 2016; Panitz-Cohen, 2006).

4.3. Technological choices in black decoration In ancient ceramics, black decorations on pottery could be obtained with three alternative techniques: carbon-black, ferrous-iron and ferromanganese pigments (Maggetti and Schwab, 1982). Aloupi et al. (2001a, 2001b) and Aloupi-Siotis and Lekka (2017) show a chronological development in the use of different black decoration techniques in Cyprus. They have reported that in Cypriot paint-decorated wares, manganese-based pigments were preferred for black decoration from the end of the LBA onwards (~1050–325 BCE). In contrast, in earlier periods, from the Neolithic to the Middle Bronze Age (~5000–1625 BCE), black decoration on Cypriot pottery was obtained 12

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Fig. 7. EPMA-WDS elemental maps (oxides; color scale in mass %) scanned from the black decoration on sample Esur-115B (corresponding to the SEM images in Fig. 5c, d): (a) SiO2; (b) Al2O3; (c) Fe2O3; (d) MnO; (e) CaO; and (f) MgO.

4.4. Sourcing the ferromanganese pigment

2001a; Aloupi-Siotis and Lekka, 2017). They appear in Upper Turonian pelagic sediments over the ophiolite pillow basalts (Constantinou and Govett, 1972; Robertson, 1975; Robertson and Hudson, 1973, 1974). In order to try to source the ore utilized for the black pigments under study, we conducted and present in Figs. 10 and 11, LA-ICP-MS analyses of the major and the trace elements in manganese ores of Timna and Faynan (Table 6) and umber ore of Cyprus (data for both from Shalvi et al., 2019b); these are compared to the compositions of the black decoration on the LBA Canaanite pottery (Table 5) and on Cypriot White Slip II ware imports at Tel Esur (data from Shalvi et al., 2019b). The amounts of MnO in the black decorations on specimens of the two pottery groups and in the comparative pigment ores vary. In order to put the concentrations of the elemental assemblages composing the black pigments and the ores on the same scale level when comparing them, the data of all the individual specimens in Figs. 10 and 11 are normalized per 10% MnO. The results are interpreted in the following paragraphs.

Ferromanganese ores are very rare in the region of historical Canaan (Ilani et al., 1990) and absent from its coastal plain. Extensive manganese ores are not common even in farther regions of the southern Levant, however such ores exist in Timna (Israel) and Faynan (Jordan), both situated in the arid Aravah valley, about 200 km south of the Sharon plain, as the crow flies. In Timna and Faynan the large manganese ores are found in Cambrian rocks in association with copper ores that were extensively (but intermittently) mined in antiquity (Ben-Yosef et al., 2012; Dill et al., 2013; Hauptmann, 2007; Yahalom-Mack et al., 2014; and see more below). In addition to these ores, some localized manganese occurrences are also found within the Cretaceous carbonate strata in present-day Israel (Ilani et al., 1990). The latter mineralizations are restricted to fault zones associated with the Dead Sea Rift Valley and also to the contact zones between sedimentary rocks and intrusive magmatic bodies. Because the latter ores are episodic, they appear to have been too limited to be used as viable sources of pigments. Indeed, no ancient mining of these manganese ores has been reported (in contrast to the black pigment, sources of iron ores available for red decorations are common in the region; Ilani et al., 1985). Beyond Canaan, in close-by Cyprus, the relatively widespread umber ores were the source of manganese-based pigments (Aloupi et al., 2000,

4.4.1. Comparison between the black pigments with the Cypriot Mn ores It is expected that the chemical signature of the pigments will be similar to those of the distinct manganese ores used, with some differences due to manipulations during the production process. The manganese ores from Timna and Faynan consistently reveal higher 13

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Fig. 8. EPMA-WDS elemental maps (oxides; color scale in mass %) scanned from the red decoration on sample Esur-103R (corresponding to the SEM images in Fig. 5e, f): (a) SiO2; (b) Al2O3; (c) Fe2O3; (d) MnO; (e) CaO; and (f) MgO.

concentrations of MnO than Fe2O3 (Fig. 10a), while the opposite is true for the Cyprus umber ore (Fig. 10b). The higher concentrations of Fe2O3 compared to MnO in the black pigment on the Canaanite pottery (Fig. 10c) negate the use of the Timna-Faynan ore sources (Fig. 10a). Rather, the ratio of these oxides in the black pigment resembles those in the Cyprus umber ore sources. Some CaO and P2O5 in the black pigment on the Canaanite pottery (Fig. 10c) may indicate a contribution from

the underlying ceramic body, or may be the result of mixing the pigment ore with local calcareous clays during the preparation of the pigment for painting (Shalvi et al., 2019b). Significant differences were observed in the relative amounts of trace elements in the ore sources of the two regions we compared. The manganese ores from Timna and Faynan contain pronounced concentrations of Cu and Pb (Fig. 11a), whereas the Cyprus umber ore

Table 7 EPMA-EDS analysis of the major elements (oxides; in mass %) of the ceramic body (c), the black (b) and the red (r) decorations on selected painted Canaanite pottery vessels.

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

Esur-25c

Esur-25b

Esur-103c

Esur-103r

Esur-106c

Esur-106b

Esur-115c

Esur-115b

Esur-210c

Esur-210b

Esur-210r

0.2 1.5 20.1 40.4 0.5 2.0 1.8 22.5 0.9 0.1 10.0 100

0.2 2.0 10.8 41.5 0.9 0.6 1.0 24.6 1.4 4.9 12.1 100

1.0 2.0 18.0 43.7 0.3 2.0 1.5 25.5 0.5 0.0 5.5 100

0.0 2.1 18.4 41.8 0.4 3.1 2.0 11.5 1.0 0.6 19.1 100

0.0 4.0 15.8 40.8 0.2 2.4 2.1 25.7 0.6 0.0 8.4 100

0.0 4.1 17.2 56.2 1.8 2.0 0.0 8.1 0.0 4.0 6.6 100

0.5 1.5 20.5 47.6 0.3 2.5 2.0 14.5 1.0 0.1 9.5 100

0.6 2.0 15.1 43.2 0.5 1.8 2.5 14.0 0.8 4.5 15.0 100

0.5 1.9 19.9 45.3 0.8 2.5 1.8 19.1 0.7 0.0 7.5 100

0.4 1.3 8.6 58.6 1.0 0.5 0.6 3.5 1.0 4.5 20.0 100

0.1 2.0 10.0 41.5 3.0 0.6 2.0 8.5 0.9 0.4 31.0 100

14

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34

57

32

52 :

47 42

8

37

6

32 4

7 2 72

77

82

87

92

97

2

:2

2

7

32

37

42

47

52

57

62

Fig. 9. Results of the pXRF analysis of selected elements (oxides; in mass %) in the ceramic body, the black decoration and the red decoration of painted Canaanite pottery from Tel Esur (data in Tables 3, 4): (a) CaO versus SiO2 + Al2O3; and (b) MnO versus Fe2O3.

consists of pronounced concentrations of Zn and Sr (Fig. 11b). As well, the concentrations of Cu and Ba in the latter ores are lower than in the former. The higher concentrations of Zn and Sr and lower concentrations of Cu and Pb in the black pigment on the painted Canaanite pottery (Fig. 11c) relative to that of the Timna and Faynan (Fig. 11a) disprove the use of this ore source for the pigments. The lower concentrations of Cu and Pb in the black pigment on this pottery (Fig. 11c) resemble those in the Cyprus umber ore (Fig. 11b).

White Slip-II ware (Fig. 11d). Both pottery groups contain Zn and Sr, which supports the hypothesis of a Cypriot umber ore source. The higher concentrations of Co and lower concentrations of Cu in the black pigments of part of the Canaanite pottery (Fig. 11c) compared to that on the Cypriot White Slip-II ware (Fig. 11d) may be associated with some variation in the composition of the raw umber ore collected in different Cypriot locations or may result from mixing the pigment ore with local clays during the preparation of the pigment (Shalvi et al., 2019b).

4.4.2. Comparison between the black pigments on Canaanite and Cypriot wares The major elemental compositions of the black pigment on the painted Canaanite pottery (Fig. 10c) correspond to those in the Cypriot White Slip-II ware (Fig. 10d). The black pigments in the two pottery groups contain higher concentrations of Fe2O3 compared to MnO and both consist of some CaO and P2O5. This indicates that the black pigments in the two pottery groups were produced from similar ferromanganese ore sources, which seem to be Cypriot umber ores. The compositions of the trace elements of the black pigments on the painted Canaanite pottery (Fig. 10c) also match those on the Cypriot

4.5. Trade in pigments The corresponding compositions of the black decorations on the Canaanite pottery, the Cypriot White Slip II ware and the Cypriot umber ore (Figs. 10, 11), support the possibility that the source of the ferromanganese pigment used for black decoration in at least some of the LBA Canaanite workshops on the southern Levantine coastal plain was umber ore imported from the island. In contrast, the diverse compositions vs. the manganese ores from Timna and Faynan indicate that these ores were not used for these pigments. These observations fit

Fig. 10. Diagrams comparing the LA-ICP-MS analyses of the major elements (mass %): (a) Mn-ores of Timna and Faynan (data in Table 6); (b) Cyprus umber Mn-ore, data from Shalvi et al., 2019b); (c) black pigments on Canaanite pottery (data in Table 5); (d) black pigments on Cypriot White Slip II ware at Esur (data from Shalvi et al., 2019b). The data of the individual specimens are normalized per 10% MnO. 15

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Fig. 11. Diagrams comparing the LA-ICP-MS analyses of the trace elements (ppm): (a) Mn-ores of Timna and Faynan (data in Table 6); (b) Cyprus umber Mn ore, data from Shalvi et al., 2019b); (c) black pigment on Canaanite pottery (data in Table 5); (d) black pigment on Cypriot White Slip II ware (data from Shalvi et al., 2019b). The data of the individual specimens are normalized per 10% MnO.

the historical context. Cypriot centrality in Mediterranean, especially East Mediterranean networks during the LBA, specifically as the main regional supplier of copper, and also as distributor of large quantities of ceramics in this framework, requires no elaboration (Gittlen, 1981; Gomez et al., 2002; Grave et al., 2014; Kassianidou, 2013; Knapp, 2008, 2016; Maguire, 1995; Panitz-Cohen, 2014; Sherratt, 2014; Steel, 2002, 2014; Tschegg et al., 2008). Particularly, intensive trade between the northern Sharon and Carmel coasts with Cyprus is well documented (Artzy, 2001; 2006). Finally, since the maritime distribution of many archaeologically invisible commodities, including minerals, is a wellknown phenomenon in the Bronze Age Mediterranean (Altenmüller and Moussa, 1991; Knapp, 1991; Marcus, 2007), trade in ores for pigments, or in the pigments themselves should come as no surprise–piggy backed on ships carrying the primary commodities. On the other hand, very little to no human activity is attested in the Timna and Faynan mines in the 15th and 14th centuries (Ben-Yosef et al., 2012; Finkelstein, 1995; Hauptmann 2007; Yahalom-Mack et al., 2014).

technique arrived to the Syro-Palestinian coast between 1200 and 1000 BCE through Cypriot cultural influences. Their claim, however, was only based on the visual examination of a small number of Levantine ceramics and we accord this assumption an analytical ground. The earlier date of the Tel Esur assemblage (late LB IB/early LB IIA; circa 1400–1350 BCE), suggests that the manganese-based technology was used in Canaan at least 150 years earlier. Understanding the socio-economic implication of this phenomenon, however, is hampered by the fact that the beginning of the use of this technology in the Levant is still unknown. Examination is required, for example, of the composition of black pigments on Canaanite Middle Bronze Age pottery, a period when copper in the Levant was also supplied by Cyprus (Cohen, 2014), pottery was exchanged between the two regions and a vivid and multifaceted discourse is evident between Canaanite and Cypriot ceramic production (e.g. Artzy 2019). Such an examination is currently in progress.

4.6. Technology transfer

1. The application of ceramic-petrography and microbeam methods to analyze LBA painted Canaanite pottery from Tel Esur has produced insights and a multi-analytical database regarding the compositions, ceramic technologies, raw materials, origin, and cultural meaning of the vessels. 2. Petrography reveals production of the painted vessels mainly in the immediate vicinity of Tel Esur, but also in at least three more subregions of the southern Levantine coastal plain. 3. The microbeam analyses demonstrate the utilization of ferromanganese pigments for the black decoration and a ferric-iron pigment for the red decoration. This combination facilitated the execution of two-colored decorations simultaneously by a single firing in oxidizing atmosphere. 4. The adoption of the manganese-based technique in Canaanite workshops seems to be an early LBA technological progress, explaining the sharp increase in the production of two-colored Canaanite pottery during that period. The first adoption of this technique, however, will have to be investigated by analyzing

5. Summary

The use of ferromanganese pigments for black decoration on LBA Canaanite pottery parallels the use of the same technique in Cyprus (e.g., Aloupi et al., 2000, 2001a; Aloupi-Siotis and Lekka, 2017). This analogous use may reflect transference of the manganese-based technology from Cyprus to Canaan. In Cyprus, the shift from the iron reduction decoration technique to the manganese black technique occurred during the Late Cypriot period (roughly the LBA and the beginning of the Iron Age in the Levant; Aloupi et al., 2000, 2001a; Aloupi-Siotis and Lekka, 2017). A possible association of metal industry with Cypriots has been suggested for the nearby site of Tel Zeror (Kochavi, 1993; Ohata and Kochavi, 1966–1970), which lies on the route from the coast to Tell Esur (Fig. 1) and may have served as the site’s anchorage on the Hadera stream during most of this period (LBA). All these circumstances may reinforce our assumption that the manganese-based technology arrived to the Canaanite workshops by an exchange of ideas associated with the Cypriot-Canaanite trade. Aloupi et al. (2001a) indeed proposed that the manganese-based 16

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earlier painted Canaanite vessels. 5. Ferromanganese ore sources available for producing the black pigment in the Canaanite workshops are rare in Canaan and absent from its coast; this required importation of raw material from external ore sources, which seem to have been Cypriot umber ores. 6. The analogous use of the manganese-based technique in Canaan and Cyprus suggests that both pigments and technology were transferred from Cyprus to Canaan, highlighting a ‘new’ aspect in the multifaceted Cypro-Canaanite liaisons of this period. 7. Considering that the Tel Esur LBA Canaanite pottery dates circa 1400–1350 BCE, this technology transference occurred at least 150 years earlier than previously assumed, under different historical circumstances.

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Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgments The present study was conducted within the framework of Golan Shalvi’s MA Thesis at the Department of Archaeology, University of Haifa. This study is an integral part of a wider, comprehensive research of paint-decorated Bronze and Iron Age pottery in the Eastern Mediterranean partly supported by the Israel Science Foundation (grant no. 209/14, awarded to Gilboa and Shoval) and the Research Funds of the Open University of Israel, Israel (grants nos. 37179 and 31016, awarded to Shoval). We gratefully acknowledge these grants. Part of this work was done while Shoval was a visiting scientist at the Institute of Earth Sciences at the Hebrew University of Jerusalem (HU). He expresses his appreciation for Oded Navon (HU) for his collaboration. Ayelet Gilboa was visiting professor at the Archaeology and Anthropology Department, University of Bristol and conveys her gratitude to the department and especially to Tamar Hodos for very fruitful discussions. The LA-ICP-MS, EPMA and pXRF analyses were conducted at the HU Institute of Earth Sciences 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 Sariel Shalev and Paula Waiman-Barak (University of Haifa) for letting us use the optical mineralogy laboratory at this university. We thank Dana Harari for assistance and Sapir Haad for illustrating the ceramics. Finally, we acknowledge the contributions of three reviewers to the comprehensiveness of this paper. References Aloupi, E., Karydas, A.G., Paradellis, T., 2000. Pigment analysis of wall paintings and ceramics from Greece and Cyprus: the optimum use of X-ray spectrometry on specific archaeological issues. X-Ray Spectrom. 29, 18–24. Aloupi, E., Karydas, A.G., Kokkinias, P., Paradellis, T., Lekka, A., Karageorhis, V., 2001a. Nondestructive analysis and visual recording survey of the pottery collection in the Nicosia Museum, Cyprus, in: Bassiakos, Y., Aloupi, E., Facorellis, Y. (eds.), Archaeometry Issues in Greek Prehistory and Antiquity, Athens, pp. 397–410. Aloupi, E., Perdikatsis, V., Lekka, A., 2001b. Assessment of the White Slip classification scheme based on physico-chemical aspects of the technique, in: Karageorghis, V., Czerny, E., Todd, I.A., (eds.), The White Slip Ware of Late Bronze Age Cyprus, Österreichischen Akademie der Wissenschaften, Denkschriften der Gesamtakademie, Band XX, Vienna, pp. 15–26. Aloupi-Siotis, E., Lekka, A., 2017. “Black”, a tale of two pigments in Cyprus: the chemistry of decoration and the Late Cypriot III-Cypro-Geometric pottery production. In: Vlachou, V., Gadolou, A. (Eds.), ΤΕΡΨΙΣ: Studies in Mediterranean Archaeology in Honour of Nota Kourou. Centre de Recherches en Archeologie et Patrimoine (CReAPatrimoine), Universite libre de Bruxelles, Brussels, pp. 121–144. Altenmüller, H., Moussa, A.M., 1991. Die Inschrift Amenemhets II. aus dem Ptah-Tempel von Memphis. Ein Vorbericht. Studien zur altägyptischen Kultur, 18, 1–48. Attaelmanan, A.G., Yousif, E.A., 2012. EDXRF analysis of pigment used for the decoration of Mleiha pottery. J. Archaeol. Sci. 39, 2231–2237.

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