CYPRIOT BYZANTINE GLAZED POTTERY: A STUDY OF THE PAPHOS WORKSHOPS*

CYPRIOT BYZANTINE GLAZED POTTERY: A STUDY OFTHE PAPHOS WORKSHOPS*

A. C. CHARALAMBOUS,1,2 A. J. SAKALIS,2 N. A. KANTIRANIS,3

L. C. PAPADOPOULOU,3 N. C. TSIRLIGANIS,2 and J. A. STRATIS1†

1Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, GR-54124, Thessaloniki, Greece2Laboratory of Archaeometry, Cultural and Educational Technology Institute, ‘Athena’ Research Centre, Tsimiski 58,

GR-67100, Xanthi, Greece3Department of Mineralogy-Petrology-Economic Geology, Aristotle University, GR-54124, Thessaloniki, Greece

Twenty-five samples of Byzantine glazed pottery from two archaeological sites between Limas-sol and Paphos region (Cyprus), dated between the 12th and 15th century AD were studiedusing micro X-ray fluorescence spectroscopy, scanning electron microscopy and X-ray dif-fraction analysis. It was found that all the glazes contain lead, following the main manufac-turing process of medieval pottery in the Mediterranean territory, while some of them containtin, possibly for better opacity. Furthermore, it is shown that copper, iron and cobalt withnickel are responsible for the decoration colours. Finally, the application of principal com-ponent analysis revealed significant differentiation for some of the samples.

KEYWORDS: CYPRUS, MICRO X-RAY FLUORESCENCE SPECTROSCOPY,X-RAY DIFFRACTION ANALYSIS, SCANNING ELECTRON MICROSCOPY,

PRINCIPAL COMPONENT ANALYSIS

INTRODUCTION

Cyprus presents a long tradition in glazed pottery, mainly dated from the 12th to the 15th centuryad. Archaeological findings confirm the presence of several glazed pottery workshops in manyareas of Cyprus. The most important workshops were in the area of Paphos, on the southwesternside of the island, and in the area of Lapithos, on the northern side of the island, near the city ofKyrenia. The specific workshops of Paphos and Lapithos were active from the 12th century andsome of them, especially in the area of Lapithos, until the 19th century. Because of the locationof the island, between three continents and near the Middle East, occupation by the Franks(1192–1489) and the Venetians (1489–1572), and due to trade, the manufacture and the decora-tion technology of the local glazed pottery exhibits significant influences from these areas(Papanikola-Bakirtzis 1996).

Pottery receives more attention perhaps than any other type of artefact since large amountsare continuously excavated at archaeological sites. Its typological and analytical study enablesthe investigation of many interesting aspects of ancient culture, trade and technology (Rice1987). Lead-glazed pottery was widely spread around the regions of the Mediterranean Sea.The main characteristic of the 12th century Byzantine glazed pottery, developed mainly withinthe Byzantine Empire, was the application of the sgraffito technique. Sgraffito is the term usedto describe redware pottery in which, with the aid of a sharp tool, decorations have been

*Received 7 November 2008; accepted 27 June 2009†Corresponding author

Archaeometry 52, 4 (2010) 628–643 doi: 10.1111/j.1475-4754.2009.00502.x

© University of Oxford, 2009

scratched into a thin layer of clay slip. Byzantine potters used to apply a coating of white slipand a colourless lead (Pb) glaze over the ceramic body, and further decorated the surfaces witha colourful variety of incised and painted designs (Papanikola-Bakirtzis 1999). The ByzantinePb glazes are easily formed, obtain lustrousness and opacity at low temperatures and are alsoeasily coloured with oxides of other metals, such as copper (Cu) and iron (Fe). The maincharacteristics of the Paphos workshops are the reddish clay ceramics with white slip coatingand mainly sgraffito decoration with a glaze of green, yellow, brown and orange colour.Cypriot glazed pottery should be considered and studied as a branch of Byzantine glazedpottery displaying the same technology and decorative techniques as pottery in Byzantium(Papanikola-Bakirtzis 1996).

An important category of glazed pottery is the tin-opacified glazes, originally produced in Iraqduring the eighth century ad (Mason and Tite 1997). Initially, tin-opacified glazes were alkaliglazes containing only 1–2% PbO. However, in Spain and for the early production of Italianmajolica, the lead oxide contents tended to be higher (up to about 55% PbO) with lower alkalicontents (down to about 3% Na2O plus K2O) (Tite et al. 1998).

Glazed pottery from Cyprus has not attracted much interest in terms of analytical studies. Todate, only a few studies on the provenance of the Cypriot ceramics have been performed.Specifically, instrumental neutron activation analysis (INAA) was used to study pottery samplesfrom southwestern Cyprus (including the Paphos area) obtained from 38 archaeological sites,dated from the Neolithic through to the Roman period. The results indicated that the largemajority of the ceramics are likely to be local products (King et al. 1986; King 1987).Furthermore, Megaw and Jones studied glazed ceramic material dated from the fifth to the 15thcentury from three regions in Cyprus (Lapithos, Lemba and Dhiorios) with optical emissionspectroscopy, revealing discrimination of the three regions (Megaw and Jones 1983; Jones1986).

Micro X-ray fluorescence spectroscopy (m-XRF) is a non-destructive, fast, multi-elementaltechnique, which analyses the surface layer and determines major, minor and trace elements inthin and thick samples of all sizes and forms (Padilla et al. 2005; Papadopoulou et al. 2006).Together with the micro-XRF technique, X-ray diffraction (XRD) and scanning electron micro-scopy (SEM-EDS) techniques are widely used to complete an archaeometric characterization ofpottery (Rice 1987).

In the present work, a portable m-XRF spectrometer is used for the non-destructive analysis of25 medieval glazed ceramics from two different archaeological sites in Cyprus. Additionally,XRD and SEM-EDS are used to study certain samples in order to confirm the experimentalresults from m-XRF analysis.The basic aims of this study were:(1) To determine the mineralogical and chemical composition of the ceramic bodies in order toinvestigate their manufacture technology and the provenance of the specific samples.(2) To determine the chemical composition of the glazes in order to characterize the colours ofthe decorations.(3) To suggest possible origins of the studied material and to contribute to the explanation ofobserved technological differences based on existing archaeological knowledge which claimsthat the material originates from Paphos workshops.Furthermore, the statistical treatment of the quantitative data using multivariate exploratorytechniques (principal component analysis, PCA) in combination with the archaeological infor-mation provides certain indications concerning the provenance of the studied material and offerspossible justifications for any observed discrimination of the material. This study is expected toprovide useful knowledge on the local glazed pottery technology.

Cypriot Byzantine glazed pottery 629

© University of Oxford, 2009, Archaeometry 52, 4 (2010) 628–643

EXPERIMENTAL PROCEDURE

Description of samples

The investigated glazed ceramic sherds were excavated at the Kepir Mosque in the city ofLimassol and at the church of Panagia Galactotrofousa in the Fasouri area, 15 km west ofLimassol, both located in the south of Cyprus. Kepir Mosque was built during the 16th centurynear a Byzantine church, while Panagia Galactotrofousa was built during the 11th century. Theexcavation of the Kepir Mosque was performed in 1993 and the church of Panagia Galactotro-fousa in 2002 under the supervision of the Cyprus Department of Antiquities (Prokopiou 1997).The samples are dated between the 12th and the 15th century ad. The archaeologists believethat the origin of the samples is from the Paphos area workshops, due to the similarities inthe manufacture technology (plain, painted and especially scraffito decoration with glaze layermainly on the inner side of the ceramic object) and the colour of the glazes (green, yellow, brownand orange). Quantitative analysis was performed for all the samples by non-destructive means,using m-XRF spectroscopy, while further analysis applying SEM-EDS and XRD techniqueswas performed on specific samples of interest in order to minimize the destruction of samples.Samples K1–K18 were excavated in the Kepir Mosque, while the remaining samples, K27 –K33,were excavated in Panagia Galactotrofousa (Table 1). The samples were decorated using green,yellow, orange, brown, black and blue glazes, as shown in Table 1. Furthermore, samples K18,K32 and K33 show optical differences in both the clay microstructure and the glaze decorationstyle compared with all the other samples. Specifically, these samples have painted decoration ofblue and light blue, which is typical of Italian majolica pottery. Therefore they could be tradeproducts due to the occupation of Cyprus by Venice during the 15th century.

Micro X-ray fluorescence spectroscopy

Quantitative analysis of the ceramic bodies was performed using portable m-XRF spectroscopy.The portable m-XRF spectrometer (SPECTRO, COPRA model, Austria) used in this workincorporates a side window X-ray tube with Mo anode (Oxford Instruments, Series 5011 XTF),a straight monocapillary lens and a solid-state Si Peltier-cooled detector (8 mm Be window,3.5 mm2 active area, 300 mm nominal thickness). The maximum tube voltage is 50 kV and itsmaximum current is 1 mA. The nominal beam diameter is <150 mm at the position of the sample.The angle of incidence of the primary X-ray beam on the sample surface is 48° (relative to thesurface), while the angle between the sample and the detector is 42°. All measurements areperformed under atmospheric pressure and no filters were used.

The m-XRF measurements were performed in a point scan mode on several points, which wereselected to cover the entire surface of the glaze. In particular, three to five measurements wereperformed on the surface of the glaze-over-paste in all colour areas. Furthermore, three mea-surements were performed on the ceramic body for each sample, after removal of a small part ofthe surface ceramic body layer with a drill and a tungsten carbide cutter to eliminate possiblesurface contamination effects. All samples were cleaned with ultra-pure water and dried in theoven at 110°C. Reported concentrations are mean values of the three or five measurements persample. The applied voltage was 40 kV, the current 0.7 mA and the measurement time 300 s,based on a preliminary investigation of the optimum experimental parameters. The standardreference material SARM 69 (MINTEK, Republic of South Africa) was used as a calibrationstandard, while the standard reference material Geostandard VS-N (SARM-CNRS, France) was

630 A. C. Charalambous et al.


Tabl

e1

Des

crip

tion

ofth

est

udie

dsa

mpl

es

Sam

ple

inde

xE

xcav

atio

nar

eaC

lay

colo

ur(M

unse

llra

nge)

Mac

rosc

opic

char

acte

riza

tion

Gla

zede

cora

tion

K1

K.M

.R

eddi

sh-2

.5Y

R4/

8Fi

negr

aine

dG

reen

glaz

eK

2K

.M.

Red

dish

-2.5

YR

5/6

Coa

rse

grai

ned

Bro

wn

and

red

glaz

eK

3K

.M.

Red

dish

-2.5

YR

4/6

Fine

grai

ned

Bro

wn

glaz

eK

4K

.M.

Whi

tish-

10Y

R7/

2Fi

negr

aine

dO

rang

egl

aze

K5

K.M

.R

eddi

sh-1

0R5/

2C

oars

egr

aine

dY

ello

w,g

reen

and

brow

ngl

aze

K6

K.M

.W

hitis

h-7.

5YR

7/4

Fine

grai

ned

Yel

low

glaz

eK

7K

.M.

Red

dish

-10R

5/2

Coa

rse

grai

ned

Yel

low

,bro

wn

and

gree

ngl

aze

with

blac

klin

esK

8K

.M.

Red

dish

-2.5

YR

4/6

Coa

rse

grai

ned

Bro

wn

glaz

eK

9K

.M.

Red

dish

-2.5

YR

6/8

Fine

grai

ned

Gre

enan

dbr

own

glaz

eK

10K

.M.

Red

dish

-2.5

YR

5/6

Coa

rse

grai

ned

Yel

low

and

brow

ngl

aze

K11

K.M

.W

hitis

h-10

YR

8/4

Fine

grai

ned

Yel

low

glaz

eK

12K

.M.

Red

dish

-2.5

YR

4/6

Fine

grai

ned

Yel

low

and

brow

ngl

aze

with

blac

klin

esK

13K

.M.

Whi

tish-

10Y

R7/

4C

oars

egr

aine

dB

lue

deco

ratio

nK

14K

.M.

Red

dish

-2.5

YR

6/6

Fine

grai

ned

Ora

nge

glaz

eK

15K

.M.

Red

dish

-7.5

YR

8/4

Fine

grai

ned

Bro

wn

glaz

eK

16K

.M.

Red

dish

-2.5

YR

4/4

Coa

rse

grai

ned

Gre

enan

dbr

own

glaz

ew

ithbl

ack

lines

K17

K.M

.R

eddi

sh-2

.5Y

R5/

6Fi

negr

aine

dY

ello

wan

dbr

own

glaz

eK

18K

.M.

Whi

tish-

5Y9/

2Fi

negr

aine

dB

lue

glaz

eK

27P.

G.

Red

dish

-2.5

YR

6/6

Coa

rse

grai

ned

Gre

engl

aze

with

blac

klin

esK

28P.

G.

Red

dish

-5Y

R7/

8Fi

negr

aine

dY

ello

wan

dgr

een

glaz

eK

29P.

G.

Red

dish

-2.5

YR

6/6

Coa

rse

grai

ned

Bro

wn

glaz

eK

30P.

G.

Red

dish

-5Y

R7/

6Fi

negr

aine

dY

ello

wan

dgr

een

glaz

eK

31P.

G.

Red

dish

-2.5

YR

5/6

Fine

-gra

ined

Yel

low

glaz

eK

32P.

G.

Whi

tish-

2.5Y

9/4

Fine

grai

ned

Lig

htbl

uegl

aze

K33

P.G

.W

hitis

h-2.

5Y9/

4Fi

negr

aine

dB

lue

gree

ngl

aze

K.M

.=K

epir

Mos

que;

P.G

.=Pa

nagi

aG

alac

totr

ofou

sa.



used for the quantification of Pb and the standard reference material GBW07706 (China NationalAnalysis Center for Iron and Steel, Beijing) was used for the quantification of tin (Sn). Allstandard reference materials were prepared in pressed pellets by thoroughly mixing the powderwith a cellulose binder in a 4:1 (reference material/binder) ratio, while pressing was performedusing an 11-ton hydraulic press (Specac, UK). X-ray spectra were deconvoluted and fitted usinga suitable software package (WinAxil v 4.0.1).

X-ray diffraction

The quantitative mineralogical composition of the samples was determined by powder XRD.Powder XRD analysis was performed using a diffractometer with an Ni-filtered Cu Ka radiation(Philips PW1710, The Netherlands) source on randomly oriented samples. Subsamples were cutoff the glazed ceramic samples and powdered in an agate mortar. The samples were scanned overthe interval 3–63° 2q at a scanning speed of 1.2°/min. Quantitative estimates of the abundance ofthe mineral phases were derived from the powdered XRD data, using the intensity of specificreflections, the density and the mass absorption coefficient for Cu Ka radiation for the mineralspresent. Corrections were made using external standard mixtures of the detected mineral phases(Guinier 1963; Kantiranis et al. 2004). Amorphous phase content was calculated according to themethodology proposed by Kantiranis et al. (2004). The detection limit for crystalline and amor-phous phases was 12% w/w.

Scanning electron microscopy

The morphology and chemical microanalysis of the studied glazed pottery sherds was performedon the outer surface and on polished sections by SEM-EDS (Jeol JSM-840, Japan), a scanningelectron microscope, equipped with an Oxford ISIS300 Energy Dispersion Analyser. To mini-mize volatilization of alkalis in the studied samples, the electron beam spot size was enlarged andthe counting time decreased. The measuring conditions were: voltage 15 kV, electron beamcurrent ~3 nA and spot size 1 mm2, while counting time was 60 s. Different minerals (micas,carbonates, feldspars) and pure metals were used as probe standards.

RESULTS AND DISCUSSION

Micro X-ray fluorescence spectroscopy

Most of the ceramic bodies have a reddish colour while samples K4, K6, K11, K13, K18, K32and K33 are characterized by a yellow-white colour (see Table 1).

The m-XRF spectra of Figure 1 present the differences between the ceramic body and the glazecomposition of sample K18. The main differences were the high amounts of Ca, Ti, Fe and Sr inthe ceramic body and the high amounts of S and Pb in the glaze. These significant differencesexist in the composition of the ceramic body and the glaze in all samples. All ceramic bodiescontain a small amount of Pb as a result of the leaching of Pb from the transparent glaze duringfiring (Fabbri et al. 2000). The main characteristic of the glazes is the high amount of Pb thatfollows the main manufacturing trend in Cyprus during the studied Byzantine period (12th–15thcenturies ad). The two primary methods of producing lead glazes were either to apply Pb, PbOto the surface of the pottery body, or to apply a mixture of PbO and silica (Tite et al. 1998). Thepresence of significant amounts of Sn in the ceramic body (0.08–0.18% w/w) of samples K18,



K32 and K33 is probably due to the leaching of Sn from the transparent glaze during firing(Fig. 1). Sn was used in glazed pottery for the creation of opacified glass (Allan 1973; Al-Saad2002).

The chemical compositions of both the ceramic bodies and the glazes are presented in Tables 2and 3, respectively.

PCA of the ceramic bodies, based on m-XRF elemental analysis data, illustrates the differencesof the samples, as shown in Figure 2. A weak difference of the studied material is observed basedon the first principal component. Samples on the left side of the PCA (K1, K2, K10, K13) showincreased concentration of K and Si together with low concentrations of Cr and Ca. However,samples on the right of the PCA (K4, K6, K29) present high concentrations of Cr, Ca and Ni. Thechemical composition of the ceramic bodies is compared with already analysed material from thePaphos (Lemba, Kouklia) (Megaw and Jones 1983; Jones 1986) and Limassol areas (Amathus)(Jones 1986), taking into consideration the different techniques used for analysis (Fig. 3).According to this comparison, glazed ceramic samples with increased Cr and Ca concentrationsseem to originate from Limassol while samples with low concentration of Cr and Ca couldpossibly originate from Paphos (Fig. 2). Samples K3 and K8 are different from the other samplesdue to their higher content of Ti while sample K33 has a very high amount of Ca and significantamounts of Mn and Cu. Samples K3, K8 and K33 reveal stronger differences and could possiblyhave been manufactured in different workshops from other areas of Cyprus or were tradeproducts from other territories.

The green colour of the lead glazes is usually related to the presence of Cu2+ or Fe2+ in theglaze, whereas the yellow to brown colours are related to Fe3+ oxides and complexes (Moleraet al. 1999). Elemental analysis of the glazes confirms these observations, showing that greenglazes are rich in Cu, as seen in Figure 4. The blue glaze (sample K18) contains Co, Sn andsignificant amounts of Ni. It seems that Co-based pigments were well known for their beautifulblue colour due to the CoO4 complex. Finally, Fe3+ is responsible for the brown, yellow, black andred in the glazes; however, black glazes also contain Mn and yellow glazes also contain Cr.

Figure 1 m-XRF spectra of the clay and the blue glaze of the sample K18.



Tabl

e2

m-X

RF

elem

enta

lan

alys

isof

the

clay

sof

the

sam

ples

SiO

2K

2OC

aOTi

O2

Fe 2

O3

MnO

Cr

Ni

Cu

Zn

wt%1

stde

vw

t%1

stde

vw

t%1

stde

vw

t%1

stde

vw

t%1

stde

vw

t%1

stde

vpp

m1

stde

vpp

m1

stde

vpp

m1

stde

vpp

m1

stde

v

K1

61.0

01

2.00

2.441

0.07

3.631

0.20

0.891

0.10

7.601

0.50

0.111

0.02

2501

6012

51

5020

01

4012

51

25K

258

.001

2.00

3.081

0.26

5.871

0.59

0.821

0.16

6.771

0.55

0.071

0.01

1501

80701

20651

10851

20K

354

.001

2.00

1.371

0.11

4.431

0.32

2.231

0.25

12.8

31

0.21

0.221

0.02

1301

70501

10851

2012

01

20K

458

.331

3.51

1.501

0.26

15.8

01

0.66

0.811

0.10

8.801

1.01

0.211

0.02

4701

200

2301

100

701

20901

20K

559

.551

2.08

3.081

0.03

5.731

0.96

0.861

0.12

7.371

0.31

0.091

0.01

3301

6010

01

3012

51

25701

20K

656

.331

2.00

2.001

0.05

22.3

31

1.15

0.661

0.11

6.871

0.32

0.151

0.01

7001

300

3001

130

901

20901

20K

755

.671

2.00

3.311

0.17

3.271

0.31

0.761

0.04

6.831

0.35

0.091

0.01

5001

200

1201

50501

10801

20K

854

.001

3.00

0.841

0.05

3.011

0.53

1.401

0.17

10.0

71

0.90

0.221

0.03

2301

100

1001

5030

01

60801

20K

951

.001

2.00

3.471

0.03

8.571

0.90

0.921

0.08

7.601

0.36

0.091

0.01

5001

300

1401

60731

20901

20K

1053

.501

2.31

3.131

0.62

6.201

0.85

0.711

0.16

7.071

1.47

0.071

0.02

1201

50801

20731

20871

20K

1156

.331

2.52

2.011

0.14

24.3

31

0.58

0.641

0.03

7.301

0.46

0.161

0.01

2301

100

1901

100

901

2011

01

20K

1252

.331

3.79

3.131

0.45

8.001

1.00

0.831

0.12

8.131

1.01

0.101

0.02

4651

100

1601

60701

20501

10K

1352

.671

5.13

0.751

0.06

7.031

1.17

0.121

0.02

0.831

0.15

0.071

0.03

1601

7010

01

50901

20801

20K

1453

.671

2.52

3.141

0.22

6.101

0.20

0.791

0.06

7.301

0.30

0.151

0.01

5001

200

1601

90501

10801

20K

1551

.331

3.51

2.961

0.28

19.7

01

3.16

0.721

0.13

5.601

0.78

0.091

0.01

1201

70821

20801

2010

01

20K

1654

.331

6.35

3.001

0.46

19.3

31

1.23

1.071

0.25

9.271

0.60

0.151

0.04

4001

100

1201

2016

01

50701

15K

1755

.671

3.03

3.421

0.33

6.431

0.32

0.931

0.15

8.201

0.56

0.141

0.02

1901

100

1201

50801

2011

01

20K

1844

.671

2.53

1.631

0.21

19.3

31

3.79

0.731

0.12

6.231

1.33

0.111

0.02

1701

4011

01

2015

01

40901

20K

2756

.001

4.16

2.771

0.59

21.3

31

4.04

0.91

0.11

9.331

0.58

0.131

0.01

5001

100

1901

7014

01

30851

15K

2858

.001

3.00

3.471

0.20

13.1

71

0.32

0.921

0.07

10.5

31

0.49

0.161

0.01

2001

100

1901

3510

01

2012

01

20K

2954

.671

3.13

1.371

0.21

13.0

01

3.46

0.871

0.21

11.6

71

2.52

0.021

0.00

145

01

130

2501

80901

20601

10K

3055

.331

1.53

3.051

0.04

11.9

31

0.55

0.871

0.05

8.471

0.15

0.131

0.01

2301

100

1251

70701

2011

01

20K

3153

.671

1.53

2.501

0.05

8.671

0.49

0.811

0.13

6.731

0.21

0.161

0.03

1601

8012

01

70801

20801

20K

3245

.001

3.46

0.481

0.02

16.1

31

0.51

0.711

0.01

7.231

0.15

0.161

0.02

2601

100

1001

60901

2013

01

30K

3347

.671

2.87

1.201

0.02

23.3

31

2.65

0.871

0.06

8.001

0.52

0.271

0.08

2401

3510

01

2043

01

60701

10



Tabl

e3

m-X

RF

elem

enta

lan

alys

isof

the

glaz

esof

the

sam

ples

Sam

ple

SiO

2K

2OC

aOTi

O2

Fe 2

O3

MnO

Cr

Ni

Cu

Zn

PbO

SnO

2C

oOw

t%1

stde

vw

t%1

stde

vw

t%1

stde

vw

t%1

stde

vw

t%1

stde

vpp

m1

stde

vpp

m1

stde

vpp

m1

stde

vpp

m1

stde

vpp

m1

stde

vw

t%1

stde

vw

t%1

stde

vw

t%1

stde

v

K1-

Gre

en54

.191

1.58

0.551

0.06

0.551

0.01

0.41

0.01

0.51

0.08

1701

5030

01

100

2801

7036

001

300

601

2022

.771

0.59

0.171

0.05

n.d

K2-

Bro

wn

52.2

91

2.39

0.551

0.02

2.621

0.25

0.251

0.01

4.621

0.12

2301

40901

5010

01

5035

01

70501

1027

.181

0.95

n.d

n.d

K2-

Yel

low

59.91

10.

721

0.02

2.671

0.35

0.271

0.02

3.41

0.24

1701

3010

01

5012

01

7030

01

60401

1027

.751

0.98

n.d

n.d

K3-

Ora

nge

54.2

21

1.15

0.31

0.04

1.341

0.36

0.331

0.02

1.341

0.1

2801

5012

01

5010

01

50901

20401

1024

.241

0.55

n.d

n.d

K4-

Ora

nge

54.2

21

0.58

0.941

0.07

0.911

0.11

0.331

0.02

3.221

0.09

2101

4021

01

6013

01

6019

01

40501

2022

.631

0.71

n.d

n.d

K5-

Gre

en55

.451

1.69

0.351

0.02

0.381

0.03

0.251

0.02

0.361

0.07

1501

3021

01

7022

01

9040

001

400

1101

2021

.311

0.50

0.21

0.03

n.d

K5-

Gre

enY

ello

w52

.051

1.15

0.41

0.04

0.61

0.02

0.31

0.01

0.341

0.02

1001

3010

01

5012

01

6023

01

50401

1021

.691

0.21

n.d

n.d

K5-

Ora

nge

52.0

41

1.58

0.31

0.01

0.811

0.02

0.351

0.04

31

0.16

1601

4011

01

6011

01

6024

01

50501

2026

.521

0.38

n.d

n.d

K5-

Yel

low

50.6

41

3.51

0.351

0.02

0.591

0.07

0.281

0.02

0.371

0.04

1001

4011

01

6014

01

8021

01

40401

1024

.861

1.04

n.d

n.d

K5B

-Bla

ck46

.361

2.08

0.361

0.01

0.921

0.03

0.231

0.01

3.061

0.12

1501

4011

01

40901

4018

01

40401

1022

.741

0.72

n.d

n.d

K5B

-Yel

low

57.0

71

0.58

0.241

0.02

0.781

0.17

0.251

0.01

2.531

0.21

1401

5010

01

5010

01

5017

01

30401

1022

.71

1.21

n.d

n.d

K6-

Ora

nge

57.7

91

2.24

0.731

0.08

5.21

0.67

0.251

0.03

1.491

0.14

1401

4013

01

5010

01

5020

01

50401

1020

.551

3.29

n.d

n.d

K6-

Yel

low

47.8

11

1.73

0.481

0.04

11.8

91

2.13

0.281

0.03

0.861

0.14

1901

4018

01

6012

01

5025

01

50501

1025

.021

1.12

n.d

n.d

K7-

Bro

wn

58.1

91

1.15

0.541

0.03

2.131

0.76

0.221

0.01

2.81

0.34

1401

4015

01

5011

01

6035

01

60501

2024

.241

1.97

n.d

n.d

K7-

Gre

en58

.511

1.63

0.841

0.05

13.4

71

1.67

0.31

0.02

0.791

0.14

2301

5030

01

100

2001

8047

001

800

1301

3025

.111

2.52

0.281

0.05

n.d

K7-

Yel

low

53.4

81

2.34

0.871

0.03

6.111

1.13

0.321

0.02

0.411

0.04

1801

4015

01

6015

01

8042

01

80801

2026

.941

1.26

0.141

0.02

n.d

K7B

-Bro

wn

53.4

91

1.53

0.461

0.02

3.081

0.1

0.231

0.01

5.821

0.65

2501

4015

01

7010

01

4019

01

40801

2024

.641

2.79

n.d

n.d

K8-

Bro

wn

54.9

21

1.72

0.291

0.02

0.641

0.04

0.621

0.04

3.751

0.49

3701

5011

01

6010

01

30801

20501

2026

.081

1.91

n.d

n.d

K9-

Gre

en51

.361

1.35

0.711

0.05

2.71

0.1

0.241

0.02

1.361

0.04

2001

4011

01

6013

01

7027

001

400

701

2024

.21

0.51

0.241

0.02

n.d

K9-

Gre

enO

rang

e53

.591

2.1

0.691

0.03

2.661

0.12

0.181

0.02

1.221

0.03

2501

3031

01

100

1601

9023

001

400

701

2023

.551

1.85

0.241

0.05

n.d

K10

-Bro

wn

51.3

41

2.13

0.551

0.11

3.821

0.2

0.331

0.02

3.21

0.25

1801

4011

01

6010

01

6021

01

40501

1020

.831

1.33

n.d

n.d

K10

-Gre

en53

.481

3.25

0.591

0.05

3.961

0.78

0.181

0.02

3.51

0.35

1901

40901

5011

01

6016

01

30501

2025

.641

0.78

n.d

n.d

K10

-Ora

nge

49.21

10.

571

0.02

4.481

0.82

0.251

0.02

3.11

0.11

2001

40801

30901

5014

01

30501

1026

.691

1.03

n.d

n.d

K10

-Yel

low

54.6

21

2.73

1.21

0.15

1.011

0.19

0.331

0.02

0.341

0.01

1101

7010

01

6011

01

6021

01

40401

1028

.091

1.23

n.d

n.d



Tabl

e3

(Con

tinu

ed)

Sam

ple

SiO

2K

2OC

aOTi

O2

Fe 2

O3

MnO

Cr

Ni

Cu

Zn

PbO

SnO

2C

oOw

t%1

stde

vw

t%1

stde

vw

t%1

stde

vw

t%1

stde

vw

t%1

stde

vpp

m1

stde

vpp

m1

stde

vpp

m1

stde

vpp

m1

stde

vpp

m1

stde

vw

t%1

stde

vw

t%1

stde

vw

t%1

stde

v

K11

-Ora

nge

51.3

41

1.83

1.41

0.34

4.381

0.76

0.231

0.03

1.861

0.06

1601

70701

2012

01

6013

01

30451

1026

.151

3.36

n.d

n.d

K11

-Yel

low

52.91

2.68

0.961

0.26

5.311

1.12

0.351

0.03

0.631

0.12

901

4017

01

8012

01

7021

01

40441

1023

.391

2.99

n.d

n.d

K12

-Red

56.3

51

2.15

0.461

0.08

2.091

0.3

0.231

0.04

2.721

0.3

1601

4011

01

4010

01

4035

01

100

201

1026

.451

1.40

n.d

n.d

K12

-Yel

low

60.0

41

2.52

0.391

0.08

1.121

0.1

0.221

0.03

2.281

0.3

1301

4014

01

4012

01

4030

01

100

201

1024

.781

1.51

n.d

n.d

K12

B-B

lack

52.0

91

2.08

0.461

0.03

13.9

91

1.15

0.221

0.02

1.621

0.15

1801

6013

01

3012

01

4012

01

40301

1026

.541

2.48

n.d

n.d

K14

-Ora

nge*

57.0

71

1.58

0.591

0.02

9.751

1.18

0.391

0.02

2.491

0.37

3601

6013

01

6012

01

60701

20401

1024

.511

0.91

n.d

n.d

K14

-Ora

nge

49.9

11

0.58

0.571

0.07

2.491

0.56

0.191

0.01

1.741

0.09

2801

4050

01

200

2001

70801

20401

2025

.811

1.72

n.d

n.d

K14

B-O

rang

e68

.461

2.89

0.691

0.03

4.571

1.29

0.451

0.05

2.961

0.17

3801

5018

01

8012

01

50901

20401

1022

.81

2.12

n.d

n.d

K15

-Yel

low

52.3

61

1.97

1.181

0.11

8.991

2.15

0.321

0.02

1.791

0.04

2601

4018

01

7011

01

4011

01

2011

01

2023

.051

2.51

n.d

n.d

K16

-Bla

ck54

.911

1.53

0.441

0.03

2.791

0.26

0.351

0.02

1.241

0.15

2401

6014

01

4027

01

8077

001

2000

901

2025

.41

1.72

0.211

0.03

n.d

K16

-Bro

wn

51.3

41

1.77

0.251

0.04

1.921

0.12

0.31

0.01

3.531

0.29

2701

7025

01

100

2201

6035

001

800

501

1027

.511

1.06

0.121

0.02

n.d

K16

-Gre

en59

.91

20.

761

0.06

2.611

0.12

0.431

0.01

0.671

0.03

1301

4013

01

4028

01

7077

001

2000

801

2021

.881

1.50

0.171

0.03

n.d

K16

-Lig

htG

reen

57.7

61

3.43

0.421

0.05

1.441

0.06

0.451

0.06

0.571

0.03

1501

5017

01

5027

01

8051

001

1000

601

2020

.941

0.81

0.111

0.02

n.d

K16

B-R

ed51

.331

1.73

0.511

0.16

6.481

1.18

0.281

0.03

91

1.73

2801

7012

01

4015

01

3010

001

100

301

1022

.231

2.06

0.11

0.02

n.d

K17

-Ora

nge*

51.3

51

3.21

0.541

0.11

1.341

0.44

0.221

0.04

1.211

0.19

2601

4027

01

8017

01

60601

10401

1020

.81

2.95

n.d

n.d

K17

-Yel

low

50.6

31

1.53

0.921

0.11

1.231

0.35

0.171

0.01

0.541

0.03

1601

4014

01

5016

01

50801

20401

2021

.231

1.83

n.d

n.d

K18

-Blu

e53

.11

3.43

4.731

0.12

1.921

0.06

0.181

0.02

2.391

0.12

3001

80801

3018

001

300

1501

50201

1035

.81

1.57

2.241

0.12

0.421

0.05

K18

-Lig

htB

lue

52.81

2.97

5.261

0.12

3.921

0.17

0.251

0.03

1.711

0.2

2701

7010

01

4060

01

100

801

30201

1034

.741

1.67

2.371

0.12

0.111

0.01

K27

-Gre

en57

.771

1.53

0.481

0.06

1.641

0.15

0.351

0.01

0.671

0.02

1201

4014

01

4015

01

5055

001

600

501

2027

.771

1.16

n.d

n.d

K27

-Gre

enL

ine

50.6

41

1.72

0.241

0.02

3.931

0.42

0.151

0.02

0.891

0.11

801

3010

01

3011

01

3031

001

300

301

1025

.071

2.67

n.d

n.d

K28

-Gre

en56

.321

2.08

1.481

0.35

1.361

0.06

0.081

0.02

1.621

0.12

3801

9010

01

3013

01

5064

001

1000

501

2023

.421

2.55

n.d

n.d

K28

-Yel

low

57.0

51

1.58

1.241

0.12

0.711

0.08

0.051

0.02

1.141

0.05

4001

100

2301

5015

01

5046

01

70201

1024

.071

1.45

n.d

n.d

K29

-Bla

ck55

.631

1.74

0.121

0.03

0.941

0.06

0.631

0.03

4.621

0.55

6001

100

1301

4014

01

4046

01

100

301

1026

.451

2.69

n.d

n.d

K30

-Gre

en62

.321

3.41

0.861

0.02

1.781

0.27

0.131

0.02

0.471

0.03

1001

4013

01

4014

01

6024

001

100

901

2021

.81

1.38

n.d

n.d

K30

-Yel

low

59.6

41

2.65

0.761

0.03

1.761

0.5

0.091

0.02

0.31

0.01

1201

3011

01

4010

01

4012

01

20301

1024

.071

2.38

n.d

n.d

K30

-Yel

low

*52

.621

2.31

1.051

0.27

4.111

0.67

0.131

0.04

0.731

0.19

1701

4028

01

7015

01

5019

01

70301

1026

.521

2.64

0.11

0.02

n.d

K31

-Yel

low

54.9

21

1.73

0.251

0.03

1.251

0.24

0.151

0.04

0.411

0.03

2001

4011

01

4014

01

4020

01

40501

2027

.431

1.74

n.d

n.d

K32

-Lig

htB

lue

60.1

61

3.12

2.541

0.04

3.321

0.54

0.231

0.02

0.971

0.16

2901

4011

01

5016

01

50801

20401

1030

.861

1.63

1.571

0.2

n.d

K33

-Blu

eGre

en58

.131

2.67

3.651

0.06

2.791

0.4

0.221

0.02

0.611

0.03

2701

7022

01

6022

01

6051

001

400

601

2032

.281

1.26

1.521

0.1

n.d

*Dec

orat

ive

patte

rn.



X-ray diffraction

Mineralogical analysis was performed for samples K1, K12, K16, K18, K27, K28, K29, K32 andK33. The results are presented in Table 4. All samples contain quartz and plagioclase. Calcite ispresent in all samples except K29 and K32, while hematite is present in all samples expect K18,K28, K32 and K33. Gehlenite is present only in sample K18, while analcime is present insamples K32 and K33 (Fig. 5). Additionally, samples K18, K32 and K33 contain high amountsof pyroxene (diopside), while they contain the lowest amount of quartz among all analysedsamples. An amorphous phase is also present in significant amounts in all samples. Diopside,plagioclase and gehlenite are the major minerals newly formed during the firing process of theceramics (Heimman and Maggetti 1979; Maggetti 1981; Buxeda i Garrigós 1999), while anal-cime is formed after firing, mainly during burial diagenesis, by crystallization from penetratingsolutions or by alteration and transformation of certain firing minerals (Maggetti 1981) or fromthe alteration of the glassy amorphous phase (Buxeda i Garrigós and Kilikoglou 2001; Schwedtet al. 2006). According to Heimman and Maggetti (1979), calcareous sherds of raw and fineceramics develop diospide and gehlenite during firing. The latter mineral is obviously metastablewith respect to the composition of typical potter’s clay, and therefore has the tendency to reactwith silica to yield anorthite at higher temperatures (>1050°C). This formation of high-temperature minerals depends on the original clay minerals and calcite contents of a sample, theirgrain size distribution and the duration of firing. For example, K1 is moderately calcareous(3.63% CaO) but contains detectable amounts of CaCO3 but no diopside and therefore it seemsto have been fired at a lower temperature than sample K29, which is highly calcareous (13.00%CaO) without any calcite, which means that all the calcite has been decomposed. Furthermore,K29 contains the highest amount of anorthite, which signifies a high firing temperature. Also,sample K32 is highly calcareous without any calcite and all the CaCO3 has been involved in the

Figure 2 PCA of ceramic bodies, using m-XRF elemental analysis.



formation of high-temperature phases, which means that sample K32 must also have been firedat a higher temperature than the other samples. Mineralogical analysis therefore shows differ-ences in some of the samples such as K29 and K32, which suggests the existence of differentmanufacturing technology probably involving a different firing process.

Scanning electron microscopy

The results of the glaze microanalysis of samples K1, K18 and K33 are presented in Figure 6. Ascan be seen, sample K1 contains a significantly higher amount of alumina and iron oxides (Fe2O3)but a lower amount of PbO compared with the glazes of the other two samples, which is inagreement with Tite et al. (1998). The alkali and the silica content of the glazes are quite similarfor all three samples K1, K18 and K33.

The optical differences of the quality of the ceramic body and glaze of samples K1 and K18are shown in Figures 7 (a) and 7 (b). The ceramic body of sample K1 shows detrital quartz in an

Figure 3 Map of southern Cyprus with the excavation areas of the studied samples and the sites of the other analysedmaterial. Mean values of Cr and Ca concentrations of analysed samples: Lemba (Megaw and Jones 1983), Kouklia(Jones 1986), Amathus 1 and 2 (Jones 1986), analysed samples with low Cr, Ca concentrations, analysed samples withhigh Cr, Ca concentrations.



amorphous matrix. The clay quality of sample K18 is much better. The white bubbles in the glazeof sample K18 (Fig. 7 (d)) are particles of Sn. Therefore SEM-EDS analysis confirms the m-XRFand XRD results on the differences between K18 and K33 compared with K1 (Figs 7 (a) and7 (c)), which is considered to be a local product, possibly from the workshops of Paphos. SamplesK18 (Figs 7 (b) and 7 (d)) and K33 show typical Italian majolica pottery decoration and couldpossibly be regarded as trade products.

CONCLUSIONS

The study of 25 Byzantine glazed ceramics from two archaeological sites in the Limassol areaprovides significant information on the elemental and mineralogical characterization, the prov-enance and the manufacturing techniques used for their production. In particular, the presentstudy has shown that all samples follow the main technological characteristics of lead-glazedByzantine pottery. Some of them (K18, K32, K33) are Sn-opacified glazed pottery and, based onXRD and SEM-EDS analysis, they could be either trade products or local products of workshopsthat followed specific technologies. The chemical composition of the ceramic bodies was com-pared with already analysed material from the Paphos (Lemba, Kouklia) and Limassol areas(Amathus). According to this comparison, the samples with increased Cr and Ca concentrationsseem to originate from the Limassol area while samples with low concentrations of Cr and Cacould originate from the Paphos area. Finally, samples K3 and K8 show significant differencesdue to the high content of TiO2, and together with samples K18, K32 and K33, which show strongarchaeological differences, could be regarded as possible trade products or local products ofdifferent decoration technology.

Concerning the glazes, the blue colour is due to the presence of Co and Ni oxides, the greencolour is due to Cu oxides and the yellow, orange, red and black colours are due mainly to Feoxides, in combination with Mn and Cr oxides.

Figure 4 PCA of glazes using m-XRFelemental analysis.



Tabl

e4

Min

eral

ogic

alco

mpo

siti

on(w

t%)

ofse

lect

edcl

aysa

mpl

es,c

arri

edou

tby

XR

D

Sam

ple

Qua

rtz

Fel

dspa

rsP

yrox

ene2

Cal

cite

Mic

aH

emat

ite

Geh

leni

teA

nalc

ime

Am

orph

ous

Pota

ssiu

mPl

agio

clas

e1

K1

695

3–

4–

5–

–14

K12

666

4–

5–

9–

–10

K16

585

6–

5–

6–

–20

K18

21–

229

20–

–14

–14

K27

60–

2–

52

3–

–28

K28

4514

117

12–

––

–11

K29

52–

26–

––

12–

–10

K32

8–

1327

––

––

3616

K33

31–

825

5–

––

1021

1 Mai

nly

anor

thite

,2 diop

side

.



Further studies on more samples of glazed pottery excavated in Cyprus are in progress toenhance our knowledge of Cypriot glazed pottery.

ACKNOWLEDGEMENTS

The present work was funded partially by the Greek General Secretariat of Research andTechnology and the EC under the programme ‘Excellence in Research Institutes GSRT (2ndround)’, sub-programme ‘Support for Research Activities in C. E. T. I.’ The authors thank the

Figure 5 XRD spectrum of the clay of the sample K33.

Figure 6 SEM-EDS analysis of samples K1, K18 and K33.



archaeologist E. Charalambous for cooperation and help during the sampling and the archaeolo-gist E. Prokopiou for the samples and the information about the archaeological sites.

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Documents

CYPRIOT BYZANTINE GLAZED POTTERY: A STUDY OF THE PAPHOS WORKSHOPS*