Hyperfine Interactions 57 (1990) 2173-2178 2173

M O S S B A U E R S T U D Y O F C E R A M I C F I N D S F R O M T H E E A R L Y P H O E N I C I A N P A L A C E IN K A M I D E L - L O Z , L E B A N O N

Y. E 1 - H A G E 1, U. W A G N E R 1, F.E. W A G N E R a, j . R I E D E R E R 2, R. E C H T 3 and R. H A C H M A N N 3

i Physik-Department El5, Technische Universitiit Miinchen, D-8046 Garching, 2 Staatliche Museen Preul3ischer Kulturbesitz, Rathgen-Forschungslabor, D-IO00 Berlin, s Institut ffir Vor- und Friihgeschichte und Vorderasiatische Archiiologie, Universitil"t des Saarlandes, D-6600 Saarbriicken, F.R. G.

A M~Sssbauer typology of 120 early phoenician ceramic sherds from Kamid El-Lgz, Lebanon, is proposed. It is found to agree well with other classifications by means of neutron activation analysis and thin section microscopy. Two ancient calcium rich clays and one recent calcium poor clay from the same region were fired in the laboratory in oxidizing and reducing atmospheres, at temperatures increasing stepwise from 50~ to 1200~ with MiSssbauer spectra taken at room temperature and occasionally at 4.2 K. These model experiments were undertaken with the aim to reconstruct the firing techniques of the early phoenician potters. The firing temperature of the locally made pottery appears to have been low.

1. Archaeological aspects

A n early phoen ic i an se t t l ement at the Tell K~mid E1-L~z in the Biqa' p la teau be tween the L e b a n o n and the A n t i l e b a n o n has been excava ted dur ing the years 1963 to 1981 by teams of the Univers i ty of Saarbr i icken. It is located at the crossing of two ma jo r ancient roads and was one of the i m p o r t a n t late b ro n ze age centers in the N e a r East region (1500 -1100 B.C.). Most of the ceramic finds

ana lysed here s tem f rom a late b ronze age pa lace and cons t i tu te a closed find. In this con tex t it is of interest to dis t inguish locally m ad e ware f ro m im p o r t ed mater ia l . O the r sherds used in the cons t ruc t ion of walls and p r o b a b l y or ig ina t ing

f rom an earl ier pa lace were also invest igated.

2. Experimental methods

N e u t r o n ac t iva t ion analysis (NAA) was used to charac ter ize the mater ia l on accou n t of its e lement compos i t ion . I n f o r m a t i o n on the minera l con ten t f rom thin sec t ion mic roscopy (TSM) was c o m b i n e d with the results f rom Mi3ssbauer spec t ro scopy (MS) in an a t t emp t to assess the ancient fir ing condi t ions .

�9 J.C. Baltzer A.G. Scientific Publishing Company

2174 Y. El-Hage et al. / M . S . of ceramicfindsfrom Lebanon

For MS the different layers of 120 selected sherds were separated according to their colour. M~Sssbauer spectra were taken from each layer at RT and occasion- ally at 4.2 K. For comparison two samples of archaeological clays (KL 80 :427 /a and b) and one recent clay from Dahr E1-Ahmar were fired in the laboratory in air for 48 h from 5 0 ~ to 1150~ in steps of 5 0 ~ with M~Sssbauer spectra taken after each step at RT. Reductions were performed for 3 h with charcoal in a closed vessel. Samples reduced at 8 0 0 ~ were also subjected to an oxidizing firing cycle. The spectra were fitted with a superposition of Lorentzian lines. In temperature regions where mineral transformation or magnetic ordering occur, distributions of hyperfine fields exist which were approximated by fitting up to 9 sextets.

3. Results and discussion

The cluster analysis of twenty element contents determined by NAA yields 6 groups of sherds and a 7th group containing unclassifiable pieces (fig. 4). Three of the groups are characterized by a high Ca content. The results of TSM are in good agreement with those of NAA.

The M~3ssbauer spectra for the differently coloured layers of the sherds can be phenomenologically divided into six different groups which are found to be correlated with the classification obtained by the other methods (fig. 1). Types 1, 2 and 3 do not contain Fe 2+ but growing amounts of increasingly better ordered iron oxides. Fe 2+ shows up in Type 4 together with an oxide pattern. Type 5 is the least homogeneous group. Its characteristic feature is the near absence of oxidic components and the appearance of one or two Fe 2+ quadrupole doublets with a variety of splittings. Fe z+ is dominant in spectra of Type 6.

100-

I -10 0 +10 -.,o0i -+

9,1 -10 0 +10

100 V-

-10 0 +10

92

-6 velor

+6 (ram/s)

98- KL 78:811135 ~ Type3

] -10 0 +10

89

-6 0 +6

Fig. 1. Six types of M~Sssbauer spectra for ceramics from Kamid EI-Lrz. Note the different velocity scales.

Y. El-Hage et al. / M.S. of ceramic finds from Lebanon 2175

Fig. 2. Temperature dependence of M~Sssbauer spectra for firing of the two archaeological clays KL 80:427/a (left) and KL 80:427/b (right). On top, the firing series in air (O) is shown for M~,ssbauer measurements at RT (first row) and 4.2 K (second row). Identical series for a sample which was reduced at 800~ prior to oxidation in air (RO) and for reducing treatment (R) at different

temperatures are shown in the third and fourth row.

2176 Y. El-Hage et al. / M.S. of ceramic finds from Lebanon

Fig. 3. Same as fig. 2 for the recent calcium poor clay from Dahr E1-Ahrnar. Spectra measured at RT.

In order to interpret the MiSssbauer spectra of ceramics, laboratory firing series have proved useful [2]. We have studied two archaeological clays from K~mid EI-L~z and one recent clay from Dahr E1-Ahmar under oxidizing, reducing and varying firing conditions. The results are shown in figs. 2 and 3. In the ancient clays KL 80 :427 /a and b with about 20% of Ca, oxidic iron components are t ransformed into iron bearing sificates [3] during firing. Gehlenite was occasion- ally identified by X-ray diffraction on firing these clays and retiring some of the ceramics at temperatures above 850 ~ An additional componenet with a nega- tive isomer shift appears on firing above 850 o C. The absence of this phase in the untreated ceramics indicates a rather low ancient firing temperature. Hemat i te formation is dominant in the firing of the calcium poor clay from Dahr E1-Ahmar (fig. 3). A detailed discussion of the processes taking place during firing as shown in figs. 2 and 3 will be published elsewhere [4]. The results of all applied methods are summarized in fig. 4.

Hoinly frLuortz-Crtlcite Temper- ~olci te--Eztremel I Fine- ---Fine ~ste----Organic-- Tempa paste ~fusions

�9 NiNh Co Content Low Co Content - - 14os-tlrpes 1.2,,~&5- 1 4 o s - t l p e s l & 2 ~ 14,s-tnml3zl. -)4os-typaS-- --J4os-typal,-- -J4os-trp.i,-

Voriabte Firing- Oxid.Firing bloinly Redut.Firir~l- tocol Potte~lr- - - k ~ p o r t e d Pollery ' -I/,~ertoJn~Recent-

Fig. 4. Summary of NAA, TSM and MS results of a study of 120 sherds from K~mid EI-Lgz together with a tentative archaeological classification.

Y. El-Hage et al. / M.S. of ceramic finds from Lebanon 2177

Acknowledgement

We would like to thank M. Bartel and J. Punsch for careful help during sample preparation and measurements and Dr. R. Gebhard for continuous and critical interest. One of us (Y.E.H.). is indebted to the Deutscher Akadernischer Austauschdienst for a stipend. Support of the Deutsche Forschungsgemeinschaft is very gratefully acknowledged.

References

[1] R. Hachmann, Saarbriicker Beitriige zur Altertumskunde, Vol. 36 (Habelt GmbH, 1986). [2] U. Wagner, F.E. Wagner, A. Stockklauser, R. Salazar, J. Riederer and F. Kauffmann-Doig,

Hyp. Int. 29 (1986) 1113. [3] Y. Maniatis, A. Simopoulos and A. Kostikas, J. Am. Ceram. Soc. 64 (1981) 263. [4] Y. El-Hage, PhD. Thesis, Technische Universit~it Mianchen, 1990.