Journal of Archaeological Science: Reports 22 (2018) 506–512

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Chemical compositional analysis of glass from the north cemetery of ancient T

Demetrias (Thessaly)
⁎
Melina Smirnioua, , Bernard Gratuzeb, Eleni Asderakic, Elisavet Nikolaouc
a
University of Lincoln, School of History & Heritage, Lincoln, UK
b
IRAMAT-CEB, UMR 5060, CNRS/Univ. Orléans, Orléans, France
c
Ephorate of Antiquities of Magnesia, Archaeological Museum of Volos, Greece

A R T I C L E I N F O A B S T R A C T

Keywords: The city of Demetrias was founded in the early third century BCE and became the second capital of the
Glass Macedonian kingdom and an important naval station for the Macedonian fleet. Demetrias flourished from third
Hellenistic until the first centuries BCE when its importance started to diminish. In the present study we examine the
Trace elemental analysis chemical composition of finished glass objects from the north cemetery of ancient Demetrias dated to the
Laser ablation ICPMS
Hellenistic times looking at the specific chemical signature in order to better understand the various composi-
tional groups of the period.

1. Introduction compositional groups pointing to primary production in Syro-Palestine

Thessaly, with a continuous occupation since Neolithic times, con-
stitutes an important crossroad on the main communication route be-
tween northern and central Greece. Coastal settlements on the Pagasetic
gulf flourished since Bronze Age partly as an effect of the maritime
connectivity of the harbour sites serving as a centre for local, regional
and international trade.
Three coastal cities were founded on the Pagasetic gulf around
300 BCE. Demetrias was founded in 290 BCE and became the major
harbour in the area emerging in the centre of a maritime trade network
in Hellenistic and Roman times (Renders, 1988). The town's strategic
location made it the second capital of the Macedonian kingdom and one
of the most important naval harbours for the Macedonian fleet.
Glass from the Late Bronze Age, from Roman and late antiquity has
been studied extensively and substantial compositional and isotopic
data have been published aiding our understanding and interpretation
(e.g. Rehren and Pusch, 2007; Jackson and Nicholson, 2007; Jackson,
2005; Freestone, 2006; Degryse, 2014). In the early first millennium
BCE the raw materials used in glass production changed with natron, a
natural occurring mineral source, replacing plant ash as a flux and sand
replacing quartz pebbles as the silica source (Sayre and Smith, 1967).
At present, for the late Roman period the dominant model is that of a
central primary production close to the raw materials supplying a large
number of secondary workshops that re-melted glass and shaped it into
objects (Brill, 1999; Freestone, 2008; Jackson and Paynter, 2016). This
model has been strengthened by the presence of only a few distinct
and Egypt (Freestone et al., 2005). For earlier glass it is not very clear
whether such a centralised model was in place or a more localised
model supporting several regional production centres in eastern Medi-
terranean, Egypt and the western Mediterranean or North Africa is
more applicable (Silvestri, 2008; Degryse, 2014). With limited ar-
chaeological evidence pointing to primary glass production sites,
especially in the early periods, provenance of glass has relied on ar-
chaeometrical data to gain a better understanding of primary produc-
tion and glass exchange.
Archaeological finds document an expansion of the glass industry
during Hellenistic times which in sequence led to an extensive dis-
tribution and consumption of glass objects (Larson, 2016; Henderson,
2013). It seems that the change in consumption during this period fa-
cilitated the technological innovations in glassmaking of the Roman
word. Apart from Brill (1999) of first millennium BCE, glass studies of
early periods include the analyses of Hellenistic glass from Pherai in
Thessaly (Connolly et al., 2012), and from Jebel Khalid in Syria (Reade
and Privat, 2016), some late Hellenistic glass from Pergamon (Rehren
et al., 2015) as part of a wider study, glass from the 8th to 4th centuries
BCE from Pieria in Macedonia (Blomme et al., 2017), first millennium
BCE glass from the Black Sea (Shortland and Schroeder, 2009), and
European Iron Age glass from 9th century to 4th–3rd centuries BCE
(Arletti et al., 2010; Arletti et al., 2011; Conte et al., 2016; Oikonomou
et al., 2017). Most studies favour a model of less centralised production
serving a local or regional market. Production evidence has been ex-
amined for primary glassmaking in Hellenistic Rhodes (Rehren et al.,

⁎
Corresponding author.
E-mail address: msmirniou@lincoln.ac.uk (M. Smirniou).

https://doi.org/10.1016/j.jasrep.2018.02.008
Received 23 July 2017; Received in revised form 29 January 2018; Accepted 8 February 2018
Available online 03 March 2018
2352-409X/ © 2018 Elsevier Ltd. All rights reserved.
M. Smirniou et al.
2005), however this is debatable with new isotope studies rejecting the
suitability and compatibility of sand from the region (Blomme et al.,
2016) to the composition of glass from that period.
The present study examines fifteen samples from the north cemetery
of Hellenistic Demetrias in Thessaly in order to contribute composi-
tional and trace elemental data and to assist in better understanding of
glass production and exchange in the period between 3rd and 1st
centuries BCE.
2. Glass samples from the site of Demetrias
In the coastal area 1.5 km south of today's city of Volos in north-
eastern Greece, three major ancient settlements flourished from
Neolithic to early Christian times (Batziou-Efstathiou and
Triantafyllopoulou, 2012). One of these settlements, the city of Deme-
trias, was founded in the early third century BCE by Demetrius Po-
liorcetes, king of Macedonia (294 to 288 BCE), near the site where the
Pagasae had occupied during the Classical period (5th and 4th centuries
BCE). Demetrias became a major port of Macedonian rule and the
presence of a palace signifies the city's important status as Macedonian
land controlled by the king (Batziou-Efstathiou and Pikoulas, 2006).
The city was of major strategic importance, a regional and international
trade centre, until the 1st century CE when it started diminishing but
with continuous occupation. Between 217 and 168 BCE, during its
peak, the city had around 25,000 inhabitants. The settlement was
abandoned in the middle 6th century CE when the inhabitants moved to
the site Kastro-Palaia in neighbouring Volos.
The glass finds examined in the present study were recovered from
the rescue excavations undertaken in 1995–1996 at the north cemetery
of the city of Demetrias where a total of 919 tombs were discovered.
Most of the tombs had funerary gifts, but only a few of them contained
glass objects (Nikolaou, 2000). The cemeteries lay outside the walls of
the city and were organised in three major areas. The tombs of the
northern area where the glass samples were recovered date from the
early third to the first centuries BCE from Hellenistic context.
Most of the glasses excavated from the cemetery of the city of
Demetrias are vessels, either complete or fragmentary. There are sev-
eral core-formed alabastra with dark blue ground glass; several col-
ourless and aqua (blue-green) unguentaria and one hydria; a few
yellow-brown vessel fragments; several spherical coloured beads with
perforations; several gaming pieces, astragaloi (knucklebones) and
game counters (Fig. 1). Most of the finds are in good condition, some
vessel fragments are coated in iridescent layers on the surface. Fifteen
samples from a range of tombs were selected for chemical analysis.
Most of the samples are vessel fragments. There are also two beads with
perforations, and four gaming pieces (one astragalos/knucklebone and
three game counters) included in the samples. The glass samples have
been dated from the late 3rd to the 1st centuries BCE. A fragment from
each fragmented glass vessel and most small objects were selected for
analysis as these – and not complete vessels - were given permission to
be exported. All glass finds have been accessioned and are now stored at
the Museum of Volos. The samples are representative of the glass ob-
jects found in the cemetery excluding the core-formed alabastra which
were all complete vessels.
3. Analytical technique
Laser ablation inductively coupled plasma mass spectrometry (LA-
ICPMS) was used to analyse the glass samples. There was no special
preparation for the samples. Pre-ablation time of 20s was used to reach
the glass matrix below the corroded layers so the major, minor, and
trace elements were fully characterised. Analysis was carried out at the
CNRS/IRAMAT laboratory in Orléans. Pre-ablation parameters (dura-
tion and laser pulse frequency) can be adjusted depending on the cor-
rosion layer of the glass. In the present study, all samples had a thin
corrosion layer and 20 s of pre-ablation were sufficient to ensure that
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Journal of Archaeological Science: Reports 22 (2018) 506–512
uncorroded glass was reached. Gratuze (2016) describes the protocol in
detail as well as how the parameters can be adjusted according to the
corrosion layer of archaeological glass.
The ablation system consists of a Resonetics M50E excimer laser
working at 193 nm coupled with a Thermo Fisher Scientific ELEMENT
XR mass spectrometer. The excimer laser was operated at 5 mJ with a
repetition rate of 10 Hz. The beam diameter was adjusted between 80
and 100 μm to avoid saturation of the SEM detector by elements such as
manganese or antimony. A pre-ablation time of 20 s is set in order to
eliminate the transient part of the signal which is then acquired for 45 s
corresponding to 15 mass scans from lithium to uranium (the signal in
count/s is measured in low resolution mode for 58 different isotopes).
Two ablation passes were performed and the average was calculated.
The National Institute of Standards and Technology (NIST) standard
reference materials 610 along with Corning glass B, C and D and an
archaeological sample APL1 (an in-house standard glass with compo-
sition determined by Fast Neutron Activation Analysis which is used for
chlorine quantification) were used for external standardisation.
Reference material Corning glass A and NIST612 were regularly used to
check the calibration procedure. Concentrations were calculated ac-
cording to Gratuze (2016). Using the analytical protocol defined by
Gratuze (2016), the detection limits range from 0.01% to 0.1% for the
major elements, and between 20 and 500 ppb for all the other elements.
4. Results
Most samples are either naturally coloured or demonstrate the
presence of a decolouriser, antimony or manganese; they do not have
any colourant added deliberately in the mix apart from two dark blue,
and one purple/black glass.
All samples are soda-lime-silica glass (Table 1) produced using mi-
neral natron as the flux and a calcareous coastal sand as the silica
source. Low contents of MgO, K2O and P2O5 as well as high contents of
Cl of > 1% signify the use of natron. A consistent composition of low
iron, elevated alumina (Fig. 2a), as well as low Zr (< 40 ppm) and high
Sr contents (between 300 and 600 ppm) suggest the use of a lime-rich
coastal sand (Freestone et al., 2005; Brems and Degryse, 2014).
The major elements demonstrate a homogeneous composition with
SiO2 content ranging from 68% to 72%, Na2O between 15.6% and
19.4%, and Al2O3 between 1.8% and 2.9% (Fig. 2b). Lime levels are
more varying spreading from 5.2% to 9.4%. However, apart from three
samples with relatively lower CaO around 5.5% and two with higher
levels close or over 9.0% (Fig. 2c), the majority of the samples have a
very tight range between 7.0% and 7.8%. The minor elements have also
a consistent composition for most of the samples within a narrow range
with iron oxide concentrations between 0.3% and 0.5%, and MgO and
K2O below 0.8%. The trace elements (Table 2) are also consistent
throughout most of the samples.
Trace elemental studies (Shortland et al., 2007; Degryse and
Shortland, 2009; Brems and Degryse, 2014) have identified diagnostic
markers associated with the raw materials and specifically with the
sand used in the glass batch. Looking at the trace elements, the De-
metrias samples very clearly demonstrate similar patterns to first mil-
lennium BCE glass and glass from the Roman period. All samples have
low La and low Cr with a ratio for Cr/La in the range between 1.0 and
2.0 that corresponds to 4th century BCE glass from Pieria (Blomme
et al., 2017), with the 4th century BCE glass from Pichvnari in Georgia
(Shortland and Schroeder, 2009), as well as with late Hellenistic and
early Roman glass from Pergamon (Rehren et al., 2015). Similarly,
Demetrias Ti and Zr levels, associated with the silica source, plot very
closely to glass from these sites (Fig. 3).
Similarly to glass from later periods (Rehren et al., 2015; Jackson
and Paynter, 2016), the glass samples from Hellenistic Demetrias fall
into the compositional groups described below. The groups have very
similar base glass composition and here they are categorised according
to the presence of (de)colouring agents:
M. Smirniou et al. Journal of Archaeological Science: Reports 22 (2018) 506–512

Fig. 1. Some of the glass samples from the site of Demetrias: black astragalos; Sb-decoloured glass fragment; glass counter; colourless vessel fragments.

1. Colourless glass decoloured by the use of antimony (Sb-decol), 2.
Naturally coloured glass with a blue-green hue containing either a
combination of antimony and manganese both lower than 1% (Sb-Mn),
or low manganese of < 1% (low Mn), 3. Colourless glass decoloured by
the use of manganese of > 1% (high Mn), 4. Naturally coloured glass of
amber or yellow-brown hue with no colourant or de-colourant present
(amber), 5. Coloured samples with the deliberate use of a colouring
agent; these are three samples that are deliberately coloured: one
purple/black with high levels of manganese, and two cobalt-blue
glasses.
4.1. Antimony-decoloured samples
Antimony-rich glass has been produced since 6th century BCE
(Sayre and Smith, 1967) with higher concentrations of antimony re-
ported in the earlier periods, while a very consistent composition with
low lime, high soda and lower antimony levels is observed in from late
Hellenistic and early Roman periods onwards (Connolly et al., 2012;
Jackson and Paynter, 2016).
Four of our samples fall under this category and form two distinct
subgroups. Two of the antimony-decoloured samples from the 1st
century BCE (BE15912a and BE15912c) correspond well with late

Table 1
Major and minor oxide compositions of glass from the site of Demetrias. Analysis obtained by LA-ICP-MS. Data reported in wt%.

No Type Tomb no Date Colour Group SiO2 Na2O K2O MgO Al2O3 CaO FeO TiO2 Sb2O5 MnO Cl P2O5

BE15912a Vessel T405 1st BCE Colourless Sb-decol 71.4 18.2 0.32 0.37 1.76 5.64 0.30 0.06 0.47 0.01 1.32 0.02
BE15912c Vessel T405 1st BCE Colourless Sb-decol 71.8 17.6 0.39 0.36 1.94 5.19 0.30 0.06 0.88 0.01 1.30 0.02
AE1103 Vessel T260 Late 3rd BCE Colourless Sb-decol 69.7 15.9 0.48 0.50 2.03 7.52 0.38 0.05 1.90 0.01 1.35 0.04
ID51821 Glass counter T320 Late 3rd BCE Colourless Sb-decol 69.2 16.9 0.77 0.45 2.46 7.62 0.36 0.05 0.47 0.01 0.99 0.09
AE61 Vessel T12 2nd BCE Blue-green SbMn 69.5 17.6 0.49 0.56 2.19 6.97 0.48 0.08 0.38 0.47 1.02 0.11
BE15927 Vessel T128 1st BCE Blue-green SbMn 68.8 17.4 0.65 0.54 2.32 7.29 0.47 0.07 0.25 0.85 0.94 0.13
BE15909b Vessel T223 2nd BCE Blue-green Low Mn 69.3 19.4 0.61 0.48 2.21 5.97 0.33 0.05 0.00 0.36 1.14 0.06
BE15912b Vessel T405 1st BCE Blue-green Low Mn 71.3 15.4 0.46 0.48 2.46 7.73 0.34 0.06 0.00 0.38 1.06 0.13
AE64 Vessel T12 2nc BCE Colourless High Mn 67.8 17.1 0.70 0.55 2.63 7.84 0.40 0.06 0.00 1.58 1.03 0.16
BE15909a Astragalos T223 2nd BCE Purple/black Purple/black 69.7 14.6 0.79 0.62 2.15 7.39 0.40 0.07 0.00 2.70 1.24 0.09
ID51824 Glass counter T320 Late 3rd BCE Blue Coblue 68.8 17.3 0.42 0.48 2.52 7.68 0.72 0.06 0.00 0.39 1.19 0.05
BE18078 Bead T814 Late 3rd BCE Dark blue Coblue 71.8 15.6 0.38 0.50 2.24 7.80 0.51 0.05 0.04 0.01 0.79 0.04
AE1763 Vessel T419 1st BCE Amber nonC 68.0 18.1 0.44 0.42 2.92 8.22 0.34 0.05 0.00 0.07 1.27 0.07
BE18067 Bead T815 Late 2nd BCE Yellow-brown nonC 69.0 16.5 0.89 0.52 2.69 8.82 0.30 0.05 0.00 0.02 1.01 0.11
ID51823 Glass counter T320 Late 3rd BCE Yellow-brown nonC 68.7 16.1 0.57 0.93 2.39 9.40 0.46 0.08 0.02 0.02 1.09 0.06
Corning A analysed (average of multiple runs) 66.8 13.9 2.83 2.56 0.9 5.66 1.08 0.78 1.67 1.02 0.14 0.11
Given values (Brill, 1999) 66.6 14.3 2.87 2.66 1.00 5.03 0.98 0.80 1.72 1.00 0.10 0.13

508
M. Smirniou et al.
Fig. 2. a: Alumina and potash content of glass samples from Demetrias indicating a
consistent composition. b: Lime and alumina content of glass samples from the site of
Demetrias. The samples in red circle are the yellow-brown glasses containing no (de)
colourising agent. c: Soda and lime content of glass samples from Demetrias. Comparative
data from Blomme et al. (2017) for the Pieria samples; Rehren et al. (2015) for the
Pergamon samples; Connolly et al. (2012) for the Pherai samples. (For interpretation of
the references to colour in this figure legend, the reader is referred to the web version of
this article.)
Hellenistic and early Roman Sb-decolourised glasses as reported in the
literature (Foster and Jackson, 2010; Connolly et al., 2012; Rehren
et al., 2015; Jackson and Paynter, 2016) produced by a pure sand de-
monstrating lower levels of lime of an average of 5.4%, lower alumina
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Journal of Archaeological Science: Reports 22 (2018) 506–512
of around 1.8%, potash lower than 0.4%, high silica of around 71% and
high soda close to 18%. The two other samples (AE1103 and ID51821),
from 3rd century BCE, have slightly different composition with higher
lime, slightly higher potash and magnesia, lower soda and higher an-
timony level for one of them (AE1103). These earlier samples corre-
spond better to earlier antimony decolourised glass from 4th century
BCE Pieria (Blomme et al., 2016) (Fig. 4). One of the early samples
demonstrates high lead content pointing to perhaps a lead-rich anti-
mony source (Jackson and Paynter, 2016). The Cr contents of the two
early samples are a little bit more elevated at 11–14 ppm instead of
6–8 ppm but in accordance with some antimony-rich colourless glasses
from Pieria (Blomme et al., 2016).
4.2. Manganese-rich samples
Manganese has been used as a principal decolourant in glass since
the second century BCE (Sayre and Smith, 1967) and is one of the most
frequently observed glass from the first until the fourth century CE
(Silvestri, 2008; Rehren et al., 2015; Jackson and Paynter, 2016).
Manganese, similarly to antimony, is used to suppress the effects of iron
in the sand to produce a colourless glass. However, larger quantities
of > 1.0% of manganese is needed to completely decolourise the glass,
while in lower quantities a glass with a blue-green (“aqua”) hue is
produced.
Three of our samples have significant content of manganese asso-
ciated with low content of antimony, two have a pale blue colour with
MnO close to 0.4% (BE15909b and BE15912b) while the third sample
(AE64) is colourless with 1.6% of MnO. Apart from the manganese
content there is no other significant difference in the composition of the
three samples. The samples date to the second and first centuries BCE.
Two other samples (AE61 and BE15927) contain both antimony
(0.4% and 0.25%) and manganese oxides (0.5% and 0.85%) and cor-
respond well to the early blue-green Sb-Mn reported from Pergamon
(Rehren et al., 2015). The samples show slightly elevated levels and a
broader range in contents of Cu, Zn, Sn although lower than 100 ppm,
but Pb between 115 and 271 ppm perhaps reflecting the effects of re-
cycling glass. It is very possible that this type of glass was produced by
mixing antimony-rich and manganese decolourised glasses as observed
in later period (Jackson and Paynter, 2016, Rehren et al., 2015).
4.3. Deliberately coloured glass
Three samples (one purple/black and two dark blue) are deliber-
ately coloured by the addition of a colouring agent. These are two
gaming pieces (one astragalos and one game counters), and one sphe-
rical bead.
The purple/black sample (BE15909a) is a glass gaming piece (as-
tragalos or knucklebone) very similar to the composition of glass BG2
reported by Cagno et al. (2014). The sample has high levels of man-
ganese of 2.7% which is responsible for the colour of the glass. This
sample has low potash and low magnesia below 0.8%, low Fe2O3 of
around 0.4% and low titania of 0.07%, elevated alumina of 2.15%,
demonstrating a relatively similar and consistent composition to the
antimony and manganese decolourising base glass.
The two cobalt blue samples are a bead (BE18078), and a glass
counter (ID51824) and they demonstrate varying but equal contents of
copper and cobalt ranging between 400 and 700 ppm (Smirniou and
Rehren, 2013). A cobalt source commonly used in Egyptian Late Bronze
Age cobalt blue glasses has been associated with increased levels of
alumina, manganese, arsenic, nickel and zinc oxides which are con-
taminations of the cobaltiferous alum ore of the Western desert oases in
Egypt (Kaczmarczyk, 1986; Tite and Shortland, 2003; Shortland and
Eremin, 2006). Here the cobalt-blue glass counter (ID51824) shows
some elevated Ni, Fe, Zn, and Mn levels, but not substantially high,
suggesting a potential cobalt source rich in these elements. Sample
BE18078 though has much lower content of these elements and
M. Smirniou et al. Journal of Archaeological Science: Reports 22 (2018) 506–512

Table 2
Trace elemental composition of glass from the site of Demetrias. Analysis obtained by LA-ICP-MS. Data reported in ppm.

Number Comp group Li B Ti Cr Mn Co Ni Cu Zn As Sn Sb Pb Sr Y Zr Ba La Ce Nd Th U

BE15912a Sb-decol 1.2 201 371 7 112 1.0 3 8 14 16 0.3 3895 6 342 5.4 40 125 6 10 5.1 0.8 0.9
BE15912c Sb-decol 1.1 157 379 8 102 1.0 2 5 11 17 6.4 7341 328 310 5.2 45 144 6 10 5.0 0.9 0.8
AE1103 Sb-decol 3.5 130 317 14 87 1.8 16 3 11 22 0.4 15,861 78 403 6.8 37 146 7 11 6.2 0.9 0.9
ID51821 Sb-decol 1.4 158 320 11 92 2.2 4 28 9 4 0.8 3958 4667 390 6.6 34 197 7 11 6.0 0.8 1.0
AE61 SbMn 1.5 176 468 5 3634 3.2 7 21 20 13 11.3 3145 115 393 6.3 50 216 7 11 5.8 0.9 1.0
BE15927 SbMn 4.3 168 437 6 6588 7.4 7 27 20 17 13.4 2088 271 432 6.3 44 256 6 11 6.0 0.9 0.9
BE15909b Low Mn 3.2 115 329 3 2787 3.6 5 4 9 0.8 0.3 3 n.d. 344 5.5 35 199 5 10 5.1 0.7 0.8
BE15912b Low Mn 0.9 177 370 12 2931 6.1 9 11 14 1.2 1.0 25 5.0 417 6.9 40 211 7 12 6.3 0.8 0.8
AE64 High Mn 6.5 173 380 n.d 12,250 11.9 8 6 15 1.1 0.4 6 5.4 464 7.0 37 362 7 11 6.3 0.8 0.9
BE15909a Purple/black 4.5 181 402 3 20,916 21 23 11 33 4 1 0.5 19 658 7 47 308 7 11 6.2 0.9 0.7
ID51824 Coblue 0.6 221 360 11 3052 608 99 744 87 5 21 9 34 424 7 31 194 7 12 6.4 0.8 0.9
BE18078 Coblue 1.5 191 327 7 96 420 4 463 61 3 0.4 344 19 422 6 37 165 6 11 5.8 0.7 1.6
AE1763 nonC 4.0 51 301 n.d 547 17 2 42 9 0.2 1.7 10 1 435 7 39 228 7 12 6.3 1.0 1.5
BE18067 nonC 0.3 145 308 10 119 0.8 3 25 8 1.1 0.3 6 93 482 7 34 220 7 13 6.6 0.8 0.7
ID51823 nonC 2.2 215 486 11 147 2 4 5 8 1.9 0.3 163 10 552 7 39 186 7 13 6.8 0.8 1.0
NIST612a 36.8 34.3 40.2 33.7 39.2 36.1 37.6 36.8 35.8 33.5 35.0 36.1 30.3 74.9 37.2 37.6 35.9 37.5 37.9 35.5 37.5 37.7
Given valuesb 40.2 34.3 44.0 36.4 38.7 35.5 38.8 37.8 39.1 35.7 38.6 34.7 38.6 78.4 38.3 37.9 39.3 36.0 38.4 35.5 37.8 37.4

a
Average of multiple runs.
b
Jochum et al. (2011).

elevated antimony suggesting a different colourant source.

4.4. Naturally coloured glass with no (de)colourant

The three samples that have no colourant or decolourising agent

Fig. 3. Trace elements (Cr, La, Zr, Ti) for the glass samples from the site of Demetrias
compared to the 4th century BCE sites in Pieria (Blomme et al., 2017) and Pichvnari
(Shortland and Schroeder, 2009), and the late Hellenistic/early Roman samples from
Pergamon (Rehren et al., 2015).
have a yellowish brown hue; one is a fragmented vessel (AE1763), one
bead (BE18067) and one glass counter (ID51823). Their colour are
likely to represent the formation of an iron sulphur chromophore under
reducing furnace conditions as has been discussed previously (Brill,
1988; Freestone and Stapleton, 2015; Paynter and Jackson, 2017). They
demonstrate elevated lime between 8.22% and 9.40% and slightly
higher alumina between 2.4% and 2.9%. Potash and magnesia are low
below 0.8%, iron oxide and titania are also low below 0.4% and 0.08%
respectively. Trace elements are very similar to the rest of the samples.
Manganese is slightly elevated between 120 and 550 ppm although in
low levels that does not indicate deliberate addition. They are identical
in composition to late Hellenistic and early Roman amber glass noted in
literature (Paynter and Jackson, 2017; Oikonomou et al., 2017; Reade
and Privat, 2016) and very similar to blue-green glass of the same
period but without the manganese content (Paynter and Jackson,
2017).

5. Discussion

The samples from Demetrias were compared to published analyses

Fig. 4. Lime and alumina content of antimony decolourising glass samples. Sample
AE1103 plots closely to the samples from 4th century BCE Pieria. Comparative data from
Blomme et al. (2017) for the Pieria samples; Rehren et al. (2015) for the Pergamon
samples; Connolly et al. (2012) for the Pherai samples.
of colourless and naturally coloured glass from Iron Age to early
Roman: from 8th to 4th centuries BCE Pieria in Greece (Blomme et al.,
2016), from the end of 3rd to the 1st century BCE (Hellenistic) Pherai in
Thessaly (Connolly et al., 2012), from the 2nd century BCE to the 2nd
century CE Pergamon in Anatolia (Rehren et al., 2015), and from 1st to
3rd century Roman York (Jackson and Paynter, 2016). All the colour-
less Iron Age glass from Pieria has been decoloured by the addition of
antimony and there is no glass that appears to be decoloured by ele-
vated levels of manganese. From 3rd century BCE to 3rd century CE (in
Pherai, Demetrias, Pergamon, and York) the colourless Sb glass coexists
with a blue-green Mn-decoloured group demonstrating mostly low le-
vels of manganese oxide of < 1%, along with a third group of mixed Sb-
Mn glass very likely due to recycling from the two traditions. This is
demonstrated in all Hellenistic and early Roman assemblages studied
from Pherai, Demetrias, Pergamon and York. The Demetrias Sb-deco-
loured glass shows two variants; one (from 1st century BCE) that is very
close in composition to the Roman Sb-decoloured glasses and an earlier
subgroup (from the late 3rd century BCE) that matches the chemical
signature of the Iron Age Sb-decoloured glasses from Pieria.

510
M. Smirniou et al.
Fig. 5. Lime and alumina content of antimony and manganese decolourising glass sam-
ples from 4th century BCE to 3rd century CE. Comparative data from Blomme et al.
(2017); Rehren et al. (2015); Connolly et al. (2012); Jackson and Paynter (2016).
Most of the glasses from all sites form a tight group as of the flux
used with both MgO and K2O at concentrations of < 0.8%. Most glasses
also group tightly with low levels of iron oxide of < 0.6%.
Soda concentrations range from 16.0% to 20.0% with the majority
of the Hellenistic Mn-decoloured and the mixed Sb-Mn glasses showing
lower content (< 17.5%), the Roman Mn-decoloured having a wider
distribution (between 16.0% and 19%), while the Roman Sb-deco-
loured and the early Sb-decoloured having consistently higher levels
of > 18.5% and 17.5% respectively.
On the basis of lime and alumina concentrations there are two
distinct groups forming (Fig. 5). One with low lime (5%–7%) and low
alumina (1.5–2.2%), probably from a pure sand source, where all the
Roman Sb-decoloured, half of the mixed Sb-Mn group and some of the
Hellenistic Sb-decoloured lie. A second group with high lime (7%–10%)
and relatively higher alumna (2.2%–3.0%) where all the Mn-deco-
loured (Roman and Hellenistic), half of the mixed Sb-Mn and the early
Sb-decoloured (all the Pieria samples and two from 3rd century BCE
Demetria) belong.
The chemical consistency of the Mn decoloured group suggests a
relationship between the Hellenistic and the Roman productions with
similar recipes and raw materials.
The Sb decoloured glass presents two subgroups. A chronologically
earlier variant that its chemical signature is not inconsistent to the later
Mn group suggesting perhaps a common origin. This earlier Sb deco-
loured glass shows variations to the later Sb group that is present from
around 1st BCE to 3rd CE indicating differing production sites.
6. Conclusion
The samples from Hellenistic tombs of Demetrias show a close si-
milarity to first millennium BCE and later Roman natron glass reported
in the literature. Based on the chemical signature, all samples have been
produced by the use of natron as flux mixed with a calcareous silica-rich
sand.
The base glass composition of most samples is quite tight and
classification into groups is done based on the colourant or decolour-
ising agents used.
For the antimony-decoloured glasses we see a slight different com-
position richer in lime and antimony for earlier glasses as supported by
similar signature from 4th century BCE Pieria (Blomme et al., 2017)
transitioning to a differing production with low lime and low levels of
antimony from late Hellenistic period onwards (Connolly et al., 2012;
Jackson and Paynter, 2016).
In Hellenistic Demetrias north cemetery, we observe the preference
of colourless glass for higher quality tableware while coloured glass is
511
Journal of Archaeological Science: Reports 22 (2018) 506–512
limited to either non-vessel small objects, or the more luxurious core-
formed cosmetic vessels.
Evidence of recycling is not substantial in the samples analysed here
suggesting that at this earlier pre-Roman period raw glass was readily
available. Perhaps the location of Demetrias at the centre of maritime
trade facilitated access to either finished objects or raw glass chunks.
However, there is recycling observed with the mixed anti-
mony‑manganese decoloured group.
The consistent compositional data throughout the samples analysed
support a model of a centralised primary glass production, however a
larger dataset would be required to make a conclusive case.
Acknowledgements
We would like to thank the Ephorate of Antiquities of Magnesia and
the Hellenic Ministry of Culture that kindly permitted the temporary
export of selected samples for analysis by LA-ICPMS. Special thanks to
Dr. Artemios Oikonomou and Prof. Julian Henderson for organising
“Glass Reflections” and for inviting us to participate to the workshop.
Detailed comments from three reviewers are gratefully acknowledged
and have helped us to strengthen the paper; any remaining errors are
our own responsibility.
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