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XII/1/2021
INTERDISCIPLINARIA ARCHAEOLOGICA
NATURAL SCIENCES IN ARCHAEOLOGY
homepage: http://www.iansa.eu
Possibilities and Limitations of Non-Invasive Analytical Methods in the
Examination of Garnet- and Niello-Inlaid Precious Metal Objects –
Case Study of Three Polychrome Animal-Style Silver Buckles
from the 5th-Century Carpathian Basin
Viktória Mozgai1*, Eszter Horváth2, Bernadett Bajnóczi1
1Institute for Geological and Geochemical Research, Research Centre for Astronomy and Earth Sciences, Eötvös Loránd Research Network (ELKH),
Budaörsi út 45, 1112 Budapest, Hungary
2Department of Archaeometry and Archaeological Methodology, Institute of Archaeological Sciences, Eötvös Loránd University, Múzeum körút 4/B,
1088 Budapest, Hungary
1. Introduction
The use of non-destructive and non-invasive analytical
methods is widespread in the archaeometric study of metal
objects, particularly in the case of precious metal artefacts,
from which sampling is not allowed (or only in a very limited
way) due to their high value. However, beside the advantage
of their non-destructive nature, each analytical method has
its own limitations as well, which have to be taken into
consideration during data evaluation and interpretation (e.g.,
precision, accuracy, surface morphology, surface alterations,
and object size). The advantages and limitations of non-
destructive analytical methods are presented in this paper
in connection with the detailed archaeometric study of three
cast, silver, rhomboid belt buckles from the second half of
the 5th century AD (Figure 1).
This study aims to determine the elemental composition
of the metal alloy and characterise the decoration
techniques (gilding, niello and garnet inlays). The
opportunities and limitations to the investigation. The
reconstruction of the organisational background of the
production; i.e., in revealing the sort of preceding use and
application phases, which attests the economic value of
the given raw materials in the period, and on the other
*Corresponding author. E-mail: mozgai.viktoria@csfk.org
ARTICLE INFO
Article history:
Received: 9th
Accepted: 12th
Key words:
polychrome precious metal object
Carpathian Basin
garnet provenance
gilding
hXRF
SEM-EDX
µ-XRD
ABSTRACT
The use of non-destructive and non-invasive analytical methods is widespread in the archaeometric
study of metal objects, particularly in the case of precious metal artefacts, from which sampling is not,
or in a limited way, allowed due to their high value. In this study, we highlight the main advantages and
limitations of non-destructive analytical methods used on three polychrome animal-style silver buckles
from the mid-to-late-5th-century Carpathian Basin. Optical microscopic observations, handheld XRF,
SEM-EDX and µ-XRD analyses were performed to determine the chemical composition of the metals
and their decoration (gilding, garnet and niello inlays), as well as the microtexture and mineralogical
composition of the niello, in order to gain a better understanding of the materials used and reconstruct
the manufacturing techniques in detail. The buckles were manufactured from relatively high-quality
silver derived from the re-use of gilded silver scrap metal and intentionally alloyed with brass or leaded
time, when copper sulphide niello is observed on a silver object. The almandine garnets most probably
originate from Southern India and Sri Lanka.
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
hand, in assessing the presence of any alloying practice and
standardisation.
From the middle of the 5th century AD, silver became
a more important raw material than gold. The combination
of these two precious metals provided a new opportunity to
material or gold plates on silver objects, typical for the
(Horváth et al.et al.
the key to identify the process of its making and fusing.
Since the discussed buckles have close relations with late
Roman military equipment in several aspects (Böhme,
microtexture of niello inlays may provide relevant new
results. Analytical data are expected to prove or disprove the
continuity of the late Roman niello recipes and technology.
In contrast with the silver alloy and niello inlay,
the garnet inlays represent a primary raw material of
natural origin. During data evaluation, no chemical
be considered. Therefore, in the case of garnet, we could
target the localisation of potential geological sources or
e.g., alluvial or mined
garnet). The proportions of major, minor and trace elements,
as well as the combination of special inclusions, have proved
Figure 1. The analysed polychrome animal-style rhomboid silver buckles. A: the buckle from Zsibót-Domolospuszta (buckle ZsD) (Janus Pannonius
provenance (buckle UP) (Hungarian National Museum, Budapest). The tongues associated with the buckle with unknown provenance (buckle UP).
D: tongue decorated with a bird’s head; E: tongue decorated with a bird and boar head (photos: E. Horváth).
0 10 cm
0 10 cm
0 10 cm
0 10 cm
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
provenances. Corresponding archaeometric investigations
are being performed worldwide, used as a reference for our
new measurements (e.g.et al.
Gilg et al.et al.
et al.et al.
studies are performed in order to extend our knowledge
about the used trade links and the organisational background
of supply in the Early Middle Ages, when garnet inlaid
jewellery had an unprecedented spread.
2. Archaeological background and analysed artefacts
The belt buckles involved in the analysis represent one of
the most emblematic metal artefacts in the middle-second
half of the 5th century AD. Their main characteristics are
the silver metal, the rhomboid shape and the decoration in
polychrome animal style (Table 1; Figure 1). All of the three
examples discussed here are from the Middle Danube Region
Table 1. The analysed polychrome animal-style rhomboid silver buckles, their decoration techniques and the number of garnet inlays. L: length; H: height;
W: width.
Provenance site Abbreviated
name
Sizes Decoration techniques Garnet inlays
(original/missing)
Chip-carving Gilding Niello inlays Garnet inlays Loop Tongue Plate
Zsibót-Domolospuszta buckle ZsD
L: 15.3 cm
X X X X –
unknown
(Hungary) buckle UP
L: 22.1 cm
X X X X
Bácsordas
(Karavukovo)
W: 5.9 cm
X X X X –
Figure 2. Distribution of cast silver rhomboid belt buckles with polychrome ornamentation in the Middle Danube Region (after Horváth et al.
previously analysed (Horváth et al.
an unknown Hungarian site.
0 10 cm
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
(hereafter called: buckle ZsD; Baranya county, Hungary;
Figure 1A), the second one from Bácsordas (hereafter called:
Serbia; Figure 1B), and the third one from an unknown
Hungarian site (hereafter called: buckle UP; Figure 1C). Two
th century (Hampel,
These examples have around a dozen close analogies
spread around by the Great Migrations (4th–5th centuries
AD) from the Middle Danube Region to Northern Italy and
Only one of them, the buckle from Gáva (Szabolcs-Szatmár-
Bereg county, Hungary; Hampel 1911; Figure 2), had been
investigated by archaeometric analysis (Horváth et al.
Using the available data, we are focusing on this buckle as a
highlighted item of comparison in our study.
Besides their common material and technological traits,
ornamentation and style. The items discussed here represent
subgroup (buckles from Bácsordas and Zsibót) are decorated
down, and a round or drop-shaped garnet inlay in the middle
of the front-plate (Figure 1A–B). In the second subgroup (the
buckle of unknown provenance), the front-plate is framed
with a bird-head frieze. In the middle of the plate, there
are garnet inlays in rhomboid shape cloisonné (cellwork)
(Figure 1C). The third subgroup (the buckle from Gáva)
represents the so-called mask buckles (Maskenschallen) that
are characterised by a mask motif and a plate closing in the
(Figure 2).
These buckles were unique prestige objects of the mid-
to-late 5th-century female aristocracy. They were produced
and worn in a short period spanning one or two generations.
between the Hunnic Period (early-to-mid 5th century AD)
th century AD) in which mass
products were more typical. In the Hunnic Period, hammered
and soldered gold objects are abundant, whereas the
of the goldsmithing traditions and their organisational
background are expected to be manifested on these objects.
The studied buckles were constructed of three, separately
cast elements and a hammered piece. The former, i.e., the
rhomboid-shaped, highly decorated front-plate (body), the
joined to each other by hinge and hook. The fourth element,
an undecorated thin back-plate, which might have served to
clamp the belt, was fastened by rivets. Among the analysed
objects, the back-plate was preserved only on buckle ZsD
(Figure 1A). Broken remains of fastening rivets suggest that
originally, similar back-plates might have been attached to
the rhomboid body of the other buckles too (Figure 1B–C).
The cast parts were manufactured by lost-wax casting,
probably prepared by applying two-part auxiliary moulds,
which represented the negative version of the main design:
the base form and most of the chip-carving ornamentation.
The wax model itself represented the positive, i.e. identical
such as cavities for inlays, holes for fastening rivets and
even some of the punch marks were created at this stage by
modelling the wax. The casting resulted in an intermediary
design of the artefact; the following post-casting process
included the decorative techniques and at the end, the
construction of the separately made elements.
Figure 3.
techniques used on the buckles resulting
gilding (yellow arrows), niello inlaying
(blue arrows), garnet inlaying (red arrows)
(photo: E. Horváth).
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
49
The characteristic polychrome decoration appears in the
of periods and geographic areas, the combination of these
two is a speciality, typical only for the mid-to-late 5th-century
Buckles B and ZsD were preserved in their original (in
some places incomplete) state during restoration, while the
broken hinge of buckle UP was reinforced with a modern
supplement (Figure 1C).
Two loose tongues were supposed as potential accessories
that belonged to buckle UP; one of these has an ornament
in the shape of a bird’s head, while the other is decorated
with a bird and boar head (Figure 1D–E). As a detailed
archaeometric analysis had not been conducted before, it
was unclear which of these tongues could originally belong
to buckle UP. The tongue with a bird’s head has the richest
niello decoration. This artefact has a unique ornamentation,
as niello mass was applied irregularly on the inner surface
of the tongue in addition to the pre-made (punched, carved)
depressions (Figure 1C).
3. Methodology
In accordance with the artefact protection regulations, only
non-destructive and non-invasive methods were allowed to
be used. In addition, the size of the objects also limited the
range of available methods and analytical equipment that
could be used, requiring the use of either handheld equipment
Furthermore, the surface and accessibility of the measurement
points were not always optimal either. The polished surface
similar to that of polished sections, whereas in the case of
post-burial alteration (e.g., corrosion processes). Post-burial
alteration did not modify the mineralogy of the inlays (e.g.,
Table 2.et al.
Analytical method Application Pros Cons
hXRF*
– chemical composition
– simultaneous, multi-element
method
– full concentration range (Z=12–92)
– major, minor, trace elements
– fast
– cheap
– portable
– non-destructive
– no sampling is needed (non-
invasive)
– in most cases, no sample
preparation is needed
– surface method (upper few tens
or hundreds of micrometres)
(inhomogeneities in the objects
due to e.g., phase segregation,
corrosion, surface treatments)
are needed)
– standardisation
SEM-EDX
– chemical composition and
microtexture
– major and minor elements
– elemental mapping
(tool marks, wear traces, etc.)
– fast
– cheap
– small spot size (1 µm)
– non-destructive
– no sampling or special sample
preparation are needed for
conductive materials (non-invasive)
– surface method (upper few
micrometres) (inhomogeneities in
the object and surface treatments)
are needed)
– sample chamber limits the size of
the objects to be analysed
– in case of non-conductive materials
(e.g. garnets, glass inlays) special
sample preparation is needed
– standardisation
µ-XRD**
– mineralogical composition (phase
– fast
– non-destructive
– no sampling or special sample
preparation is needed (non-
invasive)
sample may cover certain areas of
the detector, some higher dhkl values
cannot be detected)
single crystal, nor represent ideal
powder, therefore the measured
peak intensities are increased
crystallographic directions due to
preferred orientation
– during data evaluation only peak
positions can be used
– the smaller collimator is used, the
longer measurement time is needed
– sample size is limited
IANSA 2021 ● XII/1 ● 45–67
Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
garnet or niello), only corrosion products of the metal can
deposit on their surfaces. However, during the corrosion of
precious metal objects (e.g., silver alloys), the base metals
(copper, lead) are leached out and silver and gold is enriched
et al.
microscopy to characterise the manufacturing techniques,
tool marks and garnet inclusions. The chemical composition
of the metal alloy and the gilding was analysed by using
cleaning was performed prior to the measurements, and we
and niello inlays. The high value of the objects meant that it
was not appropriate to abrade the surface in order to expose
the underlying metal over an area of about 3 mm in diameter
2); large enough to match the XRF beam, especially
on the highly decorated, clearly visible sides; therefore, the
reverse, undecorated sides were measured. Each part of the
buckles was analysed at 1–2 points. The hXRF is not an ideal
method for analysing niello and garnet inlays. The niello
inlays are too small and could not be analysed separately
from the metal alloy. In addition, due to limitations of the
built-in calibrations of hXRF, the exact composition of the
garnet inlays could not be determined either. Therefore,
SEM-EDX was used to determine the chemical composition
and microtexture of the niello inlays as well as the chemical
composition of the garnet inlays.
As garnets are non-conductive materials, a special sample
et al.
was wrapped by using aluminium foil and carbon tapes.
The foil was pierced above the garnets, leaving a small
“window” to be carbon coated. After the coating process,
the object is unwrapped making it possible to analyse the
garnet and niello inlays and the metal alloy simultaneously.
As surface treatments (e.g.
the imaging, the analysed area was thoroughly cleaned with
more problematic in the case of SEM-EDX than in the case
of hXRF; therefore, we tried to analyse surfaces that are as
polished garnet surfaces immediately after measurements by
using ethanol and gentle manual rubbing.
The mineralogical composition of the niello inlays of the
buckles presumed on account of the SEM-EDX results was
3.1 Optical microscopy (OM)
microscopes and a Zeiss AxioScope A1 upright light
microscope equipped with a Zeiss AxioCam MRc5
microscope camera (5MP) were used.
3.2 Handheld X-ray uorescence spectrometry (hXRF)
Elements” built-in calibration, 3 mm measurement area,
calibration does not calculate the mercury content; therefore,
the presence of mercury can only be determined qualitatively
based on the hXRF spectra.
3.3 Scanning electron microscopy with energy-
dispersive X-ray spectrometry (SEM-EDX)
with Oxford Instruments INCA ISIS energy-dispersive X-ray
quantitative analysis, the following built-in factory standards
were used: MgO, Al2O3, SiO2, wollastonite, Ti, Cr, Mn, Fe,
FeS2, Cu, Ag, Au, and HgTe. Each garnet was analysed with at
least three (in the case of non-ideal surfaces more than three)
point (spots 1 µm in diameter) and one area measurements
“Excellent” results were used for interpretation. The average
in those cases where no better-quality measurements were
received. The “poor-quality” data were treated separately.
3.4 Micro-X-ray diractometry (µ-XRD)
third generation microfocus, sealed tube X-ray generator
and a curved imaging plate detector, was used. The
radiation generated
analyses. A built-in CCD camera was used to select the
measurement areas. A laser scanning readout system reads
the imaging plate detector in about 1 min. RIGAKU 2D
Data Processing software 2DP was used to record the
software was used for data processing.
4. Results
4.1 Silver alloy composition
The buckles were manufactured from high-quality silver
Figure 4). Beside the typical minor and trace elements (gold,
lead, and bismuth), zinc was detected in each of the buckles.
plate) of buckle ZsD (Figure 1A) were manufactured from
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
51
Table 3.
Description Ag Cu Au Pb Bi Sn Zn Au/Ag Bi/Pb Hg
The buckle from Zsibót–Domolospuszta (buckle ZsD)
loop 2.1 1.2 < LOD –
tongue 5.9 < LOD –
back-plate 95.4 2.9 < LOD < LOD –
front-plate 1.5 1.5 < LOD –
gilding 19.9 < LOD < LOD < LOD +
The buckle with unknown provenance (buckle UP)
loop 12.9 < LOD 1.4 –
front-plate < LOD –
tongue with bird-head 1.2 < LOD –
tongue with bird- and boar-head < LOD < LOD –
gilding 13.9 1.3 < LOD < LOD < LOD +
The buckle from Bácsordas (buckle B/K)
front-plate 91.1 1.2 < LOD 1.2 –
loop 2.5 < LOD 1.1 –
tongue 5.3 < LOD 1.2 –
gilding 14.4 1.4 < LOD < LOD < LOD +
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
52
buckle
B/K (Figure 1B) were manufactured from a rather similar
the lowest gold content among the buckles. In contrast, there
buckle UP
of the tongue with the bird’s head is similar to that of the
front-plate of the artefact, while the tongue decorated with
4.2 Niello inlays
The buckles were extensively decorated with niello inlays.
The design of the niello decoration usually shows coherency
ornamentation is mostly smooth and regular on the loop and
the tongue, while on the plate it is conceptually defective and
deteriorated in several places.
The elemental composition of the niello inlays is very
sulphide (Table 4; Figure 5). The surface of the niello inlays
of the niello shows inhomogeneities: lighter and darker
phases alternate with each other in the BSE images. In the
niello inlays of buckles ZsD and UP the irregular darker
phases a few tens of micrometres in size are Ag-Cu sulphides
or Cu-sulphides, while lighter phases are metallic silver-
copper alloy (irregular shaped, a few tens of micrometres
in size) or contamination with mercury and gold (narrow
strings along the grain boundaries, a few micrometres in
darker phases a few hundreds of micrometres in size are Ag-
Cu sulphides with higher copper content, while the irregular,
string-like lighter phases a few tens of micrometres in size
Figure 4. Composition of the three buckles based on the hXRF measurements. Black triangle: tongue with a bird’s head of the buckle UP, white triangle:
tongue with a bird and boar heads of the buckle UP. Elemental composition of silver objects from the 5th century AD is depicted for comparison (unpublished
data).
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
53
Table 4.
Description wt% → Ag Cu S Au Hg at% → Ag Cu S Au Hg
The buckle from Zsibót-Domolospuszta (buckle ZsD)
front-plate niello 1 sp5 lighter
niello 2 sp1 lighter 2.1 13.1 3.2
sp2 darker 15.1 21.2 29.9
niello 3 sp2 lighter 21.9 2.9 12.2
sp4 lighter 1.1 14.4
sp5 lighter 1.9 9.9 15.4 5.9
niello 4 sp2 lighter 5.4 11.3
sp3 lighter 12.4 5.9
loop niello 4 sp1 lighter
sp2 darker 2.5 34.5
sp3 lightest 23.9 14.2
niello 5 sp2 darker 2.5 1.3
sp3 lightest 19.5
sp4 lighter 15.3 32.2
sp1 darker 13.5 19.9
sp1 darker 12.9 1.2
sp2 lighter 44.5 15.3 41.2 31.5
niello 9 sp2 darker 34.3
sp3 lighter 52.9 25.3
sp1 darker 21.9
sp3 lightest 24.9 12.3 42.9
sp4 lighter 45.9 45.4 32.9
niello 13 sp1 darker 2.1
sp2 lighter 35.4 3.4
sp3 lighter 31.4 12.3 25.5 34.3 4.3
sp4 lightest 2.4 15.9
niello 15 sp1 darkest 19.3 4.5 33.1
sp2 darker 52.3 31.3
sp3 lighter 31.1 23.1 4.2
tongue niello 1 sp3 lighter 21.5
sp4 darker 59.9 21.5
sp5 lighter 13.3 43.3
niello 3 sp2 darker 19.3 25.9
sp3 lighter 1.4 2.4
sp4 darker 9.1
sp5 lighter 3.3 5.4 2.9
niello 5 sp2 lighter 1.1 1.9
sp3 darker 15.2
sp4 lighter 2.1 3.5
sp5 darker 23.2
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
54
Description wt% → Ag Cu S Au Hg at% → Ag Cu S Au Hg
The buckle with unknown provenance (buckle UP)
front-plate niello 1 sp3 lighter 52.4
sp4 darker
niello 2 sp2 darker 21.3 45.5 33.2
sp3 lighter 44.5 39.5
sp1 lighter 35.2
sp2 darker 53.4 32.1 31.3
sp4 lighter 39.3
sp5 darker 31.3
sp1 lighter 51.3 34.9
sp2 lightest 2.1 5.9 4.2
sp3 lighter 41.3 42.2 24.5 42.4 33.1
sp5 lighter 15.4
darker 33.5 45.3 35.9
The buckle from Bácsordas (buckle B/K)
plate niello 3 sp1 darker 15.3 34.2
sp3 lighter 12.1 14.1
sp1 lighter 13.2 32.1
sp2 lightest 94.9 3.9 1.2 3.9
sp4 darker 39.4 32.9
niello 4 sp1 darker 39.1 23.4
sp2 darker 35.2 14.5
sp3 lighter 43.9 31.5
sp3 lightest 95.4
sp4 darker 33.2
sp5 lighter 49.9 11.4 23.9 52.3
niello 5 sp1 lighter 9.2 3.1
sp2 darker 43.4 24.3
sp3 darkest
niello 4 sp1 darker 39.3 14.3
sp2 lighter 5.3
sp1 darker 33.5
sp2 lighter
sp1 lighter 14.3 19.2
sp3 darker 29.9
sp1 lighter 4.4
sp2 darker 19.1 32.5
sp4 darker 29.3 12.1
sp5 lighter 39.9 24.2
Table 4.Continuation)
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
55
As these pieces are mounted, it proved impossible to analyse
the full range of mineral inclusions in the individual garnets.
This limited access is a general problem; loose, unmounted
their morphology. Most of these are accessory minerals
(e.g., rutile needles, ilmenite plates, isometric zircon, and
xenomorph quartz crystals) that are not indicators for the
source rocks. From this aspect, kyanite crystals and curved
needles of sillimanite, detected in a group of the slabs, are
of greater importance since they indicate medium- to high-
grade metamorphism at medium pressure (Figure 9A–B)
(Spear, 1995). One typical combination of inclusions occurs
extensively in the garnets of buckle ZsD: these are extremely
the large, clear apatite crystals in the garnets of the tongue
with the bird and boar heads, belonging to buckle UP.
From among the 55 garnet inlays preserved in the settings
of the buckles, 45 pieces were analysed by SEM-EDX.
Based on the chemistry, the garnets used for inlays are
from the pyralspite (pyrop-almandine-spessartine) series,
namely almandine with varying Ca, Mg and Fe contents
Mg concentrations, often referred to as intermediate
The results of the µ-XRD measurements proved the
presence of stromeyerite (AgCuS), digenite (Cu9S5)
and metallic silver in the niello inlays of the buckles
boar heads was studied only by using µ-XRD and revealed
that the niello inlay is composed not only of stromeyerite
and metallic silver, but also jalpaite (Ag3CuS4) and acanthite
(Ag2
4.3 Gilding
The buckles were extensively gilded. The gold content of the
on the hXRF measurements (Table 3), indicating a rather
thick gilding. The thickness of the gilding is estimated to be
around several tens of micrometres based on BSE images
4.4 Garnet inlays
Red garnet inlays played an important role in the decoration
of the buckles. Highlighting the eyes and mouth of the bird
precious metals and niello (Figure 3). The prevailing shape
rectangular, lunula- and drop-shaped pieces are also present.
Figure 5.
1.55CuS-Ag1.5CuS); Skinner et al. CuS-
Ag1.25CuS), and Frueh (1955) and Tokuhara et al.Cu1.1S-AgCuS), respectively.
IANSA 2021 ● XII/1 ● 45–67
Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
Figure 6. Backscattered electron images of the niello inlays and gilding of the buckles. A–B: niello inlays were put in previously carved recesses, the surface
pyrope-almandine crystals (Gilg et al.
on the buckles.
5. Discussion
5.1. Silver alloy composition
The buckles were manufactured from relatively high-quality
the general trend that during the 5th-century AD a gradual
debasement of silver alloys occurred towards the end of
the century (Figure 4) (Horváth et al.et al.,
th century AD is characterised
with high-quality silver alloys with low Au, Pb and Zn
and varying Bi content similar to late Roman silver alloys
et al.
et al.
et al.et al.et al.,
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
Figure 7. Typical µ-XRD patterns of the niello from the buckles. A: tongue of buckle ZsD; B: loop of buckle ZsD; C: tongue with a bird’s head of buckle
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
Figure 8. Typical XRF spectra of the gilded areas of the buckles.
Figure 9.
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
59
Figure 10. Ternary plots showing the composition of the garnets from the buckles based on the cation occupancy of the X site in the garnet structure
calculated from the SEM-EDX data (after Grew et al.
and boar heads of buckle UP.
et al.
alloys with high Cu, Pb, Zn and Sn content, reaching even the
1:1 Ag:Cu ratio (Figure 4), are more typical for the end of the
5th century AD (Horváth et al.et al.
Pure silver is too soft for making silver objects of use,
bend and wear easily. The most common alloying metal in
silver is copper, which improves the mechanical properties
of soft silver (e.g., increases strength and durability). During
silver extraction, the copper content could be reduced to even
The measured elements other than silver and copper are
naturally occurring, unintentionally or intentionally added
elements, deriving from the silver ore or from the copper
In antiquity, the main source of silver was silver-
silver ores were roasted, melted and cupelled during silver
from impurities (mainly from antimony, arsenic, tin, iron,
and zinc; less well from copper, gold and bismuth). The
volatile elements (antimony, arsenic, mercury, tin and zinc)
disappear from molten silver during cupellation (Pernicka,
et al.
pure copper, but brass was added to the silver as an alloying
the melting point. The more copper is added to molten
silver; the more yellowish tint the alloy will have. This can
be overcome by adding zinc to the alloy, which will act as a
addition of zinc also prevents molten silver from oxidation and
bubbling, and enhances tarnish-proofness resulting in a much
ductility making tin-enriched silver alloys more ideal for sheet
th-century
alloyed the silver with Zn (or Sn), beside copper.
If silver originates from silver-bearing lead ores (galena,
anglesite or cerussite), the lead content in the silver alloy
indicating that leaded copper or leaded brass was used for
alloying.
Bismuth is a good geochemical indicator that helps
identifying the provenance of silver objects, as its concentration
remains relatively constant during cupellation (Pernicka and
et al.
Based on experiments, bismuth is oxidised only in the very
last stages of cupellation and, therefore, bismuth in silver
objects is correlated with the degree of cupellation. However,
initial Bi content of the silver-bearing lead ores (L’Héritier
et al.
consistent, except the back-plate of buckle ZsD (Figure 4),
which is typical for the silver alloys from the middle and end
of the 5th century AD (Horváth et al. et al.,
5th century AD and from late Roman times. The latter usually
et al.,
et al. et al.
Mozgai et al.et al.
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
Table 5.
Description No. SiO2Al2O3MgO CaO MnO FeO
The buckle from Zsibót-Domolospuszta (buckle ZsD)
front-plate grt 1 3 31.5±1.4
grt 2 1 3.3 31.4
grt 3 2 3.1
grt 4 4
grt 5 5
1 25.9 2.2 43.4
3
4 41.1±1.5
1 5.4 2.3
grt 11 4
grt 12 2 22.3 3.3 31.4
tongue grt 1 2 35.3 3.1 2.4 33.2
grt 2 1 21.3 4.4 1.4 32.9
The buckle with unknown provenance (buckle UP)
front-plate grt 1 1
grt 2 4
grt 3 1 5.3 2.1
grt 4 1 29.9
grt 5 1 5.4 1.4 32.9
4
1 1.3 1.2 34.9
1 31.5
grt 9 3
2
grt 11 1
grt 12
grt 13 1 32.1
grt 14 1 1.4 2.3 29.3
grt 15 1 21.1 3.3
4
grt 19 4
2 31.4
grt 21 1 21.5 1.4 1.2 29.5
grt 22 3
grt 23 3
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of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
Description No. SiO2Al2O3MgO CaO MnO FeO
tongue with bird- and boar-head grt 1 1 4.5
tongue with bird-head grt 1 1 39.1 21.3 1.4
The buckle from Bácsordas (buckle B/K)
front-plate grt 2 4
grt 3 3
grt 4 1 21.4 12.3 3.3
grt 5 3
2 19.9 5.9 1.3
2 1.3 29.9
1 1.5
grt 9 2 41.1 11.3 2.1 23.2
4
Table 5.
Continuation)
5th century AD may be the result of gradual recycling and
Gold is completely miscible with silver. During
metallurgical processes, the gold content of the silver
does not change radically (L’Héritier et al.
are possible for higher gold concentrations, e.g., remnants
of former gilding, the re-use of scrap gilded silver, or the
use of gold-silver ores. In the case of buckles, as recycling
was proven by other elements as well, it is safe to say that
most probably re-used scrap gilded silver was utilised for
manufacturing.
The polychrome animal-style silver buckle from Gáva,
previously analysed by Horváth et al.
from Gáva, indicating the use of leaded bronze or gunmetal
for alloying.
manufacture. The shortage of raw materials towards the end
of the 5th century AD resulted in the re-use and recycling
alloy compositions, even within one single object, indicate
that there was no conscious or standardised alloying practice
adopted by 5th-century AD goldsmiths.
The only undecorated back-plate that was analysed in the
of the buckle and shows similarities to late Roman silver
alloys (high silver content, relatively low gold, lead and
copper content, and no zinc) (Figure 4). It may have been
manufactured by melting Roman silver objects directly,
without further alloying.
5.2 Niello inlays
The bluish-black niello has been widely used to decorate
silver, gold and copper-based alloy objects. Chemically,
niello is composed of the sulphide of one or more metals,
fused or inlaid into a recess carved into the metal surface.
The composition of niello changed over the course of time
depending on what type of metal it decorated (Rosenberg,
et al.
et al.
Niello technique was much used in the early Middle
Ages, but there are still uncertainties concerning the niello
technique (exact composition, preparation and application)
used in this particular period. It has been widely accepted
that during the Roman period niello was generally composed
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
of the sulphide of only one metal, namely the same as the
metal it decorates: silver sulphide (acanthite Ag2S) for silver
objects and mixtures of copper sulphides (chalcocite Cu2S,
digenite Cu9S5 and covellite CuS) for copper-based alloy
objects. Intentional use of binary silver-copper sulphide
niello (stromeyerite AgCuS) is assumed to have started
only at the end of the 5th century AD (Moss, 1953; Dennis,
et al. et al.,
Recent studies have proved that silver-copper sulphide niello
(reaching the composition of stromeyerite) was already
being used in Roman times (Mozgai et al.
The studied buckles were decorated with silver-copper
µ-XRD measurements proved the presence of stromeyerite
(AgCuS), digenite (Cu9S5) and metallic silver. The niello
inlays of the buckle from Gáva are also silver-copper sulphides
with sporadically detected lead and tin contents, which was
interpreted as niello prepared from debased silver (Horváth
et al.
the 5th century AD proved the presence of mixed silver-copper
et al.
et al.
silver objects, reaching even the composition of pure copper
sulphide, has not yet been described.
The use of silver-copper sulphide niello by the craftsmen
can be threefold (Mozgai et al.
use, when the goldsmith was not aware of the copper content
of the silver alloy used for the preparation of the niello;
(ii) intentional use, when the silversmith was aware of the
variable copper content of the silver alloy available to him,
but did not care; and (iii) technological innovation, when the
silversmith intentionally prepared a starting silver-copper
alloy using a recipe to gain either technological or economic
The short supply of metals in the period could have led to
a wider use of cheaper materials and also to a more frequent
sulphides look exactly the same. The craftsman clearly felt
no need to distinguish between them and he did not bother to
The presence of metallic silver in the niello inlays can be
interpreted as not all the silver metal reacted with sulphur
during preparation or the niello decomposed at elevated
temperatures, as silver-copper sulphides start to decompose
to elemental silver in an oxidising atmosphere before
et al.
Previous studies on objects decorated with silver-
copper sulphide niello from the early medieval ages
(5thth century) were interpreted as their niello not
malleable at room temperature, and even more when
heated; experiments proved that it is possible to inlay
niello in solid form, softening them a little by heating
the literature for the application of silver-copper sulphide
niello in solid form: either in powder form or as compact
strips. In the case of the powder form the craftsman has to
and to reach a compact polishable surface (Moss, 1953;
et al. et al.
rubbing heated niello particles into the recesses during
become completely compacted together and did not leave
a homogeneous sulphide inlay (Stemann-Petersen, 1995;
buckles do not look even and compact enough.
The patches of mercury and gold on the surface of the
niello inlays are the remnants of gilding, during which
mercury or gold amalgam spread over the surface of the
niello, as well as reacting with the material of the niello
forming silver amalgam.
5.3 Gilding
The buckles were extensively gilded with a relatively thick
gold layer. Mercury was detected in the gilding of the
on objects from the 5th century AD have also proved the
et al.
The buckle from Gáva was also decorated with this type of
gilding (Horváth et al.
Fire gilding was most probably invented in China in the
4th
mercury and the resulting gold amalgam was rubbed on to the
cleaned metal surface, after the object was heated for a few
avoid any overheating of the object: if silver is overheated,
the gold will discolour or even disappear into the substrate.
porous, matte gilded layer will form, which then needs to
be burnished. This technique is still used in Nepal (Oddy,
is mentioned as a rare and costly method by Pliny in the
1st century AD, but became the standard method of gilding in
the 3rd–4th centuries AD and continued in use throughout the
Migration Period and medieval Europe until the invention
of electroplating in the mid-19th
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to the metal surface to be gilded and then lay pieces of gold
leaf on top. The gold leaf dissolves in mercury creating a
gold amalgam in situ, after which the object is heated and
Fire gilding superseded gold-plating during the second
half of the 5th century AD (Mozgai et al.
et al.
sophisticated gilding method indicating the development of
goldsmithing skills during the 5th century AD.
5.4 Garnet inlays
garnets, were widespread during the Hellenistic, Roman and
the archaeological material of the Carpathian Basin, garnet
inlay decoration was a characteristic feature over around
three centuries, from the Hunnic Period through the age
of the Gepidic and Langobardic Kingdoms until the Avar
inlays have come into focus since the end of the last century.
or at one-time, mine districts facilitated their increasingly
detailed geochemical characterisation (recently: Schmetzer
et al.et al.,
and trace elements) with similar datasets of recent geological
samples has proved to be the key to the localisation of
potential geological sources.
The garnets in the buckles are almandine, and on
rare occasions intermediate pyrope-almandine, from the
pyralspite series. The chemical composition of the garnet
slabs was compared to the chemical composition of garnets
from those deposits which were certainly known and used
in the Migration Period, as attested by the analyses of other
contemporaneous objects. The chemical composition and the
characteristic inclusion assemblages revealed that European
deposits can be excluded as possible sources (Figure 11).
(Cluster A) and to a heterogeneous group (Group X)
requiring further division (Gilg et al.
and only a few garnets belong to Group X. Contrarily, the
inlays on buckle ZsD are mainly Group X garnets and only
a few Cluster A garnets are present (Figure 11). The garnet
inlays on the buckle from Gáva belong to both Cluster A and
Group X (Horváth et al.
Cluster A garnets, generally comprised of chromium-
bearing almandines originating most probably from Southern
et al.et al.
Carpathian Basin, applied from the beginning of the Hunnic
Period (Horváth et al.
with a higher magnesium content, originate from the placer
Figure 11.
et al.et al.
represents garnets with variable chemical and gemmological characteristics that derive from various, unknown deposits and cover possible new clusters:
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Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
et al.
Gilg et al.
suggesting that a number of primary sources may be
involved, and the group comprises, most probably, several
clusters (Gilg et al.
et al.et al., in
preparation). Based on the chemistry, garnets from Ratnapura
(Sri Lanka) and Elahera (Sri Lanka) deposits might be
investigations are in progress on the mineral inclusions of
the garnets of these two deposits and further potential source
materials (Gilg, personal communication). Most of the
garnets from buckle ZsD may originate from a third cluster
based on the chemical composition and especially on the
characteristic mineral inclusions (Figure 9C–D; Figure 11),
but investigations on geological samples are required to
prove this hypothesis. Prospective measurements of the trace
minor element compositions.
Group X and Cluster A garnets were predominant all over
Europe during the 5th century AD. As Sri Lanka and Southern
India are close to each other geographically, most probably
their garnets were transported via common long-distance
originating from Northern India, were observed on the buckles.
Northern Indian garnets became commonly used only from
th century AD (Gilg et al.
6. Conclusion
Three polychrome animal style silver buckles, dated to the
second half of the 5th century AD, were analysed in order to
determine the elemental composition of their metal alloys and
to explore techniques of their manufacture and decoration
(gilding, niello and garnet inlays). Non-destructive and
non-invasive analytical methods, such as handheld XRF,
SEM-EDX and µ-XRD, were successfully used, while their
limitations – such as using a special preparation technique
needed for the SEM-EDX analysis of mounted garnets;
in situ microtextural and mineralogical analysis of the niello
inlays, and geometric and calibration limitations – were also
kept in mind.
The buckles were manufactured from high-quality silver,
but a gradual decrease in the silver quality is evident towards
the end of the 5th century AD. The elevated lead and zinc
contents indicate that silver was intentionally alloyed with
shortage of raw material caused mainly by the decrease of
primary mining.
Each buckle is richly decorated by chip-carving, gilding,
niello and garnet inlaying. The presence of mercury indicates
composed of mixed silver-copper sulphides with relatively
high copper contents, even reaching the composition of pure
copper sulphide. Copper sulphide niello on a silver object has
not yet been reported before. The presence of metallic silver
the niello’s surface suggest that it was made by an unskilled
craftsman. Based on their chemistry and mineral inclusions,
the almandine garnets of the buckles most probably derive
from Southern India and Sri Lanka.
It is unequivocal from the similarity of the elemental
composition of its silver alloy and garnet inlays to the other
parts of the buckle that the tongue with bird’s head belonged
to buckle UP originally. The tongue with bird and boar heads
could have been the accessory of another buckle.
The buckles could not be related to the work of a single
goldsmith, or workshop; it is much more likely that these
are products from workshops that operated in the same
region and followed, more or less, similar practices. The
localisation of the workshops remains an open question, but
the late Roman metalwork in the provinces along the limes
must have had an impact. Based on the prevalence of the
hypothetically localise the workshops near the centres of
barbaric power (Germanic tribal kingdoms) in the former
remains to be done in the light of further evidence.
Acknowledgements
Tóth (IGGR RCAES ELRN), Máté Szabó (IGGR RCAES
ELRN), Péter Németh (IMEC RCNS ELRN), Zsuzsanna
Hajnal ((Hungarian National Museum, Budapest), Gergely
Kovaliczky (Janus Pannonius Museum, Pécs) and Marianna
Dági (Museum of Fine Arts, Budapest).
References
The Garnet Millennium: The Role of Seal Stones
in Garnet Studies. In: Ch. Entwistle and N. Adams, eds. “Gems of
Heaven”: Recent Research on Engraved Gemstones in Late Antiquity
c. AD 200–600.
ALLAN, J. W., Persian Metal Technology 700–1300 AD. London:
Ithaca Press.
ANHEUSER, K.
Gilding Techniques. The Journal of The Minerals, Metals & Materials
Society
and Social Implications. Stockholm: Kungliga Vitterhets Historie och
Antikvitets Akademien, Almqvist & Wiksell International.
AXBOE
carving Ornament. Universitetets Oldsaksamlings Skrifter, 5, 31–42.
IANSA 2021 ● XII/1 ● 45–67
Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
E.,
analytical method for polished stone tools and gems: opportunities and
limitations. Archeometriai Műhely
BIERBRAUER, V. Die ostgotischen Grab- und Schatzfunde in
Italien
BÖHME, H. W., Germanische Grabfunde des 4. und 5.
Jahrhunderts zwischen unterer Elbe und Loire. Studien zur Chronologie
CALLIGARO, T., COLINART, S., POIROT, J.-P., SUDRES, C.,
Combined external-beam PIXE and µ-Raman characterisation of
garnets used in Merovingian jewellery. Nuclear Instruments & Methods
in Physics Research Section B – Beam Interactions with Materials and
Atoms
Contribution à l’étude des grenats mérovingiens (Basilique de Saint-
Denis et autres collections du musée d’Archéologie nationale, diverses
collections publiques et objects fouilles récentes). Antiquités Nationales,
Le commerce des grenats à l’époque
mérovingienne. Archéopages, 5. Les archéologues face à l’économie,
COWELL, M., HOOK, D.
C. Johns, ed. The Hoxne Late Roman Silver Treasure: gold jewellery and
silver plate.
CRADDOCK, P., COWELL, M., HOOK, D., HUGHES, M., LA NIECE,
S., MEEKS, N.,
metalwork from the Carpathian Basin. The British Museum Technical
Research Bulletin
Archäologische Denkmäler der Gepiden in
Mitteldonaubecken
National Museum.
Niello: a technological study. In: Papers presented
by trainees at the Art Conservation training programs conference.
A Janus
Pannonius Múzeum Évkönyve,
hoard from Vinkovci, Croatia – a preliminary technological overview.
Historical Metallurgy
Le trésor d’argenterie gallo-romaine de Thil (Haute-
Garonne) dit « Trésor de Caubiac. In: F. Baratte and N. Duval, eds.
Argenterie romaine et byzantine: actes de la table ronde, Paris 11–13
octobre 1983 Archéologie de l’antiquité tardive. Paris: De Boccard, pp.
FORBES, R. J., Studies in Ancient Technology. Volume VIII. –
Metallurgy in Antiquity Part 1: Early metallurgy; the smith and his tools;
gold, silver and lead, zinc and brass. Leiden: Brill Ltd.
FRUEH, A. J., 1955. The Crystal Structure of Stromeyerite, AgCuS:
A Possible Defect Structure. Zeitschrift für Kristallographie,
GENRICH
Kunde
(Neue Folge).
Vom Karfunkelstein.
In: L. Wamser, ed. Karfunkelstein und Seide. Neue Schätze aus Bayerns
Frühzeit.
GILG, H. A., SCHMETZER, K., SCHÜSSLER, U.,
Byzantine Engraved Almandine from the Garibpet Deposit, Telangana
State, India: Evidence for Garnet Trade along the Ancient Maritime Silk
Road. Gems & Gemology
GILG, H. A., SCHÜSSLER, U., KRAUSE. J., SCHULZ, B.,
The use of phosphate inclusions in origin determination of ancient and
medieval garnets. In: 36th International Gemmological Conference –
Book of Abstracts, Nantes, pp. 41–43.
GREIFF, S.
rheinfrankischer Provenienz. Jahrbuch des Römisch-Germanisches
Zentralmuesum,
Technological Implications of Debased Alloy Compositions with Zinc,
Tin and Lead. In: B. Tobias, ed. Die Archäologie der Frühen Ungarn
Chronologie, Technologie und Methodik. Internationaler Workshop des
Archäologischen Instituts der Ungarischen Akademie der Wissenschaften
und des Römisch-Germanischen Zentralmuseums Mainz in Budapest
am 4. und 5. Dezember 2009.
GREIFF, S.,
Silberkanne. In: A. Kaufmann-Heinimann and M. Martin, eds. Die
Apostelkanne und das Tafelsilber im Hortfund von 1628. Trierer
Silberschätze des 5. Jahrhunderts. Trier: Rheinisches Landesmuseum,
GREW, E. S., LOCOCK, A. J., MILLS, S. J., GALUSKINA, I. O.,
GALUSKIN, E. V., HÅLENIUS, U.,
of the garnet supergroup. American Mineralogist
jalpaite. The American Mineralogist,
HALL, E. T., Archaeometry,
Alterthümer des frühen Mittelalters in Ungarn I–III.
Braunschweig: F. Vieweg und Sohn.
HAMPEL, J., 1911. A gávai sírlelet. Archaeologiai Értesítő
HOOK, D., CALLEWAERT, M.,
examination and analysis of some of the Roman silver artefacts from the
Coleraine treasure. In: F. Hunter and K. Painter, eds. Late Roman Silver:
The Traprain Treasure in Context. Edinburgh: Society of Antiquaries of
the Carpathian Basin: the Hunnic and Early Merovingian Periods.
Dissertationes Archaeologicae ex Instituto Archaeologico Universitatis
de Rolando Eötvös nominatae
Provenance study on a collection
of loose garnet from a Gepidic period grave in Northeast Hungary.
Archeometriai Műhely
of the polychrome metalwork from Gáva (North-East Hungary). In:
M. Hardt and O. Heinrich-Tamáska, eds. Macht des Goldes, Gold der
Macht. Herrschafts- und Jenseitsrepräsentationen zwischen Antike und
Frühmittelalter im mittleren Donauraum. Weinstadt: Forschungen zu
Fine metalwork between two periods: tracing changes in
goldsmithing tradition and craft organisation in the mid-to-late 5th century
Carpathian Basin by the investigation of polychrome goldsmiths’ works.
In: 5th International Conference Archaeometallurgy in Europe 2019 –
Book of Abstracts. Miskolc, p. 23.
in preparation. Avar Period
Garnet Jewellery from the Carpathian Basin – the Case of the Garnet
Raw Material. In: S. G, A. Hilgner anduast, eds. Universal
Framework – Changes in the cultural signicance of early medieval
gemstone jewellery considered against the background of economic
history and the transfer of ideas and technologies.
HUGHES, M. J., HALL, J. A.
Roman and Sassanian silver plate. Journal of Archaeological Science
321–344.
Die Skiren im Karpatenbecken, ihre Wohnsitze und
ihre materielle Hinterlassenschaft. Acta Archaeologica Academiae
Scientiarum Hungaricae, 35, 95–131.
KOLITSCH, U.,
mckinstryite. Mineralogical Magazine,
LANG, J., Baratte,
J. Lang, S. La Niece and C. Metzger, eds. Le Trésor de Carthage:
contribution à l’étude de l’orfévrerie de l’antiquité tardive. Paris: CNRS
LANG, J., HUGHES, M.,
Aspects of Construction and Decoration. In: R. Hobbs, ed. The Mildenhall
Treasure: Late Roman Silver Plate from East Anglia. London: British
IANSA 2021 ● XII/1 ● 45–67
Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
other Items. In: H.A. Cahn and A. Kaufmann-Heinimann, eds. Der
spätrömische Silberschatz von Kaiseraugst. Derendingen: Basler
LA NIECE, S., The
Antiquaries Journal
LECHTMAN, H. N.,
from the Old and the New Worlds. In: R. H. Brill, ed. Science and
Archaeology
Z., ZALAR, A.,
Surface and Interface Analysis
F.,
production. Journal of Archaeological Science,
Journal
of Archaeological Science,
LOCOCK, A. J.,
into end-member components, and a synopsis of the crystal chemistry of
natural silicate garnets. Computers & Geosciences
MGarnet chemistry from
the Slöinge Excavation, Halland and additional Swedish and Danish
excavations – comparisons with Garnet Occurring in a Rock Context.
Journal of Archaeological Sciences,
MASS, J., MATSEN, C.,
A.N. Shugar and J.L. Mass, eds. Handheld XRF for art and archaeology.
Studies in Archaeological Sciences, 3. Leuven: Leuven University Press,
Materials and Manufacture in Ancient
Mesopotamia. Oxford: The Evidence of Archaeology and Art, BAR
MOSS, A. A., 1953. Niello. Studies in Conservation,
elemental composition of Roman silver artefacts: preliminary results.
In: I. Montero-Ruiz and A. Perea, eds. Archaeometallurgy in Europe IV.
(RIGAKU DMAX RAPID II) in the archaeometric analysis of
archaeological artefacts – Case studies of metal objects. Archeometriai
Műhely
of polychrome gold and gilded silver brooches from the 5th century AD
Carpathian Basin. In: YRA 2019 Paris: Maison Archéologie-Ethnologie
(MAE, Nanterre), p. 1.
Pannonia (Hungary). Archaeological and Anthropological Sciences,
vizsgálatában. Possibilities and limitations of the use of handheld XRF in
the archaeometric study of Roman silver platters. Archeometriai Műhely,
destructive handheld XRF study of archaeological composite silver
objects – the case study of the late Roman Seuso Treasure. Archaeological
and Anthropological Sciences
Tierdarstellungen und der germanische Tierstil I im
Gebiet der Mittleren Donau (3.–6. Jahrhundert n. Chr.). Állatábrázolások
és az I. germán állatstílus a Közép-Duna-vidéken. (Kr. u. 3–6. század).
Monumenta Germanorum Archaeologica Hungariae, 5, Budapest:
Hungarian National Museum.
NEWMAN, R., DENNIS, J. R., FARREL, E
niello. Journal of the American Institute for Conservation
NORTHOVER, P., LA NIECE, S.,
In: A.I. Shortland, I. Freestone and T. Rehren., eds. From Mine to
Microscope: Advances in the Study of Ancient Technology. Oxford:
Oxbow Books, pp. 145–154.
Process in the Old World. Gold Bulletin
N. Duval, eds. Argenterie romaine et byzantine: actes de la table ronde,
Paris 11–13 octobre 1983 Archéologie de l’antiquité tardive. Paris: De
Boccard, pp. 9–21.
1991. Gilding: an outline of the technological history of the
plating of gold on to silver or copper in the Old World. Endeavour, New
Series, 15(1), 29–33.
1993. Gilding of metals in the Old World. In: S. La Niece, P.
Craddock, eds. Metal Plating and Patination – Cultural, Technical and
Historical Developments. Oxford: Butterworth-Heinemann Ltd., pp.
A History of Gilding with Particular Reference to Statuary.
In: T. Drayman-Weisser, ed. Gilded Metals – History, Technology and
Conservation. London: Archetype Publications, pp. 1–19.
of Niello Decoration on Gold, Silver and Bronze in the Antique and
Mediaeval Periods. Studies in Conservation
Note sur l’origine des grenats
A. Bollók, G. Csíky and T. Vida, eds. Between Byzantium and the steppe:
archaeological and historical studies in honour of Csanád Bálint on
the occasion of his 70th birthday. Budapest: Institute of Archaeology,
Research Center for the Humanities, Hungarian Academy of Sciences,
PERNICKA, E.,
of ancient silver and gold. In: H.H. Meller, R. Rish and E. Pernicka,
eds. Metals of power – Early gold and silver – Part 1. Halle (Saale):
PERNICKA, E., BACHMANN, H. G.,
Untersuchungen zur antiken Silbergewinnung in Laurion – III. Das
Verhalten einigen Spurenelemente beim Abtreiben des Bleis. Erzmetall,
, eds. The Oxford
Handbook of the Merovingian World
Mineralogische Untersuchungen zur
Herkunft der Granate merovingzeitlicher Cloisonnéarbeiten. Germania,
Spätrömische Kunstindustrie. Wien. Österreichische
Staatsdruckerei.
ROSENBERG, M., , ed. Geschichte der
Goldschmiedekunst auf technischer Grundlage. Frankfurt a. M.: Verlag
Beiträge zur
allgemeinen und vergleichenden Archäologie
SCHMETZER, K., GILG, H. A., SCHÜSSLER, U., PANJIKAR, J.,
in India at the Arikamedu historical site and their source at the Garibpet
deposit. The Journal of Gemmology
Economic Geology
SKINNER, B.J., JAMBOR, J.L., ROSS, M.
Economic Geology
SPEAR, F. S., 1995. Metamorphic Phase Equilibria and Pressure-
Temperature-Time Paths. Washington: Mineralogical Society of America.
STEMANN-PETERSEN, K., 1995. Danish niello inlays from the Iron
Age – A technological investigation. Journal of Danish Archaeology, 12,
133–149.
STEMANN-PETERSENrd to 12th century niello
inlays found in Denmark. In: Archaeometallurgy in Europe: International
Conference: 24–25–26 September 2003 Milan, Italy: Proceedings Vol. 1.,
IANSA 2021 ● XII/1 ● 45–67
Viktória Mozgai, Eszter Horváth, Bernadett Bajnóczi: Possibilities and Limitations of Non-Invasive Analytical Methods in the Examination
of Garnet- and Niello-Inlaid Precious Metal Objects – Case Study of Three Polychrome Animal-Style Silver Buckles from the 5th-Century Carpathian Basin
SCHWEIZER, F., 1993. Nielle byzantine: étude de son evolution. Geneva,
late antique Nubia, Sudan. Archaeometry
3CuS2 from the elements
under hydrothermal conditions. Journal of the Ceramic Society of Japan,
Metallurgy in Archaeology. London: Edward
Arnold Publishers.
treasure of Late Roman silver plate: preliminary report. Journal of Roman
Archaeology
2S oxidation in air. Journal of
Thermal Analysis and Calorimetry
