U.P.B. Sci. Bull., Series , Vol. , Iss. , 20 1 ISSN 1223 -7027 [620591]

U.P.B. Sci. Bull., Series …, Vol. …, Iss. …, 20 1 ISSN 1223 -7027
EVALUATION OF SOME R OMANIAN ARTEFACTS BY SEM

Brandusa GHIBAN1, Ionut Valentin DRAGOIESCU2

Preservation of the cultural and metal artefacts, is a
necessary response to a dual requirement to protect and ensure the
continuity of their study. Cultural goods and objects discovered in
archaeological sites on primary information they disclose specialists
comes from research materials, and functionality of those pieces.
Anthropic stage, known as the ending period the use of the item and
depositing it in the soil, the key to understanding the changes in the
physical degradation, chemical and biological. Information potential
transmitted stems from the interpretation stage of degradation object
when digging out, leading us to a better understanding of the
internal s tructure and external cultural good at the time of removal
from service thereof, and knowledge of processing goods at the time
of exit from service. Geological factors such as soil type, pH,
temperature, radiation and the hydrologic conditions (water flow
through the layers of soil drainage, soil chemical composition)
contribute to the corrosion of metal objects.
This paper aims to assess excavated artefacts belonging to
the Romanian Dacian period by stereomacroscope and scanning
electron microscope analys is, thereby enriching the database.

Keywords : artefacts, Dacian period, scanning electron microscopy.
1. Introduction
Preservation of the cultural and metal artefacts, is a necessary response to a
dual requirement to protect and ensure the continuity of t heir study. Cultural
goods and objects discovered in archaeological sites on primary information they
disclose specialists comes from research materials, and functionality of those
pieces. Anthropic stage, known as the ending period the use of the item and
depositing it in the soil, the key to understanding the changes in the physical
degradation, chemical and biological. Information potential transmitted stems

1 Prof., Dept. of Metallic Materials Science , University POLITEHNICA of Bucharest, Romania , e-
mail: [anonimizat]

2 Historic ., National Museum of Romanian History , Romania , e-mail:
[anonimizat]

Brandusa Ghiban, Valentin Dragoiescu

from the interpretation stage of degradation object when digging out , leading us to
a better unde rstanding of the internal structure and external cultural good at the
time of removal from service thereof, and knowledge of processing goods at the
time of exit from service. Geological factors such as soil type, pH, temperature,
radiation and the hydrolo gic conditions (water flow through the layers of soil
drainage, soil chemical composition) contribute to the corrosion of metal objects
[15].
Romania has a temperate continental climate transition, specific to Central
Europe, with four distinct seasons. Local differences are caused by altitude and by
slight oceanic in the west of the Mediterranean in th e southwest and continental
east. In winter the average temperature falls below – 3°C and in summer is
between 22°C and 24°C. Average annual temperatures are 11 °C in the south and
8°C in the north. Minimu m temperature recorded was – 38.5°C at Bod in the
Brasov Depression, and the maximum is + 44.5°C at Ion Sion Baragan. Average
annual rainfall decreases slightly from west to east. Average annual rainfalls total
637 mm, with higher values in the mountain (1400 -1000 mm/year) and lowest in
Baragan (500 mm/year), Dobrogea and the Danube Delta (400 mm /year). All
these climate conditions are reflected in excavated artifacts, which immediately
after excavation are much corroded.
This paper aims to a ssess excavated arte facts belonging to the Romanian
Dacian period by stereomacroscope and scanning electron microscope analy sis,
thereby enriching the database.

1. Materials and Experimental Procedure
The present paper analyzed two Romanian excavated Dacian artifacts,
respectively: a piece of breastplate and a piece of sheat, with the macroscopic
appearance shown in figure 1.
Stereomacroscopic anlysis was made on an OLYMPUS type stereomicrosope
type SRZ 57, equiped with QuickMicroPhoto 2.2 image software.
Electron microanalyses were performed with a SEM , type XL-30-ESEM TMP
electronic microscope; stage Peltier; system control software packet and
equipment analysis. equipped w ith EDX analyzers. All components of the
artifacts were documented in Secondary Electr on mode and after that manifold
electron microanalyses were made on their surfaces.

Evaluation of Some Romanian Artifacts by SEM

a b
Figure 1 – Macroscopic appearance of the Romanian Dacian excavated Artifacts:
a- breastplate, b – sheat

2. Results and Interpretations
The investigations made o n the two pieces owing to the Romanian Dacian
period reveal interesting observations concerning the surface appearance and
degradation in such long period of time.

a. Romanian Dacian breast analysis
The stereomacroscopic analysi s of the Romanian Dacian Breas t, shown in
figure 2, at different magnifications reveal the fact that this piece is much
corroded. All the surface has a dark brown colour, as a sign of an advanced
corrosion. Also, the surface has many big dimples and rough and smooth surface
(fig.2 and fig.2b), as a local pitting corrosion phenomenon, due to aggressively of
the environment in such a long time. On some remark the presence of the yellow
corrosion products (fig.2c and fig.2d)

a b

Brandusa Ghiban, Valentin Dragoiescu

c d
Figure 2 – Stereomacroscopic appearance of Romanian Dacian excavated breast:
a- Front side; b – lateral side; c, d – inner part

a b

c d
Figure 3 – SEM images of Breastplate belonging to Romanian excavated Dacian Period

Evaluation of Some Romanian Artifacts by SEM
Table 1
Local microchemical composition of breastplate b elonging to Dacian period
zone Local microchemical composition, %Wt.
C O Na Al Si P S Cl K Ca Fe
Zone 1 62.93 17.93 0.45 0.33 0.43 – 0.37 0.67 – 0.27 16.61
Zone 2 39.04 26.99 0.36 0.25 0.42 – – – – 0.25 32.44
Zone 3 36.69 32.93 0.46 0.84 1.76 0.52 0.25 0.14 0.23 0.38 25.8

b. Romanian Dacian sheat analysis
The stereomacroscopic analysis of the Romanian Dacian sheat , shown in figure
4, at different magnifications reveal the fact that this piece is also much corroded.
All the surface has a dark brown colou r, as a sign of an advanced corrosion. In
cross section one may remark a brittle appearance of fracture, with also many
coloured particles (fig.4a). Also, the surface has many big dimples (fig. 4b), as a
local pitting corrosion phenomenon, due to aggressive ly of the environment in
such a long time.

a b
Figure 4 – Stereomacroscopic appearance of Romanian excavated Dacian sheat:
a- cross section side; b – surface side

a b
Figure 5 – Stereomacroscopic appearance of Romanian excavated Dacian She at in a fractured cross
section (detailed of figure 4a), at different magnifications

Brandusa Ghiban, Valentin Dragoiescu

a b

c d
Figure 6 – SEM images of sheath belonging to Romanian excavated Dacian Period

Table 2
Local microchemical composition of sheath belonging t o Dacian period
zone Local microchemical composition, %Wt.
C O Al Si P S Cl Fe
Zone 1 14.18 24.3 0.74 1.35 0.49 0.59 0.59 57.5
Zone 2 6.22 19.09 0.6 0.91 – – – 73.18
Zone 3 13.37 22.03 0.48 0.45 – – 0.39 63.27

Elements such as Si, Na, P, and Ca may be attributed as external markers.
Hydroxypyromorphite is usually found in soil rich in phosphorus (Cao et al., [6]).
As discussed above, the observed presence of phosphorus in the archaeological
site soil is due to sealers’ activity leading to the deposit of hunted animal bones in
the soil. As showed by Lower et al. [7], the hydroxylapatite (Ca 5(PO 4)3OH)
present in bones can react with the Pb in objects through the following mechanism
of dissolution of hydroxylapatite (Ca 5(PO 4)3OH) and precipitation of
hydroxypyromorphite (Pb 5(PO 4)3OH):

Evaluation of Some Romanian Artifacts by SEM
Ca5 (PO 4)3OH + 7H+  5Ca2+ + 3H2PO−4 + H2O 5Pb 2+ + 3H2PO−4 + H2O 
Pb5 (PO 4 )3OH + 7H+

Zapata et al. [7] studied the presence of Pb in archaeological bones and
attributed this to a diagenesis process of reaction of phospha tes from bones with
Pb in soil. They also proposed that the enrichment of Pb in bones was due to the
formation of hydroxypyromorphite. Remazeilles & Conforto [8] identified
hydroxypyromorphite in a Roman bronze inkwell. They attributed the formation
of thi s compound to a reaction of phosphates in agricultural fertilizers with Pb in
bronze alloy. Henry [9] identified hydroxypyromorphite in leaded Islamic
ceramics from the tenth to thirteenth centuries. The ceramics were found under a
Christian cemetery and b ones were identified as sources of phosphates.
Hydroxypyromorphite is a highly insoluble material. The good state of
preservation of the lead artifacts can be attributed to its formation as a passive,
adherent, and insoluble corrosion layer. It is importan t to emphasize that
according to White et al. [10], regular Pb corrosion products in polar
environments consist of carbonates, chlorides, sulfates, and basic salts. The use of
phosphates was suggested by this author to immobilize Pb ions as insoluble and
stable compounds in these regions. The human ’ activity provided phosphates to
this immobilization. Studies of elements in soils in these regions (Villagran &
Schaefer, [11]) did not show the presence of Pb. Since there were many artifacts
the humans made us ing these metals, this suggests the efficiency of phosphates in
immobilizing Pb, thus avoiding its spreading in soils.
Further evidence of organic matter is the presence of phosphorus (P) in the
artifacts. Phosphorus is an important indicator of human impr ints as it is a
byproduct of human activity (Hutson et al., [12]; Luzzadder -Beach et al., [13]).
This element was already identified in the archaeological sites and also attribu ted
to an anthropogenic source [14] . One of the main activities developed in th ese
sites was the hunting of different animals [14]. It is proposed that the organic
matter constitutes residues of these animals.

Conclusions
This paper aims to assess excavated arte facts belonging to the Romanian
Dacian period by stereomacroscope and scanning electron microscope analy sis,
thereby enriching the database. Two different types of pieces were investigated: a
piece of breastplate and a piece of sheat. There were described for each piece the
main structural features concerning the corrosion pro ducts and the chemical
composition of different zones on their surfaces. Elements such as Si, Na, P, and
Ca may be attributed as external markers. The presence of phosphorus and
phosphates is an important marker of human imprints.

Brandusa Ghiban, Valentin Dragoiescu

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