Feature Archaeotechnology

Initial Experiments on Arsenical

Bronze Production
B. Earl and A. Adriaens

The work reported in this article forms the basis for an extended study of arsenic
bronze. The ease with which a copper-arsenic alloy could be prepared by fusing
copper metal with arsenopyrite has been shown; conditions can be readily
adjusted to yield alloys with compositions equivalent to those made in antiquity.
While iron-metal prills were found in the fused crucible remains, it is probable
that such metallic iron will only be observed in ancient crucible sherds when full
vitrification has taken place, otherwise the iron will weather over time to oxide.

Authors Note: All compositions are given in weight percent molten copper, oxidizing the lead to tain a copper metal that could then be
unless otherwise indicated. molten litharge (PbO), which is blownalloyed with a suitable arsenic source.
off the melt and absorbed in the furnace
The Bakiray orestuff, which is likely to
INTRODUCTION
bed. During this procedure, any arsenic
have been the source of the copper for
Ancient arsenical copper-bronze al- that is present is rapidly oxidized and
the lkiztepe arsenical copper objects, is
loys are particularly interesting to ar- released as fume (As2O3). The process is
certainly lead-bearing; much galena (PbS)
chaeologists, as their sources and modes is present, along with other contami-
particularly efficient in oxidizing the ar-
of preparation and/or selection reflect senic since copper oxide is formed tonants, such as zinc (as sphalerite ZnS). 4
the skills available to ancient societies as some extent during the operation, and It has been suggested that arsenical
well as the distribution of the people this has a powerful oxidizing effect. Af-
copper-bronze could result from the
with these skills. If copper were reduced ter the lead and other contaminants, smelting of ore-stuff containing a cop-
from an orestuff composed of either cop- such as arsenic, iron, and zinc, haveper-arsenic mineral, such as tennantite
per ore and arsenic ore, such as arse- been removed, charcoal is added to the
(Cu, Fe)12 As4S13 .5,6 In the Bakiray area,
nopyrite (FeAsS), or a copper ore con- melt to reduce any copper oxide to cop-
little such material can be found; how-
taining arsenic, then a high-arsenic cop- per metal. By this means, if arsenic is
ever, chalcopyrite-malachite-galena-
per (up to five percent arsenic or more) present in the original ore its finalsphalerite (and, possibly, arsenopyrite
can be obtained by direct smelting, as in content is reduced to under 1% in thein places) mixed lodestuff is widespread
the smelting of arsenical coppers in the final copper. 3 in many lodes exposed by early mining.7
South Americas. However, if lead ores Much of the copper orestuff in In addition, the waste dumps contain
are present in the orestuff, the removal Anatolia is lead-bearing, making it most
specimens of material-in-process consist-
of the lead results in the virtual elimina- probable that cupellation had to be un-
ing of rough, white, metallic material
tion of arsenic in the copper. 1 dertaken by the ancient smelters to ob-
chiefly composed of copper-lead-iron, a
A copper-lead few pieces of
mixed ore source which can be cu-
requires a refin- pelled to yield
ing stage during good copper met-
the smelting op- al with little or no
erations to reduce arsenic. Other
the lead content samples with a
if a reasona- high iron content
bly pure copper are very refrac-
metal is required. Pre-Heating Plug tory, which is
A well-estab- probably why
lished and an- they were re-
cient process for jected.
achieving this is Apart from
Crucible Mold Crucible Charging Funnel Closing Ball
through oxidiz- the direct smelt-
ing fire refining ing of an arseni-
in effect, a cupel- cal-copper min-
lation. 2 An air eral or arsenopy-
blast is played 3 mm rite-containing
over a bath of Figure 1. The materials used in the copper/arsenopyrite fusion experiments. ores with little

14 JOM March 2000

other contamination, several possible
routes for preparing a Cu-As alloy can
be followed. For example, arsenic metal
can be introduced into molten copper.
The preparation of arsenic metal is a
somewhat delicate operation, requiring
a retorting stage. Alternatively, arsenious
oxide (As2O3) prepared by the oxidizing
roast of arsenopyrite followed by collec-
tion of the sublimate can be added to
molten copper.
It is far simpler, and more likely, that
the addition of the mineral arsenopyrite
(FeAsS) in a direct fusion with copper
would have been the method used for
copper originating in the Bakiray area.
There are notable deposits of arsenopy-
rite separate from, but close to, the mixed-
copper orestuff.7,8 The work reported
here was an initial investigation of the
possibility of this route, particularly to
see how easily an alloy could be made
that would duplicate the archaeological
materials that have been assayed. The
work also noted the influence of the
fusion on the container (crucible) (i.e.,
diffusion of charge constituents into the
crucible fabric or assimilation of crucible
material by the molten alloy).
Two melts were attempted. The first
melt determined if the addition of arse-
nopyrite to molten copper under reduc-
ing conditions would yield a Cu/As al-
loy, and if so, what concentration of the
metals could be expected under the fir-
ing conditions. The other melt mixed
cold copper metal and arsenopyrite in a
crucible and then heated the mixture to
above the melting point of copper, again
under reducing conditions. Both melts
were run in a clay crucible made of equal
volumes of modeling clay/powdered
charcoal/quartz sand and ex-Leswidden
china clay pit. A cover and balls, made of
this clay mixture, were stoppers.
Preparing an arsenical bronze that
duplicated typical early bronze was
found to be entirely practical. In addi-
tion, the introduction of iron, originat-
ing in the arsenopyrite, could be a sig-
nificant factor in preparing an alloy par-
ticularly suitable for tools and weap-
ons.9 A refined copper may have only a
Figure 2. The set-up of the second firing. The crucible is placed in a bed of burning charcoal.
2000 March JOM
a 0.5 mm
the metal of the first firing. The alpha phase is
b 0.5 mm
Figure 3. Metal prills from (a) the first and (b)
second firing.
low iron content, so that its introduction
by the use of arsenopyrite would have
been important.
EXPERIMENTAL PROCEDURES
In the first melt, 101 mg of BCR CRM
74 copper was put into a crucible (Figure
1). The stopper was used to prevent char-
coal and other materials from entering
too soon. The crucible was placed in a
bed of burning charcoal in a small blast
furnace and heated to a bright yellow
beat. After the stopper was removed,
uncovering the molten copper, 32 mg of
powdered Cornish arsenopyrite were
shot in via a copper funnel, quickly fol-
lowed by enough powdered charcoal to
cover the charge. Volumes of arsenic
fumes (detected by their smell) were
released. Immediately after adding the
charcoal, the clay ball was dropped into
the crucible, followed by more powdered
charcoal to fill the crucible to the top. The
heat was sustained for ten minutes be-
fore the crucible was cooled and broken
to remove the metal prill with slag. The
crucible had been considerably vitrified.
100 m
Figure 4. A backscattered-electron image of
composed of regular grains that contain 3%
arsenic. Along the grain boundaries, Cu3As
intermetallics with an arsenic concentration
up to 28% (bright phase) are present next to
copper-sulfide inclusions (dark phase).
For the second melting, 135 mg of BCR
CRM 74 copper and 80 mg of powdered
arsenopyrite were charged into a cold
crucible, covered with a layer of pow-
dered charcoal followed by a clay ball,
then filled with more powdered char-
coal (Figure 2). The crucible was heated
to a bright yellow color and held at this
temperature for five minutes. The well-
vitrified crucible was allowed to cool
and then broken to extract the prill of
metal and slag. No arsenic fumes were
noted during this firing.
Figure 3 shows the metal prills of the
two firings. Optical microscopy (Re-
ichert, Austria) and electron probe x-ray
microanalysis (EPMA) using a Jeol Su-
perprobe JXA 733 with an energy-dis-
persive spectrometer system were used
to examine and analyze the metal and
slag. A 25 kV, 1 nA electron beam was
used to bombard the sample, and sig-
nals were accumulated for 20 seconds.
Standard ZAF corrections were used for
obtaining quantitative results.
RESULTS AND DISCUSSION
The overall bulk composition of both
metal prills clearly shows the presence
of arsenic. For the first firing, the bulk
arsenic content is 5.1% 0.5%. The alpha
phase is composed of regular grains that
contain 3% arsenic. Along the grain
boundaries, the gamma phase (Cu3As
intermetallics with an arsenic concen-
tration up to 28%) is present next to
copper-sulfide inclusions (dark areas in
Figure 4). The remaining composition
of the first firing is 94.2% 0.6% copper
and 0.6% 0.2% sulfur.
The bulk arsenic concentration in the
metal obtained from the second firing is
significantly higher13.8% 0.2%. The
alpha phase contains 6% arsenic. The
gamma phase and CuS inclusions are
also visible in this metal (Figure 5a); all
phases contain a significantly higher
amount of iron. The metal prill from the
second firing is surrounded by a copper-
15
sulfide border that is rich in tiny metal
prills with more or less the same compo-
sition as the main prill. The remaining
composition of the second firing is 74.1%
0.2% copper, 10.12% 0.01% iron, and
2.01% 0.05% sulfur.
The bulk composition of the slag in the
first firing is 61.7% SiO2, 17.3% Al2O3,
11.6% CaO, 3.0% K2 O, 2.7% MgO, 2.6%
FeO, 1.1% Na2O, 0.5% TiO 2, and 0.3%
CuO. The composition of the second
firing slag is 59.7% SiO2, 16.8% Al2O3,
11.7% CaO, 5.4% FeO, 3.1% K2O, 2.3%
MgO, 0.6% TiO2, 0.3% Na2O, 0.2% As2O3,
and 0.1% CuO. Both samples are alumin-
osilicates with a very similar elemental
composition. Significantly different is
the iron concentration, which is twice as
high in the slag from the second firing.
Note that the copper and arsenic con-
centrations are extremely low. The two
slag materials contain inclusions of
quartz and iron-metal prills (Figure 5b).
No metallic copper or arsenic was ob-
served.
Why people adopted a tin-bronze al-
loy raises some interesting questions. At
the time, the physical properties of the
two types of alloy were not significantly
different. 5 One often-cited reason for the
selection is that the poisonous proper-
ties of arsenic promoted the change.6
However, at the arsenic calciners in Corn-
wall during the late 1940s, many tonnes
of arsenic were burned off ore concen-
trate and collected in sublimation cham-
a 250 m
b 10 m
Figure 5. Backscattered-electron images of
the metal from the second firing showing (a)
the alpha phase (6% arsenic) with Cu3As
intermetallics and CuS inclusions (the metal
prill is surrounded by a copper-sulfide border)
and (b) iron prills in the slag.
16
Figure 6. Refined white arsenic being dug out of the collecting chambers of the English Arsenic
Company works at Roseworthy, Cornwall. Note that the operator has cotton wool plugs in his nose
and his face is smeared with fullers earth (ca. 1905).
bers. No particular worries were ex-
pressed when the calciners sight door
was opened to view the blue arsenic
flame coming of the bed, nor when tonnes
of hot arsenic soot were dug out of the
collection chambers and put into wheel-
barrows (Figure 6). The only precau-
tions taken were to plug the nose with
cotton wool and rub the exposed face
and hands with fullers earth to prevent
arsenic poxthe development of pain-
ful sores.8 No dust-extraction equipment
or extraction fans were found.
Bearing in mind the quantities being
handled in the 1940s as compared with
those in antiquity and the likelihood that
safety standards were less rigorous in
antiquity than in mid-20th century Eng-
land, it is improbable that the poisonous
nature of arsenic was a major influence
in the transition to tin-bronze, particu-
larly considering the semiprecious na-
ture of tin. Early smelters recognized the
poisonous nature of arsenic, but this was
not sufficient to stop working with ar-
senical metal, as is evident from the fire
refining of arsenic-contaminated copper,
which was practiced on a major scale
into the 20th century.3 However, the color
of tin-bronze, approximately that of gold
over a wide range of tin content, could
have been of major significance to the
ancients. 1012
ACKNOWLEDGEMENTS
This work has been performed in the frame-
work of the BritishFlemish Academic Re-
search Collaboration Program. A. Adriaens
also acknowledges FWOVlaanderen.
References
1. J. Mitchell, Manual of Practical Assaying, 2nd ed. (London:
Hippolyte Baillere, 1854), pp. 270271.
2. V. Biriguccio, The Pirotechnia, by C.S. Smith and M.T.
Gnudi (New York: American Institute of Mining and Metal-
lurgical Engineers, 1942), pp. 170172.
3. C. Schnabel, Handbook of Metallurgy, vol.1 (London:
Macmillen, 1905), pp. 243247.
4. K.A. Yener, E. Ceckinli, and H. zbal, A Brief Survey of
Anatolian Metallurgy Prior to 560 BC. Archaeometry 94, ed. S.
Demirci et al. (Ankara: Tubitak, 1996) pp. 378379.
5. H. Lechtman, Arsenic Bronze: Dirty Copper or Chosen
Alloy, J. Field Archaeology, 23 (1996), pp. 477514.
6. J.A. Charles, Early Arsenical BronzeA Metallurgical
View, Amer. J. Archaeology, 71 (1968), pp. 2126.
7. H. zbal et al., Minor Metallic Components Associated
with Anatolian Copper and Bronze Artifacts: Indications of
the Utilization of Polymetallic Ores, Proceedings of the 31st
International Symposium on Archeometry (Budapest-Oxford:
Archaeolingua, in press).
8. B. Earl, Arsenic Winning and Refining Methods in the
West of England, J. Trevithick Society, 10 (1983), pp. 929.
9. P. Craddock and N.D. Meeks, Iron in Ancient Copper,
Archaeometry, 29 (1987), pp. l87204.
10. C. Gillis, The Economic Value and Color Symbolism of
Tin (Paper presented at the Metals in Antiquity Sympo-
sium, Harvard Univ., Cambridge, Massachusetts 1997).
11. E.J. Holmyard, Alchemy (Harmondsworth: Penguin,
1957) for discussions on the significance of color in metallurgy.
12. G. Plattes, A Discovery of Subterranean Treasure (London:
Emery, 1639).
B. Earl is a consultant mining engineer. A. Adriaens is
with the University of Antwerp.
For more information, contact A. Adriaens,
University of Antwerp, Department of Chemistry,
Universiteitsplein 1, B-2610 Antwerp, Belgium;
e-mail mieke.adriaens@uia.ua.ac.be.
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