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The working of copper-arsenic alloys in the Early Bronze Age and

the effect on the determination of provenance.

Hugh McKerrell and R. F. Tylecote

Proceedings of the Prehistoric Society / Volume 38 / December 1972, pp 209 - 218

DOI: 10.1017/S0079497X00012111, Published online: 27 May 2014

Link to this article: http://journals.cambridge.org/abstract_S0079497X00012111

How to cite this article:

Hugh McKerrell and R. F. Tylecote (1972). The working of copper-arsenic alloys in the Early Bronze Age and
the effect on the determination of provenance. . Proceedings of the Prehistoric Society, 38, pp 209-218
doi:10.1017/S0079497X00012111

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 7. Hugh McKerrell, R. F. Tylecote. THE WORKING OF COPPER-ARSENIC ALLOYS

The working of copper-arsenic alloys in the Early

Bronze Age and the effect on the
determination of provenance
HUGH MCKERRELL
National Museum of Antiquities of Scotland
R. F. TYLECOTE
University of Newcastle-upon-Tyne

The earliest copper alloy of the British Bronze Age is arsenical copper, a material
relatively short-lived when compared with the succeeding tin bronze but of no
little importance when tracing the stages and progress of prehistoric metal work-
ing. Like tin, arsenic functions as a mild deoxidant and confers the useful property
of work-hardening upon the metal. Copper-arsenic alloys need to be strengthened
by cold working, and it was probably this requirement as much as any other that
would have led to their eventual disuse and replacement by cast tin bronzes. The
normal source of arsenic for such alloys is generally agreed as a constituent of the
copper ore actually smelted, usually the grey tetrahedrite tennantite mineral
(Coghlan and Case, 1957; Tylecote, 1962), although other suggestions have been
made (Charles, 1967).
The choice of this ore, at the beginning of the Bronze Age, seems to have been
very deliberate and the arsenic content retained by correct smelting procedure.
It would be natural to assume that such care could have been extended to a choice
of ore of varying arsenic content, as dictated by the required alloy property
(Coghlan and Case, 1957). A low arsenic ore would be preferable for a halberd
rivet to facilitate its closing over an organic hilt whereas the blade itself would
more usefully be produced from a high arsenic ore. The possibility of a more
direct control of the alloy arsenic content, by smelting or working under oxidizing
conditions, has never been given serious consideration, the ore selection process
being preferred. We shall show, however, that control of the arsenic content,
by oxidative loss, is entirely feasible and was, in all probability, the technique
actually used to reduce the arsenic content of North British halberd rivets.
Moreover, the idea of either deliberately controlling the arsenic content under the
reducing conditions in the liquid state that would obtain in typical furnace con-
ditions, or the accidental loss of significant quantities of arsenic during smelting,
would seem not to be borne out by experiment.
209
 THE PREHISTORIC SOCIETY

EXPERIMENTAL

Our aim with the experimental work was to determine those furnace or working
conditions that would be effective in lowering the arsenic content of arsenical
copper. Bearing in mind the typical prehistoric alloy (rarely more than 7 per cent
of arsenic) and likely working conditions, we have here deliberately used
material containing about 10 per cent of arsenic and temperatures of up to
II5O°C.

( i ) PRELIMINARY WORK—REDUCING CONDITIONS

Two preliminary experiments indicated the useful direction in which to pursue more detailed work.
Thus, under the mild reducing conditions of a gas fired injector furnace, a copper-arsenic alloy was
prepared and maintained in the molten state at 1,000 °C for several hours. No significant arsenic
loss was noticed during this period and samples were taken for analysis throughout the experiment.
The arsenic contents of these and all other specimens were determined by X-ray fluorescence and the
results are listed in Table 1. Careful comparative work indicated a likely accuracy of about ±0.5 per
cent on an arsenic content of 10 per cent. It was suspected that some segregation had occurred during

TABLE I : ATTEMPTED ARSENIC REMOVAL FROM MOLTEN ARSENICAL COPPER UNDER

REDUCING FURNACE CONDITIONS AT I.OOO °C

Sample % Arsenic
Triplicate Analyses Mean
A Copper only o-o o-i o-i o-i%
B Prepared alloy. Time o hr o min. 9-8 9-8 9-6 97%
C Prepared alloy. Time ohr 12 min. 9-4 9-3 9-1 9'3%
D Prepared alloy. Time o hr 20 min. 9-8 9-6 9-7 9*7%
E Prepared alloy. Time o hr 52 min. 9*5 9*5 9*6 9'6%

TABLE 2 : ARSENIC LOSS FROM ARSENICAL COPPER UNDER OXIDIZING WORKING

CONDITIONS

Sample % Arsenic
Run 1
Initial arsenic content 9-7
Sample above after melting and cooling twice 8-7
Sample above after melting once more, hot working twice 7-3
Sample above after melting once more, hot working five times 4-2
Run 2
Initial arsenic content 4*2
Sample above after melting once, hot working three times 2*9
Sample above after further hot working (10 minutes) o-8

ANTIMONY LOSS FROM ANTIMONIACAL COPPER UNDER OXIDIZING WORKING CONDITIONS

Sample % Antimony
Initial antimony content 4*3
Sample above after melting and hot working three times 2'6
Sample above after further melting and hot working 0-9
(10 minutes)

2IO
 7. Hugh McKerrell, R. F. Tylecote. THE WORKING OF COPPER-ARSENIC ALLOYS
the run but clearly no serious arsenic loss has occurred under these conditions. This is in agreement
with such calculations as can be made about the thermodynamic activity of arsenic in copper, there
being no actual experimental data available, and with the results obtained by Lorenzen (1965) who,
in reduction-smelting an arsenical-copper oxide ore, obtained nearly 100 per cent recovery of the
arsenic. It must be stressed that such a recovery could not be expected when smelting a sulphide ore
in which various stages of oxidation would be required. But the difficulty of removing the last traces
of arsenic from such ores today suggests that a proportion at least would remain after the smelting
of ores of the tennantite (Cu3AsS3) type.
After melting, the copper-arsenic alloy was cast into small ingots in a chill (cast iron) mould. It was
observed that under these conditions the alloy showed marked inverse segregation, in which the
surface has a much higher arsenic content than the interior. While this form of segregation is known
to occur on tin-bronzes and some other copper-base alloys it seems to be far more marked on the
copper-arsenic alloys.
The copper-arsenic system is eutectiferous and produces a eutectic with an arsenic content of
21.5 per cent and a melting point of 689 °C. The limit of solid solubility is about 7 per cent which
means that under equilibrium conditions any alloy having a composition above this would contain
some of the low-melting-point eutectic. Under practical (non-equilibrium) conditions this eutectic
would be expected to appear at a much lower arsenic content, probably around 3 per cent.

(ii) HOT WORKING IN AIR—PRELIMINARY WORK

A series of hot working and melting experiments were carried out under oxidizing conditions on
ingots of arsenical copper. The results are presented in Table 2 which is self-explanatory and shows
clearly that a significant and rapid loss of arsenic can be brought about under oxidizing conditions.
Clearly then the mechanism for release of the arsenic is totally different under oxidizing conditions
and we shall discuss this further. Also included in Table 2 are the results of similar removal of anti-
mony from an alloy with copper. This will also be discussed in more detail later.

(iii) CONTROLLED FURNACE RUNS

A series of experiments using the same arsenical copper in the molten state with different atmospheres
and controlled flow rates was next completed. The results are listed in Table 3. A temperature of
1,150 °C was maintained throughout so that all specimens were entirely molten and as hot as would
probably be possible under typical prehistoric furnace conditions. And the molten state would of
course be far more effective than the solid for potential arsenic loss. A number of points derive from
these experiments. Clearly the preliminary work is confirmed; arsenic loss does not occur under
non-oxidizing conditions but is most marked when oxygen is present. The differing gas flow rates

TABLE 3 : LOSS OF ARSENIC BY VOLATILIZATION IN THE MOLTEN STATE:

X-RAY FLUORESCENCE ANALYSES ( % ARSENIC)

Nitrogen; 1,150 °C Air; 1,150 °C

Initial composition "•9% "•9%
£ hr gas flow 20 ml/min. n-4% 7-2%
i hr gas flow 20 ml/min. n-6% 2-3%
1 hr gas flow 20 ml/min. "•9% 2-2%

£ hr gas flow 100 ml/min n-8% Fully oxidized

£ hr gas flow 4 ml/min. io-4%* 2-3%

•The slight drop in arsenic content here is probably due to some entry of air into the furnace with the
low flow rate of nitrogen used.
211
 THE PREHISTORIC SOCIETY
are also a dependent variable in the case of oxidative loss but quite clearly have no effect in a non-
oxidizing atmosphere. There is thus no question of reducing the arsenic content by 'sweeping away'
the slight arsenic partial pressure with a non-oxidizing flow of gas. The equilibrium vapour pressure
of arsenic, even at 1,150 °C in the molten state, is too low to be of any significance as a means of arsenic
loss. We see the mechanism of such loss, under oxidizing conditions, as proceeding by the solution of
oxygen in the metal followed by reaction with the arsenic and subsequent volatilization of the readily
removed arsenic trioxide. If the volatilization of arsenic was the main rate-determining process we
would not expect oxygen to be any more effective in removing arsenic than a rapid flow of some non-
oxidizing gas such as nitrogen. The reaction must proceed by some significantly different process,
possibly that outlined. From the point of view of smelting conditions, usually mildly to strongly
reducing, it would therefore seem improbable that any significant loss of arsenic should occur. Unless
a preliminary oxidizing ore roast was to be carried out it is likely that complete transfer of arsenic
from an ore to the metal would obtain. Obviously, direct smelting experiments are here desirable and
we are currently pursuing this as part of a programme of experimental smelting runs. Significant
arsenic loss, to the point of poisoning early bronze-smiths, as has been thought probable, must thus
be considered rather unlikely.

(iv) DIFFUSION STUDIES

The next series of experiments related to the solid phase. Here the intention was to study any diffusion
of arsenic away from the edges of solid specimens and the analytical technique used was electron-
probe microscopy. The furnace conditions used are listed in Table 4 along with the main diffusion

TABLE 4 : SOLID STATE ARSENIC DIFFUSION LOSS INVESTIGATION:

MICROPROBE ANALYSED SAMPLES, ALL 9 2 PER CENT COPPER, 8 PER CENT ARSENIC INITIALLY

Furnace conditions Diffusion and arsenic loss observations

Nitrogen: £ hr gas flow 20 ml/min. (PL xx) Inverse segregation present providing two- to threefold
Nitrogen: 1 hr gas flow 20 ml/min. excess of arsenic at surfaces. About 10 microns thick-
Nitrogen: 6 hr gas flow 20 ml/min. ness. Diffusion loss of arsenic not observed over more
than 1 micron (io~6 m.).

Nitrogen: ^ hr gas flow 100 ml/min. As above. No increase in diffusion gradient.

Air: % hr gas flow 20 ml/min.
Air: i hr gas flow 20 ml/min.
850° C
95o°C
Nitrogen: £ hr gas flow 20 ml/min.
Nitrogen: 1 hr gas flow 20 ml/min. (PL xix)
Nitrogen: 6 hr gas flow 20 ml/min.
No inverse segregation. Diffusion loss of arsenic not
observed over more than 1 micron into metal. Arsenic
content of oxide layer variable.
Severe, but variable, inverse segregation, providing
two- to threefold excess of arsenic at surfaces. Up to
0-5 mm thickness. Diffusion loss of arsenic not
observed over more than 1 micron into metal.

Air: 5 min. gas flow 20 ml/min. No inverse segregation. Diffusion loss of arsenic not
Air: £ hr gas flow 20 ml/min. (PL xx) observed over more than a few microns into metal.
Air: $ hr gas flow 20 ml/min. Arsenic content of oxide layer very variable.

Air: 5 min. gas flow 100 ml/min. Severe and rapid overall oxidation. Comments directly
above still apply, however.

Air: static, 600 °C, 1 hr No inverse segregation. Diffusion loss of arsenic not
Air: Static, 700 °C, 1 hr observed over more than a few mcirons into metal.

212
 >

Copper-arsenic alloy after heating in nitrogen at 950 °C for 1 hour. The arsenic and copper traces indicate variation
in the concentration of those elements across the specimen. Magnification X40.
to
HI
N
 PLATE XX

Lower: Copper-arsenic alloy after heating in nitrogen at 850 CC for 30 minutes. The
arsenic and copper traces indicate variation in the concentration of those elements
across the specimen. Magnification X 4000.
Upper: Copper-arsenic alloy after heating in air at 950 °C for 15 minutes. The arsenic
and copper traces indicate variation in the concentration of those elements across the
specimen. Magnification X 400.
 7. Hugh McKerrell, R. F. Tylecote. THE WORKING OF COPPER-ARSENIC ALLOYS
observations. In summary, in non-oxidizing conditions, no arsenic diffusion loss was observed.
Instead, the high concentration of arsenic near the sample edges due to inverse segregation of the
low melting eutectic is maintained. This is clearly to be seen in Plates XIX and XX, lower. In oxi-
dizing conditions (PL XX, upper) the inverse segregation peak has disappeared but even at the highest
magnification (2,200 times) significant arsenic diffusion from the interior of the specimen was not
detected. This shows how little arsenic loss would occur from within the heated solid metal during
adherent scale conditions, an observation confirmed by the fact that even in the oxide scale there is
still a significant quantity of arsenic present (about one half that in the metal). Arsenic loss from the
solid alloy thus occurs only under oxidizing conditions and proceeds only as the metal as a whole
oxidizes. No depletion of the arsenic concentration into the metal proper was observed.

( v ) THERMOGRAVIMETRIC WORK
Finally, a few experiments were completed which involved continuously weighing samples of copper
and arsenical copper in a temperature-controlled air atmosphere. The alloy investigated contained
10 per cent As, and the temperatures chosen were 600 and 700 °C, respectively below and above the
melting point of the copper-arsenic eutectic (689 °C). In neither case was the oxidation of the para-
bolic type which is normal for pure copper at these temperatures (Tylecote, 1950), but the rate of
increase of weight with time due to the absorption of oxygen from the atmosphere was rather less,
no doubt due to increased loss of arsenic. The difference between the weight gain after 30 minutes
at 600 °C and that at 700 °C was of the order of 40 times, an enormous increase in the rate of scaling
and clearly due to the presence of the liquid Cu-As phase. At 700 °C the Cu-10 per cent As alloy
scales about 25 times as much as pure copper at the same temperature. This explains the relative y
rapid reduction in As content during the hot working of such alloys.

HALBERD/RIVET ANALYSES
With the completion of the Early Bronze Age Scottish analyses in the Stuttgart
programme (Junghans et ah, 1968) the number of related halberd and rivet
analyses from Britain was increased to twenty-four. These are all listed in Table 5
along with the relevant analytical contents of arsenic, antimony, silver and nickel.
It may be observed that, with one exception, the rivet arsenic and antimony con-
tents are significantly less than in the halberds, a state of affairs necessary if work-
ing and closing of the rivets is to be achieved without damaging the hilt or fracture
of the metal. At first glance it may well seem impossible to deduce whether ore
selection or oxidative melting or working has been used to achieve the lower rivet
arsenic contents; however, the situation is in fact resolvable if we consider the
difference between halberd/rivet analyses and those of halberds alone. Thus figure 1
shows the arsenic and antimony contents of the published halberd analyses and
figure 2 correlates the quantities of those same elements for the related halberds
and rivets. From figure 1 it is clear that there is no correlation at all between the
arsenic and antimony contents of halberds. In other words deliberate selection of
an ore with a low arsenic content may or may not provide a low antimony content
as well. Similarly a high arsenic ore is just as likely to have a low antimony content
as it is to have a high content. The antimony content of those arsenical coppers is
thus clearly quite independent of the arsenic content. However, figure 2 shows
that there is a definite relative dependence for arsenic and antimony when we
213
 THE PREHISTORIC SOCIETY

compare halberd/rivet pairs. And, moreover, it may be noted that both the arsenic
and antimony contents are tending to move towards the graph axis, i.e. zero
concentration in both cases. Clearly this situation would not come about from a
process of low arsenic ore selection for the rivets since figure i indicates the ran-
dom variation we would predict for ore selection. This is simply not observed in
the related halberd and rivet analyses. Some other process must here be responsible
for lowering both the arsenic and antimony contents of the rivets. Bearing in mind

TABLE 5 : SCOTTISH AND IRISH HALBERD/RIVET ANALYSES

Analysis Reference 0/
/o
0/ 0/ 0/
/o Object analysed
/o /o
Arsenic Antimony Silver Nickel
SAM 2, 3 7429 3-2 o-6 o-33 Tr Halberd (DJ 3)
7430 2 0-26 0-36 O-O22 Rivet
SAM 2, 3 7432 1-35 o-5 0-41 OOO3 Halberd (DJ 6)
7433 0-46 0-3 0-24 Tr Rivet
SAM 2, 3 7437 3-35 Tr 0-047 0-46 Halberd (DJ 34)
7438 Tr Tr O-II Tr Rivet
SAM 2, 3 74S8 3-4 0-39 0-3 Tr Halberd (DJ 24)
74S9 0-69 Tr 0-29 Tr Rivet
SAM 2, 3 7460 0-96 0-4 0-29 Tr Halberd (DJ 1)
7461 2-7 1-23 o-53 Tr Rivet
SAM 2, 3 7463 2-32 0-31 0-27 Tr Halberd (DK 2)
7464 0-44 0-32 0-16 Tr Rivet
SAM 2, 3 7466 3-i I*I 0-39 Tr Halberd (DK 9)
7467 i-75 o-57 0-42 Tr Rivet
SAM 2, 3 7469 i-55 0-77 0-31 Tr Halberd (DK 25)
7470 0-46 031 0-18 Tr Rivet
SAM 2, 3 9287 3'3 0-65 0-23 0-03 Halberd
9288 0-24 O-II 0-19 0-04 Rivet
PPS I9S7 48 2-IO 0-70 0-41 o-oi Halberd
74 o-55 0-38 0-27 o-oi Rivet
PPS 1957 59 2-10 o-75 O-20 0-006 Halberd
7i O-20 0-18 O-2O 0-02 Rivet
PPS I9S7 67 2-OO 0-50 0-44 o-oi Halberd
z 76 O-OO5 o-oi 0-18 o-oi Rivet
SAM 2, 3. Junghans, S. E., Sangmeister, E. and Schroder, M., 1968. Studien zu den Anfangen der
Metallurgie (SAM 2, 3). Berlin.
PPS 1957. Coghlan, H. H. and Case, H., 1957. 'Early metallurgy of copper in Ireland and Britain',
PPS, 22, 91.

the arsenic and antimony volatilization experiments previously described it would

seem highly probable that those losses have been brought about by deliberate
oxidative working. We here emphasize the word deliberate. Actual experiment
with the working of arsenical copper has convinced us that this would be a
deliberate process. The correlation between the malleability of an alloy and both
the amount of 'white arsenic smoke' given off on melting in air and the white
residue left on the working tool would certainly not escape the attention of a
skilled bronze-smith.
214
7. Hugh McKerrell, R. F. Tylecote. THE WORKING OF COPPER-ARSENIC ALLOYS

5--

4--

3--

7. *
ARSENIC
2- -

OS 1-0 1-5

V. ANTIMONY

Fig. I

5--

• HALBERD
O RIVET
4 • -

3 -

7.
ARSENIC
2--

1 • •

10 VS

•/. ANTIMONY
Fig. 2

215
 THE PREHISTORIC SOCIETY

PROVENANCE
In any classification of analyses attempting to relate copper alloys to ore deposits,
the above conclusions have obvious relevance. If arsenic or antimony contents
be used as provenance parameters (Junghans et al., 1968; Coles, 1969) then clearly
consideration has to be given as to whether or not the artifact under consideration
would be likely to have been subjected to oxidative melting or working.
Additionally, however, we must consider the metallurgical phenomenon of
inverse segregation. Already mentioned and clearly illustrated in Plates 1 and 2, this
is particularly common with copper-arsenic alloys. The exact cause of this process
is still not completely understood but essentially it occurs during casting in the
early stages of solidification when a high-arsenic-content eutectic is forced to the
surface of the alloy. The arsenic content of this eutectic is 21*5 per cent and

TABLE 6 : VARIATION OF INTERNAL COMPOSITION OF A COPPER-ARSENIC ALLOY WITH DIFFERING DEGREES

OF INVERSE SEGREGATION. EUTECTIC FORMATION ASSUMED

Inverse Initially Initially Initially

segregation 2-5% arsenic 5-0% arsenic 10% arsenic
Artifact surface layer
thickness thickness Final internal Final internal Final internal
% arsenic content % arsenic content % arsenic content

0*25 cm. o-i mm. o-8 3-6 9-0

0-25 mm. 0-9 71
0-5 mm

O'5 cm. o-i mm. 1-7 4-3 9-5

0-25 mm. 0-4 3*2 8-7
0-5 mm. 0-9 7-1

i-o cm. o-i mm. 2-1 4-7 98

0*25 mm. i-5 4-i 94
0*5 mm. 0-4 3-2 8-7

clearly a resulting surface layer of any thickness might well be a source of apparent
arsenic loss from the bulk of the metal. We have observed during this work such
surface layers of up to 0-5 millimetres thickness and this, for a typical EBA axe,
could contain from a quarter to a third of all the arsenic in the artifact. Subsequent
hot working could obviously remove some of this by diffusion and as an oxide
scale but from the point of view of actually detecting such losses we have to con-
sider the situation as actually encountered by the analyst today. Invariably the
object to be analysed will be corroded and sampled by drilling (Caley, 1964;
Organ, 1963). Naturally the corrosion-rich surface layer is rejected and one
samples and analyses the internal metal. So analytical results could here be in
error if it is the original pre-cast metal composition in which we are interested.
From the point of view of correlating ore and metal this is of course the case.
216
 7. Hugh McKerrell, R. F. Tylecote. THE WORKING OF COPPER-ARSENIC ALLOYS
Although inverse segregation, as we have here observed it, is a highly variable
event it is much more severe with copper-arsenic alloys than with tin bronze. To
avoid the problem of scrap remelting and metal re-use it is only the EBA that has
been seriously considered from the provenance point of view. The main alloy of
this period has, however, often been found to be arsenic-rich material (Junghans
et ah, 1968; Coghlan and Case, 1957), so clearly it is in fact here that we are most
likely to suffer from difficulties with the inverse segregation problem. Table 6
illustrates typical calculated figures for artifacts of varying thickness and different
degrees of inverse segregation and clearly shows the care which must be taken in
interpretation of arsenic analyses.
Nor is it, we believe, a problem restricted to the arsenic content alone. Although
the subject requires lengthy and detailed research our preliminary results indicate
that a similar analytical disparity can arise with other metallic impurities which
remain, during casting, preferentially dissolved in the eutectic and are eventually
forced to the casting surface. Table 7 illustrates the results of silver analyses
following inverse segregation of a copper-arsenic alloy. Here the actual eutectic
was analysed as well as the surface and internal metal and, as may be noted, vari-
ation of up to 30 per cent in the silver content was detected.

TABLE 7 : SILVER CONTENT VARIATION WITH INVERSE SEGREGATION OF A COPPER-ARSENIC ALLOY

(Samples melted in air; analyses relatively accurate to ±2%)
Run 1 0/
Arsenic % Silver
/o
Ingot initial composition 5-1 1-24
Composition of ingot top surface after melting once 8-6 4-28
Composition of sample ejected (molten) during working 14-0 2-03

Run 2 0/
/o Arsenic % Silver

Ingot initial composition 1-24

Composition of ingot top surface after melting once 15-2 3-63
Composition of ingot bottom surface after same melting 13-4 6-02
Composition of ingot (internal) after same melting 3-3 o-86

Clearly the implications of this for provenance are considerable. Bearing in

mind that inverse segregation may or may not occur, and when it does to a variable
extent at that, the idea of attempting to differentiate between metal from different
sources simply by fixing particular elemental concentrations (Junghans et al.,
1968) may be too rigid a procedure. A wider tolerance, with a large proportion of
artifacts inevitably on the border-line, would seem more likely to be realistic.
However, as we have stressed, much work needs to be done upon the problem
before coming to any final conclusions. If we do no more than induce an air of
caution to interpretations related to provenance analyses we shall here be satisfied.
217
 THE PREHISTORIC SOCIETY

SUMMARY
Loss of arsenic from the arsenical copper typical of the British Early Bronze Age
was found experimentally to occur only under oxidizing conditions. No loss of
any practical consequence was observed under non-oxidizing conditions at
temperatures of up to 1,150 °C.
The deliberate control of the arsenic content of EBA metal by melting and
working in oxidizing conditions seems highly probable for halberd rivets.
Finally, arsenic losses under such oxidizing conditions and surface arsenic
gains by inverse segregation must reduce the reliability of that element as a pro-
venance parameter. It seems likely that other metallic impurities could also be
subjected to variable segregation during casting of arsenical copper and caution
in use of rigid analytical levels as an indication of provenance seems desirable.

REFERENCES
Caley, E. R., 1964. Analysis of ancient metals. London.
Charles, J. A., 1967. 'Early arsenical bronzes—a metallurgical view1, Am. J. Arch., 71, 21.
Coghlan, H. H. and Case, H., 1957. 'Early metallurgy of copper in Ireland and Britain', PPS, 22, 91.
Coles, J. M., 1969. 'Scottish Early Bronze Age metalwork', PSAS, 101, 1.
Junghans, S. E., Sangmeister, E., and Schroder, M., 1968. Studien zu den Anfangen der Metallurgie
(SAM 2, 3). Berlin.
Lorenzen, W., 1965. Helgoland und das fruheste kupfer des Nordens. Ottendorf.
Organ, R. M., 1963. 'Are analyses of uncorroded ancient alloys representative?', Studies in Conser-
vation, 7, 48.
Tylecote, R. F., 1950. 'The oxidation of copper at 350-900 °C in air', J. Inst. Metals, 78, 327.
, 1962. Metallurgy in archaeology. London.

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