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Archacometry 35, 1 (1993). 35-47.

Printed in Great Britain

THE METALLURGY OF THE NAHAL MISHMAR HOARD


RECONSIDERED*

S . SHALEV
Institute of Archaeology. Tel Aviv University. Ramat Aviv, Israel

and J. P. NORTHOVER
Department of Materials. University of Oxford, Parks Road, Oxford, OX1 3PH. U.K.

The Nahal Mishmar hoard,found in a cave in the Judean Desert in 1961, is a keyfindfor the
study of Chalcolithic metallurgy in Israel and the Levant. Recent analyses of Chalcolithic
metalwork from sites such as Shiqmim in Israel raised doubts about the validity ofpublished
analyses from the hoard. Accordingly a programme of re-analysis was established using
atomic absorption spectrometry and electron probe microanalysis. The new analyses
confirmed the doubts andshowed that the metallurgy of Nahal Mishmar was the same as that
at the other sites. The alloys used for the cast products in the hoard were generally ternary
arsenic-antimony copper alloys with up to 20% alloy content; less common were
compositions with arsenic and nickel. The unusual metallography of these alloys is described.
Some suggestions are offered as to the mode of manufacture of the alloys.

KEYWORDS: ISRAEL, CHALCOLITHIC, NAHAL MISHMAR, ANALYSIS,


ARSENIC-ANTIMONY-COPPER ALLOYS, ARSENIC-COPPER-NICKEL ALLOYS,
METALLOGRAPHY, SMELTING

INTRODUCTION

On 21 March 1961 the archaeologist Pesah Bar Adon discovered a treasure of 429 objects
wrapped in a thin reed mat (Figure 1) in a remote cave situated in the cliffs of Nahal
Mishmar, in the Judean Desert near the Dead Sea (Figure 2; Bar Adon 1971 and 1980). Of
the 429 artefacts, the majority (416) are made of copper-based metals. Despite the 30 years
that have elapsed since it was found, this hoard is still the largest and, almost certainly, the
oldest in the entire Near East. Therefore, it is not surprising that it has become one of the
major sources for the study of the Chalcolithic culture of the fourth millennium BC to which
it belongs.
A pioneering metallurgical investigation of the hoard was conducted by C . A. Key of the
Geochemistry Division, Geological Survey of Israel (Key 1964, 1971, and 1980). His work
was the first systematic analysis of trace elements for metalwork finds from the ancient
southern Near East. Key’s work emerged in what was almost a vacuum of knowledge and its
impact was therefore correspondingly large. Even now, more than a quarter of a century
later, his work is still playing a major role in our understanding of the early history of
metallurgy. The aim of this paper is to re-evaluate these metallurgical data and their
subsequent interpretation in the light of new analytical work.
* Received 12 February 1991, accepted 19 March 1992.

35
36 S. Shalev and J . P . Northover

(a) The hoard in its discovered location ( W . Braun).

(b) A selection of objects in the collection of the Israel Antiquities Aulhoriry (exhibitedand photographed in the Israel
Museum).
Figure 1 The hoard of Nahal Mishmar (ufter Metropolitan Museum of Art 1986)

METALLURGICAL ANALYSTS

Preliminary X-ray fluorescence analysis by L. Heller of the Geological Survey of Israel


revealed a significant amount of arsenic in some of the mace heads from the hoard. This led
C . A. Key to postulate the use of sulphide ores; to pursue this question he decided to analyse
more fully the trace elements in some 30 artefacts from the hoard as well as three related ones
from other sites. Spark emission spectroscopy was used to measure the concentrations of
nine elements (As, Sb, Ag, Bi, Pb, Ni, Sn, Zn, Co). Technical details, limits of detection and
estimates of precision are given by Key (1964 and 1980). The limits of detection quoted are
The metallurgy of the Nahal Mishmar hoard reconsidered 37

Figure 2 Distribution of metal products and industrial remains (after Shalev 1991).

300 ppm or less except for arsenic where the limit was 1.9%; no explanation was offered for
this value which is high compared with the performance of other contemporary analysis
programmes.
The analytical data were correlated with the metallographic study carried out by
R. Potaszkin and K. Bar Avi (1971 and 1980) and helped to define the technological
differences between two groups of objects, the ornaments and the tools. With one exception
(at 1.9% As), the nine analysed tools from the hoard as well as one from Nahal Zeelim were
all made from impure but ‘unalloyed’ copper. The 22 analysed ornaments from the hoard as
well as the two from Nahal Zeelim and Abu Matar were, with two exceptions, all recorded as
being made of copper-arsenic ‘alloys’. The arsenic content ranged from 1.9% to I 1.9%, while
nickel, lead, antimony, silver and bismuth were found as impurities in concentrations
varying up to approximately 0.5%.
On the basis of these data Key concluded: (1) the simple shapes and metal compositions of
the tools might have resulted from their being either older than the ornaments or being made
by different craftsmen; (2) the compositions and structures of the tools might represent the
forging of native copper; (3) the compositions of the ornaments show that copper sulfo-salts
(here sulf-arsenates) were deliberately used for their manufacture; (4)the nearest such sulf-
arsenate ore sources (e.g. enargite and tenantite) described in contemporary geological
literature were in Transcaucasia, in Armenia and Azerbaijan; ( 5 ) the use of such a complex
sulphide ore in the fourth millennium BC required not only long-distance cultural contacts
but also the knowledge of roasting the ore before smelting.
38 S. Shalev and J . P . Northover

(a) Microstructure of the mace head from the Nahal Mishmar hoard (after Potaszkin and Bar-Avi 1980).

(b) Microstructure of the mace head from Shiqmim (at a higher magnification than (a), showing an irregular as-cast
dendriric structure in an As-Cu-Sb alloy (after Shalev et al. 1992).
Figure 3 Similarities in the microstructure of mace head.s casi over a core.

HISTORY OF RESEARCH

Over a quarter of a century after their first publication, both Key’s analyses and his
interpretations are widely accepted. His suggestion that the origin of the arsenical ore used
for the manufacture of the ornamental objects was in an area more than 1300 km distant
from the site of their discovery is still seen as reasonable. As noted by Moorey (1988, 185),
this view is even now used to reinforce arguments about cultural diffusion and the foreign
The metallurgy of the Nahal Mishmar hoard reconsidered 39

(a) Merallography of a hammered copper axe from the Nahal Mishmar hoard (after Potaszkin and Bar-Avi 1980).

(b) Metallography of a copper chisel from Makuch showing a deformed recrystallized grain structure with annealing
twins and slip traces.
Figure 4 Similarities in the manufacture and microstructure of toots.

origin of the hoard which have been favoured on other grounds by various scholars (e.g.
Perrot 1968, 441; Hauptmann 1989, 131; Mazar 1990, 73). Recent analytical work (Shalev
and Northover 1987; Shalev 1991; Levy and Shalev 1989) has demonstrated that the direct
correlation between two metal types and two categories of artefacts (tools and prestige/cult
objects) seen a t Nahal Mishmar (Figures 3 and 4) is also found in a group of habitation and
burial sites in southern Israel (Figure 2). This differentiation between two contemporary
metallurgies has been accepted by others (Moorey 1988; Gilead 1988; Ilan and Sebbane
40 S . Shalev and J . P . Northover

1989; Hauptmann 1989;Tadmor 1989; Mohen 1990).The analysis of crucibles, slags and ore
from these sites (Shalev and Northover 1987)demonstrated clearly that the tools were locally
manufactured and thus clarified the archaeological and technological context of the tools in
the Nahal Mishmar hoard. However, the context of the majority of the hoard, the
ornaments, remains unclear.
The analysis of a mace head from the Chalcolithic site of Shiqmim (Shalev et al. 1992)
showed that the same manufacturing process (lost wax casting over a stone core) was used as
in the one example from the Nahal Mishmar hoard that was examined metallographically
(Figure 3; Potaszkin and Bar-Avi 1980). However, the objects from Shiqmim showed an
important and consistent difference from those analysed by Key. According to Key the
prestige/cult objects in the Nahal Mishmar hoard were ‘alloyed’ only with arsenic; the
analyses from Shiqmim, while showing comparable concentrations of arsenic, had higher
levels of antimony than of arsenic. The Shiqmim data, however, agree very well with the
analysis by A. Lupu of a standard from a Chalcolithic burial cave at Palmahim (Gophna and
Lifshitz 1980) and the analysis by M. R. Notis et al. (1984) of a mace head supposedly from a
Judean Desert cave.
The differences between these analyses and the consistent low antimony content in Key’s
data could simply be explained by the choice of a distinctly different type of ore. However,
the typological and technological similarities between these objects and the majority of the
Nahal Mishmar hoard only emphasized the discrepancy in apparent chemical composition.
It was therefore decided that some of the material from the Nahal Mishmar hoard should be
re-examined in order to establish whether Key’s data were correct or whether the Nahal
Mishmar compositions did parallel those of other Chalcolithic finds.

RE-ANALYSIS

From among the objects analysed by Key, four mace heads and one standard from the Nahal
Mishmar hoard and one axe and three mace heads from Nahal Zeelim were re-analysed. The
samples were obtained by drilling, using a 0.5 mm diameter bit. For further comparison, nine
more objects from the Nahal Mishmar hoard were sampled by drilling and, where possible,
by taking a cut sample for metallographic study, using a jeweller’s piercing saw. The samples
were hot-mounted in a copper-filled acrylic resin, ground and polished, the final polish being
with 1 pm diamond paste.
All samples were analysed by electron probe microanalysis (EPMA) with wavelength
dispersive spectrometry (WDS) (for a description of the method and its precision, see
Heinrich and Newbury 1986). Comparative analyses were made in the Institute of
Archaeology, Tel Aviv University, using atomic absorption spectrophotometry (AAS)
following the methods of Hughes et af. (1976). Details of the operating conditions for both
methods are given in the Appendix.
The comparison of the new quantitative analyses with those obtained by Key is shown in
Table 1. It is not clear which of the three mace heads from Nahal Zeelim was analysed by
Key; all three EPMA analyses are therefore included for comparison. The EPMA analyses
were made on sound metal and totals were close to 100%; the compositions were therefore
normalized to 100% whereas the AAS data were not normalized. All concentrations are
given in weight per cent.
The metallurgy of the Nahal Mishmar hoard reconsidered 41
Table 1 Comparison of Key’s results with new quantitative analyses of the same objects (wt %)

As Sb Ag Bi Pb Ni Sn Zn Co Fe Cu Au

NAHAL MISHMAR
Mace heads
61-351
Key 3.50 0.18 0.12 tr. 0.03 0.17 n.d. n.d. n.d.
EPM A 3.41 5.59 0.33 0.57 0.27 0.30 0.01 n.d. 0.01 0.04 89.5 n.d.
AAS 2.24 4.20 0.32 0.33 0.18 0.25 tr. 0.19 n.d. 0.15 70.0 tr.
61-226
Key 6.90 0.60 0.16 0.03 0.07 0.84 n.d. n.d. n.d.
EPM A 4.63 0.02 0.03 0.06 0.23 7.96 0.02 n.d. 0.03 0.01 87.0 tr.
AAS 2.52 0.07 0.03 0.04 0.14 8.27 tr. 0.05 0.03 0.06 79.4 0.02
6 1-278
Key 6.50 0.20 0.01 tr. n.d. 1.35 n.d. n.d. n.d.
EPMA 4.43 0.27 0.03 tr. 0.02 4.42 tr. n.d. n.d. 0.03 90.8 0.03
AAS 3.78 0.19 0.02 tr. n.d. 3.98 0.23 0.08 n.d. 0.07 87.4 0.02
61-311
Key 6.60 0.58 0.08 0.02 0.32 0.59 n.d. n.d. n.d.
EPMA 1.48 0.50 0.13 0.39 0.06 0.08 0.01 n.d. tr. tr. 97.3 n.d.
AAS 2.18 0.54 0.15 0.40 0.05 0.09 n.d. 0.06 n.d. 0.04 88.5 n.d.
Standard
61-104
Key n.d. n.d. n.d. n.d. n.d. 0.10 n.d. n.d. n.d.
EPMA 0.14 0.01 0.04 n.d. 0.02 0.13 tr. 0.01 tr. 0.02 99.6 0.03

NAHAL ZEELIM
Mace head
Key 4.60 0.28 0.11 0.01 0.09 0.34 n.d. n.d. n.d.
87-491 EPMA 4.05 5.20 0.40 0.36 0.25 0.38 0.04 n.d. 0.01 0.01 89.2 0.10
87-492 EPMA 3.85 5.24 0.28 0.31 0.26 0.63 0.03 n.d. 0.01 0.03 89.3 0.02
87-493 EPMA 3.52 6.34 0.21 0.30 0.34 0.63 0.04 n.d. n.d. 0.01 88.5 0.09
Axe
Key tr. 0.01 0.03 tr. n.d. 0.50 n.d. n.d. n.d.
87-494 EPMA 0.26 0.02 0.02 0.01 0.02 0.02 0.01 n.d. tr. tr. 99.6 0.02

Key: results obtained by Key using spark emission optical spectroscopy.


EPMA: results obtained by electron probe microanalysis.
AAS: results obtained by atomic absorption spectro-photometry.
n.d.: not determined; tr.: trace.

DISCUSSION

These results show relatively good agreement between the two techniques used in our study.
The differences between EPMA and AAS have a number of causes. For arsenic, the
sensitivity and accuracy of AAS was reduced because flameless atomization was not
available. More generally, the AAS data are affected by the state of corrosion of the objects
and by samples smaller than the ideal. The small sample size has its greatest impact on the
determination of those elements in the greatest concentration, here copper, because of the
42 S. Shalev and J . P.Northover

large dilutions necessary. The castings are heterogeneous both in terms of dendritic and
other segregation and by the variable degree of corrosion, non-metallic inclusions and
porosity. The EPMA method enables the analyst to choose areas of sound metal for analysis
by means of an optical or electron image but, of course, such areas may not be fully
representative of the whole object. On the other hand, with AAS there is no metallographic
guide to sample quality. For example, corrosion could well account for the higher level of
iron in the AAS analysis of 61-351. On the other hand, the high As/Sb phases are more
resistant to corrosion and these areas are preferentially selected for EPMA analysis, possibly
giving the higher levels of arsenic seen in 61-35 1 and 61-226. It can be said, therefore, that to
obtain the fullest understanding of the composition of these objects it is preferable to use the
two techniques together rather than either one separately.
In contrast to this general agreement between EPMA and AAS, the discrepancies with
Key’s data are striking. For unalloyed copper the differences are relatively small except for
arsenic, where the limit of detection was poor, and for nickel. For ‘alloyed’ artefacts Key
correctly identified, in most cases, the occurrence of arsenic; his measured concentrations
tend to be higher than those in our re-analysis but this could be attributed to differences in
sample location. However, it is now apparent that the concentrations of virtually all the
other elements estimated by Key need to be reconsidered. For some elements it could be
argued that segregation within the castings could account for significant variability. For
example, lead and bismuth are insoluble and segregate as inclusions in the interdendritic
material but even here, however, it is the AAS and EPMA data that are in good agreement
and Key’s that is at variance. The same applies to other potential segregates such as silver.
Other differences are less explicable; some, such as the recording of 0.8% nickel rather
than 8% measured by both techniques in the re-analysis could be a misprint or a
misidentification of the sample in the original publication. The most obvious discrepancy,
however, cannot be explained in this way. This is the constant minimal detection of
antimony when it is present in quantities higher than arsenic. The results show one of the re-
analysed mace heads from Nahal Mishmar and all three from Nahal Zeelim to be of copper
alloyed with antimony and arsenic, with Sb > As. These results parallel the recently
published data from other sites. Further data on the extent of use of these alloys are provided
by EPMA and AAS analyses of nine more samples from the Nahal Mishmar hoard. The
results are given in Table 2. The associated microstructures are the subject of continuing
research which will be published elsewhere.
In two cases in Table 2 two samples were available for microprobe analysis: both analyses
and their means are given to illustrate the variability in composition within these objects. In
two samples (61-115, 61-94) only areas rich in high alloy phases were accessible for fully
quantitative analyses as the results make clear.
The alloying of copper with arsenic and antimony is thus seen to be a consistent feature of
the prestige/cult objects. Nickel may also be present at ‘alloy’ levels while bismuth, lead and
silver are consistent impurities. Alloys with arsenic and nickel, with antimony only at
impurity levels, are a rarer alternative. The highly alloyed coppers of the Nahal Mishmar
hoard have, due to their composition, a silvery-grey appearance, quite distinct from the red
colour of the tools. Moreover, this metal is harder than copper and easily polished. The gloss
would match that of the drilled and polished mace heads of haematite although the
underlying colour of haematite would be noticeably darker.
There is still much work to be done on the provenance of the ores and the smelting
The metallurgy of the Nahal Mishmar hoard reconsidered 43

Table 2 New quantitative analyses of objects from the Nahal Mishmar hoard

As Sb Ag Bi Pb Ni Sn Zn Co Fe Cu Au

NAHA L MISHMA R
Mace heads
61-1 15
EPMA 8.22 18.29 0.98 1.00 0.02 0.08 0.11 n.d. 0.02 n.d. 71.3 n.d.
6 1-400
EPMA 3.25 5.71 0.37 0.49 1.30 0.24 0.04 n.d. tr. tr. 88.6 0.05
AAS 3.OO 5.90 0.45 0.38 0.90 0.22 tr. 0.06 n.d. 0.18 75.0 0.02
61-223
EPMA 2.75 5.30 0.25 0.25 0.25 0.39 0.02 n.d. tr. 0.02 90.7 0.03
AAS 3.27 5.30 0.25 0.24 0.25 0.34 0.21 0.10 n.d. 0.19 78.4 n.d.
61-249
EPMA 2.57 4.76 0.31 0.42 0.13 0.35 0.01 n.d. tr. 0.03 91.4 tr.
AAS 3.48 3.70 0.32 0.23 0.12 0.30 tr. 0.05 n.d. 0.13 87.1 tr.
61-373
EPMA I .85 5.48 0.41 0.34 0.56 0.30 0.04 n.d. tr. 0.01 91.0 0.05
AAS 1.65 4.80 0.43 0.33 0.33 0.30 tr. 0.06 n.d. 0.08 88.5 tr.
61-371
EPMA 2.68 2.87 0.26 0.42 0.54 0.22 0.02 n.d. n.d. 0.02 93.0 tr.
AAS 2.25 4.00 0.40 0.47 0.58 0.28 tr. 0.06 n.d. 0.08 85.0 tr.

Standard
6 1-94
EPMA 6.29 22.55 0.63 1.40 3.01 0.18 0.12 n.d. 0.01 0.12 65.7 n.d.

'Crown'
61-179
EPMAjI 3.05 4.28 0.20 1.07 1.25 1.57 0.06 n.d. n.d. 0.03 88.4 0.05
EPMA/2 2.23 1.78 0.30 0.64 0.65 1.37 0.01 n.d. n.d. tr. 93.0 n.d.
EPMA/mean 2.64 2.99 0.25 0.86 0.95 1.47 0.04 n.d. n.d. 0.02 90.7 0.03

Basket-like vessel
61-162
EPMAjl 6.44 15.95 0.62 0.95 0.39 1.45 n.d. n.d. 0.01 0.18 73.9 n.d.
EPMA/2 6.27 8.20 0.49 0.73 0.27 2.00 0.08 n.d. 0.01 0.10 81.9 0.08
EPMA/mean 6.36 12.08 0.56 0.84 0.33 1.73 0.04 0.01 0.14 77.9 0.04
AAS 6.56 10.31 0.98 0.83 0.32 2.50 0.13 0.01 0.23 62.5 n.d.

See Table 1 for key.

technology involved. The question of provenance is being pursued elsewhere (Stos-Gale


1991) and discussion here will consider only the production of these alloys. Recent research
on primitive smelting of arsenic- and antimony-rich coppers (Pollard el al. 1990a and 1990b;
Rostoker and Dvorak 1991) have suggested possible mechanisms. The experiments of
Pollard et al. are concerned with the smelting of high grade oxide ores at temperatures
significantly below the melting point of copper. They demonstrate that in these conditions
(around 900 "C) copper, arsenic, antimony and other elements can be fully reduced to the
44 S . Shalev and J . P . Northover

(a) Microstructure of another mace head from Shiqmim: striations in the ternary high alloy phase

(b) Microstructure afa fragment of a crown,froni Shiqmim: acicular structure in the ternary high alloy phase with a
higher proportion of antimony than in (a).
Figure 5 Microstructures of ternary As-Cu-Sb ulloys.

solid state with minimal losses to the vapour phase. Diffusion of the alloying elements raises
their concentration in the copper to such an extent that the liquidus temperature of the alloy
formed is eventually less than the reaction temperature and the alloy melts. This model is
attractive because the recovery of alloying elements is very high and oxide ores are used, the
low sulphur content (0.01-0.06%) of the Nahal Mishmar material arguing for the use of such
ores and against the use of sulfo-salt ores (cf. Rapp 1989).
Rostoker and Dvorak used smelting temperatures of 1250-1 300 “Censuringthe fluidity of
both metal and slag. Their experiments involved both oxide and sulphide ores, the sulphur in
sulf-arsenate minerals itself being employed as a reducing agent when realgar was co-smelted
The metallurgy of the Nahal Mishmar hoard reconsidered 45

with malachite. Arsenic recovery was high with an average concentration reaching 9.7%
when the crucible was closed with a lid and production of toxic fumes was almost eliminated.
It is also noteworthy that the Cu3As phase in the experimental microstructures produced by
Rostoker and Dvorak (1991,12-13, figs. 1-2) show the same striated appearance as in some
examples from the Chalcolithic (Figure 5 (a)). The striated structure is not well understood
but occurs when the phase is rich in arsenic and based on Cu3As. As antimony increases the
phase changes to one based on Cu3Sb which undergoes different transformations, possibly
martensitic (Figure 5 (b)).
Although we can see from the compositions and casting techniques that the prestige
metalwork was the product of an industry separate from that producing tools, no site
evidence for its manufacture has yet been found. So far, comparison with Early Bronze Age
metalwork in Israel shows that this technology with its As-Cu-Sb alloys was unknown in the
Early Bronze Age.

CONCLUSIONS

It is beyond the scope of this paper to investigate in detail the technical reasons for Key’s
inaccuracies. Analytical techniques have advanced dramatically in the last 30 years and their
application is much more reliable and reproducible. Spark emission spectroscopy is a far
from simple technique and requires great care in setting up, exposure and measurement of
the spectrographic plate. It also appears that, while the artefact analyses were by spark
emission, the standardization was carried out by arc emission on pure elements.
It seems that incorrect analyses, as well as the absence of more contextual archaeological
evidence, led Key to his main conclusions regarding the origin of the Nahal Mishmar
treasure. With our new data and the ideas now emerging concerning the production of these
ternary alloys a simpler working hypothesis can be provided for future research. Not only
can the small group of tools from the hoard be linked to a distinct temporal and spatial
context, but also most of the prestige objects are found to bear a close metallurgical
resemblance to those retrieved from well-dated Chalcolithic sites in southern Israel. We can
now emphasize the localized distribution of the prestige/cult end-products and speculate
about the existence of a production centre appreciably nearer than Anatolia or Trans-
caucasia (Shalev et al. 1992). Based on this altered evidence, we can now interpret the
Chalcolithic hoard from Nahal Mishmar not only via its typological and cultural context
(Moorey 1988) but from the viewpoint of its metallurgy as well.
Even so, we must not forget that Key’s pioneering work in the 1960s was the starting point
for the reconstruction of the beginnings of metallurgy in our region. When, at the end of the
1980s, it failed to explain the accumulating archaeological and metallurgical evidence, it had
to be re-examined. Our work, at present, is based on a significantly improved metallurgical
and technological data base, but further refinements in knowledge and techniques could well
alter the interpretation in the same way as re-excavation of a site can do for the field
archaeologist.

ACKNOWLEDGEMENTS
The authors wish to thank A. Drori, R. Peled and B. Brandel of the Antiquities Authority and M. Tadmor from the
Israel Museum for permission to sample the material; Y . Deutsch and S. Ehrlich of the Geological Survey of Israel
for helping to trace Key’s analytical equipment and methods; Professor Sir Peter Hirsch, Department of Materials,
46 S . Shalev and J. P. Northover

University of Oxford, and Professor J. Yakar, Institute of Archaeology, Tel Aviv University, for laboratory
facilities. Special thanks are due to N. Halperin, also from the Institute of Archaeology, who assisted with the AAS
analyses; B. Eliel and S. Gasner who helped in bringing this article to its present state; and C. A. Key who in his
pioneering work left us an example to follow.

APPENDIX: DETAILS O F ANALYTICAL ROUTINES


Electron probe microanalysis was carried out on the CAMEBAXm automated instrument in the Department of
Materials, University of Oxford, using wavelength dispersive spectrometry. For electron probe microanalysis the
operating conditions were an accelerating voltage of 25 kV, an absorbed electron current a t the sample of
approximately 30 nA, and an X-ray take-off angle of 40".Pure element standards were used for all elements.
Detection limits for most elements were 100-200 ppm, but 300 ppm for gold and 0.10% for arsenic. This last is
because of the compromises made to avoid the well-known interference between the strongest lines in the lead and
arsenic spectra, the lead La and arsenic Ka lines. Here the moderately strong lead Ma line was used but the weak
arsenic KB line had to be used. The arsenic La line could not be used in conjunction with the high accelerating
voltage as the ZAF corrections become so large as to make accuracy very poor. At least three areas, each 50 pm
square, were analysed on each sample; only the mean analyses are used in the tables. A further modification in the
limits of detection occurs for zinc in copper where there is a zero error of up to 300 ppm caused by the measurement
of the background at a location that is affected by the tail of the Cu KB peak.
For atomic absorption spectrophotometry standard techniques were used (e.g. Hughes et al. 1976). The
instrument used was an Instrumentation Laboratory 157. The samples were dissolved in aqua regia (1 HNO3:3
HCI). Limits of detection were less than 200 ppm for all elements except for Cu (0.15%), arsenic (400 ppm) and tin
(0.12%) based on a sample of 10 mg in 10 ml. However, some samples were smaller than this ideal with a
corresponding effect on the limits of detection.

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