Archaeometry
Archacometry 35, 11 (1993),
(1993). 35-47. Printed
Printed in Great
Great Britain
Britain
THE METALLURGY
METALLURGY OF THE
THE NABAL
NAHAL MISHMAR
MISHMAR HOARD
THE
RECONSIDERED*
RECONSIDERED*
S.
S . SHALEV
SHALEV
Institute
Institute of
of Archaeology,
Archaeology. Tel
Tel Aviv
Aviv University,
University. Ramat
Ramat Aviv,
Aviv, Israel
and J.
J. P. NORTHOVER
NORTHOVER
Department of
Department
of Materials,
Materials. University
University of
of Oxford,
Oxford, Parks
Parks Road,
Road, Oxford,
Oxford, OXJ
OX1 3PH,
3PH. U.K.
U.K.
The Naha/
find for the
Nahal Mishmar
Mishmar hoard.found
hoard,found in a cave in the Judean
Judean Desert
Desert in 1961,
1961, is a key
keyfindfor
study
Chalcolithic
study of Cha/eolithic
Chalcolithic metallurgy
metallurgy in Israel
Israel and the Levant.
Levant. Recent
Recent analyses
analyses of Cha/eolithic
metalwork
metalwork from
from sites such as Shiqmim
Shiqmim in Israel
Israel raised
raised doubts
doubts about
about the validity
validity ofpublished
ofpublished
analyses
analyses from
from the hoard.
hoard. Accordingly
Accordingly a programme
programme of re-analysis
re-analysis was established
established using
atomic absorption
absorption spectrometry
spectrometry and electron
electron probe
probe microanalysis.
microanalysis. The
The new analyses
analyses
atomic
same as that
Mishmar was the same
Nahal Mishmar
that the metallurgy
andshowed
doubts and
confirmed the doubts
confirmed
showed that
metallurgy of Naha/
other sites.
sites. The
The alloys
alloys usedfor
used for the cast products
products in the hoard
hoard were generally
generally ternary
ternary
at the other
arsenic-antimony
arsenic-antimony copper alloys
alloys with up to 20%
common were
content; less common
20% alloy
alloy content;
compositions
described.
compositions with arsenic
arsenic and nickel.
nickel. The
The unusual
unusual metallography
metallography of these
these alloys
alloys is described.
Some
Some suggestions
suggestions are offered
offered as to the mode
mode of manufacture
manufacture of the alloys.
alloys.
KEYWORDS:
KEYWORDS: ISRAEL,
ISRAEL, CHALCOLITHIC,
CHALCOLITHIC, NAHAL
NAHAL MISHMAR,
MISHMAR, ANALYSIS,
ANALYSIS,
ARSENIC-ANTIMONY-COPPER
ALLOYS, ARSENIC-COPPER-NICKEL
ARSENIC-COPPER-NICKEL ALLOYS,
ALLOYS,
ARSENIC-ANTIMONY-COPPER ALLOYS,
METALLOGRAPHY,
METALLOGRAPHY, SMELTING
SMELTING
INTRODUCTION
INTRODUCTION
On
On 21 March 1961
1961 the archaeologist
archaeologist Pesah
Pesah Bar
Bar Adon discovered
discovered a treasure of 429
429 objects
objects
thin reed
reed mat (Figure 1) in a remote
remote cave
cave situated in
in the
the cliffs
cliffs of Nabal
Nahal
wrapped in a thin
Mishmar, in the
the Judean Desert
Desert near the Dead
Dead Sea
Sea (Figure 2; Bar
Bar Adon 1971
1971 and
and 1980).
1980). Of
Mishrnar,
the 429 artefacts,
artefacts, the
the majority (416)
(416) are made
made of copper-based
copper-based metals.
metals. Despite
Despite the 30 years
years
the
have elapsed
elapsed since
since it was
was found,
found, this
this hoard is still
still the largest
largest and,
and, almost certainly,
certainly, the
that have
oldest
oldest in the
the entire
entire Near East.
East. Therefore,
Therefore, it is not surprising
surprising that
that it has become
become one
one of the
major sources
sources for the
the study
study of the
the Chalcolithic
Chalcolithic culture of the
the fourth
fourth millennium
millennium BC to which
which
it belongs.
belongs.
A pioneering
pioneering metallurgical
metallurgical investigation
investigation of the
the hoard
hoard was
was conducted by
by C.
C . A.
A. Key
Key of the
Geochemistry
Geochemistry Division,
Division, Geological
Geological Survey
Survey of Israel
Israel (Key
(Key 1964,
1964, 1971,
1971, and
and 1980).
1980). His
His work
was
was the
the first
first systematic
systematic analysis
analysis of trace elements
elements for
for metalwork finds
finds from
from the ancient
ancient
southern Near East.
East. Key's
Key’s work
work emerged
emerged in what was
was almost
almost a vacuum
vacuum of knowledge
knowledge and its
its
impact was
was therefore
therefore correspondingly
correspondingly large.
large. Even
Even now,
now, more
more than
than a quarter
quarter of a century
century
impact
later,
the early
later, his
his work
work is still
still playing
playing a major role
role in our
our understanding of the
early history of
metallurgy. The
The aim
aim of this
this paper is to re-evaluate
re-evaluate these
these metallurgical
metallurgical data
data and their
metallurgy.
subsequent
subsequent interpretation in the
the light
light of new analytical
analytical work.
work.
12 February
February 1991, accepted 19
19 March
March 1992.
1992.
•* Received 12
35
35
S.
S. Shalev and J.
J . P.
P . Northover
Northover
36
(a)
(a) The
The hoard in its discovered
discovered location
location (( W.
W . Braun).
Braun).
(b) A selection of
and photographed
of objects
objects in the collection
collection of
of the Israel Antiquities
Antiquities Authority
Aulhoriry (exhibited
(exhibitedand
photographed in lhe
the Israel
Museum).
Museum).
Figure
Figure 11
The
after Metropolitan
The hoard of Naha/
Nahal Mishmar
Mishmar ((ufter
Metropolitan Museum
Museum of
of Art 1986).
1986)
METALLURGICAL
ANALYSTS
METALLURGICAL ANALYSTS
X-ray fluorescence
fluorescence analysis
analysis by L. Heller
Heller of the Geological Survey
Survey of Israel
Israel
Preliminary X-ray
revealed a significant
significant amount
amount of arsenic
arsenic in some
some of the mace
mace heads from
from the hoard.
hoard. This
This led
led
revealed
C.
C . A.
A. Key
Key to postulate
postulate the use
use of sulphide
sulphide ores;
ores; to pursue
pursue this question
question he
he decided to analyse
analyse
more
more fully
fully the
the trace
trace elements
elements in
in some
some 30 artefacts
artefacts from
from the hoard
hoard as
as well
well as
as three
three related ones
ones
from
from other
other sites.
sites. Spark
Spark emission
emission spectroscopy
spectroscopy was
was used
used to measure
measure the concentrations
concentrations of
nine elements
elements (As,
(As, Sb,
Sb, Ag,
Ag, Bi, Pb,
Pb, Ni, Sn,
Sn, Zn, Co).
Co). Technical
Technical details,
details, limits
limits of detection
detection and
and
estimates
1980). The
estimates of precision are
are given
given by
by Key
Key (1964
(1964 and 1980).
The limits
limits of detection
detection quoted
quoted are
are
The metallurgy
metallurgy of the Naha/
Nahal Mishmar
Mishmar hoard reconsidered
o
37
20
.. Crown
t Standard
• Macehead
, Axe/Chisel
I Awl
Sile with Industry
e
O Sile without Indus.
~-,
=-lfü
::::... 1
§.§.
?
ºPalmahim
1
·t1
Bir Uda8
•2
e3 t2
••
t 1 '4
t1Qt
Arad
Beter
~
•
1
-•
Masos
Shrqmime'Matar•
~•
'
~
Safadi·Neve Noy
•
4
ì
Figure 2 Distribution of metal products
products and industrial remains
remains (after
(after Shalev
Shalev 1991).
1991).
300 ppm
ppm or less except
except for arsenic
arsenic where
where the
the limit
limit was 1.9%; no
no explanation
explanation was offered
offered for
for
this value
value which
which is high
high compared
compared with
with the
the performance
performance of other contemporary
contemporary analysis
analysis
programmes.
programmes.
The
The analytical
analytical data were correlated
correlated with
with the
the metallographic
metallographic study
study carried
carried out by
R.
R. Potaszkin
Potaszkin and
and K.
K. Bar Avi (1971 and
and 1980) and helped
helped to define
define the
the technological
technological
differences
differences between
between two
two groups
groups of objects,
objects, the
the ornaments
ornaments and
and the
the tools.
tools. With
With one
one exception
exception
(at
(at 1.9%
1.9% As),
As), the
the nine
nine analysed
analysed tools
tools from
from the
the hoard as well as
as one
one from
from Nabal
Nahal Zeelim
Zeelim were
all made
made from
from impure
impure but 'unalloyed'
‘unalloyed’copper.
copper. The
The 22 analysed
analysed ornaments
ornaments from
from the
the hoard as
well as the
the two from
from Nabal
Nahal Zeelim
Zeelim and
and Abu
Abu Matar were,
were, with
with two
two exceptions,
exceptions, all recorded
recorded as
being made
made ofcopper-arsenic
of copper-arsenic 'alloys'.
‘alloys’.The
The arsenic
arsenic content
content ranged
ranged from
from 1.9% to 11.9%,
I 1.9%, while
nickel, lead,
lead, antimony,
antimony, silver and
and bismuth
bismuth were found
found as
as impurities
impurities in concentrations
concentrations
varying
varying up
up to approximately
approximately 0.5%.
0.5%.
On
On the basis
simple shapes
basis of these
shapes and metal
these data Key
metal compositions
compositions of
Key concluded:
concluded: (1) the simple
the
the tools
tools might
might have
have resulted
resulted from
from their
their being
being either
either older
older than the
the ornaments
ornaments or being
being made
made
by different
tools might
different craftsmen;
craftsmen; (2) the
the compositions
compositions and
and structures
structures of the
the tools
might represent
represent the
the
forging
forging of native
native copper;
copper; (3) the
the compositions
compositions of the
the ornaments
ornaments show
show that copper
copper suifo-salts
sulfo-salts
(here
(here sulf-arsenates)
sulf-arsenates) were
were deliberately
deliberately used for
for their
their manufacture;
manufacture; (4)
(4)the
the nearest
nearest such
such sulf­
sulfarsenate
arsenate ore
ore sources
sources (e.g.
(e.g. enargite
enargite and
and tenantite)
tenantite) described
described in contemporary
contemporary geological
geological
literature
literature were in Transcaucasia,
Transcaucasia, in Armenia
Armenia and
and Azerbaijan;
Azerbaijan; (5)
( 5 ) the
the use of such
such a complex
complex
sulphide
sulphide ore
ore in the
the fourth millennium
millennium BC required
required not only
only long-distance
long-distance cultural contacts
contacts
but
but also
also the
the knowledge
knowledge of roasting
roasting the
the ore
ore before
before smelting.
smelting.
S.
S. Shalev and J.
J . P.
P . Northover
Northover
38
(a) Microstructure
after Potaszkin
Microstructure of the mace
mace head
head from
from the Naha/
Nahal Mishmar
Mishmar hoard
hoard ((after
Potaszkin and
and Bar-Avi
Bar-Avi 1980).
1980).
(b) Microstructure
Microstructure of the mace head from
from Shiqmim
Shiqmim (ata
(at a higher
higher magnification
magnification than
than (a),
(a), showing
showing an irregular as-cast
as-cast
(b)
Shalev et al. 1992
(after Shalev
As-Cu-Sb alloy
alloy (after
1992).
dendriric structure
structure in an As-Cu-Sb
dendritic
J.
Figure
Figure 3
Similarities
Similarities in the microstructure
microstructure of mace
mace heads
head.s cast
casi over a core.
core.
HISTORY OF
OF RESEARCH
RESEARCH
HISTORY
Over
Over a quarter of a century
century after
after their
their first
first publication,
publication, both
both Key's
Key’s analyses
analyses and
and his
interpretations
interpretations are
are widely
widely accepted.
accepted. His
His suggestion
suggestion that the
the origin
origin of the
the arsenical
arsenical ore
ore used
used
for
for the
the manufacture
manufacture of the
the ornamental
ornamental objects
objects was
was in an
an area
area more
more than 1300 km
km distant
from the site of their
their discovery
discovery is still seen as reasonable.
noted by Moorey
Moorey ((1988,
from
reasonable. As noted
1988, 185),
this
this view is even now
now used to
to reinforce
reinforce arguments
arguments about cultural
cultural diffusion
diffusion and
and the
the foreign
foreign
The metallurgy of
of the Naha/
Nahal Mishmar
Mishmar hoard reconsidered
The
39
39
(a)
(a) Metallography
Merallography of a hammered
hammered copper
copper axe from
from the Naha/
Nahal Mishmar hoard
hoard (after
(after Potaszkin and Bar-Avi 1980).
1980).
(b) Metallography
Metallography of a copper
copper chisel from
from Makuch
Makuch showing
showing a deformed
deformed recrystallized
recrystallized grain
grain structure
structure with
with annealing
annealing
twins
slip traces.
traces.
twins and slip
Figure
Figure 44 Similaríties
Similarities in
in the manufacture
manufacture and microstructure
microstructure of tools.
toots.
origin of the hoard
hoard which have been favoured on other
other grounds
grounds by
by various
various scholars
scholars (e.g.
Perrot
Perrot 1968, 441; Hauptmann
Hauptmann 1989,
1989, 131;
131; Mazar
Mazar 1990, 73). Recent analytical
analytical work (Shalev
Northover 1987;
1987; Shalev 1991;
1991; Levy and Shalev 1989)
1989) has demonstrated
demonstrated that
that the direct
direct
and Northover
correlation between two metal types and
and two categories of artefacts
artefacts (tools
(tools and prestige/cult
prestige/cult
correlation
objects) seen
seen at
a t Nabal
Nahal Mishmar
Mishmar (Figures
(Figures 3 and
and 4) is also
also found
found in a group
group of habitation
habitation and
and
southern Israel (Figure
(Figure 2). This differentiation
differentiation between two contemporary
contemporary
burial sites in southern
metallurgies has been accepted by others
others (Moorey
(Moorey 1988;
1988; Gilead
Gilead 1988; Ilan and
and Sebbane
Sebbane
metallurgies
40
40
S . Shalev and J.
J . P.
P . Northover
Northover
S.
1989;
1989;Hauptmann
Hauptmann 1989;
1989;Tadmor
Tadmor 1989;
1989;Mohen
Mohen 1990).
1990).The
The analysis
analysis of crucibles,
crucibles, slags
slags and
and ore
ore
from
from these
these sites
sites (Shalev
(Shalev and Northover
Northover 1987)
1987)demonstrated
demonstrated clearly
clearly that
that the tools
tools were
were locally
locally
manufactured
technological context
manufactured and
and thus clarified
clarified the archaeological
archaeological and
and technological
context of the tools
tools in
the
the Nabal
Nahal Mishmar
Mishmar hoard.
hoard. However,
However, the context
context of the
the majority
majority of the
the hoard,
hoard, the
ornaments,
ornaments, remains
remains unclear.
unclear.
The
The analysis
analysis of a mace
mace head from
from the Chalcolithic
Chalcolithic site
site of Shiqmim
Shiqmim (Shalev
1992)
(Shalev et al. 1992)
showed
showed that
that the
the same
same manufacturing
manufacturing process
process (lost
(lost wax
wax casting
casting over
over a stone
stone core)
core) was
was used
used as
as
in the one
one example
example from
from the Naha]
Nahal Mishmar
Mishmar hoard
hoard that
that was
was examined
examined metallographically
metallographically
(Figure
(Figure 3; Potaszkin
Potaszkin and Bar-Avi
Bar-Avi 1980).
1980). However,
However, the objects
objects from
from Shiqmim
Shiqmim showed
showed an
an
important
important and
and consistent
consistent difference
difference from those
those analysed
analysed by
by Key.
Key. According
According to
to Key
Key the
the
prestige/cult
prestige/cult objects
objects in the Nabal
Nahal Mishmar
Mishmar hoard
hoard were
were 'alloyed'
‘alloyed’ only
only with arsenic;
arsenic; the
analyses
analyses from
from Shiqmim,
Shiqmim, while
while showing
showing comparable
comparable concentrations
concentrations of arsenic,
arsenic, had higher
levels
arsenic. The
The Shiqmim
Shiqmim data,
data, however,
however, agree
agree very
very well
well with
with the
the
levels of antimony
antimony than
than of arsenic.
analysis
analysis by A. Lupu
Lupu of a standard
standard from a Chalcolithic
Chalcolithic burial cave
cave at
at Palmahim
Palmahim (Gophna
(Gophna and
and
Lifshitz
R. Notis
Notis et al. (1984)
(1984) of a mace
mace head supposedly
supposedly from
from a
Lifshitz 1980)
1980)and
and the
the analysis
analysis by
by M.
M. R.
Judean
Judean Desert
Desert cave.
cave.
The
The differences
differences between
between these
these analyses
analyses and
and the consistent
consistent low
low antimony
antimony content
content in
in Key's
Key’s
data could
could simply
simply be
be explained
explained by the choice
choice of a distinctly
distinctly different
different type
type of ore.
ore. However,
However,
the
the typological
typological and
and technological
technological similarities
similarities between
between these
these objects
objects and
and the majority
majority of the
the
Nabal
Nahal Mishmar
Mishmar hoard
hoard only
only emphasized
emphasized the discrepancy
discrepancy in apparent
apparent chemical
chemical composition.
composition.
It was
was therefore
therefore decided
decided that
that some
some of the material
material from
from the Nabal
Nahal Mishmar
Mishmar hoard
hoard should be
re-examined
re-examined in order
order to establish
establish whether Key's
Key’s data
data were
were correct
correct or
or whether the
the Nabal
Nahal
Mishmar
Mishmar compositions
compositions did
did parallel those
those of other
other Chalcolithic
Chalcolithic finds.
finds.
RE-ANALYSIS
RE-ANALYSIS
From
From among
among the objects
objects analysed
analysed by
by Key,
Key, four mace
mace heads
heads and
and one
one standard
standard from
from the Nabal
Nahal
Mishmar
Mishmar hoard
hoard and
and one
one axe
axe and
and three mace
mace heads
heads from
from Nabal
Nahal Zeelim
Zeelim were
were re-analysed.
re-analysed. The
The
samples were
were obtained
0.5 mm diameter
diameter bit.
bit. For
For further
further comparison,
comparison, nine
obtained by drilling,
drilling, using
using a 0.5
samples
more
more objects
objects from the Nabal
Nahal Mishmar
Mishmar hoard
hoard were
were sampled
sampled by
by drilling
drilling and,
and, where
where possible,
possible,
by taking
taking a cut sample
sample for metallographic
metallographic study,
study, using
using a jeweller's
jeweller’s piercing
piercing saw.
saw. The
The samples
samples
were
were hot-mounted
hot-mounted in
in a copper-filled
copper-filled acrylic
acrylic resin,
resin, ground
ground and
and polished,
polished, the
the final
final polish
polish being
being
with
with 11 µm
pm diamond
diamond paste.
paste.
All
microanalysis (EPMA)
All samples
samples were
were analysed
analysed by
by electron
electron probe
probe microanalysis
(EPMA) with wavelength
wavelength
dispersive
dispersive spectrometry
spectrometry (WDS)
(WDS) (for
(for a description
description of the method
method and
and its precision,
precision, see
see
Heinrich
the Institute
Heinrich and
and Newbury
Newbury 1986). Comparative
Comparative analyses
analyses were
were made
made in
in the
Institute of
Archaeology,
Archaeology, Tel
Tel Aviv
Aviv University,
University, using
using atomic
atomic absorption
absorption spectrophotometry
spectrophotometry .(AAS)
(AAS)
following
following the
the methods
methods of Hughes
Hughes et al.
af. (1976)
(1976).. Details of the operating
operating conditions
conditions for
for both
both
methods
methods are given
given in
in the Appendix.
Appendix.
The
The comparison
comparison of the
the new
new quantitative
quantitative analyses
analyses with
with those
those obtained
obtained by
by Key
Key is shown
shown in
in
Table
Table 1.
1. lt
It is not clear
clear which
which of the three
three mace
mace heads
heads from
from Nabal
Nahal Zeelim
Zeelim was
was analysed
analysed by
by
Key;
Key; all
all three EPMA
EPMA analyses
analyses are
are therefore
therefore included
included for
for comparison.
comparison. The
The EPMA
EPMA analyses
analyses
were
were made
made on
on sound
sound metal
metal and
and totals
totals were
were close
close to 100°/o;
100%; the compositions
compositions were
were therefore
therefore
normalized
normalized to 100°/o
100% whereas
whereas the AAS
AAS data
data were
were not normalized.
normalized. All
All concentrations
concentrations are
are
given
given in weight
weight per cent.
cent.
41
41
The metallurgy
metallurgy of
of the
the Nahal
Naha/ Mishmar
Mishmar hoard
hoard reconsidered
reconsidered
The
Table 11 Comparison
Comparison of
of Key’s
Key's results
results with
with new
new quantitative
quantitative analyses
analyses of
of the
the same
same objects
objects (wt
(wt %)
o/o)
Table
As
As
Sb
Sb
Ag
Ag
Bi
Bi
Pb
Pb
Ni
Ni
Sn
Sn
Zn
Zn
Co
Co
Fe
Fe
Cu
Cu
Au
Au
3.50
3.50
3.41
3.41
2.24
2.24
0.18
0.18
5.59
5.59
4.20
4.20
0.12
0.12
0.33
0.33
0.32
0.32
tr.
tr.
0.57
0.57
0.33
0.33
0.03
0.03
0.27
0.27
0.18
0.18
0.17
0.17
0.30
0.30
0.25
0.25
n.d.
n.d.
0.01
0.01
tr.
tr.
n.d.
n.d.
n.d.
n.d.
0.19
0.19
n.d.
n.d.
0.01
0.01
n.d.
n.d.
0.04
0.04
0.15
0.15
89.5
89.5
70.0
70.0
n.d.
n.d.
tr.
tr.
61-226
61-226
Key
Key
EPMA
A
EPM
AAS
AAS
6.90
6.90
4.63
4.63
2.52
2.52
0.60
0.60
0.02
0.02
0.07
0.07
0.16
0.16
0.03
0.03
0.03
0.03
0.03
0.03
0.06
0.06
0.04
0.04
0.07
0.07
0.23
0.23
0.14
0.14
0.84
0.84
7.96
7.96
8.27
8.27
n.d.
n.d.
0.02
0.02
tr.
tr.
n.d.
n.d.
n.d.
n.d.
0.05
0.05
n.d.
n.d.
0.03
0.03
0.03
0.03
0.01
0.01
0.06
0.06
87.0
87.0
79.4
79.4
tr.
tr.
0.02
0.02
661-278
1-278
Key
Key
EPMA
EPMA
AAS
6.50
6.50
4.43
4.43
3.78
0.20
0.20
0.27
0.27
0.19
0.01
0.01
0.03
0.03
0.02
0.02
tr.
tr.
tr.
tr.
tr.
tr.
n.d.
n.d.
0.02
0.02
n.d.
1.35
4.42
4.42
3.98
3.98
n.d.
n.d.
tr.
tr.
0.23
0.23
n.d.
n.d.
n.d.
0.08
0.08
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
0.03
0.03
0.07
90.8
90.8
87.4
87.4
0.03
0.03
0.02
0.02
61-311
61-311
Key
Key
EPMA
EPMA
AAS
6.60
1.48
1.48
2.18
2.18
0.58
0.50
0.50
0.54
0.54
0.08
0.08
0.13
0.13
0.15
0.15
0.02
0.02
0.39
0.39
0.40
0.40
0.32
0.32
0.06
0.06
0.05
0.05
0.59
0.59
0.08
0.08
0.09
0.09
n.d.
n.d.
0.01
0.01
n.d.
n.d.
n.d.
n.d.
n.d.
0.06
0.06
n.d.
tr.
n.d.
n.d.
tr.
0.04
0.04
97.3
97.3
88.5
88.5
n.d.
n.d.
n.d.
n.d.
Standard
61-104
61-104
Key
Key
EPMA
EPMA
n.d.
n.d.
0.14
n.d.
n.d.
n.d.
0.01
0.01
0.04
0.04
n.d.
n.d.
n.d.
n.d.
0.02
0.02
0.10
0.10
0.13
0.13
n.d.
n.d.
tr.
n.d.
0.01
0.01
n.d.
tr.
0.02
0.02
99.6
99.6
0.03
0.03
NAHAL ZEELIM
ZEELIM
NAHAL
Mace head
Key
Key
87-491 EPMA
EPMA
87-491
EPMA
87-492 EPMA
EPMA
87-493 EPMA
4.60
4.60
4.05
4.05
3.85
3.52
3.52
0.28
5.20
5.20
5.24
5.24
6.34
6.34
O. I 1
0.11
0.40
0.40
0.28
0.28
0.21
0.21
0.01
0.01
0.36
0.36
0.31
0.31
0.30
0.09
0.09
0.25
0.25
0.26
0.26
0.34
0.34
0.34
0.34
0.38
0.38
0.63
0.63
0.63
0.63
n.d.
0.04
0.04
0.03
0.03
0.04
0.04
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
0.01
0.01
0.01
0.01
n.d.
n.d.
0.01
0.01
0.03
0.03
0.01
0.01
89.2
89.3
88.5
88.5
0.10
0.10
0.02
0.02
0.09
0.09
tr.
0.26
0.26
0.01
0.01
0.02
0.02
0.03
0.03
0.02
0.02
tr.
tr.
0.01
0.01
n.d.
n.d.
0.02
0.02
0.50
0.50
0.02
0.02
n.d.
n.d.
0.01
0.01
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
tr.
tr.
99.6
99.6
0.02
0.02
NAHAL MISHMAR
MISHMAR
NAHAL
Mace heads
heads
Mace
61-351
61-351
Key
Key
EPMA
EPM
A
AAS
AAS
Axe
Key
Key
87--494 EPMA
EPMA
87-494
Key: results
results obtained
obtained by Key using spark
spark emission
emission optical spectroscopy.
spectroscopy.
Key:
EPMA: results
results obtained
obtained by electron
electron probe
probe microanalysis.
microanalysis.
EPMA:
AAS: results
results obtained
obtained by atomic
atomic absorption
absorption spectro-photometry.
spectro-photometry.
AAS:
n.d.: not determined;
determined; tr.:
tr.: trace.
trace.
n.d.:
DISCUSSION
DISCUSSION
These results
results show relatively
relatively good
good agreement
agreement between
between the two techniques
techniques used
used in our study.
study.
These
The
The differences
differences between
between EPMA and AAS
AAS have
have a number of causes.
causes. For arsenic, the
sensitivity
sensitivity and
and accuracy
accuracy of AAS
AAS was reduced
reduced because
because flameless
flameless atomization was
was not
available. More generally,
generally, the AAS
AAS data are
are affected
affected by the state of corrosion of the
the objects
objects
available.
and by samples
samples smaller
smaller than the ideal.
ideal. The
small sample
sample size has
has its greatest
greatest impact on the
the
and
The small
determination of those
those elements
elements in the greatest
greatest concentration, here
here copper,
copper, because
because of the
42
S. Shalev
Shalev and JJ.. P.
P. Northover
large dilutions
dilutions necessary.
necessary. The
The castings
castings are heterogeneous
heterogeneous both in terms
terms of dendritic and
large
segregation and by the variable degree
degree of corrosion,
corrosion, non-metallic
non-metallic inclusions
inclusions and
other segregation
porosity. The
The EPMA method enables
enables the analyst to choose
choose areas of sound metal for analysis
porosity.
means of an optical
optical or electron
electron image
image but, of course,
course, such areas may not be fully
fully
by means
whole object. On the other hand,
hand, with
with AAS
AAS there is no metallographic
metallographic
representative of the whole
sample quality. For example, corrosion
corrosion could well account
account for the higher level of
guide to sample
AAS analysis of 61-351.
61-351. On the other hand, the high As/Sb
As/Sb phases are more
iron in the AAS
these areas are preferentially selected
selected for EPMA analysis,
analysis, possibly
possibly
resistant to corrosion and these
giving the higher
higher levels
levels of arsenic
arsenic seen
seen in 61-35
61-3 511 and 61-226.
61-226. It can be said, therefore, that to
giving
fullest understanding
understanding of the composition
composition of these
these objects
objects it is preferable to use the
obtain the fullest
two techniques together rather than
than either one
one separately.
separately.
two
contrast to this
this general
general agreement between EPMA and AAS,
AAS, the discrepancies with
with
In contrast
Key's data are striking. For unalloyed
unalloyed copper the differences
differences are relatively
relatively small
small except
except for
Key’s
arsenic, where
where the limit
limit of detection was poor, and for nickel.
nickel. For ‘alloyed’
'alloyed' artefacts Key
arsenic,
correctly identified,
identified, in most
most cases,
cases, the occurrence of arsenic; his measured concentrations
concentrations
correctly
those in our re-analysis
re-analysis but this
this could be attributed
attributed to differences
differences in
tend to be higher than those
sample location.
location. However, it is now apparent
apparent that the concentrations
concentrations of virtually all the
sample
elements estimated by Key need
need to be reconsidered.
reconsidered. For some
some elements it could
could be
other elements
segregation within
within the castings could account for significant
significant variability. For
argued that segregation
bismuth are insoluble and segregate as inclusions in the interdendritic
interdendritic
example, lead and bismuth
here, however,
however, it is the AAS
AAS and EPMA data
data that are in good agreement
material but even here,
Key's that is at variance.
variance. The
The same
same applies
applies to other potential segregates
segregates such
such as silver.
silver.
and Key’s
differences are less explicable;
explicable; some,
some, such as the recording of 0.8%
O.So/o nickel
nickel rather
Other differences
8°/o measured by both techniques in the re-analysis
re-analysis could
could be a misprint or a
than 8%
misidentification of the sample
sample in the original
origina) publication.
publication. The most obvious discrepancy,
discrepancy,
misidentification
however, cannot be explained
explained in this way.
way. This is the constant
constant minimal
minimal detection of
however,
antimony when
when it is present in quantities
quantities higher than arsenic.
arsenic. The results
results show
show one
one of the rere­
antimony
analysed mace
mace heads from
from Nahal
Nabal Mishmar and all three from Nahal
Nabal Zeelim
Zeelim to be of copper
analysed
alloyed with
with antimony
antimony and arsenic, with
with Sb
Sb>
These results parallel the recently
recently
alloyed
> As. These
sites. Further
Further data
data on the extent of use of these
these alloys
alloys are provided
published data from other sites.
AAS analyses
analyses of nine
nine more samples
samples from
from the Nahal
Nabal Mishmar hoard.
hoard. The
The
by EPMA and AAS
results are given in Table
Table 2. The
The associated
associated microstructures
microstructures are the subject of continuing
results
research which
which will be published elsewhere.
elsewhere.
research
cases in Table 2 two samples
samples were
were available for microprobe
microprobe analysis:
analysis: both analyses
analyses
In two cases
means are given to illustrate the variability in composition within
within these
these objects.
objects. In
and their means
samples (61-115,
(61-115, 61-94)
61-94) only
only areas rich in high
high alloy
alloy phases were accessible
accessible for fully
fully
two samples
quantitative analyses
analyses as the results
results make clear.
clear.
quantitative
The alloying of copper with arsenic
arsenic and antimony
antimony is thus seen
seen to be a consistent feature of
the prestige/cult objects.
objects. Nickel may
may also
also be present at ‘alloy’
'alloy' levels
levels while
while bismuth, lead and
silver are consistent impurities.
impurities. Alloys with arsenic and nickel,
nickel, with antimony only at
silver
alternative. The highly
highly alloyed
alloyed coppers of the Nahal
Nahal Mishmar
impurity levels, are a rarer alternative.
have, due to their composition, a silvery-grey
silvery-grey appearance, quite
quite distinct from
from the red
hoard have,
tools. Moreover, this metal
metal is harder
harder than copper and easily
easily polished.
polished. The
The gloss
gloss
colour of the tools.
drilled and polished
polished mace
mace heads of haematite although the
would match that of the drilled
underlying
underlying colour of
of haematite
haematite would
would be
be noticeably
noticeably darker.
darker.
still much work to be
be done on the
the provenance of
of the ores
ores and the
the smelting
There is still
The metallurgy
metallurgy of
of the Naha/
Nahal Mishmar
Mishmar hoard
hoard reconsidered
reconsidered
The
43
hoard
Mishmar hoard
Nahal Mishmar
analyses of
quantitative analyses
from the Naha/
Table 2 New
New quantitative
of objects
objects from
Table
As
Sb
Sb
Ag
Bi
Pb
Ni
Sn
Zn
Zn
Co
Fe
Cu
Cu
Au
61-1 15
61-115
EPMA
EPMA
8.22
8.22
18.29
18.29
0.98
0.98
1.00
I.OO
0.02
0.02
0.08
0.08
0.11
0.11
n.d.
n.d.
0.02
0.02
n.d.
n.d.
71.3
71.3
n.d.
6 1-400
61-400
EPMA
EPMA
AAS
AAS
3.25
3.25
3.OO
3.00
5.71
5.71
5.90
5.90
0.37
0.37
0.45
0.45
0.49
0.49
0.38
0.38
1.30
1.30
0.90
0.90
0.24
0.24
0.22
0.22
0.04
0.04
tr.
n.d.
n.d.
0.06
0.06
tr.
tr.
n.d.
tr.
tr.
0.18
0.18
88.6
88.6
75.0
75.0
0.05
0.05
0.02
0.02
61-223
61-223
EPMA
EPMA
AAS
AAS
2.75
2.75
3.27
3.27
5.30
5.30
5.30
5.30
0.25
0.25
0.25
0.25
0.25
0.25
0.24
0.24
0.25
0.25
0.25
0.25
0.39
0.39
0.34
0.34
0.02
0.02
0.21
0.21
n.d.
0.10
0.10
tr.
n.d.
n.d.
0.02
0.02
0.19
0.19
90.7
90.7
78.4
0.03
0.03
n.d.
n.d.
2.57
2.57
3.48
3.48
4.76
3.70
3.70
0.31
0.31
0.32
0.32
0.42
0.42
0.23
0.23
0.13
0.13
0.12
0.12
0.35
0.35
0.30
0.30
0.01
0.01
tr.
n.d.
n.d.
0.05
0.05
tr.
n.d.
n.d.
0.03
0.03
0.13
0.13
91.4
91.4
AAS
AAS
87.1
87.1
tr.
tr.
61-373
61-373
EPMA
EPMA
AAS
AAS
I .85
1.85
1.65
1.65
5.48
5.48
4.80
4.80
0.41
0.41
0.43
0.43
0.34
0.34
0.33
0.33
0.56
0.56
0.33
0.33
0.30
0.30
0.30
0.04
0.04
tr.
n.d.
n.d.
0.06
0.06
tr.
n.d.
0.01
0.01
0.08
0.08
91.0
91.0
88.5
88.5
0.05
0.05
tr.
61-371
61-371
EPMA
EPMA
AAS
AAS
2.68
2.68
2.25
2.25
2.87
2.87
4.00
4.00
0.26
0.26
0.40
0.40
0.42
0.42
0.47
0.47
0.54
0.54
0.58
0.58
0.22
0.22
0.28
0.28
0.02
0.02
tr.
n.d.
n.d.
0.06
0.06
n.d.
n.d.
n.d.
n.d.
0.02
0.02
0.08
0.08
93.0
93.0
85.0
85.0
tr.
Standard
Standard
6 1-94
61-94
EPMA
EPMA
6.29
6.29
22.55
22.55
0.63
0.63
1.40
1.40
3.0
3.01l
0.18
0.12
0.12
n.d.
n.d.
O.O
0.01I
0.12
0.12
65.7
65.7
n.d.
n.d.
61-179
61-179
EPMAjI
EPMA/1
EPMA/2
EPMA/2
EPMA/mean
EPMA/mean
3.05
3.05
2.23
2.64
2.64
4.28
4.28
1.78
1.78
2.99
2.99
0.20
0.20
0..30
0.30
0.25
0.25
1.07
1.07
0.64
0.64
0.86
0.86
1.25
1.25
0.65
0.65
0.95
0.95
1.57
1.57
11.37
. 37
1.47
1.47
0.06
0.06
0.01
0.04
0.04
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
0.03
0.03
tr.
0.02
0.02
88.4
88.4
93.0
90.7
90.7
0.05
0.05
n.d.
0.03
0.03
Basket-like
Basket-like vessel
61-162
EPMAjl
EPMA/1
EPMA/2
EPMA/2
EPMA/mean
EPMA/mean
AAS
AAS
6.44
6.44
6.27
6.27
6.36
6.36
6.56
6.56
15.95
15.95
8.20
8.20
12.08
12.08
10.31
10.31
0.62
0.62
0.49
0.49
0.56
0.56
0.98
0.98
0.95
0.95
0.73
0.84
0.84
0.83
0.83
0.39
0.39
0.27
0.27
0.33
0.33
0.32
0.32
1.45
l.45
2.00
2.00
1.73
1.73
2.50
n.d.
0.08
0.08
0.04
0.04
n.d.
n.d.
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.18
0.18
0.10
0.10
0.14
0.14
0.23
0.23
73.9
73.9
81.9
81.9
77.9
62.5
0.08
0.08
0.04
NAHAL
MISHMA R
NAHA L MISHMAR
Mace heads
Mace
61-249
EPMA
EPMA
tr.
tr.
'Crown'
'Crown'
0.13
0.13
n.d.
n.d.
See Table
Table I1 for key.
key.
See
technology
technology involved.
involved. The
The question
question of provenance
provenance is being
being pursued elsewhere
elsewhere (Stos-Gale
(Stos-Gale
1991) and discussion
discussion here
here will consider
consider only
only the
the production
production of these
these alloys.
alloys. Recent
Recent research
research
on
990a and 1990b;
1990b;
on primitive
primitive smelting
smelting of arsenicarsenic- and antimony-rich
antimony-rich coppers
coppers (Pollard
(Pollard et
el al.
al. I1990a
Rostoker and Dvorak 1991)
1991) have
have suggested
suggested possible
possible mechanisms
mechanisms.. The
The experiments
experiments of
Pollard
Pollard et al. are
are concerned
concerned with
with the
the smelting
smelting of high
high grade
grade oxide
oxide ores
ores at temperatures
temperatures
significantly
significantly below
below the
the melting
melting point of copper.
copper. They demonstrate
demonstrate that
that in these
these conditions
conditions
(around
(around 900
900 ºC)
"C)copper,
copper, arsenic,
arsenic, antimony
antimony and other elements
elements can
can be
be fully
fully reduced
reduced to
to the
the
S.
S . Shalev and J.
J . P.
P . Northover
Northover
44
(a) Microstructure
Microstructure of
of another mace
mace head
head from Shiqmim:
Shiqmim: striations
striations in the
the ternary
ternary high alloy
alloy phase.
phase
(a)
with a
phase with
ternary high alloy phase
structure in the ternary
fragment of
Shiqmim: acicular structure
afaafragment
crown,froni Shiqmim:
(b) Microstructure
Microstructure of
of a crownfrom
(b)
higher proportion
proportion of
of antimony
antimony than in (a).
(a).
Figure
Figure 5
ternary As-Cu-Sb
of ternary
Microstructures of
As-Cu-Sb alloys.
ulloys.
Microstructures
solid state
state with
with minimal
minimal losses
losses to the
the vapour phase.
phase. Diffusion
Diffusion of the
the alloying
alloying elements
elements raises
raises
solid
such an
an extent
extent that
that the
the Jiquidus
liquidus temperature
temperature of the
the alloy
alloy
their concentration
concentration in the
the copper
copper to such
their
formed
is
eventually
less
than
the
reaction
temperature
and
the
alloy
melts.
This
model
formed
eventually
the reaction temperature and the alloy melts. This model is
attractive
because
the
recovery
alloying elements
elements is very
very high
high and oxide
oxide ores
ores are
are used,
used, the
the
attractive because the recovery of alloying
sulphur content
content (O.O
(0.01-0.06%)
the Nabal
Nahal Mishmar
Mishmar material
material arguing
arguing for
for the
the use
use of such
such
low sulphur
1-0.06°/o) of the
ores and against
against the
sulfo-salt ores
ores (cf.
(cf. Rapp
Rapp 1989).
1989).
ores
the use of suifo-salt
and Dvorak used smelting
smelting temperatures
temperatures of 1250-1300
1250-1 300 "Censuring
“Censuringthe
the fluidity
fluidity of
Rostoker and
both metal
metal and
and slag.
slag. Their
Their experiments
experiments involved
involved both oxide
oxide and sulphide
sulphide ores,
ores, the
the sulphur in
both
suif-arsenate
sulf-arsenate minerals
minerals itself
itself being
being employed
employed as
as a reducing
reducing agent
agent when
when realgar
realgar was
was co-smelted
co-smelted
The metallurgy
metallurgy oof
the Nahal
Naha/ Mishmar
Mishmar hoard
hoard reconsidered
reconsidered
The
f the
45
45
with malachite.
malachite. Arsenic
Arsenic recovery
recovery was
was high
high with
with an
an average
average concentration
concentration reaching
reaching 9.7%
9.7°/o
with
when the
the crucible
crucible was
was closed
closed with
with aa lid
lid and
and production
production of
of toxic
toxic fumes
fumes was
was almost
almost eliminated.
eliminated.
when
lt is
is also
also noteworthy
noteworthy that
that the
the Cu3As
Cu3As phase
phase in
in the
the experimental
experimental microstructures
microstructures produced
produced by
by
It
Rostoker and
and Dvorak (1991,12-13,
( 1991, 12-13, figs.
figs. 1-2)
1-2) show
show the
the same
same striated
striated appearance
appearance as
as in
in some
some
Rostoker
examples from
from the
the Chalcolithic (Figure 5 (a)).
(a)). The striated structure
structure is
is not
not well
well understood
understood
examples
but occurs when
when the phase is
is rich in arsenic
arsenic and based on Cu3As.
Cu3As. As antimony increases
increases the
but
changes to one based on Cu3Sb
Cu3Sb which
which undergoes different
different transformations,
transformations, possibly
possibly
phase changes
martensitic (Figure 5 (b)).
prestige
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
manufacture has yet been found. So far, comparison
comparison with Early Bronze
Bronze Age
evidence
Israel shows
shows that this technology
technology with its As-Cu-Sb alloys
alloys was unknown in the
metalwork in Israel
Bronze Age.
Early Bronze
CONCLUSIONS
CONCLUSIONS
lt is beyond the scope
scope of this paper to investigate in detail the technical
technical reasons for Key’s
Key's
It
inaccuracies.
Analytical
techniques
have
advanced
dramatically
in
the
last
30
years
and
their
inaccuracies.
have
dramatically
their
reliable and reproducible.
reproducible. Spark emission
emission spectroscopy is a far
application is much more reliable
from simple
simple technique and requires great care in setting up, exposure
exposure and measurement of
of
from
spectrographie plate.
plate. It also
also appears that,
that, while
while the artefact
artefact analyses
analyses were
were by spark
the spectrographic
emission, the standardization
standardization was
was carried out by arc
arc emission
emission on pure elements.
elements.
emission,
seems that incorrect analyses,
analyses, as well as the absence
absence of more contextual archaeological
archaeological
It seems
evidence, led Key to his main
main conclusions
conclusions regarding the origin of the Nahal
Nabal Mishmar
evidence,
With our new data
data and the ideas
ideas now
now emerging
emerging concerning the production
production of these
these
treasure. With
alloys a simpler
simpler working hypothesis can be provided for future research. Not only
only
ternary alloys
group of
of tools from the hoard be linked
linked to a distinct temporal
temporal and spatial
can the small group
context, but also
also most of the prestige
prestige objects
objects are found to bear a close
close metallurgical
context,
resemblance to those retrieved
retrieved from well-dated
well-dated Chalcolithic
Chalcolithic sites
sites in southern
southern Israel. We
We can
resemblance
now emphasize
emphasize the localized
localized distribution
distribution of the prestige/cult end-products
end-products and speculate
speculate
now
about the existence
existence of a production
production centre appreciably
appreciably nearer than Anatolia
Anatolia or TransTrans­
about
(Shalev et al. 1992). Based
Based on this
this altered evidence,
evidence, we can now interpret
interpret the
caucasia (Shalev
Chalcolithic hoard from Nahal
Nabal Mishmar
Mishmar not only
only via its typological and cultural
cultural context
Chalcolithic
from the viewpoint of its metallurgy as well.
well.
(Moorey 1988) but from
Even so,
so, we must not forget that Key’s
Key's pioneering work
work in the 1960s
1960s was
was the starting
starting point
Even
reconstruction of the beginnings
beginnings of metallurgy
metallurgy in our region. When,
When, at the end
end of the
for the reconstruction
failed to explain the accumulating
accumulating archaeological
archaeological and metallurgical
metallurgical evidence,
evidence, it had
1980s, it failed
re-examined. Our
Our work, at present, is based on a significantly
significantly improved
improved metallurgical
to be re-examined.
data base,
base, but further
further refinements
refinements in knowledge
knowledge and techniques
techniques could well
and technological data
the interpretation
interpretation in the same
same way
way as re-excavation of a site
site can do for the field
field
alter the
archaeologist.
archaeologist.
ACKNOWLEDGEMENTS
ACKNOWLEDGEMENTS
authors wish to thank
thank A. Drori,
Peled and B. Brandel
Brandel of the Antiquities
Antiquities Authority
Authority and
and M.
M. Tadmor
Tadmor from the
Drori, R. Peled
The authors
Israel Museum
Museum for permission
permission to sample
sample the material;
material; Y
Y.. Deutsch
Deutsch and S. Ehrlich
Ehrlich of the Geological
Geological Survey
Survey of Israel
for
helping to trace Key’s
Key's analytical
analytical equipment
equipment and
and methods;
methods; Professor
Hirsch, Department of Materials,
for helping
Professor Sir Peter
Peter Hirsch,
Materials,
46
P. Northover
SS.. Shalev and J. P.
University of
of Oxford,
Oxford, and
and Professor
Professor J.
J. Yakar,
Yakar, Institute
Institute of
of Archaeology,
Archaeology, Tel
Tel Aviv
Aviv University,
University, for
for laboratory
laboratory
University
facilities. Special
Special thanks
thanks are
are due
due to
to N.
N. Halperin,
Halperin, also
also from
from the
the Institute
Institute of
of Archaeology,
Archaeology, who
who assisted
assisted with
with the
the AAS
AAS
facilities.
analyses; B.
B. Eliel
Elie] and
and S. Gasner
Gasner who
who helped
helped in
in bringing
bringing this
this article
article to
to its
its present
present state;
state; and
and C.
C. A.
A. Key
Key who
who in
in his
his
analyses;
pioneering work
work left
left us
us an
an example
example to
to follow.
follow.
pioneering
APPENDIX: DETAILS
DETAILS O
OF
ANALYTICAL ROUTINES
ROUTINES
APPENDIX:
F ANALYTICAL
Electron probe
probe microanalysis
microanalysis was
was carried
carried out
out on the CAMEBAXm
CAMEBAX® automated
automated instrument
instrument in the
the Department
Department of
of
Electron
Materials, University
University of
of Oxford,
Oxford, using
using wavelength
wavelength dispersive
dispersive spectrometry.
spectrometry. For electron
electron probe
probe microanalysis
microanalysis the
Materials,
operating conditions
conditions were
were an accelerating
accelerating voltage
voltage of
of 25 kV, an absorbed
absorbed electron
electron current
current aatt the sample
sample of
of
operating
approximately 30 nA, and
and an X-ray
X-ray take-off
take-off angle
angle of 40".
40º. Pure
Pure element
element standards
standards were
were used
used for all elements.
elements.
approximately
Detection limits
limits for most
most elements
elements were
were 100-200 ppm, but 300 ppm
ppm for gold
gold and
and 0.10%
0.10°/o for arsenic. This
This last is
Detection
because of the compromises
compromises made
made to avoid
avoid the well-known
well-known interference
interference between
between the strongest
strongest lines
lines in the lead
lead and
and
because
arsenic spectra,
spectra, the
the lead
lead La
Lex and
and arsenic
arsenic Ka
Ka: lines.
lines. Here
Here the
the moderately
moderately strong
strong lead
lead Ma
Mex line
line was
was used
used but
but the
the weak
weak
arsenic
arsenic KB
Kß line
line had
had to
to be
be used.
used. The
The arsenic
arsenic La
Lex line
line could
could not
not be
be used
used in
in conjunction
conjunction with
with the
the high
high accelerating
accelerating
arsenic
voltage as
as the
the ZAF
ZAF corrections
corrections become
become so large
large as
as to
to make
make accuracy
accuracy very
very poor.
poor. At
At least
least three
three areas,
areas, each
each 50
50 pm
µm
voltage
square, were
were analysed
analysed on each
each sample;
sample; only
only the mean
mean analyses
analyses are
are used
used in
in the
the tables.
tables. A
A further
further modification
modification in
in the
the
square,
limits of
of detection
detection occurs
occurs for zinc
zinc in copper
copper where
where there
there is a zero
zero error
error of
of up
up to
to 300 ppm
ppm caused
caused by
by the measurement
measurement
limits
background at a location
location that
that is affected
affected by the tail of
of the Cu
Cu KB
Kß peak.
peak.
of the background
For atomic
atomic absorption
absorption spectrophotometry
spectrophotometry
standard techniques
techniques were
were used
used (e.g. Hughes
Hughes et al. 1976).
1976). The
The
For
standard
instrument used
used was an Instrumentation
Instrumentation Laboratory
Laboratory 157.
157. The
The samples
samples were
were dissolved
dissolved in aqua regia (1
(I HNO3:3
HN03: 3
instrument
HCI). Limits
Limits of detection
detection were
were less than
than 200 ppm
ppm for all elements
elements except
except for Cu (0.15%),
(0.15 %), arsenic
arsenic (400 ppm)
ppm) and
and tin
HCI).
(0.12°/o) based
based on a sample
sample of 10 mg in 10 ml. However,
However, some
some samples
samples were
were smaller
smaller than
than this ideal
ideal with
with a
(0.12%)
corresponding effect on the limits
limits of detection.
detection.
corresponding
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