Chemical Geology 163 2000.

139149
www.elsevier.comrlocaterchemgeo

Determination of natural Cu-isotope variation by plasma-source

mass spectrometry: implications for use as geochemical tracers
X.K. Zhu
a

a,)

, R.K. ONions a , Y. Guo a , N.S. Belshaw a , D. Rickard

Department of Earth Sciences, Uniersity of Oxford, Parks Road, Oxford, OX1 3PR UK
b
Department of Earth Sciences, Uniersity of Wales, Cardiff, CF1 3YE UK
Received 21 December 1998; accepted 29 April 1999

Abstract
Techniques for the high precision measurement of 65Cur63Cu ratios by multiple-collector plasma-source mass spectrometry has been developed. Two approaches, namely Zn-doping and sample-standard bracketing, have been exploited. By
using the sample-standard bracketing technique, a range of samples including native copper, Cu-carbonate and
Cu-sulphides from terrestrial and marine environments have been analysed. An overall variation in 65Cur63Cu of 22 parts
per 10 4 22 units. is observed. This is more than 30 times the 2 s analytical uncertainty of the technique employed, and
thus demonstrates the great potential for using stable Cu isotopes as tracers in geological and planetary processes. The
variations in 65Cu values observed in this study display some regularity. Those samples involving formation through low
temperature aqueous solutions display large differences in 65Cu values even at a single locality, whereas chalcopyrite
samples hosted in igneous rocks show similar Cu-isotope compositions worldwide. This indicates that the 65Cu variations
arise principally through mass fractionation in low temperature aqueous processes, rather than through source heterogeneity.
In contrast to continental sulphides, chalcopyrites from black smoker sulphide chimneys on the ocean floor show large
variations in 65Cu values. Relative to active high temperature hydrothermal vents, the old inactive vent deposits are
enriched in 63Cu and show smaller variations in 65Cu values. Within in a single active chimney, Cu isotopes become lighter
from bottom to top. This variation pattern is explained tentatively by means of a two-stage-process model, which involves:
1. the preferential leaching of 65Cu by hydrothermal processes, and 2. subsequent isotopic exchange between the early
formed Cu-sulphides and 65Cu-depleted late-stage hydrothermal fluids. This new capability for Cu-isotope measurement is
expected to have a major impact across disciplines ranging from cosmochemistry and geochemistry through biogeochemistry
to biochemistry and alimentology. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: Cu-isotopes; Sulphides; Plasma-source mass spectrometry; Hydrothermal systems; Black smokers; Isotope fractionation

1. Introduction
Natural variations in stable isotope abundances
have over the years provided profound insights into
)

Corresponding author. Tel.: q44-1865-272075; fax: q441865-272072; E-mail: xiangz@earth.ox.ac.uk

processes operating during the formation of the solar

system and the evolution of the Earth. For example
our present understanding of paleoclimate, hydrothermal processes in the lithosphere and the carbon cycle itself derive in no small part from C, O, H
and S stable isotope studies. However due to analytical difficulties, stable isotope variations have re-

0009-2541r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 5 4 1 9 9 . 0 0 0 7 6 - 5

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X.K. Zhu et al.r Chemical Geology 163 (2000) 139149

mained unexplored in many elements. The introduction of multiple collector plasma source mass spectrometry Walder and Freedman, 1992; Walder et al.,
1993; Halliday et al., 1998. has changed the situation
dramatically and in principle stable isotope abundances in 10 or more additional elements with masses
less than 100 amu are now accessible. Of particular
interest here are the stable isotopes of the transition
metals. These have the potential to provide new
insights into processes such as occurred in the solar
nebula, during planetary accretion and melting as
well as those that link inorganic and biological
chemistry in low temperature environments.
The aim of the project is to investigate the use of
isotopic measurements in the study of inorganic and
biological geochemistry and cosmochemistry of Fe,
Cu and Zn. It commences here with Cu-isotopes in
terrestrial materials. The first search for natural variations in Cu-isotope abundances was made by Walker
et al. 1958. who claimed a total range of 9 per mil
in 65 Cur63 Cu ratios in Cu minerals, sediments and
organic samples. These results were supported by the
more extensive study of Shields et al. 1965., but in
both cases the analytical precision achieved between
1 and 1.5 per mil was relatively poor by modern day
standards. More recently, some preliminary results
on Cu isotope measurements using plasma-source
mass spectrometry have been reported Marechal et
al., 1998, 1999; ONions et al., 1998..
In this study, the detailed methodology for high
precision measurement on Cu isotopes using multiple-collector plasma-source mass spectrometry is
presented together with the results obtained on a
range of native copper, Cu-carbonate and Cu-sulphide
samples from terrestrial and marine environments.
The observed variations in 65 Cur63 Cu ratios are
some 40 times the analytical precision at 2 s level.
The potential of Cu isotopes as tracers for hydrothermal systems is evaluated and a preliminary model
for the Cu-isotopic variation in hydrothermal sulphides is proposed.

isotopic ratio measurements e.g., Walder and Freedman, 1992.. It has been successfully applied to the
analyses of W, Hf and Nd isotopes where mass
discrimination effects have been corrected for using
a pair of stable and non-radiogenic isotopes e.g.,
Walder et al., 1993; Lee and Halliday, 1995; Halliday et al., 1996., or by the addition of Tl as a dopant
in the case of Pb Walder et al., 1993; Belshaw et al.,
1998; Halliday et al., 1998.. For Cu, which has two
isotopes, 63 Cu and 65 Cu, the natural variation in
65
Cur63 Cu ratio is determined relative to a Cu standard such as NIST 976, and the isotopic variability
expressed in relative term as has been the practice
for O and C isotopes. A further requirement for
highly precise and accurate isotopic measurements is
to ensure that any mass spectral interferences are
either eliminated or negligible, and to ascertain that
no isotope fractionation occurred during sample
preparation and its introduction into the mass spectrometer.

2. Analytical methodology

2.2. Repeatability of

Multiple collector plasma source mass spectrometry is a relatively new technique for high precision

2.1. Sample selection and preparation

This project has utilised materials which after
dissolution may be analysed directly by plasma
source mass spectrometry, thus avoiding any possibility of chromatographic fractionation of Cu isotopes. This is important because preliminary results
in this laboratory show that without extreme care ion
exchange chromatography may produce significant
isotope effects on Cu, as also shown in the study of
Marechal et al. 1999.. Thus, only the minerals in
which Cu is a major element have been chosen for
this study. These include native Cu, malachite
wCu 2 OH. 2 CO 3 x, azurite wCuOH. 2 CO 3 . 2 x and chalcopyrite CuFeS 2 ..
Native Cu samples were cleaned by etching in 5
M HNO 3 and rinsing with ultrapure H 2 O. Cusulphide and -carbonate minerals were cleaned ultrasonically in H 2 O and dissolved in 5 M HNO 3 . All
samples and standards were prepared at the same
concentration of 1 ppm in 0.1 M HNO 3 for mass
spectrometric analysis.

65

65

Cu r63Cu measurements

Cur63 Cu ratios have been measured using a Nu

Instruments multiple collector plasma source mass

X.K. Zhu et al.r Chemical Geology 163 (2000) 139149

141

spectrometer. This instrument, described by Belshaw

et al. 1998., has variable dispersion ion optics and a
fixed array of 11 Faraday collectors. All 65 Cur63 Cu
ratios of samples in this paper are reported relative to
the measured ratio for NIST 976 Cu-isotope standard, which has a recommended value of 63 Cur65 Cu
s 2.24 " 0.0021, as follows:

65 Cu s

R sample
R standard

y 1 = 10 000

1.

where R sample and R standard are the measured 65 Cur

63
Cu ratios for the unknown sample and NIST 976,
respectively.
The performance of the instrument for 65 Cur63 Cu
ratio measurement has been assessed using two procedures. The first involves addition of a Zn-dopant to
Cu, which is analogous to the Tl-doping technique
used for Pb-isotope analysis Walder et al., 1993;
Belshaw et al., 1998.. Zn was added to a standard
Cu solution Romil. in a 1:1 concentration ratio to
ensure similar ion signal levels and minimise error
propagation during mass-bias correction. The dopant
68
Znr66 Zn ratio is used to estimate a discrimination
factor which is applied to the measured 65 Cur63 Cu
ratio. As with the Tl-doping technique used for
Pb-isotope analysis a correction factor for the discrimination which has an exponential dependence on
mass is employed Belshaw et al., 1998; Marechal et
al., 1999.. The 65 Cur63 Cu and 68 Znr66 Zn ratios for
the Zn-doped Romil Cu standard solution are measured sequentially with a simultaneous adjustment of
the magnetic field and zoom lens in between. The
results of repeated 65 Cur63 Cu ratio measurement
over a period of one week using these techniques are
illustrated in Fig. 1a which shows an external 2 s
error better than 0.3 units.
The second approach used to determine repeatability is the so-called standard-sample bracketing
technique where the 65 Cur63 Cu ratio in a sample is
bracketed by measurements of the Cu standard. For
this purpose Romil Cu solution is the sample and
NIST 976 is the standard. The 65 Cur63 Cu ratio of
Romil Cu is expressed as a deviation from the
interpolated 65 Cur63 Cu ratio for the NIST 976 using
Eq. 1.. The results of repeated measurement using

Fig. 1. Repeatability of 65 Cur63 Cu ratio measurements. a. Repeatability of 65 Cur63 Cu ratio measurements using a Zn-doping
technique. The measurements are expressed as 65 Cu units which
are parts per 10 4 deviation from the average value of Romil
Cu-solution. Mass spectrometric discrimination is corrected by
normalising 68 Znr66 Zn ratio of dopant zinc to a fixed value. The
analyses were carried out over a period of one week which
demonstrate a repeatability better than 0.3 units at 2 s level. b.
Repeatability of 65 Cur63 Cu ratio measurements using the standard-sample-standard approach. The sample used here is
Romil Cu-solution, and the standard is NIST 976. The results
were acquired over a period of two weeks and demonstrate an
external precision better than 0.6 units at 2 s level. The 65 Cu
value of the Romil Cu-solution obtained is 3.43"0.16 2 sm .
relative to the standard material NIST 976. Error bars represent
the internal precision at 2 s level.

this technique over a period of 2 weeks are plotted in

Fig. 1b which shows a repeatability of better than 0.6
units at 2 standard deviation level. The 65 Cu
value of the Romil Cu solution obtained from these
analyses is 3.43 " 0.16 2 sm . relative to NIST 976
standard.
In both approaches, the mass fractionation observed for Cu isotopes is ca. 3% amuy1 under the

142

X.K. Zhu et al.r Chemical Geology 163 (2000) 139149

working conditions used. However, the mass fractionation may vary with different operating conditions and during the course of an analytical session.
Variation of mass fractionation between analyses of
sample and standard is a source of error and overall
results in the repeatability of 65 Cur63 Cu measurements being significantly worse than the precision of
single measurements Fig. 1..
The two approaches described above are both
applicable to geological and biological samples. The
advantage of the standard-sample bracketing
technique is that Cu may be analysed in the presence
of other elements so long as they do not interfere
spectrally or influence the mass discrimination. The
Zn-doping technique however involves fewer measurements and is both faster and more time efficient.
It further offers improved repeatability Fig. 1a and
b. through minimisation of any time-dependence in
the mass discrimination. For the present study of
Cu-minerals, the standard-sample bracketing
method has been chosen. This is because, to avoid
any possibility of chromatographic fractionation of
Cu isotope, samples used in this study are not subjected to chemical purification. This method enables
the variation in Cu-isotopes observed to be confidently ascribed to processes occurring in nature.

necessary when the Cu samples are not subjected to

chemical purification andror when a dopant is added.
Analogous to the usage of the term in SIMS e.g.,
Reed et al., 1979; Eiler et al., 1997; Zhu et al.,
1998., matrix effects refers to variations in the mass
fractionation that occurs during the mass spectrometry with changes in sample composition under a
given set of working conditions. Of primary concern
in this study is the effect of Fe on 65 Cur63 Cu ratio,
since Fe is a major element in the sulphide samples.
This has been examined for seven synthetic mixtures
with Fe:Cu molar ratios of 0.1, 1, 2, 4, 5, 10 and 15.
Results of these analyses are plotted in Fig. 2. There
is no clear dependence of 65 Cur63 Cu on FerCu
molar ratio and the data obtained vary within 0.6
units which is the external precision of this technique
defined in Fig. 1b. Thus, it is demonstrated that
Fe contents, at least up to 15 times higher than
Cu in solution, exert no significant effects on the
65
Cur63 Cu ratio measurements under the working
conditions used in this study.

2.3. Isobaric interference and matrix effects

Potential isobaric interferences exist in the measurement of 65 Cur63 Cu ratios. These include
23 Na40Ar.q and 23 Na 216 O1 H.q for 63 Cu and,
25 Mg40Ar.q for 65 Cu. This issue has been investigated by measuring both the abundances of Na and
Mg in the samples and the proportions of these
elements occurring as interfering polyatomic ions.
The measured NarCu and MgrCu ratios are less
than 10y4 and 10y3 , respectively in all the samples
used in this study, whereas the abundances of the
polyatomic ions relative to Naq and Mgq are
; 10y4 under the working conditions used. It is
concluded, therefore, that in the case of this study,
the isobaric interference of these polyatomic ions is
negligible.
The possibility of matrix effects on measured
65
Cur63 Cu ratios has also been investigated. This is

Fig. 2. Assessment of the effect of Fe on 65 Cur63 Cu ratio

measurements. Synthetic mixtures with Fe:Cu molar ratios of 0.1,
1, 2, 4, 5, 10 and 15 have been analysed for 65 Cur63 Cu ratios.
65 Cu values were calculated relative to undoped NIST 976. NIST
976 is used as both the standard and as the Cu in the synthetic
mixtures. In all solutions, Cu was maintained at 1 ppm in 0.1 M
HNO 3 . The two dashed lines bracket the repeatability which is
0.56 65 Cu units as defined in Fig. 1b and the solid line is the
65 Cu value for NIST 976. No clear dependence of 65 Cu value
on FerCu molar ratio is observed. Error bars represent the
internal precision at 2 s level.

X.K. Zhu et al.r Chemical Geology 163 (2000) 139149

143

2.4. Data acquisition

3. Results

The sample-standard bracketing technique was

employed for all sample analyses reported in this
study. The system was operated under computer
control with samples, standards and washes being
selected automatically using a CETAC MCN 6000
sampler. Runs of sample and standard were separated by washes using 2% HNO 3 for 5 min. Data
was acquired in blocks of 10 ratios with 10-s integration times, and background measurements were taken
prior to each data block.

Samples of native copper, carbonate and chalcopyrite from continental and ocean floor deposits
have been analysed. The results of 65 Cur63 Cu analyses are presented in Tables 1 and 2 as 65 Cu units
deviations in parts per 10 4 . relative to the NIST 976
Cu standard. The results of repeat analyses are also
presented Tables 1 and 2., which show an excellent
agreement with the external precision of 0.6 units
defined by the instrument repeatability Fig. 1b..
These results show an overall variation of 22 in

Table 1
Cu-isotope results for samples from continental ore deposits
Sample
Natie copper
OUM22647
OUM15126
OUM15120
OUM00061
OUM15127
OUM00078
Ditto
Average
Malachite [Cu 2 (OH)2 CO3 ]
OUM23585
Azurite [Cu(OH)2 (CO3 )2 ]
OUM1616
OUM11242
OUM6629
OUM1637
Ditto
Average
Chalcopyrite (CuFeS2 )
E147
OUM25139
Acc. Ser. 25526
OUM22443
OUM21981
Acc. Ser. 25295
Ditto
Acc. Ser. 25300
Acc. Ser. 25301
Acc. Ser. 25309
Ditto
Acc. Ser. 25312
Ditto
Average

Locality

65 Cu

Bisbee, AZ, USA

Michigan, USA
Lake Superior, North America
Yekaterinburg, Russia
Cornwall, England
St. Cleer, Cornwall, England

y2.00
4.47
5.40
y3.31
4.05
12.50
12.30
3.84

Wheal Basset, Cornwall, England

y2.58

Bisbee, AZ, USA

Burra, South Australia
Chessy, Lyons, France
Chessy, Lyons, France

Granite, locality unknown

Granite, Cornwall, England
Mafic Rock, Cornwall, England
Stavoren Mine, Bushveld complex, South Africa
Outokumpo Mine, Finland, Mafic Rock
Sudbury CuNi deposit, Canada
Sudbury CuNi deposit, Canada
Sudbury CuNi deposit, Canada
Sudbury CuNi deposit, Canada
Sudbury CuNi deposit, Canada

All samples listed in this table are from the Oxford University Museum of Natural History.

15.85
14.60
14.71
4.43
4.58
12.42
y1.07
0.65
1.28
y1.46
y1.43
y1.88
y2.27
3.98
y1.84
y2.20
y1.83
y5.26
y6.17
y0.97

X.K. Zhu et al.r Chemical Geology 163 (2000) 139149

144

Table 2
Cu-isotope composition in chalcopyrite from black smoker sulphides deposits
Age ka. a

Sample

Locality

114-2-15
1156-2-3
1154-1-2
Ditto
Average

Active hydrothermal vent, Axial Graben, 218N EPR

Active hydrothermal vent, Axial Graben, 218N EPR
Active hydrothermal vent, Axial Graben, 218N EPR

HR2505
HR2504
HR1805
Ditto
Average

Inactive vent, western flank of Marginal High, 138N EPR

Inactive vent, western flank of Marginal High, 138N EPR
Active vent, Axial Graben, 138N EPR

G-4
G-7
G-17
G-22
G-14
Ditto
Average

Inactive vent, Site B, 868 W Galapagos Rift

Inactive vent, Site B, 868 W Galapagos Rift
Inactive vent, Site B, 868 W Galapagos Rift
Inactive vent, Site B, 868 W Galapagos Rift
Inactive vent, Site B, 868 W Galapagos Rift

2625-4-3
Ditto
2625-3-1
Ditto
2625-3-3
Ditto
2625-3-4
Ditto
Average

Beehive top, Site 4, Axial Graben, Broken Spur.

Top pipe, Site 3, Axial Graben, Broken Spur MAR 298N..
Massive chimney wall, Site 3, Axial Graben Broken Spur.
Massive chimney wall, Site 3, Axial Graben, Broken Spur.

65 Cu
7.75
3.40
11.47
11.71
7.58

20
20

y4.82
y1.86
6.80
7.79
0.21

9
9
9
9
9

y4.43
y3.67
y3.45
y2.37
y4.55
y4.43
y3.68
3.38
3.09
3.57
3.24
6.46
6.36
10.87
11.30
6.04

Age data are from Lalou et al., 1985. The age for active vent is zero.

65 Cu which is some 40 times the analytical precision.

3.1. Copper ore deposits from continental enironments
3.1.1. Natie Cu and Cu-carbonate
Six samples of native Cu and five samples of
Cu-carbonate malachite and azurite. from ore deposits in North America, Europe and Russia were
selected from collections in the Oxford University
Museum of Natural History OUM.. The results for
the 11 samples are presented in Table 1 and Fig. 1a
and b. The 65 Cu values of the native copper samples analysed vary from y3.31 to 12.50, and a
similar range of y2.58 - 65 Cu - 15.85 is defined
by the carbonate samples. However the carbonate

samples show a tendency towards to enrichment in

the heavy isotope Fig. 3a and b., which is consistent
with the observation of Shields et al. 1965.. Another
important feature is that samples from the same
localities, such as OUM1637 and OUM6629 from
Chessy, Lyons, and OUM22647 and OUM1616 from
Bisbee, AZ, show significant difference in their Cuisotope ratios Table 1..
3.1.2. Continental sulphides
Ten samples of chalcopyrite from igneous-hosted
ore deposits located in Europe, Africa and North
America were selected from collections in OUM. In
contrast to the samples of native copper and copper
carbonates described above, the 65 Cu values obtained from these sulphides show smaller variation
from y6.17 to 3.98 Table 1, Fig. 3c.. This variation

X.K. Zhu et al.r Chemical Geology 163 (2000) 139149

145

Fig. 3. Histogram showing the distribution of 65 Cu values in a selection of Cu-minerals from continental ore deposits. Results are
expressed as 65 Cu values relative to NIST 976. a. Native copper samples from North America, Europe and Russia. b. Cu-carbonates
from North America, Europe and Russia. c. Chalcopyrite samples from igneous-hosted ore deposits in North America, Europe and Africa.
Overall, carbonate samples tend to be enriched in 65 Cu, whereas the igneous-hosted chalcopyrites show smaller variation and 63 Cu
enrichment.

in 65 Cu is reduced to y2.27 to 1.28, if the Sudbury

sulphides are excluded. Whether or not the larger
variability in 65 Cu values of Sudbury sulphides is
related to their possible origin by meteorite impact
Dietz, 1964; Faggart et al., 1985; Deutsch and
Grieve, 1994., is an interesting topic for further
study. Overall these igneous-hosted sulphides are
collectively enriched in 63 Cu compared to the native
copper and Cu-carbonates which are products of
supergene enrichment.
3.2. Ocean floor hydrothermal sulphides
Samples of chalcopyrite from ocean floor black
smoker sulphide chimneys were selected from collections at Cardiff. These include both samples of
active high temperature vents as well as inactive
vents at 218N, 138N, on the East Pacific Rise EPR.,
868W on the Galapagos Rift, Pacific, and the Broken
Spur field at 298N on the Mid-Atlantic Ridge MAR..
These samples have been described in some detail by
Knott 1995. and, in contrast to continental chalcopyrite samples, show a larger variation in 65 Cu
values from y4.81 to 11.47 Table 2. with some
interesting features. First, the 65 Cu values obtained
from these samples show significant variations both
between and within each hydrothermal field. For

example, the samples from EPR 218N display 65 Cu

values from 3.40 to 11.47 Fig. 4a. with an average
of 7.54, whereas the 65 Cu values from EPR 138N
vary between y4.86 and 4.90 Fig. 4b. with an
average of y0.59. Secondly, samples from old inactive vents tend to have lower 65 Cu values and show
less variability in Cu isotope composition as compared to samples from active high temperature hydrothermal vents. Chalcopyrite samples from a single
inactive vent on the Galapagos Rift at 868W, which
is 9 ka old Lalou et al., 1985., have 65 Cu within a
small range between y4.44 and y2.37 Table 2 and
Fig. 4c. with an average of y3.53 for the five
samples. This is ca. 10 65 Cu units lower than the
mean value defined by samples from EPR 218N,
where the samples were collected from axial active
high temperature black smoker chimneys. At the
EPR 138N locality, two samples HR2504 and
HR2504. collected from a 20-ka-old inactive vent
Lalou et al., 1985. give 65 Cu values of y1.86 and
y4.81, respectively, whereas sample HR1805 collected from an active chimney from the same field
has a high 65 Cu value of 4.90 Table 2.. Lastly,
65 Cu values of chalcopyrite samples from a single
active vent at Broken Spur, MAR 298N, appear to
vary according to their positions in the chimney
Table 2.. Two samples 2625-3-3 and 2625-3-4.
collected from the lower parts of a massive chimney

146

X.K. Zhu et al.r Chemical Geology 163 (2000) 139149

4. Discussion
4.1. The natural ariation of Cu isotopes and low
temperature mass fractionation

Fig. 4. Histogram showing 65 Cu distribution in samples of

chalcopyrite separated from hydrothermal sulphide deposits in the
Pacific and Atlantic Oceans. Note that Samples from inactive
vents are relatively depleted in 65 Cu. a. Samples from active
hydrothermal vents at 218N, East Pacific Rise. b. Samples from
138N, EPR. Two samples showing lower 65 Cu values are from
inactive vents, and the one with higher 65 Cu value is from an
active vent. c. Samples from a single inactive vent at 868W,
Galapagos Rift. d. Samples from two active vents some 30 m
apart at Broken Spur, 298N MAR. The two samples collected
from chimney tops have the lowest 65 Cu values, and those
samples from the lower chimney wall show higher 65 Cu.

A variation of 22 units in Cu-isotope compositions has been observed in this study. This result
unambiguously demonstrates that natural variations
in 65 Cur63 Cu exist as claimed in the earliest studies
by Walker et al. 1958. and Shields et al. 1965..
These authors reported variations in Cu isotope ratios of 8 and 12 per mil, respectively. However, of
the more than 140 samples analysed, over 90% show
Cu isotopic variations which are within or around
their analytical errors of 1 to 1.5 per mil. Taken
together, these indicate that the Cu isotope variations
in the majority of natural samples are within the
range observed in this study. It is worth pointing out
that the variation of 22 units observed in this
study is some 40 times the analytical uncertainty at
95% confidence. This immediately demonstrates the
enormous potential for using stable Cu isotopes as
tracers in geological and planetary processes.
The variations in 65 Cu values observed in this
study display some interesting regularities. Samples
of native copper, carbonate and black smoker chalcopyrite display large differences in 65 Cu values
even at a single locality, whereas chalcopyrite samples in igneous-hosted continental deposits show remarkably similar Cu-isotope compositions worldwide. It is worth pointing out that those samples with
highly variable 65 Cu values have involved aqueous
solutions at relatively low temperature in their formation. This suggests that isotopic variations principally reflect mass fractionation in response to low
temperature processes rather than the source heterogeneity.
4.2. Cu isotopic ariation in black smoker sulphides
and hydrothermal circulation

wall give 65 Cu values of 6.46 and 10.45, respectively, whereas sample 2625-3-1 which was collected
from the chimney top of the same vent Site 3. has
65 Cu s 3.57. Sample 2526-4-3 collected from the
beehive top of another chimney Site 4., which is
some 30 m apart from Site 3, yields a 65 Cu value of
3.38 Table 2..

As described above, 65 Cu values in chalcopyrites

from ocean-floor hydrothermal deposits vary widely.
This variation could in principle arise from a variety
of factors including source heterogeneity, mass fractionation in hydrothermal processes, or mixing of
different sources of copper. It has been demonstrated experimentally Seewald and Seyfried, 1990;

X.K. Zhu et al.r Chemical Geology 163 (2000) 139149

Seyfried and Ding, 1993. that sulphide deposits developed at the sites of black smokers in the oceans
derive their Cu predominantly from a mantle source.
Moreover, the Cu concentration in seawater of ca
0.001 to 0.007 mmol kgy1 Wu and Boyle, 1997. is
exceedingly low compared to that of 9.7 to 150
mmol kgy1 Elderfield and Schultz, 1996; Edmonda
et al., 1996. in high temperature hydrothermal fluids.
Although the Cu isotope composition in seawater is
presently unknown, it is unlikely that the difference
in 65 Cu between seawater and the sulphides is
sufficiently large to produce an observable effect
given the limitations imposed by the elemental mass
balance. Furthermore, mid-ocean ridge sides where
the samples were collected are sediment-starved, and
little possibility exists therefore for the incorporation
of significant amounts of Cu come from a sedimentary source. Therefore mixing models between seawater and hydrothermal fluids or mantle source used
to explain S-isotopes in these sulphide deposits
Woodruff and Shank, 1988; Knott, 1995; Duckworth et al., 1995. and Li isotopes in ocean basalts
Chan et al., 1992, 1993. are unlikely to be relevant
to the observed 65 Cu variations. Also, it seems
unlikely that the Cu-isotopic variations in the mantle
will much exceed the variations of 65 Cu in
igneous-hosted sulphides. Therefore, 65 Cu variations recorded in the black smoker sulphides are
thought to predominantly reflect processes operating
in the hydrothermal systems themselves.
It should be recalled that the 65 Cu values from
the black smoker sulphides display the following
features: 1. relative to active high temperature hydrothermal vents, the old inactive sulphide deposits
have lower 65 Cu values and show smaller variations; 2. in a single active chimney, 65 Cu value
decreases from the bottom to top. These observations
may be explained by means of a two-stage model,
which involves: 1. the preferential leaching of 65 Cu
during the hydrothermal processes, and 2. subsequent isotopic exchange between the early formed
Cu-sulphides and 65 Cu-depleted late-stage fluids.
Analogous to the mechanism suggested to explain
Li isotopes Chan et al., 1993., the heavy isotope of
Cu may be preferentially leached from the basalt
source and the Cu-isotope composition of the hydrothermal fluids is then time-dependent. Thus, early
formed sulphides deposited in the lower part of a

147

chimney will be enriched in 65 Cu compared to the

sulphides developed at later stage at the chimney top,
as observed at Broken Spur. The large Cu-isotope
variations in the sulphides from active hydrothermal
vents at 138N and 218N EPR might simply be due
differences in hydrothermal stage at which they crystallised.
Sulphides crystallised at an early stage of the
hydrothermal process are known to undergo extensive chemical and textural modifications during the
subsequent hydrothermal diagenesis Knott, 1995..
This may lead to reactions between the 65 Cu-depleted late-stage fluids and the early-formed sulphides, as well as to induce isotopic homogenisation
within the sulphides. This would produce both a shift
towards overall lower and reduced range of 65 Cu
values.
Although this model is speculative and remains to
be further tested by future studies, it is, however,
fully consistent with the present observations.

5. Conclusions and remarks

Techniques for the high-precision determination
of Cu isotope ratios by plasma-source multiple-collector mass spectrometry have been developed. Two
approaches, namely Zn-doping and sample-standard
bracketing, have been investigated. The external precision for the methods are better than 0.3 and 0.6
units 2 s ., respectively. By applying the samplestandard bracketing technique to natural samples,
variations in Cu isotope composition of some 40
times the analytical uncertainty have been observed.
It appears that isotopic variability principally reflects
mass fractionation which occurred at relatively low
temperature hydrothermal systems, rather than heterogeneity in source. The 65 Cu variations in sulphides from ocean floor hydrothermal vents are tentatively explained on the basis of a two-stage model,
which involves the preferential leaching of 65 Cu
during the hydrothermal processes and the subsequent isotopic exchange between the crystallised
Cu-sulphides and hydrothermal fluids.
As a relatively volatile element, Cu-isotopes are
expected to provide important information on the
early solar system. As a redox element, Cu plays
some important roles in low temperature geochemi-

148

X.K. Zhu et al.r Chemical Geology 163 (2000) 139149

cal and biochemical processes. As an element which

is essential for aerobic life but is also highly toxic, it
bears special importance in environments and nutrition. This new capability for Cu isotope measurement is therefore expected to have a major impact
across disciplines ranging from cosmochemistry and
planetary geochemistry through biogeochemistry to
biochemistry and nutrition. It will now be necessary
to investigate systematically the basic inorganic and
biological chemistry of Cu and other transition metals through their natural stable isotope fractionation.

Acknowledgements
We thank M.T. Price for providing the samples
from the Oxford University Museum of Natural History. A.N. Halliday is thanked for his comments on
an early version, and R.J.P. Williams is thanked for
his interest in this project. Ariel Anbar and an anonymous reviewer are thanked for their formal comments on the paper. [MB]

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