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184
Os/ 188 Os and 186 Os/ 188 Os measurements by Negative Thermal
Ionisation Mass Spectrometry (N-TIMS): Effects of interfering
element and mass fractionation corrections
on data accuracy and precision
Ambre Luguet ⁎, Geoff M. Nowell, D. Graham Pearson
Arthur Holmes Isotope laboratory, Department of Earth Science, University of Durham, South Road, Durham DH1 3LE, UK
Received 28 February 2007; received in revised form 22 October 2007; accepted 24 October 2007

Abstract

Precise and accurate measurements of 186Os/188Os and 184Os/188Os ratios are a key requirement in the search for evidence of
interaction between the Earth's core and mantle [e.g., Brandon, A.D., Walker, R.J., 2005. The debate over core–mantle interaction.
Earth Planet. Sci. Lett. 232, 211–225] and in understanding nucleosynthetic processes, in particular the P-process, occurring in
stars [e.g., Liu, Y., Huang, M., Masuda, A., Inoue, M., 1998. High-precision determination of osmium and rhenium isotope ratios
by in-situ oxygen isotope correction using negative thermal ionisation mass spectrometry. Int. J. Mass Spectrom. Ion Process 173,
163–175.; Brandon, A.D., Walker, R.J., Puchtel, I.S., 2006. Platinum–osmium isotope evolution of the Earth's mantle: constraints
from chondrites and Os-rich alloys. Geochim. Cosmochim Acta 70, 2093–2103.]. Here we present a detailed study of the effects of
polyatomic interferences, mass fractionation and correction procedures that influence and ultimately limit the quality of Os isotope
data that can be obtained using the N-TIMS method. Among the polyatomic interferences monitored closely, O isotopic
interferences can lead to a 21 ppm deviation of the 186Os/188Os depending on the O isotopic composition used for correction. We
found that because of the variation of the O isotopic composition within and between analyses, O isotopic composition should be
determined in-run.
Significant PtO−2 signals are generated during typical N-TIMS analyses of Os and yet these interferences have not been
commonly corrected for. While oxide interferences from PtO−2 are negligible on the 186Os/188Os ratio, they are very significant on
the 184Os isotope (up to 1.2% deviation). Hence, particular care must be given to PtO−2 monitoring if 184Os/188Os is to be used to
investigate supernova nucleosynthetic p-processes or used as a measure of any potential WO−3 interferences. On the basis of
detailed scans using a secondary electron multiplier, we find no evidence for the presence of PtO−3 , PtCl− and BaCl−3 interferences.
Similarly, experiments using Os runs doped with W indicate that WO−3 is not a common interference during typical N-TIMS
analyses of Os. Among the 3 Os isotopic ratios commonly used for mass fractionation correction, the use of 189Os/188Os
(i.e. 1.21978) leads to the largest shift on the 186Os/188Os, lowering it by 115 ppm on average. To aid future consistency we
recommend that mass fractionation corrections are made relative to a 192Os/188Os value of 3.083 [e.g. Brandon, A.D., Walker, R.J.,
Puchtel, I.S., 2006. Platinum–osmium isotope evolution of the Earth's mantle: constraints from chondrites and Os-rich alloys.
Geochim. Cosmochim Acta 70, 2093–2103.].

⁎ Corresponding author. Tel.: +44 191 334 2339/2324; fax: +44 191 334 2301.
E-mail addresses: ambre.luguet@durham.ac.uk (A. Luguet), g.m.nowell@durham.ac.uk (G.M. Nowell), d.g.pearson@durham.ac.uk
(D.G. Pearson).

0009-2541/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemgeo.2007.10.013
 A. Luguet et al. / Chemical Geology 248 (2008) 342–362 343

We have analysed 3 different Os reference materials. For all reference materials, we obtain an excellent agreement and very good
long-term reproducibility for 190Os/188Os, 189Os/188Os and 187Os/188Os ratios compared with previously published values, or with
new values obtained by MC-ICP-MS using large Os signals [Nowell, G.M., Luguet, A., Pearson, D.G., Horstwood, M.A., 2008-this
volume. Precise and accurate 186Os/188Os and 187Os/188Os measurements by Multi-Collector Plasma Ionisation Mass
Spectrometry (MC- ICP-MS) part I: solution analyses. Special Issue on Highly Siderophile Element Geochemistry. Chem. Geol.
doi:10.1016/j.chemgeo.2007.10.020.]. The disagreement for 186Os/188Os and 184Os/188Os between our values and either previously
published values, or with the new MC-ICP-MS data is more significant. Persistence of a residual correlation between 186Os/188Os and
184
Os/188Os for the 3 Os reference materials following O isotope, PtO−2 interference, and mass fractionation corrections suggests the
presence of an additional interference affecting both 184Os and 186Os. This is unlikely to be WO−3 ions since their presence during Os
analysis has been discounted from our W-doped experiments. Similarly, discrepancies (70–90 ppm) in the 186Os/188Os between MC-
ICP-MS results and our data when a correction for the residual correlation is applied also suggest the presence of additional
interference that may affect the mass 234 during N-TIMS measurements. If 186Os is to be used to trace core–mantle interactions, and
nuclear and supernova nucleosynthetic processes, further detailed investigation is required to precisely characterise these interferences
and a common measurement and data processing procedure must be adopted in order to allow inter-laboratory comparisons.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Osmium isotopes; Pt–Os system; N-TIMS; Core–mantle interaction

1. Introduction is the presence of numerous other molecular species in the

Among the radiogenic Os isotopes, 186Os has received
particular attention for the past decade because of its
potential ability to trace core–mantle interactions in
planetary systems (see Brandon et al., 2006 and references
therein). 186Os is produced by the radiogenic decay of 190Pt
with a half-life of 468 Ga (Begemann et al., 2001). This
very long half-life, combined with the very low abundance
of the parent isotope (0.0129% of 190Pt) means that the
natural variation in the 186Os/188Os ratio is very small (e.g.
80 ppm variation in the 186Os/188Os ratio for mantle
evolution over 3 Ga, see Brandon et al., 2006). To detect
the small variations in 186Os/188Os and hence use the Pt–
Os system as a geochemical tracer requires very precise
interference-free measurements. Similarly precise mea-
surements are also required for the identification of fine-
scale Os isotopic anomalies in meteorites, which reflect
nucleosynthetic processes occurring in the stars in which
they formed (Takahashi et al., 1976; Yokoyama et al.,
2007; Reisberg et al., 2007). This is especially true for the
p-process nuclide 184Os as it is the least abundant of the Os
isotopes (0.02% vs. 1.58% for 186Os) and therefore is
potentially the most sensitive to polyatomic interferences.
186
Os/188Os measurements on mantle samples and
meteorites, published to date, have been exclusively per-
formed using Negative Thermal Ionisation Mass Spectro-
metry (N-TIMS). As Os is efficiently ionised by N-TIMS
(1–5%) as a negative oxide (OsO3−), large signals are
generated even for relatively small Os samples, ensuring
good counting statistics. As with all analytical techniques,
there are trade-offs. A complication inherent with any tech-
nique involving the generation of negative molecular ions
mass spectrum. In addition, for oxide measurement, precise
and accurate oxygen-based interference corrections are
required. 184Os, 186Os and 187Os oxides are potentially
subject to numerous polyatomic interferences (e.g. PtO2−,
ReO3−, WO3−) as well as oxygen isotope interferences oc-
curring as isobaric M − 1Os16Ox17 − M −2
− 1O , Os16Ox18 −
− 1O ,
M −3 16 17 18 −
Os Ox − 2O O present over the whole mass range
of OsO3− ions. In previous 186Os studies, O isotope inter-
ferences have been corrected using a constant O isotope
composition throughout the analytical sessions. The O
isotope composition used in such corrections were either
the Nier O isotope composition (R.J. Walker, pers. comm.
to D.G. Pearson) or a composition determined for a given
instrument with a fixed O supply by running a Re standard
(see for example Walker et al., 2005; Brandon et al., 2006).
Nevertheless, both Harper and Jacobsen (1996) and Liu
et al. (1998) showed that the O isotope composition could
vary significantly during a single analysis or between
analyses, as a function of the O pressure in the ion source
chamber.
In addition to O isotope interferences, 186WO3− has the
potential to interfere on 186OsO3− and compromise ac-
curate and precise 186Os/188Os ratio measurements (e.g.
Brandon et al., 1999). As pointed out by Meibom et al.
(2004), a 10 μV 186WO3− signal on 200 mV 186OsO3−
beam would generate a 50 ppm shift in the 186Os/188Os
ratio. In the past, the 186WO3− interferences have been
monitored by measuring the 184Os/188Os ratio during
Faraday runs (Brandon et al., 1999, 2003, 2005) since
184
OsO3− (mass 232) is also potentially affected by
184
WO3− interferences. However, because 184OsO3− sig-
nals are very small (natural abundance of 184Os is 0.02%),
344 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
measurement of 184Os/188Os has a limited ability to
precisely identify any small contribution from 184WO3−.
To better identify this interference, Meibom et al. (2004)
and Walker et al. (2005) monitored 182WO3− and 183WO3−
(masses 230 and 231). However, these 2 masses (as well
as masses 232 and 234) are also affected by PtO2− inter-
ferences. Despite signals from PtO2− ions having been
observed (see Brandon et al., 2005), they were not
corrected for because the signals were small (a few mV)
and their effect on the precision and accuracy of the
186
Os/188Os ratios was expected to be insignificant. How-
ever, natural variation in 186Os/188Os is also small so it is
important to quantify and evaluate the significance of all
these interferences.
Here, we present a systematic review of interfer-
ences affecting the mass range of Os isotopes during N-
TIMS measurements. We closely examine mass fractiona-
tion behaviour and we quantify the different approaches to
O isotopes and other polyatomic interference corrections.
In doing this, we present data obtained on 2 isotopically
distinct Os reference materials (RMs), commonly used to
assess the quality of 186Os measurements by N-TIMS; the
Johnson Matthey Maryland University solution (UMd)
provided by R.J. Walker and the Johnson Matthey solution
from the Department of Terrestrial Magnetism (DTM)
provided by R.W. Carlson. In the 186Os literature, these Os
reference materials have been previously referred to as the
Johnson Matthey Os standard and the JWM standard,
respectively. In addition, we also report preliminary N-
TIMS values for a new Os reference material soon to be
distributed for use as an inter-laboratory standard for Os
isotope measurements: the Durham Romil Osmium Stan-
dard or DROsS. This solution supersedes LOsST used
previously to evaluate the need for an international Os
reference material (Meisel, unpublished).
The reporting of isotope data follows the guidelines
outlined by the Chemical Geology Editorial board
(2003). The errors for the short-term reproducibility of
standards analysed in a single analytical session and/or
long-term reproducibility over multiple sessions are
quoted as 2 standard deviations (2SD). Within-run
errors for individual analyses are quoted as 2 standard
errors of the mean (2SE = 2SD/n0.5; where n = 270).
2. Mass spectrometry
Os isotope ratios were measured on a Thermo-Finnigan
Triton TIMS instrument operating in the negative ion
mode at the Arthur Holmes Isotope Geology Laboratory,
Department of Earth Science, Durham University over a
period of 12 months between January 2006 to 2007. This
instrument is equipped with 9 Faraday collectors. The ion
source chamber and associated ion optics used for the Os
measurements in this study is a system dedicated to
negative ion Os isotope analyses. It has never been
exposed to Re or W filaments.
2.1. Sample loading
Os reference materials were run on Pt single
filaments obtained from Electronic Space Products
Inc. (0.02 × 0.001 in.). Prior to loading, the Pt filament
material was cleaned by ultrasonification in acetone for
10 min, followed by leaching in 8 mol/L HNO3 and in
Milli-Q for at least 24 h (but usually for several weeks)
on a hot plate at 80 °C. Once made, the Pt filaments are
outgassed in air for 20 min and allowed to cool before
proceeding with sample loading. Os blanks for the Pt
filament material are on average 10 ± 5 fg over the
period of this study.
The amount of Os loaded on the Pt filament for
analysis varies between 10 and 100 ng. Reference
materials are loaded in 3–6 mol/L HCl. After being
dried down in the air using a heating lamp, 0.8 μL of a
NaOH–Ba(OH)2 activator was loaded as a small spot on
top of the reference material load and dried down with a
heating lamp. Two batches of a mixed NaOH–Ba(OH)2
activator solution (see Appendix A for details of the
NaOH–Ba(OH)2 preparation method) were tested dur-
ing the course of this study, one prepared in June 2001
and the other one in May 2006. As no efficiency
difference was observed between these batches, all the
analyses reported in this study were performed using the
2001 NaOH–Ba(OH)2 batch.
2.2. Instrumentation and data measurement method
Because of the limited amounts of Os available in
samples (e.g. peridotites), a multi-dynamic routine that
allows for correction of differences in Faraday cup
efficiency was not considered practical, especially when
we require an extra high-mass peak jump for the O
isotope measurements. Os isotope measurements were
therefore performed using a two-sequence static multi-
collection routine. The first sequence of the routine we
used allows data acquisition on the OsO3− masses
ranging from 232 to 240 amu. Sequence 2 allows in-
run measurements of the O isotope composition
involving acquisition of masses 239, 241, 242 and
243 amu (see Table 1). Peak centering was done using
188
Os16O3− (mass 236).
Each measurement consists of 270 ratios in blocks of
10 cycles. Integration time was 8 seconds for the main
OsO3− measurement sequence and 4 sec for the in-run O
 A. Luguet et al. / Chemical Geology 248 (2008) 342–362 345

Table 1
Cup configuration for the static multi-collection routine used for high-precision and high accuracy 186Os measurements on the Triton N-TIMS at
Durham University
L4 L3 L2 L1 Axial H1 H2 H3 H4
Cup configuration
Mass 232 234 235 236 237 238 240
SEQ1 184
Os16O−3 186
Os16O−3 187
Os16O−3 188
Os16O−3 189
Os16O−3 190
Os16O−3 Os16O−3
192

Mass 236 238 239 240 241 242

SEQ2 188
Os16O−3 190
Os16O−3 190
Os16O17
2 O
− 192
Os16O−3 192
Os16O17
2 O
− 192
Os16O18
2 O
−

isotope measurement sequence. Idle time was 4 sec
between each measurement sequence. The combination
of 270 ratio measurements with beam intensities on
186
OsO3− and 187OsO3− (masses 234 and 235) higher than
80 mV (≈ 8 × 10− 13 A signal with 1011 Ohm resistors)
allows a 10–30 ppm within-run precision (2SE) on
186
Os/188 Os and 187Os/188 Os to be achieved. In addition
to the baseline and amplifier gain calibration performed
at the start of each day, a 30 second instrumental baseline
was also measured at the beginning of each block by
deflecting the beam away from the detectors. Data were
collected using the virtual amplifiers which are unique to
the Thermo-Finnigan Triton TIMS and the Neptune MC-
ICP-MS. The virtual amplifier system allows the signal
from each Faraday to be passed through each amplifier
using a relay matrix that switches between blocks and
ultimately cancels out variations in amplifier efficiency.
Oxygen pressure, maintained by a sapphire needle valve,
is measured in the mid-point of the ion source chamber
and was maintained at 2.2–2.7 × 10− 7 mbar. In total, a
Faraday measurement lasts approximately 2 h.
In addition to the Faraday measurements, possible
PtO2−, ReO3− , WO3− interferences (see Table 2) on
184
OsO3−, 186OsO3− and 187OsO3− were quantified by
measuring masses 228, 230–233 (i.e. 196 Pt 16 O2− ,
198 16 − 183
Pt O2 , W16O3− , 184Os16O3−and 185 Re16O3−) on a
secondary electron multiplier, hereafter referred to as an
ion counter (IC), before and after each Faraday
measurement. Each IC measurement includes 1 block
of 10 ratios for a total analysis time of 10 min. Peak
centering was done on 198PtO2−, 196PtO2− and 184OsO3−
(masses 228, 230 and 232).
2.3. Data processing
Following measurements, data were exported and
reprocessed off-line. Corrections were made in the
following order: abundance sensitivity, PtO2− and ReO3−
interferences, WO3− interferences, O isotope composition
interferences followed by mass fractionation. Corrections
were made on a cycle-by-cycle basis, determining the
oxygen isotope composition for each mass scan so that
any change is accounted for through a run (see below).
Abundance sensitivity corresponds to the ratio
between a signal at mass M and a signal observed at
mass M − 1 on the low-mass side of a mass M peak. The
abundance sensitivity for the Triton was determined by
turning up a 50 ng Os load of the UMd RM until a stable
192
OsO3− beam of approximately 3.5 V was obtained.
The average intensity of the 192 OsO3− was then
measured using a 1 min acquisition. Following this, an
IC scan, taking a total of 2 min, was performed on the
low-mass side of the 192OsO3− peak down to and
including mass 239. Since the signal at mass 239 is
comprised mainly of the 190Os16O217O− peak, the raw
data from the IC scan was exported and the signal
intensity due to the tail of 192OsO3− at mass 239 was
extrapolated beneath mass 239 using a curve fitting
program. The abundance sensitivity determined for the
Os analyses on the Durham Triton TIMS is 0.3 ppm.
Despite being negligible, an abundance sensitivity
correction was nevertheless systematically applied to
masses 234–241 (186 OsO3− to 192Os16O217O−).
In the second step, 184OsO3−, 186 OsO3− and 187OsO3−
signals were corrected for PtO2− and ReO3− interferences
by using the IC analyses of 196Pt16O2−, 198Pt16O2− and
185
Re 16 O 3− . For this, 196 Pt 16 O 2− , 198 Pt 16 O 2− and
185
Re16O3− beam sizes were extrapolated for the 270
ratios of the Faraday measurements by using the pre-
and post-run IC measurement routines and assuming a
linear behaviour for the different signals throughout the
Faraday measurement. This extrapolation approach,
despite being simplistic, allows us to account for the
different behaviour of 196 Pt 16 O2− , 198 Pt 16 O2− and
185
Re16O3− beams compared to the 184OsO3− beam, as
reflected by the variations of the 184Os/198Pt ratios
(mass 232/mass 228 = 0.39–1.83) during and between
IC measurements on different filaments. These variable
184
Os/198 Pt ratios imply that Pt and Os sources are
different, Pt ions likely come from the heated Pt filament
material while the osmium is ionised from the reference
material. In contrast, the constant 185 Re/184Os ratios
 346
Table 2
Inventory of the known or potential (italic) polyatomic interferences present on the mass spectrum of OsO−3 ions during N-TIMS analysis
Mass 228 230 231 232 233 234 235 236 237 238
184
Os16O−3 186
Os16O−3 187
Os16O−3 188
Os16O−3 189
Os16O−3 190
Os16O−3
O isotope interferences
186 − − − −
Os16O17
2 O
187
Os16O17
2 O
188
Os16O17
2 O
189
Os16O17
2 O
184 − − − −
Os16O18
2 O
186
Os16O18
2 O
187
Os16O18
2 O
188
Os16O18
2 O
184 − − − −
Os17O16
2 O
186
Os17O16
2 O
187
Os17O16
2 O
188
Os17O16
2 O
184
Os17O−3 186
Os17O−3 187
Os17O−3
16 17 18 −
184
Os O O O 186
Os16O17O18O− 187
Os16O17O18O−
184 − −
Os17O18
2 O
186
Os17O18
2 O
Os16O18O−2
184 186
Os16O18O−2
184
Os17O18O−2
184
Os18O−2

A. Luguet et al. / Chemical Geology 248 (2008) 342–362

Polyatomic interferences
183
W 16O3− 184
W 16O3− 186
W 16O3−
185
Re16O−3 Re16O−3
187

Ba 35Cl3−
130 132
Ba 35Cl3−
194 35 195 35 −
196
Pt 35Cl − 195 37 −
198
Pt 35Cl − 198 37 −
Pt Cl Pt Cl Pt Cl Pt Cl
Pt Cl −
194 37
Pt Cl −
196 37
196
Pt16O−2 198
Pt16O−2 196
Pt18O−2
198 17 −
Pt O2 198
Pt18O−2 190
Pt 16O−3
198 16 18 −
Pt O O
Signal 265,000– 75,000–
b500 b 200,000 b 300
(cps) 1,900,000 542,000
Mass 239 240 241 242 243 244 245 246
192
Os16O−3
O isotope interferences
190 − −
Os16O17
2 O
192
Os16O17
2 O
189 − − −
Os16O18
2 O
190
Os16O18
2 O Os16O18
192
2 O
189 − − −
Os17O16
2 O
190
Os17O16
2 O
192
Os17O16
2 O
188
Os17O−3 189
Os17O−3 190
Os17O−3 192
Os17O−3
16 17 18 −
188
Os O O O 189
Os16O17O18O− 190
Os16O17O18O− Os16O17O18O−
192
187 − − − − −
Os17O18
2 O
188
Os17O18
2 O
189
Os17O18
2 O
190
Os17O18
2 O Os17O18
192
2 O
187
Os16O18O−2 188
Os16O18O−2 189
Os16O18O−2 190
Os16O18O−2 Os16O18O−2
192
186
Os17O18O−2 187
Os17O18O−2 188
Os17O18O−2 189
Os17O18O−2 190
Os17O18O−2 192
Os17O18O−2
186
Os18O−2 187
Os18O−2 188
Os18O−2 Os18O−2
189 190
Os18O−2 192
Os18O−2
Polyatomic interferences

134
Ba 35Cl3− 135
Ba 35Cl3− Ba 35Cl3−
136 137
Ba 35Cl3− Ba 35Cl3−
138 138
Ba 35Cl237Cl −

192
Pt 16O−3 194
Pt 16O−3 195
Pt 16O−3 196
Pt 16O−3 198
Pt 16O−3
Signal
b 500,000 b 2,500,000 b 2000 b 500 b 60 bb 60
(cps)

Signals are in counts/s (cps).

 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
(0.0013–0.0014) of the IC measurements suggest that
ReO3− is mostly released from the reference material.
196 18 − 198 17 − 198 16 18 − 198 18 −
Pt O2 , Pt O2 , Pt O O , Pt O2 and
187
ReO3− were then recalculated using the O isotope
composition determined for each of the 270 ratios and
were subtracted from masses 234, 236 and 237. It is
important to note that our calculation did not take into
account the effect of instrumental mass fractionation of
the Re isotopes when calculating the 187ReO3− signal
from the 185 ReO3− as it cannot be done in a two isotope
system. This approach was justified by the negligible
effect that this correction has on the recalculated
187
Os/188 Os (0.01–0.07 ppm).
The potential presence of WO3− interferences was
determined by subtracting first 196 Pt 17 O 18 O − and
198 16 17 −
Pt O O signals from the 183 WO3− peak intensity
(mass 231) in order to correct this mass for the PtO2−
interferences. When 183WO3− was observed, 184WO3−
and 186WO3− beam sizes were recalculated using the
relative abundance of these 3 W isotopes and then
subtracted from the measured mass 232 and 234 beams.
The O isotope composition was determined in-run
using measurements on masses 239 and 241–243 which
correspond to various combinations of 16O, 17O and 18O
with 190Os and 192Os (see Table 2). Other workers have
used in-run determined O isotope measurements to
correct for W or Os isotope ratio determinations (Harper
and Jacobsen, 1996; Liu et al., 1998). While these authors
determined the O isotopic composition using several or all
of the O–Os isotope combinations, we only consider the
various combinations of O isotopes with the 192Os isotope
in our calculation. Because 192Os is the most abundant Os
isotope and because of the very low probability of
multiples 17O or 18O, masses 240, 241 and 242 were
assumed to be 192Os16O3−, 192Os16O217O−,192Os16O218O−,
respectively. 17O/16O was then determined from the mass
241/240 ratio and 18O/16O from the mass 242/240 ratio.
In order to obtain the signal intensity at mass 240
corresponding to only the 192Os16O3− signal, we first
stripped the mass 240 peak of the various OsO3−
interferences using the O isotopic composition deter-
mined by running a Re load (Ogas) for the first of the 270
ratios obtained for a Faraday analysis and by using the
previous in-run O isotopic composition for any subse-
quent ratios. This correction procedure can also be
performed iteratively but we found no discernable
difference in doing it in the manner described above.
Finally, instrumental mass fractionation was cor-
rected using the 192Os/188 Os ratios relative to a value of
3.083 together with an exponential law. The
192
Os/188 Os value of 3.083 was selected to be consistent
with the most recent 186Os/188Os measurements made
347
using Triton instruments (Walker et al., 2005; Brandon
et al., 2006). The final step of data processing for each
analysis is the rejection of individual integrations
outside of 2SD of the mean value for the analysis.
No mass fractionation correction is applied to the
oxygen isotope composition determined by our method
before making the O interference corrections. This is
almost impossible to do because oxygen may be
fractionated in the gas introduction system of the mass
spectrometer and then via processes that lead to
formation of the OsO3− molecule on the filament; both
of which may not fit to exponential or power law
fractionation models. The O is already fractionated
before it combines with Os to form OsO3− and so it is the
fractionated or ‘measured’ O composition that is needed
to make an accurate interference correction and should
not be corrected for mass fractionation. The nature of
these processes will also vary throughout a run and
from filament to filament so corrections for molecular
oxygen-based interferences are done “within-run” for
each individual integration using the measured O
isotope composition for each integration.
3. O isotope interferences and determination of O
isotope composition
In previous 186Os studies, O isotope interferences on
OsO3− ions have been corrected using either the Nier O
isotope composition (ONier; R.J. Walker, pers. comm to
D.G. Pearson) or using the O isotope composition
determined for the O gas bled in the ion source chamber
(Ogas). This Ogas isotope composition was determined
by analysing, on Faraday cups, a Re standard for ReO4−
ions (masses 249–254 amu) which corresponds to
various combinations of O isotopes with Re (i.e.
185
Re16O4−, 185Os16O317O−, 187Re16O4−, 185Re17O316O−,
187
Re16O318O− and 187Re16O217O18O−). In reality, the O
isotope composition determined this way could be a
combined function of O from the NaOH–Ba(OH)2
activator and the Ogas. The Ogas isotope composition
determined for our O bottle using this approach is
18
O/ 16O = 0.0020349 and 17O/16O = 0.0003835. This
Ogas as well as our in-run measurements of O isotopic
composition (Oin-run) are relatively close to literature
values previously obtained during the isotopic analysis
of a number of different elements in different labora-
tories (e.g. Nier, 1950; Wasserburg et al., 1981; Reisberg
and Zindler, 1986; Thirlwall, 1991; Chavagnac, 1998;
Griselin et al., 2001; see Fig. 1). Moreover, our Oin-run
shows less scatter than the O isotopic composition
determined by Liu et al. (1998) when running either
different samples or multiple runs of the same sample.
348 A. Luguet et al. / Chemical Geology 248 (2008) 342–362

Fig. 1. Variations of the O isotopic composition used to correct for O interferences during TIMS analyses of Os–Re–Pt and Sm–Nd isotopic system.
TFL represents the terrestrial fractionation line. Note that the fractionation of the Oin-run determined during this study follows the terrestrial
fractionation and show less scatter than the Oin-run of Liu et al. (1998).

Repeated analyses by Brandon et al. (2006) on the isotope composition is much larger when we compare
Johnson Space Center Triton showed that the O isotope different runs over our analytical period of 1 year. The
composition of a single O bottle is constant over period difference between the average 18O/16O ratio of various
of several months. In contrast, in-run O isotope
measurements revealed very variable O isotope compo-
sition within and between filaments (Liu et al., 1998).
The O isotope composition may be expected to vary during
an analytical run as Ogas is probably not the only source
of O able to combine with Os. The NaOH–Ba(OH)2
activator could also provide a source of O for the OsO3−
and its O isotope composition is likely to be different
from the Ogas.
Our in-run measurements of O isotope composition
also allowed us to observe O variations during a single
run. This procedure permits comparisons of O isotope
fractionation between various runs of both UMd and
DTM RMs (Fig. 2). The variation of 18O/16O ratio Fig. 2. Variation of in-run 18O/16O ratios within and between Os
reference material analyses. Each filament is represented by a different
during a single run reaches a max of 500 ppm (2SE) but symbol. The plain line is the 18O/16O ratio determined for our
is commonly 230 ppm and 140 ppm on average for instrument by running a Re standard, this corresponds to the Ogas. The
UMd and DTM RMs, respectively. The range of the O dashed line represents the Nier 18O/16O ratio (ONier).
 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
runs reaches a maximum of 14,000 ppm. This is com-
parable to the 30,000 ppm variation range for 18O/16O
reported by Liu et al. (1998) for a 4 month analytical
period. These authors interpreted the 18O/16O scatter as
resulting from O pressure fluctuations in the source
chamber during the measurement.
Fig. 2 also shows that our Ogas is well within the
range of our Oin-run values. However, the average Oin-run
calculated for each of our Os RM analyses can differ
significantly from that of the Ogas, with a maximum
deviation of 8000 ppm. The same is true for ONier except
that the maximum difference from the average Oin-run is
13,000 ppm, because ONier is close to our highest
18
O/16O determined in-run.
The documented differences between Ogas, ONier and
Oin-run have repercussions for O-corrected Os isotope
ratios of the RM runs. The 234 mass (nominal
186
Os16O3−) will be affected by interferences from
184
Os17O216O− and 184Os16O218O− (Table 2). In fact,
considering the beam size of 184Os16O3− and the low
abundance of 18O and 17O over 16O, only relatively
small differences in the 186Os/188 Os ratios are observed
for differing O isotope compositions. Comparison
between 186Os/188 Os ratios corrected using Oin-run and
186
Os/188 Os corrected using Ogas reveals differences
ranging between − 5.7 ppm and 5.8 ppm with an average
difference of 1.5 ppm. This is well within our in-run
measurement uncertainty. The average difference in
186
Os/188 Os rises to 15 ppm when comparing Oin-run-
corrected 186 Os/188Os and 186Os/188 Os corrected for O
interferences using the Nier O isotope composition. It is
also worth noting that similar differences are observed
between Oin-run and Ogas and Oin-run and ONier for
187
Os/188 Os (2–5 ppm and 19–35 ppm), 189Os/188 Os
(1 ppm and 31–37 ppm) and 190Os/188 Os (4 ppm and
16 ppm).
In summary, for 186Os/188Os measurements, it is
necessary to make some attempt at measuring the likely
O isotope composition during a run, although there is
only a relatively small difference in the resulting Os
isotopic ratios resulting from the use of either Ogas or
Oin-run. In contrast, if the O values of Nier are used,
significant differences in the composition of all Os
isotope ratios are observed. In the case of 186Os/188 Os,
these differences represent 12.5% on average of the total
expected natural variation of the 186Os/188 Os ratio in the
mantle (120 ppm for the mantle evolution over 4.55 Ga).
4. PtO2−, PtO3−, ReO3− and WO3− interferences
Table 2 shows the numerous polyatomic interfer-
ences due to Pt, W and Re oxides on the mass spectrum
349
of OsO3− ions. The Os isotopes most likely to be affected
by those isobaric interferences are 184OsO3−, 186OsO3−
and 187 OsO3− . Therefore, thorough screening of inter-
ferences on masses 232, 233 and 234 are crucial for the
use of the Pt/Os and Re/Os as chronometers and
geochemical tracers.
4.1. PtOx− interferences
Pt16O2− and Pt16O3− molecular ions may be generated
in the 222–230 and 240–246 amu mass ranges. PtO3−
ions, as 190 Pt16O3− and 192 Pt16O3− are potential isobaric
interferences on 190 Os16O3− and 192Os16O3−. If present,
such interferences could potentially be significant
problems because 192Os/188Os is used to correct for
the in-run mass fractionation. IC scans performed
between 220 and 246 amu reveal no convincing PtO3−
signals. On the other hand, PtO2− ions could interfere on
184
OsO3− and 186 OsO3− if 17O and 18O are present within
the 196PtO2− and 198PtO2− polyatomic ions. Monitoring of
196
PtO2− and 198PtO2− on the IC before and after the
Faraday runs shows that the intensity of these peaks
ranges between 265,000–1,900,000 cps (counts/sec-
onds) and 75,000–542,000 cps respectively. This
corresponds to 4–30 mV (average 14 mV) and 1–
8 mV (average 4 mV) signals on the Faraday with 1011
Ohm resistors. No precise indication of the size of these
peaks is available from other high-precision 186Os/188 Os
studies. Only Brandon et al. (2005) reported beam
intensities for PtO2−, however they merely stated that
they were lower than 7 mV for the 224–230 amu range.
Despite the presence of PtO2−, Brandon et al. (2005) did
not apply any PtO2− correction.
The most significant influence of a PtO2− interference
will be observed on 184OsO3− and will only be minor for
186
OsO3−, because of the size of the PtO2− peak involved
and the low abundance of 18O and 17O isotopes relative
to 16O. The sizes of the interferences are around 5–
35 μV on 184 OsO3− signals and 0.005–0.035 μV on
186
OsO3−. Although these signals are small, it must be
remembered that the typical 184OsO3− signal at mass 232
is also very small (a few mV) and so the PtO2−
interferences would typically represent b1.2% of the
total signal at mass 232. Comparison between the Pt-
corrected and raw Os isotopic ratios show that PtO2−
corrections lower the 184 Os/188 Os ratio by 2500–
11,500 ppm (Fig. 3) while the 186Os/188Os ratio is
only shifted by − 0.03 to − 0.13 ppm.
The largest magnitude PtO2− corrections were applied
to the UMd RM runs and are reflected by 184Os/188 Os
data for this RM showing the greatest discrepancy
between raw and Pt-corrected data (Fig. 3). Most of
350 A. Luguet et al. / Chemical Geology 248 (2008) 342–362

When compared with the average 184Os/188Os ratios

Fig. 3. Effect of PtO−2 correction on 184Os/188Os for UMd and DTM
reference materials. Black square: raw data for UMd, square with
cross: PtO−2 corrected UMd data, white square: raw data for DTM, grey
square: PtO−2 corrected DTM data. Error bars on data points are within-
run 2 standard errors. Plain line and grey field represent our average
184
Os/188Os after PtO−2 correction and the 2SD uncertainty range.
Dashed line and dotted field represent the average and 2SD uncertainty
range for the Neptune MC-ICP-MS data (Nowell et al., 2008-this
volume). Average 184Os/188Os and uncertainty range reported for
comparison and obtained by N-TIMS are 1: Brandon et al. (1999), 2:
Walker et al. (2005); 3: Walker et al. (2005), 4: Puchtel et al. (2004), 5:
Brandon et al. (2005) for UMd measurements; 6: Brandon et al. (2005)
for osmiridiums and 7: Brandon et al. (1999) for DTM RM.
the UMd Pt-corrected 184Os/188Os ratios are very close
to the lowest 184 Os/188Os values obtained so far on
our N-TIMS instrument. In addition to lowering the
184
Os/188 Os ratio, improved reproducibility of the
184
Os/188 Os is observed after PtO2− correction for the
3 RMs analysed here (e.g. from 7500 ppm within-run
precision down to 4500 ppm for DTM, see Table 3).
previously reported in the literature by Brandon et al.
(1999, 2006), Puchtel et al. (2004) and Walker et al.
(2005) for both UMd and DTM RMs, our average Pt-
corrected 184 Os/188 Os is much lower (Fig. 3). In
contrast, MC-ICP-MS yield consistently the lowest
184
Os/188Os ratios on the various Os RMs (Nowell et al.,
2008-this volume). The significance of this scatter in the
184
Os/188Os data will be discussed in Section 6.
Brandon et al. (2003) also suspected the presence of
195 37 −
Pt Cl ions on mass 232 (184 OsO3−). However, if
true, 2 additional peaks corresponding to 194 Pt37Cl−,
196 35 −
Pt Cl and 196 Pt37Cl− should be observed at masses
231 and 233. Signals on mass 231 should be significant
as both 194Pt37Cl− and 196 Pt35Cl− are expected to be
large peaks because of the high natural abundance of
194
Pt and 35Cl. Therefore, the peak at mass 231 should
be at least 1.3 times greater than that at mass 233. The
absence of such observations during detailed scans on
the IC allowed us to rule out the presence of 195 Pt37Cl−
on mass 232.
4.2. WO3− interferences
In contrast to PtO2− interferences which have only a
minor impact on 186 OsO3−, WO3− ions could, if present,
produce a far more significant effect on both the
184
OsO3− and 186 OsO3− via overlap of 184 W16O3− and
186
W16O3− (Meibom et al., 2004). Because of this, it is
crucial to thoroughly evaluate and document the
possible presence of these interferences.
Since 184OsO3− could also be affected by WO3−
interferences, the presence of 186WO3− interferences was
assessed, in previous studies (e.g. Brandon et al., 1999,

Table 3
Os isotopic compositions for UMd, DTM and DROsS Os reference materials
184
Os/188Os 186
Os/188Os 187
Os/188Os 189
Os/188Os 190
Os/188Os
DTM
N-TIMS our study (n = 14) 0.001306 ± 6 0.1199649 ± 37 0.173927 ± 5 1.219708 ± 9 1.983803 ± 17
N-TIMS1 0.001321 ± 3 0.1199755 ± 48 0.173918 ± 7
MC-ICP-MS2 (n = 84) 0.001299 ± 3 0.119957 ± 6 0.173925 ± 26 1.219713 ± 21 1.983834 ± 76

UMd
N-TIMS our study (n = 35) 0.001304 ± 13 0.1198427 ± 67 0.113787 ± 8 1.219710 ± 17 1.983801 ± 26
N-TIMS3 (n = 39) 0.001309 ± 6 0.1198470 ± 16 0.113791 ± 4 1.219692 ± 15 1.983793 ± 19
MC-ICP-MS2 (n = 41) 0.001300 ± 1 0.119830 ± 4 0.113790 ± 9 1.219717 ± 11 1.983836 ± 122

DROsS
N-TIMS our study (n = 8) 0.001305 ± 5 0.1199293 ± 58 0.160924 ± 4 1.219705 ± 15 1.983803 ± 15
MC-ICP-MS2 (n = 21) 0.001298 ± 2 0.119920 ± 2 0.160924 ± 3 1.219722 ± 11 1.983788 ± 14
1: Brandon et al. (1999), 2: average of N1 ppm solution run of Nowell et al. (2008-this volume), 3: Brandon et al. (2005). Uncertainty is reported
as 2SD.
 A. Luguet et al. / Chemical Geology 248 (2008) 342–362 351

Fig. 4. IC scans (800 steps) over the 228.5 and 233.5 mass range for WO−3 interference monitoring. In scan A, the plain line represents a blank filament
scan (no Os loaded, only NaOH–Ba(OH)2 activator) and the dotted grey line represents a UMd filament scan. Scans in window B are the W-doped Os
reference material where the plain line scan was obtained at 1080 mA and the dotted grey scan at 1160 mA. Note the elevated baseline over the 228.5–
231.2 mass range, preventing any detection of any low signal of 183WO−3 , if it exists.

2003), by monitoring the 184OsO3− beam during the
Faraday measurements and looking at the variations of
the 184Os/188Os ratio. This approach faces two pro-
blems. First, as the 184 OsO3− beam is very small (a few
mV), Faraday measurements are not precise enough to
detect minuscule variations of the 184Os/188Os ratio due
to the presence of small WO3− interferences. Secondly,
since 184 OsO3− is known to be affected by PtO2− inter-
ferences in addition to possible WO3− ions, variations of
the 184Os/188Os ratio will not uniquely signify the
presence of 184WO3− . In order to circumvent this
problem, more recent 186 Os studies monitored
183
WO3− and 182WO3− using the electron multiplier
detector and no WO3− peak was observed (Walker et al.,
2005; Meibom et al., 2004). 183WO3− and 182WO3− were
chosen because they are free from any OsO3− peaks.
However, in this case too, the problem of PtO2−
interferences persists as 183WO3− and 182WO3− are
affected by 198Pt16O17O− and 198Pt16O2−. In order to
identify the nature of the peak at mass 231 and
determine the true size of the 183WO3− peak, if it exists,
we monitored 183WO3− and 198Pt16O2− during the IC
measurements and corrected the signal at mass 231 for
PtO2− interferences. In addition to the IC measurements,
we also performed a detailed IC scan over the 228.5–
233.5 mass range for every filament analysed to check
for the presence of any identifiable interferences.
A blank filament (with NaOH–Ba(OH)2 activator but
no Os loaded on it) shows well-defined peaks at masses
229, 230, 231 and 232 which correspond to PtO2−
interferences (Fig. 4A). Surprisingly, scans of filaments
loaded with Os RMs show a systematically elevated
baseline which hampers the detection of the mass 231
peak (Fig. 4A). This elevated baseline is likely due to
352 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
the reflection of an ion beam somewhere within the
flight tube. However, the elevated baseline in this mass
range is not expected to be present on all N-TIMS
instruments because of variations in instrument geome-
try and deviations in the angle of the anti-reflection
baffles. Further tests on W interferences were performed
by running one filament loaded with 50 ng Os and
0.5 ng W. IC scans during these tests (Fig. 4B) revealed
a generally elevated background but no convincing
WO3− peaks over the temperature range which Os
analyses are usually performed at. This finding confirms
the statements of Brandon et al. (2003, 2005, 2006),
Walker et al. (2005) and Meibom et al. (2004) who
discounted WO3− interferences as being significant on
186
Os/188 Os for Os RM and mantle samples.
4.3. BaCl3− interferences
At the other end of the mass range of OsO3−,
interferences due to BaCl3− ions have been suggested
to be present. The possibility arises because of the Ba-
rich activator solution. 135Ba35Cl3− would interfere on
192
OsO3−, one of the two isotopes used to correct for the
instrumental mass fractionation. Because of the overlap
with OsO3− isobars, possible presence of a 135Ba35Cl3−
interference was assessed by performing IC scans of
Fig. 5. IC scan (800 steps) of a DROsS filament over the 240.5 and 246.5 mass range for BaCl−3 and PtO−3 interference monitoring.
other BaCl3− masses (241–245 amu) on filaments loaded
with Os RMs. Masses 241–245 also correspond to the
various combinations of 17O and 18O with 192 Os.
However, because of the relatively low probability of
forming a 17O3 and 17O18O2 ions and the high natural
abundance of 138 Ba (71.7%), if present, BaCl3− mole-
cular ions should be most likely observed on masses
243 and 245, corresponding to 138 Ba 35 Cl 3− and
138
Ba35Cl237Cl−. IC scans show the equivalent of a
1 μV signal intensity for mass 245 (62 cps) and a 30 μV
signal for mass 243. This latter signal is likely due to O
isotope interferences from 192 OsO3− (Fig. 5). If we
assume that 138Ba35Cl237Cl − is the only molecular
species present at mass 245, the signal intensity of
135
Ba35Cl3− at mass 240 would be 0.28 μV. This
corresponds to a fractional contribution of 0.04 ppm
on a 7–8 V signal intensity at mass 240 (192OsO3−).
Because of its very small size, this interference was not
corrected for during our measurements.
4.4. ReO3− interferences
To monitor 187Re16O3− interferences, we measure
the 185Re16O3− beam at mass 233 on the IC before
and after every Faraday measurement. 185 Re16O218O−,
185
Re16O17O2−, and 187 ReO3− beam sizes were calculated
 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
using the relative natural abundance of 185 Re and 187 Re
and the in-run O isotope composition and then
subtracted from the mass 235 beam. The 185ReO3−
beam size ranges generally between 100 and 300 cps
which translates into a total 2.7–8 μV for 185Re16O218O,
185
Re16O17O2− and 187 ReO3−. Such corrections will
lower the 187Os/188 Os ratios by 13 to 40 ppm, which
is close to the 2SD precision of our measurements.
5. Mass fractionation
5.1. Mass fractionation behaviour
Fig. 6 shows the mass fractionation behaviour of
186
Os/188 Os and 192 Os/188Os after O isotope correction
but before any PtO2−, WO3−, ReO3− interference and mass
fractionation correction was applied. All 12 DTM
analyses as well as the 35 UMd analyses define two
parallel linear negative trends (Fig. 6), whose slopes
are a function of the mass difference between the
two ratios involved. For ln–ln plots of 186Os/188Os vs.
192
Os/188 Os, the expected slope is − 0.5078 for the
exponential mass fractionation law and − 0.4998 for the
power law. The slope defined by the UMd RM is very
close to the value expected for the exponential law
(− 0.5077 ± 0.018 vs. − 0.5078). The slope defined by
the DTM RM measurements is somewhat lower but,
because of the larger error on the regression through
smaller sample numbers, is still within error of the
exponential law slope (− 0.4841 ± 0.036). Because the
variation in mass fractionation is relatively small for
Fig. 6. ln–ln plots between O isotope interference-corrected
186
Os/188Os and 192Os/188Os ratios. Black square: UMd, White square:
DTM.
353
TIMS compared with MC-ICP-MS, it is difficult to
precisely and accurately define mass fractionation lines
without large numbers of data.
5.2. Effect of mass fractionation correction
In previous studies where N-TIMS 186Os/188Os
measurements have been published, when information
is provided, instrumental mass fractionation has been
corrected by applying an exponential law and using
either the 189 Os/188Os (accepted value = 1.21978) or
192
Os/188 Os ratios. Two 192Os/188Os values have been
reported in the literature (3.083 and 3.08271). The first
value was used in recent studies to correct for mass
fractionation of TIMS measurements (see Walker et al.,
2005). The second value was also used by Walker et al.
(2005) but to correct for the mass fractionation during
LA-ICP-MS measurements. The two different
192
Os/ 188 Os values result in a constant 47 ppm
difference in the 186Os/188Os ratio. Some earlier studies
of high-precision 186 Os measurements (Walker et al.,
1997; Brandon et al., 1999; Meibom et al., 2004) also
used the 189 Os/188Os ratio for fractionation correction.
Using this ratio produces an even greater impact on the
absolute value of 186 Os/188Os ratio, which is on average
115 ppm lower for both UMd and DTM RMs. Such
large differences demonstrate that the 189 Os/188Os and
192
Os/188 Os ratios commonly used for mass fractiona-
tion correction are not internally consistent. This
prevents meaningful comparison of datasets corrected
for mass fractionation using different ratios. In the
case of 186 Os studies, this is problematic because
the anomalous 186Os signatures, which are the founda-
tion of the core–mantle interaction hypothesis, were
obtained using 189Os/188Os for mass fractionation cor-
rection (Walker et al., 1997; Brandon et al., 1999, 2003)
while more recent studies (Walker et al., 2005; Brandon
et al., 2005, 2006) used the 192Os/188 Os ratios. It is
therefore essential to adopt a single isotopic ratio and a
unique value for this ratio, so that systematic inter-
laboratory comparisons of data can be made. For the rest
of this paper, we adopt the 192Os/188 Os ratio of 3.083
used in the more recent studies (see Walker et al., 2005;
Brandon et al., 2005, 2006) and correct mass fractiona-
tion using an exponential law.
5.3. Post mass fractionation residual correlations
Although the Os isotopic data, after O isotope
interference corrections, approximate closely to the
theoretical mass fractionation law used (Fig. 6), when
relationships between ratios are examined after mass
354 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
Fig. 7. Residual correlation between 186Os/188Os and 184Os/188Os
ratios observed after O isotope and PtO−2 interference and mass
fractionation correction for UMd (top diagram) and DTM (bottom
diagram). The slopes of the residual correlation were determined using
a York fit on Isoplot.
fractionation correction, small residual correlations are
found. For example there is a general positive correla-
tion between the corrected 184Os/188 Os and 186Os/188 Os
ratios (Fig. 7) for both the UMd and DTM RMs. The
quality of this correlation varies depending on the RM
analysed although this may be simply a function of the
frequency and the period over which the different RMs
were run. A similar correlation was observed for three
consecutive runs of a single filament at increasing tem-
perature done on the Thermo-Finnigan factory Triton in
Bremen, Germany (J. Lassiter, pers. comm. 2006). Such
residual correlations have also been observed previously
for high-precision TIMS measurements of Nd isotopes
(Thirlwall, 1991) and could have at least 2 origins. They
could result from a mis-match between the real mass
fractionation behaviour of Os during N-TIMS runs and
the theoretical model used to correct for this behaviour.
Alternatively, they could result from incomplete inter-
fering element corrections.
If residual mass fractionation was responsible for the
residual correlations, the slope of the natural logarithms
of 186Os/188 Os vs. 184Os/188 Os, or 189Os/188Os vs.
190
Os/188Os would be very close to the ratio of the mass
difference between the two isotopic ratios considered.
Residual mass fractionation would also affect the
various Os RMs in a similar way for a given Os isotope
pair, so slopes of the residual correlations for our 3
RMs should be identical. However, as shown by Fig. 7
and Table 4, while 186Os/188 Os vs. 184Os/188Os and
189
Os/ 188 Os vs. 190 Os/ 188 Os are the best defined
residual correlations, slopes of these correlations are
very different from the expected theoretical values and
are also different between DTM, UMd and DROsS RMs
(0.009–0.017 against ≈ 0.5 and 0.51–0.85 against ≈ 2,
respectively). The weaker correlation coefficients
observed for DTM and DROsS RMs (Table 4) likely
results from their smaller degree of mass fractionation
due to fewer analyses performed (12 and 8 respectively).
It is important to note that there is no other residual
correlation observed for any other given isotopic pairs.
This contrasts with the behaviour observed for TIMS Nd
isotope analyses (Thirlwall, 1991) and indicates that
there are is no systematic relationships in terms of the
occurrence and value of a residual slope.
Similarly, if residual mass fractionation effects were
present, the slope of the residual correlations should
vary as a function of the « average mass » ratio between
the 2 isotopic ratios involved in the correlation. This
effect is expected to increase when the average mass
ratio gets larger, which means that greater effects should
be seen when there is a large difference between the
average mass of the 2 isotopic ratios (for example
184
Os/188Os and 190Os/188Os). No such effect was ob-
served for any of the 3 RMs when considering all
possible binary plots between the Os isotopic ratios. On
the basis of this observation as well as the variability of
the residual slope for a given pair of Os isotope ratios,
we conclude that our data do not show any convincing
evidence of a residual mass fractionation effect. This
conclusion is also supported by the absence of corre-
lation between the interference and mass fractionation-
corrected 186Os/188 Os ratios and the raw 192Os/188Os for
all 3 Os reference materials.
An alternative hypothesis is that the residual correla-
tion between 184Os/188Os and 186Os/188Os is due to
 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
Table 4
Slope and correlation coefficients of residual correlations observed after interferences and mass fractionation correction for some representative Os
isotopic ratios
ln(186Os/188Os) vs. ln(190Os/188Os) vs.
ln(184Os/188Os) ln(184Os/188Os)
UMd Slope 0.0066 −0.0007
r2 0.59 0.32
DTM Slope 0.0093 −0.0007
r2 0.64 0.13
DROsS Slope 0.0053 −0.0012
r2 0.21 0.45
Slopes were calculated for a robust fit in Excel.
interferences on both masses 184OsO3− and 186OsO3−. A
good candidate able to account for such interferences
would be W (as WO3−) as it possesses 184W and 186W
isotopes. However, as demonstrated above, no convin-
cing WO3− signal was identified in the course of this study
(see Section 4.2 WO3− interferences). In addition, if the
residual correlation between 184Os/188Os vs. 186Os/188Os
was due only to W interferences, the slope should be
within error and very close to the natural 186 W/184W
ratio (0.93). Indeed, the DTM slope is similar within
uncertainty to the natural 186 W/184W ratio (0.83 ± 0.37)
but this is not the case for the UMd or DROsS RMs
(0.63 ± 0.16 and 0.54 ± 0.88, respectively). Even if a W
interference was affecting the 184 OsO3− and 186 OsO3−
signals, it could not be the only interference present
since it could not account for the difference in the
slopes of the residual correlations. In addition, W
interferences would not be able to explain the residual
correlation between 189 Os/188 Os and 190 Os/188 Os.
We discount any effects from our oxide correction
procedures being responsible for generating the residual
correlations because if this was the case we would
expect residual correlations for all isotope pairs.
Furthermore, 184 Os and 186Os have the smallest oxide
interferences whereas 189Os, 190Os and 192 Os have the
largest oxide interferences and therefore ratio pairs
incorporating the latter should show the strongest
correlations if resulting from the oxide correction
procedure. However, the opposite is observed.
Clearly, more detailed work is needed to identify the
cause of the observed residual correlations.
5.4. Double normalisation
Despite our inadequate understanding of the cause of
the post-mass fractionation residual correlations, it is
possible to make a secondary correction to normalise
out the inaccuracy. The residual correlations previously
observed for TIMS Nd isotopic analyses between
355
ln(187Os/188Os) vs. ln(189Os/188Os) vs. ln(189Os/188Os) vs. ln(190Os/188Os) vs.
ln(186Os/188Os) ln(186Os/188Os) ln(187Os/188Os) ln(189Os/188Os)
0.5521 − 0.0799 − 0.0844 0.7038
0.43 0.24 0.17 0.60
0.0061 − 0.0714 − 0.0132 0.6638
0.0001 0.23 0.0023 0.34
0.2984 0.0678 0.1100 0.4751
0.34 0.09 0.06 0.53
142
Nd/ 144 Nd, 143 Nd/ 144 Nd and 145 Nd/ 144 Nd ratios
were used to apply a secondary correction of the data,
to the accepted 142Nd/144Nd value (Thirlwall, 1991). In
our case, a secondary correction on the 186Os/188 Os
values was made using a fixed 184 Os/188Os ratio and the
average residual slope between these 2 isotopic pairs.
We chose the average 184 Os/188Os ratio obtained by
Neptune MC-ICP-MS measurements on the Os RMs
(0.001300) as the fixed 184Os/188Os ratio. The average
Neptune 184 Os/188Os ratio is assumed to be the best
estimate of the true 184Os/188Os ratio since during MC-
ICP-MS analyses, the 184 Os beam is only affected by W
interferences which are more easily identified and
corrected than during the N-TIMS measurements
(Nowell et al., 2008-this volume). This is reflected in
the excellent reproducibility of the 184 Os/188 Os ratio
for the Neptune measurements for 4 different Os
RMs (Nowell et al., 2008-this volume) compared to
the N-TIMS (0.001300 ± 7 vs. 0.001305 ± 11, see
Table 3). It is worth noting that the 184 Os/188 Os ratio
we used for the double normalisation finds some sup-
port from our own N-TIMS data. As shown on Fig. 3,
the Pt-corrected 184 Os/188 Os ratios for UMd cluster
around 0.001300. However, two samples show lower
184
Os/188 Os (∼ 0.001290) suggesting that 184 Os beam
was overcorrected for Pt interferences. This could be
due to a non-linear behaviour of the Pt beam during
the Faraday run while a linear behaviour was assumed,
to perform the interference corrections.
This double normalisation produces lower average
186
Os/188 Os ratios than the un-normalised data for the 3
Os RMs. For UMd, the 186Os/188 Os value drops from
0.1198451 to 0.1198427, which corresponds to a devia-
tion of 20 ppm. Similar observations are made for
DROsS and DTM RMs, for which the average double-
normalised 186 Os/188Os ratios are 21 and 42 ppm lower,
respectively. As noted previously for MC-ICP-MS Nd
isotopic analyses (Vance and Thirlwall, 2002; Albarede
et al., 2004; Pearson and Nowell, 2005), the secondary
356 A. Luguet et al. / Chemical Geology 248 (2008) 342–362

correction significantly improves the reproducibility of

the 186Os/188 Os ratios from 50 to 31 ppm for UMd and
from 87 to 55 ppm for DTM.
The drawback of having to perform a secondary
normalisation on the Pt-corrected 186Os/188Os ratio is
that it requires multiple analyses of the same sample or
reference material (i.e. single analyses of multiple
filaments or multiple runs of the same filament) in
order to determine the slope of the residual correlation
between 186Os/188 Os and 184Os/188 Os for the specific
RM or sample. This can be very difficult to achieve in
the case of real samples for which the amount of Os
available for analysis is generally very limited.

6. Precision and accuracy of reference materials

All data discussed in this section have been corrected

for O isotope and PtO2− interferences and mass fractiona-
tion. They are presented in Table 3. The 186Os/188Os
ratios have been recalculated following the double
normalisation procedure described above.

6.1. Os stable isotope ratios

6.1.1. 189Os/188Os and 190Os/188 Os ratios

Our average 189Os/188 Os and 190 Os/188Os for the Os
RMs are 1.219709 ± 16 (2SD) and 1.983802 ± 22 (2SD).
Our 190 Os/188Os value compares well with the N-TIMS
literature data (1.983793 ± 19; Brandon et al., 2005) and
show a similar long-term reproducibility (12 ppm; 2SD).
Our 189Os/188Os ratio is 14 ppm higher than the value
published by Brandon et al. (2005) (1.219692 ± 15),
Fig. 8. Variation of the stable Os isotopic ratios 184Os/188Os,
almost within our 2SD uncertainty range and agrees 189
Os/188Os and 190Os/188Os for UMd (black square), DTM (white
well with the values determined on the Neptune. The square) and DROsS (circle) reference materials. Error bars on data
reproducibility of our 189Os/188Os dataset is relatively points are within-run 2 standard errors. The dotted lines and the grey
small with 2SD precision of 13 ppm, similar to the field represent our average ratios and the 2SD uncertainty range,
external reproducibility reported by both Brandon et al. respectively. Oblong field on the right hand side of plots are the
Brandon et al. (2005) N-TIMS data (oblique dashed field) and Nowell
(2005) or by Nowell et al. (2008-this volume) for MC- et al. (2008-this volume) MC-ICP-MS data (dotted field).
ICP-MS measurements (Fig. 8).

6.1.2. 184Os/188Os ratios between several filaments for UMd (0.001306–

Our average 184Os/188 Os ratio based on all our Os
RM measurements is 0.001305 ± 11 (2SD). Fig. 8 shows
that these values are very different from both the N-
TIMS data of Brandon et al. (2005) and the Neptune
data of Nowell et al. (2008-this volume). Even larger
differences can be noticed with other N-TIMS published
data (Fig. 3). In fact, all previous studies on high-
precision 186Os/188 Os measurements show systemati-
cally higher 184Os/188Os data, with the DTM data of
Brandon et al. (1999) being the highest. These authors
also reported large variations of 184Os/188Os ratio
0.001325), which represent a 14,000 ppm variation
range (Brandon et al., 1999).
The difference between the literature data and our N-
TIMS average for 184 Os/ 188 Os varies between
2700 ppm and 12000 ppm. These are similar to the
differences reported between our raw and PtO2− cor-
rected 184 Os/ 188 Os ratios (2500–11,500 ppm, see
above). The higher values for N-TIMS 184Os/188 Os
reported in the literature likely result from the fact that
none of these previous studies corrected for PtO2−
interferences on 184 OsO3− signals.
 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
The long-term reproducibility of our Pt-corrected
184
Os/188 Os ratio measurements is 8500 ppm (2SD),
approximately twice the reproducibility of the majority
of the published N-TIMS data apart from Brandon et al.
(1999). The large scatter of our PtO2− corrected
184
Os/188 Os (Figs. 3 and 7) suggests that 184Os may
be affected by additional interferences other than PtO2−.
The same conclusion can be drawn when comparing
the average 184Os/188Os for our N-TIMS instrument
with the average 184Os/188 Os obtained by Neptune MC-
ICP-MS measurements (see Nowell et al., 2008-this
volume). The MC-ICP-MS values show the lowest and
most reproducible 184Os/188 Os ratios reported so far
(0.001300 ± 7). This is probably because 184Os is mea-
sured as an Os ion (i.e. not an oxide) and is only affected
by very small isobaric W interferences which can be
corrected very accurately and precisely as shown by the
W-doped RM analyses (Nowell et al., 2008-this
volume). The better internal precision and possibly the
absolute value and reproducibility of the 184Os/188 Os
ratios determined by MC-ICP-MS (Nowell et al., 2008-
this volume) are probably also a reflection of the much
higher 184Os beam intensities obtained during Neptune
runs compared to N-TIMS (10–20 mV vs. 2–4 mV). It is
important to note that lower 184 Os/188Os values than our
N-TIMS average were also obtained on a Nu MC-ICP-
MS instrument (0.001302, Nowell et al., 2008-this
volume), confirming that the best estimate of the true
184
Os/188 Os value is probably very close to the average
value determined by Nowell et al. (2008-this volume) via
MC-ICP-MS measurements. Therefore, the fact that our
average Pt-corrected N-TIMS 184Os/188 Os is higher than
the MC-ICP-MS data by 3600 ppm, also supports the
idea that the 184Os signal is still affected by significant
interferences even after PtO2− correction. In fact, an
average 3600 ppm deviation of 184Os/188 Os would
correspond to a 11 μV interfering beam on a 3 mV
184
OsO3− signal. It is important to note, on the other hand,
that the lowest of our Pt-corrected 184 Os/188Os values
cluster at 0.001295–0.001300, very close to the average
184
Os/ 188 Os determined by Neptune MC-ICP-MS
(Fig. 8). This demonstrates that the molecular species
interfering on the 184OsO3− beam (other than PtO2−) are
not systematic and that magnitude of this interference
can vary between filaments.
6.2. Radiogenic Os isotopic ratios
6.2.1. 186Os/188Os
UMd has been the Os reference material used almost
exclusively so far to assess data quality for high-
precision 186Os/188Os studies. Our average double-
357
normalised 186 Os/188Os ratio for UMd is 0.1198427 ± 67
(2SD, Fig. 9). As for the 184Os/188 Os ratio, our average
186
Os/188 Os ratio is lower than those reported in the
literature over the last 10 years. There is a systematic
deviation of 20–45 ppm. Similar observations can be
made for our analyses of the DTM reference material.
Our average double-normalised value for the DTM
186
Os/188 Os ratio is 0.1199649 ± 37 (2SD) while the
only published value of Brandon et al. (1999) gives
0.119975 ± 5. The difference between these two values
is 83 ppm. Like the DTM RM, the DROsS RM has a
radiogenic composition. The first 8 N-TIMS measure-
ments indicate a 186 Os/188Os ratio of 0.1199293 ± 58
(2SD; Fig. 9).
The 2SD reproducibility of the 186 Os/188Os ratios is
variable between reference materials. The best 2SD
reproducibility is obtained for DTM (30 ppm), while
those for DROsS and UMd are poorer (48 and 56 ppm,
respectively). Long-term reproducibility reported pre-
viously in the literature is lower for DTM (see Brandon
et al., 1999). Meibom et al. (2004) reported reproduci-
bility for UMd 186Os/188Os similar to ours (48 ppm vs.
56 ppm). In contrast, UMd 186Os/188Os data obtained by
Brandon et al. (1999, 2003, 2005, 2006), Puchtel et al.
(2004) and Walker et al. (2005) appear to be more
reproducible than ours (13–20 ppm vs. 56 ppm). It is
important to note that in some cases, these previous
studies appear to have quoted the 2SE internal precision
(reported as 2σmean, see Brandon et al., 2006) instead of
the 2SD that we report for our long-term reproducibility.
The fact that our average 186Os/188 Os data are
systematically lower than published N-TIMS values
may in-part result from the interference corrections and
the secondary normalisations that we apply to the
186
Os/188 Os ratios. Some difference may also arise
because the O isotope interferences were corrected with
the fixed O isotope composition, which can lead to a
difference of 5 to 18 ppm on the 186Os/188 Os depending
on O isotope composition used (Ogas or ONier, see
above). There is a positive trend between 186Os/188 Os
and 184Os/188 Os for our Pt-corrected data, our double
normalised and Pt-corrected data and the Brandon et al.
(2005) for UMd and Brandon et al. (1999) data for DTM
(Fig. 10, Table 3). The positive trend for UMd is also
observed when data from Walker et al. (2005) and
Puchtel et al. (2004) are plotted. Similar correlations
were found among our data on the run-by-run basis
(Fig. 7). However, these correlations have not been
observed by other authors (see Brandon et al., 1999) and
are absent in the dataset of Brandon et al. (2005), which
is the only N-TIMS dataset for which all relevant ratios
have been reported. The absence of correlations in the
358 A. Luguet et al. / Chemical Geology 248 (2008) 342–362

Fig. 9. Comparison of 186Os/188Os and 187Os/188Os ratios between our reference material dataset (white field), the data of Brandon et al. (2005)
(oblique dashed field) and the MC-ICP-MS data of Nowell et al. (2008-this volume) (dotted field). Plain lines on each oblong field are average ratios,
width of field denotes the 2SD reproducibility.
 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
Fig. 10. Linear variation between 186Os/188Os and 184Os/188Os
observed for UMd and DTM reference material average data. Black
square: Brandon et al. (2005); Circle: Pt-corrected data (this study),
triangle: Pt-corrected and double-normalised data (this study). Error
bars on data points are 2 standard deviations.
Brandon et al. (2005) dataset may be due to differing
degrees of mass fractionation. The 186Os/188 Os vs.
184
Os/188 Os trend demonstrates coupled variations of
186
Os/188 Os and 184Os/188 Os and suggests that the data
of Brandon et al. (1999, 2005, 2006) and Walker et al.
(2005) may be affected by polyatomic interferences on
masses 232 and 234, potentially similar to that high-
lighted by the residual correlations of Fig. 7.
In comparison, the Neptune MC-ICP-MS
186
Os/188 Os ratios obtained for the same 3 RMs are
systematically lower than our N-TIMS values (Fig. 9)
but overlap within the 2SD uncertainty for DTM and
UMd (Nowell et al., 2008-this volume). However,
although UMd and DTM data overlap within 2SD
uncertainty, the difference of the average 186Os/188 Os
ratio between MC-ICP-MS and our N-TIMS data are
359
fairly constant and show a 67–89 ppm deviation.
Because we perform a secondary correction on
186
Os/188 Os ratios using the 184Os/188Os ratio obtained
by MC-ICP-MS as the fixed value, we would expect the
doubled-normalised N-TIMS 186 Os/188Os value to be
similar to the MC-ICP-MS values. The difference
between the two datasets of 186 Os data could be
explained by a cup efficiency problem on either the
Durham MC-ICP-MS or the Durham N-TIMS. How-
ever, the Neptune MC-ICP-MS 186Os/188 Os ratios have
been obtained using two different cups configurations
and the values have also been reproduced on the NIGL
Nu MC-ICP-MS. Similarly, our N-TIMS 186Os/188 Os
ratio are within error of the Brandon et al. (2005) and
Meibom et al. (2004) which were run on the Johnson
Space Center Triton N-TIMS and the Copenhagen
University VG sector 54-IT N-TIMS, respectively. It
would be a striking coincidence if either the 2 MC-ICP-
MS or the 3 N-TIMS manufactured by different
companies, had a cup efficiency problem of the same
magnitude on the cup analysing 186 OsO3−. An alternative
explanation is that the systematically higher N-TIMS
186
Os/188 Os could reflect the presence of an additional
interference which only affects the 186 OsO3− mass (234).
Several polyatomic interferences related to Ba and Br
ions were suggested by Yin et al. (1993) to interfere
on the Os isotope mass spectrum. Among those,
138
Ba16 OH79Br − and 138Ba16O6− interfere on mass
234. Ba ions are provided by the NaOH–Ba(OH)2
activator. Br− ions are ubiquitous and can be generated
during an analysis even when HBr is not used as the
loading acid. Both Ba and Br could therefore be present
during any run. However, analyses performed with
different loads of NaOH–Ba(OH)2 (0.5, 0.7 and 1 μL)
do not show any difference in the corrected 186Os/188 Os
ratio and hence provide no support for the presence of
such complex molecular ions. Considering the amount
of polyatomic interferences potentially present on the
OsO3− mass range, where there is never less than 2
polyatomic ions/mass, confidently identifying the ion(s)
interfering on the 186Os beam is at this stage very
difficult.
Finally, it is worth pointing out that if we apply a
double normalisation to the 3 N-TIMS analyses of the
same filament provided by J. Lassiter (unpublished
data), the 186 Os/ 188 Os ratio of UMd would be
∼ 0.1198312 ± 56 (2SD), almost within the 2SD uncer-
tainty of our value but deviating substantially from the
Brandon et al. (2005) values (0.119843 ± 7 and
0.119847 ± 2, respectively). This very low 186Os/188 Os
value is very similar to that reported by Nowell et al.
(2008-this volume; 0.119832 ± 13; see Table 3).
360 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
Fig. 11. Linear positive trend between 187Os/188Os and 184Os/188Os
observed for UMd RM average data. Symbols as in Fig. 9. Error bars
on data points are 2 standard deviations.
Therefore, independent 186Os measurement tests on the
UMd Os RM on different instruments (Neptune MC-
ICP-MS, Durham University and Triton N-TIMS,
Thermo-Finnigan, Bremen, Germany) indicate system-
atically lower 186 Os/ 188 Os values than the ones
published so far for UMd.
6.2.2. 187Os/188Os ratios
Our average 187Os/188Os is 0.113787 ± 7 (2SD) for
UMd RM and is 0.173926 ± 5 (2SD) for DTM RM. Those
values are in excellent agreement with the previously
published N-TIMS values (Brandon et al., 1999; 2005)
and the Neptune MC-ICP-MS values (Fig. 9). Our
average 187 Os/ 188 Os for DROsS is 0.160924 ± 4
(Table 3). No other N-TIMS data are available for the
DROsS RM in the literature but our N-TIMS and MC-ICP-
MS values are identical (0.160924 ± 4 vs. 0.160924 ± 3).
The long-term reproducibilities of those RMs for
187
Os/188Os range between 26 and 67 ppm (Fig. 9),
DTM and DROsS showing the most reproducible results.
As observed for the 186Os/188Os measurements, the
average 187Os/188Os of Brandon et al., 2005) and ours for
both Pt-corrected and; Pt-corrected and double-normal-
ised data define a positive trend with the 184Os/188Os
ratios (Fig. 11). This is only observed for the UMd RM. It
is important to note that such a relationship was already
observed among all our UMd runs (see Table 4). The
origin of this relationship is not presently clear but it could
likely provide more information on the identity of the
interfering species responsible of the residual 186Os/188Os
vs. 184Os/188Os correlation.
7. Conclusion
Measurements of natural variations of 186Os/188 Os
have generated considerable interest over the past de-
cade because of its potential to trace core–mantle
interaction and stellar and supernova nucleosynthetic
processes. Obtaining precise and accurate Os isotope
ratio measurements by N-TIMS however requires a
detailed understanding of the interferences present on
the mass spectrum of the OsO3− ions.
Tests performed on 3 Os reference materials (UMd,
DTM and DROsS) show excellent agreement for
187
Os/188Os, 189Os/188Os and 190Os/188Os between
our dataset, new MC-ICP-MS measurements (Nowell
et al., 2008-this volume) and previous N-TIMS studies
Fig. 12. Effect of polyatomic interference and mass fractionation
corrections on the 186Os/188Os of Os reference materials expressed as
deviation (Δ) from the 186Os/188Os ratio obtained after O isotope
interference correction using Oin-run and mass fractionation corrected
using 192Os/188Os of 3.083. Data reported in this diagram are a
compilation of all the UMd, DTM, DROsS reference material analyses
run over the analytical period of 1 year. Size of oblong black fields
represents 2SD reproducibility. The type of corrections performed is
denoted on x-axis. MF1 and MF2 represent the effect of mass
fractionation correction using 192Os/188Os ratio and a value of 3.08271
and using 189Os/188Os, respectively. Double normalisation 186Os/188Os
ratio was obtained after both normalisation and PtO−2 interference
corrections. The range of the 186Os/188Os mantle evolution over
4.55 Ga was calculated after Brandon et al. (2006). The deviation of
plume-related lava signatures from the present-day mantle 186Os/188Os
ratio is from Walker et al. (1997), Brandon et al. (1999, 2003). Note
that the spread of the 186Os/188Os ratios recorded by the various
corrections performed on the Os reference materials is larger than the
mantle evolution range and the deviation range of the plume-related
lavas.
 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
on 186Os/188 Os ratios (e.g. Walker et al., 2005; Brandon
et al., 2006). However, major differences were observed
for both 186 Os/188Os and 184Os/188Os ratios because
of the very small 184 Os and 186Os beam intensities and
the overlapping of numerous and complex polyatomic
interferences.
O isotope compositions vary within and between
runs leading us to use the O isotope composition
measured in-run to correct the OsO3− signals for O
interferences. We report up to 21 ppm difference in the
186
Os/188 Os ratio compared with previous O inter-
ference correction approaches (Fig. 12). While PtO2−
interferences are insignificant for the 186 Os/ 188 Os,
they are critical for the 184Os/188 Os ratio (0.25–1.2%
deviation) especially since previous Os studies have
used 184 Os/188 Os to monitor W interferences that
might be present on 186Os/188 Os. Monitoring and
correcting PtO2− interferences on 184 Os/ 188 Os should
also be considered mandatory if the nucleosynthetic p-
process is to be studied. Detailed IC scans and tests
using W-doped Os RMs appear to confirm the absence
of WO3− ions during typical OsO3− analysis. Apart from
polyatomic interferences, an additional limitation to
inter-laboratory data comparison is the use of different
mass fractionation ratios in the published literature.
Our calculations show that up to 120 ppm of difference
on the 186 Os/188 Os ratio can result from the use of
different ratios for the mass fractionation corrections
(Fig. 12).
Our data show the existence of a systematic
correlation between 186 Os/188Os and 184Os/188Os that
remains after interference and mass fractionation
correction for UMd, DTM and DROsS reference
materials. While unlikely to result from residual mass
fractionation, the molecular species which could
produce this correlation by interfering on both 184 Os
and 186 Os beam remain unconstrained. Another uni-
dentified but significant interference (138 Ba16OH79Br−
and/or 138Ba16O6− perhaps) is suspected on 186Os as the
186
Os/188 Os ratio obtained after normalisation to a fixed
184
Os/188 Os (determined by MC-ICP-MS) remains
systematically 70–90 ppm higher than the 186Os/188 Os
obtained by MC-ICP-MS. On the other hand, 186Os/188Os
vs. 184Os/188Os correlations between our data and pre-
vious datasets (e.g. Brandon et al., 2005; Walker et al.,
2005) suggest that these published studies could also be
affected by such additional interferences. More extensive
studies need to be made in the range of the OsO3− mass
spectrum to solve these issues. However, due to the
complexity and the number of interferences on the mass
spectrum of the OsO3− ions, identification of the
interfering elements could be very difficult or even im-
361
possible. As such, they impose a limiting factor, above the
counting statistics, for precise 186Os/188Os measurements.
To address some of the issues raised in this study, we
suggest the adoption of uniform measurement and off-
line data processing protocols in order to minimise any
data variation related to interfering element or mass
fractionation correction. We suggest the adoption of
systematic in-run measurements of the O isotope com-
position and monitoring of PtO2− interferences on ap-
propriate masses (228–231 amu) in order to correct or at
least monitor effects on 184Os/188 Os and 186Os/188 Os
ratios. Where residual correlations are observed, we
recommend secondary normalisation to be performed to
a fixed 184 Os/188Os of 0.001300 as this value can be
considered the best estimate of the true 184Os/188 Os
ratio. Finally, mass fractionation correction should be
performed using 192Os/188Os of 3.083 except when
studying nucleosynthetic effects (cf. Brandon et al.,
2005).
Acknowledgements
The authors would like to thank R.J. Walker and
R.W. Carlson for providing the UMd and DTM Os
reference materials. We are grateful to A. Brandon
and J. Lassiter for sharing data and for discussion
regarding the high-precision 186 Os measurement
method. We thank Ronny Schoenberg and John
Lassiter for their thorough reviews and Thomas
Meisel for editorial handling. AL thanks the Eur-
opean Community for the Marie Curie post-doctoral
fellowship (EIF-ENV-009752), during which this
work was done. The instrumentation used in this
study was supported by NERC/HEFCE grant JREI
JRDUPEEQ.
Appendix A. NaOH–Ba(OH)2 activator
preparation method
The NaOH–Ba(OH)2 activator for Os isotope
analysis in this study is prepared using NaOH (Alfa,
99.996% purity) and Ba(OH)2 (Alfa, 94.98% purity).
0.1 mol/L Na(OH) solution is first prepared by mixing
0.174 g of NaOH powder with 30 mL MQ water. As
NaOH is very corrosive, we used a plastic spatula for
manipulation. In a second step, 0.56 g Ba(OH)2 powder
is added to the 0.1 mol/L Na(OH) solution. Pellets
which formed at the bottom of the vials right after the Ba
(OH)2 addition dissolve after a few tens of minutes.
Once they are dissolved, the solution is put on the hot
plate at 70 °C for half a day. The prepared solution
carries a sediment of precipitated NaOH–Ba(OH)2.
362 A. Luguet et al. / Chemical Geology 248 (2008) 342–362
When kept tightly sealed and aliquoted sparingly it is
stable over periods of N 5 years.
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