Mattias
Ek
*,
Alison C.
Hunt
and
Maria
Schönbächler
Institute of Geochemistry and Petrology, ETH Zürich, Clausiusstrasse 25, 8092 Zürich, Switzerland. E-mail: mattias.ek@erdw.ethz.ch
First published on 23rd February 2017
This paper presents a new method for high precision Pd isotope analyses in iron meteorites. First, Pd is separated from the sample matrix by a novel two-stage anion exchange procedure after which isotopic measurements are carried out using MC-ICP-MS. Analyses of doped standard solutions show that isobaric interference from Ru and Cd can be adequately corrected for Ru/Pd < 0.0005 and Cd/Pd < 0.025. This is frequently achieved using the presented separation method. The purified Pd fraction after ion exchange chromatography is also sufficiently devoid of Ni (Ni/Pd < 0.04), Zr (Zr/Pd < 0.0002) and Zn (Zn/Pd < 0.06) for precise and accurate measurements because these elements produce molecular interference on the masses of the Pd isotopes. An external reproducibility of 1.29 for ε102Pd, 0.22 for ε104Pd, 0.11 for ε106Pd, and 0.27 for ε110Pd is calculated based on the repeated analyses of five independently processed aliquots of the IAB iron meteorite Toluca. The method was verified by the analysis of three metals from IVB iron meteorites and the results show excellent agreement with previous data. The new method enables accurate analysis of all Pd isotopes, and in particular 102Pd, which is of major interest for cosmochemical applications.
First, in recent years it has become obvious that many elements display small, but well resolvable, nucleosynthetic variations (0.1 per mil range) in meteorites compared to terrestrial samples. Meteorite parent bodies, Mars, and the Earth display unique isotope compositions for a range of elements (e.g., Cr, Ti, Ni, Zr and Mo; e.g., ref. 5–8). These variations stem from the heterogeneous distribution of presolar dust in the solar system carrying highly anomalous isotopic compositions that were synthesised in various stellar environments. They are extremely useful for meteorite provenance studies and provide important constraints on mixing processes in the early solar system. Iron meteorites are thought to represent the core of asteroids that formed, and were subsequently destroyed, throughout the solar system during the early stages of planet formation.9 Nucleosynthetic isotope variations in iron meteorites are reported for Ni, Ru, Mo, W and Pd (e.g., ref. 10–17). Palladium is an ideal element to further investigate these variations because it features six stable isotopes that are produced in different stellar environments: one p-process isotope (102Pd), one s-process isotope (104Pd), one predominately r-process isotope (110Pd) and three isotopes (105Pd, 106Pd, and 108Pd) that contain a mixture of s- and r-process components.18 Accurate measurements of the p-process isotope 102Pd are necessary to differentiate between the s-process and r-process variations that would otherwise be indistinguishable in meteorites. A recent Pd isotope study investigating IVB iron meteorites16 has reported that Pd nucleosynthetic isotope variations are smaller than those of Ru and Mo, and suggested that this reflects selective destruction of their carrier phases in the solar nebula. However, further high precision Pd isotope analyses of other iron meteorite groups are needed to better constrain this observation.
Moreover, meteorites are exposed to galactic cosmic rays (GCR) during their travel in space. Modelling of GCR exposure for iron meteorites shows that significant isotopic shifts can be induced in many elements, including Pd.19 Thus, it is important to quantify the GCR effects on Pd isotopes, because Pd isotope variations can be the result of both nucleosynthetic processes and exposure to GCR in space. Isotopic shifts are caused by the capture of secondary neutrons produced by nuclear reactions in meteorites due to irradiation by GCR . The magnitude of these reactions depends on several factors: (i) isotope-specific properties such as the neutron capture cross section; (ii) meteorite properties such as the matrix composition, original depth of the sample within the meteoroid and time of exposure to GCR; and (iii) epithermal burnout of other elements resulting in the production of unstable isotopes that decay to the isotopes of interest
. All Pd isotopes possess relatively small neutron capture cross sections resulting in small (∼<0.2ε) isotopic shifts, even for samples with an optimal sample depth and large exposure times. Nevertheless, epithermal burnout of 103Rh can lead to larger (>1ε) isotopic shifts in 104Pd, particularly due to the similar abundance of Rh and Pd in iron meteorites. Epithermal burnout of 107,109Ag also occurs but due to the low Ag/Pd (∼<1 × 10−4) ratio in iron meteorites this reaction is negligible with current precision.
Another motivation to understand and quantify GCR effects in Pd isotopes is the Pd–Ag dating system (e.g.ref. 20 and 21). This chronometer is based on the short-lived isotope 107Pd, which decays to 107Ag with a half-life of 6.5 Ma. Cosmogenic production of the short-lived isotope 107Pd could affect the accuracy of the Pd–Ag dating system.19,22 High precision Pd isotope analyses, together with the well-established Pt GCR neutron dosimeter, should enable a thorough evaluation of the GCR effects on Pd–Ag chronometry.
Finally, Pd isotopes are a potentially powerful tool to determine the origin of Pd and other HSEs in the Earth. There are two end member scenarios to explain the origin of the HSEs in the Earth's mantle. One proposes that the concentration of HSEs in the mantle reflects the addition of a so-called ‘late veneer’ to the Earth, post core formation (e.g., ref. 23 and 24). The second scenario states that the Pd (and other HSEs) concentration of the mantle may be achieved during metal-silicate fractionation and core formation in a deep magma ocean, negating the need for a late veneer.3,25 The terrestrial nucleosynthetic signature relative to meteorites may provide constraints on the source of Pd in the Earth, particularly when correlated with other elements (e.g., Mo10 and Ru5,12).
In order to achieve accurate high precision Pd isotope measurements, it is important that Pd is thoroughly separated from matrix elements, which can cause interference and matrix effects during analysis. For example, Pd isotopes suffer from isobaric interference from Ru and Cd isotopes (Table 1). While Cd abundances are low in iron meteorites, Ru can occur in concentrations similar to Pd (e.g., ref. 26). In particular, high precision measurements of the low abundance 102Pd (1.02%) are hampered due to the high abundance of 102Ru (30%), if Ru is not sufficiently removed prior to mass spectrometry analysis. Molecular interference from matrix elements (i.e., Ni, Zn, and Zr) can also affect the precision and accuracy of the isotopic analyses. Existing procedures for Pd separation from geological matrices are either aimed at abundance determination and do not sufficiently remove matrix elements to enable accurate high precision isotope analyses,27,28 or fail to efficiently separate Pd from Ru.16
101 | 102 | 104 | 105 | 106 | 107 | 108 | 110 | 111 | |
---|---|---|---|---|---|---|---|---|---|
Collector configuration | |||||||||
Cup | L4 | L3 | L2 | L1 | C | H1 | H2 | H3 | H4 |
Resistor (Ω) | 1012 | 1011 | 1011 | 1011 | 1011 | 1011 | 1011 | 1011 | 1012 |
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Isotope abundances of Pd and isobaric elements (in %; ref. 37 ) | |||||||||
Ru | 17.06 | 31.55 | 18.62 | ||||||
Pd | 1.02 | 11.14 | 22.33 | 27.33 | 26.46 | 11.72 | |||
Cd | 1.25 | 0.89 | 12.49 | 12.8 | |||||
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Major molecular interferents and their isotopic abundance (in %; ref. 37 ) | |||||||||
M1H | 100Ru (12.59) | 101Ru (17.06) | 104Ru (18.62) | ||||||
103Rh (100) | |||||||||
107Ag (51.83) | 109Ag (48.16) | ||||||||
M40Ar | 61Ni (1.14) | 62Ni (3.63) | 64Ni (0.93) | ||||||
64Zn (49.17) | 66Zn (27.73) | 68Zn (4.04) | 68Zn (18.45) | 70Zn (0.61) | |||||
M16O | 90Zr (51.45) | 91Zr (11.22) | 92Zr (17.15) | 94Zr (17.38) | |||||
92Mo (14.65) | 94Mo (9.19) | 96Mo (15.87) |
Here we present a new method for high precision Pd isotope measurements involving a two-step ion exchange procedure to separate Pd from an iron meteorite matrix. Initial separation of Pd is achieved using a modified version of the ion exchange procedure of Rehkämper and Halliday,28 described in further detail by Hunt et al.29 This method allows the collection of both Pd and Pt from the same sample aliquot, enabling direct comparison with the well-established Pt neutron dosimeter. The Pd elution from the first ion exchange column requires further purification before isotopic measurements and a novel procedure to achieve this goal is presented here. First, Ru is removed from the Pd fraction by utilising its volatile nature. Then Pd is separated from the remaining matrix elements using an anion exchange column. This yields a final Pd fraction that is sufficiently devoid of matrix elements, including Ru, to allow for high precision isotopic measurements of all isotopes via multi-collector ICP-MS (MC-ICP-MS). The accuracy of our method was verified by processing one IAB, three IVB iron meteorites and terrestrial standard solutions. Our new analytical method achieves the necessary precision and accuracy to enable the thorough evaluation of GCR effects and nucleosynthetic isotope variations in iron meteorites.
First ion exchange procedurea | Second ion exchange procedure | ||||
---|---|---|---|---|---|
Resin volume: 1.25 ml AG1-X8 | Resin volume: 0.5 ml AG1-X8 | ||||
Step | Acid | Volume | Step | Acid | Volume |
a From Hunt et al.29 b As bromine saturated water. c Loaded in 5 steps of 2 ml. | |||||
Cleaning | 0.8 M HNO3 | 20 ml | Cleaning | 0.8 M HNO3 | 10 ml |
Concentrated HCl | 10 ml | Concentrated HCl | 10 ml | ||
Concentrated HNO3 | 25 ml | Concentrated HNO3 | 10 ml | ||
6 M HCl | 40 ml | 6 M HCl | 20 ml | ||
Preconditioning | 0.5 M HCl + 10% Br2b | 8 ml | Preconditioning | 4 M HF | 8 ml |
Sample loading | 0.5 M HCl + 10% Br2b | 10 ml | Sample loading | 4 M HF | 1 ml |
Rinse matrix | 1 M HCl + 10% Br2b | 12 ml | Fe, Ni, Ru | 4 M HF | 1 ml |
Rinse matrix | 0.8 M HNO3 + 10% Br2b | 5.5 ml | Ru, Mo | 6 M HNO3 | 5 ml |
Ru | Concentrated HCl | 12 ml | Ru, Mo | Concentrated HCl | 4 ml |
Pd, Ru | 8 M HNO3 (80–90 °C)c | 10 ml | Pd | Concentrated HCl | 4 ml |
Pt, Ir | 13.5 M HNO3 | 14 ml | Pd (Ru) | 13.5 M HNO3 | 6 ml |
Ruthenium was removed from the Pd fraction via volatilisation. The Pd fraction from the first ion exchange column was refluxed in 2 ml aqua regia for 48 hours at 110 °C, after which the solution was allowed to cool before 0.3 ml HClO4 was added. The solution was then dried at 210 °C. This step was repeated twice to ensure maximum Ru loss before the second ion exchange column. Tests revealed that evaporation of Ru after the second ion exchange column was much less efficient.
The second ion exchange column was designed to remove matrix elements (notably Fe, Mo, Ru, Ni, and Zr) that remained in the Pd fraction after the first column. In preparation for the second column the Pd fractions were refluxed overnight (∼18 hours) in 1 ml 4 M HF before being taken to dryness and again refluxed overnight in 1 ml of 4 M HF. Teflon columns (with an internal diameter of 5 mm) were loaded with 0.5 ml BioRad AG8-X1 resin and rinsed with 10 ml 0.8 M HNO3, 10 ml concentrated HCl, 10 ml HNO3, and finally 20 ml 6 M HCl, before being preconditioned with 8 ml 4 M HF (Table 2). The sample was loaded onto the column, and rinsed with 1 ml 4 M HF. Most non-transition metals have very low absorption in HF onto the anion resin and eluted directly.30,31 This was followed by 5 ml of 6 M HNO3 to elute remaining Ru and Mo. Subsequently, 4 ml concentrated HCl was added to reduce tailing of Ru into the Pd fraction. Palladium was then eluted in 4 ml concentrated HCl followed by 6 ml 13.5 M HNO3. The final Pd fraction was generally devoid of elements that potentially form molecular interference (see Section 4.1–2) to enable accurate isotopic determination. This sequence of HCl and HNO3 minimised the tailing of Pd that occurred otherwise. The Pd cuts were taken to dryness, and then refluxed in 1 ml 5 M HNO3 at 110 °C overnight before evaporation and preparation for isotopic analyses.
Interference from Ni (on 101Ru, 102Pd and 104Pd) and Zn (on 104Pd and 106Pd) argides produces isotopic shifts outside of our external reproducibility at Ni/Pd > 0.04 and Zn/Pd > 0.06 (Table 3 and Fig. 2). The samples processed through our ion exchange procedure rarely yielded Ni/Pd ratios above 0.005 and no sample was above the threshold ratio of 0.04. For Zn/Pd, ratios below 0.06 were consistently achieved after the ion exchange chemistry (Table 3 and Fig. 2B). Our analyses showed that the main source of Zn in our solutions was contamination during the final stages of sample preparation and it is therefore important to monitor the Zn/Pd ratio of samples before every analysis. Our doping tests revealed that production of xZr16O depends on the instrumental settings and that ZrO/Zr ratios up to 0.2 can be produced. It is therefore vital to determine ZrO/Zr prior to each analytical session. Typically, the instrument was calibrated to achieve ZrO/Zr ratios < 0.02. Zirconium/Pd ratios below 0.0002 do not induce isotopic shifts outside of our external reproducibility, when ZrO/Zr = 0.02 (Table 3 and Fig. 2C). Generally, most samples yielded Zr/Pd ratios below 0.00015 after ion exchange chromatography, which is below the threshold if the production of ZrO is minimised. No isotopic shifts were observed for Mo/Pd ratios below 0.34 (Table 3), while Mo/Pd in sample solutions after ion exchange chemistry is typically below 0.005. Additionally, standards with Pt/Pd ratios of up to 0.22 did not introduce resolvable isotopic shifts. This ratio is higher than the typical values obtained for iron meteorites after our ion exchange procedure. Rhenium and Ag can cause both isobaric interference in the form of hydrides and tailing effects on adjacent isotopes (Table 1). However, doping tests at up to Rh/Pd = 0.5 and Ag/Pd = 0.28 show no resolvable isotopic shifts. These levels are well above what is observed in samples (Rh/Pd < 0.01, Ag/Pd < 0.0001) after ion exchange chemistry. The samples with elemental ratios exceeding the stated thresholds (Table 3) were re-processed through the second ion exchange procedure to further purify the samples and achieve accurate results.
102Pd | 104Pd | 106Pd | 110Pd | |
---|---|---|---|---|
a An interference correction is applied to correct for isobaric interference from Ru and Cd. The correction yields erroneous Pd isotope data if concentrations exceed the indicated limits. b This ratio is dependent on the ZrO production during the analyses on the Neptune MC-ICP-MS, which varies from session to session. The limits stated are for a ZrO/Zr value of 2%. c No isotopic shifts were detected for this ratio, which is at least 10 times larger than that in sample solutions. | ||||
Ru/Pda | 0.0005 | 0.0005 | ||
Cd/Pda | 0.1 | 0.025 | ||
Ni/Pd | 0.04 | 0.1 | ||
Zn/Pd | 0.06 | 0.1 | ||
Zr/Pdb | 0.0002 | 0.0005 | ||
Mo/Pdc | >0.34c | |||
Rh/Pdc | >0.5c | |||
Ag/Pdc | >0.28c |
Sample namea | Ru/Pd | ε 102Pd | 2 seb | ε 104Pd | 2 seb | ε 106Pd | 2 seb | ε 110Pd | 2 seb |
---|---|---|---|---|---|---|---|---|---|
a Number after the sample name denotes sample aliquot and the letter indicates duplicate analyses of the sample aliquot. Each aliquot was processed separately through the entire separation procedure. b Uncertainties in the individual analyses are reported as the 2σ standard errors (2 se) on the mean of the individual ratios obtained in a single analysis, while uncertainty in the mean of each aliquot is reported as the 2 se of the analyses. For means calculated based on analyses from multiple aliquots the uncertainty is reported as 2 sd. c Mean calculated based on the entire data set of that sample. | |||||||||
NIST SRM 3138 Pd 1a | 0.00013 | −0.18 | 0.37 | −0.01 | 0.11 | −0.03 | 0.06 | −0.03 | 0.13 |
NIST SRM 3138 Pd 1b | 0.00013 | −0.25 | 0.40 | 0.06 | 0.12 | −0.01 | 0.08 | −0.03 | 0.11 |
NIST SRM 3138 Pd 1c | 0.00012 | 0.55 | 0.34 | 0.03 | 0.11 | 0.03 | 0.08 | 0.07 | 0.11 |
NIST SRM 3138 Pd 1d | 0.00015 | 1.16 | 0.41 | −0.07 | 0.12 | 0.13 | 0.08 | 0.01 | 0.13 |
NIST SRM 3138 Pd 1e | 0.00016 | −1.07 | 0.36 | −0.03 | 0.12 | −0.03 | 0.07 | −0.07 | 0.14 |
NIST SRM 3138 Pd 1f | 0.00018 | −0.26 | 0.43 | −0.10 | 0.12 | −0.03 | 0.08 | −0.12 | 0.14 |
NIST SRM 3138 Pd 1 mean (n = 6) | 0.00014 | −0.01 | 0.63 | −0.02 | 0.05 | 0.01 | 0.05 | −0.03 | 0.05 |
NIST SRM 3138 Pd 2a | 0.00005 | 1.58 | 0.35 | 0.12 | 0.13 | −0.06 | 0.08 | −0.09 | 0.11 |
NIST SRM 3138 Pd 2b | 0.00005 | 0.40 | 0.55 | −0.08 | 0.13 | 0.07 | 0.07 | 0.03 | 0.13 |
NIST SRM 3138 Pd 2c | 0.00004 | 0.65 | 0.40 | 0.01 | 0.12 | 0.11 | 0.06 | 0.13 | 0.16 |
NIST SRM 3138 Pd 2d | 0.00003 | 1.25 | 0.42 | 0.00 | 0.12 | −0.03 | 0.08 | −0.05 | 0.15 |
NIST SRM 3138 Pd 2e | 0.00003 | −0.37 | 0.36 | 0.02 | 0.16 | −0.03 | 0.09 | 0.03 | 0.15 |
NIST SRM 3138 Pd 2 mean (n = 5) | 0.00004 | 0.70 | 0.68 | 0.01 | 0.06 | 0.01 | 0.06 | 0.01 | 0.08 |
NIST SRM 3138 Pd 3a | 0.00010 | 0.18 | 0.33 | 0.04 | 0.14 | 0.03 | 0.06 | 0.09 | 0.12 |
NIST SRM 3138 Pd 3b | 0.00011 | 0.38 | 0.51 | 0.02 | 0.14 | 0.03 | 0.08 | 0.04 | 0.15 |
NIST SRM 3138 Pd 3c | 0.00009 | 0.92 | 0.48 | −0.10 | 0.12 | −0.06 | 0.07 | 0.13 | 0.15 |
NIST SRM 3138 Pd 3d | 0.00010 | 0.62 | 0.39 | 0.05 | 0.13 | −0.07 | 0.09 | 0.17 | 0.12 |
NIST SRM 3138 Pd 3 mean (n = 4) | 0.00010 | 0.53 | 0.32 | 0.00 | 0.07 | −0.02 | 0.05 | 0.11 | 0.06 |
NIST SRM 3138 Pd mean (n = 15) | 0.37 | 1.42 | 0.00 | 0.12 | 0.00 | 0.12 | 0.02 | 0.17 |
Sample namea | Ru/Pd | ε 102Pd | 2 seb | ε 104Pd | 2 seb | ε 106Pd | 2 seb | ε 110Pd | 2 seb |
---|---|---|---|---|---|---|---|---|---|
a Number after the sample name denotes sample aliquot and the letter indicates duplicate analyses of the sample aliquot. Each aliquot was processed separately through the entire separation procedure. b Uncertainties in the individual analyses are reported as the 2σ standard errors (2 se) on the mean of the individual ratios obtained in a single analysis. The 2 se uncertainty in the mean of an aliquot is calculated as the 2 sd of the aliquot or the 2 sd of the Toluca mean (whichever is larger) divided by the square root of n. For means calculated based on analyses from multiple aliquots the uncertainty is reported as the 2 sd. c Mean calculated based on the entire data set of that sample. d Tawallah Valley has a high Ni/Pd ratio (∼0.03) which may affect the accuracy of the ε102Pd data. | |||||||||
Toluca 1a | 0.00002 | −0.64 | 0.49 | −0.17 | 0.16 | −0.02 | 0.08 | 0.13 | 0.18 |
Toluca 1b | 0.00001 | 0.34 | 0.37 | 0.03 | 0.10 | −0.07 | 0.07 | −0.23 | 0.15 |
Toluca 1c | 0.00001 | 1.57 | 0.41 | 0.31 | 0.15 | 0.00 | 0.08 | −0.20 | 0.14 |
Toluca 1d | 0.00071 | −0.17 | 0.50 | −0.03 | 0.15 | 0.06 | 0.09 | −0.14 | 0.15 |
Toluca 1 (IAB) mean (n = 4) | 0.00019 | 0.28 | 0.95 | 0.04 | 0.20 | −0.01 | 0.06 | −0.11 | 0.17 |
Toluca 2a | 0.00003 | 0.67 | 0.35 | −0.04 | 0.11 | −0.03 | 0.07 | −0.12 | 0.14 |
Toluca 2b | 0.00002 | −0.55 | 0.40 | −0.11 | 0.12 | 0.03 | 0.06 | −0.01 | 0.14 |
Toluca 2c | 0.00002 | 0.63 | 0.51 | −0.16 | 0.19 | −0.04 | 0.09 | −0.20 | 0.14 |
Toluca 2d | 0.00003 | −0.35 | 0.54 | −0.06 | 0.13 | −0.11 | 0.09 | 0.02 | 0.14 |
Toluca 2 (IAB) mean (n = 4) | 0.00003 | 0.10 | 0.65 | −0.09 | 0.11 | −0.04 | 0.06 | −0.08 | 0.14 |
Toluca 3a | 0.00022 | 0.31 | 0.36 | −0.06 | 0.14 | −0.02 | 0.07 | −0.25 | 0.13 |
Toluca 3b | 0.00022 | 0.54 | 0.36 | −0.02 | 0.11 | −0.03 | 0.07 | −0.05 | 0.12 |
Toluca 3c | 0.00050 | 1.17 | 0.41 | 0.08 | 0.10 | −0.04 | 0.07 | −0.04 | 0.12 |
Toluca 3d | 0.00051 | −0.08 | 0.42 | −0.04 | 0.14 | −0.02 | 0.07 | 0.06 | 0.14 |
Toluca 3 (IAB) mean (n = 4) | 0.00036 | 0.49 | 0.65 | −0.01 | 0.11 | −0.03 | 0.06 | −0.07 | 0.14 |
Toluca 4a | 0.00000 | −0.59 | 0.29 | −0.23 | 0.11 | −0.03 | 0.06 | 0.02 | 0.13 |
Toluca 4b | 0.00000 | −0.56 | 0.39 | −0.08 | 0.11 | −0.01 | 0.08 | −0.05 | 0.13 |
Toluca 4c | 0.00000 | 0.19 | 0.47 | −0.03 | 0.14 | 0.02 | 0.07 | 0.29 | 0.14 |
Toluca 4d | 0.00000 | 1.19 | 0.40 | 0.06 | 0.13 | −0.04 | 0.08 | −0.02 | 0.14 |
Toluca 4 (IAB) mean (n = 4) | 0.00000 | 0.06 | 0.83 | −0.07 | 0.12 | −0.02 | 0.06 | 0.06 | 0.17 |
Toluca 5a | 0.00006 | 0.78 | 0.39 | 0.01 | 0.14 | 0.01 | 0.06 | −0.15 | 0.13 |
Toluca 5b | 0.00006 | 0.70 | 0.39 | 0.00 | 0.15 | 0.15 | 0.07 | −0.09 | 0.13 |
Toluca 5c | 0.00007 | 0.20 | 0.43 | 0.02 | 0.13 | 0.07 | 0.08 | 0.06 | 0.14 |
Toluca 5d | 0.00007 | −0.13 | 0.38 | −0.02 | 0.14 | −0.03 | 0.07 | 0.13 | 0.15 |
Toluca 5 (IAB) mean (n = 4) | 0.00007 | 0.39 | 0.65 | 0.00 | 0.11 | 0.05 | 0.08 | −0.01 | 0.14 |
Toluca (IAB) mean (n = 20) | 0.26 | 1.29 | −0.03 | 0.22 | −0.01 | 0.11 | −0.04 | 0.27 | |
Tawallah Valley 1a | 0.00020 | −0.75 | 0.49 | −0.25 | 0.17 | 0.04 | 0.10 | 0.58 | 0.20 |
Tawallah Valley 1b | 0.00017 | 0.65 | 0.53 | −0.49 | 0.14 | −0.03 | 0.08 | 0.55 | 0.16 |
Tawallah Valley 1c | 0.00017 | 1.92 | 0.52 | −0.49 | 0.13 | −0.01 | 0.09 | 0.64 | 0.17 |
Tawallah Valley 1d | 0.00012 | 2.00 | 0.42 | −0.47 | 0.12 | −0.13 | 0.08 | 0.49 | 0.15 |
Tawallah Valley 1e | 0.00013 | 0.81 | 0.75 | −0.50 | 0.14 | −0.08 | 0.09 | 0.61 | 0.16 |
Tawallah Valley 1f | 0.00015 | 2.11 | 0.44 | −0.21 | 0.17 | −0.12 | 0.09 | 0.50 | 0.16 |
Tawallah Valley 1g | 0.00014 | 1.31 | 0.51 | −0.21 | 0.13 | −0.11 | 0.08 | 0.67 | 0.15 |
Tawallah Valley 1h | 0.00015 | −0.30 | 0.47 | −0.30 | 0.16 | −0.06 | 0.07 | 0.53 | 0.14 |
Tawallah Valley 1i | 0.00015 | 0.97 | 0.40 | −0.16 | 0.10 | 0.07 | 0.08 | 0.56 | 0.13 |
Tawallah Valley (IVB) mean (n = 9) | 0.00015 | 0.97 | 0.67 | −0.34 | 0.10 | −0.05 | 0.05 | 0.57 | 0.09 |
Santa Clara 1a | 0.00012 | −0.92 | 0.50 | −0.25 | 0.17 | 0.00 | 0.11 | 0.55 | 0.14 |
Santa Clara 1b | 0.00009 | −1.63 | 0.58 | −0.03 | 0.17 | 0.02 | 0.10 | 0.44 | 0.18 |
Santa Clara 1c | 0.00008 | 0.32 | 0.40 | −0.11 | 0.11 | 0.01 | 0.07 | 0.62 | 0.11 |
Santa Clara 1d | 0.00008 | −0.07 | 0.42 | 0.00 | 0.13 | −0.01 | 0.07 | 0.83 | 0.14 |
Santa Clara 1e | 0.00008 | 0.30 | 0.62 | 0.05 | 0.12 | −0.07 | 0.07 | 0.81 | 0.14 |
Santa Clara 1f | 0.00008 | −0.12 | 0.43 | −0.10 | 0.13 | 0.02 | 0.07 | 0.76 | 0.16 |
Santa Clara 1g | 0.00008 | −0.09 | 0.38 | −0.12 | 0.12 | 0.02 | 0.08 | 0.47 | 0.15 |
Santa Clara 1h | 0.00009 | −0.25 | 0.36 | 0.02 | 0.12 | 0.08 | 0.07 | 0.47 | 0.13 |
Santa Clara (IVB) mean (n = 8) | 0.00009 | −0.31 | 0.47 | −0.07 | 0.08 | 0.01 | 0.04 | 0.62 | 0.11 |
Hoba 1a | 0.00004 | −1.17 | 0.41 | −0.32 | 0.12 | −0.02 | 0.07 | 0.38 | 0.15 |
Hoba 1b | 0.00004 | −0.68 | 0.42 | −0.37 | 0.12 | −0.04 | 0.08 | 0.46 | 0.17 |
Hoba 1c | 0.00004 | −0.35 | 0.42 | −0.21 | 0.16 | −0.01 | 0.09 | 0.39 | 0.14 |
Hoba 1d | 0.00004 | −0.77 | 0.42 | −0.16 | 0.15 | −0.06 | 0.08 | 0.24 | 0.17 |
Hoba (IVB) mean, (n = 4) | 0.00004 | −0.74 | 0.65 | −0.27 | 0.11 | −0.03 | 0.06 | 0.37 | 0.14 |
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Fig. 5 The mean Pd isotope compositions of three IVB iron meteorites (Hoba, Santa Clara, and Tawallah Valley) from this study (filled symbols) compared to those reported by Mayer et al.16 (open symbols). The uncertainties in our values are given as the 2 se of several analyses, while the uncertainty of the data from Mayer et al.16 represents the 2 se internal uncertainty. The values from the two studies are in excellent agreement for ε104Pd, ε106Pd and ε110Pd. The ε102Pd values from Mayer et al.16 are not shown because of large Ru interference. |
In contrast, the Pd isotope analyses of the IAB meteorite Toluca yield identical isotope compositions to the terrestrial standard. This indicates that our Toluca sample was not strongly exposed to GCR. This is in agreement with a study of the GCR exposure of the Toluca 1 aliquot by Hunt et al.39 using Pt isotopes. Moreover, the data also testify to the absence of nucleosynthetic variations in IAB meteorites, which confirms results from other elements, such as Mo10 and Ru.12
The Pd isotope compositions of the three IVB iron meteorites are consistent with the presence of a nucleosynthetic s-process deficit/r-process excess, while the data for Toluca indicate that these effects are absent in IAB meteorites. Further work, however, is required for a thorough evaluation of GCR effects in IAB and IVB iron meteorites.
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