Chemical Geology 406 (2015) 10–17

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Chemical Geology

journal homepage: www.elsevier.com/locate/chemgeo

Disequilibrium-induced initial Os isotopic heterogeneity in gram aliquots

of single basaltic rock powders: Implications for dating and
source tracing
Jie Li a,⁎, Xuan-Ce Wang b, Ji-Feng Xu a, Yi-Gang Xu a, Gong-Jian Tang a, Qiang Wang a,c
a
State Key Laboratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
b
ARC Centre of Excellence for Core to Crust Fluid Systems (CCFS) and The Institute for Geoscience Research (TIGeR), Department of Applied Geology, Curtin University, GPO Box U1987,
Perth 6845, Australia
c
CAS Center for Excellence in Tibetan Plateau Earth Sciences

a r t i c l e i n f o a b s t r a c t

Article history: The Re–Os isotopic heterogeneity of mantle-derived rocks has been well documented. However, it is unclear
Received 30 January 2015 whether and how the Os isotopic heterogeneity of a mantle source can influence Re–Os isotopic dating and
Received in revised form 27 March 2015 source tracing of mantle-derived melts. Here we report that replicate analyses of gram aliquots of single basaltic
Accepted 16 April 2015
powders (one of reference material BHVO-2 and three of the Hatu basalts from the western Junggar region,
Available online 28 April 2015
China) show large variations in both Os concentrations and isotopic ratios. More importantly, these replicate
Editor: K. Mezger data define good apparent Re–Os isochron correlations, yielding ages significantly older than their formation
ages, and display remarkable correlations between the 187Os/188Os ratio and the reciprocal of the common Os
Keywords: concentration (i.e., 1/192Os). This indicates that the initial Os isotopic composition in a basaltic magmatic system
Re–Os isotopic system may be heterogeneous and cannot be homogenized by pulverizing. Theoretical and mathematical deduction
Mixing isochron demonstrates that the observed apparent Re–Os isochron correlations are the result of binary mixing without
Initial isotopic heterogeneity complete isotopic equilibrium at the time of formation, primarily due to limited diffusional exchange of Os
Equilibrium/disequilibrium isotopes between refractory Os-bearing inclusions and host minerals under mantle conditions. The regressed
Mantle-derived rock
initial Os isotopic composition may bias the true value of the mantle source. Pulsed mantle melting and
magma mixing during ascent are potential processes responsible for such initial Os isotopic heterogeneity in
basaltic rock systems. Thus, when using the Re–Os isotopic system to date and to trace the source of basaltic
rocks or other rocks with relatively low Os concentrations, it is necessary to consider whether the initial Os
isotopic composition was heterogeneous or whether it had reached complete isotopic equilibrium.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
The Re–Os isotopic system (β− decay of 187Re to 187Os with a half-life
of 41.6 Ga; Smoliar et al., 1996) has been widely used to date a variety of
materials ranging from mafic–ultramafic rocks (e.g., Walker et al., 1991;
Allègre et al., 1999; Burton et al., 2000a; Puchtel et al., 2001, 2007; Gao
et al., 2002; Gangopadhyay et al., 2003) and sulfides (e.g., Suzuki et al.,
1996; Selby et al., 2009), to black shale (e.g., Ravizza and Turekian,
1989; Cohen et al., 1999), and even oil (e.g., Selby and Creaser, 2005;
Finlay et al., 2011). Given their chalcophile and siderophile geochemical
behavior, both Re and Os have a strong affinity to trace phases
(e.g., sulfides and alloys) and, thus, their budgets in these rocks are con-
trolled mainly by these trace phases. The contribution of unequal distri-
bution of these discrete trace phases on poor reproducibility of both Re
and Os concentrations in applications of the isotopic system has been
⁎ Corresponding author.
E-mail address: jieli@gig.ac.cn (J. Li).
well documented in the past two decades, known as the nugget effect
(e.g., Reisberg and Meisel, 2002; Meisel and Moser, 2001, 2004a;
Meisel and Moser, 2004b). However, its effect on the scale of initial Os
isotopic heterogeneity is unclear.
Several recent studies have conducted replicate Re–Os isotope
analyses of individual powders (~200 mesh in size) of mafic–ultramafic
rocks (Meisel et al., 2001; Ishikawa et al., 2014; Li et al., 2014). In these
studies, replicate analyses of each sample defined a good apparent
isochron; the derived apparent isochron ages and initial Os isotopic
compositions were used to constrain the timing of geological events
and to trace the characteristics of mantle sources (Meisel et al., 2001;
Ishikawa et al., 2014; Li et al., 2014). In light of the nugget effect for
both Re and Os concentrations, it is possible that the Os isotopic compo-
sitions of individual hand-specimen samples were not totally homoge-
nized when the rocks formed. Consequently, the apparent isochrons of
replicate analyses of individual samples do not faithfully record the
radiogenic ingrowth of 187Re to 187Os, and, therefore, the apparent iso-
chron ages and the calculated initial Os isotopic compositions may

http://dx.doi.org/10.1016/j.chemgeo.2015.04.010
0009-2541/© 2015 Elsevier B.V. All rights reserved.
 J. Li et al. / Chemical Geology 406 (2015) 10–17 11

bias the timing of formation events and the tracing of mantle sources, basaltic reference materials were generally insignificant: average blank
respectively. To clarify these uncertainties, it is necessary to investigate contributions for BHVO-2 were 0.3% for Os and 1.8% for Re. The blank cor-
whether homogenization of the Os isotopic composition was achieved rections for the Os and Re concentrations of the Hatu basaltic samples
in these rock systems during their formation. were typically 0.2%–0.8% and 0.7%–1.7%, respectively. This indicates
In this study, we selected four well-characterized mafic rocks for that subtraction of the blanks cannot be a major source of uncertainty.
replicate Re–Os isotope analyses: one reference material BHVO-2 As described by Ishikawa et al. (2014), Re–Os isotope in the basaltic
(basalt, USGS) and three Hatu basalts (erupted at 315 ± 4 Ma; Tang reference material BIR-1 (USGS) is homogeneous in a 1–2 g test portion.
et al., 2012) from the western Junggar region, China. The data from Replicate digestions of the basaltic reference material BIR-1 indicate re-
the five samples highlight a common issue: heterogeneity of initial Os producibility of 0.4% for 187Os/188Os (RSD, n = 9, Table 1), and 3.2% for
isotopic compositions in 1–2 g samples of individual rock powders. Re concentration, 11.4% for Os. The average values (187Os/188Os =
The causes of this heterogeneity are systematically investigated, and 0.13369 ± 47, Os = 0.341 ± 39 ppb, Re = 0.680 ± 22 ppb, 1 SD,
its effect on dating and source tracing is evaluated. n = 9) are in good agreement with published data for BIR-1
(187Os/188Os = 0.13372 ± 40, Os = 0.355 ± 20 ppb, Re = 0.675 ±
2. Samples and methods 7 ppb, Ishikawa et al., 2014), suggesting that contamination during
analyses is unlikely to be a significant consideration.
In order to investigate the heterogeneity of initial Os isotopic compo-
sitions in individual rock powders and how such heterogeneity can in- 3. Results
fluence Re–Os isotopic dating, the reference material of BHVO-2
(basalt, USGS) and three Hatu tholeiitic basalts were selected because Data on Re and Os concentrations and Os isotopic compositions in-
(i) we found these basaltic samples are more heterogeneous in term clude previous reported data (Li et al., 2015) are presented in Table 2.
of Os concentration and Os isotopes; and (ii) their geological ages are Amongst theses Re–Os data (Table 2), some of them (Nos. 18–22) are ob-
known. According to the USGS, material used in preparation of BHVO- tained with the employment of HF desilicification prior to Carius tube di-
2 powders was taken from the surface layer of the Pahoehoe lava that gestion for complete digestion of silicate phases (Li et al., 2015). Analyses
overflowed from the Halemaumau crater in the fall of 1919, so the of BHVO-2 reference materials produced good reproducibility of Re con-
geological age of BHVO-2 can be regarded as zero. For the Hatu tholeiitic centrations in the aliquots of each sample (RSD = 7.2%, n = 22). Although
basalts (erupted at 315 ± 4 Ma; Tang et al., 2012) studied herein, the replicate analyses of the three Hatu basaltic samples also show excellent
petrology, geochemistry, and geochronology were well characterized reproducibility of 0.4%–1.5% for Re concentration (RSD, n = 8, Table 2),
by Tang et al. (2012). the Os concentrations exhibit relatively poor reproducibility (RSD =
We employed the Carius tube digestion technique commonly used 61% for BHVO-2 and 21%–54% for the Hatu basalts).
in our lab for Re–Os chemistry (Shirey and Walker, 1995). About For the Os isotopic composition, the replicate analyses of each
1–2 g of each powdered sample was digested and equilibrated with sample show a large range of 187Os/188Os ratios compared with the
185
Re- and 190Os-enriched spikes in reverse aqua regia (7.5 ml concen- analytical uncertainty. The data of BHVO-2 define good correlations
trated HNO3 + 2.5 ml concentrated HCl) for 24 h at 240 °C in sealed between 187Os/188Os and 187Re/188Os (i.e., the apparent isochron of
Carius tubes. Osmium was extracted by solvent extraction into CCl4 BHVO-2 give an age of 49.2 ± 4.7 Ma; Fig. 1a) or 1/192Os (R2 = 0.94;
and back-extraction into concentrated HBr (Cohen and Waters, Fig. 1b). Similar but diverse correlations are also observed in the three
1996; Pearson and Woodland, 2000), with subsequent cleanup by Hatu basalts (Fig. 2); these samples give apparent isochron ages of
microdistillation (Roy-Barman, 1993). The Re fraction was separated 365.1 ± 7.9, 410.6 ± 4.7, and 432.2 ± 7.8 Ma.
and purified using anion column chromatography.
Mass spectrometry procedures for the Os are given in Li et al. (2014, 4. Discussion
2015). Os was loaded onto Pt filaments and measured as OsO− 3 ions by
negative-thermal ionization mass spectrometry (N-TIMS) using the 4.1. Heterogeneity of initial Os isotopic compositions in gram aliquots of
electron multiplier mode on a Thermo-Finnigan Triton (Creaser et al., single basaltic rock powders
1991; Volkening et al., 1991) at the State Key Laboratory of Isotope
Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy For BHVO-2, the age (49.2 ± 4.7 Ma) derived from the apparent
of Sciences, Guangzhou, China. Repeated analyses of the Os standard Re–Os isochron (Fig. 1a) is significantly older than its actual geologic
solution (Merck Chemical AA standard solution) yield a mean age (zero), and the 187Os/188Os ratios are well correlated with the re-
187
Os/188Os value of 0.1202 ± 3 (2 SD, n = 12) for the period of analysis. ciprocal of the common Os concentrations (i.e., 1/192Os; Fig. 1b). This
These values are in good agreement with a value of 0.12022 ± 2 (2 SD,
n = 14) measured on the same mass spectrometer in Faraday cup mode Table 1
(Li et al., 2010). Re–Os isotopes data of BIR-1 obtained by Carius tube digestion methods.
Rhenium mass fraction was analyzed by inductively coupled plasma- No. Re ±2σ Os ±2σ 187
Os/188Os ±2σ 187
Re/188Os ±2σ
mass spectrometry (Thermo Elemental X2 Series) at the State Key Labo- (ppt) (ppt)
ratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, 1 704 16 352.1 0.9 0.13367 0.00018 9.64 0.22
Chinese Academy of Sciences, Guangzhou, China. A conventional low- 2 694 6 377.1 1.9 0.13360 0.00021 8.87 0.09
volume quartz impact bead spray chamber with a Peltier cooled (3 °C) 3 678 7 376.6 0.7 0.13444 0.00017 8.68 0.09
and a 0.4 ml min−1 borosilicate nebulizer (MicroMist GE) was used in 4 694 8 338.5 0.7 0.13267 0.00034 9.88 0.11
5 690 13 373.2 1.7 0.13382 0.00036 8.91 0.18
the determinations. Ion lens settings, nebulizer gas flow rate and torch
6 644 4 307.6 0.5 0.13398 0.00021 10.09 0.06
position were optimized daily using a 10 ng ml−1 tuning In–Ce mixture 7 642 5 357.0 1.0 0.13366 0.00031 8.66 0.07
standard solution in order to obtain the high instrumental sensitivity 8 684 7 329.3 1.1 0.13352 0.00025 10.01 0.10
and low oxide production levels. A peristaltic pump was not used, as 9 686 8 257.9 0.5 0.13381 0.00015 12.81 0.15
Mean 680 341 0.13369 9.7
free aspiration of the nebulizer provided better signal stability. The details
SD 22 39 0.00047 1.3
of measurements are described elsewhere (Li et al., 2014). RSD (%) 3.2 11.4 0.4 13.3
Total procedural blanks (TPBs) were 0.28 ± 0.20 pg (1σ, n = 12) Ishikawa 675 7 355 20 0.13372 0.00040 9.6 0.6
with an 187Os/188Os ratio of 0.259 ± 0.038 (1σ, n = 12) on average for et al.
Os and 8.8 ± 3.2 pg (1σ, n = 12) for Re. All data were corrected for (2014)

the procedural blank for each analytical batch. Blank contributions for Measured uncertainties (2σ) are 2 standard errors.
12 J. Li et al. / Chemical Geology 406 (2015) 10–17

Table 2
Re–Os isotopes data of BHVO-2 and Hatu basalts obtained by Carius tube digestion methods.

No. Mass (g) Re (ppt) ±2σ Os (ppt) ±2σ 187

Os/188Os ±2σ 187
Re/188Os ±2σ 1/192Os (ppt−1) 187
Os/188Osi

BHVO-2
1 0.7765 554 3 90.9 0.1 0.1528 0.0003 29.45 0.17 0.027 0.1528
2 1.1724 539 4 42.2 0.1 0.1785 0.0005 61.97 0.51 0.058 0.1785
3 1.3036 522 4 63.8 0.1 0.1599 0.0004 39.60 0.29 0.038 0.1599
4 1.1212 553 4 96.9 0.2 0.1517 0.0005 27.56 0.20 0.025 0.1517
5 0.8770 571 4 73.5 0.1 0.1586 0.0004 37.54 0.30 0.033 0.1586
6 0.9765 554 4 52.2 0.1 0.1698 0.0006 51.35 0.36 0.047 0.1698
7 0.8750 553 7 58.2 0.0 0.1682 0.0003 45.99 0.54 0.042 0.1682
8 0.9540 543 4 75.1 0.1 0.1573 0.0004 34.97 0.27 0.033 0.1573
9 0.9691 551 7 58.4 0.1 0.1630 0.0004 45.64 0.60 0.042 0.1630
10a 0.8077 556 10 68.2 0.1 0.1561 0.0004 39.38 0.69 0.036 0.1561
11a 0.9107 554 8 70.4 0.1 0.1573 0.0004 38.06 0.52 0.035 0.1573
12a 1.0026 541 3 69.9 0.1 0.1552 0.0004 37.40 0.20 0.035 0.1552
13a 1.1038 526 8 96.6 0.1 0.1459 0.0003 26.26 0.40 0.025 0.1459
14a 1.2056 549 6 73.5 0.1 0.1565 0.0004 36.09 0.42 0.033 0.1565
15a 1.0352 561 7 72.4 0.1 0.1556 0.0006 37.42 0.45 0.034 0.1556
16a 1.0447 575 9 107.9 0.2 0.1498 0.0003 25.72 0.43 0.023 0.1498
17a 1.0139 544 5 155.4 0.2 0.1411 0.0002 16.87 0.16 0.016 0.1411
18a 0.8039 627 4 177.4 0.3 0.1447 0.0003 17.10 0.10 0.014 0.1447
19a 0.9015 648 11 319.2 0.7 0.1351 0.0002 9.80 0.20 0.008 0.1351
20a 1.0021 613 13 168.4 0.2 0.1379 0.0002 17.50 0.40 0.015 0.1379
21a 1.1141 634 16 97.0 0.1 0.1508 0.0002 31.60 0.80 0.025 0.1508
22a 1.1934 669 9 125.0 0.2 0.1490 0.0005 25.80 0.40 0.020 0.1490
Mean 569.9 100.6 0.154 33.3 0.030 0.154
S 40.8 61.2 0.010 12.3 0.012 0.010
RSD (%) 7.2 60.8 6.7 36.9 39.6 6.7

XJ163-1
1 1.0035 1347 21 39.40 0.08 1.2881 0.0040 189.5 3.0 0.071 0.2909
2 1.0004 1342 8 40.30 0.08 1.2466 0.0042 183.8 1.1 0.070 0.2796
3 1.0033 1348 26 34.30 0.03 1.4957 0.0020 223.1 4.3 0.084 0.3220
4 1.0018 1342 18 26.87 0.04 1.9261 0.0048 297.0 4.0 0.113 0.3635
5 2.0021 1354 19 25.09 0.03 2.1321 0.0033 327.8 4.7 0.123 0.4076
6 2.0011 1346 21 28.02 0.04 1.8616 0.0029 283.9 4.5 0.107 0.3678
7 1.9938 1358 32 28.97 0.03 1.8213 0.0027 275.7 6.4 0.103 0.3706
8 1.9987 1341 28 43.48 0.05 1.1607 0.0017 168.6 3.6 0.064 0.2737
Mean 1347 33.30 1.6165 243.7 0.3345
SD 6.0 7.0 0.4 59.9 0.050
RSD (%) 0.44 21.1 22.6 24.6 14.9

XJ164-1
1 1.0028 803 15 183.2 0.6 0.2762 0.0005 21.5 0.4 0.014 0.1630
2 1.0031 805 15 82.8 0.1 0.4672 0.0012 48.9 0.9 0.031 0.2100
3 1.0008 811 17 142.8 0.2 0.3240 0.0005 28.0 0.6 0.018 0.1765
4 1.0028 796 12 232.1 0.5 0.2451 0.0005 16.8 0.2 0.011 0.1568
5 1.0000 816 26 82.3 0.1 0.4718 0.0013 49.9 1.6 0.031 0.2093
6 2.0039 809 7 68.6 0.1 0.5397 0.0008 59.8 0.6 0.038 0.2249
7 2.0029 803 10 88.1 0.2 0.4454 0.0009 45.7 0.6 0.029 0.2049
8 2.0113 807 16 64.9 0.3 0.5601 0.0026 63.2 1.3 0.040 0.2275
Mean 806 118.11 0.4162 41.7 0.1966
SD 6.1 61.6 0.1 17.5 0.027
RSD (%) 0.75 52.1 28.7 41.9 14.0

XJ165
1 1.0039 570 20 19.81 0.03 1.3060 0.0035 159.9 5.7 0.142 0.4647
2 1.0072 581 5 18.96 0.02 1.3669 0.0033 171.3 1.6 0.150 0.4654
3 1.0011 582 10 66.55 0.07 0.4446 0.0007 43.9 0.8 0.038 0.2137
4 1.0091 582 10 20.50 0.03 1.2692 0.0042 157.0 2.8 0.137 0.4429
5 2.0052 584 9 67.52 0.14 0.4424 0.0006 43.3 0.6 0.038 0.2143
6 2.0067 598 13 65.15 0.06 0.4571 0.0006 46.1 1.0 0.039 0.2145
7 1.9781 596 9 27.28 0.02 0.9557 0.0012 116.5 1.7 0.099 0.3425
8 2.0021 583 9 52.02 0.05 0.5448 0.0007 56.9 0.8 0.050 0.2452
Mean 585 42.22 0.8483 99.4 0.3254
SD 8.8 22.7 0.4 57.7 0.1
RSD (%) 1.51 53.7 49.6 58.1 36.1

Measured uncertainties (2σ) are 2 standard errors. 187Os/188Osi = initial 187Os/188Os isotope ratio calculated at 0 and 315 Ma for the BHVO-2 and Hatu basalts, respectively.
a
Re–Os isotopes data for BHVO-2 are from Li et al. (2015). Nos. 10–17 data were obtained by regular Carius tube digestion method; Nos. 18–22 data were obtained by HF desilicification
prior to Carius tube digestion by aqua regia.

suggests that the Os isotopic composition of the lava responsible for
the formation of BHVO-2 rock was not homogeneous, and also that
the Os isotopic composition of the rock material prepared for making
powders of BHVO-2 was not totally homogenized in 1–2 g aliquots of
artificially mixed powder (~ 200 mesh in size). Instead, this pattern
can be accounted for by binary mixing of components 1
(characterized by low 187Os/188Os and high Os concentrations) and
2 (characterized by high 187 Os/188Os and low Os concentrations).
Over time, the apparent Re–Os isochron of BHVO-2 will evolve to
generate an apparent isochron age that is older than its actual age.
This is also demonstrated by the three Hatu basalts (315 Ma; Tang
et al., 2012) that give apparent Re–Os isochron ages greater than
 J. Li et al. / Chemical Geology 406 (2015) 10–17 13

Fig. 1. Measured 187Re/188Os vs. 187Os/188Os (a) and inverse of 192Os concentration vs. 187Os/188Os (b) for BHVO-2. All regressions here were calculated using the program Isoplot 3.00
(Ludwig, 2003) and all uncertainties are quoted at the 2 standard error (2 SE) level. Error bars are 2 SE only shown when bigger than the symbols. The linear regression equation and
R2 value are shown on the diagram here. These good positive covariations suggest binary component mixing.

their actual age. Thus, the data from these basaltic samples highlight a
common issue: presence of heterogeneity of the initial Os isotopic com-
position in basaltic rock systems. In the following section, we mathema-
tically deduce the binary mixing that could be responsible for the initial
Os isotopic heterogeneity and observed apparent Re–Os isochrons.
4.2. Deduction of binary mixing
Magma mixing as a major petrogenetic process has received consid-
erable attention. For instance, contamination/assimilation of mantle-
derived magma with crustal rocks during emplacement has been
accepted as a general mixing mechanism (e.g., Sun et al., 1975;
Langmuir et al, 1978; Allègre and Ben, 1980; DePaolo, 1981). In terms
of quantifying physical mixing, Vollmer (1976) and Langmuir et al.
(1978) created the universal mixing equation for binary mixing
(i.e., components 1 and 2), given by:
AX m þ BX m Y m þ CY m þ D ¼ 0;
where m denotes the composition of the mixture, and A–D are constants
related to the mixing of the two end-members, given by:
C ¼ a2 b1 x2 −a1 b2 x1 ;
D ¼ a1 b2 x1 y2 −a2 b1 x2 y1 ;
And
X x axis ratio (e.g., 187Re/188Os) of end-member;
Y y axis ratio (e.g., 187Os/188Os) of end-member;
a concentration of the denominator of Y (e.g., 188Os);
b concentration of the denominator of X (e.g., 188Os).
As part of the physical mixing process during magma generation,
chemical and isotopic diffusion inevitably occurs, which causes the mix-
ture to approach chemical and isotopic equilibrium. Herein, these two
components do not represent the compositions of the two ultimate
sources, but reflect the two apparent end-members in the mixture
ð1Þ after chemical and isotopic diffusion. It should also be noted that the
powdering process is only a physical mixing process at low tempera-
ture, and no remarkable chemical and isotopic diffusion should occur.
Setting:

A ¼ a2 b1 y1 −a1 b2 y2 ;
B ¼ a1 b2 −a2 b1 ; X m ¼ Rm and Y m ¼ I m :

Fig. 2. (a) Re–Os isochron diagram for replicate analyses (n = 8) of each of the three Hatu basalts. The three samples exhibit three different apparent isochron ages with different initial
187
Os/188Os ratios. (b) 187Os/188Os plotted against 1/192Os concentration for replicate analyses of the Hatu basalts. Error bars are shown when bigger than the symbols. All three samples
show positive slopes with one sample (06XJ163-1) having a steeper slope than those of the other two, which are similar to each other.
14 J. Li et al. / Chemical Geology 406 (2015) 10–17

As both denominators are the same, then: Setting:

a1 ¼ b1 and a2 ¼ b2 : M ¼ ðK þ 1Þeλt −1: ð10Þ

So: Then the actual age t can be calculated:

 
A ¼ a1 a2 ðI1 −I 2 Þ; 1 Mþ1
t¼ ln : ð11Þ
λ Kþ1
B ¼ 0;
Similarly, the apparent age tp is given by:
C ¼ a1 a2 ðR2 −R1 Þ;
1
tp ¼ t þ ln ðK þ 1Þ: ð12Þ
λ
D ¼ a1 a2 ðR1 I 2 −R2 I1 Þ:
The difference between tp and t is as follows:
Substituting these parameters into Eq. (1), we obtain:
1
t p −t ¼ t 0 ¼ ln ðK þ 1Þ: ð13Þ
I2 −I 1 I 1 R2 −I2 R1 λ
Im ¼ Rm þ ; ð2Þ
R2 −R1 R2 −R1
Thus, the mixing isochron age is a combination of the actual age t
where I1, I2 (e.g., I = 187Os/188Os), and R1, R2 (e.g., R = 187Re/188Os) and a pseudoisochron age t0 that is named after the pseudoisochron
represent the isotopic ratios of the two end-members (1 and 2). (Brooks et al., 1976); i.e., the initial mixing line on the isochron diagram.
Setting: For instance, in this study the zero-age BHVO-2 defined the apparent
Re–Os isochron directly giving a t0 value of 49.4 ± 5.9 Ma (Fig. 1).
I2 −I1 From Eqs. (6) and (9), a suite of samples (or even a single sample)
K¼ ; ð3Þ
R2 −R1 formed by the mixing of two components with different initial
187
Os/188Os and 187Re/188Os ratios can still define a straight line on the iso-
I1 R2 −I2 R1 chron diagram. Two possible cases are taken into account here. The first
d¼ : ð4Þ
R2 −R1 case is K = 0. In this case, the initial 187Os/188Os ratios of the two compo-
nents were in equilibrium after diffusion and physical mixing in the 1–2 g
Then, aliquots of the resultant mixture (or more simply, the mixture was de-
rived from a single homogeneous component). This case, therefore, pro-
Im ¼ KRm þ d: ð5Þ duces a valid Re–Os isochron (conventional isochron) over time to yield
a true formation age (tp = t, Fig. 3a), and the intercept d gives a valid ini-
Thus, the binary mixing equation illustrates a linear correlation tial ratio. The second case is K ≠ 0. In this case, the initial 187Os/188Os ra-
between 187Os/188Os and 187Re/188Os with a slope K at the time of tios of the two components were not completely equilibrated, producing
mixing (i.e., the time of formation of the rock system): heterogeneous initial ratios in rock aliquots. The present-day apparent
    isochron is a combination of the initial mixing line and the accumulation
187
Os=188 Os ¼ K  187 Re=188 Os þ d: ð6Þ of radiogenic 187Os since time t, as shown in Fig. 3b. Similar cases have
i i
also been observed in the Rb–Sr and Sm–Nd systems (e.g., Faure,
1977; DePaolo, 1981; Chauvel et al., 1985). Here,
In the conventional Re–Os isochron equation, the present-day
measured 187Os/188Os ratio is a summation of the initial 187Os/188Os 1
and the accumulation of radiogenic Os after time t, while the present- t p −t ¼ t 0 ¼ ln ðK þ 1Þ; ð13Þ
λ
day 187Re/188Os is the result of decay of the initial 187Re/188Os. These
are given by: from Eq. (6), and the intercept d is given by:
     
d ¼ I 1 −KR1 ¼ I 2 −KR2 : ð14Þ
187
Os=188 Os ¼ 187 Os=188 Os þ 187 Re=1887 Os  eλt −1 ; ð7Þ
p i p
Thus, when K b 0, then t0 b 0, tp b t, and d N I1 and I2.
   

187
Re= 188
Os ¼ 187
Re= 188
Os  e −λt
: ð8Þ When K N 0, then t0 N 0, tp N t, and d b I1 and I2.
p i In this study, the data for the four basaltic samples studied all sup-
port K N 0, tp N t, and d b I1 and I2, thus underestimating the source
Note that Eq. (7) cannot be directly regressed in this case because values. This is consistent with the general mixing scheme between the
the initial (187Os/188Os)i can be a variable rather than a constant based mantle end-member (characterized by low 187Os/188Os (I1) and
on Eq. (6), if K ≠ 0. Substituting Eqs. (6) and (8) into Eq. (7), an appa- 187
Re/188Os (R1)) and the crustal end-member (characterized by high
rent isochron is produced and can be termed a mixing isochron (similar 187
Os/188Os (I2) and 187Re/188Os (R2)), which gives a positive value for
descriptions have been made for other isotopic systems; Bell and K from Eq. (3). For BHVO-2, given its geological age t = 0, tp = t0 =
Powell, 1969; Qin, 1987; Zheng, 1989 and references therein): 49.2 Ma, K = 8.2 × 10−4, and the initial source values after magma dif-
fusion and mixing should be greater than d = 0.1270 ± 0.0028. For the
      three Hatu basalts, given t = 315 Ma (Tang et al., 2012), they all give
187
Os=188 Os ¼ ðK þ 1Þeλt −1  187 Re=188 Os þ d: ð9Þ tp N t with variable K (from 8.33 × 10−4 to 1.95 × 10−3) and variable
p p
t0 (from 50 to 117 Ma). Such variable apparent Re–Os isochron ages in-
dicate that there were at least three end-members involved in the for-
Obviously, this mixing isochron equation is linear in isochron coordi- mation of the Hatu basalts, which is supported by the diverse mixing
nates. When K = 0, then Eq. (9) changes to the conventional isochron diagrams between 187Os/188Os and 1/192Os (Fig. 2b). Based on trace
equation (Eq. (7)). When K ≠ 0 in Eq. (9), there are two variables (K element and Sr–Nd–Hf–Os isotopic evidence, Tang et al. (2012) con-
and d) to be determined. cluded that the Hatu basalts were derived from a mixed mantle source
 J. Li et al. / Chemical Geology 406 (2015) 10–17 15

Fig. 3. Illustration of the cases of binary mixing on the Re–Os isochron diagram, from Eq. (9) as described in the text: (a) K = 0; the initial Os isotopic ratios of the two mixing components
were in equilibrium after diffusion during mixing (or the mixture was derived from a single homogeneous component). In this case, the isochron is a conventional isochron (Ap) with initial
187
Os/188Os (Ip), and the observed apparent isochron age (tp) is equal to its formation age (t). (b) K ≠ 0; the initial Os isotopic ratios of the two mixing components were not in complete
equilibrium after diffusion during mixing. In this case, an apparent mixing isochron (Ap) is defined, representing a combination of an initial mixing line (IM) and the radiogenic 187Os
growth since formation (t). Such an apparent isochron (Ap) is obviously a mixing isochron that yields a geologically meaningless age (tp). Details are provided in the text.

consisting of subducted depleted oceanic lithosphere and enriched up-
welling asthenospheric mantle (Tang et al., 2012).
4.3. Causes of initial Os isotopic heterogeneity in gram aliquots of single
basaltic rock powders
As discussed above, the prominent feature of BHVO-2 and Hatu
basalts in this study is the presence of mixing relationships between
radiogenic and unradiogenic Os end-members in single powdered
rock samples (Figs. 1 and 2), suggesting disequilibrium-induced small-
scale initial Os isotopic heterogeneity. Similar Re–Os isotopic features
have been documented in other international reference mafic–ultra-
mafic rocks, such as TDB-1 and WGB-1 (Ishikawa et al., 2014; Li et al.,
2014; Chu et al., 2015). These data indicate initial Os isotopic heteroge-
neity (i.e., the coexistence of Os-bearing phases with variable Os isoto-
pic compositions) during the formation of these rocks.
Processes potentially responsible for such heterogeneity of initial Os
isotopic in basaltic rock systems include mantle melting and mixing
with other component(s) (e.g., crustal rocks) during magma ascent. It
is well known that mantle peridotites generally contain two popula-
tions of sulfides, interstitial and intragranular sulfides; the intragranular
sulfides are often called sulfide inclusions (e.g., Alard et al., 2005;
Harvey et al., 2011). In general, interstitial sulfides are characterized
by high Re/Os ratios and low Os concentrations; sulfide inclusions are
characterized by low Re/Os ratios and high Os concentrations
(e.g., Alard et al., 2005; Harvey et al., 2011). Sulfide dominates the Os
budget in mantle peridotites, but a significant portion of Re resides in
silicates (Burton et al., 1999), which is consistent with the observation
of relatively homogeneous Re concentrations but relatively heteroge-
neous Os concentrations in the 1–2 g aliquots of rock powders in this
study. Previous studies have shown that Os isotopic diffusional ex-
change between sulfide inclusions and host minerals is limited under
mantle conditions (Burton et al., 1999), while host minerals may be in
Os isotopic equilibrium with interstitial sulfides (Alves et al., 1999,
2002; Burton et al., 1999; Becker, 2000; Meibom et al., 2002; Becker
et al., 2004). Over time, interstitial sulfides show Os isotopic composi-
tions indistinguishable from the host silicate minerals, while sulfide
inclusions in silicate minerals retain a significantly less radiogenic Os
isotopic composition (e.g., Burton et al., 1999, 2000b). By inference,
within the mantle source generating the basaltic melts, these two sul-
fide populations most likely coexisted and may have developed differ-
ent Os isotopic compositions through time. It should be noted that
interstitial sulfides generally have much lower melting temperatures
than sulfide inclusions (Kullerud et al., 1969). Thus, during mantle melt-
ing, interstitial sulfides is easier to enter melts than sulfide inclusions.
Consequently, incongruent progressive or pulsed melting can generate
melts with different Os isotopic compositions. The earlier-formed
minerals could contain some sulfide inclusions that were unable to equil-
ibrate with later input melts via reaction or diffusion, primarily because of
very high sulfide/silicate or sulfide/chromite partitioning coefficients for
Os (Roy-Barman et al., 1998). Ultimately, this generates heterogeneous
Os isotopic compositions at the time of formation, as evidenced by the
variable Os isotopic compositions of the sulfides of mid-ocean ridge ba-
salts (Roy-Barman et al., 1998). Because of the scarcity of these Os-
bearing phases in basaltic rocks, this study shows that pulverizing does
not physically homogenize the initial Os isotopic compositions for small
(1–2 g) aliquots of basaltic rock powders. Alternatively, mixing with an-
other component via contamination or assimilation into mantle-derived
melts during ascent is another possible mechanism (e.g., Hauri and
Hart, 1997; Alves et al., 1999, 2002; Becker, 2000; Becker et al., 2004).
4.4. Implications for Re–Os dating and tracing of mantle sources
Duplicate analyses of a single powered whole-rock sample including
both Hatu basalts and international reference rock (BHVO-2) defined
good apparent Re–Os isotope isochron lines and linear trends between
1/192Os and 187Os/188Os diagrams (Figs. 1 and 2). This study has demon-
strated that these relationships signify the disequilibrium-induced
small-scale Re–Os heterogeneity (see Sections 4.2 and 4.3). For instance,
the calculated initial 187Os/188Os ratios based on the measured
187
Re/188Os and 187Os/188Os for BHVO-2 vary from 0.13 to 0.17
(Table 2) with average of 0.154 ± 0.010 (1 SD, n = 22). This implies
that any of the individual analyzed values cannot represent the initial
Os isotope composition of whole-rock (their source composition).
Because in most cases only one analysis was conducted on 1–2 g of ran-
dom selected aliquot of powdered whole samples, this study raises the
representative issue of individual analysis value to the source of the
whole rock. This also indicates that duplicated analysis data cannot sat-
isfy of the same initial values, one condition of Re–Os isotope isochron
techniques. This is consistent with that the apparent Re–Os isochron
of BHVO-2 yielded age significantly older than their formation ages.
According to two-end-member mixed isochron function (Section 4.2),
the older apparent age can be attributed to non-uniform initial
187
Os/188Os values, which most likely produced by disequilibrium-
induced small-scale Re–Os heterogeneity (see Section 4.3). The appar-
ent Re–Os isochron line of BHVO-2 (Fig. 1a) also yields an initial
187
Os/188Os of 0.1270 ± 0.0028, which is significantly lower than the
average value of all individual analysis. This implies that all the three
types of initial values (individual, average, and isochron line-induced)
cannot be used to constrain the source of the BHVO-2. The similar con-
clusion can be deduced for Hatu basalts. The basaltic rocks are generally
characterized by low Os and high Re/Os ratios. This feature requires
16 J. Li et al. / Chemical Geology 406 (2015) 10–17
substantial corrections for radioactive decay of 187Re to obtain the initial
Os isotope values, unless modern rocks are studied. However, this study
showed that even some modern rocks, such as BHVO-2, are not immune
to such issues. Therefore, for basaltic rock systems or other rocks with
relatively low Os concentrations, caution should be used when Re–Os
isotope isochron dating technique and individual initial Os isotopes to
investigate their mantle source, especially for the rock units with large
range of measured 187Re/188Os and 187Os/188Os ratios.
The Re–Os isotopic system has long been used successfully to date
komatiites and to trace their mantle sources (e.g., Walker et al.,
1991; Puchtel et al., 2001, 2007, 2009, 2014; Puchtel and Humayun,
2005). In comparison with low-Mg# basalts, high-Mg# komatiitic
lavas are formed from higher degrees (N25%) of mantle melting at
higher temperatures, and they contain significantly more Os-
bearing sulfides and higher Os concentrations. At such higher tem-
peratures, the heterogeneity of the initial Os isotopic composition
could be limited after faster diffusion and mixing (Burton et al.,
1999). Unlike komatiites, basaltic lavas generally have much lower
Os concentrations, and they tend to inherit the strongly hetero-
geneous Os isotopic composition present in the mantle during melt-
ing or obtained from the input of another mixing component
(e.g., crustal rocks) during magma ascent. The initial Os isotopic
heterogeneity is largely controlled by the sulfides present, and they
were unable to equilibrate via reaction or diffusion.
The difference of reproducibility of Re–Os data between BIR-1 and
BHVO-2 also supports this conclusion. The relative high-Os with mean
of 0.341 ± 39 ppb (Table 1) and low sulphur (~ 6.6 ppm; Shimizu
et al., 2015) concentration of BIR-1 gave good reproducibility in Re–Os
data regardless of whether completed or incompleted digestion
(Ishikawa et al., 2014 and references therein), whereas the low-Os
with mean of 0.078 ± 26 ppb (Table 2) and high sulphur BHVO-2
(~ 158 ppm, Shimizu et al., 2015) display poor reproducibility of
Re–Os data. More importantly, the former did not defined correla-
tions between measured 187Os/188Os ratios and 187Re/188Os and 192O.
However, the low-Os and high-sulphur BHVO-2 Re–Os data produced
tight correlations and gave an apparent isochron age. This provides
strong evidence for effect of minor sulphur phase in controlling Os
heterogeneity of low-Os basaltic rocks.
5. Summary
Replicate analyses of gram aliquots of single powdered rocks
(BHVO-2 and Hatu basalts) define good apparent Re–Os isochron
correlations, yielding ages significantly older than their formation
ages. Together with the remarkable correlations between the
187
Os/188Os ratios and the reciprocal of the common Os concentra-
tions (i.e., 1/192 Os), this indicates heterogeneity of the initial Os
isotopic composition in basaltic rock systems that cannot be homog-
enized by artificial pulverizing. Theoretical and mathematical deduc-
tion demonstrates that the observed apparent Re–Os isochron
correlations are the result of binary mixing without complete isoto-
pic equilibrium at the time of formation, primarily due to limited dif-
fusional exchange of Os isotopes between refractory Os-bearing
inclusions and host minerals under mantle conditions. The regressed
initial Os isotopic composition may bias the value of the mantle
source. Pulsed mantle melting and magma mixing during ascent
are the potential processes responsible for such initial Os
isotopic heterogeneity in basaltic rock systems. Because of the
heterogeneity of initial Os isotopic compositions in basaltic rock
systems or other rocks with relatively low Os concentrations, dating
and source tracing using the Re–Os isotopic system may yield
unreliable results. The most important implication of this study is
that the disequilibrium-induced small-scale Re–Os isotope hetero-
geneity has significantly influenced isochron dating and tracing
mantle sources.
Acknowledgments
Dr. Liu Jingao and Dr. Katsuhiko Suzuki are appreciated for construc-
tive comments and suggestions on the early version of the manuscript.
We thanked Zhao Peipei and Yin Lu for the Re–Os isotope analysis. The
helpful and constructive comments of two anonymous reviewers
together with diligent editorial handling by Prof. Klaus Mezger substan-
tially improved the manuscript, and are greatly appreciated. Financial
support was provided by the 973 project (2011CB808906) , and the
National Natural Science Foundation of China (41173038) for Jie Li, Pro-
gram (B) of the Chinese Academy of Sciences (grant no. XDB03010600)
and the National Natural Science Foundation of China (No. 41025006)
for Qiang Wang, and the Australian Research Council (ARC) Future
Fellowship (FT140100826) for Xuan-Ce Wang. This is contribution no.
IS- 2065 from GIGCAS and TIGeR publication No.615.
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