Chemical Geology 353 (2013) 83–95

Contents lists available at ScienceDirect

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

In situ U\Pb age determination and Sr\Nd isotopic analysis of perovskite from the
Premier (Cullinan) kimberlite, South Africa
Fu-Yuan Wu a,⁎, Roger H. Mitchell b, Qiu-Li Li a, Jing Sun a, Chuan-Zhou Liu a, Yue-Heng Yang a
a
State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, P. O. Box 9825, Beijing 100029, China
b
Department of Geology, Lakehead University, Ontario, Canada P7B 5E1

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

Article history: South Africa is characterized by multiple episodes of kimberlite intrusion. However, the age and Sr\Nd iso-
Accepted 8 June 2012 topic compositions of the primary magma of most of the earlier emplacement events remain unresolved.
Available online 15 June 2012 Using in situ secondary ion mass spectrometry and laser ablation multi-collector inductively coupled plasma
mass spectrometry, the U\Pb ages and Sr\Nd isotopic compositions were obtained for perovskite from the
Keywords:
Premier (Cullinan) kimberlite: one of the oldest diamondiferous kimberlites. The U\Pb perovskite ages are
Emplacement age
Nd\Sr isotopes
1150 ± 16, 1151 ± 9, and 1156 ± 12 Ma for the brown, black, and green kimberlites, respectively, demon-
Perovskite strating that the different phases of the kimberlite were emplaced contemporaneously at ~ 1150 Ma. In situ
Premier kimberlite Sr\Nd isotopic analyses of perovskite yield initial Sr isotopic ratios and εNd(t)1150 values of 0.7031 ± 4 and
1.9 ± 0.9 for the brown; 0.7025 ± 1 and 1.8 ± 0.4 for the black; and 0.7030 ± 2 and 0.8 ± 0.7 for the green
kimberlites. These are essentially identical within analytical uncertainties and suggest that the kimberlites
were derived from a moderately-depleted mantle source. In contrast, whole-rock data yield variable
Sr\Nd isotopic compositions, confirming that whole-rock isotopic data cannot be used to constrain the char-
acter of the source of kimberlitic magma due to crustal contamination, later alteration and/or weathering.
Our data also indicate that kimberlite emplacement might be considered as a prelude to mantle plume
activity beneath a craton.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction determination, Sr and Nd isotopic analyses (Heaman, 1989; Paton et

Kimberlite is a unique ultramafic rock derived from the deep mantle,
and can, together with entrained mantle xenoliths, provide information
on the nature of its mantle source and the overlying lithosphere
(Mitchell, 1986). In particular, multiple stages of kimberlite emplace-
ment within an individual craton can also shed light on the evolution
of their mantle sources.
Radiogenic isotopes, such as Sr and Nd, are widely used to constrain
the source characteristics of kimberlite. However, it is difficult to obtain
reliable Sr\Nd isotopic compositions of the primary kimberlitic magma
as it contains diverse mantle and crustal xenolithic material. Post-
emplacement alteration can also result in changes in isotopic composi-
tion. Previous studies have demonstrated that the whole-rock composi-
tions cannot provide reliable information constraining the isotopic
character of the primary kimberlitic magma (Yang et al., 2009a, 2009b,
and references therein). However, it is now recognized that perovskite
can circumvent the above problems due to its early crystallization and
robustness to later alteration and weathering (Heaman, 1989). Thus,
groundmass primary perovskite is now widely used for U\Pb age
⁎ Corresponding author. Tel.: + 86 10 82998217; fax: + 86 10 62010846.
E-mail address: wufuyuan@mail.igcas.ac.cn (F.-Y. Wu).
al., 2007; Woodhead et al., 2009; Yang et al., 2009a, 2009b; Malarkey
et al., 2010; Reguir et al., 2010; Wu et al., 2010a; Tappe et al., 2011),
by traditional isotopic dilution and/or in situ ion or laser ablation
methods.
Four stages of kimberlitic activity have been identified in south-
ern Africa: Kuruman (~ 1600 Ma); Premier (~ 1200 Ma); Zimbabwe
(~ 500 Ma); and “Southern African” (~ 250–50 Ma) (Allsopp et al.,
1989). In terms of isotopic data, the “Southern African” kimberlites
have been divided into Group I (unradiogenic Sr, radiogenic Nd and
Pb), Group II (radiogenic Sr, unradiogenic Nd and Pb) with minor
transitional kimberlites (Smith, 1983; Skinner, 1989). Note that the
term “Group II kimberlite” is a misnomer as these rocks have been
shown to be the local expression of potassic magmatism in the Kaapvaal
craton, and are termed orangeites or lamproites (var. Kaapvaal) by
Mitchell (1995), Mitchell (2006) and ultramafic lamprophyre or aillikite
by Donnelly et al. (2011) and Tappe et al. (2006). Several aspects of the
age data previously obtained remain somewhat equivocal, as most were
obtained by whole-rock, phlogopite K (Ar) \Ar, Rb\Sr, and U (Pb) \Pb
methods (Allsopp et al., 1989), with only a few determined by zircon
and perovskite U\Pb techniques (Davis et al., 1976; Kramers and
Smith, 1983; Smith et al., 1989; Zartman and Richardson, 2005;
Batumike et al., 2008; Wu et al., 2010a). Hence most of the previous
age data need to be re-evaluated due to either the application of

0009-2541/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemgeo.2012.06.002
84 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95

inappropriate analytical methods and/or large age errors associated

with these methods. The initial subdivision of kimberlites into isotopic
groups was based on whole-rock data which, as noted above, cannot
represent the isotopic compositions of primary kimberlitic magma due
to the combined effects of contamination and post-emplacement alter-
ation. According to our knowledge, few perovskites have been extracted
from kimberlites and subsequently analyzed for Sr or Nd isotopic com-
positions (Woodhead et al., 2009; Wu et al., 2010a), and in no instance
have both radiogenic isotopes been determined on a single perovskite
sample. Isotopic data are available mainly for the youngest Cretaceous
kimberlites (belonging to the “Southern African” group), and only limit-
ed data have been reported for those of the older groups (Nowell et al.,
2004; Donnelly et al., 2011).
In this study, we report U\Pb ages and Sr\Nd isotopic data for
perovskite from the Premier (Cullinan) kimberlite. In addition, we
provide Sr isotopic data for perovskites previously analyzed for their
Nd isotopic composition (Wu et al., 2010a).

2. Geological setting

Located in the central part of the Archaean Kaapvaal Craton (part of

the Kalahari Craton) (Fig. 1), the Premier (now Cullinan) kimberlite is
well known as one of the oldest kimberlites in the world (Field et al.,
2008). The kimberlite is one of a cluster of eleven intrusions near the
town of Cullinan, 30 km northeast of Pretoria (Gauteng) (Fig. 1). The Pre-
mier kimberlite has an elliptical outline with a long axis of 1 km at sur-
face (Fig. 2), and is considered as the largest pipe found in South Africa
(Field et al., 2008). According to surface and underground investigations,
the Premier kimberlite intruded rocks of the Transvaal Supergroup, the
Bushveld Igneous complex and the Waterberg Group, and was later cut
by an 1115 ±15 Ma gabbroic sill (Allsopp et al., 1967). Subsequently
the uppermost 300 m of the intrusion has been removed by erosion.
The pipe, having contributed more than 25% of the world's largest
(+400 carats) diamonds, is a complex body with numerous distinct
phases of diamondiferous kimberlite (Fig. 2). The southeastern Brown
tuffisitic kimberlite was emplaced earlier than the other phases, and
was followed by the Grey (tuffisitic), Black (macrocrystal), and Green
Fig. 2. Simplified plan and section of the Premier kimberlite (Modified from Hoal
(2003) and Field et al. (2008).
(macrocrystal) kimberlites, and a final intrusion of calcite-bearing
aphanitic kimberlite dyke. The Black kimberlite is associated with a vari-
ety known as the Piebald kimberlite. The “Brown” and “Grey” tuffisitic
kimberlites are the major rock types of the pipe (Field et al., 2008). With-
in the pipe, abundant mantle xenoliths have been found and studied,
with a conclusion, based on osmium isotopic data for the peridotitic xe-
noliths, that the lithospheric mantle was formed during the Archean–
Paleoproterozoic, and probably modified by the ~2.06 Ga Bushveld ther-
mal event (Walker et al., 1989; Pearson et al., 1995; Carlson et al., 1999).
In this study, six samples (Fig. 3) were collected from each phase of
the Premier kimberlite (Prem-A: hypabyssal, Prem-B: piebald, Prem-C:
black, Prem-D: brown, Prem-E: green, Prem-F: grey), with the objective
of determining emplacement age and the isotopic composition of the
primary kimberlitic magma. A common feature of these samples is
that they contain megacrysts of serpentinized olivine, pyroxene, garnet,
and ilmenite (Fig. 3). Samples Prem-E and Prem-F are relatively more
altered than the others.

3. Analytical methods

3.1. Major and trace element analyses of perovskite

The sample preparation and mineral separation were conducted

Fig. 1. Kimberlites in southern Africa, showing the location of the Premier kimberlite.
at the Geological Survey at Langfang, Heibei Province, China. The
kimberlite samples were first crushed using a corundum jaw crusher,
then small chips without surface alteration were powdered using
an agate mortar. The crushed material was processed for perovskite
extraction by magnetic separation, and then pure perovskite grain
without any inclusion was handpicked under a microscope.
Separated perovskites were mounted in epoxy resin, and polished
until the centers of the grains were exposed. Before isotopic analysis,
back-scattered electron (BSE) images were obtained using a JEOL
JXA8100 electron microprobe, in order to assess internal composi-
tional variation and textures, and identify potential target sites for
U\Pb and Sr\Nd analyses.
 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95
Fig. 3. Petrographic images of the Premier kimberlite, which is mostly tuffisitic in texture.
Major element compositions were obtained using a JEOL–JAX8100
electron microprobe with a 15 kV accelerating voltage and 12 nA
beam current. Counting times were 20 s. Total iron is expressed as
FeO. The analytical uncertainties are within 2% for TiO2 and CaO, but
~ 10–20% for other elements due to their low concentrations.
Trace element compositions (including REE) were determined using
an Agilent 7500a quadrupole inductively coupled plasma mass spec-
trometry (Q–ICP–MS), which is equipped with a 193 nm excimer ArF
laser ablation system (GeoLas Plus). Helium gas was flushed to mini-
mize aerosol deposition around the ablation site, and mixed with
argon gas downstream of the ablation cell. During analyses, a spot size
of 30 μm was used with a repetition rate of 6 Hz. Every five sample anal-
yses were followed by one NIST SRM 610 measurement. Each spot anal-
ysis consisted approximately of 30 s of background acquisition and 60 s
of sample data acquisition. Trace element concentrations were calculat-
ed using GLITTER 4.0 and calibrated using 40Ca as an internal standard
and NIST610 as an external reference material (Jackson et al., 2004;
Griffin et al., 2008).
3.2. In situ U\Pb analyses
The U\Pb analyses were performed in situ using the CAMECA1280
secondary ion microprobe installed at the Institute of Geology and Geo-
physics in Beijing, with the data given in the Supplementary Table 1.
The instrument description and analytical procedure can be found in
Li et al. (2010), and only a brief summary is given here. The O2− primary
ion beam was accelerated at 13 kV, with an intensity between 10 and
85
18 nA. The analyzed ellipsoidal spot size is about 20× 30 μm in size. Pos-
itive secondary ions were extracted with a 10 kV potential.
All samples analyzed in this study were cast in epoxy mounts.
Each mount was coated with about 30 nm of high-purity gold to
reach b20 Ω resistance. Sample changing effects were minimized by
optimizing the energy offset to maximum transmission in the 60 eV
energy window at the start of each analysis using the 40Ca 48Ti216O4
reference peak at mass 200. This peak of 40Ca 48Ti216O4 is a matrix ref-
erence for centering the secondary ion beam, energy and mass adjust-
ments, as well as reference for mass 200.5 (background). The field
aperture was set to 5000 μm, and the transfer optic magnification
was adjusted to 200 with Max Area of 40 μm. Rectangular lenses
were activated in the secondary ion optics to increase the transmis-
sion at high mass resolution. A mass resolution of ca. 8000 (defined
at 50% peak height) was used to separate U, Th and Pb isotopes
from isobaric interferences, such as oxides of REE (e.g., Williams,
1998). A single electron multiplier was used in the ion-counting
mode to measure secondary ion beam intensities by a peak jumping
sequence. Each measurement consisted of 10 cycles, and the total an-
alytical time was ca. 16 min. The mass fractionation of Pb isotopes and
Pb hydrides (requiring a mass resolution > 30,000) were not consid-
ered because previous studies have shown that these two effects are
negligible and there appears to be a mutual cancellation of each effect
(Li et al., 2010).
During analyses, Ice River perovskite served as the primary standard
and was measured with every three unknown perovskite grains. Howev-
er, note that an average 206Pb/238U age of 356.5 ±1.0 Ma for the Ice River
perovskite was applied for calibration of our data (Heaman, 2009),
86 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95
whereas a revised age of 361.7 ±1.0 Ma is given by Tappe and Simonetti
(2012). The Tera–Wasserburg diagram was used to give, from the lower
intercept, the crystallization age of the analyzed perovskite, assuming
the common lead content follows the model of Stacey and Kramers
(1975). However, for calculation of individual analysis, four correction
methods (i.e., 204Pb, 206Pb, 207Pb and 208Pb) can be employed for perov-
skite U\Pb age determination (Williams, 1998). For relatively young
minerals, the ages are usually calculated from the 206Pb/238U ratios,
and hence, the 206Pb correction method is less used for the Phanerozoic
minerals. In addition, the high Th contents and Th/U ratios make a 208Pb
correction inappropriate for perovskites (see details in Williams, 1998).
Therefore, the 204Pb and 207Pb corrections are the most widely used
methods for perovskite common Pb corrections when using TIMS and
SIMS analytical techniques (Williams, 1998). The 204Pb and 207Pb cor-
rection methods were used for individual analysis, and an average
206
Pb/238U age with 2σ or 95% confidence level was calculated using
ISOPLOT 3.0 (Ludwig, 2003). During analytical session, fifty-six analyses
on a secondary standard of our in-house AFK perovskite yielded a weight-
ed 206Pb/238U age of 382.7±1.7 Ma (MSWD=1.1, n=56), identical to
the TIMS age of 381.6±1.4 Ma (Wu et al., 2013–this volume).
3.3. In situ Sr\Nd isotopic analyses by laser ablation
The in situ Sr\Nd isotopic analyses were conducted using the
Neptune MC–ICPMS instrument. Detailed analytical protocols were
given by Yang et al. (2008, 2009), and only brief summary is given
here.
The Sr isotopic data were acquired in static, multi-collector mode
with low resolution using nine Faraday collectors, and the mass con-
figuration array from 83Kr to 88Sr, monitoring Kr and Rb (Yang et al.,
2009a, 2009b). Prior to analysis, collectors were aligned using a tun-
ing solution which contains Rb, Sr, Er, and Yb. An aliquot of 200 ppb
NBS 987 standard was used regularly for controlling the quality and
optimizing the operation parameters, including the torch position,
the Ar flow rate, and the ion lens focus, to obtain maximum sensitiv-
ity. During the data reduction process, the effects of interfering ele-
ments were accounted for in the order of Kr +, Yb 2+, Er 2+ and Rb +,
but interferences from Fe dioxides, and Ga and Zn oxides, are not con-
sidered due to their low signals during actual analyses. Similarly, no
corrections for 176Lu 2+ and 176Hf 2+ on 88Sr were considered as
their interferences on 88Sr are negligible. Prior to every analytical ses-
sion, the Neptune MC–ICPMS was always configured to monitor Kr in
the Ar gas after optimization, especially when a new liquid Ar tank
was installed. During analyses, a 50 second measurement of the gas
blank was carried out before ablation in order to correct for Kr. On
the basis of the method proposed by Ramos et al. (2004), we moni-
tored the presence of 167Er 2+, 171Yb 2+ and 173Yb 2+ at masses 83.5,
85.5 and 86.5. Then the contributions of 168Er 2+ and 168Yb2+ to 84Sr,
170 2+
Er and 170Yb 2+ to 85Sr (+85Rb), 172Yb 2+ to 86Sr, 174Yb 2+ to 87Sr
(+87Rb), and 176Yb2+ to 88Sr were calculated according to the isotopic
abundances of Er and Yb (Chartier et al., 1999; Vervoort et al., 2004).
The natural ratio of 85Rb/ 87Rb (2.5926) was used for isobaric correction
of Rb by the exponential law, assuming that rubidium has the same
mass discrimination as strontium (Ehrlich et al., 2001). In order to
avoid the potential matrix-matched effect, an in-house perovskite
(AFK) standard was used for potential external correction. During anal-
yses, our standard AFK perovskite yielded a weighted 87Sr/86Sr ratio of
0.70333 ± 2 (n= 35, 2σ) or 0.70333 ± 12 (n= 35, 2SD), identical to
the TIMS value of 0.70335 ± 4 (n= 5, 2SD). Therefore, no external cor-
rection was conducted for data obtained. However, in order to verify the
reliability of our methods, we have analyzed an in-house apatite stan-
dard (LAP), which yielded a weighted 87Sr/86Sr ratio of 0.71138 ± 2
(n= 31, 2 s) or 0.71137 ± 11 (n= 31, 2SD), identical to the TIMS
value of 0.71138 ± 2 (n= 4, 2SD) (Yang et al., 2009b).
The laser ablation Nd isotope technique is similar to that for Sr iso-
tope analysis as described above. Before analysis, a standard Nd solution
was used to calibrate the machine and the exponential law was applied
for mass bias correction assuming 146Nd/ 144Nd = 0.7219. During laser
analyses, the interferences are caused principally by Ce (142Ce on 142Nd)
and Sm (144Sm on 144Nd). However, our work indicates that the influence
of Ce on Nd isotope analysis is insignificant (Yang et al., 2008, 2011), al-
though much attention has to be given to the isobaric interference of
144
Sm on 144Nd (McFarlane and McCulloch, 2007). In this study, the
mass bias of Sm (βSm) was directly obtained from the 147Sm/149Sm
ratio on the sample itself and then applied in the isobaric interference cor-
rection following the method proposed by McFarlane and McCulloch
(2007) assuming 147Sm/149Sm=1.08680 (Dubois et al., 1992) and
144
Sm/149Sm=0.22332 (Isnard et al., 2005). Further, 145Nd/144Nd ratio
was used to evaluate the feasibility of our method as it has a constant
value of 0.348415 (Wasserburg et al., 1981). As suggested by recent
studies (Fisher et al., 2011; Iizuka et al., 2011), an in-house perovskite
standard (AFK, TIMS values of 147Sm/144Nd and 143Nd/144Nd are
0.0659 and 0.512609 ± 27, respectively) was used for the external cor-
rections of 147Sm/144Nd and 143Nd/144Nd in order to overcome the po-
tential matrix-matched effects. The 147Sm/144Nd and 143Nd/144Nd
ratios obtained during our analyses are 0.0660 ± 17 and 0.512587 ±33
(n= 46, 2SD), respectively, hence no correction was conducted for the
target analyses. In addition, the 147Sm/144Nd and 143Nd/144Nd ratios
obtained from an apatite standard (AP2) are 0.0772±16 and
0.510990 ± 37 (n=, 2SD), comparable with the TIMS values of 0.0763
and 0.510999 ± 12 (n= 5, 2SD) (Yang et al., 2009a, 2009b).
3.4. Whole-rock major and trace element compositions
The major element contents of the rock powders were determined
on glass beads by X-ray fluorescence (XRF) using a RIGAKU 2100
spectrometer. Thirty-eight standards, ranging from ultramafic to
felsic rocks and sediments, were used to construct calibration curves.
The standards and samples (0.5 g) were mixed with 3.6 g of Li2B4O7,
0.4 g of LiF, 0.3 g of NH4NO3 and a small quantity (b20 mg) of LiBr.
A glass bead was formed by fusion of this mixture at ~1100 °C. The
current and voltage for the XRF analyses was 50 mA and 50 kV, re-
spectively. According to the measured values of standards (GSR-1
and GSR-3), the uncertainties are ~1% for elements with concentra-
tions > 1.0 wt.%, and about 10% for the elements with concentrations
b1.0 wt.%.
Trace element concentrations, including the REE, were deter-
mined using an Agilent 7500a inductively coupled plasma mass spec-
trometer (ICP–MS). About 50 mg of crushed whole-rock powder was
dissolved using HF/HNO3 (2:1) mixtures in a Teflon reaction vessel
which was heated on a hot plate at ~ 140 °C. This was followed by
evaporation to dryness, redissolving with 1.5 mL HF and 1.5 mL
HNO3 before sealing and placing in a steel jacket, and heating in an
oven at 190 °C for 48 h. The third step was evaporating the solution
to dryness, re-dissolving it with 3 mL HNO3, and drying. Subse-
quently, 3 mL HNO3 was added before sealing and heating at
140 °C for 12 h. Finally, the solution was extracted after cooling,
and diluted to 80 g. External standards BHVO-2, AGV-2 and G-2
were used to monitor drift in mass response during mass spectro-
metric measurement.
3.5. Whole-rock Sr\Nd isotopic analyses
Strontium and Nd isotopic analyses of kimberlites were conducted
at the MC–ICP–MS Laboratory, Chinese Academy of Sciences, Beijing
using a Thermo Fisher Scientific Neptune multi-collector-ICP–MS.
About 150 mg of sample were dissolved in sealed Savilex TM beakers
for more than 2 weeks. Sr and Nd separation was made using a three-
column ion exchange technique as described by Yang et al. (2010). Dur-
ing measurements, 87Sr/86Sr and 143Nd/144Nd ratios were normalized
to 86Sr/88Sr = 0.1194 and 146Nd/144Nd= 0.7219 using the exponential
law, respectively. In the course of this study, two analyses of the NBS-
 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95 87

987 Sr standard yielded 87Sr/86Sr = 0.710268 ± 17 and 0.710265± 15,
two analyses of the JNdi-1 Nd standard yielded 143Nd/ 144Nd =
0.512113 ± 10 and 0.512116 ± 8. Analyses of BIR-1 reference mate-
rial as an unknown sample yielded 87Sr/ 86Sr = 0.703173 ± 19 and
143
Nd/ 144Nd = 0.513076 ± 32, and the above values of AGV-2 as un-
known sample are 0.704023 ± 22 and 0.512794 ± 11, respectively.
All these data agree well with those recommended values (Yang et
al., 2010).
4. Analytical data
4.1. Whole-rock geochemistry
Six different phases of kimberlite were analyzed for bulk composi-
tions (Table 1). The gain of mass on ignition was ~5.6–10.9 wt.%, consis-
tent with their high contents of volatiles and alteration as seen by
petrographic investigation. However, most of our samples have lower
contamination indicies (C.I.) of ~1.4–2.0 than those reported by Fesq
et al. (1975) and Kable et al. (1975), but comparable to those by Hoal
(2003) and Maier et al. (2005). The SiO2 concentrations range from
Table 1
Whole-rock compositions of the Premier kimberlite.
Sample Prem-A Prem-B Prem-C Prem-D Prem-E
35.7 to 47.9 wt.%, and MgO concentrations range from 25.5 to
28.9 wt.%, indicating that the Premier kimberlites are not primitive
(according to the proposed criteria of Mitchell, 1986; Price et al.,
2000; Le Roex et al., 2003; Kopylova et al., 2007) , and have been
contaminated by crustal material. This is consistent with their
tuffisitic character and the occurrence of quartzite xenoliths within
the kimberlite.
In terms of trace elements, the Premier kimberlites have high Ni
(1066–1263 ppm), Cr (1031–1379 ppm), and Ba (138–823 ppm) con-
tents. The primitive mantle normalized “spidergrams” demonstrate a
strong enrichment of the incompatible elements, such as Ba, Th, U, Nb,
Ta, Pb, Sr and light rare earth elements (LREEs), with depletions of K,
Sr, Zr, Hf, and heavy REE (Fig. 4a). The REE patterns show that this kim-
berlite is LREE enriched with (La/Yb)N ratios ranging from 28–95
(Fig. 4b), slightly lower than other kimberlites (Mitchell, 1986; Tappe
et al., 2011), and the primitive kimberlite proposed by Price et al.
(2000).
4.2. Perovskite composition
The major and trace element data for the perovskites investigated
are listed in Table 2 and rare earth element (REE) distribution pat-
terns are shown in Fig. 4b. These perovskites have similar composi-
tions to those occurring in other kimberlites (Chakhmouradian and
Prem-F

SiO2 35.65 39.27 40.34 42.63 40.99 47.94

TiO2 1.73 2.01 2.16 2.40 1.85 1.66
Al2O3 2.64 3.16 2.90 3.66 3.76 3.46
TFeO 8.66 9.69 9.78 9.65 9.02 8.89
MnO 0.20 0.13 0.14 0.15 0.13 0.12
MgO 25.64 27.09 28.85 25.47 27.54 25.82
CaO 13.01 7.23 5.38 6.49 6.34 5.04
Na2O 0.23 0.24 0.29 0.85 0.46 0.54
K2O 0.61 0.96 0.83 0.91 0.39 0.34
P2O5 0.18 0.56 0.19 0.31 0.15 0.15
LOI 10.90 9.05 9.05 7.40 8.78 5.57
Total 99.45 99.39 99.91 99.92 99.41 99.53
C.I. 1.43 1.47 1.43 1.73 1.60 1.96
Cs 1.4 21 12 3.2 14 1.7
Li 5.2 17 7 21 25 22
Sc 9.8 12 11 11 10 9.1
V 78 102 114 126 99 94
Cr 1170 1072 1379 1058 1140 1031
Co 81 83 90 83 89 82
Ni 1109 1181 1403 1123 1263 1066
Cu 76 59 54 71 39 64
Zn 201 65 68 74 63 61
Ga 6.0 6.9 5.9 6.6 6.8 6.1
Rb 47 145 79 53 42 18
Sr 383 373 309 462 281 173
Ba 453 345 453 823 231 138
Zr 80 108 77 126 96 103
Hf 1.8 2.3 1.8 2.6 2.2 2.3
Nb 190 93 87 116 74 70
Ta 7.3 8.1 8.0 10.1 7.8 7.3
Pb 32 3.1 5.3 7.0 3.9 18
Th 5.2 5.6 4.7 7.3 5.0 5.4
U 2.4 1.4 1.0 1.6 1.1 1.2
La 99 58 32 46 26 27
Ce 181 89 61 80 49 54
Pr 21 9.5 6.7 9.0 5.6 6.2
Nd 69 32 23 31 19 21
Sm 10 4.7 3.6 4.7 3.0 3.4
Eu 2.8 1.3 1.1 1.3 0.69 0.88
Gd 7.5 3.7 2.9 3.6 2.4 2.6
Tb 0.82 0.42 0.34 0.43 0.30 0.33
Dy 4.2 2.6 1.9 2.5 1.8 2.0
Ho 0.52 0.36 0.27 0.35 0.27 0.30
Er 1.1 0.84 0.61 0.82 0.64 0.73
Tm 0.13 0.12 0.09 0.12 0.09 0.11
Yb 0.68 0.71 0.49 0.68 0.56 0.65
Lu 0.09 0.10 0.07 0.10 0.09 0.10
Fig. 4. Spidergrams and REE distribution patterns of whole-rocks and perovskites from
Y 14 9.1 7.2 9.7 6.8 7.9
the Premier kimberlite. Normalized values of the primitive mantle are from Sun and
C.I. (Contamination Index) = (SiO2 + Al2O3 + Na2O)/(MgO + 2 ∗ K2O). McDonough (1989).
88 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95

Table 2 points with the least Pb loss (n = 6) yield a lower intercept age
Compositions of perovskite from the Premier kimberlite. of 1155 ± 23 Ma on the Tera–Wasserburg diagram (Fig. 6c), and
206
Sample Prem-C Prem-D Prem-E Pb/ 238U ages of 1156 ± 19 ( 207Pb correction) or 1150 ± 16
( 204Pb correction) Ma (Fig. 6d). All these ages are comparable
TiO2 56.97 55.33 56.60
Al2O3 0.20 0.00 0.00 to those of the Prem-C. The Pb loss is consistent with the alter-
FeO 0.72 0.86 0.81 ation observed by the BSE investigation.
CaO 39.52 37.89 39.26 Perovskite from sample Prem-E shows less Pb isotopic variation
La2O3 0.15 0.42 0.19
than Prem-C, hence the obtained lower intercept age of 1164± 28 Ma
Ce2O3 0.09 0.87 0.19
Nd2O3 0.13 0.51 0.22 on the Tera–Wasserburg diagram has a larger error than that of sample
Nb2O5 0.36 0.47 0.35 Prem-C (Fig. 6e). However, the weighted 206Pb/238U ages of 1155 ± 12
ThO2 0.02 0.24 0.05 (207Pb correction) and 1156± 12 Ma (204Pb correction) are consistent
Total 98.16 96.59 97.67 with those of Prem-C (Fig. 6e and f). Therefore, these data indicate
Rb 0.73 1.0 27
that three samples of perovskite from the Premier kimberlite yield al-
Sr 869 1198 1460
Ba 15 6419 763 most the same U\Pb ages of ~1150 Ma.
Nb 2412 7805 2522
Ta 330 1377 142 4.4. Sr\Nd isotopic data of perovskite and whole-rock
Zr 164 632 2451
Hf 6.7 32 51
Pb 55 255 20 The perovskite Sr contents are ~870 (Prem-C), 1200 (Prem-D) and
Th 637 5061 162 1500 (Prem-E), with very low Rb contents (Table 2), making it possible
U 77 274 35 to obtain in situ Sr isotopic analyses using laser ablation techniques.
La 2238 10341 880 Among the three samples, Prem-D shows a large range of Sr isotopic
Ce 4998 22,861 1715
composition, indicating that this sample is not a closed Rb\Sr isotopic
Pr 561 2625 187
Nd 2200 10,135 697 system, or was reset during a later process (Fig. 7a). The analysis point
Sm 318 1383 106 with the lowest 87Sr/86Sr ratio is 0.70321, corresponding to an initial Sr
Eu 82 334 30 isotopic ratio of 0.7031 (Table 3). However, perovskites from Prem-C
Gd 165 673 61
and E give initial Sr isotopic ratios of 0.7025 and 0.7030, respectively
Tb 17 67 7.4
Dy 68 249 33
(Table 3). Therefore, the Premier kimberlite has an initial Sr isotopic
Ho 8.8 31 4.9 ratio of ~0.7025–0.7030, similar to those determined by Woodhead et
Er 15 51 10 al. (2009).
Tm 1.3 4.2 1.2 In contrast to Sr isotopes, all three perovskite samples are closed for
Yb 6.0 19 6.4
Nd isotopic systems (Fig. 7b), and give εNd(t)1150 values of +1.8 ± 0.4
Lu 0.6 1.6 0.7
Y 151 518 129 (Prem-C), +1.9± 0.9 (Prem-D) and +0.8 ± 0.7 (Prem-E), respectively
(Table 3). In the Sr\Nd isotopic diagram (Fig. 8a), the three perovskites
show a limited compositional variation.
Mitchell, 2001), in consisting mainly of TiO2 (55.3–57.0 wt.%) and CaO The whole-rock samples have a range of initial Sr isotopic ratio from
(37.9–39.5 wt.%) with minor FeO (0.7–0.9 wt.%). With respect to trace 0.7005 to 0.7076 (Table 3), and hence very different to those of the pe-
elements, the perovskites are characterized by high concentrations rovskites (Fig. 8). Similarly, the whole-rock samples have more variable
of Sr (869–1460 ppm), Nb (2412–7805 ppm), Ta (142–1377 ppm), Nd isotopic compositions (εNd(t)1150 values from +3.4 to −2.9) than
Zr (164–2451 ppm), Hf (5–51 ppm), U (35–274 ppm), Th (162– perovskites although both have similar 147Sm/144Nd values (Table 3
5061 ppm), and minor Rb (0.7–27 ppm). The REE distribution patterns and Fig. 8). For our samples, the initial Sr isotopic ratios increase,
can be divided into two subgroups. Prem-C and Prem-D perovskites while εNd(t)1150 value decrease with increasing of SiO2. However, an in-
show extreme light REE (LREE) enrichment with La abundances of 7106 verse trend exists with increasing of Sr concentration (Fig. 9). Among
and 32,828 times higher than those of chondrites and with (La/Yb)N ratios these samples, Prem-F, with the highest SiO2 content of 47.9 wt.%, has
of 248 and 365 (Fig. 4b). However, Prem-E perovskite has much lower the least depleted isotopic compositions with initial 87Sr/ 86Sr ratio of
REE concentration and lower (La/Yb)N ratio of 60 from those of Prem-C 0.7076 and εNd(t)1150 value of −2.9 (Table 3).
and Prem-D (Fig. 4b).
5. Discussion
4.3. Perovskite U\Pb age
5.1. Emplacement age of the Premier kimberlite
Among the six samples, perovskite was only recovered from
Prem-C, Prem-D and Prem-E. Microprobe analysis indicates that the According to the available data, the Premier intrusion has been
perovskite from each sample is homogeneous with respect to major considered as one of the oldest kimberlites in the world. However,
elements. However, compared to the other two samples, perovskite precise age data for this kimberlite are lacking although numerous
from Prem-D shows some degree of alteration as revealed by BSE im- isotopic techniques have been applied during the past three decades
aging (Fig. 5). This sample of perovskite is also low in CaO and TiO2, (Table 4). Using the Pb\Pb technique, Kramers and Smith (1983)
but high in rare earth elements (Table 2), as clearly shown by its obtained an isochron age of 1202 ± 72 Ma for the whole-rock, mag-
REE distribution pattern (Fig. 4b). netic and non-magnetic fractions from this kimberlite. The other
Perovskite from Prem-C, D and E were analyzed by CAMECA 1280 ages were obtained from the megacrystal garnet, clinopyroxene,
SIMS using the technique described above. For sample Prem-C, twenty orthopyroxene and ilmenite, with an additional Rb\Sr isochron age
analyses define a discordia line with a lower intercept age of 1163± of 1115 ± 15 obtained from biotite in the late gabbroic sill (Table 4).
19 Ma on the Tera–Wasserburg diagram (Fig. 6a), if an initial common For those ages obtained by isochron technique, it is not assured that
lead composition is assumed according to the model of Stacey and the analyzed minerals are cogenetic. For two Ar\Ar ages (1185 ± 94
Kramers (1975). The weighted 206Pb/238U ages are 1147±10 Ma for and 1198 ± 28 Ma) provided by Burgess et al. (1989) and Phillips et
207
Pb correction, but 1151±9 Ma for 204Pb correction (Fig. 6a and b). al. (1989), the analyzed mineral was clinopyroxene, which, is not a
Perovskite from Prem-D has experienced significant Pb loss (Fig. 6c suitable mineral for Ar\Ar geochronology due to its low potassium
and d), making age determination difficult. However, the analytical content. In addition, some ages were obtained from the mineral
 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95
Fig. 5. BSE image of perovskite from the Premier kimberlite.
inclusions within diamond; these cannot be used to constrain the
kimberlite eruption time. In summary, the available age data range
from 1150 to 1266 Ma with some unusually old ages of 1930 Ma
(Richardson et al., 1993). These data are not precise and reliable
enough to constrain the emplacement age of the Premier kimberlite,
although it is generally accepted that this pipe was emplaced at
~ 1.2 Ga.
Perovskite provides an excellent opportunity to remove the un-
certainties in the determination of the age of the Premier kimberlites
as it crystallizes directly from the kimberlitic magma and contains
enough U for precise Pb isotopic analyses, and hence reliable U\Pb
age determination (Kramers and Smith, 1983; Heaman, 1989; Smith
et al., 1989; Wu et al., 2010a and references therein). Currently, pe-
rovskite U\Pb isotopic analyses are usually conducted by traditional
TIMS (Kramers and Smith, 1983; Heaman, 1989; Smith et al., 1989; Li
et al., 2010, 2011; Tappe et al., 2011, 1012), and in situ techniques, in-
cluding SIMS (Kinny et al., 1997) and laser ablation (Cox and Wilton,
2006; Batumike et al., 2008; Yang et al., 2009a, 2009b; Reguir et al.,
2010; Wu et al., 2010a). Recent studies by Yang et al. (2009a,
2009b) have indicated that perovskite is not as resistant to alteration
as previously thought, and some Pb loss has been documented,
suggesting that in situ isotopic analyses might be better to provide
more reliable age information.
In this study, three samples were selected for perovskite U\Pb
isotopic analyses. These data indicate that perovskites from Prem-D
show variable amounts of Pb loss, confirming the conclusion of
Yang et al. (2009a, 2009b) that perovskite is not resistant as previous-
ly thought. Excluding those with significant Pb loss, the perovskite
analyses yield U\Pb ages of 1150 ± 16 (Prem-D, Brown kimberlite),
89
1151 ± 9 (Prem-C, Black kimberlite), and 1156 ± 12 Ma (Prem-E,
Green kimberlite), respectively. From the geological investigation
(Fig. 2), the Brown and Green kimberlites are considered as the earli-
est and the latest phases of the kimberlitic intrusions The perovskite
U\Pb ages indicate that the different phases were contemporaneous
with a weighted average age of 1152 ± 6 Ma, which we consider as
the best estimate of the emplacement time of the Premier kimberlite.
5.2. Sr\Nd isotopic composition of the Premier kimberlite
The Premier kimberlite has not been extensively investigated with
respect to its Sr and Nd isotopic composition (Table 3). Mitchell and
Crocket (1971) initially reported Sr isotopic data and obtained an initial
Sr isotopic ratio of 0.7093–0.7169 for three weathered kimberlites. Sub-
sequently, Basu and Tatsumoto (1979) found that one sample yielded
an εNd(t)1150 value of −2.1. A Piebald kimberlite analyzed by Nowell
et al. (2004) yielded an initial 87Sr/86Sr ratio of 0.7034 and εNd(t)1150
value of +2.4. Recently, Woodhead et al. (2009) analyzed two kimber-
lite perovskites and obtained initial 87Sr/86Sr ratios of 0.70282± 13 and
0.70262 ± 31 using in situ laser ablation technique.
In this study, six whole-rock samples yielded a large range of initial
87
Sr/86Sr ratios of 0.7005–0.7076 and εNd(t)1150 values of −2.9–+3.4
(Table 3, Fig. 8). However, these compositions cannot be considered
as the isotopic composition of the primary kimberlitic magma due to
crustal contamination and/or later alteration as shown in Fig. 9.
In contrast, it has been found that perovskite crystallizes early
from the kimberlitic magma, and relatively, it can significantly resist
later alteration, compared with other minerals (Chakhmouradian
and Mitchell, 2001). Therefore, perovskite has proven to be an
90 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95
Fig. 6. U-Pb Concordia diagrams after Tera–Wasserburg (data plotted not corrected for common Pb) and Wetherill (common Pb corrected) of the Premier perovskites.
excellent mineral to provide the Sr\Nd isotopic composition of the
primary kimberlitic magma (Heaman, 1989; Yang et al., 2009a,
2009b; Wu et al., 2010a; Tappe and Simonetti, 2012; Beyer et al.,
2013–this volume). Note that Malarkey et al. (2010) have proposed
that apatite and phenocrystal olivine might provide better estimates
of initial isotopic compositions. However we consider that olivine is a
most unsatisfactory mineral for this purpose as it is commonly exten-
sively altered and has extremely low Sr and Nd contents. Moreover,
the limited Sr and Nd contents might originate from tiny fluid and/or
melt inclusions, and not from olivine lattice sites. Among our analyses,
perovskites from sample Prem-D show a large Sr isotopic variation,
but not Nd isotopic composition. Combined with petrographic
examination, we propose that this variation results from alteration. If
the lowest 87Sr/86Sr ratio is accepted to record the primary Sr
isotopic composition, sample Prem-D has an initial 87Sr/86Sr ratio of
0.7032 ± 4 (Table 3). As documented for other cases, perovskites from
Prem-C and Prem-E do not show any Sr and Nd isotopic disturbance,
and have 87Sr/ 86Sr ratios of 0.7025 ± 1 and 0.7032 ± 2, and εNd(t)1150
values of +1.8 ± 0.4 and +0.8 ± 0.7.
In summary, analyses of perovskites from the Premier kimberlites
yield 87Sr/ 86Sr ratios of 0.7025–0.7032 and εNd(t)1150 values of
+0.9–+1.9, much narrower than those obtained from the whole-
rock analyses (Fig. 8). As a groundmass mineral crystallized earlier
from the magma, it is accepted here that perovskites record the isotopic
compositions of the primary kimberlitic magma, and the whole-rock
compositions do not represent the compositions of the primary
magma from which the rock crystallized. Consequently, the Premier
kimberlite has a low initial Sr isotopic ratio and a positive εNd(t)1150
value, implying derivation from a moderately depleted mantle source.
This conclusion is comparable to those derived from perovskite data
obtained from other kimberlites (Fig. 10).
5.3. Geodynamic implications
Kimberlites are an example of continental intraplate magmatism
whose geodynamic setting remains controversial (Mitchell, 1986;
Ernst and Buchan, 2003; Jelsma et al., 2009; Kaminsky, 2012). The
emplacement of the Mesozoic kimberlites of southern Africa is not
related to rifting or focused hot spot magmatism and is controlled
by major crustal lineaments (e.g., Mitchell, 1986; Schissel and Smail,
2001; Jelsma et al., 2009; Moore et al., 2008). In this case, it appears
that the lithosphere structure (rheological anisotropy not only
 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95 91

Fig. 8. Sr\Nd isotopic compositions of perovskites from kimberlites in South Africa.

Fields of Group I, Group II (orangeite) and Transitional kimberlites are from Becker
and Le Roex (2006); Becker et al. (2007); Fraser et al. (1985); Heaman (1989); Nowell
et al. (2004) and Smith (1983). Whole-rocks data are from Hoal (2003) and Nowell et
al. (2004) and this study.

cannot be lithospheric mantle which has been enriched during later

Fig. 7. In situ Sr\Nd isotopic compositions of the Premier perovskites. 87Rb/86Sr = 0.06
is the maximum limit to get reasonable correction for 87Rb on 86Sr (Yang et al., 2009b.).
localized the sites of kimberlite eruption but also provided the re-
quired conditions for decompressional melting of metasomatized
mantle lithosphere.
As illustrated by Fig. 9, kimberlites are characterized by moderately-
depleted isotopic compositions, which require that the kimberlite source
metasomatism. In addition, the heat source for the production of
kimberlitic magma is also enigmatic. Many kimberlites occur in clusters
and do exhibit linear distribution patterns, indicating that a large scale
thermal anomaly is necessary for the initiation of kimberlitic magmatism.
On the basis of the xenocryst suite and mineral inclusions in dia-
mond, it is proposed that the kimberlite eruption might be triggered
by a mantle plume (Haggerty, 1994; Harte, 2010; Kerschhofer et al.,
2000; Walter et al., 2011, and references therein), a concept which
is also supported by a regional investigation based on the precise
age data of kimberlite (Heaman et al., 2004), hence the popular idea
for the generation of kimberlite. However, the genetic relationship
between the small volumes of kimberlite magma and the much larger
volumes of mafic rocks remains unresolved, as the latter are generally
considered as the representatives of the large igneous provinces
(picrites-flood basalts and/or related ultramafic–mafic intrusions)
triggered by mantle plumes (Ernst and Buchan, 2001). Data for the
Phanerozoic indicate that the kimberlites can pre-date, be coeval with,
or post-date the eruption of flood basalts (Chalapathi Rao and Lehmann,
2011). For example, in the Kola alkaline province, the “kimberlite” and al-
kaline ultramafic rocks were emplaced at ~380 Ma (Wu et al., 2010c,
2013–this volume), i.e. approximately ~10–20 Ma earlier than the

Table 3
Sr\Nd isotopic data of perovskites from the Premier kimberlite.
87
Sample Location Mineral Age (Ma) Rb/86Sr 87
Sr/86Sr 2σ ISr 147
Sm/144Nd 143
Nd/144Nd 2σ εNd(t) 2σ fSm/Nd Reference

Prem-A Premier WR 1150 0.3551 0.70967 2 0.7038 0.0901 0.512006 4 3.38 0.08 − 0.54
Prem-B Premier WR 1150 1.1260 0.71909 3 0.7005 0.0902 0.511925 5 1.79 0.10 − 0.54
Prem-C Premier WR 1150 0.7401 0.71376 2 0.7016 0.0935 0.511963 5 2.02 0.10 − 0.52
Prem-D Premier WR 1150 0.3320 0.71007 2 0.7046 0.0921 0.511906 3 1.14 0.06 − 0.53
Prem-E Premier WR 1150 0.4326 0.71101 3 0.7039 0.0948 0.511855 6 − 0.27 0.12 − 0.52
Prem-F Premier WR 1150 0.3012 0.71260 2 0.7076 0.0970 0.511737 4 − 2.90 0.08 − 0.51
Prem-C Premier Prv 1150 0.0047 0.70253 13 0.7025 0.0946 0.511957 22 1.76 0.43 − 0.52
Prem-D Premier Prv 1150 0.0069 0.70321 36 0.7031 0.0912 0.511937 44 1.87 0.86 − 0.54
Prem-E Premier Prv 1150 0.0111 0.70315 23 0.7030 0.0934 0.511900 33 0.82 0.65 − 0.53
Premier Premier WR 1150 0.0933 0.511752 27 − 2.06 0.53 − 0.53 1
P-Piebald Premier WR 1150 0.0077 0.70353 10 0.7034 0.0941 0.511985 6 2.38 0.12 − 0.52 2
SHR207 Premier WR 1150 0.2413 0.70642 0.7024 0.511870 3.07 3
Premier WR 1150 0.1535 0.7156 1 0.7131 4
Premier WR 1150 0.5271 0.7180 5 0.7093 4
Premier WR 1150 0.2752 0.7214 7 0.7169 4
173/53/K001/51 Premier Prv 1150 0.7028 5
SA133 Premier Prv 1150 0.7026 5

References: 1: Basu and Tatsumoto (1979); 2: Nowell et al. (2004); 3: Hoal (2003); 4: Mitchell and Crocket (1971); 5: Woodhead et al. (2009).
92 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95

Fig. 9. Whole-rock Sr\Nd isotopic variations. Data for sample SHR207 are from Hoal (2003).

Pripyat–Dneiper–Donets mafic flood basalts (Wilson and Lyashkevich, Griffin et al., 2005), approximately ~5–10 Ma younger than the main
1996). In the Saõ Francisco craton of Brazil, the kimberlites are mostly mafic event. In southern African, however, multiple occurrences of man-
emplaced at ~90–100 Ma, followed by kamafugite, carbonatite and alka- tle plumes make correlation problematic (Schissel and Smail, 2001).
line syenite emplaced at ~90–80 Ma, and finally by the ~80 Ma Trindade Within the Precambrian, the above temporal relationships are less
mafic event (Gibson et al., 1995; Wu et al., 2010b; Guarino et al., 2013– clear. For the Bushveld igneous event in South Africa, our work indicates
this volume). The Siberian area, which is characterized by extensive that the Phalaborwa carbonatite is about 5 Ma older than the main
flood basalt and related mafic–ultramafic intrusions at ~251 Ma Bushveld mafic intrusion (Wu et al., 2011). Additionally, it has been pro-
(Reichow et al., 2009, and references therein); with the related posed that the ~1.4–1.1 Ga kimberlite, alkaline rocks and carbonatites in
Kharamai kimberlite emplaced at ~240–245 Ma (Kinny et al., 1997; southern Africa, represent another period of plume activity, accompanied
by a large scale of mafic event in the Mesoproterozoic (Fig. 1a, Hanson et
al., 2006; Kumar et al., 2007). The available data indicate that the alkaline
syenites (Pilansburg and Pienaars River) and carbonatites (Stukpan and
Spitskop) were emplaced at 1.35–1.40 Ga (Hanson et al., 2006), some
Table 4
Geochronological data of the Premier kimberlite. 200–250 Ma earlier than the Premier kimberlite. In contrast, mafic intru-
sions, having an area of ~2 ×106 km2 and represented by the Umkondo
Sample Age (Ma) Method Reference
mafic sills and related volcanic rocks in Zimbabwe, Botswana, Namibia
Kimberlite 1202 ± 72 Pb\Pb isochron Kramers and Smith and South Africa, were emplaced within a narrow time frame at
(WR-mineral) (1983)
1112–1106 Ma (Fig. 1a, Hanson et al., 1998, 2004, 2006; Wingate,
Unknown 1179 ± 36 Rb\Sr isochron (Cpx) Allsopp et al. (1989)
Megacryst 1198 ± 32 Sm\Nd isochron Jones (1987)
2001), approximately ~ 40 Ma later than the Premier kimberlite, in
(Gt-Cpx) accord with the intrusion of gabbroic sill into the Premier kimberlite
Eclogite 1150 ± 60 Sm\Nd isochron Richardson et al. (1993) (Fig. 2c). Therefore, if the Meso-proterozoic igneous activity was re-
(Gt-Cpx) lated to a mantle plume, it changed from alkaline and carbonatitic, to
Inclusion in diamond 1185 ± 94 40Ar/39Ar (Cpx) Burgess et al. (1989)
kimberlitic and ultimately to mafic magmatism.
Inclusion in diamond 1198 ± 28 40Ar/39Ar (Cpx) Phillips et al. (1989)
Peridotite xenolith 1150 ± 41 Sm\Nd isochron Pearson et al. (1995) From a global viewpoint, a contemporaneous ~1.1 Ga igneous event
(Gt-Cpx-Opx) is widely developed in other areas of the world (Hanson et al., 2006;
Megacryst 1192 ± 62 Sm\Nd isochron Nowell et al. (2004) Kumar et al., 2007). In northern America, the ~1.1 Ga magmatism
(WR-mineral)
was documented by various types of magmatic rocks, including
Megacryst 1266 ± 51 Lu\Hf isochron Nowell et al. (2004)
(Gt-Cpx-Ilm)
ultrapotassic and alkaline rocks, the Midcontinent rift tholeiites, and
Gabbroic sill 1115 ± 15 Rb\Sr isochron (Biotite) Allsopp et al. (1967) the extensive layered mafic intrusive rocks (Hanson et al., 2006). Age
Brown kimberlite 1150 ± 16 U\Pb (Perovskite) This study determinations indicate that the carbonatite, kimberlite and alkaline
Black kimberlite 1151 ± 9 U\Pb (Perovskite) This study rocks were mainly emplaced at 1160–1130 Ma (Heaman et al., 2004;
Green kimberlite 1156 ± 12 U\Pb (Perovskite) This study
Rukhlov and Bell, 2010; Wu et al., 2010c), whereas the Midcontinental
 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95
Fig. 10. Temporal variations of Sr (a) and Nd (b) isotopes for the various stages of kimberlites
in the world. Only data with coupled Sr and Nd isotopes from perovskites are plotted. All data
except the present work are listed in the Supplementary Table 2. Mengyin (Yang et al.,
2009a); Somerset Island (Wu et al., 2010a); Iron Mountain (Supplementary Table 2);
Dharwar (Chalapathi Rao et al., 2013–this volume); Brazil (Guarino et al., 2013–this volume);
West Greenland (Tappe et al., 2011); and Yakutia, Siberia (Kamenetsky et al., 2009).
rift mafic magmatism took place around 1109–1087 Ma (Heaman et al.,
2007), consistent with the conclusion suggested for southern Africa.
It is considered that the earliest melts generated in a plume environ-
ment originate within the lithospheric mantle, which is relatively
volatile-rich and readily fusible (Chalapathi Rao and Lehmann, 2011).
During rising of mantle plume, the lithosphere is extended, and results
in a continuous alkaline and carbonatitic magmatism. Finally, large scale
of tholeiitic mafic magmatism is initiated due to significant lithospheric
thinning by thermal erosion (White and McKenzie, 1989; Davies, 1994).
However, if the lithosphere is thick or the plume is not hot enough,
there would be no large scale of mafic magmatism. We conclude that
kimberlite, the deepest of the magmas originating from the mantle
(Ringwood et al., 1992; Mitchell, 2006), might be considered as a
prelude to major mantle plume-related mafic magmatism.
6. Conclusion
Geochemical data for the Premier (Cullinan) kimberlite lead to the
following conclusions:
1) U\Pb perovskite age determination indicates that the different
phases of the Premier kimberlite were emplaced coevally at
~1150 Ma; and that this is the best estimate of the age of this
kimberlite;
2) The emplacement age of the Premier kimberlite is ~30 Ma earlier
than those of kimberlites in the Dhawar craton, indicating that
the 1.1 Ga kimberlitic magmatism in the world is not coeval;
93
3) In situ Sr\Nd isotopic analyses of perovskite suggest that the
Premier kimberlite magma was derived from moderately depleted
mantle, and is thus comparable to other kimberlites;
4) Kimberlite is usually emplaced prior to the eruption of extensive
flood basalt in a mantle plume setting, and can serve as a prelude
to major plume-related magmatism,
Supplementary data to this article can be found online at http://
dx.doi.org/10.1016/j.chemgeo.2012.06.002.
Acknowledgments
Xian-Hua Li, Yu Liu, Guo-Qiang Tang, Wei-Qiang Ji, Zhi-Chao Liu, Qin
Zhou, Jing-Yuan Chen and many other staff of the SIMS and MC–ICP–MS
laboratories at the Institute of Geology and Geophysics are thanked for
their assistance during sample preparation and analyses. Roger Mitchell
thanks DeBeers Consolidated Mines for access to the Premier kimber-
lite. Constructive comments by Sebastian Tappe, Jan Kramers and an
anonymous referee improved the manuscript. This work was supported
by the Natural Science Foundation of China (Grant 41130313).
References
Allsopp, H.L., Burger, A.J., Van Zyl, C., 1967. A minimum age for the Premier kimberlite
pipe yielded by biotite Rb\Sr measurements, with related galena isotopic data.
Earth and Planetary Science Letters 3, 161–166.
Allsopp, H.L., Bristow, J.W., Smith, C.B., Brown, R., Gleadow, A.J.W., Kramers, J.D., Garvie,
O.G., 1989. A summary of radiometric dating methods applicable to kimberlites
and related rocks. In: Ross, J. (Ed.), Kimberlites and related rocks. Their composi-
tion, occurrence, origin and emplacement: Geological Society of Australia Special
Publication, 14, pp. 343–357.
Basu, A.R., Tatsumoto, M., 1979. Samarium–Neodymium systematics in kimberlites and
in the minerals of garnet lherzolite inclusions. Science 205, 398–401.
Batumike, J.M., Griffin, W.L., Belousova, E.A., Pearson, N.J., O'Reilly, S.Y., Shee, S.R., 2008.
LAM–ICPMS U\Pb dating of kimberlitic perovskite: Eocene–Oligocene kimberlites
from the Kundelungu Plateau, D. R. Congo. Earth and Planetary Science Letters 267,
609–619.
Becker, M., Le Roex, A.P., 2006. Geochemistry of South African on- and off-craton, Group I
and Group II kimberlites: petrogenesis and source region evolution. Journal of Petrol-
ogy 47, 673–703.
Becker, M., Le Roex, A.P., Class, C., 2007. Geochemistry and petrogenesis of South African
transitional kimberlites located on and off the Kaapvaal Craton. South African Journal
of Geology 110, 631–646.
Beyer, C., Berndt, J., Tappe, S., Klemme, S., 2013. Trace element partitioning
between perovskite and kimberlite to carbonatite melt: New experimental constraints.
Chemical Geology 353, 132–139 (this volume).
Burgess, R., Turner, G., Laurenzi, M., Harris, J.W., 1989. 40Ar\39Ar laser probe dating
of individual clinopyroxene inclusions in Premier eclogitic diamonds. Earth and
Planetary Science Letters 94, 22–28.
Carlson, R.W., Pearson, D.G., Boyd, F.R., Shirey, S.B., Irvine, G., Menzies, A.H., Gurney, J.J.,
1999. Re\Os systematics of lithospheric peridotites: implications for lithosphere
formation and preservation. In: Gurney, J.J., Richardson, S.R. (Eds.), Proceedings
of the 7th International Kimberlite Conference, pp. 99–108.
Chakhmouradian, A.R., Mitchell, R.H., 2001. Occurrence, alteration patterns and composi-
tional variation of perovskite in kimberlites. The Canadian Mineralogist 38, 975–994.
Chalapathi Rao, N.V., Lehmann, B., 2011. Kimberlites, flood basalts and mantle plumes:
new insights from the Deccan Large Igneous Province. Earth-Science Reviews 107,
315–324.
Chalapathi Rao, N.V., Wu, F.-Y., Mitchell, R.H., Li, Q.-L., Lehmann, B., 2013.
Mesoproterozoic U\Pb ages, trace element and Sr\Nd isotopic composition of pe-
rovskite from kimberlites of the Eastern Dharwar craton, southern India: Distinct
mantle sources and a widespread 1.1 Ga tectonomagmatic event. Chemical Geolo-
gy 353, 48–64 (this volume).
Chartier, F., Aubert, M., Salmon, M., Tabarant, M., Tran, B.H., 1999. Determination of
erbium in nuclear fuels by isotope dilution thermal ionization mass spectrometry
and glow discharge mass spectrometry. Journal of Analytical Atomic Spectrometry
14, 1461–1465.
Cox, R.A., Wilton, D.H.C., 2006. U\Pb dating of perovskite by LA–ICP–MS: an example
from the Oka carbonatite, Quebec, Canada. Chemical Geology 235, 21–32.
Davies, G.F., 1994. Thermomechanical erosion of the lithosphere by mantle plumes.
Journal of Geophysical Research 99, 15709–15722.
Davis, G.L., Krogh, T.E., Erlank, A.J., 1976. The ages of zircons from kimberlites from
South Africa. Year Book - Carnegie Institution of Washington 75, 821–824.
Donnelly, C.L., Griffin, W.L., O'Reilly, S.Y., Pearson, N.J., Shee, S.R., 2011. The kimberlites
and related rocks of the Kuruman kimberlite Province, Kaapvaal Craton, South Africa.
Contributions to Mineralogy and Petrology 161, 351–371.
Dubois, J.C., Retali, G., Cesario, J., 1992. Isotopic analysis of rare earth elements by total
vaporization of samples in thermal ionization mass spectrometry. International
Journal of Mass Spectrometry and Ion Processes 120, 163–177.
94 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95
Ehrlich, S., Gavrieli, I., Dor, L.B., Halicz, L., 2001. Direct high-precision measurements of
the 87Sr/86Sr isotope ratio in natural water, carbonates and related materials by
multiple collector inductively coupled plasma mass spectrometry (MC–ICP–MS).
Journal of Analytical Atomic Spectrometry 16, 1389–1392.
Ernst, R.E., Buchan, K.L., 2001. Large mafic magmatic events through time and links
to mantle-plume heads. In: Ernst, R.E., Buchan, K.L. (Eds.), Mantle Plumes:
Their Identification Through Time: Geological Survey of America Special Paper,
vol. 352, pp. 483–575.
Ernst, R.E., Buchan, K.L., 2003. Recognizing mantle plumes in the geological record.
Annual Review of Earth and Planetary Sciences 31, 469–523.
Fesq, H.W., Kable, E.J.D., Gurney, J.J., 1975. Aspects of the geochemistry of kimberlites
from the Premier Mine, and other selected South African occurrences with
particular reference to the rare earth elements. Physics and Chemistry of the
Earth 9, 687–707.
Field, M., Stiefenhofer, J., Robey, J., Kurszlaukis, S., 2008. Kimberlite-hosted diamond
deposits of southern Africa: a review. Ore Geology Reviews 34, 33–75.
Fisher, C.M., McFarlane, C.R.M., Hanchar, J.M., Schmitz, M.D., Sylvester, P.J., Lam, R.,
Longerich, H.P., 2011. Sm\Nd isotope systematics by laser ablation-multicollector-
inductively coupled plasma mass spectrometry: methods and potential natural and
synthetic reference materials. Chemical Geology 284, 1–20.
Fraser, K.J., Hawkesworth, C.J., Erlank, A.J., Mitchell, R.H., Scott-Smith, B.H., 1985. Sr, Nd
and Pb isotope and minor element geochemistry of lamproites and kimberlites.
Earth and Planetary Science Letters 76, 57–70.
Gibson, S.A., Thompson, R.N., Leonardos, O.H., Dickin, A.P., Mitchell, J.G., 1995. The late
Cretaceous impact of the Trindade mantle plume-evidence from large-volume,
mafic, potassic magmatism in SE Brazil. Journal of Petrology 36, 189–229.
Griffin, W.L., Natapov, L.M., O'Reilly, S.Y., van Achterbergh, E., Cherenkova, A.F.,
Cherenkov, V.G., 2005. The Kharamai kimberlite field, Siberia: modification of the
lithospheric mantle by the Siberian Trap event. Lithos 81, 167–187.
Griffin, W.L., Powell, W.J., Pearson, N.J., O'Reilly, S.Y., 2008. GLITTER: data reduction
software for laser ablation ICP–MS. In: Sylvester, P. (Ed.), Laser ablation-ICP–MS
in the earth sciences: current practices and outstanding issues: Mineralogical Asso-
ciation Canada Short Course, 40, pp. 308–311.
Guarino, V., Wu, F.-Y., Lustrino, M., Melluso, L., Bratzu, P., Gomes, C.d.B., Ruberti, E.,
Tassinari, C.C.G., Svisero, D.P., 2013. U\Pb ages, Sr\Nd isotope geochemistry,
and petrogenesis of kimberlites, kamafugites and pholgopite-picrites of the Alto
Paranaiba Igneous Province, Brazil. Chemical Geology 353, 65–82 (this volume).
Haggerty, S.E., 1994. Superkimberlites: a geodynamic window to the Earth's core. Earth
and Planetary Science Letters 122, 57–69.
Hanson, R.E., Martin, M.W., Bowring, S.A., Munyanyiwa, H., 1998. U\Pb zircon age
for the Umkondo dolerites, eastern Zimbabwe: 1.1 Ga large igneous province in
southern Africa/East Antarctica and possible Rodinia correlations. Geology 26,
1143–1146.
Hanson, R.E., Crowley, J.L., Bowring, S.A., Ramezani, J., Gose, W.A., Dalziel, I.W.D.,
Pancake, J.A., Seidel, E.K., Blenkinsop, T.G., Mukwakwami, J., 2004. Coeval large-
scale magmatism in the Kalahari and Laurentian cratons during Rodinia assembly.
Science 304, 1126–1129.
Hanson, R.E., Harmer, R.E., Blenkinsop, T.G., Bullen, D.S., Dalziel, I.W.D., Gose, W.A., Hall,
R.P., Kampunzu, A.B., Key, R.M., Mukwakwami, J., Munyanyiwa, H., Pancake, J.A.,
Seidel, E.K., Ward, S.E., 2006. Mesoproterozoic intraplate magmatism in the
Kalahari Craton: a review. Journal of African Earth Sciences 46, 141–167.
Harte, B., 2010. Diamond formation in the deep mantle: the record of mineral inclu-
sions and their distribution in relation to mantle dehydration zones. Mineralogical
Magazine 74, 189–215.
Heaman, L.M., 1989. The nature of the subcontinental mantle from Sr\Nd\Pb isotopic
studies on kimberlitic perovskite. Earth and Planetary Science Letters 92, 323–334.
Heaman, L.M., 2009. The application of U\Pb geochronology to mafic, ultramafic and
alkaline rocks: an evaluation of three mineral standards. Chemical Geology 261,
42–51.
Heaman, L.M., Kjarsgaard, B.A., Creaser, R.A., 2004. The temporal evolution of North
American kimberlites. Lithos 76, 377–397.
Heaman, L.M., Easton, R.M., Hart, T.R., Hollings, P., MacDonald, C.A., Smyk, M., 2007.
Further refinement to the timing of Mesoproterozoic magmatism, lake Nipigon re-
gion, Ontario. Canadian Journal of Earth Sciences 44, 1055–1086.
Hoal, K.O., 2003. Samples of Proterozoic iron-enriched mantle from the Premier kim-
berlite. Lithos 71, 259–272.
Iizuka, T., Eggins, S.M., McCulloch, M.T., Kinsley, L.P.J., Mortimer, G.E., 2011. Precise and
accurate determination of 147Sm/144Nd and 143Nd/144Nd in monazite using laser
ablation-MC–ICPMS. Chemical Geology 282, 45–57.
Isnard, H., Brennetot, R., Caussignac, C., Caussignac, N., Chartier, F., 2005. Investigations
for determination of Gd and Sm isotopic compositions in spent nuclear fuels sam-
ples by MC ICPMS. International Journal of Mass Spectrometry 246, 66–73.
Jackson, S.E., Pearson, N.J., Griffin, W.L., Belousova, E.A., 2004. The application of laser
ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) to in situ
U\Pb zircon geochronology. Chemical Geology 211, 47–69.
Jelsma, H., Barnett, W., Richards, S., Lister, G., 2009. Tectonic setting of kimberlites. Lithos
112S, 155–165.
Jones, R.A., 1987. Strontium and neodymium isotopic and rare earth element evidence
for the genesis of megacrysts in kimberlites of southern Africa. In: Nixon, P.H. (Ed.),
Mantle Xenoliths. Wiley and Sons, Chichester, pp. 711–724.
Kable, E.J.D., Fesq, H.W., Gurney, J.J., 1975. The significance of the inter-element rela-
tionships of some minor and trace elements in South African kimberlite. Physics
and Chemistry of the Earth 9, 709–734.
Kamenetsky, V.S., Mass, R., Kamenetsky, M.B., Paton, C., Phillips, D., Golovin, A.V., Gornova,
M.A., 2009. Chlorine from the mantle: magmatic halides in the Udachnaya-east
kimberlite, Siberia. Earth and Planetary Science Letters 285, 96–104.
Kaminsky, F., 2012. Mineralogy of the lower mantle: a review of “super-deep” mineral
inclusion in diamond. Earth-Science Reviews 110, 127–147.
Kerschhofer, L., Schärer, U., Deutsch, A., 2000. Evidence for crystals from the lower
mantle: baddeleyite megacrysts of the Mbuji Mayi kimberlite. Earth and Planetary
Science Letters 179, 219–225.
Kinny, P.D., Griffin, B.J., Heaman, L.M., Brakhfogel, F.F., Spetsius, Z.V., 1997. SHRIMP
U\Pb ages of perovskite from Yakutian kimberlites. Russian Geology and Geo-
physics 38, 97–105.
Kopylova, M.G., Matveev, S., Raudsepp, M., 2007. Searching for parental kimberlite
melt. Geochimica et Cosmochimica Acta 71, 3616–3629.
Kramers, J.D., Smith, C.B., 1983. A feasibility study of U\Pb and Pb\Pb dating of kim-
berlites using groundmass mineral fractions and whole-rock samples. Isotope Geo-
science 1, 23–38.
Kumar, A., Heaman, L.A., Manikyamba, C., 2007. Mesoproterozoic kimberlites in south
India: a possible link to 1.1 Ga global magmatism. Precambrian Research 154,
192–204.
Le Roex, A.P., Bell, D.R., Davis, P., 2003. Petrogenesis of Group I kimberlites from Kim-
berley, South Africa: evidence from bulk rock geochemistry. Journal of Petrology
44, 2261–2286.
Li, Q.L., Li, X.H., Liu, Y., Wu, F.Y., Yang, J.H., Mitchell, R.H., 2010. Precise U\Pb and
Th\Pb age determination of kimberlitic perovskites by secondary ion mass spec-
trometry. Chemical Geology 269, 396–405.
Li, Q.L., Wu, F.Y., Li, X.H., Qiu, Z.L., Liu, Y., Yang, Y.H., Tang, G.Q., 2011. Precisely dating
Paleozoic kimberlites in the North China Craton and Hf isotopic constraints on
the evolution of its subcontinental lithospheirc mantle. Lithos 126, 127–134.
Ludwig, K.R., 2003. ISOPLOT 3.0—a geochronological toolkit for Microsoft Excel. Berkeley
Geochronology Center Special Publication, No. 4. 70 pp.
Maier, W.D., Peltonen, P., Juvonen, R., Pienaar, C., 2005. Platinum-group elements in
peridotite xenoliths and kimberlite from the premier kimberlite pipe, South Africa.
South African Journal of Geology 108, 413–428.
Malarkey, J., Pearson, D.G., Kjarsgaard, B.A., Davidson, J.P., Nowell, G.M., Ottley, C.J.,
Stammer, J., 2010. From source to crust: tracing magmatic evolution in a kimberlite
and a melilitite using microsample geochemistry. Earth and Planetary Science
Letters 299, 80–90.
McFarlane, C.R.M., McCulloch, M.T., 2007. Coupling of in-situ Sm\Nd systematics
and U\Pb dating of monazite and allanite with applications to crustal evolution
studies. Chemical Geology 245, 45–60.
Mitchell, R.H., 1986. Kimberlites: Mineralogy, Geochemistry, and Petrology. Plenum
Press, New York. 442 pp.
Mitchell, R.H., 1995. Kimberlites, orangeites, and related rocks. Plenum Press, New
York. 410 pp.
Mitchell, R.H., 2006. Potassic magmas derived from metasomatized lithospheric man-
tle: nomenclature and relevance to exploration for diamond-bearing rocks. Journal
of the Geological Society of India 67, 317–327.
Mitchell, R.H., Crocket, J.H., 1971. The isotopic composition of strontium in some South
African kimberlites. Contributions to Mineralogy and Petrology 30, 277–290.
Moore, A., Blenkinsop, T., Cotterill, F., 2008. Controls on post-Gondwana alkaline volca-
nism in Southern Africa. Earth and Planetary Science Letters 268, 151–164.
Nowell, G.M., Pearson, D.G., Bell, D.R., Carlson, R.W., Smith, C.B., Kempton, P.D., Noble,
S.R., 2004. Hf isotope systematics of kimberlites and their megacrysts: new
constraints on their source regions. Journal of Petrology 45, 1583–1612.
Paton, C., Hergt, J.M., Phillips, D., Woodhead, J.D., Shee, S.R., 2007. New insights into the
genesis of Indian kimberlites from the Dharwar Craton via in situ Sr isotope anal-
ysis of groundmass perovskite. Geology 35, 1011–1014.
Pearson, D.G., Carlson, R.W., Shirey, S.B., Boyd, F.R., Nixon, P.H., 1995. Stabilization of
Archaean lithospheric mantle: a Re\Os isotope study of peridotite xenoliths
from the Kaapvaal craton. Earth and Planetary Science Letters 134, 341–357.
Phillips, D., Onstott, T.C., Harris, J.W., 1989. 40Ar/39Ar laser-probe dating of diamond in-
clusions from the Premier kimberlite. Nature 340, 460–462.
Price, S.E., Russell, J.K., Kopylova, M.G., 2000. Primitive magma from the Jericho Pipe,
NWT, Canada: constraints on primary kimberlite melt chemistry. Journal of Petrol-
ogy 41, 789–808.
Ramos, F.C., Wolff, J.A., Tollstrup, D.L., 2004. Measuring 87Sr/86Sr variation in minerals
and groundmass from basalts using LA– MC–ICPMS. Chemical Geology 211,
135–158.
Reguir, E.P., Camacho, A., Yang, P., Chakhmouradian, A.R., Kamenetsky, V.S., Halden,
N.M., 2010. Trace-element study and uranium–lead dating of perovskite from the
Afrikanda plutonic complex, Kola Peninsula (Russia) using LA-ICP-MS. Mineralogy
and Petrology 100, 95–103.
Reichow, M.K., Pringle, M.S., Al'Mukhamedov, A.I., Allen, M.B., Andreichev, V.L., Buslov,
M.M., Davies, C.E., Fedoseev, G.S., Fitton, J.G., Inger, S., Medvedev, A.Ya., Mitchell, C.,
Puchkov, V.N., Safonov, I.Yu., Scott, R.A., Saunders, A.D., 2009. The timing and ex-
tent of the eruption of the Siberian Traps large igneous province: implications for
the end-Permian environmental crisis. Earth and Planetary Science Letters 277,
9–20.
Richardson, S.H., Harris, J.W., Gurney, J.J., 1993. Three generations of diamonds from
old continental mantle. Nature 366, 256–258.
Ringwood, A.E., Kesson, S.E., Hibberson, W., Ware, N., 1992. Origin of kimberlites and
related magmas. Earth and Planetary Science Letters 113, 521–538.
Rukhlov, A.S., Bell, K., 2010. Geochronology of carbonatites from the Canadian and Baltic
shields, and the Canadian Cordillera: clues to mantle evolution. Mineralogy and
Petrology 98, 11–54.
Schissel, D., Smail, R., 2001. Large mafic magmatic events through time and links
to mantle-plume heads. In: Ernst, R.E., Buchan, K.L. (Eds.), Mantle Plumes:
Their Identification Through Time: Geological Survey of America Special Paper,
vol. 352, pp. 291–322.
 F.-Y. Wu et al. / Chemical Geology 353 (2013) 83–95
Skinner, E.M.W., 1989. Contrasting group I and group II kimberlite petrology: towards a
genetic model for kimberlites. In: Ross, J. (Ed.), Kimberlites and related rocks: their
composition, occurrence, origin and emplacement: Geological Society of Australia.
Special Publication, 14, pp. 528–544.
Smith, C.B., 1983. Pb, Sr and Nd isotopic evidence for sources of southern African
Cretaceous kimberlites. Nature 304, 51–54.
Smith, C.B., Allsopp, H.L., Gravie, O.G., Kramers, J.D., Jackson, P.F.S., Clement, C.R., 1989.
Note on the U\Pb perovskite method for dating kimberlites: examples from the
Wesselton and De Beers mines, South Africa, and Somerset Island, Canada. Chem-
ical Geology 79, 137–145.
Stacey, J.S., Kramers, J.D., 1975. Approximation of terrestrial lead isotope evolution by a
two-stage model. Earth and Planetary Science Letters 26, 207–221.
Sun, S.S., McDonough, W.F., 1989. Chemical and isotopic systematics of oceanic basalts: im-
plications for mantle composition and processes. In: Saunder, A.D., Norry, M.J. (Eds.),
Magmatism in the Ocean Basins: Geological Society Special Publications, 42, pp.
313–345.
Tappe, S., Simonetti, A., 2012. Combined U\Pb geochronology and Sr\Nd isotope
analysis of the Ice River perovskite standard, with implications for kimberlite and
alkaline rock petrogenesis. Chemical Geology 304 (305), 10–17.
Tappe, S., Foley, S.F., Jenner, G.A., Heaman, L.M., Kjarsgaard, B.A., Romer, R.L., Stracke, A.,
Joyce, N., Hoefs, J., 2006. Genesis of ultramafic lamprophyres and carbonatites at
Aillik Bay, Labrador: a consequence of incipient lithospheric thinning beneath
the North Atlantic craton. Journal of Petrology 47, 1261–1315.
Tappe, S., Pearson, D.G., Nowell, G.M., Nielsen, T.F.D., Milstead, P., Muehlenbachs, K.,
2011. A fresh isotopic look at Greenland kimberlites: cratonic mantle lithosphere
imprint on deep source signal. Earth and Planetary Science Letters 305, 235–248.
Vervoort, J.D., Patchett, P.J., Soderlund, U., Baker, M., 2004. Isotopic composition of Yb
and the determination of Lu concentrations and Lu/Hf ratios by isotopic dilution
using MC–ICPMS. Geochemistry, Geophysics, Geosystems 5, Q11002, http://
dx.doi.org/10.1029/2004GC000721.
Walker, R.J., Carlson, R.W., Shirey, S.B., Boyd, F.R., 1989. Os, Sr, Nd, and Pb isotope system-
atics of southern African peridotite xenoliths: implications for the chemical evolution
of subcontinental mantle. Geochimica et Cosmochimica Acta 53, 1583–1595.
Walter, M.J., Kohn, S.C., Araujo, D., Bulanova, G.P., Smith, C.B., Gaillou, E., Wang, J.,
Steele, A., Shirey, S.B., 2011. Deep mantle cycling of oceanic crust: evidence from
diamonds and their mineral inclusions. Science 334, 54–57.
Wasserburg, G.J., Jacobsen, S.B., DePaolo, D.J., McCulloch, M.T., Wen, T., 1981. Precise
determination of Sm/Nd ratios, Sm and Nd isotopic abundances in standard solu-
tions. Geochimica et Cosmochimica Acta 45, 2311–2323.
White, R.W., McKenzie, D.P., 1989. Magmatism at rift zones: the generation of volcanic
continental margins and flood basalts. Journal of Geophysical Research 94,
7685–7729.
Williams, I.S., 1998. U\Th\Pb geochronology by ion microprobe. In: McKibben,
M.A., ShanksIII III, W.C., Ridley, W.I. (Eds.), Applications of Microanalytical
95
Techniques to UnderstandingMineralizing Processes: Reviews in Economic
Geology, 7, pp. 1–35.
Wilson, M., Lyashkevich, Z.M., 1996. Magmatism and the geodynamics of rifting of the
Pripyat–Dnieper–Donets rift, East European Platform. Tectonophysics 268, 65–81.
Wingate, M.T.D., 2001. SHRIMP baddeleyite and zircon ages for an Umkondo dolerite
sill, Nyanga Mountains, eastern Zimbabwe. South African Journal of Geology 104,
13–22.
Woodhead, J.D., Hergt, J.M., Phillips, D., Paton, C., 2009. African kimberlites revisited: in
situ Sr-isotope analysis of groundmass perovskite. Lithos 112S, 311–317.
Wu, F.Y., Yang, Y.H., Mitchell, R.H., Li, Q.L., Yang, J.H., Zhang, Y.B., 2010a. In situ U\Pb
age determination and Nd isotopic analyses of perovskites from kimberlites in
southern Africa and Somerset Island, Canada. Lithos 115, 205–222.
Wu, F.Y., Yang, Y.H., Marks, M.A.W., Liu, Z.C., Zhou, Q., Ge, W.C., Yang, J.S., Zhao, Z.F.,
Mitchell, R.H., Markl, G., 2010b. In situ U\Pb, Sr, Nd, and Hf isotopic analysis of
eudialyte by LA–(MC)–ICP–MS. Chemical Geology 273, 8–34.
Wu, F.Y., Yang, Y.H., Mitchell, R.H., Bellatreccia, F., Li, Q.L., Zhao, Z.F., 2010c. In situ U\Pb
and Nd\Hf\ (Sr) isotopic investigations of zirconolite and calzirtite. Chemical
Geology 277, 178–195.
Wu, F.Y., Yang, Y.H., Li, Q.L., Mitchell, R.H., Dawson, J.B., Brand, G., Yuhara, M., 2011. In situ
determination of U\Pb ages and Sr\Nd\Hf isotopic constraints on the petrogenesis
of the Phalaborwa carbonatite complex, South Africa. Lithos 127, 309–322.
Wu, F.-Y., Arzamastsev, A.A., Mitchell, R.H., Li, Q.-L., Sun, J., Yang, Y.-H., Wang, R.-C.,
2013. Emplacement age and Sr\Nd isotopic compositions of the Afrikanda alka-
line ultramafic complex, Kola Peninsula, Russia. Chemical Geology 353, 210–229
(this volume).
Yang, Y.H., Sun, J.F., Xie, L.W., Fan, H.R., Wu, F.Y., 2008. In situ Nd isotopic measure-
ments of geological samples by laser ablation. Chinese Science Bulletin 53,
1062–1070.
Yang, Y.H., Wu, F.Y., Wilde, S.A., Liu, X.M., Zhang, Y.B., Xie, L.W., Yang, J.H., 2009a. In situ
perovskite Sr\Nd isotopic constraints on petrogenesis of the Mengyin kimberlites
in the North China Craton. Chemical Geology 264, 24–42.
Yang, Y.H., Wu, F.Y., Xie, L.W., Yang, J.H., Zhang, Y.B., 2009b. In-situ Sr isotopic measure-
ment of natural geological samples by LA-MC-ICP-MS (in Chinese with English ab-
stract). Acta Petrologica Sinica 25, 3431–3441.
Yang, Y.H., Zhang, H.F., Chu, Z.Y., Xie, L.W., Wu, F.Y., 2010. Combined chemical separa-
tion of Lu, Hf, Rb, Sr, Sm and Nd from a single rock digest and precise and accurate
isotope determinations of Lu\Hf, Rb\Sr and Sm\Nd isotope systematics using
Multi-Collecter ICP-MS and TIMS. International Journal of Mass Spectrometry
290, 120–126.
Yang, Y.H., Chu, Z.Y., Wu, F.Y., Xie, L.W., Yang, J.H., 2011. Precise and accurate determi-
nation of Sm, Nd concentrations and Nd isotopic compositions in geological sam-
ples by MC-ICP-MS. Journal of Analytical Atomic Spectrometry 26, 1237–1244.
Zartman, R.E., Richardson, S.H., 2005. Evidence from kimberlitic zircon for a decreasing
mantle Th/U since the Archean. Chemical Geology 220, 263–283.