Earth and Planetary Science Letters 522 (2019) 79–86

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Earth and Planetary Science Letters

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Light Mg isotopes in mantle-derived lavas caused by chromite

crystallization, instead of carbonatite metasomatism
Ben-Xun Su a,b,c,∗ , Yan Hu b , Fang-Zhen Teng b,∗∗ , Yan Xiao d , Hong-Fu Zhang c,d,e ,
Yang Sun b,d , Yang Bai a,b,c , Bin Zhu d , Xin-Hua Zhou c,d , Ji-Feng Ying c,d
a
Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
b
Department of Earth and Space Sciences, University of Washington, Seattle, WA 98195, USA
c
University of Chinese Academy of Sciences, Beijing 100049, China
d
State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
e
State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Xi’an 710069, China

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

Article history: Carbonatite metasomatism plays an important role in modifying the composition of Earth’s mantle,
Received 25 January 2019 however, its effect on mantle Mg isotopic composition is poorly constrained. Here, we report high-
Received in revised form 19 May 2019 precision mineral Mg isotope data for three suites of mantle peridotite xenoliths that experienced variable
Accepted 15 June 2019
degrees of carbonatite metasomatism. The δ 26 Mg values of minerals in these xenoliths are variable
Available online xxxx
and range from −0.32 to −0.11h in olivine, from −0.28 to −0.09h in orthopyroxene, from −0.27 to
Editor: F. Moynier
−0.05h in clinopyroxene, from 0.06 to 0.44h in spinel and from −0.61 to −0.37h in garnet. Calculated
Keywords: bulk-rock δ 26 Mg values of the peridotites vary from −0.27 to −0.10h, falling within and slightly higher
carbonatite metasomatism than the normal mantle range (−0.25 ± 0.07h). The coexisting minerals are in isotopic equilibrium,
lithospheric mantle with clinopyroxene δ 26 Mg values correlated with the carbonatite metasomatic indices such as MgO and
Mg isotopes Na2 O in orthopyroxene. These results suggest that carbonatite metasomatism does not produce light Mg
peridotite xenoliths isotopic signature in mantle peridotites as previously suggested, instead it might slightly elevate their
chromite crystallization
δ 26 Mg values. Therefore, carbonatite-metasomatized peridotites in the mantle cannot be the primary
source rocks of low-δ 26 Mg mantle-derived magmas. Instead, fractional crystallization and accumulation
of chromite during ascent of the basaltic magmas may explain the isotopically light basalts, as supported
by the covariations of δ 26 Mg with chemical indices of chromite crystallization (e.g., Cr, V, Fe and Ti).
Consequently, chromite crystallization may significantly influence the physiochemical processes on the
genesis of basalts, which would require comprehensive evaluation in future studies.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction chemical signatures in mantle xenoliths (e.g., Rudnick et al., 1993;

Mantle heterogeneity caused by carbonatite metasomatism has
been well documented through studies of petrology and geochem-
istry. Carbonatite melts originate from partial melting of carbon-
atite metasomatized-peridotite mantle (e.g., Wallace and Green,
1988; Harmer and Gittins, 1998; Ying et al., 2004), or fractional
crystallization and separation from silicate melts by liquid immis-
cibility (e.g., Gittins, 1988; Brooker and Hamilton, 1990; Chen et
al., 2013; Guzmics et al., 2015). Their interaction with lithospheric
mantle during ascent generates some unique petrological and geo-
*Corresponding author at: Key Laboratory of Mineral Resources, Institute of Ge-
ology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China.
** Corresponding author.
E-mail addresses: subenxun@mail.igcas.ac.cn (B.-X. Su), fteng@uw.edu
(F.-Z. Teng).
Coltorti et al., 1999; Halama et al., 2008; Su et al., 2010). Car-
bonatite metasomatism typically transforms orthopyroxene in peri-
dotite to clinopyroxene due to the Si-undersaturation nature of
carbonatite, leading to the formation of wehrlite (e.g., Yaxley et
al., 1991, 1998; Ionov et al., 1996; Laurora et al., 2001; Xiao et
al., 2010, 2013). It can also slightly elevate forsterite (Fo) con-
tent in olivine because of the high Mg/Fe ratio of carbonatite
(Fig. 1a; Su et al., 2010). In addition, carbonatite metasomatism
displays high La/Yb and low Ti/Eu ratios compared to silicate
metasomatism (Fig. 1b) because carbonatites are extremely rich
in rare earth elements (particularly light ones) and relatively de-
pleted in high field strength elements (e.g., Rudnick et al., 1993;
Coltorti et al., 1999). Recently, Li isotopic studies also indicate that
carbonatite metasomatism leads to the preferential Li enrichment
and significant low-δ 7 Li in olivine compared to silicate metaso-

https://doi.org/10.1016/j.epsl.2019.06.016
0012-821X/© 2019 Elsevier B.V. All rights reserved.
80 B.-X. Su et al. / Earth and Planetary Science Letters 522 (2019) 79–86
Fig. 1. (a) δ 7 Li vs. Fo for olivine, (b) Ti/Eu vs. (La/Yb)N (chondrite-normalized) ratio
for clinopyroxene, and (c) δ 7 Li vs. Li for olivine in the Mingxi, Haoti and Dayishan
peridotite xenoliths. Data are from Su et al. (2012, 2014a, 2018) and Supplementary
Table S1. Normal mantle values and trends of carbonatite and silicate metasomatism
are defined by Rudnick et al. (1993), Coltorti et al. (1999), Woodland et al. (2004)
and Su et al. (2014a, 2014b). The trends in Fig. 1b represent binary mixing of aver-
age carbonatite (Ti/Eu = 20; (La/Yb)N = 80) with the normal mantle (Ti/Eu = 7738;
(La/Yb)N = 1) and refractory mantle (Ti/Eu = 2000; (La/Yb)N = 0.2) (Rudnick et al.,
1993; Yaxley et al., 1998), and the numbers are in percentage. Analytical uncer-
tainties are all smaller than symbols shown. (For interpretation of the colors in the
figure(s), the reader is referred to the web version of this article.)
matism (Woodland et al., 2004; Su et al., 2014a, 2014b, 2018)
(Fig. 1c).
Recent studies of continental basalts and arc lavas found
mantle Mg isotopic heterogeneity, which calls subducted car-
bonates as the possible explanation (e.g., Yang et al., 2012;
Huang et al., 2015; Li et al., 2016a). However, the mechanisms
on how Mg isotopic signatures were imprinted into these basaltic
rocks are unclear. The prevailing hypothesis ascribes their low
δ 26 Mg values to carbonatite metasomatized-peridotite sources
(e.g., Yang et al., 2012; Huang et al., 2015; Li et al., 2016a), which
gained the light Mg isotopic signature from subducted sedimen-
tary carbonates that have δ 26 Mg down to −6h (see summaries
in Ke et al., 2011 and Teng, 2017). Paradoxically, binary mix-
ing between mantle peridotite and sedimentary carbonate cannot
account for the low-δ 26 Mg signature, given their large contrast
in the MgO content (Su et al., 2017a). More importantly, recent
studies found carbonatites, different from carbonate sediments,
do not always have light Mg isotopic compositions. For exam-
ple, natrocarbonatites are characterized by heavy Mg isotopes
(Ling et al., 2013; Li et al., 2016b; Cheng et al., 2017), while cal-
ciocarbonatites display large δ 26 Mg variations (Ling et al., 2013;
Cheng et al., 2017) and result from variable extents of separa-
tion of silicate melt during liquid immiscibility (Chen et al., 2013;
Li et al., 2016b). Carbonatite metasomatism therefore might not
be able to produce the light Mg isotopic signature as expected
in previous studies. Alternatively, these light basalts could re-
sult from variable degrees of partial melting of isotopically dis-
tinct minerals or lithologies (Su et al., 2015; Zhong et al., 2017;
Stracke et al., 2018) or fractional crystallization and accumulation
of oxides (Xiao et al., 2016; Su et al., 2017b; Chen et al., 2018).
The direct test on the above discrepancy is to study Mg iso-
topic compositions of carbonatite-metasomatized mantle xenoliths.
Here, we report Mg isotopic compositions of major rock-forming
minerals in a set of well-characterized carbonatite-metasomatized
peridotite xenoliths from Haoti, Dayishan and Mingxi, China. Our
results reveal that carbonatite metasomatism does fractionate Mg
isotopes at both intra- and inter-mineral scales, however, this pro-
cess overall elevates δ 26 Mg of mantle xenoliths, hence cannot rep-
resent the potential sources of isotopically light mantle-derived
magmas. Instead, fractional crystallization and accumulation of
chromite during basaltic ascent likely account for the light basalts.
2. Carbonatite-metasomatized peridotite xenolith samples
The studied samples were collected from three localities (Ming-
xi, Haoti and Dayishan) and consist of mainly harzburgite and
lherzolite, with a few dunite, wehrlite and/or websterite. They are
variably carbonatite-metasomatized and can represent carbonatite-
metasomatized lithospheric mantle. Mingxi in the South China
Block crops out abundant spinel- and/or garnet-phase lherzo-
lite with minor harzburgite and dunite. Haoti xenoliths in Qin-
ling Orogen (central China) are mostly lherzolite, varying from
garnet and garnet-spinel to spinel phases, with minor harzbur-
gite and wehrlite. Dayishan xenoliths from northeastern China are
all spinel-phase lherzolite with additional harzburgite and one
websterite (Supplementary Table S1). The presence of carbonatite
metasomatism in these three suites of xenoliths has been well
documented by their petrology (e.g., presence of wehrlite), min-
eralogy (e.g., presence of carbonate mineral), mineral chemistry
(e.g., Ti/Eu and La/Yb in clinopyroxene) and bulk rock elemental
(e.g., CaO content) and isotopic (Sr-Nd-Pb isotopes) compositions
(Mingxi: Xu et al., 2000, 2003; Haoti: Su et al., 2010, 2012; Dayis-
han: Zhang et al., 2011; Su et al., 2018; Fig. 1b). Particularly, olivine
grains in these samples have higher Fo and Li contents than what
is commonly observed in mantle xenoliths, and their δ 7 Li values
mostly plot in the field of carbonatite metasomatism (Fig. 1a, c).
The outliers of the Dayishan samples are probably related to a sil-
icate metasomatic agent prior to carbonatite metasomatism (Su et
al., 2018).
3. Analytical methods
Major element compositions of minerals were analyzed on pol-
ished thin sections using JEOL JXA8100 electron probe microana-
lyzer (EPMA) at the Institute of Geology and Geophysics, Chinese
Academy of Sciences (IGGCAS). The analyses were carried out at an
 B.-X. Su et al. / Earth and Planetary Science Letters 522 (2019) 79–86 81

accelerating voltage of 15 kV, 10 nA beam current, 5 μm beam spot

size and 10-30 s peak counting time. Natural and synthetic min-
eral standards were used for calibration. A program based on the
ZAF procedure was used for matrix corrections. Typical analytical
uncertainty for the analyzed elements was better than 1.5%.
Mineral separates were handpicked under binocular microscope
and their Mg isotope analyses were performed at the Isotope Lab-
oratory of the University of Washington, Seattle, following the
method described in previous studies (Teng et al., 2010, 2015). The
mineral separates were dissolved in a mixture of HF-HNO3 -HCl in
sealed 7-ml Teflon beakers and heated on a hot plate in a laminar
flow exhaust hood. The samples were then dried and re-dissolved
in 1 N HNO3 for chromatographic separation. Magnesium was
purified on a cation exchange resin (Bio-rad AG50W-X8) in 1 N
HNO3 media. The same column procedure was repeated in order
to effectively remove matrix elements. Magnesium isotopic ratios
were measured on a Nu Plasma multi-collector inductively coupled
plasma mass spectrometer. Three standards (Hawaiian seawater,
JB-1 basalt, and PCC-1 peridotite) were processed and analyzed
with each batch of samples to assess the accuracy and repro-
ducibility. The results of these standards (Supplementary Table S1)
agree well with the recommended values (Teng et al., 2015).

4. Results

The Mingxi, Haoti and Dayishan xenoliths display similar Mg

isotopic compositions in olivine and pyroxene, with δ 26 Mg ranging
from −0.32 to −0.11h in olivine, from −0.28 to −0.09h in or-
thopyroxene and from −0.27 to −0.05h in clinopyroxene (Supple-
mentary Table S1). The δ 26 Mg value of phlogopite (−0.17h) in one
garnet lherzolite is identical to those of the coexisting olivine and
pyroxenes (Fig. 2). Spinel has high δ 26 Mg (0.06 to 0.44h) while
garnet has low δ 26 Mg values (−0.61 to −0.37h) when compared
to coexisting minerals. The magnitudes of Mg isotopic fractiona-
Fig. 2. Mineral and estimated bulk-rock Mg isotopic compositions of carbonatite-
tion between minerals are variable with 26 Mgorthopyroxene–olivine metasomatized peridotite xenoliths from Mingxi, Haoti and Dayishan. Error bars
= −0.07 to 0.14h, 26 Mgclinopyroxene–olivine = −0.06 to 0.20h, represent analytical uncertainties (2SD). The δ 26 Mg ranges for normal mantle, conti-
nental basalt, sedimentary carbonate, eclogite, and mantle pyroxenite are shown for
26 Mgspinel–olivine = 0.29 to 0.70h and 26 Mggarnet–olivine =
comparisons (data sources from Ke et al., 2011 and Teng, 2017). Natrocarbonatite
−0.43 to −0.26h (Supplementary Table S1). data are from Li et al. (2016b). Calciocarbonatite data are from Ling et al. (2013)
and Cheng et al. (2017). Magnesiocarbonatite data are from Cheng et al. (2017).
5. Discussion

The mantle xenoliths from the Mingxi, Haoti and Dayishan ar-
eas have been metasomatized by carbonatitic melts (e.g., Xu et
al., 2000, 2003; Su et al., 2010, 2012, 2018; Zhang et al., 2011).
In this section, we first explore the genetic connection of min-
eral Mg isotopic variations with carbonatite metasomatism. Then,
we discuss the possibility of carbonatite-metasomatized mantle to
be a primary source of the low-δ 26 Mg basalts. Finally, we propose
that crystallization of chromite leads to the formation of isotopi-
cally light basalts and plays an important role in the genesis of
basalts.
5.1. Effects of carbonatite metasomatism on mantle peridotite
The Mg isotopic composition of the Earth’s mantle has been
well constrained from studies of mantle peridotites and oceanic
basalts, which yield values similar to that of chondrites (aver-
age δ 26 Mg = −0.25 ± 0.07h; summarized in Teng, 2017 and
references therein). The carbonatite-metasomatized peridotites in
this study exhibit normal-mantle-like Mg isotopic compositions
in their major constituent minerals (olivine and pyroxenes) with
a few higher δ 26 Mg values (Fig. 2). The Mg isotope fractiona-
tions between co-existing pyroxene, olivine and spinel plot close to
the theoretically calculated lines of equilibrium fractionation at a
temperature range of 800-1180 ◦ C, indicating an equilibrium inter-
mineral Mg isotopic fractionation (Fig. 3). The calculated bulk-
rock δ 26 Mg values of the peridotites vary from −0.27 to −0.10h
(Supplementary Table S2), consistent with that the Mg budget of
the peridotites is controlled by olivine and pyroxenes. Hence, the
carbonatite-metasomatized lithospheric mantle, as represented by
the samples studied here, has normal-mantle-like or slightly heav-
ier Mg isotopic compositions.
Carbonatite metasomatism is a process during which orthopy-
roxene is consumed to form clinopyroxene, producing a rock se-
ries ranging from harzburgite and/or (clinopyroxene-rich) lherzo-
lite to wehrlite (Yaxley et al., 1991, 1998; Ionov et al., 1996;
Laurora et al., 2001; Xiao et al., 2010, 2013; Su et al., 2012).
As a consequence, the chemistry of orthopyroxene and clinopy-
roxene in peridotites is sensitive to carbonatite metasomatism.
Carbonatite metasomatism would increase CaO and Na2 O con-
tents and decrease MgO content in orthopyroxene due to the
contrasting contents of these oxides between orthopyroxene and
carbonatite melt (e.g., Yaxley et al., 1991; Sweeney et al., 1995;
Su et al., 2012). The equilibrated and small inter-mineral Mg
fractionation between the orthopyroxene and olivine in all stud-
ied samples (Fig. 3a) suggests that these two phases retain their
Mg isotopic compositions during carbonatite metasomatism, most
likely due to their high MgO contents. The clinopyroxene is equi-
librated with the coexisting orthopyroxene and olivine and has
82 B.-X. Su et al. / Earth and Planetary Science Letters 522 (2019) 79–86

Fig. 3. Correlations of inter-mineral fractionations (Opx–Ol, Cpx–Ol and Sp–Ol) with 106 /T2 (T in K). Error bars represent error propagation for calculated 26 Mg. The
theoretically calculated lines of equilibrium fractionation (Schauble, 2011) are plotted for comparison.

Fig. 4. Clinopyroxene δ 26 Mg with MgO (a) and Na2 O (b) of orthopyroxene and Mg# (c) and FeO (d) of clinopyroxene in carbonatite-metasomatized peridotite xenoliths from
Mingxi, Haoti and Dayishan. Error bars represent analytical uncertainties (2SD).

overall highly variable δ 26 Mg values compared to orthopyroxene
and olivine (Figs. 2, 3b). Furthermore, δ 26 Mg increases with Mg#
and decreases with FeO content in clinopyroxene, which might
reflect their crystallization and growth with variable degrees of
carbonatite metasomatism (Fig. 4c, d). In particular, the clinopy-
roxene δ 26 Mg also correlates with other carbonatite metasomatic
indices such as MgO and Na2 O contents in orthopyroxene (Fig. 4a,
b). These trends thus indicate that in the early stage of metaso-
matism, Mg isotopic compositions of clinopyroxene were mainly
inherited from carbonatite melts, and the role of orthopyroxene
became dominant as metasomatism progressed. The δ 26 Mg values
of spinel, garnet and newly-formed phlogopite display large varia-
tions (Figs. 2, 3c) and appear to have been modified by carbonatite
melts.
5.2. Carbonatite-metasomatized peridotites and carbonatite magmas
The melts involved in mantle carbonatite metasomatism are
generally considered as carbonatite magmas (e.g., Rudnick et al.,
1993; Coltorti et al., 1999). Results of the carbonatite-metasoma-
tized peridotite xenoliths in this study are consistent with the
positive δ 26 Mg signatures of natrocarbonatites (Li et al., 2016b)
and some calciocarbonatites (Ling et al., 2013; Cheng et al., 2017)
reported so far. Binary mixing calculations indicate that Mg iso-
topic variations of the studied peridotites are attributed to over-
all <12% natrocarbonatite and a maximum involvement of 20%
isotopically heavy calciocarbonatite (Fig. 5), which are consistent
with the estimates (mostly <20%) from Ti/Eu and La/Yb ratios
of clinopyroxenes in the peridotites (Fig. 1b) and with the gen-
eral estimates (<12%) from harzburgite to wehrlite during car-
 B.-X. Su et al. / Earth and Planetary Science Letters 522 (2019) 79–86
Fig. 5. Binary mixing calculations for Mg isotopic variations of mantle peridotites
metasomatized by different types of carbonatites by using their highest or lowest
δ 26 Mg values in Fig. 2. Initial harzburgite is assumed to have MgO content of 46
wt.% (Yaxley et al., 1998) and δ 26 Mg of −0.25h. The studied peridotites are also
shown for comparison. Calculated results are available in Supplementary Table S3.
bonatite metasomatism (Rudnick et al., 1993; Yaxley et al., 1998).
Magnesiocarbonatites and some calciocarbonatites have normal
mantle-like or lower δ 26 Mg values (Fig. 2; Ling et al., 2013;
Cheng et al., 2017) and cannot account for the isotopic compo-
sitions of the studied peridotites.
The above interpretation also provides a possible explanation
on the rare occurrence of alkali-rich natrocarbonatite. Carbonatite
worldwide is dominated by Ca (calcite)- or Mg (dolomite)-rich
magmatic carbonates, with much less alkali-rich natrocarbonatite
(Woolley and Kjarsgaard, 2008). However, recent studies suggest
that alkali-enriched carbonatite melts should have been more
prevalent than those preserved in the geological record, and their
rare occurrence might be due to the loss of their original alka-
lis during ascent (Chen et al., 2013; Guzmics et al., 2015). Our
study here indicates that the alkali components are mainly con-
sumed by mantle metasomatism, as supported by the Na2 O enrich-
ment of clinopyroxene (up to 2.0 wt.%; Supplementary Table S1),
which implies the initial enrichments of alkaline components. Py-
roxenes, particularly clinopyroxene as metasomatic products, tend
to take up heavy Mg isotopes compared to carbonatite melts. The
loss of isotopically heavy alkali-rich components could produce
the alkali-poor and isotopically light carbonatite melts (Schauble,
2011; Macris et al., 2013). Therefore, carbonatite metasomatism,
which occurred at depth of 60-100 km (Xu et al., 2003; Zhang
et al., 2011; Su et al., 2012), leads to the formation of slightly
heavy Mg isotopic composition of carbonated peridotites, and at
the same time, produces the alkali-poor and isotopically light car-
bonatite melts. When the residual carbonatite melts ascended,
silicate-carbonatite liquid immiscibility would occur, which further
shifted the residual carbonatite melts towards light isotopic com-
positions (Li et al., 2016b), as observed in magnesiocarbonatites
and some calciocarbonatites (Fig. 2).
5.3. Origins of mantle-derived low-δ 26 Mg lavas: chromite
crystallization
Increasing reports of light Mg isotopic signatures in continental
basalts, eclogites and pyroxenites (Fig. 2) point towards spatial Mg
isotope variability in Earth’s mantle. These isotopically light fea-
tures cannot be attributed to silicate metasomatism because the
high MgO content of the mantle cannot be altered by basaltic
magmas characterized by their low MgO and identical δ 26 Mg to
the mantle. Alternatively, recycled sedimentary carbonate has been
invoked in a variety of ways, such as metasomatizing mantle peri-
dotite sources of continental basalts (e.g., Yang et al., 2012; Li et
83
al., 2016a), carbonate-silicate interaction during subduction (e.g.,
Wang et al., 2012, 2014; Tao et al., 2018), and interaction/mixing
of partial melts from carbonated eclogite with mantle peridotite
(e.g., Sun et al., 2017). The carbonatite-metasomatized peridotites
studied here cannot be the source of isotopically light continen-
tal basalts because of their overall high instead of low δ 26 Mg
values. Peridotites metasomatized by isotopically light calciocar-
bonatite or magnesiocarbonatite melts could shift their δ 26 Mg to
lower values, nonetheless, >20% of calciocarbonatite or >40% of
magnesiocarbonatite melts would be required (Fig. 5). The exist-
ing dataset reveals that carbonated eclogite and pyroxenite (Fig. 2)
may account for the direct sources of the low-δ 26 Mg continen-
tal basalts. However, the rarity and small amount of such car-
bonated eclogite and pyroxenite in the mantle cannot generate
widespread and large volumes of intra-continental basalts such as
those present in East Asia (e.g., Huang et al., 2015; Su et al., 2017a;
Sun et al., 2017).
Here we propose that crystallization of oxides, in particular
chromite, is an important process responsible for producing the
isotopically light continental basalts. Alkaline basaltic magmas are
normally low degree partial melting products of the mantle and
may experience oxide (chromite/spinel, ilmenite and magnetite)
fractional crystallization during their ascent (e.g., Kamenetsky et
al., 2001; Kumar and Rathna, 2014). The oxide crystallization re-
sults in low oxygen fugacity and depletions in Fe and enrich-
ment in Ti contents in magmas (Hill and Roeder, 1974; Toplis
and Carroll, 1995). Ilmenite is commonly present at the late stage
of magma solidification and contains low MgO contents (mostly
<4.0 wt.%; Chen et al., 2018). Hence, fractional crystallization
and accumulation of ilmenite, though isotopically heterogeneous
(Sedaghatpour et al., 2013; Chen et al., 2018; Sedaghatpour and
Jacobsen, 2019), will unlikely produce a significant effect on Mg
isotopic composition of evolving magmas. Chromite, on the other
hand, is an early crystallization phase in basaltic magmas and is
Mg-rich (MgO contents >10 wt.%) and isotopically heavier (δ 26 Mg
= −0.10 to 0.40h) than silicate minerals (Xiao et al., 2016;
Su et al., 2017b). Crystallization of chromite thus has the potential
to modify Mg isotopic compositions of magmas. The correlations
of δ 26 Mg with Cr, V, Fe and Ti contents (Fig. 6) in basalts strongly
indicate a causal relationship of increasingly light Mg isotopic
compositions of evolving magmas and fractional crystallization of
chromite. Modeling results using MELTS program and Rayleigh
fractionation with average chromite-melt fractionation factors of
δ 26 Mgchromite-melt of 0.2h and 0.4h demonstrate that a max-
imum of 7% and 4% chromite fractionation could result in the
δ 26 Mg values of these continental basalts (Fig. 6d).
The extent of chromite crystallization is highly variable, de-
creasing from boninites and arc tholeiites, to mid-ocean ridge
basalts (MORBs) and oceanic island basalts (OIBs), then to back-
arc basalts (e.g., Dick and Bullen, 1984). Both MORBs and OIBs do
not exhibit correlations between δ 26 Mg values and their Cr, V or
TiO2 contents (Fig. 6). This can be explained by the thin oceanic
lithosphere and typically low oxygen fugacity, which is different
from their continental counterparts and does not favor significant
fractional crystallization and accumulation of chromite. The large
variations of Cr, V and TiO2 contents in MORBs and OIBs instead
reflect variable degrees of partial melting in the mantle sources
(e.g., Hofmann, 2003), and their restricted, identical δ 26 Mg range
suggests that partial melting does not result in significant Mg iso-
tope fractionation.
Our study suggests chromite crystallization can control Mg iso-
topic composition of continental basalts, hence needs to be con-
sidered before using Mg isotopic systems of continental basalts to
trace mantle Mg isotopic heterogeneity and global carbon cycle. In-
stead, Mg isotopes are great indicators of fractional crystallization
of chromite during the evolution of continental magmas. Further-
84 B.-X. Su et al. / Earth and Planetary Science Letters 522 (2019) 79–86

Fig. 6. δ 26 Mg with (a) Cr, (b) V, (c) FeO and (d) TiO2 contents of the continental basalts reported in Yang et al. (2012), Huang et al. (2015), Tian et al. (2016), Su et al. (2017a)
and Sun et al. (2017) and MORBs and OIBs in Bourdon et al. (2010) and Teng et al. (2010). Error bars represent analytical uncertainties (2SD). The Cr, V, FeO and TiO2 contents
in basalts are indicators of chromite crystallization as Cr, V and Fe are compatible while Ti is incompatible in chromite (e.g., Zhou et al., 2014; Su et al., 2019). Modeling of Mg
isotopic variations during fractional crystallization of chromite from basaltic melt is shown in Fig. 6d. Red and blue solid lines represent calculated Mg isotopic compositions
of residual melts by assuming a Rayleigh distillation process. Proportions (percentage numbers in diagram) of chromite crystallized from the melts and TiO2 contents of
the residual melts are modeled using MELTS, where sample 08NM-4 (Sun et al., 2017) having higher MgO content (16.37 wt.%) among the continental basalts was used as
compositions of the initial melt. The equation that governs isotopic fractionation in a Rayleigh distillation process is: δ 26 Mgmelt = (δ 26 Mg0 + 1000) f (α −1) − 1000 where F
is the fraction of melts remaining and is calculated from MELTS. The δ 26 Mg0 is the initial Mg isotope of melts, which is consistent with the average Mg isotopes of mantle
peridotite. The fraction of Mg remaining in the melt is f = (F × Cmelt )/C0 , where Cmelt and C0 represent the MgO concentration in the remaining melts and the initial melts.
The fractionation factor α is calculated by (26 Mg/24 Mg)crystal /(26 Mg/24 Mg)melt , and the average crystal-melt fractionation factors (26 Mgcrystal-melt = δ 26 Mgcrystal -δ 26 Mgmelt )
vary from 0.2h for magnesiochromite to 0.4h for spinel. Modeling and calculation results are shown in Supplementary Table S4.

more, chromite fractionation plays an important role to the petro-
genesis of continental basalts in addition to source heterogeneity,
crustal assimilation and fractional crystallization of silicates. Hence,
elemental and isotopic compositions as well as oxygen fugacity of
continental basalts, at least those can be affected by chromite crys-
tallization, do not necessarily reflect their mantle sources.
6. Conclusions
The main conclusions to be drawn from the high-precision Mg
isotopic analyses of typically carbonatite-metasomatized peridotite
from Mingxi, Haoti and Dayishan localities are:
(1) The δ 26 Mg values of minerals in the studied xenoliths range
from −0.32 to −0.11h in olivine, from −0.28 to −0.09h in or-
thopyroxene, from −0.27 to −0.05h in clinopyroxene, from 0.06
to 0.44h in spinel and −0.61 to −0.37h in garnet. The coexisting
minerals are in isotopic equilibrium.
(2) Calculated bulk-rock δ 26 Mg values of the peridotites vary
from −0.27 to −0.10h. Interactions with carbonatite melts can
slightly elevate the δ 26 Mg of the major minerals of the mantle
peridotite. Thus, these carbonatite-metasomatized peridotites can-
not be the source rocks of low-δ 26 Mg mantle-derived magmas.
(3) The fate of recycled sedimentary carbonate in the man-
tle cannot be directly linked to carbonatite magmas through
carbonatite-metasomatized peridotite and Mg isotope systemat-
ics. Isotopically heavy carbonatite melts that are enriched in alkali
component were consumed by mantle metasomatism, resulting in
their rare occurrences.
(4) Covariations of δ 26 Mg with chemical indices of chromite
crystallization suggest that fractional crystallization and accumula-
tion of chromite play an important role in Mg isotope fractionation
during basaltic magma evolution and may have significantly in-
fluenced the physiochemical processes on the genesis of basalts,
which would require comprehensive evaluation in future studies.
Acknowledgements
We appreciate Frederic Moynier, Martin Schiller and another
anonymous reviewer for their constructive comments, which sig-
nificantly improved the manuscript. This study was financially
supported by the National Key Research and Development Pro-
gram of China (2017YFC0601306) and the National Natural Science
Foundation of China (Grants 41673037, 41688103, 41729001 and
91755205).
Appendix A. Supplementary material
Supplementary material related to this article can be found on-
line at https://doi.org/10.1016/j.epsl.2019.06.016.
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