Lithos 304–307 (2018) 95–108
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Lithos
j ourna l homepage: www.e lsev ie r .com/ locate / l i thosOrigin of sapphirine- and garnet-bearing clinopyroxenite xenoliths
entrained in the Jiande basalts, SE ChinaYan Xiao a,⁎, Hong-Fu Zhang a,b, Zi Liang a,c, Ben-Xun Su c,d, Bin Zhu a, Patrick Asamoah Sakyi e
a State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
b State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Xi'an 710069, China
c University of Chinese Academy of Sciences, Beijing 100049, China
d Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
e Department of Earth Science, University of Ghana, PO Box LG 58, Legon-Accra, Ghana⁎ Corresponding author.
E-mail address: xiaoyan@mail.iggcas.ac.cn (Y. Xiao).
https://doi.org/10.1016/j.lithos.2018.02.004
0024-4937/© 2018 Elsevier B.V. All rights reserved.a b s t r a c ta r t i c l e i n f oArticle history:
Received 15 August 2017
Accepted 3 February 2018
Available online 07 February 2018We present petrological and geochemical data of sapphirine- and garnet-bearing clinopyroxenite xenoliths
entrained in the Jiande Cenozoic basalts, SE China, to investigate their igneous andmetamorphic history, and re-
construct of the thermal-tectonic evolution of the lithospheric mantle. These xenoliths have an unusual mineral
association consisting of clinopyroxene + garnet/kelyphite + spinel (±sapphirine). Clinopyroxene has high
Mg# (89–93) and displays convex-upward REE pattern. Garnet, partially to completely kelyphitized, is rich in py-
rope end-member. It usually includes relics of spinel, suggesting that garnetwas formed at the expense of spinel.
The spinel has highMgO (20.8–22.9 wt%) and Al2O3 (64.8–67.9 wt%) contents. Sapphirine, forming a rim on spi-
nel, has homogeneous SiO2 (14.5–14.9 wt%), Al2O3 (60.9–61.7 wt%) and MgO (19.7–20.1 wt%) contents,
interpreted to be ofmetamorphic origin. The subsolidus reaction for the formation of sapphirine is as follows: spi-
nel + garnet = sapphirine + clinopyroxene + orthopyroxene. Thus, the earliest mineral assemblage recorded
in these xenoliths was spinel + clinopyroxene. The clinopyroxene in the Jiande clinopyroxenite xenoliths has
Li abundances (1.04–1.63 ppm) similar to high-P mafic cumulate but much lower than those in crustal eclogite.
In addition, the clinopyroxene and garnet do not show positive Eu anomalies. Therefore, the protolith of these
three clinopyroxenite xenoliths was most likely a pyroxenite, originating as clinopyroxene + spinel cumulates
frommaficmelts percolating through themantle.Many reaction textures such as formation of garnet and sapphi-
rinewere developed during decompression possibly coupledwith cooling andmelt percolation. During this pro-
cess, the earlier composition of clinopyroxene and spinel also changed. The latest P-T conditions recorded in
these xenoliths were at pressure of 8–10 kbar and temperatures of 1069–1094 °C. These observations imply
that these rocks have been tectonically uplifted to shallower levels. The uplift process may have been related
to lithospheric thinning process accompanied by lithosphere extension and upwelling of the asthenosphere in
eastern China.
© 2018 Elsevier B.V. All rights reserved.Keywords:
Sapphirine
Clinopyroxenite xenolith
Li abundances
Uplift
Lithospheric mantle1. Introduction
Sapphirine is a relatively rare mineral and occurs mostly in Mg- and
Al-rich and Ca-poor rocks from several high-temperature granulite ter-
ranes, which have been experienced high-grade regional metamorphism
(Galli et al., 2011; Jiao et al., 2015; Jiao and Guo, 2011; Lal et al., 1987;
Okay, 1994; Santosh et al., 2007, 2009). Sapphirine is commonly associ-
ated with orthopyroxene, cordierite and sillimanite. However, experi-
mental studies suggest that sapphirine could be stable under upper-
mantle conditions, if appropriate bulk compositions are available(Ackermand et al., 1975).Mantle-derived sapphirine has, to date, been re-
ported the following localities: (1) pyroxenite xenoliths from kimberlites
in Stockdale, Kansas (Meyer and Brookins, 1976), (2) basaltic breccia
pipes in Delegate, New South Wales, Australia (Griffin and O'Reilly,
1986), (3) basalts inHannuoba, easternChina (Su et al., 2012), (4) basaltic
lavas in Tel Thanoun, Syria rift (Bilal, 2016), (5) garnet clinopyroxenites
from the Beni Bousera massif, Morocco (Kornprobst et al., 1990), (6) the
Ronda peridotite massif, Spain (Morishita et al., 2001) and (7) the Finero
phlogopite-peridotite massif, Italy (Giovanardi et al., 2013). Mantle-
derived sapphirine usually coexists with clinopyroxene and has a limited
stability field of about 8 to 15 kbar and at 800 to 900 °C in the pyroxenite
stability field (Su et al., 2012). Previous studies have shown that sapphi-
rine occurs either as rim on spinel or as elongated lamella intergrowth
with clinopyroxene in garnet-clinopyroxene granulite and eclogite
96 Y. Xiao et al. / Lithos 304–307 (2018) 95–108
Fig. 1. Simplified geological map showing major tectonic units and xenolith location in eastern China (modified after Huang and Xu, 2010).
Y. Xiao et al. / Lithos 304–307 (2018) 95–108 97xenolith (Griffin andO'Reilly, 1986;Meyer andBrookins, 1976). It also oc-
curs as rim on spinel in spinel pyroxenites (Su et al., 2012; Bilal, 2016).
This paper focuses on newly discovered clinopyroxenite xenoliths
from Jiande Cenozoic basalts in Zhejiang Province, SE China.
These xenoliths have an unusual mineral association consisting of
clinopyroxene + garnet/kelyphite + spinel (±sapphirine). We carry
out petrological and geochemical studies for these clinopyroxenite xeno-
liths, determine their P-T conditions and compare them with other
sapphirine-bearing mafic rocks worldwide. These new findings have
been used to constrain the origin of sapphirine and the nature of
clinopyroxenite, to further constrain their thermal history and possible
connection with the evolution of the SE China lithosphere.
2. Geological setting and sample description
Eastern China has been divided into three tectonic blocks, namely;
the Xing-Meng Block, the North China Craton and the South China
Block. The South China Block consists of two major blocks, with the
Yangtze block to the northwest and the Cathaysia block to the southeast
(Fig. 1). In the Cathaysia Block, the late Neoproterozoic to Phanerozoic
sedimentary rocks and Paleozoic to Mesozoic igneous rocks are widely
distributed (Li et al., 2014). Outcrops of pre-Neoproterozoic basement
rocks are rare, and the oldest rocks are the Late Paleoproterozoic igne-
ous and metamorphic rocks in the northeastern part of the Cathaysia
block (Li et al., 2012; Liu et al., 2009; Xia et al., 2012; Yu et al., 2010).
There is no Archean rock exposed in the Cathaysia block, although Ar-
chean detrital and/or xenocrystal zircons are founded in various rocks
(Li et al., 2014). Cenozoic basaltic rocks are widely distributed from
north to south in the Cathaysia block, i.e., the Zhejiang, Fujian, Guang-
dong and Hainan provinces, and contain a wide variety of deep-seated
xenoliths (Zhang and Cong, 1987; Fig. 1). In the Zhejiang Province, Ce-
nozoic volcanism is distributed in the Xinchang, Xilong and Jiande fields
and host abundant peridotite xenoliths such as spinel lherzolite and
garnet lherzolite (Hao et al., 2014; Liu et al., 2012; Lu et al., 2015; Xiao
et al., 2017; Fig. 1). Based on Ar-Ar data, Ho et al. (2003) suggested
that the Cenozoic basaltic eruptions in the Zhejiang Province occurred
in two stages, namely; (1) 26.4–15.6 Ma, which is mainly composed of
basanites and nephelinites, and (2) 10.5–2.5 Ma, which dominantly
comprises alkali basalts and tholeiites.
In this study, three scarce clinopyroxenite xenoliths were collected
from the Jiande basalts. They are large in size (~15 cm in diameter)Table 1
Mineral modal abundance (vol%) andmajor element data (wt%) of Jiande clinopyroxenite
xenoliths.
Sample SZZ12-02 SZZ12-09 SZZ12-14
Rock type Clinopyroxenite Clinopyroxenite Clinopyroxenite
Modes Cpxa 65.0 68.0 79.0
Grt 22.0 17.0 16.0
Spl 10.0 11.5 5.00
Spr 3.00 3.00 0.00
Pl 0 0.5 0
Major element SiO2 39.5 41.1 45.6
TiO2 0.10 0.17 0.21
Al2O3 21.6 21.2 13.5
TFe2O3 4.26 4.66 5.96
MnO 0.07 0.08 0.14
MgO 15.5 15.5 15.2
CaO 15.2 14.3 15.9
Na2O 0.87 0.90 0.82
K2O 0.26 0.20 0.11
P2O5 0.01 0.10 0.20
Cr2O3 0.18 0.22 0.16
NiO 0.10 0.06 0.03
LOI 1.92 1.02 1.62
Total 99.5 99.5 99.4
Mg# 87.9 86.9 83.6
a Grt, garnet; Cpx, clinopyroxene; Spl, spinel; Pl, plagioclase.and gray-green in color. These xenoliths have a granuloblastic meta-
morphic texture with clinopyroxene (65–79%), garnet/kelyphite (16–
22%) and spinel (5–11.5%) as the major phases, two of which contain
sapphirine (0–3%) (Table 1; Figs. 2 and 3).
In two sapphirine-bearing clinopyroxenite xenoliths, clinopyroxene
crystal is 3.0–4.0 mm in size and does not show detectable zoning on
BSE images. The garnet typically forms large grains and is partially or
completely replaced by an extremely fine-grained, symplectitic
“kelyphite”, consisting of orthopyroxene, plagioclase and spinel (Figs. 2
and 3a-d). Themicrostructure of kelyphite is characterized by the occur-
rence of small elongated patches of plagioclase enclosed in much larger
crystals of orthopyroxene, and thin vermicular lamellae of spinel (2e,
f). Spinel occurs as rounded grain in the kelyphite (or clinopyroxene)
or at the contact between the clinopyroxene and kelyphite (Figs. 2b–f
and 3b–d). Sapphirine is anhedral and usually occurs as a rim on spinel
(Figs. 2b-f and 3b-d). The boundary of sapphirine and spinel is sharp
(Fig. 4). Plagioclase is polygonal and occurs as an accessory mineral
(0.5%) in one xenolith (Sample SZZ12-09; Table 1 and Fig. 3b).
The mineral assemblage in the other sapphirine-free clinopyroxenite
is clinopyroxene + garnet + spinel with the clinopyroxene typically
showing sieve-textured rims, the garnet completely kelyphitized, and
the spinel, as the core of kelyphite, generally rounded and 0.5–1.0 mm
in size (Fig. 3e and f).
3. Analytical method
3.1. Elemental mapping and energy dispersive spectrometry
Elemental mapping and energy dispersive spectrometry were ana-
lyzed by SEM on a FEI NOVA nano450 scanning electron microscope at
the Institute of Geology and Geophysics (IGG), Chinese Academy of Sci-
ences. They were obtained at 15 kV accelerating voltage and 3.5 nA
beam current.
3.2. Major element analysis of whole rocks
Major element analysis was carried out using a Phillips PW 2400 se-
quential X-ray fluorescence spectrometer (XRF) instrument at the IGG,
Chinese Academy of Sciences. The samples were powdered with an
agate mill to 200 mesh and 0.5 g powder was mixed with 5 g Li2B4O7.
A glass bead was formed by fusion.
3.3. Major element analysis of minerals
Major element compositions of minerals were obtained by
wavelength-dispersive spectrometry using JEOL JXA8100 electron
probe micro analyzer operating at an accelerating voltage of 15 kV,
beam current of 10 nA, 5 μm beam spot and 10–30 s counting time on
peak. The spot size is 5 μm. The precisions of all analyzed elements are
better than 1.5%. The analysis was carried out at the IGG, Chinese
Academy of Sciences.
3.4. In-situ trace element analysis of minerals
Trace elements of clinopyroxene were analyzed using a laser abla-
tion inductively coupled plasma mass spectrometer at the State Key
Laboratory of Geological Processes and Mineral Resources, China Uni-
versity of Geosciences, Wuhan. The detailed description of the method
has been given in Liu et al. (2008). Laser sampling was performed
using an ArF excimer laser ablation system (193 nm wavelength),
which was connected to an Agilent 7500a ICP-MS instrument with a
1 m transfer tube. A spot size of 60 μm and a repetition rate of 8 Hz
were used during the analyses. The NIST SRM 610 glass standard was
used as an external calibration standard.
98 Y. Xiao et al. / Lithos 304–307 (2018) 95–108
Fig. 2. Photomicrograph of thin section (a) and backscattered electron images of sapphirine (Spr)-bearing clinopyroxenite sample SZZ12-02 (b–f). Garnet (Grt) is partially to completely
replaced by kelyphite (b–f). Spinel (Spl) occurs either as inclusions in kelyphite (b) or as discrete grains between adjacent minerals (c, d; clinopyroxene (Cpx) and garnet). Sapphirine
(Spr) is anhedral and always surround spinel (b–d). Vermicular intergrowths of plagioclase (dark gray patches), orthopyroxene (light gray background) and spinel (f).3.5. In-situ lithium (Li) isotopic analysis of clinopyroxene
In-situ Li contents and isotopic compositions of clinopyroxene on
thin sections were performed on Cameca IMS-1280 SIMS at IGG,
Chinese Academy of Sciences, following the established methods
(Su et al., 2015; Zhang et al., 2010). Sampleswere sputteredwith O-pri-
mary ion beam at 13 kV and an intensity of about 15 to 30 nA. The
spot was approximately 20 × 30 μm in size. The Li isotopic
compositions are expressed as δ7Li relative to the NIST L-SVEC standard
{δ7Li = [(7Li/6Li) 7sample / ( Li/6Li)L-SVEC − 1] × 1000}. Clinopyroxene of
the peridotite samples 06JY29 and 06JY31 were analyzed multiple times
for accuracy check during the course of the analysis and yielded anaverage δ7Li value of −2.56± 0.70 (n=4) and −2.37± 0.48 (n=6),
respectively, consistent with the recommended values (Su et al., 2015).
4. Results
Mineral modal abundance and bulk composition of the Jiande
clinopyroxenite xenoliths are reported in Table 1. Representative elec-
tron microprobe analyses of their minerals are reported in Table 2. Re-
sults of in-situ trace element data of clinopyroxene and kelyphite from
the Jiande and Hannuoba clinopyroxenite xenoliths are reported in
Table 3. In-situ Li isotope analysis of clinopyroxene from Jiande
clinopyroxenite xenoliths are reported in Table 4. The temperature
Y. Xiao et al. / Lithos 304–307 (2018) 95–108 99
Fig. 3. Photomicrographs of thin section (a, e) and backscattered electron images of sapphirine-bearing clinopyroxenite sample SZZ12-09 and SZZ12-14 (b, c, d and f). Plagioclase (Pl)
commonly occurs along the grain boundaries of clinopyroxene and garnet (b). Garnet is partially to completely replaced by kelyphite (b, c, d and f). Spinel occurs either as inclusions
in kelyphite or as discrete grains between adjacent minerals (b, c, d and f; clinopyroxene and garnet). Sapphirine is anhedral and surround spinel (c).and pressure estimates based on different geothermobarometers are
provided in Table 5.
4.1. Whole-rock major element composition
The three Jiande clinopyroxenite xenoliths have different bulk chem-
ical compositions (Table 1). The two sapphirine-bearing clinopyroxenite
xenoliths are rich in Al2O3 (21.2–21.6 wt%) and poor in SiO2 (39.5–41.1
wt%), similar to the sapphirine-bearing clinopyroxenite xenolith from
Hannuoba basalts and sapphirine-bearing garnet pyroxenites from
Ronda peridotite massif (Fig. 5; Morishita et al., 2001; Su et al., 2012).
The other sapphirine-free clinopyroxenite has lower Al2O3 (13.5 wt%),Mg# (83.6) and higher SiO2 (45.6 wt%) than the two sapphirine-
bearing clinopyroxenite samples (Fig. 5 and Table 1).
4.2. Mineral chemistry
4.2.1. Clinopyroxene
Clinopyroxene from the Jiande clinopyroxenite xenoliths
has restricted Al2O3 (10.5–11.5 wt%), CaO (22.3–22.6 wt%), TiO2
(0.20–0.27 wt%) contents, and Mg# (89–93) and can be named as alu-
minous diopside (Morimoto, 1989; Table 2). These clinopyroxenes are
similar to those in sapphirine-bearing pyroxenites worldwide and gar-
net pyroxenites from the Ronda peridotite massif, but different from
100 Y. Xiao et al. / Lithos 304–307 (2018) 95–108
SZZ12-02 Cpx
Spl
Spr
Kelyphite
Fig. 4. Backscattered electron images (a) and elemental mapping (b-d) of sapphirine-spinel association.those in sapphirine-bearing granulites worldwide (Fig. 6a; Arima and
Barnett, 1984; Christy, 1989; Gregoire et al., 2001; Griffin and O'Reilly,
1986; Kornprobst et al., 1990; Lal, 1997; Lal et al., 1987; Morishita
et al., 2001, 2009; Okay, 1994; Sutherland et al., 2003).
4.2.2. Garnet/kelyphite
Most garnets in these three clinopyroxenite xenoliths are replaced by
kelyphites, although rare fresh relic garnets have been observed in the
two sapphirine-bearing clinopyroxenite xenoliths (Figs. 2b and 3d).
These kelyphites still possess bulk chemical composition almost identical
to that of garnets, with only few analyses on the kelyphite rim yielding
lower CaO content (Table 2). The garnet/kelyphite is rich in pyrope
end-member (pyrope: 62.5–71.4, almandine: 13.4–19.5, grossular:
16.0–18.0) and shows narrow Al2O3 (22.7–24.1 wt%), CaO (5.68–8.16
wt%) and TiO2 (0–0.08 wt%) contents (Table 2). These features are simi-
lar to those in garnet pyroxenites from Hannuoba (Hu et al., 2016) and
Ronda (Fig. 6b; Morishita et al., 2009). Their CaO and Cr2O3 contents
mostly fall within the websteritic field (Fig. 6b; Sobolev et al., 1973).
4.2.3. Spinel
Spinel from the Jiande clinopyroxenite xenoliths is magnesian and
aluminous (MgO: 20.8–22.9 wt%; Al2O3: 64.8–67.9 wt%) with low
Cr2O3 (0.93–1.99 wt%) and TiO2 (b0.02 wt%) contents (Table 2). It falls
within the field of pyroxenite xenoliths in eastern China (Hu et al.,
2016; Su et al., 2012; Xu et al., 1996; Yu et al., 2003), but different
from those in sapphirine-bearing granulites and khondalite (Fig. 6c;
Arima and Barnett, 1984; Christy, 1989; Griffin and O'Reilly, 1986; Jiao
et al., 2015; Lal, 1997; Lal et al., 1987; Santosh et al., 2007; Sutherland
et al., 2003).
4.2.4. Sapphirine
Sapphirine from two Jiande clinopyroxenite xenoliths has narrow
compositional ranges in SiO2 (14.5–14.9 wt%), Al2O3 (60.9–61.7 wt%),
MgO (19.7–20.1 wt%), FeO (2.41–2.73 wt%) and Cr2O3 (0.44–0.96 wt%)
(Table 2). It has a general formula of (Mg3.48Fe IV0.26Ni0.01)
(Al VI8.48Cr0.05) Si1.72O20 (Table 2), which shows higher MgO and
Cr2O3 than those from pyroxenites, granulites and khondalite world-
wide (Fig. 6d; Arima and Barnett, 1984; Christy, 1989; Gregoire et al.,
2001; Griffin and O'Reilly, 1986; Jiao et al., 2015; Kornprobst et al.,1990; Lal, 1997; Lal et al., 1987; Morishita et al., 2001; Okay, 1994;
Santosh et al., 2007; Su et al., 2012; Sutherland et al., 2003).
4.3. Trace element compositions of clinopyroxene and kelyphite
Clinopyroxene is homogeneous within and between grains in the
Jiande clinopyroxenite xenoliths and displays a convex-upward REE pat-
tern (Fig. 7a). The depletion of HREE in clinopyroxene may be due to
partitioning into co-existing garnet. However, clinopyroxene from the
Hannuoba sapphirine-bearing clinopyroxenite xenolith displays an al-
most flat REE pattern (Fig. 7a). Notably, their trace element patterns
are similar, showing negative anomalies of the HFSE (i.e., Zr, Nb, Y and
Ti; Fig. 7b). Different from garnet pyroxenites from the Ronda,
sapphirine-bearing clinopyroxenite xenoliths from Jiande andHannuoba
do not show positive Eu-Sr anomalies (Fig. 6a, b; Morishita et al., 2009).
Kelyphite in the Jiande clinopyroxenite xenoliths is characterized by
LREE-depleted pattern (Fig. 7c). In primitive mantle-normalized trace
element diagrams, it has a remarkable positive U anomaly and negative
Ti and Y anomalies without positive Eu and negative Sr anomalies
(Fig. 7d).
4.4. The Li isotopic composition of clinopyroxene
Clinopyroxene in the Jiande clinopyroxenite xenoliths shows homo-
geneous Li abundances (1.04–1.63 ppm),much lower than those in gar-
net pyroxenites from Hannuoba (1.61–79.8 ppm) and Ronda (10–20
ppm), and crustal ecolgites (N8.6 ppm) (Fig. 8a, b and Table 4;
Morishita et al., 2009; Su et al., 2014; Woodland et al., 2002). The δ7Li
value (−3.31 to −12.19‰) of clinopyroxene is also lower than that of
the normal mantle (2–6‰; Tomascak et al., 2008) and those in
Hannuoba pyroxenites (−5.7–13.2‰; Fig. 8b and Table 4; Su et al.,
2014).
4.5. Temperature and pressure estimates
Equilibrium partitioning of Mg-Fe between clinopyroxene and
kelyphite, as indicated by the 1:1 linear correlations between the Mg#
of these two minerals (not shown), permits temperature estimates for
the Jiande clinopyroxenite xenoliths. Temperatures estimated using
three different garnet-clinopyroxene Fe-Mg thermometers fall within
Y. Xiao et al. / Lithos 304–307 (2018) 95–108 101
Table 2
Representative chemical composition of minerals in Jiande clinopyroxenite xenoliths (wt%).
Sample SZZ12-02 SZZ12-02 SZZ1209
Mineral Cpx1a Cpx2 Cpx3 Grt1 Grt2 Grt3 Kelyphite1 Kelyphite2 Kelyphite3 Spl1 Spr1 Spl2 Spr2 Spl3 Spr3 Spl4 Spr4 Spl5 Spr5 Cpx1 Cpx2 Cpx3 Grt1 Grt2 Grt3
Core Mantle Rim in beside Core Spr Core Spr Core Spr Core Spr
Grt cpx rim rim rim rim
SiO2 49.3 49.5 49.1 43.0 42.7 42.9 43.3 42.6 42.7 43.3 42.1 0.00 14.8 0.00 14.7 0.00 14.5 0.00 14.6 0.00 14.5 48.9 49.9 49.1 42.5 42.7 42.4
TiO2 0.08 0.10 0.11 0.04 0.01 0.04 0.04 0.03 0.08 0.04 0.01 0.01 0.04 0.02 0.04 0.00 0.00 0.01 0.01 0.01 0.00 0.11 0.14 0.13 0.00 0.06 0.01
Al2O3 11.4 11.3 11.5 23.5 23.8 23.2 23.9 24.1 23.7 23.9 23.9 66.6 61.3 66.2 61.7 66.4 61.4 66.5 60.9 67.1 61.7 12.3 10.8 11.6 23.7 23.7 23.3
Cr2O3 0.26 0.31 0.23 0.17 0.20 0.20 0.15 0.18 0.18 0.15 0.18 1.87 0.96 1.99 0.70 1.35 0.86 1.56 0.68 1.52 0.70 0.26 0.26 0.26 0.18 0.18 0.15
FeO 1.99 1.86 1.92 7.11 7.10 6.87 6.77 6.90 6.94 6.77 6.86 7.06 2.55 7.12 2.48 7.17 2.41 7.20 2.56 7.18 2.57 2.16 1.88 1.84 7.36 7.42 7.48
MnO 0.04 0.03 0.06 0.22 0.21 0.21 0.18 0.20 0.20 0.18 0.18 0.02 0.03 0.03 0.01 0.01 0.00 0.05 0.00 0.02 0.05 0.06 0.06 0.00 0.22 0.28 0.26
MgO 13.7 13.8 13.7 20.5 20.5 20.5 20.0 20.1 20.7 20.0 19.9 22.8 20.0 22.8 19.8 22.8 19.9 22.9 19.8 22.5 20.1 13.2 13.7 13.3 20.0 20.1 19.8
CaO 22.3 22.2 22.2 6.32 6.35 6.44 6.31 6.30 5.82 6.31 6.16 0.00 0.06 0.00 0.05 0.00 0.09 0.00 0.04 0.00 0.07 22.2 22.7 22.7 6.35 6.54 6.54
Na2O 1.09 1.01 1.06 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 1.01 1.04 0.97 0.01 0.00 0.01
K2O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
NiO 0.03 0.03 0.05 0.00 0.02 0.02 0.00 0.00 0.01 0.00 0.01 0.38 0.15 0.41 0.14 0.38 0.14 0.36 0.15 0.34 0.12 0.01 0.01 0.05 0.00 0.00 0.00
Total 100 100 99.9 101 101 100 101 100 100 101 99.2 98.7 99.9 98.6 99.6 98.1 99.3 98.6 98.8 98.7 99.8 100 100 100.0 100 101 99.9
Mg# 92.5 93.0 92.8 83.8 83.9 84.3 84.2 84.0 84.3 84.2 83.9 85.3 93.4 85.2 93.5 85.1 93.7 85.1 93.3 84.9 93.4 91.7 92.9 92.9 83.0 82.9 82.6
O= 6 6 6 12 12 12 12 12 12 12 12 4 20 4 20 4 20 4 20 4 20 6 6 6 12 12 12
Si 1.777 1.784 1.777 3.013 2.991 3.018 3.032 2.995 3.001 3.033 2.994 0.000 1.727 0.000 1.718 0.000 1.702 0.000 1.721 0.000 1.699 1.764 1.795 1.776 2.997 2.997 3.007
Ti 0.002 0.003 0.003 0.002 0.001 0.002 0.002 0.002 0.004 0.002 0.001 0.000 0.003 0.000 0.004 0.000 0.000 0.000 0.001 0.000 0.000 0.003 0.004 0.004 0.000 0.003 0.001
Al 0.486 0.479 0.489 1.941 1.967 1.924 1.969 1.997 1.965 1.969 2.000 1.960 8.432 1.953 8.497 1.963 8.495 1.958 8.471 1.975 8.489 0.525 0.460 0.493 1.973 1.961 1.948
Cr 0.007 0.009 0.007 0.010 0.011 0.011 0.008 0.010 0.010 0.008 0.010 0.037 0.089 0.039 0.064 0.027 0.079 0.031 0.064 0.030 0.065 0.008 0.008 0.007 0.010 0.010 0.009
Fe2+ 0.060 0.056 0.058 0.416 0.416 0.405 0.396 0.405 0.408 0.396 0.408 0.144 0.249 0.141 0.242 0.140 0.237 0.140 0.252 0.150 0.251 0.065 0.057 0.056 0.434 0.436 0.444
Fe3+ 0.003 0.008 0.010 0.011 0.000
Mn 0.001 0.001 0.002 0.013 0.013 0.012 0.011 0.012 0.012 0.011 0.011 0.000 0.002 0.001 0.001 0.000 0.000 0.001 0.001 0.000 0.004 0.002 0.002 0.000 0.013 0.017 0.016
Mg 0.739 0.743 0.737 2.140 2.144 2.154 2.086 2.107 2.170 2.084 2.107 0.848 3.484 0.852 3.453 0.852 3.472 0.852 3.481 0.837 3.495 0.708 0.734 0.719 2.104 2.099 2.091
Ca 0.862 0.860 0.860 0.474 0.477 0.486 0.473 0.474 0.438 0.473 0.469 0.000 0.008 0.000 0.006 0.000 0.011 0.000 0.006 0.000 0.008 0.858 0.873 0.881 0.480 0.492 0.497
Na 0.076 0.071 0.075 0.000 0.000 0.000 0.000 0.000 0.001 0.000 0.000 0.000 0.004 0.000 0.000 0.000 0.001 0.000 0.000 0.000 0.002 0.071 0.072 0.068 0.001 0.000 0.002
K 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Ni 0.001 0.001 0.001 0.000 0.001 0.001 0.000 0.000 0.000 0.000 0.000 0.008 0.014 0.008 0.013 0.008 0.013 0.007 0.014 0.007 0.011 0.000 0.000 0.001 0.000 0.000 0.000
Total 4.012 4.004 4.008 8.009 8.018 8.012 7.977 8.001 8.008 7.976 8.000 3.000 13.998 2.995 13.985 2.997 13.998 3.000 13.996 2.991 14.025 4.003 4.003 4.003 8.012 8.014 8.014
(continued on next page)
102 Y. Xiao et al. / Lithos 304–307 (2018) 95–108
Table 2
RTaebplrees2en(ctaotnitvienucehde)mical composition of minerals in Jiande clinopyroxenite xenoliths (wt%).
Sample SZZ12-09 SZZ12-09 SZZ12-14
Mineral Kelyphite1 Kelyphite2 Kelyphite3 Spl1 Spl2 Spr2 Spl3 Spr3 Spr4 Pl1 Pl2 Pl3 Cpx1 Cpx2 Cpx3 Kelyphite1 Kelyphite2 Kelyphite3 Spl1 Spl2 Spl3
Core Rim in Core Spr Core Spr An-rich An-rich An-rich Core Mantle rim in in in
Grt rim rim Grt Grt Grt
SiO2 42.5 42.5 42.4 42.5 0.00 0.00 14.5 0.00 14.5 14.9 47.3 47.3 47.4 48.7 49.0 49.1 42.1 42.3 41.8 42.6 41.9 0.00 0.00 0.00
TiO2 0.05 0.03 0.04 0.00 0.00 0.00 0.03 0.01 0.01 0.00 0.01 0.00 0.00 0.17 0.18 0.17 0.03 0.02 0.06 0.00 0.02 0.00 0.04 0.02
Al2O3 24.0 23.8 24.0 24.1 66.9 67.2 60.6 67.9 61.7 61.8 33.5 33.8 33.4 11.5 10.4 11.5 23.5 24.1 22.7 23.6 23.4 64.8 65.3 65.6
Cr2O3 0.11 0.18 0.16 0.12 1.53 0.93 0.48 0.94 0.44 0.49 0.03 0.00 0.00 0.17 0.20 0.20 0.17 0.15 0.20 0.15 0.17 1.68 1.69 1.67
FeO 7.31 7.15 7.16 7.11 7.33 7.61 2.73 7.61 2.71 2.70 0.12 0.05 0.07 2.90 2.79 3.15 9.29 8.60 10.17 8.97 9.37 10.2 10.3 10.4
MnO 0.24 0.26 0.22 0.28 0.04 0.05 0.04 0.05 0.04 0.05 0.02 0.05 0.00 0.08 0.07 0.06 0.32 0.26 0.38 0.29 0.33 0.08 0.05 0.07
MgO 19.6 19.2 19.7 19.9 22.9 22.5 19.7 22.3 19.7 19.9 0.02 0.04 0.04 13.3 13.3 13.3 17.5 16.1 19.5 16.8 17.7 20.9 20.9 20.8
CaO 6.41 6.73 6.47 6.53 0.00 0.00 0.07 0.00 0.08 0.12 17.0 17.0 16.8 21.8 22.4 21.7 7.01 8.16 5.68 7.64 6.74 0.00 0.00 0.00
Na2O 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.01 0.02 1.98 1.92 1.98 1.06 0.98 1.08 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
K2O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
NiO 0.01 0.01 0.01 0.00 0.33 0.33 0.12 0.34 0.13 0.12 0.00 0.00 0.02 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.31 0.32 0.35
Total 100 99.8 100 101 99.0 98.6 98.3 99.2 99.2 100 100 100 99.7 99.7 99.3 100.1 100.0 99.7 100.4 100.1 99.6 98.0 98.6 98.9
Mg# 82.8 82.8 83.2 83.4 84.9 84.2 92.9 84.1 92.9 93.0 27.3 58.9 53.4 89.2 89.6 88.3 77.3 77.1 77.5 77.1 77.3 78.6 78.5 78.2
O= 12 12 12 12 4 4 20 4 20 20 8 8 8 6 6 6 12 12 12 12 12 4 4 4
Si 2.998 3.015 2.995 2.992 0.000 0.000 1.722 0.000 1.698 1.730 2.172 2.167 2.181 1.771 1.792 1.777 3.011 3.029 2.985 3.043 3.007 0.000 0.000 0.000
Ti 0.003 0.001 0.002 0.000 0.000 0.000 0.002 0.000 0.001 0.000 0.000 0.000 0.000 0.005 0.005 0.005 0.002 0.001 0.003 0.000 0.001 0.000 0.001 0.000
Al 1.996 1.985 1.995 1.998 1.964 1.978 8.465 1.986 8.533 8.480 1.815 1.826 1.811 0.492 0.449 0.491 1.984 2.036 1.912 1.986 1.984 1.952 1.955 1.958
Cr 0.006 0.010 0.009 0.007 0.030 0.018 0.045 0.018 0.041 0.045 0.001 0.000 0.000 0.005 0.006 0.006 0.010 0.008 0.012 0.009 0.010 0.034 0.034 0.033
Fe2+ 0.432 0.424 0.423 0.418 0.144 0.155 0.271 0.158 0.266 0.263 0.004 0.002 0.003 0.088 0.085 0.095 0.556 0.515 0.608 0.536 0.563 0.198 0.204 0.208
Fe3+ 0.009 0.004 0.000 0.019 0.014 0.011
Mn 0.014 0.015 0.013 0.016 0.001 0.001 0.004 0.001 0.004 0.005 0.001 0.002 0.000 0.003 0.002 0.002 0.020 0.016 0.023 0.018 0.020 0.002 0.001 0.001
Mg 2.063 2.025 2.073 2.082 0.849 0.839 3.490 0.826 3.446 3.457 0.002 0.003 0.003 0.723 0.723 0.715 1.870 1.714 2.072 1.785 1.892 0.795 0.790 0.783
Ca 0.485 0.511 0.490 0.492 0.000 0.000 0.009 0.000 0.010 0.014 0.836 0.834 0.828 0.851 0.878 0.841 0.538 0.626 0.435 0.584 0.518 0.000 0.000 0.000
Na 0.000 0.000 0.000 0.000 0.000 0.000 0.004 0.000 0.003 0.004 0.176 0.171 0.177 0.075 0.070 0.076 0.000 0.000 0.000 0.000 0.001 0.000 0.000 0.000
K 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Ni 0.000 0.001 0.000 0.000 0.007 0.007 0.011 0.007 0.012 0.012 0.000 0.000 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.006 0.006 0.007
Total 7.997 7.986 8.001 8.006 3.003 2.995 14.012 2.991 14.003 14.010 5.007 5.005 5.001 4.013 4.010 4.008 7.990 7.947 8.050 7.960 7.996 3.000 2.999 3.003
Y. Xiao et al. / Lithos 304–307 (2018) 95–108 103
Table 3 Table 4
Mineral trace element compositions of Jiande clinopyroxenite xenoliths (in ppm). Li concentration and isotopic composition of clinopyroxene in Jiande clinopyroxenite xe-
noliths and reference materials.
Sample SZZ12-02 SSZ12-09 SZZ12-14 JSB10-57a
Sample Mineral Position Spot δ7Li 1se Li 1se
Mineral Kelyphite Cpx Kelyphite Cpx Cpx Kelyphite Cpx
ppm
Li 5.21 1.50 2.42 1.11 1.34 0.11 7.96
SZZ12-02 Cpx1 Rim 1 −7.15 0.67 1.32 0.01
P 12.9 6.90 12.3 7.20 45.1 48.5 32.2
Clinopyroxenite Core 2 −7.43 0.57 1.48 0.01
Sc 60.1 7.59 109 11.4 21.9 111 47.0
(Cpx + Grt + Spl + Spr) Cpx2 Rim 1 −5.43 0.60 1.32 0.01
Ti 147 742 115 549 815 155 712
Mantle 2 −7.11 0.66 1.34 0.01
V 53.0 226 44.9 148 285 70.0 250
Core 3 −7.68 0.57 1.48 0.01
Cr 1734 2121 1230 911 967 839 683
Cpx3 Rim 1 −3.31 0.56 1.17 0.01
Mn 2013 247 2165 307 521 2578 717
Core 2 −6.20 0.56 1.45 0.01
Co 62.8 21.7 53.8 18.1 34.1 66.4 17.1
Average −6.33 1.37
Ni 29.8 237 23.6 194 236 25.4 134
SZZ12-09 Cpx1 Rim 1 −6.72 0.57 1.17 0.01
Cu 10.0 1.56 1.14 1.50 1.53 0.20 2.10
Clinopyroxenite Core 2 −7.33 0.61 1.49 0.01
Zn 4.50 3.04 3.96 2.35 11.0 10.9 0.76
(Cpx + Grt + Spl + Spr) Cpx2 Rim 1 −4.07 0.79 1.04 0.01
Ga 3.00 7.70 6.43 4.61 11.5 3.33 4.15
Core 2 −5.55 0.63 1.27 0.01
Ge 1.84 1.00 2.95 1.25 1.22 1.59 1.00
Cpx3 Rim 1 −6.58 0.53 1.27 0.01
Rb 0.34 0.37 0.21 0.12 0.05 0.05 0.05
Core 2 −6.94 0.69 1.25 0.01
Sr 3.89 3.23 2.73 1.96 1.37 0.01 25.5
Average −6.20 1.25
Y 11.4 0.53 16.2 0.74 1.68 13.0 5.64
SZZ12-14 Cpx1 Rim 1 −11.16 0.58 1.26 0.01
Zr 1.64 0.74 2.14 0.61 0.46 0.91 1.26
Clinopyroxenite Core 2 −10.44 0.57 1.63 0.02
Nb 0.08 0.05 0.08 0.05 0.01 0.02 0.09
(Cpx + Grt + Spl) Cpx2 Rim 1 −10.27 0.64 1.30 0.01
Mo 0.31 0.27 0.43 0.29 0.01 0.01 0.03
Core 2 −12.19 0.53 1.23 0.01
Cs 0.26 0.20 0.28 0.10 0.02 0.03 0.02
Cpx3 Rim 1 −10.03 0.67 1.29 0.01
Ba 2.59 0.71 1.37 0.30 0.07 0.01 0.03
Core 2 −9.56 0.73 1.20 0.01
La 0.11 0.06 0.12 0.07 0.01 0.01 0.62
Cpx4 Rim 1 −10.36 0.65 1.07 0.01
Ce 0.13 0.07 0.12 0.07 0.01 0.01 1.50
Core 2 −10.61 0.65 1.29 0.01
Pr 0.07 0.03 0.06 0.03 0.01 0.01 0.15
Average −10.58 1.28
Nd 0.31 0.24 0.31 0.22 0.21 0.05 0.68
Standard
Sm 0.33 0.23 0.24 0.22 0.17 0.14 0.28
06JY29 Cpx 1 −2.21 0.76
Eu 0.17 0.12 0.16 0.13 0.09 0.13 0.12
Peridotite xenolith 2 −2.93 0.79
Gd 0.92 0.52 0.95 0.55 0.39 0.61 0.57
3 −2.31 0.68
Tb 0.20 0.07 0.23 0.07 0.07 0.18 0.13
4 −2.80 0.70
Dy 1.69 0.18 2.24 0.23 0.45 1.72 1.05
06JY31 Cpx 1 −2.46 0.70
Ho 0.44 0.03 0.56 0.03 0.08 0.49 0.22
Peridotite xenolith 2 −1.61 0.65
Er 1.33 0.08 1.79 0.07 0.17 1.70 0.62
3 −2.82 0.64
Tm 0.19 0.02 0.33 0.02 0.02 0.26 0.10
4 −2.40 0.58
Yb 1.14 0.10 2.17 0.12 0.11 1.93 0.65
5 −2.88 0.72
Lu 0.16 0.04 0.33 0.04 0.01 0.30 0.07
6 −2.04 0.74
Hf 0.19 0.11 0.20 0.12 0.05 0.05 0.08
Ta 0.05 0.02 0.03 0.02 0.01 0.01 0.01
W 0.22 0.10 0.23 0.12 0.01 0.01 0.02
Pb 0.08 0.05 0.06 0.05 0.01 0.03 0.08
Th 0.03 0.01 0.02 0.01 0.01 0.01 0.01
U 0.03 0.01 0.03 0.01 0.01 0.01 0.01
(La/Yb)N 0.06 0.41 0.04 0.37 0.06 0.01 0.64
a Hannuoba clinopyroxene from Su et al. (2012).the ranges of 967–1138 °C, with an agreement well within 50 °C
(Table 5; Dahl, 1980; Krogh, 1988; Powell, 1985). Temperatures esti-
mated from sapphirine-spinel Fe2+-Mg exchange thermometer vary
from 1069 to 1094 at a pressure of 8–10 kbar (Table 5; Sato et al.,
2006; Su et al., 2012).Table 5
Temperature (°C) estimates for Jiande clinopyroxenite xenoliths.
Sample Rock type T (°C)
T(80D)a T(85P)b T(88 K)c T(2006S)d
SZZ12-02 Clinopyroxenite 1013 1040 1019 1069–1094
SZZ12–09 Clinopyroxenite 967 1019 997 1072–1090
SZZ12–14 Clinopyroxenite 1138 1059 1055
a Dahl (1980) Cpx-Grt thermometer;
b Powell (1985) Cpx-Grt thermometer;
c Krogh (1988) Cpx-Grt thermometer;
d Sato et al. (2006) Spr-Spl thermometer;5. Discussion
Abundant garnet-bearing pyroxenites are also found in the
Hannuoba Cenozoic basalts in the northern margin of the North China
Craton and the Ronda peridotite massif, southern Spain (Hu et al.,
2016; Liu et al., 2005; Morishita et al., 2001, 2003, 2009; Su et al.,
2012). The garnet pyroxenite xenoliths in Hannuoba basalts were con-
sidered to have been produced by interaction between peridotite and
melt, which resulted in formation of pyroxene and garnet at the ex-
pense of olivine (Liu et al., 2005). By contrast, Morishita et al. (2001,
2003, 2009) suggested a gabbro protolith origin for the garnet pyroxe-
nites from Ronda.
Below, we first focus on the origin of sapphirine and garnet/
kelyphite and the reactions in their formation. Subsequently, we discuss
the protolith of the Jiande clinopyroxenite xenoliths compared with
garnet pyroxenite in the Hannuoba basalts and Ronda peridotite massif
and reconstruct their P-T path.5.1. Origin of sapphirine in Jiande clinopyroxenite xenolith
Crustal-derived and mantle-derived sapphirine-bearing rocks usu-
ally display distinct chemical composition in their minerals (Fig. 6; Su
et al., 2012). The sapphirine in two Jiande clinopyroxenite xenoliths
has low Al2O3, high MgO and coexists with high Mg# minerals
(clinopyroxene, spinel). These characteristics are similar to those in
sapphirine-bearing mantle-derived pyroxenites reported in the litera-
tures (Fig. 6d; Griffin and O'Reilly, 1986; Su et al., 2012). Previous stud-
ies revealed that the occurrence of mantle-derived sapphirine is
restricted to rocks rich in Ca, Al and Mg, where the stable
assemblage is aluminous clinopyroxene+ garnet + plagioclase + sap-
phirine (±orthopyroxene± hornblende) or aluminous clinopyroxene
+ spinel + sapphirine (±orthopyroxene) (Bilal, 2016; Griffin and
O'Reilly, 1986; Kornprobst et al., 1990; Morishita et al., 2001; Su et al.,
2012). On the contrary, the mineral assemblage of the Jiande
clinopyroxenite xenolith (clinopyroxene + spinel + garnet/kelyphite
104 Y. Xiao et al. / Lithos 304–307 (2018) 95–108
Fig. 5.Al2O3/MgO versus SiO2/MgO (a) andMgO versus CaO (b) for Jiande clinopyroxenite xenoliths. Mantle-derived cumulative pyroxenites from eastern China (purple field) are shown
for comparison. Thedata of sapphirine-bearing clinopyroxenite JSB10-57 in theHannuoba are fromSu et al. (2012). Blackdashed lines represent compositional trends for pyroxenites from
Beni-Bousera and eclogite-garnet pyroxenites from Ronda and Czech Republic, respectively (Kornprobst et al., 1990; Morishita et al., 2001; Obata et al., 2006). The star denotes the com-
position of primitive mantle (P.M.) fromMcDonough and Sun (1995). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)+ sapphirine) is not stable. Sapphirine in this study displays different
stages of spinel replacement, from thin rim on the spinel (Figs. 2b, e, f
and 3c) to resorbed spinel relics inside newly formed sapphirineFig. 6. The chemical compositions of clinopyroxene (a), garnet (b), spinel (c) and sapphirine (d
from different settings, including khondalite (black solid line), granulite (gray field), and pyroxe
Gregoire et al., 2001; Griffin and O'Reilly, 1986; Jiao et al., 2015; Kornprobst et al., 1990; Lal, 199
line represents the compositional field for Hannuoba garnet pyroxenite (Hu et al., 2016). The pu
eastern China (Huang et al., 2004; Xuet al., 1996; Yu et al., 1998, 2003). Thedata of garnet pyrox
eclogitic, websteritic, and harzburgitic garnets in the Fig. 6b are from Sobolev et al. (1973). (For
web version of this article.)(Figs. 2c, d and 3c). Thus, sapphirine in this study is considered to be
of metamorphic origin. In addition, the sapphirine-spinel associations
can occur either inside the garnet or at the contact between) in the studied samples. The compositions of clinopyroxene, garnet, spinel and sapphirine
nite (black dash line) are plotted for comparison (Arima and Barnett, 1984; Christy, 1989;
7; Lal et al., 1987; Okay, 1994; Santosh et al., 2007; Sutherland et al., 2003). The pink solid
rple dashed line represents the compositional field for pyroxenite cumulate xenolith in the
enites inRondaperidotitemassif, Spain are fromMorishita et al. (2001, 2009). Thefields for
interpretation of the references to colour in this figure legend, the reader is referred to the
Y. Xiao et al. / Lithos 304–307 (2018) 95–108 105
Fig. 7. Chondrite-normalized REE patterns and primitivemantle-normalized trace element spider diagrams for the clinopyroxene (a, b) and garnet (c, d) in the studied samples. Chondrite
and primitive mantle (PM) values are from Anders and Grevesse (1989) and McDonough and Sun (1995), respectively. Gray and pink fields in the Fig. 7a and c represent clinopyroxene
and garnet trace element data of garnet pyroxenites in the Ronda peridotite massif, Spain and Hannuoba basalts, China, respectively (Morishita et al., 2009; Zhao et al., 2017). (For inter-
pretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)clinopyroxene andgarnet. These indicate that spinel and garnet ought to
be the reactants. The subsolidus reaction involved in the formation of
aluminous sapphirine is represented as follows: spinel + garnet= sap-
phirine + clinopyroxene + orthopyroxene. Since the clinopyroxene-
sapphirine stability is defined by garnet-consuming reactions (Christy,
1989), sapphirine grows at the expense of spinel during the cooling/uplift
process, whilst the Ca-rich garnet is consumed.Fig. 8. Li content vs. Li isotope of individual spot analyses in clinopyroxene from studied samples
Relationship between Li content and Na content of clinopyroxene (b). The data of sapphirine-b
and Li isotopic composition of clinopyroxene in theHannuoba pyroxenites (a) and Ronda garnet
for crustal eclogite and high-P mafic cumulate in the Fig. 8a are from Woodland et al. (2002).5.2. Origin of garnet and the sequence of kelyphitization process in the
Jiande clinopyroxenite xenolith
The kelyphite typically forms large grains and usually includes relics of
garnet and spinel, similar to the garnet pyroxenite xenoliths from
Hannuoba (Figs. 2 and 3; Hu et al., 2016; Liu et al., 2005). Most kelyphites
in this study have similar chemical composition to relic garnets. Thiscompared to those in pyroxenites fromHannuoba basalts and Ronda peridotitemassif (a).
earing clinopyroxenite JSB10-57 in the Hannuoba are from Su et al. (2014). The Li content
pyroxenites (b) are from Suet al. (2014) andMorishita et al. (2009), respectively. Thefield
106 Y. Xiao et al. / Lithos 304–307 (2018) 95–108feature demonstrates that upon further ascent anddecompression, garnet
eventually became unstable, starting to break down according to the fol-
lowing reaction: garnet= orthopyroxene+ spinel + plagioclase (Obata
et al., 2013). Thereafter, the isochemical kelyphite was formed essentially
in a chemically-closed system (Naemura et al., 2009; Obata et al., 2013).
In addition, the relic spinel displays embayed and round grain boundaries,
suggesting that garnetwas formed at a later stage at the expense of spinel.
Specifically, the Jiande clinopyroxenite xenoliths have different mineral
compositions from the Hannuoba garnet pyroxenite (Figs. 5 and 6a-c;
Hu et al., 2016). Furthermore, the clinopyroxene and kelyphite from the
Jiande clinopyroxenite xenoliths have much lower REE contents than
those in Hannuoba (Fig. 6a; Zhao et al., 2017). Thus, garnet has a different
metasomatic origin from that in Hannuoba garnet pyroxenite. The later
uplift and melt percolation caused growth of garnet and spinel coevally
at the garnet-spinel transition in the pyroxenite field (Figs. 2 and 3;
Johanesen et al., 2014). Because the deeper units remained warmer at
this point, the garnet begin to breakdown. On the other hand, the mantle
and core of the kelyphite havenearly the samebulk chemical composition
as the precursor garnet, whereas the rim of the kelyphites have higher
FeO, MgO and lower CaO than the mantle and core (Table 2). The
transition between the kelyphite rim and clinopyroxene is gradual,
indicating that the kelyphite rim of garnet could be attributed
to the following simplified reaction during decompression: garnet +
clinopyroxene = orthopyroxene + spinel + plagioclase (Kushiro and
Yoder Jr., 1966; Thompson, 1979). The temperature atwhich this reaction
took place has been estimated to be 800±50 °C, upon a further decom-
pression (Obata, 2011, Obata et al., 2013).5.3. Protolith of the Jiande clinopyroxenite xenolith
The clinopyroxenite xenoliths in Jiande show granuloblastic
metamorphic texture and consist of clinopyroxene, partially to
completely kelyphitized garnet, and spinel with minor amounts of
sapphirine and plagioclase (Figs. 2 and 3). The occurrence of sapphi-
rine, which always surrounds spinel, suggests their formation during
the cooling/uplift process. The isochemical kelyphite usually en-
closes primitive spinel, indicating primary garnet would be formed
at the expense of spinel at the garnet-spinel transition. Thus,
microtextural and reaction relationships suggest that the mineral as-
semblage at the earliest metamorphic conditions in these xenoliths
was clinopyroxene and spinel.
Obata et al. (2006) demonstrated that cumulus gabbros which orig-
inally precipitated from basaltic magmas at low pressure are character-
ized by a clear linear trend between Al2O3/MgO and SiO2/MgO. The
Jiande clinopyroxenite xenoliths do not define a linear correlation
(Fig. 5a). Furthermore, the clinopyroxene and garnet do not have posi-
tive Eu anomalies that are typical for oceanic gabbros (Fig. 7; Jacob,
2004;Morishita et al., 2003). In addition, the Li content of clinopyroxene
in eclogitic rocks occurring in a variety of geologic settings has been
used to provide constraints on the origin of these rocks (Woodland
et al., 2002). Metabasaltic (metagabbroic) eclogites from high-
pressure terranes have high Li contents, whereas all kimberlite- and
basanite-hosted xenoliths representing high-pressure cumulates have
low Li contents (Fig. 8a; Woodland et al., 2002). The clinopyroxenes in
the Jiande clinopyroxenite xenoliths have Li abundances similar to
high-P mafic cumulate but much lower than those in the Hannuoba
and Ronda pyroxenites, and crustal eclogite (Fig. 8a; Morishita et al.,
2009; Woodland et al., 2002). These features suggest that the Jiande
clinopyroxenite xenolith is not a plagioclase-rich, low-pressure cumu-
late (Morishita et al., 2001, 2003, 2009), but is most likely a pyroxenite,
originating as clinopyroxene + spinel cumulate from mafic melts
percolating through the mantle. However, upon further ascent and
melt percolation, the garnet/kelyphite and sapphirine occurred. The
earlier compositions of clinopyroxene and spinel change due to re-
equilibration with metamorphic minerals.5.4. P-T path for the Jiande clinopyroxenite xenolith
As noted above, the earliestmetamorphicmineral assemblageswere
characterized by clinopyroxene+ spinel. Temperature and pressure at
which the earliest mineral assemblages were equilibrated is difficult
to estimate frommineral compositions using geothermometers because
the minerals were significantly affected by chemical re-equilibration.
Reaction textures, such as garnet and sapphirine formation,
kelyphitization of garnet followed by disappearance of garnet, were
formed during decompression processes. Since most kelyphites have
chemical composition similar to relic garnets, three different garnet-
clinopyroxene thermometer for garnet pyroxenite could be used to cal-
culate the latest T condition (Dahl, 1980; Krogh, 1988; Powell, 1985).
The calculated temperatures for the Jiande clinopyroxenite xenoliths
fall within the ranges of 967–1138 °C (Table 5). The occurrence of sap-
phirine could also provide an additional P-T mineral estimates
(Christy, 1989; Sato et al., 2006; Su et al., 2012). Sapphirine has a limited
stability field in mantle conditions of about 8–10 kbar spinel pyroxenite
stability field, corresponding to the crust-mantle boundary (Su et al.,
2012). At this pressure, the sapphirine-spinel geothermometer gave
temperatures of 1069–1094 °C (Sato et al., 2006), overlapping with
the estimates using garnet-clinopyroxene thermometer. Thus, we con-
cluded that the latest P-T condition recorded in the Jiande
clinopyroxenite xenoliths was at P=8–10 GPa and T=1069–1094 °C.
Cenozoic Jiande basalts host abundant peridotite xenoliths and
minor pyroxenite. Pressure recorded in the Jiande lherzolites is at 15
kbar (~51 km; Hao et al., 2014). If this pressure estimate is valid, it im-
plies that these clinopyroxenite xenoliths may originated from similar
levels. This pressure condition is higher than the stability field of sapphi-
rine formation (8–10 kbar). Therefore, these xenolithswere tectonically
emplaced at shallow levels before being entrained in the host magmas
due to the uplift of the lithospheric mantle.
Eastern Chinahas been strongly affected by the subduction of the Pa-
cific Plate (Sun et al., 2007). The lithospheric thinning process occurred
and accompanied the extension of the lithosphere and upwelling of the
asthenosphere (Fan et al., 2000; Griffin et al., 1998; Liu et al., 2012,
2017; Lu et al., 2013, 2015; Xu et al., 2000, 2003; Yu et al., 2003;
Zheng et al., 2001, 2004). It is therefore possible that the Jiande
clinopyroxenite xenoliths were probably lifted during this episode.
6. Conclusions
The occurrence of rare sapphirine- and garnet-bearing
clinopyroxenite xenolith coexisting with abundances of spinel
lherzolites entrained in the Jiande basalts provides an insight into
their petrogenesis and metamorphic history of the crust-mantle transi-
tion region. Spinel and clinopyroxene are the main phases in the Jiande
clinopyroxenite xenoliths. Reaction textures, such as sapphirine forma-
tion, kelyphitization of garnet followed by disappearance of the garnet,
were formed during decompression. The latest P-T conditions recorded
by the occurrence of sapphirine in the Jiande clinopyroxenite xenoliths
were at P= 8–10 GPa and T= 1069–1094 °C. The equilibriumpressure
estimated by coexisted lherzolites is at 15 kbar, representing the esti-
mate for the formation of spinel + clinopyroxene at mantle depth.
Therefore, these clinopyroxenite xenoliths were tectonically emplaced
at shallow levels before being entrained in the host magmas due to
the uplift of the lithospheric mantle.
Acknowledgements
We would like to thank Di Zhang, Qian Mao and Yu-Guang Ma for
their assistance with the electron microprobe analyses, and Guo-Qiang
Tang, Xiao-Xiao Ling and Jiao Li for the SIMS analyses. Many thanks to
Johnnie Chamberlin and Chen Chen for comments on the early version
of the manuscript. Constructive and detailed comments from Tomoaki
Morishita are greatly appreciated. Marina Koreshkova and another
Y. Xiao et al. / Lithos 304–307 (2018) 95–108 107anonymous reviewer are warmly acknowledged for their careful and
constructive reviews, which considerably improved this paper. This
study was supported by the National Natural Science Foundation of
China (Grants 41673037 and 41273020) and Youth Innovation Promo-
tion Association, Chinese Academy of Sciences (Grant 2017095).
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