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Geochimica et Cosmochimica Acta 317 (2022) 552–573
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In situ geochemical composition of apatite in granitoids from

the eastern Central Asian Orogenic Belt: A window into
petrogenesis
Chen-Yang Sun a,b,c, Peter A. Cawood b, Wen-Liang Xu a,d,⇑,
Xiao-Ming Zhang a, Jie Tang a, Yu Li e, Zhong-Xing Sun f, Ting Xu f
a
College of Earth Sciences, Jilin University, Changchun 130061, China
b
School of Earth, Atmosphere and Environment, Monash University, Melbourne, VIC 3800, Australia
c
State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Xi’an 710069, China
d
Key Laboratory of Mineral Resources Evaluation in Northeast Asia, Ministry of Natural Resources of China, Changchun 130061, China
e
Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
f
State Key Laboratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China

Received 25 May 2021; accepted in revised form 27 October 2021; Available online 30 October 2021

Abstract

The compositional record of accessory minerals can provide insights into the character and petrogenesis of the parental
magma. We demonstrate apatite’s applicability to petrogenetic studies through in situ trace element analysis of apatite in
60 granitoid plutons from the eastern Central Asian Orogenic Belt (CAOB). Rare earth element (REE) patterns of apatites
usually mimic the trend of the host rock but are slightly enriched in MREE (middle REE), which is predominantly controlled
by parental melt composition and REE partitioning. However, the REE patterns of apatites that are decoupled from those of
host rocks, such as the depletions of LREE (light REE) and MREE, as well as the HREE (heavy REE) enrichment, result
from the early crystallization of other REE-bearing minerals and late-stage metamorphism. Our data displays no significant
relationship between apatite trace elements and highly fractionated granitoids in the eastern CAOB, highlighting the limita-
tion of assessing the degree of magma differentiation through apatite geochemistry. More significantly, the variation of Sr in
apatite shows a close correlation with the early crystallization of plagioclase, and the linear correlations of SrPl-SrWR,
SrPl-SrAp, and SrAp-SrWR imply constant Sr partition coefficients of plagioclase and apatite. Furthermore, a partition coeffi-
cient of Sr between apatite and bulk rock is proposed (DSr Apatite=bulk rock ¼ 0:69). Our results also imply that apatite crystallizing
from adakites inherits the typical trace element signatures of the adakitic melt and is characterized by high Sr, low HREY
(Gd  Lu + Y) contents and lack of Eu anomaly. In conclusion, apatite provides a vital bond to understand the petrogenesis
of granitoids and shows the potential to track granitic sources in detrital grains.
Ó 2021 Elsevier Ltd. All rights reserved.

Keywords: Eastern CAOB; Erguna and Xing’an massifs; Granitoids; Apatite; Rare earth elements; Petrogenesis; Adakite

⇑ Corresponding author at: 2199 Jianshe Street, College of Earth Sciences, Jilin University, Changchun 130061, China.
E-mail addresses: chenyang.sun@nwu.edu.cn (C.-Y. Sun), peter.cawood@monash.edu (P.A. Cawood), xuwl@jlu.edu.cn (W.-L. Xu),
zxm21@jlu.edu.cn (X.-M. Zhang), tangjie_jlu@163.com (J. Tang), liyu19900821@126.com (Y. Li), sunzhongxing17@mails.ucas.ac.cn
(Z.-X. Sun), xuting191@mails.ucas.ac.cn (T. Xu).

https://doi.org/10.1016/j.gca.2021.10.028
0016-7037/Ó 2021 Elsevier Ltd. All rights reserved.
 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573
1. INTRODUCTION
Apatite, Ca5(PO4)3(F,Cl,OH), is a common accessory
mineral in igneous, sedimentary, and metamorphic rocks
due to its wide stability that ranges from the Earth’s surface
to the lithospheric mantle, across a range of geological pro-
cesses (Watson, 1980; Sha and Chappell, 1999; Hoskin
et al., 2000; O’Reilly and Griffin, 2000; Hughes and
Rakovan, 2015; Bruand, Storey and Fowler, 2016). Ca
atoms in the apatite lattice occupy two structural sites
(Ca1 with nine-fold coordination & Ca2 with seven-fold
coordination), allowing for the high concentrations of
many trace elements (including Fe, Mn, Mg, Na, Sr, Y,
Ba, REE, Pb, Th, and U) via diverse substitution reactions
(some of these are coupled-substitutions; Pan and Fleet,
2002; Klemme et al., 2013; Harlov, 2015; Hughes and
Rakovan, 2015; Ladenburger et al., 2016; Mao et al.,
2016). Most of the trace elements are sensitive to changes
in the crystallization environment as their residence is con-
trolled through melt/phosphate mineral equilibria (Hughes,
Cameron and Mariano, 1991; Toplis and Dingwell, 1996;
Sha and Chappell, 1999; Belousova et al., 2001, 2002;
Chu et al., 2009; Szopa et al., 2013). Consequently, apatite
is used to unravel the geochemistry of rock suites and has
been used as an indicator of petrogenetic processes and/
or mineral exploration potential.
The application of apatite to petrogenetic studies has
been demonstrated by Belousova et al. (2001, 2002), Chu
et al. (2009), Miles et al. (2014), Bruand et al. (2014,
2016), Bruand et al. (2017, 2020), and Nathwani et al.
(2020), who link variations of apatite chemical composition
to magmatic differentiation and whole-rock parameters
such as rock type, fO2, SiO2 content, and aluminum satura-
tion index [ASI, molar Al2O3/(CaO + K2O + Na2O)]. In
addition, the abundances and ratios of many minor and
trace elements within apatite have also been used to differ-
entiate S- and I-type granites and trace petrogenetic pro-
cesses such as fractional crystallization and magma
mixing (Sha and Chappell, 1999; Hsieh et al., 2008; Chu
et al., 2009). Also, apatite has comparable potential to
whole-rock in terms of Sr (e.g., Zaitsev and Bell, 1995;
Yang et al., 2014; Emo et al., 2018; J.F. Sun et al., 2019;
Yu et al., 2019) and Nd (e.g., Yang et al., 2008, 2014;
Sun et al., 2010; Hammerli, Kemp and Spandler, 2014;
Xu et al., 2015; Malusà et al., 2017; Zhou et al., 2020) iso-
topes to indicate the nature of magma source. In mineral
exploration, multiple approaches, including fractionation
and oxidation state (e.g., Belousova et al., 2002; Cao
et al., 2011; Zafar et al., 2020), O-Sr-Nd isotopes (e.g.,
Xu et al., 2015; Palma et al., 2019), and the multivariate
statistical techniques for trace element compositions
(e.g., Mao et al., 2016), proved the strong potential of
apatite in pinpointing polymetallic mineralization and ore
types. As a result, apatite retains considerable chemical
and isotopic information, particularly effective in finger-
printing magmatic and metallogenic processes from
mineral- to regional-scale (e.g., Glorie et al., 2020).
The eastern Central Asian Orogenic Belt (CAOB) is
characterized by widespread Neoproterozoic to Phanero-
zoic granitoids, and studies on their geochronological
553
framework and geochemistry have been used to develop
regional tectonic models (e.g., Wu et al., 2011; Xu et al.,
2013; D.Y. Sun et al., 2013; Tang et al., 2018; C.Y. Sun
et al., 2019). However, less attention has been paid to the
origin of granitic magmas, including crystallization and dif-
ferentiation processes as well as controls on chemical-
mineralogical variations within the granites. An under-
standing of the mineral geochemistry of apatite could help
address these fundamental questions. Previous studies on
apatite geochemistry have been undertaken in regions con-
taining stable evolved crust, whereas the CAOB is a region
of juvenile crustal growth (Sß engör et al., 1993; Jahn, Wu
and Chen, 2000; Wu et al., 2011). The Erguna and Xing’an
massifs represent two microcontinents whose geological
framework within the eastern CAOB has been widely stud-
ied (Fig. 1a; W. Wang et al., 2012; Tang et al., 2014, 2015,
2016; Shi et al., 2015; Zhang et al., 2017; Li et al., 2017a,
2017b, 2018a, 2018b, 2020). This geological background
provides a well-constrained framework in which to under-
take apatite studies and reveal their relationship to pub-
lished whole-rock data. Hence, we present detailed
systematic laser ablation–inductively coupled plasma–mass
spectrometry (LA-ICP-MS) analyses of apatite trace ele-
ments in 60 granitoid samples from these two massifs, with
the aim of understanding: 1) constraints on variations in
apatite composition during magma evolution and, 2) the
degree to which apatite records petrogenetic information
or geochemical characteristics of the host granitoids.
2. GEOLOGICAL BACKGROUND
The eastern segment of the Central Asian Orogenic Belt
runs through NE China and consists of a collage of several
microcontinents, comprising, from northwest to southeast,
the Erguna, Xing’an, Songnen, Jiamusi, and Khanka mas-
sifs, separated by suture zones (Fig. 1a). Voluminous gran-
itoids are exposed through this region and cover an area of
200,000 km2 (Fig. 1b; S ß engör et al., 1993; Jahn, Wu and
Chen, 2000; Jahn et al., 2004; Li, 2006; Wu et al., 2011;
Xu et al., 2013, 2019). The region records the impact of a
number of tectonic regimes through the Phanerozoic,
including Paleozoic orogenic processes related to the clo-
sure of the Paleo-Asian Ocean between the Siberia and
the North China cratons, and overprinting by the
Mongol-Okhotsk and Circum-Pacific tectonic regimes dur-
ing the Mesozoic (Xiao et al., 2003; Li, 2006; Wu et al.,
2007, 2011; Zhang et al., 2009; T. Wang et al., 2012; Liu
et al., 2017; Sun et al., 2017; Tang et al., 2018; Xu et al.,
2019).
Three suture zones separate the Erguna and Xing’an
massifs from other microcontinents in the CAOB and are
the Mongol-Okhotsk Suture Belt to the northwest, the
Xiguitu-Xinlin Suture Belt between the two massifs, and
the Heihe-Nenjiang-Xilinhot-Airgin Sum Suture Belt to
the southeast (Fig. 1; Liu et al., 2017; Li et al., 2018b,
2020; Xu et al., 2019). The Erguna Massif is considered
the eastern extension of the Central Mongolian microconti-
nent (Wu et al., 2011). The massif contains a Precambrian
crystalline basement (Fig. 1b), including rocks related to
the breakup of the Rodinia supercontinent in the Neopro-
554 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573

Fig. 1. (a) Regional tectonic framework of the eastern CAOB, showing major tectonic divisions and the location of the study area (after Wu
et al., 2011); (b) Sampling locations and distribution of granitoids in the Erguna and Xing’an massifs.

terozoic (Tang et al., 2013; Zhao et al., 2016a) and small
areas of Paleoproterozoic granitoids in the northeastern
part of the massif (L.X. Sun et al., 2013; Li et al., 2019).
Paleozoic geological bodies are mostly distributed along
the northwestern side of the Xiguitu-Xinlin Suture Belt
and record the post-collisional evolution of the Erguna
and Xing’an massifs (Fig. 1b; Zhao et al., 2014; Feng
et al., 2015; Li et al., 2017b). Mesozoic granitoids are wide-
spread in the Erguna Massif (Fig. 1b) and are inferred to
have formed during the southward convergence of the
Mongol-Okhotsk Ocean (W. Wang et al., 2012; Tang
et al., 2014, 2015, 2016; Li et al., 2017b; Sun et al., 2017).
Whole-rock Nd and zircon Hf isotopic data from granitoids
reveal that the crustal growth of the Erguna Massif shows a
step-like pattern with three growth periods at 2.9–2.7 Ga,
2.1–1.9 Ga, and 1.7–0.5 Ga (C.Y. Sun et al., 2019).
The Xing’an Massif accreted to the Erguna Massif in the
early Paleozoic (Fig. 1b). Precambrian crystalline basement
is rare and was initially proposed on the basis of detrital zir-
cons from the Zhalantun Metamorphic Complex (Zhou
et al., 2014) and Hf-Nd isotopes of Phanerozoic granitoids
(Yang et al., 2017; Li et al., 2018b; Qin et al., 2019), but
outcrops have recently been reported near Longjiang (Wu
et al., 2018; Zhang et al., 2018). Paleozoic granitoids in
the massif are chiefly represented by subduction-related
granitoids (480–420 Ma & 360–330 Ma) and final syn- to
post-collisional granitoids (320–290 Ma) (Fig. 1b), which
record the northwestward subduction history of a branch
of the Paleo-Asian Ocean (Heihe-Nenjiang Ocean) between
the Xing’an and Songnen massifs (Shi et al., 2015; Liu et al.,
2017; Zhang et al., 2017; Li et al., 2020). The Xing’an Mas-
sif is characterized by the widespread outcrop of NE-
trending Mesozoic volcanic rocks and granitoids
(Fig. 1b), which were tectonically controlled by both the
Mongol-Okhotsk and Circum-Pacific tectonic regimes (Li
et al., 2018a; Tang et al., 2018).
3. SAMPLE AND ANALYTICAL METHOD
3.1. Granitoid samples
Granitoids dominate the tectono-magmatic record pre-
served in the eastern CAOB. Granitoid samples in this paper
are from 60 representative granitic plutons in the Erguna
Table 1
Comprehensive dataset for granitoid samples from the eastern Central Asian Orogenic Belt.
No. Sample Lithology Group Rock Major mineral phases Accessory mineral phases Age Latitude Longitude U-Pb Age- WR
type (Ma-1r) (N) (E) Refs. Geochemistry-
Refs.
Erguna Massif
1 18ER24 Granodiorite A1 Mafic I Pl + Af + Q + Bt + Hb Zr + Ttn + Ap + Ep + Aln + Mt 196 ± 1 52° 125°500 3900 C.Y. Sun This paper*
(13TH1) 280 1200 et al., 2019
2 18ER20 Monzogranite A1 Felsic I Af + Q + Pl + Bt Zr + Ap + Mt + Ttn + Aln 205 ± 1 52° 122°190 4400 C.Y. Sun This paper*
(14ER18) 530 0700 et al., 2019
3 16ER35 Syenogranite A1 Felsic A Af + Q + Pl + Bt Zr + Ap + Mt + Aln 846 ± 5 52° 122°050 3300 Zhao et al., Zhao et al.,

C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573

(13ER13) 030 2600 2016a 2016a
4 16ER19 Monzogranite A2 Felsic I Q + Pl + Af + Bt Zr + Ap + Aln + Mt + Iln 203 ± 3 50° 119°310 5300 Tang et al., This paper*
(11ER13) 460 2700 2016
5 16ER24 Monzogranite A2 Felsic I Q + Pl + Af + Bt Zr + Ap + Ttn + Mt + Aln 206 ± 2 51° 120°180 2800 Tang et al., Tang et al.,
(11ER26; 210 1400 2016 2016
12ER15)
6 16ER32 Monzogranite A2 Felsic A Pl + Af + Q + Bt Zr + Ap + Ttn + Aln 455 ± 10 51° 121°490 2800 Zhao et al., Zhao et al.,
(12ER36) (Chl) + Ms 400 0400 2014 2014
7 18ER21 Syenogranite A2 Mafic A Af + Pl + Q + Hb + Bt Ap + Zr + Aln + Ttn + Ep + Mt + Iln 481 ± 3 52° 125°050 5500 C.Y. Sun This paper*
(14ER5) 250 0300 et al., 2019
8 13ER30 Monzogranite A2 Felsic I Af + Pl + Q + Bt + Grt Zr + Ap + Mt 482 ± 3 51° 120°560 1700 C.Y. Sun This paper*
480 4300 et al., 2019
9 16ER38 Syenogranite A2 Felsic I Af + Pl + Q + Bt + Grt Zr + Ap 791 ± 5 53° 122°210 3300 Zhao et al., Zhao et al.,
(14ER17) 040 4700 2016a 2016a
10 16ER17 Syenogranite A2 Mafic A Af + Q + Pl + Bt (Chl) Zr + Ap + Mt 794 ± 4 50° 119°520 4400 Zhao et al., This paper*
(13ER44) 470 4900 2016b
11 16ER15 Syenogranite A2 Felsic A Q + Af + Bt + Pl Ap + Zr + Mt 851 ± 6 50° 120°050 5300 Tang et al., Tang et al.,
(ER7; ER21) 470 2400 2013 2013
12 12MZ2 Monzogranite B1 Felsic I Af + Pl + Q + Bt Zr + Ap + Ttn + Mt + Ep 180 ± 2 49° 117°190 1300 W. Wang Tang et al.,
(MZ18) 240 2700 et al., 2012 2016
13 16ER33 Syenogranite B1 Felsic I Af + Q + Pl + Bt + Ms Zr + Ap + Ep + Mt + Aln 206 ± 1 52° 121°390 0900 Tang et al., Tang et al.,
(12ER34) 120 2400 2016 2016
14 16ER18 Syenogranite B1 Felsic I Af + Q + Pl + Ms + Bt Zr + Ap + Mt 224 ± 2 50° 119°340 0900 Tang et al., Tang et al.,
(11ER9; (Chl) 420 2500 2016 2016
13ER45)
15 18ER23 Syenogranite B1 Mafic A Af + Q + Pl + Ms + Bt Zr + Ap + Ep + Aln + Mt 460 ± 1 52° 125°520 3400 C.Y. Sun This paper*
230 2800 et al., 2019
16 16ER16 Syenogranite B1 Felsic A Af + Q + Pl + Bt + Hb Zr + Ap + Mt 737 ± 5 50° 120°020 2200 Tang et al., Tang et al.,
(ER13; 580 4400 2013 2013
ER23)
17 16ER20 Syenogranite B2 Felsic A Af + Q + Pl + Bt Ttn + Ap + Zr + Mt + Aln 140 ± 1 50° 119°310 4500 Tang et al., Tang et al.,
(12ER8) 460 4700 2015 2015
18 18ER19 Monzogranite B2 Felsic I Af + Q + Pl + Bt + Ms Ap + Zr + Aln + Mt 211 ± 1 53° 122°060 2200 C.Y. Sun This paper*
060 0300 et al., 2019
19 16ER5 Syenogranite C1 Low Sr-Y Af + Q + Pl + Bt Zr + Ttn + Ap + Aln + Mt + Iln 155 ± 3 49° 118°490 5000 Tang et al., This paper*
(12ER1) (adakitic) 560 1300 2015

555
 556
20 16ER36 Monzogranite C1 Adakite Pl + Q + Af + Bt Ttn + Zr + Ap + Iln + Mt 173 ± 2 52° 122°320 1600 Sun et al., This paper*
(12ER31) 270 4900 2017
21 16ER40 Monzogranite C1 Adakite Pl + Q + Af + Bt + Ms Zr + Ap + Ttn + Mt 177 ± 1 52° 123°110 0600 Sun et al., This paper*
(14ER14) 440 0200 2017
22 16ER34 Monzogranite C1 Low Sr-Y Af + Q + Pl + Bt + Ms Zr + Ap + Mt 185 ± 2 52° 121°530 3600 Sun et al., This paper*
(13ER14; (adakitic) 050 4100 2017
12ER32)
23 16ER31 Granodiorite C1 Low Sr-Y Pl + Q + Af + Bt Zr + Ap + Ep + Ttn + Mt + Aln 197 ± 2 51° 121°450 3600 Tang et al., Tang et al.,
(12ER27) (adakitic) 340 4300 2016 2016
24 11ER5 Granodiorite C1 Adakite Pl + Q + Af + Bt (Chl) Ttn + Zr + Ap + Mt 241 ± 1 50° 120°050 3600 W. Wang Tang et al.,
(ER15) 470 2900 et al., 2012 2014

C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573

25 18ER15 Granodiorite C1 Adakite Pl + Q + Af + Bt + Hb Ttn + Zr + Ap 303 ± 2 49° 119°450 4500 Li et al., 2017b Li et al.,
(15ER1) 390 1300 2017b
26 16ER23 Monzogranite C1 Adakite Pl + Q + Af + Bt Ttn + Zr + Ap + Mt 762 ± 6 51° 120°150 3800 Tang et al., Zhao et al.,
(11ER24; 180 4100 2013 2016a
12ER14)
27 16ER22 Granodiorite C1 Adakite Pl + Q + Af + Bt Ttn + Ap + Zr + Mt 794 ± 4 51° 119°580 3300 Zhao et al., This paper*
(13ER41) 170 4600 2016b
28 16ER10 Monzogranite C2 Felsic I Pl + Af + Q + Bt Zr + Ap + Ttn + Mt + Iln 238 ± 1 49° 119°550 3700 Li et al., 2017b Li et al.,
(15ER12) 470 3200 2017b
Xing’an Massif
1 16DX11 Syenogranite A1 Felsic I Af + Pl + Q + Bt Ap + Zr + Mt + Aln 316 ± 1 48° 121°390 3700 Zhang et al., Zhang et al.,
(13XA28) 490 1900 2017 2017
2 17DX10 Monzogranite A1 Felsic I Pl + Q + Af + Bt + Hb Ap + Zr + Ilm + Aln + Ep + Mt + Ttn 359 ± 2 47° 122°340 4900 Li et al., 2020 Li et al., 2020
550 3200
3 17DX7 Granodiorite A2 - Pl + Af + Q + Bt Zr + Ap + Mt 230 ± 1 47° 122°340 5000 This paper# - (Serious
470 1400 weathering)
4 16DX19 Monzogranite A2 Felsic I Af + Q + Pl + Bt Ap + Zr + Mt + Ep + Ttn 304 ± 1 49° 125°440 5600 Zhang et al., Zhang et al.,
(13XA38) 510 3600 2017 2017
5 17DX24 Monzogranite A2 Felsic A Pl + Af + Q + Bt + Hb Zr + Ap + Aln + Mt 327 ± 1 47° 120°060 1200 Li et al., 2020 Li et al., 2020
130 4000
6 16DX15 Monzogranite A2 Felsic A Q + Af + Pl + Bt + Hb Zr + Ap + Aln 352 ± 1 50° 125°390 2400 Li et al., 2020 Li et al., 2020
090 2900
7 17DX22 Syenogranite B1 Felsic I Q + Pl + Af Zr + Ap + Mt 125 ± 1 50° 124°060 2700 This paper# This paper*
230 4900
8 16DX6 Monzogranite B1 Felsic I Q + Pl + Af + Bt Zr + Ap + Ep + Mt 221 ± 1 47° 122°340 4100 Li et al., 2018a Li et al., 2018a
530 0300
9 18DX3 Granodiorite B1 Felsic I Af + Q + Pl + Bt + Ms Zr + Ap 287 ± 1 47° 122°520 3900 This paper# This paper*
070 3600
10 17DX23 Syenogranite B1 Felsic I Af + Q + Pl + Bt Zr + Ap + Ttn 295 ± 1 47° 120°020 0200 Li et al., 2020 Li et al., 2020
530 2900
11 17DX13 Monzogranite B1 Felsic I Q + Pl + Af + Bt Zr + Ap + Mt 320 ± 1 48° 122°460 1900 Li et al., 2020 Li et al., 2020
000 1100
12 17DX4 Monzogranite B1 Felsic I Pl + Af + Q + Bt Zr + Ap + Ttn + Aln 355 ± 2 47° 121°490 4400 Li et al., 2020 Li et al., 2020
(Chl) + Hb 170 0700
13 17DX1 Granodiorite B2 Felsic I Pl + Q + Af + Bt + Hb Zr + Ap + Mt + Aln 125 ± 1 47° 122°100 5600 Gao et al., Gao et al.,
(Z10-03) 100 2300 2013 & This 2013
paper#
14 16DX3 Syenogranite B2 Felsic I Af + Q + Pl + Bt Zr + Ap + Mt + Iln 135 ± 1 46° 120°410 3500 Li et al., 2018a Li et al., 2018a
190 5700
15 17DX5 Monzogranite B2 Felsic I Q + Pl + Af + Bt Zr + Ap + Mt 150 ± 1 47° 121°120 3600 Li, 2018 Li, 2018
250 5800
16 15DX15 Granodiorite B2 Felsic I Pl + Q + Af + Bt Zr + Ap + Mt 177 ± 1 46° 121°170 3000 Li et al., 2018a Li et al., 2018a
(17DX26) 340 5600
17 18DX8 Monzogranite B2 Felsic I Q + Af + Pl + Bt Zr + Ap + Mt 224 ± 1 47° 122°150 3800 This paper# This paper*
110 4900
18 17DX25 Syenogranite B2 Felsic A Af + Q + Pl + Bt + Hb Zr + Ap + Aln 229 ± 1 46° 120°160 0900 This paper# This paper*
550 1800
19 16ER42 Syenogranite B2 Felsic I Af + Q + Pl + Bt Zr + Ap + Mt 295 ± 2 50° 124°140 0900 Li et al., 2020 Li et al., 2020
(13ER4) 090 3600

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20 17DX8 Syenogranite B2 Felsic I Af + Q + Pl + Bt Zr + Ttn + Ap + Mt + Ep 305 ± 1 47° 122°310 0800 Li et al., 2020 Li et al., 2020
550 1900
21 17DX12 Granodiorite B2 Mafic A Pl + Q + Af + Bt + Hb Zr + Ap + Mt 307 ± 1 47° 122°350 5900 Li et al., 2020 Li et al., 2020
580 1000
22 17DX9 Granodiorite B2 Mafic I Pl + Q + Af + Bt + Hb Zr + Ap + Mt 357 ± 2 47° 122°310 3700 Li et al., 2020 Li et al., 2020
540 2900
23 17DX18 Monzogranite C1 Adakite Af + Q + Pl + Bt Ap + Zr + Mt + Ttn 130 ± 1 49° 123°450 3500 This paper# This paper*
100 3700
24 18DX10 Monzogranite C1 Adakite Af + Q + Pl + Bt Zr + Ap + Ttn + Mt 136 ± 1 46° 122°070 2700 This paper# This paper*
290 4100
25 17DX6 Granodiorite C1 Adakite Pl + Q + Af + Hb + Bt Zr + Ap 141 ± 1 47° 122°130 0500 Li, 2018 Li, 2018
360 1700
26 16ER43 Granodiorite C1 Adakite Q + Pl + Af + Bt Ap + Zr + Ttn + Mt 174 ± 1 50° 125°390 1200 Li et al., 2018a Li et al., 2018a
220 5900
27 17DX17 Monzogranite C1 Adakite Q + Af + Pl + Bt Ap + Zr + Mt 194 ± 1 48° 123°260 0000 This paper# This paper*
400 2300
28 16DX16 Tonalite C1 Adakite Pl + Q + Af + Ms + Bt Ttn + Zr + Ap + Mt + Iln 233 ± 1 50° 125°460 5100 Hao et al., Hao et al.,
(DBS-5) 140 4000 2017 & This 2017
paper#
29 16DX18 Granodiorite C1 Adakite Pl + Q + Af + Bt Zr + Ap + Mt 237 ± 1 50° 125°420 0900 Li et al., 2018a Li et al., 2018a
(13HH13) 180 0400
30 17DX16 Syenogranite C2 Low Sr-Y Af + Q + Pl + Bt Zr + Ap + Ttn + Iln 158 ± 1 48° 123°010 5200 Li, 2018 Li, 2018
(adakitic) 330 5300
31 16DX10 Monzogranite C2 Low Sr-Y Q + Pl + Af + Bt Zr + Ttn + Ap + Iln + Mt 168 ± 1 48° 123°010 4800 Li et al., 2018a Li et al., 2018a
(adakitic) 330 5600
32 16DX17 Granodiorite C2 Low Sr-Y Pl + Q + Af + Bt (Chl) Ttn + Zr + Ap + Mt + Ep 481 ± 2 50° 125°460 5900 Ge et al., 2007 Ge et al., 2007
(GW04523) (adakitic) 140 3800 & This paper#
To ensure the geochemical data of bulk rock and apatite come from the same pluton, we tend to use the remaining samples from our previous research to select apatites. For a few plutons reported
by other teams, we resampled granitoids from the same locations to do further apatite studies (i.e., samples Z10-03, DBS-5, and GW04523). Zircon U-Pb dating of resampled granitoids was also
undertaken and showed the same age results as previous studies, implying no sampling bias. Abbreviation: Af-alkali feldspar; Aln-allanite; Ap-apatite; Bt-biotite; Chl-chlorite; Ep-epidote; Grt-
garnet; Hb-hornblende; Iln-ilmenite; Mt-magnetite; Pl-plagioclase; Q-quartz; Ttn-titanite; Zr-zircon.
#
See data in Table S1 (the analytical method is attached in Supplementary material).
*
See data in Table S2 (the analytical method is attached in Supplementary material).

557
558 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573
and Xing’an massifs that were emplaced during the Neopro-
terozoic, Paleozoic, and Mesozoic (Fig. 1b), with formation
ages ranging from 851 to 125 Ma (Table 1). The term gran-
itoids, as used here, refers to plutonic rocks that contain >63
wt.% SiO2, and is based on the boundary of granodiorite in
the total alkali versus silica (TAS) diagram (Middlemost,
1994). Our granitoid samples have SiO2 = 63.65–77.39 wt.
%, plotting into the granite, granodiorite, and quartz mon-
zonite fields in the TAS diagram (Fig. S1a). Geochemically,
all of the granitoids belong to the subalkaline series
(Fig. S1a). In addition, most are high-K calc-alkaline gran-
itoids, and a few belong to medium-K calc-alkaline and
shoshonite series (Fig. S1b). Their ASI values range from
0.94 to 1.33, including a large number of weakly peralumi-
nous (ASI = 1.0–1.1) granitoids as well as a small number
of strongly peraluminous (ASI > 1.1) and metaluminous
(ASI < 1.0) ones (Fig. S1c). Three main rock types, includ-
ing I- and A-type granitoids as well as adakites, were gener-
ated during the evolution of different tectonic regimes in the
eastern CAOB, as outlined in our dataset. Some of the pre-
vious studies on the Erguna and Xing’an granitoids did not
define rock types, in which case we classified these granitoids
following the definitions from Defant et al. (2002) and
Whalen et al. (1987) (Fig. S1d–f). Moreover, we noticed that
some previously defined ‘‘adakites” do not mirror obvious
adakite features. They show similar Sr/Y, La/Yb, and
Eu/Eu* behaviors and REE patterns with adakite
(Fig. S1d) but have relatively lower contents of Sr (mostly
< 340 ppm) and Al2O3 (12.41–16.21 wt.%). Thus, we use
the terms ‘‘adakite” and ‘‘low Sr-Y granitoid” to differenti-
ate between a true adakite and a granitoid with some
adakite-like (adakitic) characteristics. Although both are
likely related to the partial melting of a thickened mafic
lower crust or a delaminated lower crust, the melting depths
and residual phases are not identical (Li et al., 2004). To bet-
ter understand the data, I- and A-type granitoids in this
paper are further categorized following the recommenda-
tions of Sha and Chappell (1999), i.e., the granitoids with
SiO2 > 70 wt.% are termed ‘‘felsic,” whereas SiO2 < 70 wt.%
are marked ‘‘mafic.” Based on this, mafic I-, felsic I-, mafic
A-, and felsic A-type granitoids are categorized. However, in
contrast to the analysis of Sha and Chappell (1999), metalu-
minous and peraluminous samples appear in the same gran-
itoid groups, implying that the aluminum saturation index
has no obvious correlation with silica content. In addition,
our dataset includes some granitoids that have experienced
a tectonothermal event. The gneissic texture (Fig. S2a–d),
and extensive zircons in the samples showing chaotic inter-
nal textures with less primary oscillatory growth zoning
(Fig. S2e–k), imply that they have undergone up to
medium-grade, amphibolite facies, metamorphism.
The comprehensive dataset of granitoid samples, includ-
ing mineral phases, is shown in Table 1, and their whole-
rock geochemical data are summarized in Table S2.
3.2. Analytical methods
Apatite grains were extracted from selected granitoid
samples using conventional density and magnetic separa-
tion techniques and then handpicked under a binocular
microscope at the Langfang Regional Geological Survey,
Hebei Province, China. Selected apatite grains (150 grains
per sample) were mounted in epoxy and then polished to
section the crystals for observation and analysis at the
Wuhan Sample Solution Analytical Technology Co., Ltd,
Hubei Province, China. Apatite morphological observa-
tions and spot positional selections for in situ geochemical
analyses were performed based on Cathodoluminescence
(CL) and Back-scattered electron (BSE) images.
Major and trace element analyses of selected apatites
were conducted by LA-ICP-MS at the Wuhan Sample
Solution Analytical Technology Co., Ltd., Hubei Province,
China. Detailed operating conditions for the laser ablation
system, the ICP-MS instrument, and data reduction are
similar to those described by Zong et al. (2017) and Liu
et al. (2008). Laser sampling was performed using a Geo-
lasPro laser ablation system that consists of a COMPexPro
102 ArF excimer laser (wavelength of 193 nm and maxi-
mum energy of 200 mJ) and a MicroLas optical system.
An Agilent 7700e ICP-MS instrument was used to acquire
ion-signal intensities. 44/60 mm and 5 Hz were set for spot
size and frequency of the laser, respectively. Measurements
were taken on different grains in a given sample, and each
analysis included approximately 20–30 s of background
acquisition (from a gas blank) followed by 50 s of data
acquisition from the sample. The international glass NIST
610 was used as the primary standard for trace element
composition, whereas three USGS standards (glasses
BCR-2G, BHVO-2G, and BIR-1G) were used as secondary
standards and treated as unknowns. An Excel-based soft-
ware ICPMSDataCal (Liu et al., 2008), was adopted to per-
form off-line correction by using Ca as an internal standard
element. The analytical results of apatites and standards are
summarized in Table S3.
4. RESULTS
4.1. Internal morphology of apatite
Cathodoluminescence (CL) imaging of apatite is often
affected by the phosphorescence effect (Mn2+ emission)
due to the time gap between excitation and emission of
the luminescence (Götze and Kempe, 2008), i.e., the elec-
trons in apatite have essentially stored the energy of the ini-
tial activating light and then re-emit the phosphorescent
light on a delayed basis. This effect causes luminescence
‘afterglow’ (light trailing) in CL images (Fig. 2a) and makes
it challenging to observe the internal morphology of apa-
tite. Therefore, we used CL imaging, together with back-
scattered electron imaging (Fig. 2b), which shows high-
resolution images without phosphorescence disturbance,
to investigate the internal structure of apatite.
In this study, the most common apatite grains have a
euhedral–subhedral crystal morphology with long to short
prismatic forms (Fig. 2c–e), along with rare acicular grains.
The majority of apatites are 50 to 300 lm in length, with
length/width ratios ranging from 1:1 to 4:1. As seen in the
CL images, the apatite grains from a few granitoid samples
show oscillatory growth zoning (Fig. 2c), reflecting mag-
matic differentiation and a slow crystal growth rate
 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573 559

Fig. 2. CL and BSE images show the morphological and textural characteristics of representative apatites from granitoid samples. (a)
Phosphorescence effect from apatite in CL image; (b) BSE image of apatites; (c) CL image of oscillatory growth zoning of representative
apatites from granitoid samples; (d) CL image of the homogeneous texture of representative apatites from granitoid samples; (e) BSE image of
representative apatites from granitoid samples; (f) REY-depleted margins suggest metamorphic overgrowth on inherited magmatic grains; (g)
Apatite chaotic internal textures; (h) Dark zones formed around inclusions in apatite, suggesting a local component migration of REY; (i)
REY-depleted zones developed along microfractures in apatite. White circles–analysis spots of in situ apatite geochemical composition.

(Streck, 2008; Ladenburger et al., 2016; Bruand et al.,
2017). In contrast, the monotonous (textureless) zoning of
apatite, which is the most common internal texture, reflects
relatively rapid crystallization with no obvious composi-
tional variations (Fig. 2d and e; Streck, 2008;
Ladenburger et al. 2016). All of these image characteristics
of the apatites imply a magmatic origin.
A further category of apatite, featured as a reshaping of
the compositional zonation (with light-dark zoning) in sin-
gle grains, indicates recrystallization of apatite during later
metamorphism and hydrothermal alteration (Krneta et al.,
2016; Ladenburger et al., 2016). Apatites with weak recrys-
tallization show a dark overgrowth rim (Fig. 2f), whereas
those that underwent strong recrystallization display a
chaotic internal texture (Fig. 2g). Based on the detailed
research by Krneta et al. (2016), the variability of lightness
on CL/BSE images for reshaped apatites reflects a compo-
sitional difference, i.e., the bright sections are relatively
enriched in REY (REE + Y), whereas the dark sections
are the opposite. In addition, some dark sections are also
located around inclusions (Fig. 2h) and microfractures
(Fig. 2i), implying a local element migration, especially of
REY and halogens (Krneta et al., 2016).
4.2. Apatite geochemistry
Apatite grains yielding abnormally high Zr, Pb, and U
concentrations, which may indicate the ablation of unde-
tected inclusions, and non-apatite grains recognized by
their anomalous REE patterns, were discarded from the
dataset (Malusà et al., 2017). The final dataset includes
326 apatite grains that are well characterized in major
and trace elements. In addition, apatite data from each
sample and whole-rock geochemical data from each pluton
are homogeneous, which basically rules out the contamina-
tion of granitoid magma (Table S3).
The geochemical compositions of apatite from the 60
granitoid plutons show that CaO and P2O5, the principal
components of apatite, display negative correlation, rang-
ing from 51.35 to 61.58 wt.% and from 46.48 to 37.07 wt.
%, respectively. Contents of all other major elements are
low (Table S3). In addition, the concentration of apatite
trace elements varies greatly among different granitoid sam-
ples. For example, there are large rangesP in Sr (11.0–
2427 ppm), Y (114–10,071 ppm), REE (923–
19,884 ppm), and Th (0.344–180 ppm). The Sr/Y
(0.00246–14.3), Eu/Eu* (0.00481–1.17), (La/Sm)N (0.102–
30.4), (Gd/Lu)N (0.736–19.3), and (La/Yb)N (0.0723–125)
values are also heterogeneous (Table S3).
Chondrite-normalized REE patterns provide a graphical
representation of these elemental variations. Based on the
data interrogation, we define ‘‘flat” as the slope of REE
pattern equals 1 ± 25%. Therefore, the REE patterns of
apatite are right-leaning with (La/Yb)N > 1.25, similar to
the whole-rock patterns of the associated granitoids, and
are termed a ‘‘coupled REE pattern.” The REE patterns
with (La/Yb)N < 1.25 are termed a ‘‘decoupled REE pat-
tern” and marked as Group A (Fig. 3). Moreover, two
groups (B and C) are further divided from the coupled
REE patterns based on the degrees of Eu anomaly and
HREE depletion. Group B apatites are from I- and A-
type granitoids and are characterized by an obvious nega-
tive Eu anomaly and relatively higher HREE content,
whereas Group C apatites are mainly from adakites and
low Sr-Y granitoids with a weak negative Eu anomaly
and significant HREE depletion (Fig. 3). In addition, two
560 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573

Fig. 3. Chondrite-normalized REE patterns of apatite (colored lines with symbols in fig. a, b, d, e, g, h) and host-rock (black lines with
symbols in fig. a, b, d, e, g, h); Host rock-normalized REE patterns of apatite (fig. c, f, i). Chondrite values are after Boynton (1984). (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

subtypes are divided in each group on the basis of the vari-
ation of LREE or MREE (Fig. 3). This classification is
based on the general characteristics of all apatites on a
whole-rock scale, and a few apatites in a certain granitoid
sample (transitional type) do not exactly match the charac-
teristics of the subtype and are not divided into different
subtypes.
Group A. The chondrite-normalized REE patterns of
this group all show LREE depletions that are not systemat-
ically correlated with whole-rock REE (Fig. 3a–c). In detail,
apatite REE patterns in Group A1 are classified by (La/
Sm)N and (La/Yb)N < 0.75, showing significant LREE
depletion with (La/Sm)N = 0.102–0.529 and (La/Yb)N =
0.0723–0.670. As well, the Group A1 REE patterns display
a pronounced negative Eu anomaly (Eu/Eu* = 0.169 on
average) with slight HREE depletion [(Gd/Lu)N = 1.23–
2.15] (Fig. 3a; Table S3). Group A2 is characterized by
(La/Sm)N < 0.75 and 0.75 < (La/Yb)N < 1.25. A2 apatites
have a ‘‘flat” REE pattern [(La/Yb)N = 0.251–4.48] with
LREE depletion [(La/Sm)N = 0.144–1.29] and a higher
HREE fractionation compared to Group A1 [(Gd/
Lu)N = 1.62–19.3]. Group A2 apatites display the strongest
negative Eu anomaly among all groups (Eu/Eu* = 0.112 on
average) (Fig. 3b; Table S3).
Group B. The chondrite-normalized REE patterns of
apatites in this group roughly mimic the trend of host rocks
(Fig. 3d–f). Two subtypes in this group are further divided
according to the degree of LREE fractionation [0.75 <
(La/Sm)N < 1.25 and (La/Sm)N > 1.25, repectively]. Group
B1 apatites exhibit a flat LREE pattern with
(La/Sm)N = 0.390–1.87 and (La/Yb)N = 0.723–11.7,
whereas Group B2 apatites have higher values of
(La/Sm)N (0.631–12.5) and (La/Yb)N (1.69–21.1) (Fig. 3d
and e; Table S3).
Group C. Apatites in this group closely match the geo-
chemical characteristics of the adakitic melt (Table 1;
Table S2; Fig. S1d), showing a higher Sr/Y ratio (0.200–
14.3), lower Y content (114–1083 ppm), weakly negative
Eu anomaly, and more pronounced HREE depletion rela-
tive to Group B (Fig. 3g–i; Table S3). Two subtypes are rec-
ognized on the basis of the degree of MREE depletion
(Fig. 3g and h). Group C1 apatites exhibit relatively lower
(La/Sm)N (0.604–12.0) but higher (Gd/Lu)N (1.00–8.56)
values, whereas Group C2 apatites have higher (La/Sm)N
 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573 561

(5.42–30.4) but lower (Gd/Lu)N (0.736–3.74) values due to
the MREE depletion (Table S3). A remarkable concave
HREE pattern is also displayed in Group C2 apatites
(Fig. 3h).
Although apatite geochemistry varies significantly in dif-
ferent granitoid samples, some correlations can still be
found. Sr content in apatite has a broad correlation with
whole-rock SiO2 content (from 63.65 to 78.07 wt.%) and
displays a strong positive correlation with whole-rock Sr
content (Fig. 4a and b), suggesting that Sr in apatite is
probably a valuable tool to investigate the nature of paren-
tal magma. Furthermore, Sr shows a positive correlation
with Eu/Eu* (Fig. 4c). Eu/Eu* values in apatites also dis-
play a positive trend with those in host rocks (Fig. 4d).
5. DISCUSSION
5.1. Controlling factors of apatite REE patterns
The distribution of trace elements in igneous apatite is
primarily controlled and/or disturbed by four conditions:
(i) trace element partitioning between apatite and silicate
melts; (ii) geochemical compositions of magma source or
parental melt; (iii) fractional crystallization of other miner-
als before and/or concurrently with apatite; and (iv) recrys-
tallization caused by late-stage metamorphism.
The whole-rock geochemistry of a granitoid is consid-
ered to represent the composition of parental melt since
fractional crystallization in granitoids is limited due to the
high viscosity of the magma (described as crystal porridge)
(Pitcher, 1997). Compared with whole-rock REE distribu-
tions that display a right-inclined pattern with negative
Eu anomaly (Fig. 3), the general features and differences
in apatite REE patterns can be considered in terms of the
following possible controls:
5.1.1. Negative Eu anomaly in apatite
The Eu anomalies in apatite REE patterns are com-
monly negative and vary markedly from sample to sample
but display a positive relationship with whole-rock
Eu/Eu* (Fig. 4d), suggesting that this relationship is
inherited from the parental melt. Furthermore, the positive
correlation of Eu/Eu* with Sr in apatites (Fig. 4c) and,
together with the lower Sr contents and negative Eu anoma-

Fig. 4. Correlations of (a) SrAp-SiO2 WR, (b) SrAp-SrWR, (c) SrAp-Eu/Eu*Ap, and (d) Eu/Eu*Ap-Eu/Eu*WR (Ap-apatite; WR-whole-rock).
Grey symbols represent previous data from Sha and Chappell (1999), Belousova et al. (2001), Hsieh et al. (2008), Chu et al. (2009), Cao et al.
(2011), Pan et al. (2016), and Bruand et al. (2020), whereas orange symbols represent data in this study. Two granitoid samples of 16DX16 and
16DX18 from this study are not shown in fig. a–c (see data in Table S2), and high Ba-Sr granitoid samples from Bruand et al. (2020) are not
shown in fig. a, because their apatite Sr contents are much higher than others.
562 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573
lies relative to those in host rocks, indicate that the early
crystallization of plagioclase plays a significant role in
magma evolution.
Considering that Eu exists in the +2 and +3 valency
states (Roeder et al., 1987) and Eu3+ is much closer to
Ca2+ in ionic radius (1.01 Å vs. 1.06 Å for seven-fold coor-
dination; as LREE prefers Ca2 site) than Eu2+ in the apa-
tite lattice (1.20 Å), the apatite Eu anomaly is commonly
inferred as a proxy for magmatic fO2 (Sha and Chappell,
1999; Belousova et al., 2002; Pan and Fleet, 2002; Chu
et al., 2009; Cao et al., 2011; Zafar et al., 2019). However,
Bromiley (2021) argues that Eu anomalies in apatite remain
an unreliable recorder of magmatic fO2 because the correla-
tion is complicated and can be overprinted by the bulk rock
composition (feldspar crystallization in essence). Thus, the
deviations in the overall positive correlation of Eu/Eu*
between apatite and whole-rock may not result from the
changes in oxygen fugacity but could be explained as the
migration of Eu that occurred during the crystallization
of apatite to magma cooling (Fig. 4d). Moreover, although
it is not found in our dataset, it is noteworthy that if apatite
Eu anomalies from single plutons can be subdivided into
different groups, the effects of magma mixing, crustal con-
tamination, or source heterogeneity need to be considered
(Chu et al., 2009).
5.1.2. Middle REE slight enrichment and its variation in
apatite
MREE enrichment is the most common feature in apa-
tites, exhibiting lower (La/Sm)N and higher (Sm/Yb)N or
(Gd/Lu)N values than those in host rocks, except the
MREE depletion in Group C2 (Fig. 3). Partition coeffi-
cients of apatite/melt for rare earth elements in different
chemical and physical conditions (Nagasawa, 1970;
Watson and Green, 1981; Luhr, Carmichael and
Varekamp, 1984; Fujimaki, 1986; Prowatke and Klemme,
2006) indicate that the MREE are more compatible in apa-
tite compared to LREE and HREE.
The MREE depletion in Group C2 apatites (Fig. 3h)
highlights the effect of other MREE-bearing phases in the
granitic melt, especially titanite and hornblende. With
regard to titanite, the partition coefficients of titanite/
apatite for Sm  Gd are up to 1.54, but for LREE such
as La decrease to 0.88 (Henderson, 1980), which suggests
that middle rare earth elements have a greater likelihood
of being concentrated in titanite compared to LREE
(Luhr, Carmichael and Varekamp, 1984; Green and
Pearson, 1986). However, the presence of apatite inclusions
in titanite in Group C2 granitoids (Fig. S3) implies that
titanite crystallizes later than apatite and is unlikely to
account for MREE depletion in apatite. Apart from the
MREE depletion, the concave HREE pattern is displayed
both by apatites and host rocks (Fig. 3h). This reflects the
residue of hornblende in the magma source because horn-
blende has a high KD for MREE and HREE, especially
for the medium HREE (such as Dy) (Moyen, 2009). Corre-
spondingly, the shallow evolution of hornblende fractiona-
tion accompanied by plagioclase removal is likely
responsible for the adakitic affinities of Group C2
granitoids (low Sr-Y granitoids; Table 1) (Moyen, 2009).
Fig. 5. Correlation between (La/Sm)N and Eu/Eu* in apatites,
showing the possible controls on apatite LREE behavior (chondrite
values are after Boynton, 1984).
In summary, the MREE enrichment in apatite is mainly
controlled by their high partition coefficients, but apatite
crystallized from a residual melt dominated by hornblende
fractionation would result in MREE depletion (Fig. 5).
5.1.3. Light REE enrichment and its variation in apatite
Whole-rock REE distributions of granitoids always dis-
play a right-inclined pattern with different degrees of Eu
anomaly. According to the partition coefficients of apatite
obtained by experimental petrology (Watson and Green,
1981), the apatite structure exhibits no preference for
LREE and HREE. Thus the apatite geochemical composi-
tions marked by the right-inclined REE pattern (for exam-
ple, Group B & C) can be regarded as inherited from a
reservoir with LREE enrichment (Roeder et al., 1987).
Not all REE patterns in apatites are similar to those in
host rocks - the degree of LREE depletion gradually
increases from Group C2 to Group A1 (Fig. 3). The strik-
ing convergence of LREE in Group A, shown as strong
LREE depletion in apatites but enriched in their host rocks
(Fig. 3), implies that some other LREE-bearing phases are
required for mass balance. Monazite, allanite and titanite
are regarded as the major accessory minerals of concentrat-
ing LREE. However, they show significant differences in
their ability to compete for these elements, i.e., the LREE
partition coefficients of monazite are 10 times higher than
allanite and 100–1000 times that of titanite (Sha and
Chappell, 1999). Similarly, the positive correlation between
LREE and Th contents (Fig. 6a) is often interpreted to indi-
cate that monazite is the primary controller leading to the
depletion of LREE. But it is noteworthy that monazite usu-
ally crystallizes from a low-Ca and strongly peraluminous
magma, and thus only the LREE depletion in apatites from
those S-type granites (ASI > 1.1) can be ascribed to mon-
azite crystallization (Sha and Chappell, 1999; Belousova
et al., 2001; Hsieh et al., 2008; Chu et al., 2009; Cao
et al., 2011). By contrast, granitoids sampled here are
mostly formed from a calc-alkaline to a weakly peraluminous
 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573
Fig. 6. (a) Correlation between LREE and Th contents in apatites;
(b) Biplot of Sr/Y vs. LREE of apatites (Abbreviations: ALK-
alkali-rich igneous rocks; HM-partial-melts/leucosomes/high-grade
metamorphic rocks; IM-mafic I-type granitoids and mafic igneous
rocks; LM-low- and medium-grade metamorphic and metasomatic
rocks; S-S-type granitoids and high aluminum saturation index
(ASI) ‘felsic’ I-types; UM-ultramafic rocks including carbonatites,
lherzolites, and pyroxenites; after O’Sullivan et al., 2020); (c)
Correlation between apatite LREE contents and crystallization
ages of host granitoids.
environment (Fig. S1b and c), where monazite is rare.
Besides, thorium is not only enriched in monazite but can
also be concentrated in allanite through substitution
563
reactions. Evidence from the partition coefficient suggests
that allanite has the ability to enrich LREE in high-silica
melt compared to monazite in peraluminous melt
(discussed in the NLM granites in Hsieh et al., 2008).
Judging from the presence of allanite (Table 1), the scarcity
of monazite, as well as high silica contents (71% on average)
of the granitoid samples from the eastern CAOB, the
crystallization of allanite is the main factor that leads to
the LREE depletion in apatites (Fig. 5).
The considerable variation in apatite LREE patterns
means they are unlikely to be controlled by a single factor
such as allanite. The decreasing (La/Sm)N from groups
C1, B2, B1 to A2 corresponds with a similar decreasing
trend in Eu/Eu* (Fig. 5), revealing the early crystallization
of plagioclase is likely another reason for the LREE deple-
tion in apatites. Plagioclase is a major rock-forming mineral
in granitoids that prefers LREE to HREE. However, given
the much lower LREE partition coefficients of plagioclase
than that of allanite, the effect of plagioclase in a felsic melt
on LREE depletion in apatite is limited. Following the crys-
tallization of plagioclase, Eu/Eu* and Sr in apatites
decrease rapidly as their steep LREE patterns become flat
(Fig. 5). For those apatites with (La/Sm)N < 1, the early
crystallization of allanite, rather than plagioclase, should
be the dominant controller for the strong depletion of
LREE (Fig. 5). However, the effect of the early crystalliza-
tion of plagioclase in concentrating LREE is particularly
pronounced in mafic magmas, where the modal abundance
of plagioclase typically is a few hundred times that of apa-
tite (Chu et al., 2009).
In addition, LREE depletion in apatite affected by meta-
morphism has long been established (e.g., Harlov, 2015;
Henrichs et al., 2019; O’Sullivan et al., 2020; Jepson
et al., 2021). Granitoid samples 18ER24, 18ER20,
16ER35, 17DX10, 18ER21, 13ER30, 16ER38, 16ER15,
and 16DX15 all belong to Group A and have a gneissic tex-
ture (Fig. S2a–d). Correspondingly, apatites in these grani-
toids commonly show an overgrowth rim in CL images or a
chaotic internal texture (Fig. 2f and g), suggesting that such
samples were affected by metamorphism. Similarly, the
recrystallization caused by the metamorphism also affected
the zircon grains in these granitoid samples, as evidenced by
the CL images (Fig. S2e–k). In Fig. 5, apatite (La/Sm)N val-
ues in these meta-granitoid samples are inconsistent with
their decreasing trends, i.e., their LREE are more depleted
relative to other samples with approximate Eu anomalies.
Moreover, apatite data from these meta-granitoid samples
also display a metamorphic transformation in the discrimi-
nation diagram for protoliths (Fig. 6b; O’Sullivan et al.,
2020). On a plot of granitoid U-Pb age vs. apatite LREE
content (Fig. 6c), those apatites in older samples tend to
be more depleted in LREE. The older rocks experienced
one or more metamorphic events, which likely affected apa-
tite composition.
The above evidence strongly suggests that the LREE
behavior in apatite can be affected by several factors, which
may impact their utility to discriminate events/processes on
discrimination diagrams. For example, Antoine et al. (2020)
concluded that apatites from TTGs have the geochemical
signature of low (La/Yb)N values that are very distinct from
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those of apatite in other granitoid types. Their diagram of

(La/Yb)N vs. YbN seems to clearly separate TTG and
post-Archean apatites. However, numerous metamor-
phosed apatites characterized by LREE depletion in post-
Archean samples show similar behavior with the TTG
grains documented by Antoine et al. (2020). If we plot the
apatite data from high- and low-grade metamorphic rocks
from O’Sullivan et al. (2020) in the diagram proposed by
Antoine et al. (2020), there is a pronounced overlap
between metamorphosed apatite and TTG apatite
(Fig. S4). Moreover, post-Archean apatites affected by the
early crystallization of monazite and/or allanite will also
show a close affinity to TTG apatite on this diagram
(Fig. S4). Thus, LREE in apatite is not particularly robust
in rock discrimination.

5.1.4. Heavy REE depletion and its variation in apatite

Both apatite and zircon are considered early magmatic
phases, and hence the HREE depletion in apatite may have
a counterpart in zircon (Hsieh et al., 2008). However, the
model of residual liquids formed by equilibrium crystalliza-
tion of dry and hydrous parental basalts using Rhyolite-
Melts (Gualda et al., 2012) indicates that even with increas-
ing SiO2 content of a parental melt, the saturation temper-
ature difference between apatite and zircon gradually
decreases, and apatite will crystallize earlier during magma
cooling (Lee and Bachmann, 2014). This is confirmed by
petrological observations as well as zircon and apatite sat-
uration temperatures, i.e., apatite often occurs as inclusions
in zircon grains (e.g., Miles et al., 2013; Bruand, Storey and
Fowler, 2014; Antoine et al., 2020; Guo et al., 2021), and
the apatite saturation temperature is usually higher than
zircon (Fig. 7a; Table S2; calculation methods for mineral
Fig. 7. (a) Correlation between apatite saturation temperature
saturation temperatures are attached in Supplementary
(TAp, °C) and zircon saturation temperature (TZr, °C); (b)
material). It is noteworthy that some experimental Correlation between apatite (Sm/Yb)N ratios and TZr - TAp values.
researches reveal that the apatite saturation temperature Calculation methods of mineral saturation temperatures are
in highly peraluminous melts would be decreased, and attached in Supplementary material, and the results are listed in
apatite would crystallize late (Bea, Fershater and Table S2. Grey symbols represent previous data from Sha and
Corretge, 1992; Pichavant, Montel and Richard, 1992). Chappell (1999), Belousova et al. (2001), Hsieh et al. (2008), Chu
Therefore, we plot our apatite data separately according et al. (2009), and Pan et al. (2016), whereas colored symbols
to the whole-rock ASI value >1.1 or 1.1. Although we represent data in this study.
do find that the apatite saturation temperature in highly
peraluminous melts (ASI > 1.1) is more likely lower than Heavy rare earth elements in apatite do not always
zircon saturation temperature (Fig. 7a), the HREE relative retain original HREE-depleted signatures from the parental
content does not increase with the decrease of the satura- granitic melt. In one respect, the early precipitation of
tion temperature difference between zircon and apatite in allanite and plagioclase in Group A granitoids would result
the peraluminous melt. (Fig. 7b). To sum up, the HREE in a strongly LREE-depleted and slightly HREE-enriched
depletion in apatite should not be attributed to the early composition in the residual melt. Thus, apatites crystalliz-
crystallization of the HREE-enriched zircon but is more ing from such melts would naturally enhance their ability
likely inherited from an HREE-depleted parental melt. to concentrate HREE. In addition, metamorphic recrystal-
The most pronounced HREE depletion in Group C apa- lization has also been proposed as a vital factor driving
tites can be directly inherited from the adakitic magma HREE enrichment in apatites (e.g., Jepson et al., 2021),
source (Fig. 3g–i), which provides an efficient tracer to iden- although its effect is not apparent in our dataset. Two situ-
tify the adakitic affinities of host rocks (see Section 5.4 for ations have been revealed that could provide HREE to apa-
detailed discussion). It also confirms that the specific com- tites during late-stage recrystallization: 1) the dissolution of
position of a parental melt constitutes a significant control allanite, hornblende, and titanite at the Cpx-in isograd
on apatite REE patterns (Roeder et al., 1987; Belousova (Bingen, Demaiffe and Hertogen, 1996); and 2) the retro-
et al., 2002; Chu et al., 2009; Cao et al., 2011; Pan et al., gression of garnet during low-grade metamorphism would
2016). release HREE (Jepson et al., 2021 and references therein).
 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573
Therefore, TTG apatites from Bruand et al. (2020) and
Antoine et al. (2020) were potentially significantly meta-
morphosed, which further explains why they have not
inherited the REE characteristics of adakitic melt and dis-
play the pattern of LREE depletion and HREE enrichment.
5.2. Revisiting the influence of magma differentiation on
apatite geochemistry
The majority of previous research suggests that apatite
compositions generally change with increasing aluminum
saturation index accompanying the fractionation of the
parental melt. They also emphasize some REE signals of
apatite, such as LREE depletion and negative Eu anomaly,
could assess the degree of magma differentiation. However,
this view is mainly based on data from strongly peralumi-
nous rocks (S-type and highly fractionated I-type granites
from eastern Australia, south China, the Himalaya, and
central Europe) (Sha and Chappell, 1999; Belousova
et al., 2001; Hsieh et al., 2008; Chu et al., 2009). These
highly fractionated granites are treated as an important sig-
nal of crustal compositional maturity because the partial
melting product of highly fractionated granite would not
be more differentiated (Wu et al., 2017).
The CAOB, as the largest accretionary orogenic belt on
Earth (Jahn, Wu and Chen, 2000; Cawood et al., 2009),
has experienced a complex orogenic evolution impacting
crustal composition. Evidence from whole-rock Sr-Nd and
zircon Hf isotopes of granitoids of the CAOB shows an
increase in juvenile, mantle-derived compositions during
the Phanerozoic (Wang et al., 2009; Kröner et al., 2014), sug-
gesting it constitutes a region of low crustal maturity relative
to other more highly-evolved belts. Consequently, there are
very few strongly peraluminous granitoids in the eastern
CAOB (Wu et al., 2004, 2011), and the highly fractionated
I-type granites (Wu et al., 2003, 2017) cannot be distin-
guished from other weakly peraluminous granites by ASI
values (all range from 1.0 to 1.1). Correspondingly, no signif-
icant covariation is found between the aluminum saturation
index of host rocks and apatite geochemistry in our samples
compared with previous research (Fig. 8). Unlike what Sha
and Chappell (1999) found, i.e., apatites in mafic I- and felsic
I-type granitoids display two distinct evolutionary trends, no
similar geochemical variations between mafic and felsic I- &
A-type granitoids are revealed in our apatite data (Fig. S5).
Although the REE patterns of Group A1 apatites match
well with apatites crystallized from granite pegmatites
(Fig. 3a; Belousova et al., 2002) and, Group A2 apatites
show similar REE behavior of S-type & highly-
fractionated I-type granites (Fig. 3b; Sha and Chappell,
1999), the geochemical composition of their host rocks does
not support such inferences (Table 1; Table S2). There are
multiple apatite REE patterns formed in such a narrow
range of whole-rock ASI values (0.93–1.33, most of them
are weakly peraluminous with ASI value = 1.0–1.1), which
further implies the geochemical features of apatite could
not be used to assess the degree of magma differentiation
as these patterns could result from other factors, such as
the crystallization of some REE-bearing minerals and meta-
morphism. Recent research on apatite geochemistry from
565
Fig. 8. Correlation between apatite (La/Sm)N ratios and whole-
rock ASI values. Grey symbols represent previous data from Sha
and Chappell (1999), Belousova et al. (2001), Hsieh et al. (2008),
Chu et al. (2009), Cao et al. (2011), Pan et al. (2016), and Bruand
et al. (2020), whereas colored symbols represent data in this study.
Metamorphic samples are marked as different colors (identified by
petrography and/or apatite geochemical composition with
La + Ce + Pr + Nd < 1500 ppm, O’Sullivan et al., 2020). (For
interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
the Pingtan intrusive complex, SE China, shows that both
magmatic and hydrothermal apatites exist in the same gran-
ite. The former exhibits the same apatite REE pattern as
those within I-type granite, but the latter displays similar
geochemical compositions to those from S-type and
highly-fractionated I-type granites (Zhang et al., 2020).
Similarly, this highlights the limitation of assessing the
degree of magma differentiation through apatite REE pat-
terns, and comprehensive evidence is needed to substantiate
(such as internal morphology), especially in detrital apatite
studies (e.g., O’Sullivan et al., 2020). Moreover, some
research (e.g., Qu et al., 2019; Zhang et al., 2020) suggests
that volatiles and fluid-inclusions in apatite might be able
to provide a unique perspective to trace magma differentia-
tion because the mechanism for intensive fractionation of
granitic magma, in a manner, is related to the melt-fluid
interaction (Wu et al., 2017).
5.3. Sr and plagioclase crystallization: insight into the whole-
rock composition
The compositional variations in apatite are largely the
result of partition competition with pre-existing and/or
coexisting major and accessory minerals (Chu et al., 2009;
Pan et al., 2016). The correlation between Sr concentration
and Eu anomaly in apatites and the relation of apatite
Eu/Eu* to whole-rock Eu/Eu* highlight the significant role
of plagioclase in controlling apatite geochemistry (Fig. 4a
and b) (Girardi et al., 2012). The early crystallization of
plagioclase would reduce the Sr and Eu contents in residual
melt and then influence their concentrations in apatite
crystallizing from such a magma.
566 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573

Our data, along with previous studies, confirm that the

variation of Sr content in apatite enables an estimate of
the SiO2 and Sr contents of the whole-rock (Fig. 4a and
b; Belousova et al., 2001; Jennings et al., 2011; Bruand,
Storey and Fowler, 2014, 2016; Bruand et al., 2017). In
Fig. 4a, the negative correlation of SrAp-SiO2 WR could be
related to the extensive crystallization of plagioclase in sili-
cate melt and an apparent increase of the Sr partition coef-
ficient of plagioclase in high-silica melt. The dataset in this
paper contains more comprehensive data based on Bruand
et al. (2017) but shows that the correlation of SrAp-SiO2 WR
is broader than the trend previously reported. In other
words, the individual result of apatite Sr content can only
be used to estimate the range of silica content of its host
rock because the error is likely to reach up to 14 wt.%
(Fig. 4a). The potential of Sr in apatite for estimating
whole-rock SiO2 content is dependent primarily on how
well the magma SiO2 content at the time of apatite crystal-
lizing correlates with the whole-rock SiO2 of the indepen-
dent suite, because such melt was probably more mafic
than the final whole-rock composition that experienced fur-
ther fractionation (Chu et al., 2009; Nathwani et al., 2020).
A linear correlation between Sr in apatite and whole-
rock (SrAp-SrWR) implies that apatite can faithfully record
the chemical signature of Sr in the host-rock (Fig. 4b;
Bruand, Storey and Fowler, 2014, 2016; Bruand et al.,
2017) and is little affected by other factors. Considering that
the Sr in apatite is concentrated from a residual melt after
the early crystallization of plagioclase, further studies of
in situ LA ICP-MS analysis on the chemical composition
of plagioclase have been undertaken (the analytical method
is attached in Supplementary material, and the results are
listed in Table S4). The results indicate that the plagioclase
Sr content also strongly correlates with Sr contents of both
the whole-rock and apatite (Fig. 9a and b). Although the
possible mechanism for the linear relationships of
SrPl-SrWR, SrPl-SrAp, and SrAp-SrWR is unclear, it appears
to imply the constant Sr partition coefficients of two differ-
ent mineral hosts observed from large datasets (calculated
as slopes in Fig. 9). Compared to apatite, however, plagio-
clase consistently develops chemical zonation during its
crystallization history and is susceptible to alteration during
later geological processes. The results of the plagioclase Sr
content obtained by in situ ICP-MS analysis will thus be a
little more dispersed and often display a discordant alter-
ation trend at lower Sr contents (Fig. 9a and b).
A compilation of data from previous research and this
study shows that Sr content in apatite and the correspond-
ing whole-rock correlate along a 0.7 regression line (the Fig. 9. Correlations of (a) SrPl-SrWR, (b) SrPl-SrAp, and (c) SrAp-
grey line in Fig. 9c). Considering the strong concordance SrWR (Ap-apatite; Pl-plagioclase; WR-whole-rock). Grey symbols
degree of our data (R2 = 0.96) and that the analytical results represent the previous data from Sha and Chappell (1999),
were obtained under the same experimental environment, Belousova et al. (2001), Hsieh et al. (2008), Chu et al. (2009),
Cao et al. (2011), Pan et al. (2016), and Bruand et al. (2020),
the slope of the regression line from our data is recom-
whereas colored symbols represent data in this study. A few
mended as the apatite/bulk rock partition coefficient for samples are not shown in fig. b and c as their apatite Sr contents are
Sr in granitic melts (it may also work for mafic melts, but much higher than others (i.e., 16DX16 and 16DX18, see data in
more data are needed), i.e., DSr Apatite=bulk rock ¼ 0:69 (Fig. 9c). Table S2). Metamorphic samples are marked as different colors
A few scattered data are excluded in the calculation as the (identified by petrography and apatite geochemical composition
whole-rock Sr content of those samples is likely affected with La + Ce + Pr + Nd < 1500 ppm, O’Sullivan et al., 2020). (For
by plagioclase alteration. But for those altered samples, it interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
is possible to back-calculate the original content of Sr in
 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573 567

altered whole-rock from apatite Sr content by using this par-
tition coefficient (Fig. 9c; Bruand et al., 2017). In addition,
to understand if metamorphism would affect this value, we
recalculated the slope of the regression line, excluding the
metamorphosed data not only in our dataset but also in pre-
vious studies (Fig. 9c; metamorphic samples are marked in
the diagram). The result indicates that the partition coeffi-
cient of Sr between apatite and granitoid bulk rock is still
stable (0.69 for our data and 0.71 for previous data;
Fig. 9c). Thus, we conclude that even in metamorphosed
granites, the approximate Sr concentration in apatite does
not deviate from the whole-rock value on aggregate. It thus
achieves a reasonable estimation of Sr content in the source
rocks of detritus. Furthermore, Sr in whole-rock can also be
applied to estimate apatite Sr content, which is an effective
way to determine whether the apatite from the same sample
could be used to undertake in situ Sr-isotope analysis since
the Sr content in the analyzed mineral should reach the
detection limit of this experiment.
5.4. Discriminant for adakite from apatite geochemistry
Defant and Drummond (1990) first introduced the term
adakite after Kay (1978) reported ‘‘magnesian andesite” on
Adak Island to describe some intermediate-acid volcanic
rocks inferred to form from slab melting in a subduction
zone. Adakite is geochemically characterized by high
Al2O3 and Sr contents, low Y and HREE contents, lack
of Eu anomaly, coupled with high Sr/Y and (La/Yb)N
ratios (Defant and Drummond, 1990). The initial naming
of ‘‘adakite” was related to a specific tectonic setting. How-
ever, with more rocks showing similar geochemical features
with adakite, the models of petrogenesis of adakite have
progressively expanded. From the perspective of magma
evolution, the decomposition of plagioclase and the residue
of garnet & hornblende in the magma source, play a vital
role in producing the high Sr content, less pronounced to
absent Eu anomaly, and the lower HREE content assigned
to adakites (Moyen, 2009).
As described above, Group C granitoids (Fig. 3g and h)
include adakites and low Sr-Y granitoids, except sample
16ER10 (I-type granite) (Fig. S1d; relevant whole-rock data
are summarized in Table S2). Apatites in these samples
inherit the typical adakitic trace element signatures of low
HREE and Y contents, high Sr content, and a weak Eu
anomaly compared with other magma types (Fig. 3g and
h). Also, similar to the difference of whole-rock geochem-
istry between adakites and low Sr-Y granitoids, apatites
in low Sr-Y granitoids exhibit lower Sr content than those
in adakites. The above features strongly suggest that apatite
may potentially identify adakite by its geochemical compo-
sition (Pan et al., 2016).
Recently, Bruand et al. (2020) proposed a trivariate dia-
gram to discriminate TTG and sanukitoid using Sr, Y, and
LREE contents in apatites. They use the apatites from
post-Archean adakite and high Br-Sr granitoid samples
(regarded as the Archean equivalents of TTG and sanuki-
toid, respectively) to prove the robustness of their diagram,
and two fields of ‘‘TTG & adakite” and ‘‘sanukitoid & high
Ba-Sr granitoid” are defined. However, if adakite apatite
data from our study, as well as others, are plotted in their
diagram, it displays a much wider compositional range,
and very few fall into the ‘‘adakite & TTG” field
(Fig. 10a). As we discussed in Section 5.1.3, the LREE con-
tent of apatite is not suitable to be an end member for dis-
criminating rock types. Firstly, LREE in apatite can be
affected by many factors. Secondly, the ‘‘TTG & adakite”
field that Bruand et al. (2020) defined is very close to the
Y end member of the diagram, reflecting a preference for
those apatites featured by LREE depletion and HREE
enrichment. However, this kind of apatite REE pattern is
more likely to belong to metamorphic apatite (Bingen,
Demaiffe and Hertogen, 1996; Harlov, 2015; Henrichs
et al., 2019; O’Sullivan et al., 2020; Jepson et al., 2021).
Thus, the issue here is whether all the apatites from TTGs
are characterized by LREE depletion and HREE enrich-
ment, or alternatively, the ‘‘TTG and adakite” field was
based on metamorphic samples (Bruand et al., 2020).

Fig. 10. (a) Ternary discrimination diagram of 10*Sr-LREE-10*Y for apatite (after Bruand et al., 2020); (b) Ternary discrimination diagram
of 1000/(Eu/Eu*)-10*Sr-HREY for apatite; (c) Biplot of Sr vs. HREY of apatites, which shows three unique fields for adakites, low Sr-Y
granitoids, and non-adakitic rocks. Note that a few apatite data in fig. c with Sr content >1300 ppm and HREY content >11,000 ppm are not
shown, but they are plotted within the extended boundaries of the defined fields.
568 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573
Although more research on this matter is needed, post-
Archean adakite and high Br-Sr granitoid samples, as
equivalents of TTG and sanukitoid, cannot be distin-
guished in this diagram (Fig. 10a).
According to our data, we propose that Sr and HREY
(Gd  Lu + Y) contents as well as Eu/Eu* values, discrim-
inate adakites. On the one hand, although Sr and Eu bud-
gets are strongly controlled by plagioclase crystallization,
plagioclase is not a major crystallizing phase in the residual
melt. Thus, Sr and Eu in adakite apatites would be primar-
ily affected by the melt composition, and the stable correla-
tion of SrAp-SrWR particularly ensures that apatite can
genuinely reflect the source composition. On the other
hand, some potential factors that could increase the apatite
HREE composition only occur during later metamorphic
events, and the evidence for metamorphic effects on apatite
composition can be well-identified from internal morphol-
ogy and geochemistry.
Based on the robustness of Sr, HREY, as well as Eu/Eu*
in apatite, a trivariate discrimination diagram is con-
structed (Fig. 10b). 10*Sr and 1000/(Eu/Eu*) are used as
two end members in the diagram to balance the order of
magnitude. Apatite from adakitic granites is defined as a
cluster at the top left-hand side of the diagram towards
the 10*Sr corner, whereas the field at the lower section from
the center towards 1000/(Eu/Eu*) corner distinguishes non-
adakitic granitoids (Fig. 10b). The field boundaries are
determined mainly by the data population, which means a
few scattered data from different samples are excluded as
they might be affected by metamorphism or source hetero-
geneity. Considering that this diagram cannot discriminate
low Sr-Y granitoids very well, another discrimination dia-
gram is proposed based on the absolute contents of Sr
and HREY (Fig. 10c). The linear correlation between SrAp
and SrWR (DSr Apatite=bulk rock ¼ 0:69), together with the Sr con-
tent of precisely defined adakite (over 400 ppm in whole-
rock), provides an excellent boundary in using apatite Sr
content to discriminate adakite and low Sr-Y granitoids
(i.e., 270 ppm; Fig. 10c). Apatites from low Sr-Y grani-
toid samples 16ER34 and 16ER31 plot into the adakite
and non-adakite fields, respectively, and may reflect the
early geochemical composition of the magma. However,
the magma might experience a degree of late-stage differen-
tiation and evolution, which could strengthen or weaken
the adakitic nature of the residual magma.
Data from previous research are also plotted on the
same discrimination diagrams to verify the utility of this
method and fine-tune the field boundaries. It should be
noted that TTG apatite data from Antoine et al., 2020
and Bruand et al., 2020 are excluded in our diagrams as
they appear to include strongly metamorphosed analyses.
In addition, the apatite data from sanukitoids (and equiva-
lent, high Ba-Sr granitoids) fall into the adakite field
(Fig. 10b and c) because they do show similar trace element
behaviors to adakites and are usually distinguished by
whole-rock major elements. Therefore, the apatite method
for discriminating sanukitoid and TTG samples needs fur-
ther study. In addition, apatite data of samples ET026I
and T024 from Chu et al. (2009) are marked in the dia-
grams as they display abnormal behaviors relative to those
from the same type of granitoids (Fig. 10b and c). Apatites
in ET026I exhibit a different affinity with their host rock
(Fig. 10b and c), showing an inconsistent, steep LREE-
enriched REE pattern with no Eu anomaly and have much
higher Sr contents than the values expected from their
whole-rock Sr content or ASI value. Either magma mixing
or source heterogeneity can be responsible for these
inconsistent apatite REE patterns, and magma with much
higher Sr contents than the final bulk-rock must have
existed in the magma chamber or magma source (Chu
et al., 2009). The apatites in sample T024 that plotted out-
side but very close to the adakite field (Fig. 10b and c) are
explained by Chu et al. (2009) as reflecting the competition
between abundant LREE-enriched minerals such as
allanite, epidote, and feldspar (mainly K-feldspar).
However, we tend to believe they are metamorphic grains
based on the research from O’Sullivan et al. (2020) that
apatite grains with La + Ce + Pr + Nd content much less
than 1500 ppm are highly likely to be metamorphic. This
also explains why T024 apatites plot into the same field with
metamorphic TTG apatites in the diagram from Bruand
et al. (2020) (Fig. 10a).
If we exclude metamorphic and magma mixing-trend
apatites and replot the adakite data and non-adakite ones
separately, it will be more straightforward that our discrim-
ination diagrams enable the identification of adakite rock
types on apatite geochemistry (Fig. S6). Notably, our dis-
crimination diagram cannot be used for apatites from mafic
rocks because apatites derived from mafic melts would
define a field with high Sr (i.e., Fig. 4a – the negative corre-
lation between whole-rock SiO2 content and apatite Sr con-
centration) but variable HREY contents, thus there would
be an evident and undivided overlapping field for mafic
rocks and adakites.
The Central Asian Orogenic Belt is a complex accre-
tionary orogenic belt in which adakites formed in a variety
of tectonic settings with diverse petrogenesis (e.g., partial
melting of a thickened region of the mafic lower continental
crust, partial melting of a subducting oceanic slab, partial
melting of a delaminated region of the lower continental
crust). Therefore, our results, combined with the published
apatite data on adakites from different locations and with
different ages, are used to establish a discrimination dia-
gram applicable to a variety of conditions. Besides, many
large epithermal and porphyry deposits such as Au, Cu,
and Mo found worldwide are associated with adakite or
adakitic rocks. Therefore, adakite could be used as a signal
to explore these metal minerals, especially copper and gold,
in a similar manner to the way kimberlites are used to find
diamonds (Defant et al., 2002). Apatite geochemistry, with
the ability to discriminate adakite, thus provides a new
window to indicate the deposit type and genesis into the
future.
6. CONCLUSIONS
(1) Apatite REE patterns in granitoids are mainly con-
trolled by the composition of the parental melt
and element partition coefficients. However, the
 C.-Y. Sun et al. / Geochimica et Cosmochimica Acta 317 (2022) 552–573
crystallization of other REE-bearing minerals (such
as allanite, plagioclase, and hornblende) and late-
stage metamorphism can result in variations in apa-
tite REE patterns;
(2) Apatite trace elements show low potential to assess
the degree of magma differentiation in areas with
low crustal maturity, such as accretionary orogens
like the eastern CAOB;
(3) The variation of Sr content in apatite is closely related
to the early crystallization of plagioclase, and the par-
titioning of Sr in these two minerals follows a linear
correlation. A partition coefficient of Sr between apa-
tite and bulk rock is proposed (DSr Apatite=bulk rock ¼ 0:69)
for granitoids, which achieves a reasonable estimation
of the original Sr content in eroded host rock and the
source rocks of detrital apatites.
(4) Trace elements of apatite reveal a geochemical trend
of Sr, Eu/Eu*, and HREY, enabling robust and reli-
able discrimination of adakite.
Declaration of Competing Interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
ACKNOWLEDGMENTS
This study was financially supported by the National
Natural Science Foundation of China (Grant No.
41772047), Australian Research Council grant
LF160100168, the State Scholarship Fund from China
Scholarship Council (201906170217), and the Interdisci-
plinary Research Program for Ph.D. Students of Jilin
University (Grant No. 101832020DJX069). The staff of
Wuhan Sample Solution Analytical Technology Co.,
Ltd, Wuhan, China are thanked for their technical sup-
port during the in situ geochemical compositions of apatite
and plagioclase analyses. We also thank Jin-Wei Guo in
China University of Geosciences (Wuhan), Xin-Rui Wei
and You-Bo Guo in Monash University, Zeynab
Gharamohammadi in University of Tehran, Shi-Wei
Wang, Xin-Yu Long, and Jin-Peng Luan in Jilin
University, for their selfless assistance during fieldwork,
experiment preparation, data processing, and manuscript
revision.
The authors warmly thank Elizabeth A. Bell, Gary J.
O’Sullivan, and two anonymous reviewers for their insight-
ful comments and suggestions, which significantly
improved the quality of this paper. We would also like to
acknowledge associate editor Rosemary Hickey-Vargas,
for her editorial handling of this submission.
APPENDIX A. SUPPLEMENTARY MATERIAL
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.gca.2021.10.028.
569
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Associate editor: Rosemary Hickey-Vargas