Geoscience Frontiers 10 (2019) 425e437

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China University of Geosciences (Beijing)

Geoscience Frontiers
journal homepage: www.elsevier.com/locate/gsf

Research Paper

Mineral association and graphite inclusions in nephrite jade from

Liaoning, northeast China: Implications for metamorphic conditions and
ore genesis
Cun Zhang, Xiaoyan Yu*, Tianlong Jiang
School of Gemology, China University of Geosciences (Beijing), 29 Xueyuan Road, Beijing 100083, China

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

Article history: The Liaoning Province in the northeastern part of the North China Craton (NCC) hosts several
Received 18 January 2018 tremolite jade (nephrite) deposits. Here we investigate the Sangpiyu tremolite jade deposit where
Received in revised form the relationship between abundant graphite inclusions within the jade remains enigmatic. We
13 February 2018
employ petrography, electron probe microanalysis, X-ray-diffraction, and Raman spectroscopy to
Accepted 26 February 2018
characterize the tremolite jade and its inclusion minerals. The Sangpiyu jade is predominately
Available online 19 March 2018
Handling Editor: M. Santosh composed of tremolite with minor calcite, dolomite, serpentine, titanite, zoisite, allanite, chlorite,
apatite, chromite and graphite. Raman spectroscopy of graphite inclusions shows that the D1/G
Keywords:
intensity ratio ranges from 0.78 to 0.88 in deep green samples and from 0.05 to 0.23 in dark green
Tremolite jade samples. The ranges of D1/(D1 þ G) integral area ratio for these types are from 0.0548 to 0.3037
Petrology and Raman spectroscopy and 0.5528 to 0.7355 respectively. The formation temperature of graphite inclusions in the dark
Graphite green tremolite jade is computed as 549.8  C, whereas that for the deep green sample is about
Sangpiyu 343.2  C. Our results suggest that the jade formation occurred in a multi-stage process through the
North China action of hydrothermal fluids and metamorphism possibly in a subduction-related setting at
moderate to high temperatures.
Ó 2018, China University of Geosciences (Beijing) and Peking University. Production and hosting by
Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/
licenses/by-nc-nd/4.0/).

1. Introduction investigated in this study is located in the Sangpiyu, which was

discovered in 2012. Previous studies reported the mineral associ-
Tremolite jade (nephrite) with its toughness, color and trans- ation and the chemical composition of tremolite jade in this area
parency has gained importance as a collector’s item (e.g., Dorling, (Jiang, 2014; Wu, 2014). However, no detailed studies were carried
1985; Yin et al., 2014; Yu, 2016). The formation of nephrite is also out as yet on these deposits and debates surround their genesis. The
significant in terms of its petrological and tectonic settings, and has salient feature of these deposits is that many of the tremolite jade
been linked to either contact metasomatism of carbonate rocks samples contain abundant graphite inclusions, the characterization
such as dolomite and/or limestone, or between silicic rocks and of which would provide important indication on the grade of
serpentinised peridotite (Harlow and Sorensen, 2000, 2005; Liu metamorphism and petrogenetic history of these deposits (see
and Yu, 2009). In China, deposits of economic grade nephrite Table 1).
occur in Xinjiang, Qinghai, Guizhou, and Liaoning provinces (Liao Carbonaceous material (CM) is widespread in metamorphic
and Zhu, 2005; Zhang et al., 2011; Yin et al., 2014; Yu, 2016). Both rocks, especially those of metasedimentary origin (Beyssac et al.,
primary deposits of tremolite jade and secondary ore deposits 2002a, b). Carbonaceous material can be converted into anthra-
termed as “Hemo” jade occur in the Xiuyan County of Liaoning cite, meta-anthracite, semi-graphite and graphite (Kwiecin  ska and
Province in Northeast China where numerous mines operate in the Petersen, 2004) by diagenesis or progressive metamorphism. Pre-
Xiyugou, village of the Pianling Town. The tremolite deposit vious studies on graphitization process under different tempera-
ture and pressure conditions show a progressive increase in
temperature and pressure influenced by metamorphic processes
* Corresponding author. (Beyssac et al., 2002a, b). In the natural context, all types of
E-mail address: [email protected] (X. Yu).
carbonaceous material are transformed into graphite at
Peer-review under responsibility of China University of Geosciences (Beijing).

https://doi.org/10.1016/j.gsf.2018.02.009
1674-9871/Ó 2018, China University of Geosciences (Beijing) and Peking University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-
ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
426 C. Zhang et al. / Geoscience Frontiers 10 (2019) 425e437

temperatures around 450e500  C (Wang, 1989). Raman spectros- which were amalgamated along the Trans-North China Orogen
copy, high resolution transmission electron microscopy (HRTEM), (TNCO) during late Paleoproterozoic (Zhao et al., 2005; Santosh,
selected area electron diffraction (SAED), X-ray-diffraction (XRD) 2010; Zhai and Santosh, 2011; Zhao and Zhai, 2013) (Fig. 1). The
and other techniques have been employed to characterize the WB represents a composite block composed of the Yinshan and
crystallization and structure of graphite (Wang et al., 1989). Ordos sub-blocks which were welded along the intervening Inner
The Sangpiyu tremolite jade contains abundant graphite in- Mongolia Suture Zone at 1.95e1.92 Ga (also known as the Khondalite
clusions, mostly showing striated distribution pattern in dark green Belt) (Santosh, 2010; Zhao and Zhai, 2013). The EB is considered
varieties and belts of graphite in the deep green types. No detailed to have undergone Paleoproterozoic riftesubductione
studies have been done so far to characterize the occurrence and collision along the Jiao-Liao-Ji Belt during 2.2e1.9 Ga (Zhao and Zhai,
genesis of these graphite inclusions. Furthermore, the study on 2013). The belt is composed of volcano-sedimentary sequences
secondary mineral components, including the graphite inclusions, metamorphosed under greenschist to lower amphibolite facies, and
is important in evaluating the metamorphic conditions and ore in some places up to granulite facies, and invaded by granitoids and
genesis. In this study we investigate the graphite inclusions in mafic intrusions (Zhao et al., 2005; Zhao and Zhai, 2013). The Jiao-
nephrite jade through Raman spectroscopy and X-ray-diffraction to Liao-Ji belt is divided into the northern and southern domains
derive the quantitative parameters for the degree of graphitization where the former is composed of the Fenzishan, North Liaohe and
(Beyssac et al., 2002a, b). We also employ Raman spectroscopy Laoling groups, and the latter consists of the Jingshan, South Liaohe
which has been demonstrated as an effective tool (e.g., Wopenka and Ji’an groups. The Liaohe Group has been further subdivided into
and Pasteris, 1993) to distinguish between semi-graphite or the North and South Liaohe groups (Wang et al., 2017). The northern
graphite in different facies (greenschist facies-granulite facies) and domain is dominantly composed of quartzite, slate, schist, phyllite
the crystallization conditions. and marble, whereas the southern one is dominated by graphite-
bearing biotite gneiss, sillimanite-garnet-biotite gneiss, garnet-
2. Geological background schist and marble.
The Xiuyan jade deposits form part of the Liaohe Group in the
2.1. Geological background Liaoning Province of the EB. The dominant rocks in this region are
metamorphosed Paleoproterozoic rocks, and are overlain by
The North China Craton (NCC) is one of the Precambrian cores of Mesozoic and Quaternary cover. In the study area, the major
the Eurasian continental collage with an Archean to Paleoproter- metamorphic units are represented by tourmaline-bearing, boron-
ozoic basement covered by Mesoproterozoic to Cenozoic sequences rich metasediments, felsic volcanics and Mg-rich carbonates
(Zhai and Santosh, 2011; Zhao and Zhai, 2013; Liu et al., 2017) forming part of a major anticline-syncline system. Graphite-bearing
(Fig. 1). The tectonic framework of the NCC involves two major metapelitic rocks also occur in the area represented by meta-
crustal blocks, the Western Block (WB) and the Eastern Block (EB) morphosed carbonaceous pelitic sediments. The nephrite jade

Figure 1. Generalized geological and tectonic framework of the North China Craton (NCC) (after Zhao et al., 2005; Santosh, 2010). The study area is shown by blue box.
 C. Zhang et al. / Geoscience Frontiers 10 (2019) 425e437 427

deposits are mainly located in the Mg-rich metacarbonate rocks parallel to the tremolite marble strata along the margin of the mine.
which are restricted to the core of the major syncline (Wang et al., The marble layer here has a length of 130 m with an average
2007). The exposed strata in the Sangpiyu area is mainly composed thickness of 4.57 m (Fig. 2a). The tremolite-bearing marble is
of the Liaohe Group metamorphic rocks. The Sangpiyu tremolite generally white colored, and partly grey or pale green. The main
ore deposit studied in this paper is located in the Dashiqiao Group minerals are dolomite and tremolite with minor serpentine (Wang
which is rich in dolomite component. The jade deposit occurs in the et al., 2007; Jiang, 2014, Wu, 2014).
western margin of the BeiwagoueWangjiapuzieZhoujiapuzi syn- The Sangpiyu tremolite jade shows various colors including
clinorium to the north of the Hengshanli syncline. bluish white, yellow green, deep green and dark green, although
The overall structure of the Xiuyan jade mine in the Liaoning pure white variety has not yet been found (Fig. 3aeh). The bluish
Province is characterized by an arc-shaped large anticline with white sample is translucent with coarse texture and waxy-vitreous
EWeNE trending axis and three secondary anticlinal and two luster (Fig. 3a). The deep green sample is sub-translucent with
synclinal structures (Fig. 2b). The anticlinal structure is mostly more delicate texture and vitreous luster. In addition, black belts of
irregular dome type. Several faults are also developed in the mining graphite are commonly developed in them (Fig. 3b). The yellow
area (Wang et al., 2007). green sample is also sub-translucent with a delicate texture, vit-
reous luster and abundant graphite inclusions (Fig. 3c, d, g),
2.2. Orebody background whereas the dark green sample is opaque with coarse texture and
vitreous luster (Fig. 3e and f).
The nephrite jade investigated in this paper is from a marble Petrographic studies using polarizing microscope reveals that
mine located ca. 30 km northwest of the Hadapi Town in Xiuyan the main mineral composition of the Sangpiyu tremolite jade is
County, and 4 km southwest of the Xiyugou Village (coordinates: tremolite, with minor calcite, dolomite, zoisite, titanite, allanite,
40 28.6700 N, 123 02.7640 E, elevation 449 m). The orebody is apatite and graphite (Fig. 4aej). The tremolite jade formation

Figure 2. (a) Geology of the Xiuyan region, Liaoning area. (b) Structural cross-section of the Xiuyan mine in Liaoning area (modified after Wang, 2007; The 7th Geological Unit of
Liaoning Province, Dandong). Sampling area in the Dashiqiao Group is also shown.
428 C. Zhang et al. / Geoscience Frontiers 10 (2019) 425e437

Figure 3. Representative hand specimen photographs of the different types of graphite-bearing tremolite jade in the study area: (a) bluish white; (b) deep green (graphite black
belt); (ced) yellow green (d contains parallel graphite inclusions); (eef) sample cut by yellow-green (with abundant graphite inclusions); (g) the reverse side of the yellow green
sample; (h) polished slabs of the samples. Gr: graphite.
 C. Zhang et al. / Geoscience Frontiers 10 (2019) 425e437 429

Figure 4. Representative photomicrographs showing the mineral assemblages: (aeb) bluish white (crossed nicols); (cef) deep green (crossed nicols); (geh) yellow green (crossed
polarizer); (i) deep green (parallel nicols) showing black belt of graphite inclusions, mostly granular or flaky; (j) dark green (parallel nicols) with abundant graphite inclusions,
mostly disseminated granular and flaky. Tr: tremolite; Cc: calcite; Ti: titanite; Zo: zoisite; Ait: allanite; Ap: apatite; Gr: graphite.
430 C. Zhang et al. / Geoscience Frontiers 10 (2019) 425e437

Figure 5. Representative photomicrographs of graphite inclusions: (a) fracture in yellow green sample (reflected-light) showing abundant black graphite inclusions; (b) dark green
(transmitted-light) with abundant black graphite inclusions showing oriented distribution); (ced) deep green (reflected-light) with graphite showing semi-metallic luster. Gr:
graphite.

process can be divided into the following phases. The first is the Table 1
development of platy texture with coarse-grained tremolite and Quantitative parameters of Raman spectroscopy in dark green and deep green
samples.
clear mineral boundary. The grain size is more than 0.1 mm, and
some of the sectional grains reach 0.5e1 mm (Fig. 4a and b). The Quantitative Dark green Average Deep green Average
second phases is marked by columnar or lamellar texture with clear parameters sample value sample value

mineral boundary. Mineral grains show a size range of Position of the 1580.28 1578.78 1589.29 1584.81
G band 1578.78 1583.29
0.04e0.2 mm (Fig. 4d,f). The third phase shows fibrous texture with
(cm1) 1577.28 1581.85
indistinct mineral boundary, with grain size in the range of G FWHM 12.06 11.61 66.03 63.32
0.01e0.04 mm (Fig. 4c,j). The fourth stage shows an extremely (cm1) 11.46 63.47
subtle fibrous texture with indistinguishable mineral boundary. 11.31 60.46
Mineral grains are less than 0.01 mm with typical felty texture. This D1/G band 0.23 0.16 0.88 0.82
intensity 0.20 0.81
is the major texture of the high-quality tremolite jade from this ratio 0.05 0.78
area (Fig. 4h). D1/(G þ D1) 0.3037 0.2050 0.7355 0.6693
The fractures in yellow green sample under reflected-light band area 0.2566 0.7195
shows abundant black graphite inclusions (Fig. 5a). The dark ratio 0.0548 0.5528
green sample is almost opaque under transmitted-light and also
carries abundant black graphite inclusions showing oriented dis-
tribution (Fig. 5b). Graphite in the deep green sample shows semi- Electron probe analysis shows that the main chemical compo-
metallic luster under reflected-light (Fig. 5c and d). nents of the Sangpiyu tremolite in Liaoning Province are SiO2, MgO
and CaO (Kim, 2007; Liu et al., 2011a, b), in the range of 57.18e60.92
wt.%, 21.17e23.87 wt.% and 11.95e13.45 wt.%, respectively. The
3. Methods and results content of FeO varies from 0.16 wt.% to 2.07 wt.% with an average
value of 1.20 wt.%. In bluish white sample, the content of FeO is
Electron probe analyses were performed at the Electron Probe lowest with the average value of 0.30 wt.%. The contents of FeO in
Laboratory of the Chinese Academy of Geological Sciences (CAGS) yellow green sample varies greatly with an average of 1.67 wt.%. In
using JXA-8100 microprobe. The chemical compositions of the dark green sample, the content of FeO becomes more stable with an
samples were analyzed by Energy Dispersive Spectroscopy (EDS) average of 1.52 wt.%; whereas in deep green sample, the average
and the experimental conditions were 20 kV, beam current 1  108 FeO content is 1.32 wt.%. Minor Cr2O3 is detected in some samples
A. The results show that tremolite jade in Sangpiyu is predomi- such as the deep green and dark green types, where the content is
nately composed of tremolite with minor calcite, allanite, chlorite, relatively low. The content of Al2O3 varies from 0 to 1.52 wt.% with
apatite, chromite and graphite. The chromite occurs as very small an average value of 0.47 wt.%. The CaO, Na2O and K2O of alkali metal
grains of size less than 10 mm, but its presence might indicate that contents are in the range of 11.95e13.45 wt.%, 0e0.08 wt.% and
the serpentinite alteration might have also involved ultramafic 0.01e0.13 wt.% with average values of 12.69 wt.%, 0.04 wt.% and
protoliths. 0.04 wt.% respectively (Table 2).
 C. Zhang et al. / Geoscience Frontiers 10 (2019) 425e437 431

Table 2
Electron microprobe analysis of tremolite.

Number TQB-1 TQB-2 THL-1 THL-2 TML-2 TML-1 TSL-1 TSL-2

P2O5 0.000 0.000 0.000 0.291 0.000 0.000 0.030 0.000
SiO2 60.039 60.195 60.926 57.306 60.768 58.269 57.188 58.204
TiO2 0.024 0.000 0.012 0.000 0.082 0.058 0.000 0.000
Al2O3 0.000 0.105 0.461 0.450 0.415 0.369 1.525 0.473
Cr2O3 0.000 0.000 0.011 0.680 0.009 0.000 0.000 0.000
MgO 23.499 22.971 22.648 21.174 22.519 22.242 23.874 23.809
NiO 0.000 0.000 0.000 0.011 0.000 0.031 0.000 0.000
FeO 0.446 0.162 1.269 2.076 1.519 1.525 1.442 1.199
MnO 0.058 0.028 0.053 0.115 0.059 0.142 0.109 0.062
CaO 13.458 13.111 12.036 11.957 12.404 12.477 13.272 12.854
Na2O 0.000 0.021 0.069 0.040 0.039 0.059 0.029 0.087
K2O 0.006 0.027 0.110 0.131 0.053 0.019 0.017 0.010
F 0.287 0.000 0.000 0.069 0.289 0.034 0.185 0.169
Cl 0.011 0.002 0.001 0.001 0.001 0.007 0.000 0.000
Total 97.828 96.622 97.596 94.301 98.157 95.232 97.671 96.867
P 0.000 0.000 0.000 0.086 0.000 0.000 0.009 0.000
SiT* 8.000 8.000 8.000 8.000 8.000 8.000 7.947 8.000
TiC 0.000 0.000 0.000 0.000 0.008 0.012 0.000 0.000
AlT 0.000 0.000 0.000 0.000 0.000 0.000 0.053 0.077
AlC 0.000 0.017 0.107 0.111 0.064 0.060 0.197 0.000
Cr 0.000 0.000 0.000 0.113 0.000 0.000 0.000 0.000
Fe3þC 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
MgC 4.665 4.654 4.433 4.407 4.420 4.553 4.946 4.879
Ni 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Fe2þC 0.050 0.018 0.139 0.242 0.167 0.175 0.168 0.138
MnC 0.007 0.000 0.000 0.014 0.007 0.017 0.013 0.007
Mg 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Fe2þ 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Mn 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Ca 1.920 1.909 1.693 1.788 1.749 1.835 1.976 1.893
Na 0.000 0.000 0.000 0.005 0.005 0.008 0.004 0.012
K 0.000 0.000 0.000 0.005 0.004 0.000 0.000 0.000
Sum 14.641 14.598 14.373 14.771 14.425 14.660 15.314 15.007
Mg/(Mg þ Fe) 0.989 0.996 0.970 0.948 0.964 0.963 0.967 0.973

Table 3
Electron microprobe analysis of minor minerals. W R-wall rock.

Mineral Calcite Allanite Chlorite Apatite Chromite Plagioclase

Number TQB TSL THL WR THL WR TSL TSL THL THL THL THL TSL TSL THL WR
P2O5 0.000 0.029 0.268 0.026 0.063 0.014 0.035 0.000 41.211 40.411 40.141 41.194 0.042 0.117 0.083 0.006
SiO2 0.028 34.788 30.958 0.089 31.936 30.361 32.726 35.565 0.057 0.055 0.083 0.053 1.341 6.494 0.000 68.427
TiO2 0.000 0.000 0.023 0.000 1.571 0.000 0.034 0.000 0.000 0.000 0.024 0.012 0.066 0.010 0.030 0.057
Al2O3 0.014 20.060 0.810 3.232 0.536 19.716 15.221 14.799 0.000 0.070 0.004 0.000 0.106 0.648 0.162 20.321
Cr2O3 0.001 0.000 0.000 0.000 4.388 0.000 0.039 0.042 0.003 0.000 0.000 0.000 26.592 23.892 17.338 0.000
Nd2O3 0.000 0.000 0.000 5.972 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Ce2O3 0.000 5.794 3.609 34.456 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
La2O3 0.000 2.621 4.271 15.095 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
MgO 0.384 1.390 7.164 0.001 6.356 26.921 28.403 29.678 0.059 0.030 0.001 0.000 0.542 2.278 9.587 0.000
NiO 0.003 0.000 0.033 0.000 0.021 0.000 0.012 0.006 0.000 0.000 0.034 0.000 0.184 0.285 0.099 0.000
FeO 0.053 7.989 0.535 1.189 13.689 5.984 4.306 3.845 0.056 0.000 0.047 0.000 70.515 63.251 75.329 0.020
MnO 0.079 0.265 0.051 0.000 0.245 0.100 0.121 0.161 0.000 0.044 0.008 0.000 0.797 0.745 0.634 0.000
CaO 47.243 14.946 8.711 2.401 8.810 0.029 0.038 1.228 54.590 54.923 55.416 55.578 0.134 1.231 0.000 0.162
Na2O 0.034 0.000 0.147 0.000 0.046 0.003 0.094 0.045 0.016 0.035 0.004 0.000 0.026 0.031 0.004 10.407
K2O 0.000 0.024 0.415 0.002 0.050 0.013 0.102 0.000 0.000 0.000 0.001 0.000 0.003 0.000 0.007 0.088
F 0.000 0.000 2.797 0.000 0.000 0.261 0.000 0.257 2.122 2.808 1.649 1.796 0.000 0.000 0.000 0.081
Cl 0.007 0.016 0.024 8.870 0.009 0.000 0.012 0.000 0.010 0.000 0.004 0.011 0.000 0.000 0.000 0.000
Total 47.846 87.922 59.816 71.333 67.720 83.402 81.143 85.626 98.124 98.376 97.416 98.644 100.348 98.982 103.273 99.569

The secondary minerals are mainly chromite and apatite. The In order to further determine the primary and secondary min-
content of Cr2O3 in chromite ranges from 17.33 wt.% to 26.59 eral compositions of Sangpiyu tremolite jade from the Liaoning
wt.% with an average value of 22.60 wt.%, whereas FeO shows a Province, backscattered electron images (BSE) were obtained using
range of 63.25e75.33 wt.% with an average of 69.69 wt.%. The Energy Dispersive Spectroscopy (EDS). The results show that the
content of P2O5 in apatite varies from 40.14 wt.% to 41.24 wt.%, main mineral component of the Sangpiyu tremolite is tremolite,
and CaO shows a range of 54.59e55.92 wt.%. From electron probe and the secondary minerals are calcite, chlorite, chromite, allanite,
data analysis, the content of Cl is almost negligible, whereas F apatite and graphite (Fig. 6aej). The major minerals of the wall
varies from 1.65 wt.% to 2.81 wt.%, indicating that the apatite rocks are plagioclase and the secondary minerals are allanite and
belongs to the chlorapatite variety in the yellow green sample chlorite (Fig. 6j). In bluish white sample, the main mineral
(Table 3). composition is tremolite with minor calcite. In BSE images, the
432 C. Zhang et al. / Geoscience Frontiers 10 (2019) 425e437

Figure 6. Backscattered electron images of the different types of tremolite jade samples with graphite: (aeb) bluish white; (cee) deep green; (feh) yellow green; (i) dark green; (j)
wall rock. Apatite is mostly developed in the yellow green samples, whereas chromite is common in the deep green and yellow green samples. Tr: tremolite; Cc: calcite; Ait: allanite;
Chl: chlorite; Ap: apatite; Cm: chromite; Gr: graphite; Pl: plagioclase.
 C. Zhang et al. / Geoscience Frontiers 10 (2019) 425e437 433

rhombohedral cleavage of calcite is clearly visible, and partly rep- The X-ray-diffraction studies were conducted by powder X-ray-
resents metasomatie-relict texture (Fig. 6a and b). Chlorite, allanite diffraction at the China University of Geosciences (Beijing) using
and chromite are the most common minerals in the deep green Smart Lab instrument using samples powdered to 320 mesh.
samples. The color of chlorite and tremolite are markedly different Experimental conditions were: Cu target, 40 kVe100 mA, scanning
under BSE, which may be related to the content of Mg. Chromite
shows granular structure with mineral grains less than 10 mm in
size (Fig. 6c, d and e). Apatite is common in the yellow green
samples together with minor chromite and allanite (Fig. 6g and h).

Figure 8. Raman spectra of graphite inclusions: (a) deep green sample (main mineral
vibration absorption peak appears at points No.1 and No.2; D1 has a relatively wide
Figure 7. X-ray-diffraction patterns: (a) bluish white with calcite and serpentine in- band and the intensity is also relatively strong); (bec) dark green sample (the D1 broad
clusions; (b) dark green and yellow green-dark green transition zone (both contain band is relatively narrow and the intensity is lower; main mineral absorption peak is
graphite diffraction peaks); (c) comparison of diffraction patterns for different samples. also observed at point No.3).
434 C. Zhang et al. / Geoscience Frontiers 10 (2019) 425e437

speed 8 /min. The results show that the bluish white sample con- whereas this is absent in dark green sample (Fig. 8). In addition, the
tains secondary minerals such as serpentine and calcite (Fig. 7a), G band in deep green sample is wider whereas the G band in dark
whereas the yellow green and deep green samples are relatively green sample becomes sharper. In dark green sample, D2 is very
pure (Adamo and Bocchio, 2013) (Fig. 7c). Graphite inclusions are weak or absent in the right “shoulder” of G, but can be distin-
rare in deep green sample and therefore this study focuses on the guished from G; however, in deep green sample, both are insepa-
analysis of graphite inclusions in dark green sample. The graphite rable (Fig. 8).
layers in these samples show a relatively constant In summary, the characteristics of graphite Raman spectroscopy
d (002) ¼ 0.33562 (Zhang et al., 2015), and suggest that these were of the Sangpiyu tremolite jade from Liaoning Province indicate the
formed at relatively high temperature metamorphic conditions effect of metamorphism (Xiong et al., 2006; Qiu et al., 2010). With
(Fig. 7b). increasing metamorphic grade, the intensity of D1 and D2 becomes
Raman spectroscopy was performed at the National Gemstone weakened. The D1 has a wide band and high intensity in low
Testing Centre (NGTC), China, using RENISHAW Raman 1000 in- temperature metamorphic facies, whereas in high temperature
strument. The experimental conditions were: excitation light metamorphic facies, the band becomes narrower and the intensity
source wavelength 514.5 nm, resolution 4 cm1, laser power becomes lower. With increasing metamorphic grade, the G band in
30e40 mW, scanning time 20 s, measurement range of poorly crystallized graphite is wider, and is located in the range of
100e2000 cm1. 1583e1589 cm1. In this sample, it is not possible to separate the
In the first order, the approximate shape of Raman spectra can contributions of the D2 component from that of the G band,
be used as an indicator of the metamorphic grade (Pasteris and whereas in dark green sample, the wide G band splits into the two
Wopenka, 1991; Wopenka and Pasteris, 1993). In deep green sam- and the D2 component decreases with increasing metamorphic
ple, the main mineral vibration absorption peak appears at points grade. At the same time, G band becomes sharper. In low temper-
No.1 and No.2 (Tan et al., 2013); D1 has a relatively wide band and ature metamorphic conditions, poorly crystallized graphite appears
the intensity is also relatively strong (Fig. 8a). In dark green sample, at 1500 cm1 band, whereas in the high temperature metamorphic
the D1 broad band is relatively narrow and the intensity is lower environment, this band is absent.
(Fig. 8b and c). Main mineral absorption peak is also observed at In order to prove the validity of the observation, the first order
point No. 3 (Fig. 8c). In deep green sample, the band of D3 is nar- region of Raman spectrum was decomposed by the method of peak
rower, whereas the spectrum of dark green sample is wider. The fitting (Fig. 9a and b). The D1/G intensity ratio (R1), D1/(D1þG) area
deep green sample shows a weak vibration peak around 1500 cm1, ratio (R2) and the G band full width at half maximum (FWHM) are
obtained from the Lorentz function, considering the D2 deletion or
negligible integration. Based on these quantitative parameters, it is
possible to evaluate the metamorphic conditions of graphite in-
clusions in the Sangpiyu tremolite jade.
With increasing metamorphic grade, the G band becomes
smaller, showing a relatively obvious “linear” declining tendency
(Fig. 10a). The full width at half maximum (FWHM) of G band can
effectively reflect the degree of crystallinity of graphite. The average
value of G FWHM in deep green sample is about 63.32, whereas in
dark green sample, the average is about 11.61, which is much less
than that of dark green sample. This would suggest that the degree
of crystallinity of graphite in dark green sample is markedly higher
than that of graphite in deep green sample. These results indicate
two types of tremolite jade in our study area formed under distinct
metamorphic conditions (Fig. 10b).
The D1/G (R1) of graphite inclusions range from 0.78 to 0.88 in
deep green sample and from 0.05 to 0.23 in dark green sample. The
ranges of D1/(D1þG) (R2) are from 0.0548 to 0.3037 and 0.5528 to
0.7355, indicating that the graphite inclusions in the two samples
formed under high and low temperature metamorphic conditions
respectively (Fig. 10c and d).
Previous studies on the comparison between semi-graphite and
graphite have established that the degree of graphitization in-
creases with metamorphic grade. The temperature at which semi-
graphite transforms into the graphite is about 463  C (Rantitsch
et al., 2016). Based on the Raman spectroscopic parameters D1/
(D1þG), it is further confirmed that graphite in dark green sample
formed under high temperature metamorphic conditions. Howev-
er, the D1/(D1 þ G) ranges from 0.5528 to 0.7355 with an average of
0.6693 in deep green sample. This is similar to carbonaceous ma-
terial, such as that reported from Taiwan (Yui et al., 1996).
According to the equation of linear regression of Raman ther-
mometery of graphite (Beyssac et al., 2002a, b): T ( C) ¼ 445
R2 þ 641 (330< T <650  C), the metamorphic temperature of
graphite in the dark green sample is estimated as 505.9e616.6  C,
Figure 9. Representative example of decomposition peak in the first order region of
the Raman spectrum. (a) The blue line marks the peak position after fitting, in dark
with an average of 549.8  C. The R2 values are greater than 0.5 in
green sample; (b) the red, blue and green lines are the peak position after fitting, in deep green sample, taking the average value of 0.6693, the meta-
deep green sample. morphic temperature of graphite is calculated as ca. 343.2  C.
 C. Zhang et al. / Geoscience Frontiers 10 (2019) 425e437 435

Figure 10. Quantitative parameters of Raman spectroscopy in dark green and deep green samples: (a) position of the G band, (b) G band full width at half maximum (FWHM),
(c) D1/G (R1) band intensity ratio, (d) D1/(G þ D1) (R2) band area ratio.

4. Discussion Nephrite jade has been reported from various settings including
ultramafic and ophiolitic rocks in several localities in New Zealand
4.1. Mineral association and ore genesis where it is associated with narrow metasomatic reaction zones at
the margins of serpentinite in association with silicic metasedi-
Petrography, X-ray-diffraction, electronic microprobe analysis ments and metavolcanics (Adams et al., 2007). However, the more
and backscattered electron images show that the tremolite jade in evolved 87Sr/86Sr values of the nephrite-bearing rocks in these
Sangpiyu is predominately composed of tremolite with minor calcite, localities suggest inheritance from the metasediment components
dolomite, serpentine, zoisite, allanite, chlorite, apatite, chromite and rather than the mafic and ultramafic rocks (Adams et al., 2007).
graphite. Although the presence of chromite might indicate the The 1300 km long Hetian nephrite belt in the Western Kunlun
involvement of ultramafic components in the source, chromite and Mountains in China, the largest in the world, shows characteristics
spinel are common in metacarbonates. Also, the dominant host rocks of magnesian skarn with replacements of coarse-grained tremolite
in the mine area are dolomitic marbles, therefore, we consider their by fine-grained tremolite (nephrite) formed through prograde
metasomatic alteration by hydrothermal fluids containing minor Ca. metasomatism and retrograde alteration (Liu et al., 2015). There-
In the Paleoproterozoic at ca. 1.8 Ga, this region witnessed regional fore, we infer that the tremolite jade deposit in our study was
metamorphism, with the formation of dolomite marble. The dolo- formed through metamorphic-metasomatic processes of carbon-
mite marble was then replaced by siliceous hydrothermal fluids to ate lithologies associated with carbonaceous and siliceous
form serpentine. If Ca content is higher, the dolomite marble is sediments.
replaced by siliceous hydrothermal fluids to form tremolite jade ac-
cording to the reactions below (Harlow and Sorenson, 2005): 4.2. The characteristic of Raman spectrum during graphitization

6 CaMg[CO3]2 þ 4 SiO2aq þ 4 H2O / Mg6[Si4O10](OH)8 þ 6 The Raman spectra of carbonaceous material is divided into the
CaCO3 þ 6 CO2aq first and the second order regions, respectively. In the first order
region (1100e1800 cm1), the main peak located at 1350 cm1 (D1
5 CaMg[CO3]2 þ 8 SiO2aq þ H2O / Ca2Mg5[Si4O11]2(OH)2 þ 3 band) and 1580 cm1 (G band). In addition, 1150 cm1 (D4 band),
CaCO3 þ 7 CO2aq 1500 cm1 (D3 band), and 1620 cm1 (D2 band) are also observed.
436 C. Zhang et al. / Geoscience Frontiers 10 (2019) 425e437

The 1350 cm1 band (D1 band) is commonly termed as the defect temperatures of formation and probably marks only the late stages.
band, and has been attributed to in-plane defects and heteroatoms. In our study, the temperature of graphite inclusions from the
The D3 appears only as a low broadband in poorly crystallized Sangpiyu tremolite jade is in the range of 550e343  C in dark green
graphite, and has been related to defects outside the plane of aro- sample, whereas deep green sample shows a lower range of tem-
matic layers (Beny-Bassez and Rouzaud, 1985). The 1620 cm1 (D2 peratures at 223e392  C. These results indicate that the two types
band) makes a shoulder on the right side of G band. In well- have distinct genetic histories. The dark green sample belongs to
crystallized graphite, this component is absent, whereas in poorly relatively higher temperature metamorphic history, as compared to
organized CM, the G and D2 bands cannot be separated and only the deep green sample.
one broad band occurs at 1600 cm1 (Beyssac et al., 2002a, b). The
quantitative parameters such as D1, D2 and G integral area, G full 5. Conclusion
width half maximum (FWHM), and D1 and G intensity ratio in the
first order region are all significant in evaluating graphitization The characteristics and quantitative parameters of graphite in-
process and in understanding the metamorphic grade. clusions in nephrite jade from the Liaoning Province in the North
Raman spectroscopy in the present study indicates that the China Craton indicate progressive graphitization with increasing
spectral characteristics of graphite from the two tremolite jade metamorphic grade. The degree of graphite crystallinity is higher in
types differ significantly. In the lower temperature metamorphic dark green sample than in deep green sample. The graphite in-
facies, G band in poorly crystallized graphite is wider. Also, it is clusions in deep green sample correspond to semi-graphite or
impossible to separate the contributions of the D2 component from meta-anthracite.
that of the G band. In contrast, the G wide band splits into the two The graphite inclusions in the Sangpiyu tremolite jade analyzed
bands and the D2 component decreases or is absent with increasing in this study are in the range of low to high temperature meta-
metamorphic grade. At the same time, G band becomes much morphic facies. The metamorphic temperature in dark green
sharper. Thus, Raman spectra of graphite can provide robust in- sample is estimated at 550  C, which is significantly different from
formation on the metamorphic conditions. the formation conditions of the tremolite jade, suggesting that the
formation of graphite is earlier than that of tremolite jade. How-
4.3. Quantitative parameters analysis of Raman spectroscopy ever, the metamorphic temperature of graphite inclusions in deep
and XRD green sample is consistent with that of the tremolite jade, sug-
gesting syngenetic entrapment.
Based on the Raman spectra, the average value of G band FWHM
in the dark green sample is about 11.61, whereas in deep green Acknowledgments
sample, the average is about 63.32, which is markedly higher than
that of the former. This would suggest that the degree of crystal- The authors thank Prof. M. Santosh and Ms. Shan-Shan Li for
linity of graphite in the dark green sample is higher than that of valuable help with preparation of this manuscript and for guidance.
graphite in deep green sample. According to the D1/G intensity We are grateful to Jian Zhang and Bo-Yu Wang for their kind help
ratio of graphite inclusions in two samples, the D1/G (R1) of with Raman spectroscopy experiment. Journal referees Xiaofang He
graphite inclusions range from 0.78 to 0.88 with an average of 0.82 and an anonymous reviewer provided constructive criticisms and
in deep green sample, and from 0.05 to 0.23 with an average of 0.16 helpful comments which greatly improved this paper.
in dark green sample. This indicates that graphite inclusions in the
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