5.1. Types and Petrogenesis of the Protolith of “Laoshan Jade”
According to field observations and previous research [
23], the geological occurrence of the “Laoshan Jade” rock mass shows that serpentinite is in abrupt contact with the surrounding granite gneiss, which is different from the metasedimentary rock, displaying layered conformable contact. Due to their mineral compositions, “Laoshan Jade” is named serpentinite, with a high degree of serpentinization. Together with the observation under the microscope, EPMA results, and test results for whole-rock geochemistry characteristics, it can be concluded that the protolith of “Laoshan Jade” belongs to ultramafic magmatic rock, peridotite.
ACM graph (
Figure 8) shows that the protolith of “Laoshan Jade” is metamorphic peridotite. It is generally believed that the composition of the original mantle is lherzolite, which is transformed into dunite and harzburgite after partial melting [
39]. The value of (Mg + TFe)/Si, MgO + TFeO can distinguish the type of metamorphic peridotite (
Table 5) [
40].
The value of (Mg + TFe)/Si of samples is 1.23–1.92, and the value of MgO + TFeO is 45.73–56.79% (
Table 4), Most samples belong to harzburgite, yk-007 belongs to dunite, and yk-001, yk-003, yk-012 belong to lherzolite.
Based on olivine’s EPMA data, the concentrations of MgO, NiO, MnO, and Fo values are high, while CaO content is low. According to the CaO-Fo graph [
41] (
Figure 9), olivine in “Laoshan Jade” falls into the mantle peridotite area, indicating that the peridotite protolith is from the mantle.
Some accessory minerals in metamorphic rocks are from the protolith and relatively stable during the metamorphic process. Therefore, the study of accessory minerals can be used as an important basis to judge the type and evolution of the protolith.
The accessory minerals in “Laoshan Jade” samples are mainly magnetite and chromite (
Figure 4). It can be clearly seen that the disseminated magnetite was formed in the later metamorphic process, while the idiomorphic granular chromite with zonal texture was formed earlier. Researchers believed that zonal texture in chromite formed by magma crystallization shows a trend of decreasing Cr# and increasing Mg# from core to edge [
42,
43]. However, the tendency in chromite of “Laoshan Jade” is indicating a reverse trend, with increased Cr# and decreased Mg#, which demonstrates the zonal texture of chromite is not formed by magma crystallization and differentiation. Previous studies have indicated that magnetite at the edge of chromite can be formed during the process of regional metamorphism, and it is the product of chromite alteration during the serpentinization process [
44,
45,
46,
47]. From the Cr-Al-Fe
3+ graph of metamorphic facies [
48] and metamorphic temperatures graph [
46] of chromite in ”Laoshan Jade“, it can be inferred that cores fall in the mantle chromite area, indicating that chromite in the core with regular shape is of magma origin and belongs to protolith mineral, while magnetite in the edge was formed by the metamorphic alteration with a temperature lower than 500 °C (
Figure 10).
Qi has proposed that total cation numbers in edges may be less than those in cores during alteration of the original chromite, which is attributed to the out-migration of Mg
2+ and Al
3+ [
49]. Therefore, in order to maintain the balance of total electron valency, part of Fe
2+ in original minerals should be oxidized to Fe
3+, and the external Fe
3+ needs to penetrate the internal chromite [
49]. The EPMA results demonstrate that the Fe
2O
3 content (1.68–5.56 wt.%) in chromite core is much lower than that in edge (54.75–67.68 wt.%); thus, the core is not enough to provide all Fe
3+ contents in Fe
2O
3 at the edge. Moreover, since chromite crystal is very stable, it is relatively difficult to change its chemical composition only by low-pressure and low-temperature serpentinization [
50]. Combined with the fact that some magnetite was filled in the serpentine in “Laoshan Jade” samples (
Figure 3), it is deduced that chromite was once altered by Fe-rich fluid during the serpentinization process in an environment with a high oxygen fugacity, where Fe
3+ is much more than Fe
2+ and is transferred to magnetite at the edge accompanied by the replacement between Fe in fluid and Al and Cr in chromite.
As a characteristic accessory mineral, chromite is a superior geothermometer, because its elemental composition is sensitive to physical and chemical conditions of the upper mantle during the crystallization process [
51]. Due to its better resistance to metasomatism and corrosion, it is useful to explore the genetic information of the protolith by analyzing its elemental composition. In order to obtain its crystallization conditions, the following formulas were used to calculate temperature and pressure [
52]:
where
and
, respectively, represent the mole fraction of Cr
3+ and Fe
2+ in chromite.
The calculated temperature and pressure results of the chromite core are presented in
Table 6. The average crystallization temperature and pressure are 1348 °C and 3.1 GPa, respectively, which are similar to the temperature (1280–1350 °C) and pressure (3 GPa) conditions of the asthenosphere, indicating the protolith may be derived from the upper mantle asthenosphere.
Different graphs of chromite were used to determine the characteristics of the protolith. The relationship of Cr#-TiO
2 [
53] (
Figure 11) indicates that chromite is from the depleted mantle peridotite. Furthermore, both Al
2O
3-TiO
2 tectonic setting graph (
Figure 12a) and Al
2O
3-Fe
2+/Fe
3+ protolith discrimination graph [
54] (
Figure 12b) demonstrate that chromite belongs to subduction zone peridotite.
It is generally accepted that peridotite originates from the upper mantle. Comparing the oxide content after deducting LOI with that of global primitive mantle peridotite [
55], the average MgO content in “Laoshan Jade” samples is 39.92 wt.% (
Table 4), higher than that in
Table 7, with Al
2O
3 (1.78 wt.%) and CaO (0.40 wt.%) contents lower than those in
Table 7. This phenomenon indicates that the protolith of “Laoshan Jade” belongs to the depleted mantle peridotite and has undergone a certain degree of partial melting, which is consistent with the results of
Figure 11.
Based on the above analysis, it is deduced that the serpentinite protolith of “Laoshan Jade” belongs to peridotite, originated from the mantle wedge partially melted in the mantle wedge, which is consistent with the conclusions of a previous study [
23].
5.2. Serpentinization Process
The Serpentinization process of peridotite from mantle wedge is usually related to the fluid released by the subducting plate [
25]. At certain temperature and pressure conditions, large amounts of H
2O and fluid migration elements were released from the subducted slab of the underlying Yangtze plate, metasomatized with the depleted peridotite. The serpentinite was formed.
5.2.1. Types of Serpentine
Antigorite, lizardite, and chrysotile are three types of serpentine. They can be distinguished by Raman spectra.
According to the research of Bahram [
56], there are slight differences in the wavenumber positions of these spectral peaks for the three types of serpentine. Near 230 cm
−1, the spectrum peak of antigorite is located at a lower wavenumber (224–230 cm
−1), while the spectrum peak of lizardite is located at a medium wavenumber (229–231 cm
−1), and the spectral peak of the chrysotile is at a higher wavenumber position (231–235 cm
−1). Near 350 cm
−1, there is no spectral peak for the antigorite, while there are irregular weak peaks in the lizardite, and the peak is more obvious for chrysotile. Near 390 cm
−1, the peak of antigorite is at the lower wavenumber (377–382 cm
−1), while the peak of lizardite is at the middle wavenumber (382–385 cm
−1), and the peak of chrysotile is located at a higher wavenumber position (383–391 cm
−1). Near 690 cm
−1, the peak of antigorite is at a lower wavenumber position (681–688cm
-1), the peak of lizardite is located at the middle wavenumber position (685–691 cm
−1), and the peak of chrysotile is at the higher wavenumber position (689–691 cm
−1). In addition, there are common peaks near 1050 cm
−1 in antigorite, while chrysotile has a spectral peak near 1100 cm
−1, and for lizardite, there is occasionally no peak.
The Raman spectra of the samples’ serpentine are shown in
Figure 13. Four strong peaks are located near 230 cm
−1, 380 cm
−1, 690 cm
−1, and 1050 cm
−1. The main peaks and their functional group attribution are summarized in
Table 8.
According to the statistical results in
Table 8, the main spectral peaks of serpentine in the sample are mostly located at low wavenumber positions and have peaks near 1050 cm
−1. Only the spectral peak of serpentine in yk-010 is mainly located at medium wavenumber position and is missing the peak near 1050 cm
−1.
In addition, some irregular weak peaks were found and analyzed as follows: The weaker peak near 350 cm−1 in the yk-010 is attributed to the [SiO4] tetrahedral bending vibration, which is the characteristic peak of lizardite. The peak of 460 cm-1 is attributed to Si-O bending vibration. The weak peak of 520 cm−1 may be related to the deformation vibration of the Si-O tetrahedron and Al-O tetrahedron. The small peak of 630 cm−1 is attributed to the OH-Mg-OH conversion mode.
These results show that there is lizardite in the yk-010, and the serpentine of other samples belongs to the antigorite. The presence of chrysotile was not detected in samples.
In addition, lizardite contains more Al and Fe cations, while antigorite is richer in Si and poorer in Mg [
57]. Most lizardites contain 38–40 wt.% SiO
2 [
58], and most antigorite minerals contain 42–45 wt.% SiO
2 [
59,
60]. According to EPMA data (
Table S1), the SiO
2 content of serpentine is mostly between 42 wt.% and 45 wt.%.
In conclusion, most of the serpentine in the sample belongs to antigorite. Antigorite is the most common type of serpentine in the subduction zone [
61].
5.2.2. Temperature of Serpentinization Process
In the subduction zone, the conversion between serpentine minerals is mainly controlled by temperature. Lizardite exists at a low temperature of 200 °C and can be transformed into chrysotile by heating. Antigorite stably exists in a high temperature above 300 °C and starts to be dehydrated at 400 °C [
62]. According to the types of serpentine in the samples, the temperature of serpentinization can be preliminarily assessed.
Most of the serpentine minerals in “Laoshan Jade” are poor in Al and Ca, formed by alteration of olivine. Guo showed that the serpentinization of olivine has the strongest alteration at 300 °C and begins to weaken when the temperature reaches 350 °C [
25].
Figure 3 reveals that a small amount of chlorite in the serpentinite is idiomorphic to hypidiomorphic, with a pyroxene pseudomorph, indicating that it forms earlier than antigorite. Because its crystal structure and composition are very sensitive to pressure, temperature, the composition of the whole rock, and physical–chemical properties of environments [
63], chlorite is usually used as a geological thermometer to obtain the physical and chemical conditions during the crystallization process. Here, an empirical thermometer and interplanar spacing thermometer of chlorite were used to calculate its crystallization temperature. The formulas are as follows [
64,
65,
66,
67,
68,
69,
70]:
It is obvious that calculation results of the empirical thermometer are relatively consistent (
Table 9), while results of the interplanar spacing thermometer are relatively lower. Therefore, the crystallization temperature of chlorite is around 200 °C.
The BSE images (
Figure 4) show that magnetite is disseminated in antigorite, indicating its formation time is later. Previous studies have demonstrated that magnetite begins to appear at high temperatures (>300 °C) [
71,
72], and there is no magnetite crystallized at low temperatures (<200 °C) [
73,
74].
In summary, the serpentinization process of “Laoshan Jade” serpentinite can be divided into the following three stages:
1. When the temperature was lower (around 200 °C), the fluid released from the subduction zone interacted with depleted mantle peridotite. Pyroxene was altered into chlorite, and serpentinization of olivine began to form lizardite.
2. As the subduction deepened, and the temperature increased (300–350 °C), the degree of serpentinization of olivine became strongest with the formation of antigorite. At the same time, magnetite began to crystallize. The Fe-rich fluid reacted with chromite in the protolith and formed the zonal texture of chromite.
3. At higher temperatures (>350 °C), serpentinization of olivine began to weaken, and serpentinite was finally formed.