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Citation: Han, S.; Wang, S.; Duan, X.;
Santosh, M.; Li, S.; Sun, H.; Tang, Z.;
Tan, K.; Liu, S.; Chen, L.; et al.
Metallogenic Material Source and
Genesis of the Jilinbaolige Pb-Zn-Ag
Deposit, the Great Xing’an Range,
China: Constraints from Mineralogical,
S Isotopic, and Pb Isotopic Studies of
Sulfide Ores. Minerals 2022,12, 1512.
https://doi.org/10.3390/
min12121512
Received: 25 October 2022
Accepted: 24 November 2022
Published: 27 November 2022
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minerals
Article
Metallogenic Material Source and Genesis of the Jilinbaolige
Pb-Zn-Ag Deposit, the Great Xing’an Range, China: Constraints
from Mineralogical, S Isotopic, and Pb Isotopic Studies of
Sulfide Ores
Shili Han 1,2,3 , Sheng Wang 1,3, Xianzhe Duan 1,3, *, M. Santosh 4,5, Sai Li 1, Haoran Sun 1, Zhenping Tang 1,3,
Kaixuan Tan 1, San Liu 1, Liang Chen 1, Aiyang Ma 1, Shuqin Long 1and Wei Liu 1
1Department of Geology, School of Resource & Environment and Safety Engineering, University of South
China, Hengyang 421001, China
2Hunan Key Laboratory of Rare Metal Minerals Exploitation and Geological Disposal of Wastes,
Hengyang 421001, China
3Research Institute No.230, CNNC, Changsha 410007, China
4School of Earth Sciences and Resources, China University of Geosciences Beijing, 29 Xueyuan Road,
Beijing 100083, China
5Centre for Tectonics, Exploration and Research, University of Adelaide, Adelaide 5005, Australia
*Correspondence: 2014000504@usc.edu.cn
Abstract:
The Jilinbaolige Pb-Zn-Ag polymetallic deposit is located in the eastern part of Inner
Mongolia and in the central-southern part of the Great Xing’an Range, in which several large-
sized
Pb-Zn-Ag
deposits have been found. The Jilinbaolige deposit, which occurs mainly at the
contact zone between Yanshanian granite intrusion and sedimentary strata, shows strong NE-to-
NNE structural control. The deposit includes three ore-forming stages: (1) the arsenopyrite–pyrite–
chalcopyrite–sphalerite stage, (2) the galena–sphalerite–quartz stage, and (3) the pyrite–calcite–
quartz stage. In this study, we present a systematic study on the mineralogical and geochemical
characteristics (including major elements, S isotopes, and Pb isotopes) of the main sulfide ore minerals
in the Jilinbaolige Pb-Zn-Ag deposit in order to evaluate the metallogenic environment, ore-forming
material source, and genesis of this polymetallic deposit. The sulfide typomorphic characteristics,
ore fabric, and thermometry suggest that the genesis of sulfides in the deposit is closely related
to magmatic-hydrothermal activity. The early stage of mineralization might have evolved from a
high-temperature hydrothermal environment. The sulfur isotopic results show that the
δ34
S values
in the Jilinbaolige deposit range from 2.3
‰
to 6.1
‰
, with an average value of 3.98
‰
, indicating
that the sulfur originated from magmas with both mantle and crustal components. The Pb isotopic
compositions (
206
Pb/
204
Pb = 18.214–18.330,
207
Pb/
204
Pb = 15.478–15.615,
208
Pb/
204
Pb = 37.957–38.292,
µ
= 9.24–9.50,
ω
= 34.49–36.49) of the sulfide ores suggest that that the lead is of crust-mantle mixed
origin. The comparison between the S and Pb isotopic compositions of the Jilinbaolige deposit and the
polymetallic deposits from the central-southern parts of the Great Xing’an Range suggests that these
deposits have a similar metallogenic source, which is closely related to the Yanshanian granite and
medium-temperature hydrothermal fluids. These ore-bearing hydrothermal fluids that evolved from
deep magmatic sources migrated along the contact and fracture zones and during the subsequent
gradual decrease in temperature, and the metallogenic components were deposited in the relatively
open fracture and fissure space. Our results provide insights for further mineral prospecting in the
south-central part of the Great Xing’an Range.
Keywords:
Great Xing’an Range; Pb-Zn-Ag polymetallic deposit; S and Pb isotopes; magmatic-
hydrothermal fluids; Yanshanian granite intrusion
Minerals 2022,12, 1512. https://doi.org/10.3390/min12121512 https://www.mdpi.com/journal/minerals
Minerals 2022,12, 1512 2 of 23
1. Introduction
The Xingmeng orogenic belt in northern China, hosting important nonferrous poly-
metallic deposits, is characterized by complex tectonomagmatic activities and a long history
of development [
1
–
5
]. The central and southern parts of the Great Xing’an Range, located
in the southeastern Xingmeng orogenic belt, are well known for the extensive development
of nonferrous metallic deposits, attracting considerable attention in recent years [
6
–
8
].
The metallogenic systems include porphyries, skarns, hydrothermal veins, and alkaline
granites [
9
]. From the Paleozoic, the movement of the Siberian and North China plates
and the orogenic activity resulted in the east–west-oriented tectonic pattern of the North
China Craton margin [
10
]. After the subduction of the Pacific plate during the Meso-
zoic, the central-eastern Inner Mongolia region underwent various significant episodes
of faulting and volcanism. During this time, polymetallic mineralization occurred in the
south-central part of the Great Xing’an Range [
11
,
12
]. In recent years, many large-sized
deposits have been found in this area, including the Weilasituo and Bairendaba polymetallic
deposits [13,14].
In this study, we present results from detailed field investigations and geochemical
characteristics (including major elements, S isotopes, and Pb isotopes) of the main sulfide
ore minerals in the Jilinbaolige Pb-Zn-Ag deposit to understand the metallogenic environ-
ment, ore-forming material source, and genesis of the Jilinbaolige polymetallic deposit. Our
results have important significance for further mineral prospecting in the central-southern
part of the Great Xing’an Range.
The Jilinbaolige mining area is a key region where magmatic activities were most
developed during the Yanshanian period in Inner Mongolia and is located in the polymetal-
lic metallogenic belts of the Great Xing’an Range and South Gobi–Dongwuqi (Figure 1a).
Several deposits were discovered in the vicinity, including the Huanaote silver polymetallic
deposit, Harhada lead–zinc, and Chaobuleng iron–zinc, indicating the potential of this
region for mineralization [
9
,
15
–
19
]. Although the Jilinbaolige Pb-Zn-Ag polymetallic de-
posit has been investigated in previous studies, the genetic characteristics of this deposit
have not been clearly understood. For example, based on the geological characteristics,
prospecting indicators, and prospecting directions of the ore deposits, some studies [
20
–
22
]
have considered that the ore deposit is genetically related to the Yanshanian granite. Some
other studies [
23
,
24
] have suggested that the distribution of ore deposit is related to the
Variscan intermediate–felsic magmatism.
Minerals 2022,12, 1512 3 of 23
Minerals2022,12,15123of23
Figure1.(a)Mapshowingthelocationofthestudyarea.(b)Simplifiedmapshowingthestructural
outlineofInnerMongolia(Huangetal.[25]).(c)Geologicalandmineralmapofthemiddleand
southernGreatXing’anRange(Zhangetal.[26]).(d)SimplifiedgeologicmapofJilinbaolige(the
studyarea).Note:1,Indosiniangranite;2,earlyYanshaniangranite;3,MiddleHercynianGranite;
4,LateHercyniangraniteandgranodiorite;5,depositpoint;6,browngravelandsand;7,meta‐
morphosedsiltymudstoneandmudstone;8,metamorphosedmudstone,siliceousmud,andar‐
gillaceoussiltstone;9,mottledandspeckledmetamorphosedmudstoneandmetamorphosedsilty
mudstone;10,feldspathicquartzsandstoneintercalatedwithspeckledmetamorphosedmudstone;
11,biotitemonzonitegranite;12,quartzvein;13,limonitemineralizationandsilicifica‐
tion–alterationzone;14,samplinglocationandnumber;15,concealedmonzonitegranite.
2.RegionalGeologicalBackground
Thestudyarea(Figure1a)isgeotectonicallylocatedintheeasternpartofthe
Dongwuqifoldbelt(levelIV)ontheDongwuqi–Zhalantunvolcanicpassivecontinental
margin(levelIII)inthesoutheasterncontinental‐marginaccretionzone(levelII)ofthe
Siberianplate(levelI;Figure1b).DuringthemiddlepartofthelatePaleozoic,theSi‐
no–KoreanplatecollidedwiththeSiberianplate,andtheregionenteredintothein‐
tracontinentalorogenicstage.FormationoftheCentralAsianorogenicbeltisrelatedto
thisevent,accompaniedbyintensevolcanicactivityandtheintrusionofgraniticmagmas
[27–29],generatingamajormagmaticandmetallogenicbelt[30–33].TheDongwuqiarea
experiencedthetectoniccyclesofCaledonian,Hercynian,Indosinian,andYanshanian.
Thetransformationofoceanicandcontinentalcrusts,long‐termmulti‐stagesubduc‐
tion‐collision,andintracontinentalorogenyoccurredbetweentheSiberianplateandthe
China–NorthKoreaplate,consequentlyresultingintheformationofagiantorogenicbelt
withcomplextectonicmagmatypes[34].Aseriesofstrongsuperposition,recombina‐
tion,andtransformationtookplacebetweentheMeso–CenozoicBinxiPacifictectonic
metallogenicdomainintheNNEdirectionandthePaleozoicpaleo‐Asiantectonic
metallogenicdomainintheE–Wdirection,producingthetectonicmagmaticbeltofthe
GreatXing’anRangeintheNNE–NEdirection,withtheformationofsignificantlead,
zinc,silver,tin,andcopperpolymetallicdepositsthatarecloselyrelatedtotheMesozoic
volcanicmagmatisminthestudyarea(Figure1c)[35–37].
Figure 1.
(
a
) Map showing the location of the study area. (
b
) Simplified map showing the structural
outline of Inner Mongolia (Huang et al. [
25
]). (
c
) Geological and mineral map of the middle and
southern Great Xing’an Range (Zhang et al. [
26
]). (
d
) Simplified geologic map of Jilinbaolige (the
study area). Note: 1, Indosinian granite; 2, early Yanshanian granite; 3, Middle Hercynian Granite;
4, Late Hercynian granite and granodiorite; 5, deposit point; 6, brown gravel and sand; 7, metamor-
phosed silty mudstone and mudstone; 8, metamorphosed mudstone, siliceous mud, and argillaceous
siltstone; 9, mottled and speckled metamorphosed mudstone and metamorphosed silty mudstone;
10, feldspathic quartz sandstone intercalated with speckled metamorphosed mudstone; 11, biotite
monzonite granite; 12, quartz vein; 13, limonite mineralization and silicification–alteration zone;
14, sampling location and number; 15, concealed monzonite granite.
2. Regional Geological Background
The study area (Figure 1a) is geotectonically located in the eastern part of the Dong-
wuqi fold belt (level IV) on the Dongwuqi–Zhalantun volcanic passive continental margin
(level III) in the southeastern continental-margin accretion zone (level II) of the Siberian
plate (level I; Figure 1b). During the middle part of the late Paleozoic, the Sino–Korean plate
collided with the Siberian plate, and the region entered into the intracontinental orogenic
stage. Formation of the Central Asian orogenic belt is related to this event, accompanied
by intense volcanic activity and the intrusion of granitic magmas [
27
–
29
], generating a
major magmatic and metallogenic belt [
30
–
33
]. The Dongwuqi area experienced the tec-
tonic cycles of Caledonian, Hercynian, Indosinian, and Yanshanian. The transformation of
oceanic and continental crusts, long-term multi-stage subduction-collision, and intracon-
tinental orogeny occurred between the Siberian plate and the China–North Korea plate,
consequently resulting in the formation of a giant orogenic belt with complex tectonic
magma types [
34
]. A series of strong superposition, recombination, and transformation
took place between the Meso–Cenozoic Binxi Pacific tectonic metallogenic domain in the
NNE direction and the Paleozoic paleo-Asian tectonic metallogenic domain in the E–W
direction, producing the tectonic magmatic belt of the Great Xing’an Range in the NNE–NE
direction, with the formation of significant lead, zinc, silver, tin, and copper polymetallic
Minerals 2022,12, 1512 4 of 23
deposits that are closely related to the Mesozoic volcanic magmatism in the study area
(Figure 1c) [35–37].
The main ore-bearing strata in the study area are the Middle Devonian Taerbaget
Formation, the Upper Devonian Angelyinwula Formation, and the lower Permian Baoli-
gaomiao Formation. The region experienced Paleozoic rifting as well as Mesozoic intracon-
tinental orogeny, with voluminous Paleozoic strata, accompanied with criss-cross faults and
fractures and frequent magmatic activity. Hercynian and Yanshanian granites are widely
distributed in the study area. The Hercynian granites are mainly island arc syncollision
types, which are related to plate subduction associated with closure of the paleo-Asian
Ocean, whereas those in the Yanshanian are dominated by post-orogenic granites, which
were formed in an extensional tectonic setting.
3. Geological Characteristics of Ore Deposit
3.1. Geological Overview of the Jilinbaolige Mining Area
The strata exposed in the Jilinbaolige mining area are mostly late Jurassic volcanic
strata on the south and northwest parts (Figure 1d). In addition, the Late Devonian
Angeryinwula Formation is also exposed in a large area as a set of marine-continental
silty, argillaceous, and tuffaceous clastic sedimentary rocks, which have been metamor-
phosed to varying degrees into argillaceous silty slate, tuffaceous slate, metasandstone,
sericitized rock, and metamorphosed mudstone. The strike is dominantly northeast and
north–northeast, with a moderate-to-steep dip toward the northwest. Based on previous
studies and the filed investigations under this study, four lithologic sections can be identi-
fied: (1) brownish-gray and brownish-green feldspar–quartz sandstone intercalated with
speckled metamorphosed mudstone (D
3
a
2−1
); (2) grayish-yellow, purple-gray, and brick-
red variegated speckled metamorphosed mudstone and metamorphosed silty mudstone
(D
3
a
2−2
); (3) dark-gray, blue-gray, and gray-green metamorphosed mudstone, siliceous
mud, and argillaceous siltstone (D
3
a
2−3
); and (4) off-white or white metamorphosed silty
mudstone and metamorphosed mudstone (D3a2−4).
Magmatic rocks (mainly felsic intrusive rocks) are widely distributed in the study area.
In addition, diabase dikes and quartz veins are also present. The exposed width of the
diabase dykes, which are closely related to mineralization, is generally 1–2 m, extending
from tens to hundreds of meters along the strike in the direction of SN–NNE, with a dip
angle of 45–60. Quartz veins range in width from about 2 to 3 m and strikes mostly in the
NW and NE directions. These veins are not directly related with the mineralization and
are presumed to have formed during the pre-mineralization period. On the southeastern
side is the Erlianhot–Hegenshan deep fault zone, and on the northwest side is the Baiyun
Hubul–Mandu Hubaolige fault zone. The strike of the regional Huanaote–Erengaobi fault
(Figure 1d, F1) shows a change from north-northeast toward the northeast and dips steeply
toward the northwest. This fault, which is the controlling structure of the Aqinchulu intru-
sion on the northwest side and also the main geologic structure in the study area, obviously
controls both ore and host rocks within the southeastern boundary of the intrusion. The Jil-
inbaolige mining area, where the faults, folds, joints, and cleavage structures are developed,
is affected by multi-stage tectonic movements. The fold structure in the mining area is a
component of the Aqinchulu complex anticline. The Aqinchulu complex anticline can be di-
vided into one syncline (Jilinbaolige syncline) and two anticlines (Habutgai and Bayantala
anticlines), which are composed of the Upper Devonian Angeryinwula Formation.
3.2. Characteristics of Ore Bodies, Ores, and Surrounding Rocks
The Jilinbaolige Pb-Zn-Ag deposit, which appears in the form of hidden veins, is
mainly controlled by the inner and outer contact zones of the intrusion and distributed in
a nearly NE–NNE direction. Structurally controlled 138 ore (mineralized) bodies, mainly
hosted in the granite bodies in the inner contact zone, have been delineated in the mining
area. The ore-bearing elevation is 655–1127m, containing 71 industrial ore bodies and
14 main ore bodies. The detailed characteristics of the ore bodies are summarized in
Minerals 2022,12, 1512 5 of 23
Table 1. The ore minerals are mainly pyrite, sphalerite, and galena, with a small amount
of chalcopyrite, arsenopyrite, argyrite, and natural silver, while the gangue minerals are
mainly quartz and clay minerals. The textures of the ore include euhedral-subhedral
granular, allotriomorphic granular, metasomatic residual, and metasomatic dissolution.
The structures of ore mainly include disseminated, irregular, and veinlet network veins,
comparable with the main features of hydrothermal deposits. The ore deposit in the study
area shows typical hydrothermal mineral assemblages, such as pyrite, chalcopyrite, galena,
and sphalerite.
Table 1. Detailed characteristics of Jilinbaolige ore bodies.
Ore Body
Number
The Maximum
Length/m
Average Thickness
of Ore Body/m
Average Grade Occurrence
Pb/% Zn/% Ag/10−6Toward Tendency Inclination
2 610 2.26 0.65 1.07 45.26 0–10◦270◦35–50◦
4 410 1.08 0.49 1.52 19.88 0–10◦270–280◦45–55◦
5 200 1.02 0.78 3.00 34.32 22–47◦292–317◦30–53◦
14 290 2.32 1.04 2.16 29.71 15–30◦285–300◦35–70◦
14-1 230 1.62 0.74 0.77 39.05 15–30◦285–300 35–70◦
17 130 2.81 0.81 1.86 23.78 20–40◦290–310◦50–55◦
23 110 2.65 0.72 0.80 37.32 20–30◦290–300◦35–55◦
33 144 2.68 1.37 1.88 25.46 20–40◦290–310◦48–60◦
37 139 2.85 0.81 1.51 23.57 30–35◦300–305◦40–50◦
45 245 2.33 0.38 0.86 31.06 10–15◦280–285◦30–50◦
62 155 3.54 0.84 1.31 32.12 0◦270◦30–47◦
63 152 1.94 0.60 1.62 33.05 345◦255◦42◦
66 250 3.90 0.48 1.76 33.55 0◦270◦25–47◦
73 110 1.29 0.69 1.04 18.90 10◦280◦38–43◦
Alteration, such as silicification, pyritization, limonitization, sericitization, kaoliniza-
tion, epidote, and chlorite, can be observed in the near-ore surrounding rocks. The ore
bodies are closely related to the pyritization, limonitization, sericitization, and silicification.
The range and intensity of alteration in the surrounding rock are positively correlated
with the scale and grade of the ore (mineralized) bodies. The surrounding rocks on the
top and bottom of the ore body are biotite monzogranite, silty slate, tuffaceous slate, and
metamorphosed sandstone.
3.3. Metallogenic Stages
According to the assemblage and textural relationship among minerals, the formation
sequence of metallic minerals in the Jilinbaolige deposit (Table 2) is inferred as follows:
arsenopyrite
→
early pyrite
→
chalcopyrite
→
sphalerite
→
galena
→
late pyrite. Based on the
ore structure, structure, alteration characteristics of surrounding rocks, and the relationship
between the ore veins, combined with the paragenetic sequence, the Jilinbaolige deposit
can be further divided into three main metallogenic stages as follows:
Table 2. Mineral formation sequence of the Jilinbaolige deposit.
Mineral Name Hydrothermal Period
Early Stage Middle Stage Late Stage
Arsenopyrite
Minerals2022,12,15126of23
margins,fissures,andpores,replacingtheothersulfideminerals(Figure2e).
Sphaleriteoccursinsolidsolutionwithchalcopyriteandiscutbygalena(Figure
2f).
3. Pyrite–calcite–quartzstage:Thisassemblagemarkstheculminationofthehydro‐
thermalstage,mainlyrepresentedbycarbonation.Themainmineralassemblageis
quartz+calcite+pyrite.
Table2.MineralformationsequenceoftheJilinbaoligedeposit.
MineralnameHydrothermalperiod
EarlystageMiddlestageLatestage
Arsenopyrite
Pyrite
Chalcopyrite
Sphalerite
Galena
Calcite
Figure2.Photomicrographsofmineralassemblages,showingmineralogicalcharacteristicsofthe
oresamplesfromtheJilinbaoligedeposit.(a)Cubicpyrite,(b,c)dissolutionandmetasomatismby
arsenopyritepyrite,(d)latepyritefillingtheearlyarsenopyritefissures,(e)galenareplacingother
sulfideminerals,and(f)galenafillingalongsphaleritefissuressurroundingpyriteresidues.Apy,
arsenopyrite;Ccp,chalcopyrite;Gn,galena;Py,pyrite;Sp,sphalerite.
4.AnalyticalMethod
Thesamples(Table3)inthisstudy,whichwerecollectedfromdifferentdepthsof
differentboreholes,surface,andinclinedshaftpositions,werecutintothinsectionsand
polished.Themineralassemblageswerestudiedunderapolarizingmicroscope.Thein
situcompositionsofthesulfideswerethenanalyzedusinganelectronprobe(EPMA).
Threepyrite,threegalena,twosphalerite,andtwoarsenopyritesampleswereselected
forsulfurandleadisotopeanalyses.
EPMAanalysesofpyritewereconductedattheKeyLaboratoryofMinistryofEd‐
ucationforNon‐ferrousMetalMineralisationPredictionandGeologicalEnvironment
Monitoring,CentralSouthUniversity,Hunan,China.TheinstrumentusedwasaEP‐
MA‐1720HElectronProbeMicroanalyzer(ShimadzuLtd.,Kyoto,Japan).Theaccelerat‐
ingvoltageandcurrentwere15KVand10nA,respectively.Theelectronbeamdiameter
was1‐5μm.Thedatawereallcalibratedbystandardsampledetection.Theanalytical
Pyrite
Minerals2022,12,15126of23
margins,fissures,andpores,replacingtheothersulfideminerals(Figure2e).
Sphaleriteoccursinsolidsolutionwithchalcopyriteandiscutbygalena(Figure
2f).
3. Pyrite–calcite–quartzstage:Thisassemblagemarkstheculminationofthehydro‐
thermalstage,mainlyrepresentedbycarbonation.Themainmineralassemblageis
quartz+calcite+pyrite.
Table2.MineralformationsequenceoftheJilinbaoligedeposit.
MineralnameHydrothermalperiod
EarlystageMiddlestageLatestage
Arsenopyrite
Pyrite
Chalcopyrite
Sphalerite
Galena
Calcite
Figure2.Photomicrographsofmineralassemblages,showingmineralogicalcharacteristicsofthe
oresamplesfromtheJilinbaoligedeposit.(a)Cubicpyrite,(b,c)dissolutionandmetasomatismby
arsenopyritepyrite,(d)latepyritefillingtheearlyarsenopyritefissures,(e)galenareplacingother
sulfideminerals,and(f)galenafillingalongsphaleritefissuressurroundingpyriteresidues.Apy,
arsenopyrite;Ccp,chalcopyrite;Gn,galena;Py,pyrite;Sp,sphalerite.
4.AnalyticalMethod
Thesamples(Table3)inthisstudy,whichwerecollectedfromdifferentdepthsof
differentboreholes,surface,andinclinedshaftpositions,werecutintothinsectionsand
polished.Themineralassemblageswerestudiedunderapolarizingmicroscope.Thein
situcompositionsofthesulfideswerethenanalyzedusinganelectronprobe(EPMA).
Threepyrite,threegalena,twosphalerite,andtwoarsenopyritesampleswereselected
forsulfurandleadisotopeanalyses.
EPMAanalysesofpyritewereconductedattheKeyLaboratoryofMinistryofEd‐
ucationforNon‐ferrousMetalMineralisationPredictionandGeologicalEnvironment
Monitoring,CentralSouthUniversity,Hunan,China.TheinstrumentusedwasaEP‐
MA‐1720HElectronProbeMicroanalyzer(ShimadzuLtd.,Kyoto,Japan).Theaccelerat‐
ingvoltageandcurrentwere15KVand10nA,respectively.Theelectronbeamdiameter
was1‐5μm.Thedatawereallcalibratedbystandardsampledetection.Theanalytical
Minerals2022,12,15126of23
margins,fissures,andpores,replacingtheothersulfideminerals(Figure2e).
Sphaleriteoccursinsolidsolutionwithchalcopyriteandiscutbygalena(Figure
2f).
3. Pyrite–calcite–quartzstage:Thisassemblagemarkstheculminationofthehydro‐
thermalstage,mainlyrepresentedbycarbonation.Themainmineralassemblageis
quartz+calcite+pyrite.
Table2.MineralformationsequenceoftheJilinbaoligedeposit.
MineralnameHydrothermalperiod
EarlystageMiddlestageLatestage
Arsenopyrite
Pyrite
Chalcopyrite
Sphalerite
Galena
Calcite
Figure2.Photomicrographsofmineralassemblages,showingmineralogicalcharacteristicsofthe
oresamplesfromtheJilinbaoligedeposit.(a)Cubicpyrite,(b,c)dissolutionandmetasomatismby
arsenopyritepyrite,(d)latepyritefillingtheearlyarsenopyritefissures,(e)galenareplacingother
sulfideminerals,and(f)galenafillingalongsphaleritefissuressurroundingpyriteresidues.Apy,
arsenopyrite;Ccp,chalcopyrite;Gn,galena;Py,pyrite;Sp,sphalerite.
4.AnalyticalMethod
Thesamples(Table3)inthisstudy,whichwerecollectedfromdifferentdepthsof
differentboreholes,surface,andinclinedshaftpositions,werecutintothinsectionsand
polished.Themineralassemblageswerestudiedunderapolarizingmicroscope.Thein
situcompositionsofthesulfideswerethenanalyzedusinganelectronprobe(EPMA).
Threepyrite,threegalena,twosphalerite,andtwoarsenopyritesampleswereselected
forsulfurandleadisotopeanalyses.
EPMAanalysesofpyritewereconductedattheKeyLaboratoryofMinistryofEd‐
ucationforNon‐ferrousMetalMineralisationPredictionandGeologicalEnvironment
Monitoring,CentralSouthUniversity,Hunan,China.TheinstrumentusedwasaEP‐
MA‐1720HElectronProbeMicroanalyzer(ShimadzuLtd.,Kyoto,Japan).Theaccelerat‐
ingvoltageandcurrentwere15KVand10nA,respectively.Theelectronbeamdiameter
was1‐5μm.Thedatawereallcalibratedbystandardsampledetection.Theanalytical
Minerals2022,12,15126of23
margins,fissures,andpores,replacingtheothersulfideminerals(Figure2e).
Sphaleriteoccursinsolidsolutionwithchalcopyriteandiscutbygalena(Figure
2f).
3. Pyrite–calcite–quartzstage:Thisassemblagemarkstheculminationofthehydro‐
thermalstage,mainlyrepresentedbycarbonation.Themainmineralassemblageis
quartz+calcite+pyrite.
Table2.MineralformationsequenceoftheJilinbaoligedeposit.
MineralnameHydrothermalperiod
EarlystageMiddlestageLatestage
Arsenopyrite
Pyrite
Chalcopyrite
Sphalerite
Galena
Calcite
Figure2.Photomicrographsofmineralassemblages,showingmineralogicalcharacteristicsofthe
oresamplesfromtheJilinbaoligedeposit.(a)Cubicpyrite,(b,c)dissolutionandmetasomatismby
arsenopyritepyrite,(d)latepyritefillingtheearlyarsenopyritefissures,(e)galenareplacingother
sulfideminerals,and(f)galenafillingalongsphaleritefissuressurroundingpyriteresidues.Apy,
arsenopyrite;Ccp,chalcopyrite;Gn,galena;Py,pyrite;Sp,sphalerite.
4.AnalyticalMethod
Thesamples(Table3)inthisstudy,whichwerecollectedfromdifferentdepthsof
differentboreholes,surface,andinclinedshaftpositions,werecutintothinsectionsand
polished.Themineralassemblageswerestudiedunderapolarizingmicroscope.Thein
situcompositionsofthesulfideswerethenanalyzedusinganelectronprobe(EPMA).
Threepyrite,threegalena,twosphalerite,andtwoarsenopyritesampleswereselected
forsulfurandleadisotopeanalyses.
EPMAanalysesofpyritewereconductedattheKeyLaboratoryofMinistryofEd‐
ucationforNon‐ferrousMetalMineralisationPredictionandGeologicalEnvironment
Monitoring,CentralSouthUniversity,Hunan,China.TheinstrumentusedwasaEP‐
MA‐1720HElectronProbeMicroanalyzer(ShimadzuLtd.,Kyoto,Japan).Theaccelerat‐
ingvoltageandcurrentwere15KVand10nA,respectively.Theelectronbeamdiameter
was1‐5μm.Thedatawereallcalibratedbystandardsampledetection.Theanalytical
Chalcopyrite
Minerals2022,12,15126of23
margins,fissures,andpores,replacingtheothersulfideminerals(Figure2e).
Sphaleriteoccursinsolidsolutionwithchalcopyriteandiscutbygalena(Figure
2f).
3. Pyrite–calcite–quartzstage:Thisassemblagemarkstheculminationofthehydro‐
thermalstage,mainlyrepresentedbycarbonation.Themainmineralassemblageis
quartz+calcite+pyrite.
Table2.MineralformationsequenceoftheJilinbaoligedeposit.
MineralnameHydrothermalperiod
EarlystageMiddlestageLatestage
Arsenopyrite
Pyrite
Chalcopyrite
Sphalerite
Galena
Calcite
Figure2.Photomicrographsofmineralassemblages,showingmineralogicalcharacteristicsofthe
oresamplesfromtheJilinbaoligedeposit.(a)Cubicpyrite,(b,c)dissolutionandmetasomatismby
arsenopyritepyrite,(d)latepyritefillingtheearlyarsenopyritefissures,(e)galenareplacingother
sulfideminerals,and(f)galenafillingalongsphaleritefissuressurroundingpyriteresidues.Apy,
arsenopyrite;Ccp,chalcopyrite;Gn,galena;Py,pyrite;Sp,sphalerite.
4.AnalyticalMethod
Thesamples(Table3)inthisstudy,whichwerecollectedfromdifferentdepthsof
differentboreholes,surface,andinclinedshaftpositions,werecutintothinsectionsand
polished.Themineralassemblageswerestudiedunderapolarizingmicroscope.Thein
situcompositionsofthesulfideswerethenanalyzedusinganelectronprobe(EPMA).
Threepyrite,threegalena,twosphalerite,andtwoarsenopyritesampleswereselected
forsulfurandleadisotopeanalyses.
EPMAanalysesofpyritewereconductedattheKeyLaboratoryofMinistryofEd‐
ucationforNon‐ferrousMetalMineralisationPredictionandGeologicalEnvironment
Monitoring,CentralSouthUniversity,Hunan,China.TheinstrumentusedwasaEP‐
MA‐1720HElectronProbeMicroanalyzer(ShimadzuLtd.,Kyoto,Japan).Theaccelerat‐
ingvoltageandcurrentwere15KVand10nA,respectively.Theelectronbeamdiameter
was1‐5μm.Thedatawereallcalibratedbystandardsampledetection.Theanalytical
Sphalerite
Minerals2022,12,15126of23
margins,fissures,andpores,replacingtheothersulfideminerals(Figure2e).
Sphaleriteoccursinsolidsolutionwithchalcopyriteandiscutbygalena(Figure
2f).
3. Pyrite–calcite–quartzstage:Thisassemblagemarkstheculminationofthehydro‐
thermalstage,mainlyrepresentedbycarbonation.Themainmineralassemblageis
quartz+calcite+pyrite.
Table2.MineralformationsequenceoftheJilinbaoligedeposit.
MineralnameHydrothermalperiod
EarlystageMiddlestageLatestage
Arsenopyrite
Pyrite
Chalcopyrite
Sphalerite
Galena
Calcite
Figure2.Photomicrographsofmineralassemblages,showingmineralogicalcharacteristicsofthe
oresamplesfromtheJilinbaoligedeposit.(a)Cubicpyrite,(b,c)dissolutionandmetasomatismby
arsenopyritepyrite,(d)latepyritefillingtheearlyarsenopyritefissures,(e)galenareplacingother
sulfideminerals,and(f)galenafillingalongsphaleritefissuressurroundingpyriteresidues.Apy,
arsenopyrite;Ccp,chalcopyrite;Gn,galena;Py,pyrite;Sp,sphalerite.
4.AnalyticalMethod
Thesamples(Table3)inthisstudy,whichwerecollectedfromdifferentdepthsof
differentboreholes,surface,andinclinedshaftpositions,werecutintothinsectionsand
polished.Themineralassemblageswerestudiedunderapolarizingmicroscope.Thein
situcompositionsofthesulfideswerethenanalyzedusinganelectronprobe(EPMA).
Threepyrite,threegalena,twosphalerite,andtwoarsenopyritesampleswereselected
forsulfurandleadisotopeanalyses.
EPMAanalysesofpyritewereconductedattheKeyLaboratoryofMinistryofEd‐
ucationforNon‐ferrousMetalMineralisationPredictionandGeologicalEnvironment
Monitoring,CentralSouthUniversity,Hunan,China.TheinstrumentusedwasaEP‐
MA‐1720HElectronProbeMicroanalyzer(ShimadzuLtd.,Kyoto,Japan).Theaccelerat‐
ingvoltageandcurrentwere15KVand10nA,respectively.Theelectronbeamdiameter
was1‐5μm.Thedatawereallcalibratedbystandardsampledetection.Theanalytical
Minerals2022,12,15126of23
margins,fissures,andpores,replacingtheothersulfideminerals(Figure2e).
Sphaleriteoccursinsolidsolutionwithchalcopyriteandiscutbygalena(Figure
2f).
3. Pyrite–calcite–quartzstage:Thisassemblagemarkstheculminationofthehydro‐
thermalstage,mainlyrepresentedbycarbonation.Themainmineralassemblageis
quartz+calcite+pyrite.
Table2.MineralformationsequenceoftheJilinbaoligedeposit.
MineralnameHydrothermalperiod
EarlystageMiddlestageLatestage
Arsenopyrite
Pyrite
Chalcopyrite
Sphalerite
Galena
Calcite
Figure2.Photomicrographsofmineralassemblages,showingmineralogicalcharacteristicsofthe
oresamplesfromtheJilinbaoligedeposit.(a)Cubicpyrite,(b,c)dissolutionandmetasomatismby
arsenopyritepyrite,(d)latepyritefillingtheearlyarsenopyritefissures,(e)galenareplacingother
sulfideminerals,and(f)galenafillingalongsphaleritefissuressurroundingpyriteresidues.Apy,
arsenopyrite;Ccp,chalcopyrite;Gn,galena;Py,pyrite;Sp,sphalerite.
4.AnalyticalMethod
Thesamples(Table3)inthisstudy,whichwerecollectedfromdifferentdepthsof
differentboreholes,surface,andinclinedshaftpositions,werecutintothinsectionsand
polished.Themineralassemblageswerestudiedunderapolarizingmicroscope.Thein
situcompositionsofthesulfideswerethenanalyzedusinganelectronprobe(EPMA).
Threepyrite,threegalena,twosphalerite,andtwoarsenopyritesampleswereselected
forsulfurandleadisotopeanalyses.
EPMAanalysesofpyritewereconductedattheKeyLaboratoryofMinistryofEd‐
ucationforNon‐ferrousMetalMineralisationPredictionandGeologicalEnvironment
Monitoring,CentralSouthUniversity,Hunan,China.TheinstrumentusedwasaEP‐
MA‐1720HElectronProbeMicroanalyzer(ShimadzuLtd.,Kyoto,Japan).Theaccelerat‐
ingvoltageandcurrentwere15KVand10nA,respectively.Theelectronbeamdiameter
was1‐5μm.Thedatawereallcalibratedbystandardsampledetection.Theanalytical
Galena
Minerals2022,12,15126of23
margins,fissures,andpores,replacingtheothersulfideminerals(Figure2e).
Sphaleriteoccursinsolidsolutionwithchalcopyriteandiscutbygalena(Figure
2f).
3. Pyrite–calcite–quartzstage:Thisassemblagemarkstheculminationofthehydro‐
thermalstage,mainlyrepresentedbycarbonation.Themainmineralassemblageis
quartz+calcite+pyrite.
Table2.MineralformationsequenceoftheJilinbaoligedeposit.
MineralnameHydrothermalperiod
EarlystageMiddlestageLatestage
Arsenopyrite
Pyrite
Chalcopyrite
Sphalerite
Galena
Calcite
Figure2.Photomicrographsofmineralassemblages,showingmineralogicalcharacteristicsofthe
oresamplesfromtheJilinbaoligedeposit.(a)Cubicpyrite,(b,c)dissolutionandmetasomatismby
arsenopyritepyrite,(d)latepyritefillingtheearlyarsenopyritefissures,(e)galenareplacingother
sulfideminerals,and(f)galenafillingalongsphaleritefissuressurroundingpyriteresidues.Apy,
arsenopyrite;Ccp,chalcopyrite;Gn,galena;Py,pyrite;Sp,sphalerite.
4.AnalyticalMethod
Thesamples(Table3)inthisstudy,whichwerecollectedfromdifferentdepthsof
differentboreholes,surface,andinclinedshaftpositions,werecutintothinsectionsand
polished.Themineralassemblageswerestudiedunderapolarizingmicroscope.Thein
situcompositionsofthesulfideswerethenanalyzedusinganelectronprobe(EPMA).
Threepyrite,threegalena,twosphalerite,andtwoarsenopyritesampleswereselected
forsulfurandleadisotopeanalyses.
EPMAanalysesofpyritewereconductedattheKeyLaboratoryofMinistryofEd‐
ucationforNon‐ferrousMetalMineralisationPredictionandGeologicalEnvironment
Monitoring,CentralSouthUniversity,Hunan,China.TheinstrumentusedwasaEP‐
MA‐1720HElectronProbeMicroanalyzer(ShimadzuLtd.,Kyoto,Japan).Theaccelerat‐
ingvoltageandcurrentwere15KVand10nA,respectively.Theelectronbeamdiameter
was1‐5μm.Thedatawereallcalibratedbystandardsampledetection.Theanalytical
Calcite
Minerals2022,12,15126of23
margins,fissures,andpores,replacingtheothersulfideminerals(Figure2e).
Sphaleriteoccursinsolidsolutionwithchalcopyriteandiscutbygalena(Figure
2f).
3. Pyrite–calcite–quartzstage:Thisassemblagemarkstheculminationofthehydro‐
thermalstage,mainlyrepresentedbycarbonation.Themainmineralassemblageis
quartz+calcite+pyrite.
Table2.MineralformationsequenceoftheJilinbaoligedeposit.
MineralnameHydrothermalperiod
EarlystageMiddlestageLatestage
Arsenopyrite
Pyrite
Chalcopyrite
Sphalerite
Galena
Calcite
Figure2.Photomicrographsofmineralassemblages,showingmineralogicalcharacteristicsofthe
oresamplesfromtheJilinbaoligedeposit.(a)Cubicpyrite,(b,c)dissolutionandmetasomatismby
arsenopyritepyrite,(d)latepyritefillingtheearlyarsenopyritefissures,(e)galenareplacingother
sulfideminerals,and(f)galenafillingalongsphaleritefissuressurroundingpyriteresidues.Apy,
arsenopyrite;Ccp,chalcopyrite;Gn,galena;Py,pyrite;Sp,sphalerite.
4.AnalyticalMethod
Thesamples(Table3)inthisstudy,whichwerecollectedfromdifferentdepthsof
differentboreholes,surface,andinclinedshaftpositions,werecutintothinsectionsand
polished.Themineralassemblageswerestudiedunderapolarizingmicroscope.Thein
situcompositionsofthesulfideswerethenanalyzedusinganelectronprobe(EPMA).
Threepyrite,threegalena,twosphalerite,andtwoarsenopyritesampleswereselected
forsulfurandleadisotopeanalyses.
EPMAanalysesofpyritewereconductedattheKeyLaboratoryofMinistryofEd‐
ucationforNon‐ferrousMetalMineralisationPredictionandGeologicalEnvironment
Monitoring,CentralSouthUniversity,Hunan,China.TheinstrumentusedwasaEP‐
MA‐1720HElectronProbeMicroanalyzer(ShimadzuLtd.,Kyoto,Japan).Theaccelerat‐
ingvoltageandcurrentwere15KVand10nA,respectively.Theelectronbeamdiameter
was1‐5μm.Thedatawereallcalibratedbystandardsampledetection.Theanalytical
1.
Arsenopyrite–pyrite–chalcopyrite–sphalerite stage: Arsenopyrite, pyrite, chalcopy-
rite, and sphalerite are the main mineral assemblages in this stage. Under the micro-
scope, early-crystallized arsenopyrite and pyrite show good automorphism. Pyrites
are mostly medium-fine-grained euhedral and subhedral cubic grains (Figure 2a),
whereas arsenopyrite is mostly fine-grained euhedral and subhedral short, columnar.
Minerals 2022,12, 1512 6 of 23
granular crystals, showing dissolution of the early-crystallized pyrite (Figure 2b,c).
The late-crystallized pyrites are relatively less, mostly micro-fine-grained xenomor-
phic and filling fissures in early arsenopyrite fissures as a fine-vein metasomatic
structure (Figure 2d).
Minerals2022,12,15126of23
margins,fissures,andpores,replacingtheothersulfideminerals(Figure2e).
Sphaleriteoccursinsolidsolutionwithchalcopyriteandiscutbygalena(Figure
2f).
3. Pyrite–calcite–quartzstage:Thisassemblagemarkstheculminationofthehydro‐
thermalstage,mainlyrepresentedbycarbonation.Themainmineralassemblageis
quartz+calcite+pyrite.
Table2.MineralformationsequenceoftheJilinbaoligedeposit.
MineralnameHydrothermalperiod
EarlystageMiddlestageLatestage
Arsenopyrite
Pyrite
Chalcopyrite
Sphalerite
Galena
Calcite
Figure2.Photomicrographsofmineralassemblages,showingmineralogicalcharacteristicsofthe
oresamplesfromtheJilinbaoligedeposit.(a)Cubicpyrite,(b,c)dissolutionandmetasomatismby
arsenopyritepyrite,(d)latepyritefillingtheearlyarsenopyritefissures,(e)galenareplacingother
sulfideminerals,and(f)galenafillingalongsphaleritefissuressurroundingpyriteresidues.Apy,
arsenopyrite;Ccp,chalcopyrite;Gn,galena;Py,pyrite;Sp,sphalerite.
4.AnalyticalMethod
Thesamples(Table3)inthisstudy,whichwerecollectedfromdifferentdepthsof
differentboreholes,surface,andinclinedshaftpositions,werecutintothinsectionsand
polished.Themineralassemblageswerestudiedunderapolarizingmicroscope.Thein
situcompositionsofthesulfideswerethenanalyzedusinganelectronprobe(EPMA).
Threepyrite,threegalena,twosphalerite,andtwoarsenopyritesampleswereselected
forsulfurandleadisotopeanalyses.
EPMAanalysesofpyritewereconductedattheKeyLaboratoryofMinistryofEd‐
ucationforNon‐ferrousMetalMineralisationPredictionandGeologicalEnvironment
Monitoring,CentralSouthUniversity,Hunan,China.TheinstrumentusedwasaEP‐
MA‐1720HElectronProbeMicroanalyzer(ShimadzuLtd.,Kyoto,Japan).Theaccelerat‐
ingvoltageandcurrentwere15KVand10nA,respectively.Theelectronbeamdiameter
was1‐5μm.Thedatawereallcalibratedbystandardsampledetection.Theanalytical
Figure 2.
Photomicrographs of mineral assemblages, showing mineralogical characteristics of the
ore samples from the Jilinbaolige deposit. (
a
) Cubic pyrite, (
b
,
c
) dissolution and metasomatism by
arsenopyrite pyrite, (
d
) late pyrite filling the early arsenopyrite fissures, (
e
) galena replacing other
sulfide minerals, and (
f
) galena filling along sphalerite fissures surrounding pyrite residues. Apy,
arsenopyrite; Ccp, chalcopyrite; Gn, galena; Py, pyrite; Sp, sphalerite.
2.
Galena–sphalerite–quartz stage: This stage is an important metallogenic stage of
the hydrothermal period, and the ore minerals are mainly galena and sphalerite.
Galena occurs as granular aggregates. Under the microscope, galena often fills along
grain margins, fissures, and pores, replacing the other sulfide minerals (Figure 2e).
Sphalerite occurs in solid solution with chalcopyrite and is cut by galena (Figure 2f).
3.
Pyrite–calcite–quartz stage: This assemblage marks the culmination of the hydrother-
mal stage, mainly represented by carbonation. The main mineral assemblage is quartz
+ calcite + pyrite.
4. Analytical Method
The samples (Table 3) in this study, which were collected from different depths of
different boreholes, surface, and inclined shaft positions, were cut into thin sections and
polished. The mineral assemblages were studied under a polarizing microscope. The in situ
compositions of the sulfides were then analyzed using an electron probe (EPMA). Three
pyrite, three galena, two sphalerite, and two arsenopyrite samples were selected for sulfur
and lead isotope analyses.
EPMA analyses of pyrite were conducted at the Key Laboratory of Ministry of Ed-
ucation for Non-ferrous Metal Mineralisation Prediction and Geological Environment
Monitoring, Central South University, Hunan, China. The instrument used was a EPMA-
1720H Electron Probe Microanalyzer (Shimadzu Ltd., Kyoto, Japan). The accelerating
voltage and current were 15KV and 10nA, respectively. The electron beam diameter was
1–5
µ
m. The data were all calibrated by standard sample detection. The analytical accuracy
was 5%, and the detection limit was 0.01%. In total, 7 elements (As, S, Fe, Ag, Co, Ni, and
Cu) in pyrite and arsenopyrite were analyzed.
Minerals 2022,12, 1512 7 of 23
Table 3. Information about the samples analyzed in this study.
Number Position Lithology Light Flake
S01
Makido North Peak A
Silty argillaceous slate Flakes
S02
Makido North Peak B
Silty argillaceous slate Flakes
S03
Makido North Peak C
Silty slate Flakes
S04 ZK2801-380 m Metamorphosed siltstone Light sheets and
flakes
S05 ZK3001-221 m Complexly veined
pyrite–sphalerite ore Light sheets
S06 ZK3001-350 m Veinlet filled with disseminated
pyrite + chlorite
Light sheets and
flakes
S07 ZK3001-360 m Massive
pyrite–sphalerite–arsenopyrite ore Light sheets
S08 ZK3201-113 m Vein filled with
sphalerite–arsenopyrite–pyrite ore Light sheets
S09 ZK3201-279 m Irregular-vein dolomite + calcite
with iron–galena–sphalerite ore Light sheets
S10 ZK3202-80 m Silt-bearing muddy slate Light sheets and
flakes
S11 ZK3202-87 m Metamorphosed siltstone Light sheet and
flake
S12 ZK3202-271 m Silty argillaceous slate Flakes
S13 ZK3202-315 m Light-gray and brownish
argillaceous slate Flakes
S14 Survey area surface Horned purplish-red iron-bearing
sandy slate Flakes
S15
Area of detailed
investigation, within
inclined well
Light-gray medium-grained biotite
monzonite granite Flakes
Sulfur and lead isotopes were analyzed at the Analysis Research Center of the Beijing
Geological Institute of Nuclear Industry. For S isotope analysis, the isotope mass spectrom-
eter (Deltavplus) was used, with the international standard V-CDT with an accuracy of
±0.2 ×10−3.
For Pb isotope analysis, the properly weighed samples were put into a polytetrafluo-
roethylene crucible. The isotopes of the samples were analyzed after being decomposed
by sulfate acid-hydrofluoric acid-nitric acid and separated by the resin exchange method,
and fully dried. A thermal ion mass spectrometer (MAT-261) (Finnigan MAT Ltd., Bremen,
Germany) was used in the analysis, and the mass spectrometry measurements were cor-
rected with the international standard sample NBS981, with accuracies of 2
σ
< 0.05% for
the 204Pb/206 Pb ratio and 2σ< 0.005% for the 208Pb/206Pb ratio.
5. Results
The EMPA analytical results of pyrites and arsenopyrite in the first metallogenic stage
are given in Table 4. The As contents of pyrites were generally low and fluctuated from the
core to the margin of pyrite. Pyrites were slightly depleted in sulfur, with the depletion
degree decreasing gradually from the core to the margin.
The analysis results of sulfur isotopes of the sulfides (pyrite, galena, sphalerite, and
arsenopyrite) are given in Table 5. The data showed a limited range in
δ34
S (
δ34
S = 2.3
‰
–
6.1‰), with δ34S = 3.98‰, on average.
Minerals 2022,12, 1512 8 of 23
Table 4. EMPA results of pyrite and arsenopyrite in the first metallogenic stage.
Mineral Point
Number Fe S As Ag Cu Co Ni
Pyrite
S08a-1 46.151 52.672 0.223 0 0.020 0.043 0
2 46.402 51.736 0.175 0 0 0.068 0
3 46.739 51.897 0.226 0 0 0.100 0
4 46.260 52.271 0.185 0.010 0 0.062 0
S08b-1 46.593 53.103 0.220 0 0 0.038 0
2 46.445 52.403 0.946 0 0.038 0.027 0
3 46.731 52.461 0.194 0.005 0 0.088 0
S10a-1 46.886 52.358 0.225 0 0 0.034 0.029
2 46.840 52.611 0.294 0 0 0.043 0.011
3 46.654 52.120 0.295 0.011 0 0.031 0.013
4 46.717 52.001 0.229 0 0.014 0.056 0.022
S10b-1 47.105 51.995 0.193 0.005 0 0.121 0.321
2 47.057 51.011 0.214 0.006 0.023 0.083 0.020
3 46.658 52.058 0.423 0 0.042 0.085 0.054
4 46.316 52.116 0.427 0.002 0 0.087 0.062
Arsenopyrite
S08c-1 34.899 20.958 44.58 0 0.033 0.023 0.029
2 35.246 20.964 45.09 0.024 0.048 0.068 0.026
S08d-1 34.973 20.807 44.895 0 0.024 0.06 0
2 34.885 20.98 45.074 0 0.005 0.04 0
Note: “Point number” shows the analysis position of the point from the core to the edge.
Table 5.
Sulfur isotopic compositions of the sulfides in the Jilinbaolige deposit and the polymetallic
deposits in the Great Xing’an Range.
Deposit Sample Number Test Object δ34S/‰ Data Source
Jilinbaolige
Y-01 Pyrite 2.40
This study
Y-02 Pyrite 3.90
Y-03 Pyrite 5.60
Y-04 Galena 2.30
Y-05 Galena 2.40
Y-06 Galena 3.30
Y-07 Sphalerite 4.50
Y-08 Sphalerite 3.40
Y-09 Arsenopyrite 6.10
Y-10 Arsenopyrite 5.90
Huanaote
14GDSK2-40 Galena 7.05
[15]
14GDSK2-40 Galena 6.48
14GDSK2-40 Galena 6.90
14GDSK2-40 Galena 6.55
14GDSK2-40 Pyrite 5.68
14GDSK2-40 Pyrite 6.23
14GDSK2-40 Pyrite 5.16
14GDSK2-40 Pyrite 7.12
SK2-72 Sphalerite 7.38
SK2-72 Sphalerite 7.32
SK2-72 Sphalerite 7.94
SK2-72 Sphalerite 7.48
14GD-22 Galena 6.28
14GD-22 Galena 5.64
14GD-22 Pyrite 5.42
GDSK2-44 Galena 4.28
GDSK2-44 Galena 2.44
GDSK2-44 Galena 3.35
GDSK2-44 Galena 4.26
Minerals 2022,12, 1512 9 of 23
Table 5. Cont.
Deposit Sample Number Test Object δ34S/‰ Data Source
14GDSK2-87 Galena 5.50
14GDSK2-87 Galena 5.34
14GDSK2-87 Galena 4.61
14GDSK2-87 Galena 4.59
14GDSK2-87 Galena 4.59
14GDSK2-87 Galena 5.37
1017 Highland
DW-73 Pyrite 6.60
[18]
DW-74 Pyrite 6.80
DW-75 Galena 6.60
DW-77 Pyrite 8.00
DW-79 Galena 5.70
DW-82 Sphalerite 7.40
DW-93 Pyrite 3.40
DW-99 Pyrite 4.70
DW-101 Pyrite 5.10
DW-105 Pyrite 3.80
DW-106 Pyrite 3.70
DW-180 Galena 4.30
DW-181 Galena 3.40
Chaganaobao
CG7 Pyrite 2.20
[9]
CG6 Pyrite 1.30
CG2 Pyrite −1.20
CG23-1 Sphalerite 12.40
CG32 Sphalerite 8.90
CG46-1 Sphalerite 9.90
CG53 Sphalerite 10.10
CG52 Sphalerite 10.00
Aerhada
TW1 Galena 1.20
[16]
TW4 Galena 4.70
TW7 Galena 5.30
TW8 Galena 3.90
TW9 Galena 4.20
TW11 Galena 4.70
TW7 Sphalerite 6.90
TW8 Sphalerite 5.50
TW9 Sphalerite 7.50
TW10 Sphalerite 7.40
TW11 Sphalerite 7.00
TW2 Pyrite 8.60
TW3 Pyrite 7.00
TW5 Pyrite 7.20
TW8 Pyrite 6.10
TW9 Pyrite 6.66
TW10 Pyrite 7.00
TW4 Arsenopyrite 6.80
TW7 Arsenopyrite 6.60
TW11 Arsenopyrite 6.40
Chaobuleng
CBLN04 Pyrite −1.70
[38]
CBLN06 Pyrite −0.80
CBLN07 Pyrite −0.60
CBLN08 Pyrite 1.20
CBLN09 Chalcopyrite 1.40
CBLN12 Chalcopyrite 1.20
CBLN13 Chalcopyrite 2.30
CBLN14 Sphalerite 4.30
CBLN15 Sphalerite 3.80
CBLN16 Galena 2.50
Minerals 2022,12, 1512 10 of 23
Table 5. Cont.
Deposit Sample Number Test Object δ34S/‰ Data Source
CBLN17 Galena 1.80
CBLN18 Pyrite 2.50
CBLN19 Pyrite 3.20
CBLN20 Galena 1.60
CBLN21 Sphalerite 4.50
CBLN22 Sphalerite 6.00
CBLN23 Sphalerite 3.80
CBLN24 Galena 2.60
CBLN25 Pyrite 3.40
CBLN26 Pyrite 2.80
CBLN27 Pyrite 3.60
CBLN28 Pyrite 6.80
CBLN29 Pyrite −1.20
CBLN30 Pyrite −0.80
CBLN31 Pyrite 2.40
Diyanqinamu
DYW-3 Pyrite 4.50
[19]
DY-10 Pyrite 4.05
DY-25 Pyrite 6.80
DYS-62 Pyrite 8.60
DYS-35 Chalcopyrite 5.95
DYS-17-1 Chalcopyrite 10.41
DYS-17 Sphalerite 5.67
DYW-4 Sphalerite 4.40
DYW-4 Galena 1.78
DYW-5 Galena 2.27
DYW-5 Galena 2.36
Pb isotope analysis of 10 sulfide samples are shown in Table 6. The
206
Pb/
204
Pb
ratios of sulfides were 18.214–18.330, with an average value of 18.254. The ratios of
207
Pb/
204
Pb were 15.478–15.615, with 15.539, on average, whereas those of
208
Pb/
204
Pb
were
37.957–38.292
, with an average value of 38.072, indicating Th/Pb loss. These results
indicate a more or less homogenous Pb isotopic composition.
Table 6.
Lead isotopic compositions of the sulfides in the Jilinbaolige deposit and the polymetallic
deposits in the Great Xing’an Range.
Deposit Sample
Number Test Object 206Pb/204 Pb 207Pb/204Pb 208 Pb/204Pb Data
Source
Jilinbaolige
Y-01 Pyrite 18.219 15.478 37.964
This study
Y-02 Pyrite 18.214 15.487 37.957
Y-03 Pyrite 18.219 15.526 38.005
Y-04 Galena 18.321 15.582 38.254
Y-05 Galena 18.282 15.600 38.112
Y-06 Galena 18.238 15.519 37.958
Y-07 Sphalerite 18.231 15.488 37.987
Y-08 Sphalerite 18.225 15.496 37.994
Y-09
Arsenopyrite
18.330 15.615 38.292
Y-10
Arsenopyrite
18.264 15.601 38.201
Aerhada 14AEHD-17 Galena 18.439 15.650 38.458 [39]
14AEHD-18 Galena 18.427 15.641 38.400
Minerals 2022,12, 1512 11 of 23
Table 6. Cont.
Deposit Sample
Number Test Object 206Pb/204 Pb 207Pb/204Pb 208 Pb/204Pb Data
Source
14AEHD-23 Galena 18.684 15.750 39.298
14AEHD-30 Galena 18.685 15.750 39.301
15AEHD-18 Galena 18.459 15.683 38.565
15AEHD-23 Galena 18.398 15.547 38.172
Huanaote
GD-22 Galena 18.294 15.548 38.080
[15]
GD-22 Galena 18.293 15.545 38.073
SK2-44 Galena 18.303 15.549 38.095
SK2-44 Galena 18.302 15.549 38.096
SK2-44 Galena 18.298 15.548 38.090
SK2-44 Galena 18.298 15.547 38.088
SK2-44 Galena 18.293 15.543 38.076
SK2-44 Galena 18.294 15.544 38.081
SK2-44 Galena 18.310 15.550 38.095
SK2-87 Galena 18.311 15.548 38.090
SK2-87 Galena 18.309 15.550 38.095
SK2-87 Galena 18.301 15.545 38.087
SK2-87 Galena 18.313 15.553 38.115
SK2-87 Galena 18.304 15.546 38.089
SK2-87 Galena 18.304 15.545 38.087
SK2-87 Galena 18.307 15.546 38.087
SK2-87 Galena 18.298 15.545 38.081
Chaganaobao
CG23-1 Sphalerite 18.240 15.495 37.922
[9]
CG32 Sphalerite 18.288 15.534 37.988
CG46-1 Sphalerite 18.255 15.504 37.919
CG52 Sphalerite 18.238 15.551 38.113
CG53 Sphalerite 18.430 15.691 38.460
CG2 Pyrite 17.949 15.518 38.165
CG6 Pyrite 18.221 15.485 37.875
CG7 Pyrite 18.287 15.515 38.042
1017
Highland
DW-73 Sphalerite 18.400 15.562 38.177
[40]
DW-74 Galena 18.394 15.559 38.163
DW-75 Sphalerite 18.393 15.559 38.162
DW-77 Galena 18.391 15.557 38.158
DW-79 Sphalerite 18.286 15.540 38.036
DW-80 Pyrite 18.289 15.542 38.044
Chaobuleng
15CBL-20 Pyrite 18.482 15.539 38.244
[41]
15CBL-21 Pyrite 18.466 15.614 38.358
15CBL-2 Galena 18.486 15.629 38.416
14CBL-20 Galena 18.442 15.659 38.476
15CBL-6 Sphalerite 18.455 15.562 38.211
Minerals 2022,12, 1512 12 of 23
Table 6. Cont.
Deposit Sample
Number Test Object 206Pb/204 Pb 207Pb/204Pb 208 Pb/204Pb Data
Source
14CBL-22 Sphalerite 18.427 15.554 38.176
14CBL-20 Galena 18.431 15.567 38.235
14CBL-20 Galena 18.427 15.563 38.222
14CBL-20 Galena 18.424 15.561 38.221
14CBL-20 Sphalerite 18.430 15.566 38.217
15CBL-1 Galena 18.435 15.567 38.221
15CBL-1 Galena 18.433 15.565 38.228
15CBL-1 Galena 18.441 15.573 38.254
6. Discussion
6.1. Metallogenic Environment
The compositional changes in the pyrite at various stages can provide important
information about the changes in the environment of ore-forming fluids in the Jilinbaolige
Pb-Zn-Ag deposit. As Co and Ni replace Fe in pyrite in the form of isomorphism, and
the content of Co and Ni in pyrite is controlled by the physical and chemical conditions
during their precipitation, the Co and Ni in pyrite can be used to identify the environment
where pyrites were formed. The pyrites of different genetic types generally have different
Co/Ni ratios. For example, the Co/Ni ratios of cogenetic pyrites are usually <1, whereas
those of pyrites with a volcanic origin fall in the range of 5–100. In addition, the Co/Ni
ratios of hydrothermal pyrite are generally >1 [
42
,
43
]. The Co/Ni ratios (Co/Ni = 1–3) of
pyrites in this study suggest that the deposit is probably magmatic-hydrothermal in origin
(Figure 3a).
Minerals2022,12,151212of23
Thetheoreticalω(Fe)/ω(S)valueinpyriteis0.875.Theω(Fe)/ω(S)valuecanreflect
thegenesisofpyrite,asω(Fe)/ω(S)>0.875showspyritebelongingtoahydrothermal
type,whereasω(Fe)/ω(S)<0.875indicatespyriteasasedimentarytype.Theω(Fe)/ω(S)
valuesofpyritesrangefrom0.876to0.922,withanaveragevalueof0.89,higherthanthe
standardvalueof0.875[44],indicatingthatthepyritesarerichinFeanddepletedinS,
belongingtoendogenoushydrothermaltypes(Figure3b).
Figure3.Pyritetypologicalcharacteristics.(a)Co‐Nicontentsofpyrite;(b)Fe‐Scontentsofpyrite.
Inaddition,naturalbismuthandgalenaarecoevalinthelead–zincsulfideore.
Combinedwiththemeltingpoint(274°C)temperatureofnaturalbismuthundernormal
pressureconditions[45],thelead–zincsulfidesstudiedmayhaveahighermetallogenic
temperature,atleastbelongingtomedium‐temperaturehydrothermalconditions,witha
temperaturerangeof200℃‐300℃.
Thenear‐oresurroundingrocksshowsilicification,pyritization,sericitization,and
kaolinization.Theorebodyismostcloselyrelatedtopyritization,limonitization,silici‐
fication,andsericitization.Thealterationrangeandintensityarepositivelycorrelated
withthescaleandgradeoftheore(mineralized)body.Theorestructuresmainlyin‐
cludedisseminated,irregularveinsandveinletnetworkveins.Thetexturesoftheores
areeuhedral‐subhedralgranular(arsenopyriteandpyrite),allotriomorphicgranular
(pyrite,sphalerite,pyrrhotite,chalcopyrite,andgalena)andmetasomaticresidues(py‐
riteandpyrrhotite),andmetasomaticdissolutions(galenaandsphalerite).Thesetex‐
turesandstructuresareingeneraltypicalcharacteristicsofhydrothermaldeposits.In
addition,thedepositinthisstudyhastypicalhydrothermalmineralassemblages,such
aspyrite,chalcopyrite,galena,andsphalerite,whichbelongtothemedium‐temperature
hydrothermalsystem.Furthermore,thecoexistingpyrrhotite,arsenopyrite,andsphaler‐
iteindicatemedium‐temperaturehydrothermalconditionsbutwithslightlyhigherfor‐
mationtemperaturethantheformer.
Thecompositionalchangeofchloriteiscloselyrelatedtoitsformationpressure,
temperature,andphysical‐chemicalconditions.Thechloritemineralthermometerhas
beenappliedtoestimatetheformationoforedeposits[46,47].Asthechloritesstudied
arealuminum‐saturated,theirFe/(Fe+Mg)ratiosarenotcorrected.Thespeckledchlorite
thinsectioninsample11wasanalyzedusingtheenergyspectrum(Figure4).Thetem‐
peraturesoffourmicro‐zoneanalyticalpointswerecalculatedusingthetemperature
calculationformulat(℃)=‐61.92+321.98AlⅣ.Aftereliminatingpoint4,whichobviously
exceedsthetemperaturerangeofthechloritethermometer(Table7),theobtainedtem‐
peraturerangewas334.1℃‐363.1℃,withanaveragevalueof349.1℃.Inaddition,the
estimatedarsenopyritegeothermometer,basedontheEMPAresultsofarsenopyrites
withthecalculatedatomicpercentageof31.733%‐31.976%,indicatesaformationtem‐
peratureof390℃‐420℃(Figure5).Thetemperaturesobtainedwithvariousgeological
Figure 3. Pyrite typological characteristics. (a) Co-Ni contents of pyrite; (b) Fe-S contents of pyrite.
The theoretical ω(Fe)/ω(S) value in pyrite is 0.875. The ω(Fe)/ω(S) value can reflect
the genesis of pyrite, as
ω
(Fe)/
ω
(S) >0.875 shows pyrite belonging to a hydrothermal type,
whereas
ω
(Fe)/
ω
(S) <0.875 indicates pyrite as a sedimentary type. The
ω
(Fe)/
ω
(S) values
of pyrites range from 0.876 to 0.922, with an average value of 0.89, higher than the standard
value of 0.875 [
44
], indicating that the pyrites are rich in Fe and depleted in S, belonging to
endogenous hydrothermal types (Figure 3b).
In addition, natural bismuth and galena are coeval in the lead–zinc sulfide ore. Com-
bined with the melting point (274
◦
C) temperature of natural bismuth under normal
Minerals 2022,12, 1512 13 of 23
pressure conditions [
45
], the lead–zinc sulfides studied may have a higher metallogenic
temperature, at least belonging to medium-temperature hydrothermal conditions, with a
temperature range of 200 ◦C–300 ◦C.
The near-ore surrounding rocks show silicification, pyritization, sericitization, and
kaolinization. The ore body is most closely related to pyritization, limonitization, silici-
fication, and sericitization. The alteration range and intensity are positively correlated
with the scale and grade of the ore (mineralized) body. The ore structures mainly include
disseminated, irregular veins and veinlet network veins. The textures of the ores are
euhedral-subhedral granular (arsenopyrite and pyrite), allotriomorphic granular (pyrite,
sphalerite, pyrrhotite, chalcopyrite, and galena) and metasomatic residues (pyrite and
pyrrhotite), and metasomatic dissolutions (galena and sphalerite). These textures and struc-
tures are in general typical characteristics of hydrothermal deposits. In addition, the deposit
in this study has typical hydrothermal mineral assemblages, such as pyrite, chalcopyrite,
galena, and sphalerite, which belong to the medium-temperature hydrothermal system.
Furthermore, the coexisting pyrrhotite, arsenopyrite, and sphalerite indicate medium-
temperature hydrothermal conditions but with slightly higher formation temperature than
the former.
The compositional change of chlorite is closely related to its formation pressure, tem-
perature, and physical-chemical conditions. The chlorite mineral thermometer has been
applied to estimate the formation of ore deposits [
46
,
47
]. As the chlorites studied are
aluminum-saturated, their Fe/(Fe+Mg) ratios are not corrected. The speckled chlorite thin
section in sample 11 was analyzed using the energy spectrum (Figure 4). The temperatures
of four micro-zone analytical points were calculated using the temperature calculation
formula t(
◦
C) =
−
61.92 + 321.98Al
IV
. After eliminating point 4, which obviously exceeds
the temperature range of the chlorite thermometer (Table 7), the obtained temperature
range was 334.1
◦
C–363.1
◦
C, with an average value of 349.1
◦
C. In addition, the esti-
mated arsenopyrite geothermometer, based on the EMPA results of arsenopyrites with the
calculated atomic percentage of 31.733%–31.976%, indicates a formation temperature of
390
◦
C–420
◦
C (Figure 5). The temperatures obtained with various geological thermome-
ters are consistent, suggesting that the deposit has also experienced a high-temperature
hydrothermal metallogenic environment.
Table 7. Chlorite mineral thermometer estimation.
Micro-Area Analysis
Point Number Chemical Formula Temperature
1(Mg1.84Fe2.32 AlVI1.84)[(AlIV 1.28Si2.72 )O10](OH)8350.2 ◦C
2(Mg1.93Fe2.18 AlVI1.90)[(AlIV 1.23Si2.77 )O10](OH)8334.1 ◦C
3(Mg1.69Fe2.48 AlVI1.83)[(AlIV 1.32Si2.68 )O10](OH)8363.1 ◦C
4(Mg1.74Fe2.74 AlVI1.52)[(AlIV 1.49Si2.51 )O10](OH)8417.8 ◦C
Sulfides and other minerals in our study provide a wealth of information about the
genesis of the deposit. Based on the chemical compositions of pyrite, the texture and struc-
ture, and the calculated formation temperature of chlorite mentioned before, the genesis of
sulfide in the deposit is inferred to be closely related to magmatic-hydrothermal activity,
suggesting that the Jilinbaolige deposit belongs to a typical magmatic-hydrothermal Pb-Zn-
Ag polymetallic type. The geothermometers also suggest that the deposit experienced a
relatively short high-temperature hydrothermal stage.
Minerals 2022,12, 1512 14 of 23
Minerals2022,12,151213of23
thermometersareconsistent,suggestingthatthedeposithasalsoexperienceda
high‐temperaturehydrothermalmetallogenicenvironment.
Figure4.(a–d)ChloriteEDAXmicro‐areaenergyspectrumanalysis.
Figure 4. (a–d) Chlorite EDAX micro-area energy spectrum analysis.
Minerals2022,12,151213of23
thermometersareconsistent,suggestingthatthedeposithasalsoexperienceda
high‐temperaturehydrothermalmetallogenicenvironment.
Figure4.(a–d)ChloriteEDAXmicro‐areaenergyspectrumanalysis.
Figure 5.
The relationship between sulfur fugacity and temperature in the stable area of arsenopyrite.
Minerals 2022,12, 1512 15 of 23
6.2. Source of Ore-Forming Materials
6.2.1. Source of Sulfur
Sulfur isotopes offer important information about the source of ore-forming materials and
mineralization processes [
48
,
49
]. The source of sulfur before deposits is estimated based on the
isotopic composition of total sulfur in the ore-forming hydrothermal fluid during sulfide precip-
itation. The sulfur isotopic composition in the hydrothermal fluid depends on not only the
δ34
S
value of the source material but also the physico-chemical environment of sulfur-containing
materials during the migration and precipitation of the ore-forming hydrothermal solution. It
is a function of the total sulfur isotopic composition (
δ34
S
∑S
), oxygen fugacity (f
O2
), pH value,
ionic strength, and temperature in the ore-forming
solution [50,51]
. When the hydrothermal
system is dominated by H
2
S, under equilibrium conditions,
δ34SΣ≈δ34Swater ≈δ34Spyrite [52]
.
Alternatively, if pyrrhotite occurs as a stable sulfide, the pH in the hydrothermal fluid is higher
than 6, and H
2
S is the main sulfur-containing material when the temperature is lower than
500
◦
C, and the sulfur isotopic composition of the sulfide can represent that of the ore-forming
hydrothermal solution [
53
]. In addition, at high temperature (T is higher than 400
◦
C), the
sulfur in the hydrothermal system mainly occurs as H
2
S and SO
2
, whereas at medium and low
temperatures (T is lower than 350
◦
C), the sulfur in the hydrothermal system mainly occurs
as sulfate and H
2
S. Furthermore, when the oxygen fugacity is relatively low, S in the fluid
mainly occurs as S
2−
and HS
−
, and the sulfur value of the sulfide formed is similar to that of
the entire fluid. When the oxygen fugacity is high, sulfur exists in the form of SO
2−
, resulting
in the loss of
34
S in the ore-forming fluid [
50
]. The metallic mineral assemblage in this study is
mainly sulfide. The sulfur-containing minerals mainly include sphalerite, galena, pyrrhotite,
and pyrite but no sulfate minerals, suggesting that the deposit was formed under the condition
of low oxygen fugacity. In addition, the paragenetic relationship of the metal sulfides in the
deposit and the alteration characteristics of surrounding rocks indicate a medium-temperature
hydrothermal system. These features suggest that the sulfur in the ore-forming hydrothermal
system mainly occurs as H
2
S, and the sulfur isotopic composition of metal sulfide can approxi-
mately represent the total sulfur isotopic composition in the ore-forming fluid and thus can be
used to trace the source of sulfur [
50
,
53
]. The
δ34
S values of sulfides from the deposit show
the following sequence: pyrite > pyrrhotite > sphalerite > chalcopyrite > galena in the order
under the condition of equilibrium sulfur isotope fractionation [
53
]. The
δ34
S values of various
sulfides studied are in line with the enrichment order under equilibrium conditions, which
is consistent with the previous results [
54
,
55
]. The main sulfides in the mineralization stage
began to crystallize in sequence following their enrichment order with a gradual decrease in
temperature, thereby gradually decreasing the δ34S value [56].
The
δ34
S values of the sulfides in this study were concentrated in the range of 2.3
‰
to
6.1
‰
, with an average value of 3.98
‰
. The range of
δ34
S values was small (Table 5). The
δ34
S
values of sulfides in magmatic-hydrothermal deposits (
δ34
S =
−
3
‰
–1
‰
; Hoefs [
57
]) are lower
than those of the metallogenic stage studied. This may be due to the mixing of surrounding
rocks with high S content, producing a high
δ34
S value of metal sulfide ores in this study [
16
].
However, the sulfur isotopic compositions are close to those of general igneous rocks (
δ34
S
values are between
−
5
‰
to 5
‰
[
51
]) but higher than those of mantle-derived sulfurs (
δ34
S
ranges from
−
3
‰
to 3
‰
; Bi et al. [
58
]) (Figure 6). The sulfur isotopic characteristics suggest
that the source of sulfur in the ores was not provided by mantle sulfur, magmatic sulfur, or
sediments alone but by magmas with a mixture of mantle and crustal materials.
However, the Jilinbaolige deposits show
δ34
S composition characteristics similar to
those of the other deposits in the area (Figure 6). In addition, there is a small variation in
δ34
S values, reflecting the consistency of the source of S in this area. Therefore, it can be
suggested that the sulfurs in the Jilinbaolige deposit probably originated from magmatic-
hydrothermal fluids and reflect the consistency of regional sulfur sources.
Minerals 2022,12, 1512 16 of 23
Minerals2022,12,151215of23
theenrichmentorderunderequilibriumconditions,whichisconsistentwiththeprevi‐
ousresults[54,55].Themainsulfidesinthemineralizationstagebegantocrystallizein
sequencefollowingtheirenrichmentorderwithagradualdecreaseintemperature,
therebygraduallydecreasingtheδ34Svalue[56].
Theδ34Svaluesofthesulfidesinthisstudywereconcentratedintherangeof2.3‰
to6.1‰,withanaveragevalueof3.98‰.Therangeofδ34Svalueswassmall(Table5).
Theδ34Svaluesofsulfidesinmagmatic‐hydrothermaldeposits(δ34S=‐3–1‰;Hoefs[57])
arelowerthanthoseofthemetallogenicstagestudied.Thismaybeduetothemixingof
surroundingrockswithhighScontent,producingahighδ34Svalueofmetalsulfideores
inthisstudy[16].However,thesulfurisotopiccompositionsareclosetothoseofgeneral
igneousrocks(δ34Svaluesarebetween‐5‰to5‰[51])buthigherthanthoseofman‐
tle‐derivedsulfurs(δ34Srangesfrom‐3‰to3‰;Bietal.[58])(Figure6).Thesulfuriso‐
topiccharacteristicssuggestthatthesourceofsulfurintheoreswasnotprovidedby
mantlesulfur,magmaticsulfur,orsedimentsalonebutbymagmaswithamixtureof
mantleandcrustalmaterials.
However,theJilinbaoligedepositsshowδ34Scompositioncharacteristicssimilarto
thoseoftheotherdepositsinthearea(Figure6).Inaddition,thereisasmallvariationin
δ34Svalues,reflectingtheconsistencyofthesourceofSinthisarea.Therefore,itcanbe
suggestedthatthesulfursintheJilinbaoligedepositprobablyoriginatedfrommagmat‐
ic‐hydrothermalfluidsandreflecttheconsistencyofregionalsulfursources.
Figure6.DistributionofsulfurisotopiccompositionoftheJilinbaoligedepositandpolymetallic
depositsintheGreatXing’anRange.Somedataoftheoresulfurisotopecompositionsaresourced
fromZhangetal.[9],Yang[15],Jiaetal.[40],Ke[39],Chen[41],andWang[19].
6.2.2.SourcesofLead
Ingeneral,Pbhardlyundergoesfractionationintheprocessofmigrationandpre‐
cipitation.AlthoughthecompositionalcharacteristicsofPbaremainlyinfluencedbyra‐
dioactiveUandThdecayreactions,theyarenotaffectedbythechangeinphysi‐
co‐chemicalconditions.Inaddition,theU/PbandTh/Pbratioscanbealteredbypro‐
cessessuchasmagmaticevolutionanddifferentiation,hydrothermalactivityandmet‐
Figure 6.
Distribution of sulfur isotopic composition of the Jilinbaolige deposit and polymetallic
deposits in the Great Xing’an Range. Some data of the ore sulfur isotope compositions are sourced
from Zhang et al. [9], Yang [15], Jia et al. [40], Ke [39], Chen [41], and Wang [19].
6.2.2. Sources of Lead
In general, Pb hardly undergoes fractionation in the process of migration and precipita-
tion. Although the compositional characteristics of Pb are mainly influenced by radioactive
U and Th decay reactions, they are not affected by the change in physico-chemical condi-
tions. In addition, the U/Pb and Th/Pb ratios can be altered by processes such as magmatic
evolution and differentiation, hydrothermal activity and metamorphism, and surface low-
temperature weathering. Therefore, the composition and change of Pb isotopes can be
used to trace the geological evolution history and also the source of metallogenic materials
and the genesis of ore deposits [
59
,
60
]. The Pb isotopic composition of the Jilinbaolige
deposit is nearly homogeneous (Table 6), with only a small variation, which indicates the
characteristics of ordinary Pb, implying that the Pb in the deposit comes from a relatively
stable lead source. Variation in the
µ
value of Pb isotopes can also be used to constrain
the origin of Pb [
61
–
64
]. For example, higher
µ
values (>9.58) of Pb or the radiogenic Pb
located on the right side of the zero isochron was considered to be derived from the upper
crust where U and Th are relatively enriched [
63
], whereas lower
µ
values of Pb may be
contributed by the lower crust or upper mantle [
61
]. In addition, low
µ
and low
ω
values
of Pb are inherited from the characteristic of the upper mantle source [
64
], while low
µ
values and high
ω
values of Pb indicate the origin of the lower crust [
62
]. The
µ
values
of Pb in 10 ore samples from the Jilinbaolige mining area are in the range of 9.24–9.50,
with an average value of 9.36, higher than the
µ
value of Pb in the primitive mantle Pb
(
µ= 8.92
) but smaller than that in the upper crust (
µ
= 9.58); see Table 8. The
ω
values
of Pb range from 34.49 to 36.49, with 35.30, on average, lower than the crustal average
value (
µ= 36.84
) and higher than the mantle value (
µ
= 31.84) [
62
]. In addition, the Th/U
ratios of ore samples in the Jilinbaolige deposit are 3.61–3.72, with an average value of 3.65,
higher than the Th/U value of the mantle (Th/U = 3.45) but lower than the Th/U value of
crustal lead (Th/U
≈
4); see Table 8. These data together indicate that the Pb in the Baolige
deposit in Jilin is probably derived from a mixed source of the upper crust and mantle,
which is also consistent with the mixed source of the crust and mantle shown by sulfur
isotopes (Table 5).
Minerals 2022,12, 1512 17 of 23
Table 8. Lead isotopic characteristics of metallic sulfides in the Jilinbaolige deposit.
Sample Number T/Ma µ ω Th/U 4α4β4γ
Y-01 154 9.24 34.49 3.61 61.31 10.02 19.73
Y-02 169 9.26 34.57 3.61 62.17 10.67 20.18
Y-03 214 9.34 35.09 3.64 65.95 13.42 23.42
Y-04 210 9.44 36.08 3.70 71.61 17.06 29.95
Y-05 260 9.48 35.87 3.66 73.27 18.47 28.31
Y-06 192 9.32 34.74 3.61 65.35 12.86 21.2
Y-07 157 9.26 34.61 3.62 62.24 10.69 20.47
Y-08 172 9.28 34.75 3.62 63.05 11.27 21.31
Y-09 244 9.50 36.49 3.72 74.81 19.37 32.46
Y-10 274 9.48 36.35 3.71 73.32 18.6 31.33
The Pb isotopes sourced from mixed mantle-crustal materials are also supported by
Figure 7, which shows the
206
Pb/
204
Pb–
207
Pb/
204
Pb correlation, where the Pb isotopes
in the Jilinbaolige ore samples are mostly distributed in the transition zone between the
orogenic belt and the mantle evolution line, although some samples fall within the field
between the upper crust and the orogenic belt. These features suggest that that Pb has
mixed sources of the mantle and crust. The Pb isotope ratios of Chaganaobao, Aerhada,
Huanaote, 1017 Highland, and Chaobuleng deposits all fall near and on both sides of
the orogenic growth curve, also indicating that there is a mixture of mantle-derived and
crust-derived Pb in the deposits in this area.
Minerals2022,12,151217of23
Figure7.ComparisonoftheleadisotopiccompositionsoftheJilinbaoligedepositwithotherde‐
positsinthecentral‐southernpartsoftheGreatXing’anRange,aswellasthePaleozoicand
YanshanianintrusiverocksandthePermianstrata.Somedataoftheoreleadisotopecompositions
aresourcedfromZhangetal.[9],Yang[15],Jiaetal.[40],Ke[39],andChen[41];theleadisotope
compositionsofthePalaeozoicandYanshanianintrusiverocksandthePermianstrataarefrom
ZhaoandZhang[65],Zhuetal.[66],Chuetal.[67],Jiangetal.[68],andZengetal.[69];andthe
mantle,orogen,anduppercrustevolutioncurvesarefromZartmanandDoe[63].
Accordingtodifferenttectonicenvironmentsandgenesis,Zhu[72]proposedthat
theΔβ‐Δγgeneticclassificationdiagramcaneliminatetheinfluenceoftimefactorsand
hasbettertracingsignificanceforstudyingthePbsourceinore[70].ThePbisotopedata
inthisstudywerecalculatedtoobtaintherelativedeviationsΔα,Δβ,andΔγofPbin
theores,whichwereplottedinthegeneticclassificationdiagramofPbisotopes(Figure
8).ThedatapointsmainlyfallinthemagmaticPbareawherethematerialsfromthe
mantleanduppercrustaremixed.Inaddition,thepointsarealmostclosetothebound‐
aryofthePbfromthemixedmagmatismoftheuppercrustandthemantle,fromthe
orogenicbelt,andfromthemantle,indicatingthattheorePboftheJilinbaoligedeposit
hasthecharacteristicsofamixedoriginofthecrustandmantle.Inaddition,theδ
34S
valuesoftheJilinbaoligedepositshowasmallvariation(Table5),indicatingthatthe
sulfurinthedeposithasthecharacteristicsofamixeddeepmagmasourceofman‐
tle‐derivedandcrust‐derivedmaterials.ThecompositionalcharacteristicsofPbisotopes
suggestthatthePbsourceiscloselyrelatedtothedeepmagmaticactivityandproduced
byupwellingmagmaofthemantlemixedwithcrustalmaterials.Inaddition,thesulfur
andleadisotopiccompositionsofpolymetallicdepositswithmetallogenicbackgrounds
similartotheJilinbaoligedepositresemblethoseoftheJilinbaoligedeposit;the
ore‐formingfluidsinthesedepositsareanimmisciblesystemofmagmaticandmeteoric
water.Intheearlystage,themetallogenicfluidsweremainlymagmaticwater,but
mixedwithmeteoricwaterinthelatestage,furtherindicatingthatthemetallogenicma‐
terialsoftheJilinbaoligedepositwerederivedfromthemagmas.Thesourcesofsulfur
andleadintheJilinbaoligedepositaresimilartothepolymetallicdepositsrelatedto
volcanicsuitesintheGreatXing’anRange,indicatingthatthemetallogenicmaterials
haveconsistentsourcesintheregion.
Figure 7.
Comparison of the lead isotopic compositions of the Jilinbaolige deposit with other deposits
in the central-southern parts of the Great Xing’an Range, as well as the Paleozoic and Yanshanian
intrusive rocks and the Permian strata. Some data of the ore lead isotope compositions are sourced
from Zhang et al.[
9
], Yang [
15
], Jia et al. [
40
], Ke [
39
], and Chen [
41
]; the lead isotope compositions of
the Palaeozoic and Yanshanian intrusive rocks and the Permian strata are from Zhao and Zhang [
65
],
Zhu et al. [
66
], Chu et al. [
67
], Jiang et al. [
68
], and Zeng et al. [
69
]; and the mantle, orogen, and upper
crust evolution curves are from Zartman and Doe [63].
To compare the similarities and differences in Pb sources in the deposits in the southern
part of the Great Xing’an Range, the Pb isotopic compositions of the Jilinbaolige deposit
were compared with those of Paleozoic and Yanshanian intrusive rocks [
65
–
68
] as well as
the Permian strata [
67
,
69
]. The Pb isotopic compositions of Yanshanian intrusive rocks
Minerals 2022,12, 1512 18 of 23
are from feldspar separates from the intrusive rocks within or near the mining area of
the southern part of the Great Xing’an Range. Some Paleozoic intrusive rocks whose Pb
isotopic compositions come from feldspar separates or whole rock samples are corrected to
133 Ma [
70
,
71
]. It can be seen from the data (Figure 7) that the Pb isotopic compositions of
the Jilinbaolige ores are consistent with those of the Yanshanian intrusive rocks and have no
correlation with the Paleozoic intrusive rocks. The Pb isotopic compositions of Chaobuleng
and Aerhada deposits are related to the Pb isotopic composition of the Permian strata.
According to different tectonic environments and genesis, Zhu [
72
] proposed that the
∆β
-
∆γ
genetic classification diagram can eliminate the influence of time factors and has
better tracing significance for studying the Pb source in ore [
70
]. The Pb isotope data in
this study were calculated to obtain the relative deviations
∆α
,
∆β
, and
∆γ
of Pb in the
ores, which were plotted in the genetic classification diagram of Pb isotopes (Figure 8).
The data points mainly fall in the magmatic Pb area where the materials from the mantle
and upper crust are mixed. In addition, the points are almost close to the boundary of
the Pb from the mixed magmatism of the upper crust and the mantle, from the orogenic
belt, and from the mantle, indicating that the ore Pb of the Jilinbaolige deposit has the
characteristics of a mixed origin of the crust and mantle. In addition, the
δ34
S values of the
Jilinbaolige deposit show a small variation (Table 5), indicating that the sulfur in the deposit
has the characteristics of a mixed deep magma source of mantle-derived and crust-derived
materials. The compositional characteristics of Pb isotopes suggest that the Pb source is
closely related to the deep magmatic activity and produced by upwelling magma of the
mantle mixed with crustal materials. In addition, the sulfur and lead isotopic compositions
of polymetallic deposits with metallogenic backgrounds similar to the Jilinbaolige deposit
resemble those of the Jilinbaolige deposit; the ore-forming fluids in these deposits are an
immiscible system of magmatic and meteoric water. In the early stage, the metallogenic
fluids were mainly magmatic water, but mixed with meteoric water in the late stage, further
indicating that the metallogenic materials of the Jilinbaolige deposit were derived from
the magmas. The sources of sulfur and lead in the Jilinbaolige deposit are similar to the
polymetallic deposits related to volcanic suites in the Great Xing’an Range, indicating that
the metallogenic materials have consistent sources in the region.
Minerals2022,12,151218of23
Table8.LeadisotopiccharacteristicsofmetallicsulfidesintheJilinbaoligedeposit.
SampleNumbe
r
T/Maμ ωTh/U△
α
△β △γ
Y‐011549.2434.493.6161.3110.0219.73
Y‐021699.2634.573.6162.1710.6720.18
Y‐032149.3435.093.6465.9513.4223.42
Y‐042109.4436.083.7071.6117.0629.95
Y‐052609.4835.873.6673.2718.4728.31
Y‐061929.3234.743.6165.3512.8621.2
Y‐071579.2634.613.6262.2410.6920.47
Y‐081729.2834.753.6263.0511.2721.31
Y‐092449.5036.493.7274.8119.3732.46
Y‐102749.4836.353.7173.3218.631.33
Figure8.DiagramofΔγ–Δβgeneticclassificationofleadisotopesofmainmetaldepositsinthe
southernpartoftheGreatXing’anRange.Somedataoftheoreleadisotopecompositionsarefrom
Yang[15],Zhangetal.[9],Chen[41],andJiaetal.[40].FiguremodifiedaccordingtoZhu[72].
6.3.OriginofOreDepositsintheRegion
TheGreatXing’anRangeareapreservestherecordsofthelinkamongmagmatism,
mineralization,andregionaltectonics.Thedepositsinthecentral‐southernpartofthe
GreatXing’anRangewereformedbytectonomagmaticactivitiesindifferentstages,
duringwhichvariousmetallogenicmaterialsmigrated,enriched,andprecipitateddur‐
ingmagmaevolution.Asmentionedbefore,thesulfurandleadisotopiccompositionsin
theJilinbaoligedepositindicatethatthemetallogenicmaterialshavemixedcrust‐mantle
characteristics.Thesourceofmetallogenicmaterialsinthepolymetallicdeposits(e.g.,
Huanaote,1017Highland,Diyanqin’Amu,Alhada,
Chagan’Aobao,Chaobuleng)fromthecentral‐southernpartsoftheGreatXing’anRange
isconsistentwiththatintheJilinbaoligedepositandiscloselyrelatedtothegraniticin‐
trusionintheYanshanianperiod.Combinedwiththegeologicalcharacteristicsofthe
deposit,theYanshaniandeep‐sourcedintrusiverocksmighthaveprovidedthemain
metallogenicmaterials.Thecontaminationofdeep‐sourcedmagmaswithcrustalmate‐
rialswouldincreasethecontentsofore‐formingelementsinmagmas.
Figure 8.
Diagram of
∆γ
–
∆β
genetic classification of lead isotopes of main metal deposits in the
southern part of the Great Xing’an Range. Some data of the ore lead isotope compositions are from
Yang [15], Zhang et al. [9], Chen [41], and Jia et al. [40]. Figure modified according to Zhu [72].
Minerals 2022,12, 1512 19 of 23
6.3. Origin of Ore Deposits in the Region
The Great Xing’an Range area preserves the records of the link among magmatism,
mineralization, and regional tectonics. The deposits in the central-southern part of the
Great Xing’an Range were formed by tectonomagmatic activities in different stages, during
which various metallogenic materials migrated, enriched, and precipitated during magma
evolution. As mentioned before, the sulfur and lead isotopic compositions in the Jilinbaolige
deposit indicate that the metallogenic materials have mixed crust-mantle characteristics. The
source of metallogenic materials in the polymetallic deposits (e.g., Huanaote, 1017 Highland,
Diyanqin’Amu, Alhada, Chagan’Aobao, Chaobuleng) from the central-southern parts of the
Great Xing’an Range is consistent with that in the Jilinbaolige deposit and is closely related to
the granitic intrusion in the Yanshanian period. Combined with the geological characteristics
of the deposit, the Yanshanian deep-sourced intrusive rocks might have provided the main
metallogenic materials. The contamination of deep-sourced magmas with crustal materials
would increase the contents of ore-forming elements in magmas.
In addition to the granitic intrusion, the polymetallic deposits studied are also con-
trolled by the regional structure. The Jilinbaolige mining area, located in the eastern part of
the near-EW-trending Erlian–Dongwuqi polymetallic metallogenic belt, shows similarities
with the Erlian–Dongwuqi polymetallic metallogenic belt, which is affected by the metallo-
genic events of the Great Xing’an Range metallogenic belt. During the magma intrusion, in
addition to the superimposed fold deformation, the adjacent regional faults and the NE,
NNE, and NWW faults show strong activity, also generating the NW-trending secondary
faults, thereby facilitating the structural channel for the post-magmatic-hydrothermal fluid
migration to the direction of low temperature and low pressure. The contact interface
between the Aqinchulu granite body and the shallow metamorphic strata of the Ange-
lyinwula Formation on the northwest side of the mining area is generally inclined to SE,
which was conducive to the effective direct contact of the pluton and the various lithologi-
cal fabrics of the Angelyinwula Formation, as well as the formation of local tension and
fracture space along the interface, thus providing room for the effective accumulation of
ore-forming hydrothermal fluids (Figure 9).
Minerals2022,12,151220of23
Figure9.SchematicillustrationofthemetallogenicmodeloftheJilinbaoligeminingarea.Note:1,
DevonianTalbatFormation;2,DevonianAngelyinwulaFormation;3,CarboniferousBaoligemiao
Formation;4,intrusiverock;5,atmosphericprecipitation;6,magma;7,orebody;8,fault.
7.Conclusions
TheJilinbaoligedepositisatypicalmagmatic‐hydrothermalPb–Zn–Agpolymetal‐
licdepositformedunderamedium‐temperaturehydrothermalmetallogenicenviron‐
ment.Theearlystageofmineralizationmighthaveevolvedfromahigh‐temperature
hydrothermalmetallogenicenvironment.
TheSandPbisotopiccompositionsofsulfideoresinthedepositsuggestthatthe
sulfursintheoresprobablyoriginatedfromamagmaticsource,withamixtureofman‐
tleandcrustalmaterials.TheS–PbisotopiccompositionsoftheJilinbaoligedeposits
showaclosesimilaritytothoseofthepolymetallicdepositsinthecentral‐southernparts
oftheGreatXing’anRange,suggestingthatthesedepositshaveasimilarsourceof
metallogenicmaterials,whicharecloselyrelatedtothegraniteintrusionintheYansha‐
nianperiod.
Basedonthesystematicstudiesontheregionalmetallogenicandgeologicalback‐
ground,characteristicsoforedeposits,andsourceofmetallogenicmaterials,itissug‐
gestedthattheJilinbaoligedepositformedthroughthegradualevolutionofdeepmag‐
maticfluids.Theseore‐bearinghydrothermalfluidsmigratedalongthecontactzoneof
theintrusionandfracturezones.Withthegradualdecreaseintemperatureofthe
ore‐formingfluids,themetallogenicelementswereprecipitatedintherelativelyopen
fractureandfissurespace,finallyproducingtheJilinbaoligePb–Zn–Agpolymetallic
deposit.
AuthorContributions:Conceptualization,S.H.andX.D.;methodology,S.H.,S.W.andX.D.;vali‐
dation,S.H.,X.D.,S.W.,K.T.andZ.T.;datacuration,S.H.,S.W.,S.L.(SaiLi),S.L.(SanLiu)andL.C.;
writing—originaldraftpreparation,S.H.,X.D.,S.M.,S.W.,S.L.(SaiLi),S.L.(SanLiu),S.L.(Shuqin
Long),H.S.,L.C.,A.M.,S.L.andW.L.;writing—reviewandediting,S.H.,X.D.,M.S.,Q.S.,K.T.and
Z.T.Allauthorshavereadandagreedtothepublishedversionofthemanuscript.
Figure 9.
Schematic illustration of the metallogenic model of the Jilinbaolige mining area. Note:
1, Devonian Talbat Formation; 2, Devonian Angelyinwula Formation; 3, Carboniferous Baoligemiao
Formation; 4, intrusive rock; 5, atmospheric precipitation; 6, magma; 7, ore body; 8, fault.
Minerals 2022,12, 1512 20 of 23
The extraction and leaching of ore-hosting wall rocks by mixed-source fluids is an
important mechanism leading to the accumulation of ore-forming components [
73
]. The
hydrogen and oxygen isotopic compositions of the ore-forming fluids of other typical
lead–zinc–silver deposits in the Great Xing’an Range indicate the mixed characteristics
of magmatic and meteoric water [
55
]. The ore-forming fluids of Pb-Zn-Ag polymetallic
deposits in the Great Xing’an Range area are mainly magmatic water in the early stage of
mineralization but dominated by atmospheric water in the late stage [
55
]. The deposits in
this study also conform to this feature. On the basis of the geological characteristics combined
with S and Pb isotopic compositions of the deposit, it is suggested that the deep-sourced
magmatic-hydrothermal fluids migrated upward along structural faults, accompanied
by material exchange with the surrounding rocks during the migration process, thereby
gradually enriching the hydrothermal ore-forming fluids with Pb, Zn, and Ag. The mixing of
magmatic and meteoric water and the water–rock reaction led to further evolution of the ore-
forming hydrothermal solutions. These fluids migrated from deep to shallow levels, from
the inside of the rock mass to the outer strata of the contact zone, along the contact zone and
the active fracture zone, as well as the structural interface of the Angelyinwula Formation,
to reduced-pressure conditions and greater relative permeability. As the temperature of the
ore-forming hydrothermal solution decreased, the metals were precipitated in the relatively
open fracture and fissure space, forming ore bodies, veins, ore reticulates, and patches, and
thus producing the Jilinbaolige Pb-Zn-Ag polymetallic deposit (Figure 9).
7. Conclusions
The Jilinbaolige deposit is a typical magmatic-hydrothermal Pb-Zn-Ag polymetallic de-
posit formed under a medium-temperature hydrothermal metallogenic environment. The
early stage of mineralization might have evolved from a high-temperature hydrothermal
metallogenic environment.
The S and Pb isotopic compositions of sulfide ores in the deposit suggest that the
sulfurs in the ores probably originated from a magmatic source, with a mixture of mantle
and crustal materials. The S–Pb isotopic compositions of the Jilinbaolige deposits show a
close similarity to those of the polymetallic deposits in the central-southern parts of the
Great Xing’an Range, suggesting that these deposits have a similar source of metallogenic
materials, which are closely related to the granite intrusion in the Yanshanian period.
Based on the systematic studies on the regional metallogenic and geological back-
ground, characteristics of ore deposits, and source of metallogenic materials, it is suggested
that the Jilinbaolige deposit formed through the gradual evolution of deep magmatic fluids.
These ore-bearing hydrothermal fluids migrated along the contact zone of the intrusion
and fracture zones. With the gradual decrease in temperature of the ore-forming fluids, the
metallogenic elements were precipitated in the relatively open fracture and fissure space,
finally producing the Jilinbaolige Pb-Zn-Ag polymetallic deposit.
Author Contributions:
Conceptualization, S.H. and X.D.; methodology, S.H., S.W. and X.D.; valida-
tion, S.H., X.D., S.W., K.T. and Z.T.; data curation, S.H., S.W., S.L. (Sai Li), S.L. (San Liu) and L.C.;
writing—original draft preparation, S.H., X.D., M.S., S.W., S.L. (Sai Li), S.L. (San Liu), S.L. (Shuqin
Long), H.S., L.C., A.M., S.L. and W.L.; writing—review and editing, S.H., X.D., M.S., K.T. and Z.T. All
authors have read and agreed to the published version of the manuscript.
Funding:
This work was financially supported by the National Foreign Expert Project (G2022029012L),
the Outstanding Youth Project of Education Department of Hunan Province (15B201), and the Talent
foundations of University of South China (2014XQD08, 2018XQD22).
Data Availability Statement:
All data generated or used during the study appear in the submitted article.
Conflicts of Interest: The authors declare no conflict of interest.
Minerals 2022,12, 1512 21 of 23
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