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132 Chaowen Huang, Gaofeng Du, Huajun Jiang, Jianfeng Xie, Daohan Zha, Huan Li and Chun-Kit Lai

which lies in the southern part of the Sibumasu terrane (Barber and Crow, 2003; Metcalfe, 2002). The Sibumasu terrane ex-tends from Sumatra, via Peninsular Malaysia, central-eastern Thailand, eastern Myanmar to SW Yunnan, and was likely part of the Gondwana supercontinental margin connected to north-western Australia (Wu and Suppe, 2018; Hu et al., 2017; Jama-ludin et al., 2017; Burrett et al., 2014; Barber and Crow, 2003). During the Permian, Sibumasu was likely cracked off from Gondwana, drifted across the Paleotethys, and accreted onto the southeastern Eurasia margin in the Mesozoic (Ueno, 2003; Metcalfe, 1996; Şengör, 1987, 1979; Stöcklin, 1974). This formed the flysch sequences and the overlying marine sedi-mentary rocks (Metcalfe, 2002), followed by the formation of the Woyla suture zone in Sumatra after the accretion. In the Paleocene, the oblique subduction of the Indian Plate beneath Sibumasu might have occurred (Hou et al., 2006a, b), forming regional magmatism and dextral shearing.

Major rocks exposed at Sidikalang include the Carboniferous–Permian Tapanuli Group, which comprises the Alas Formation (mainly carbonate rocks) in the lower part and the Kluet Formation (mainly clastic rocks) in the upper part (Cameron et al., 1982). These Paleozoic rocks are deformed and weakly contact metamorphosed by intrusions. The Paleo-zoic sequences are almost entirely covered by the Pleistocene

tuffs centered on the Toba crater in Sumatra (Reynolds, 2004).

1.2 Ore Geology The major structure at Anjing Hitam is the NW-trending

Sopokomil dome (Fig. 2), which is about 5 km long and 2 km wide. Apart from the Sopokomil dome, a contemporaneous fault (Balga fault) is identified as the boundary fault of Anjing Hitam deposit. Multistage deformation structures of the mine are well developed. Although small-scale isoclinal folds are extensively developed, mineralization is essentially stratiform.

The Anjing Hitam Pb-Zn orebody is mainly hosted in the Kluet Formation (Figs. 3–4), which comprises three members: (from top to bottom) the Jehe Member largely comprises mas-sive thick-bedded pale to dark grey dolostones, commonly extensively brecciated and veined in multiple events. The strongly deformed Julu Member comprises carbonaceous (dolomitic) shale and siltstone. The Julu Member (main ore host) sandstone contains stratiform, lenticular and massive Pb-Zn sulfide orebodies, and commonly contains also over-printing Pb-Zn vein mineralization.

Drill-hole data reveal that the alterations at Anjing Hitam include carbonization, silicification and sericitization (Fig. 5). All lithologies within the Kluet Formation are carbonate- bearing to some extent, and all are apparently dolomitised.

Figure 1. Regional tectonic setting of Sumatra (modified after Genrich et al., 2000).

Ore-Forming Fluids Characteristics and Metallogenesis of the Anjing Hitam Pb-Zn Deposit 133

Figure 2. Regional geological map of the Anjing Hitam area (modified after Reynolds, 2004).

Figure 3. Sketch map of the Anjing Hitam Pb-Zn deposit (modified after

Reynolds, 2004).

Dolomitization is extensively developed in the marl of the Julu Member. Pyrite-calcite-dolomite assemblage has a spotty tex-ture, particularly in the footwall of the Julu Member carbona-ceous shale, which is closely spatially related to the stratiform Zn-Pb mineralisation. Silicification is less extensive and is associated mainly with the overprinting vein-type Zn-Pb min-eralization.

Based on the detailed field geological and petrographic

Figure 4. Cross-section diagram of the Anjing Hitam Pb-Zn deposit (modi-

fied after Reynolds, 2004).

observations, the Anjing Hitam Pb-Zn mineralization is divided into two stages: sedimentary and hydrothermal mineralization.

Sedimentary mineralization (stage I) is the main ore-forming stage. It occurs as multiple stratiform orebodies


within the Julu Member, particularly in the thinly bedded car-bonaceous siltstones but also in the coarser wacked interbeds. The Pb-Zn mineralization zone at Anjing Hitam is up to 800 m long and 100–300 m wide (Fig. 3; Reynolds, 2004), and up to 20 m thick (Figs. 5a–5d). The orebodies are generally strati-form, stratoid or lenticular, and extended along dip and strike with the strata. The drill hole SOP60D intersects 17.67 m of 10.6% Zn and 5.0% Pb. The ores are mainly massive, banded with local brecciation. The ore texture is dominated by subhedral-xenomorphic granular and metasomatic texture. Major metallic minerals include galena, sphalerite and pyrite, whilst gangue minerals are dominated by quartz and carbonates. Wall rock alterations include mainly weak-moderate silicifica-tion, carbonization and sericitization (Fig. 5g). The stratiform orebodies are bended by the late folding (Fig. 5d), and crosscut by irregular veins and stockworks of remobilised sulphide.

Vein mineralization (stage II) is featured by numerous large-scale polymetallic-sulfide-carbonate-quartz veins that crosscut stage I stratiform orebodies. These veins are domi-nated by calcite, dolomite and quartz, while sphalerite, galena and pyrite are sparsely disseminated in the quartz-calcite veins or stockwork (Figs. 5e–5f).

2 ANALYTICAL METHODS AND RESULTS 2.1 Analytical Methods

Based on field geology and mineralogy, representative calcite samples from the two mineralization stages were se-lected for the fluid inclusion analysis. Nine polished calcite thin sections (0.06–0.08 mm thick) were prepared for the fluid in-clusion study that used heating and freezing measurements. Microthermometric measurements were performed using a Linkam THMS600 heating-freezing stage at the Central South University (Changsha, China). The stage, which was calibrated by using synthetic fluid inclusions, has a maximum temperature limit of 600 ºC and a minimum temperature limit of -196 ºC. The estimated precisions of its measurements are ±0.1 and ±1 ºC for freezing and heating, respectively. Salinities of NaCl-H2O were estimated using the ideal geometrical mixing equation pro-posed by Brown and Lamb (1989) using the computer program FLINCOR. Analysis of fluid inclusion composition was per-formed using an SP3400-1 gas chromatograph and DX-120 ion chromatograph. Detailed operational and analytical processes were as outlined in Wang (1998) and Zhu et al. (2003).

Carbon-oxygen isotope analyses were conducted at the ALS Laboratory Group (Guangzhou), following the analytical

Figure 5. Photographs showing the geological characteristics of Anjing Hitam lead-zinc deposit. (a) Banded orebody; (b) massive orebody; (c) stratiform ore-

body; (d) sulfide and its paragenetic gangue minerals bended synchronously with fold; (e) quartz-carbonate veins cut the fold; (f) late hydrothermal superimpo-

sition and modification; (g) silicification, calcitization, sericitization; (h) skeleton crystal structure of pyrite; (i) the automorphic, hypidiomorphic and xeno-

morphic granular of the main ore textures. Qtz. Quartz; Cal. calcite; Ser. sericite; Gn. galena; Sp. sphalerite; Py. pyrite.


procedures similarly described in Li et al. (2013). Using the cavity enhanced absorption spectroscopy with the PDB and SMOW standard, the analysis accuracy was ±0.05‰.

2.2 Fluid Inclusion Petrography

Fluid inclusions in calcite were systematical studied. Cal-cite in the primary sedimentary period is presenting mostly as belt shape or contaminated products out of sphalerite, galena and pyrite. The orebody in the primary sedimentary period had folding deformation. Calcite in the hydrothermal transforma-tion period is dominantly net-veinlet and veinlet. Sphalerite, galena and pyrite are presenting mostly as belt shape or conta-minated products out of calcite.

Fluid inclusion petrography is conducted with the follow-ing rules: isolated fluid inclusions and random groups in intra-granular calcites crystals were interpreted as primary in origin, whereas those aligned along micro-fractures in transgranular trails were designated as pseudosecondary (Lu et al., 2004; Goldstein, 2003; Roedder, 1984). But secondary inclusions are small and unsuitable for analysis.

According to the phase relationships at room temperature and phase transitions during heating and cooling, the following two types of well-developed primary and pseudosecondary in-clusions were observed in these calcite samples: aqueous inclu-sions and gas-liquid two-phase inclusions. In the sedimentary- stage samples, the inclusions (2–6 μm in diameter) occur in

isolation or in cluster and are elliptical, irregular, or elongated in shape. They have varying vapor-liquid ratios of 5% to 20% (Figs. 6a–6b). The hydrothermal-stage inclusions were distri-buted in clusters, 2–8 μm in diameter, and are irregular or ellip-tical in shape and have vapor-liquid ratios of 5% to 20% (Figs. 6c–6d).

2.3 Microthermometric Results

The microthermometric results are summarized in Table 1. The sedimentary stage fluid inclusions were homogenized to liquid at 105 to 199 ºC (mostly 120 to 160 ºC; Fig. 7), averag-ing at 131 ºC. The inclusion freezing temperatures range from -14.5 to -9.5 ºC, averaging at -13.8 ºC. The calculated salinities are of 9.6 wt.% to 16.6 wt.% NaCleqiv, averaging at 13.2 wt.% NaCleqiv.

The hydrothermal-stage fluid inclusions were homoge-nized to liquid at 206 to 267 ºC, averaging at 234 ºC. The freezing temperatures of these inclusions range from -20.5 to -18.5 ºC. The calculated salinities are between 19.0 wt.% and 22.5 wt.% NaCleqiv, averaging at 20.4 wt.% NaCleqiv.

2.4 Liquid-Gas Compositions of Inclusions

Analytical results are listed in Table 2 and summarized below.

(1) For the sedimentary-stage fluid inclusions, the liquid- phase cations were mostly Na+ and Ca2+, plus minor K+ and Mg2+.

Figure 6. Microphotographs of fluid inclusions from the Anjing Hitam lead-zinc deposit. L. Liquid phase; V. vapor phase.


Figure 7. Histograms of homogenization temperature and salinity of fluid inclusion.

Table 1 Summary of microthermomentric data for fluid inclusions from the Anjing Hitam Pb-Zn deposit

Mineralization stage Mineral Freezing

temperature (Tm ice/oC)

Homogenization

temperature (Th LV/oC)

Salinity (wt.% NaCLeqiv)

Num. Range Average value Range Average value Range Average value

Primary stage Calcite 42 -14.5– -9.5 -12.6 105–199 131 9.6–16.6 13.2

Hydrothermal stage Calcite 46 -20.5– -18.5 -19.7 206–267 234 19.0–22.5 20.4

Table 2 Gas and liquid compositions of fluid inclusions

Sample Mineral Mineralization stage Liquid compositions (μg/g)

F- Cl- NO3- SO4

2- K+ Na+ Mg2+ Ca2+

S1 Calcite Primary sedimentary stage 0.1 15.8 / 6.4 1.6 17.1 / 4.5

S2 Calcite / 7.6 / 8.3 1.4 13.2 / 2.6

S3 Calcite / 9.3 / 5.2 1.1 14.7 0.1 3.7

S6 Calcite Hydrothermal stage 1.2 10.2 0.2 3.6 0.5 4.7 1.2 8.6

S7 Calcite 0.7 13.2 0.1 3.6 0.7 7.8 0.6 4.2

S8 Calcite 0.3 11.6 0.2 2.3 1.3 14.1 0.6 4.7

Sample Ore Mineralization stage Gas compositions (μL/g)

H2 N2 CO CH4 CO2 C2H6 H2O

S1 Calcite Primary sedimentary stage 3.4 0.1 / 2.2 294 0.3 1 232

S2 2.2 0.2 / 4.3 165 0.2 1 862

S3 3.6 0.1 / 5.3 453 0.2 2 376

S6 Calcite Hydrothermal stage 3.5 9.6 0.3 0.4 26.8 / 3 522

S7 1.3 2.2 0.2 0.1 10.1 / 1 180

S8 0.9 1.3 0.2 0.1 10.3 / 1 616


Table 3 Carbon and oxygen isotope compositions of Anjing Hitam Pb-Zn desposit

Sample Mineralization period Ore Mineral δ13CPDB (‰) δ18OSMOW (‰) T (oC) δ18OH2O (‰)

S1 Primary stage Banded ore Calcite -1.8 15.3 130 1.6

S2 Massive ore Calcite -2.2 18.5 130 4.8


S4 Banded ore Calcite -0.5 14.4 135 1.1


S6 Hydrothermal stage Vein ore Calcite -6.7 15.4 235 5.0

S7 Vein ore Calcite -4.8 15.2 230 7.6



The anions are dominated by Cl− and minor SO42− and F−.

These ions (in decreasing abundance) are: Na+>Cl−>SO42−>

Ca2+>K+>Mg2+>F−. The gaseous phase components are mainly H2O and CO2 with some H2, N2, and CH4, and a small amount of C2H6.

(2) For the hydrothermal reformation stage fluid inclu-sions, the liquid-phase cations are mostly Na+ and Ca2+, plus minor K+ and Mg2+. The anions are dominated by Cl−, plus some SO4

2−, F− and NO3−. These ions (in decreasing abundance)

are: Cl−>SO42−>Ca2+>Na+>Mg2+>K+. The gaseous phase com-

ponents are mainly H2O with some CO2, H2, N2, and a small amount of CH4 and CO. 2.5 Carbon and Oxygen Isotopes

Five sedimentary-stage and four hydrothermal vein-stage fluid inclusion samples from calcite were used for the carbon- oxygen isotope analyses, and the results are shown in Table 3. For the sedimentary-stage fluid inclusions, the δ18OSMOW values range from 14.4‰ to 15.3‰ (mean of 16.5‰). The δ18CPDB and δ18OH2O values range from -2.2‰ to -0.5‰ (mean of -1.6‰) and from 1.1‰ to 4.8‰ (mean of 2.8‰), respectively. For the hydrothermal vein-stage fluid inclusions, the δ18OSMOW values range from 14.8‰ to 15.4‰ (mean of 15.0‰). The δ18CPDB and δ18OH2O values range from -6.7‰ to -4.8‰ (mean of -5.6‰) and from 5.0‰ to 7.6‰ (mean of 6.8‰), respectively. 3 DISCUSSION 3.1 Ore-Forming Fluid Properties

Stage I (sedimentary) fluid inclusion assemblages of the Anjing Hitam Pb-Zn deposit are relatively simple: the inclu-sions are mainly composed of gas-liquid two-phase aqueous solution with liquid-rich phase, resembling those from MVT- or SEDEX-type deposits (Li et al., 2018; Zhou et al., 2018; Li and Xi, 2015; Chen et al., 2007). The homogenization temper-atures of stage I inclusions are 105–199 ºC, characteristic of low-temperature mineralization. The salinity is medium to low (9.6 wt.%–16.6 wt.% NaCleqiv) of typical SEDEX deposits (60–280 ºC and 4 wt.%–23 wt.% NaCleqiv, respectively; Lu and Shan, 2015; Wang et al., 2014; Wilkinson, 2014; Liu et al., 2008; Basuki, 2002; Cooke et al., 2000; Lydon, 1983; Badham and Williams, 1981).

The homogenization temperature and salinity of the stage II fluid inclusions are 206–267 ºC and 19.0 wt.%–22.5 wt.%

NaCleqiv, respectively, indicating a medium temperature and salinity for the ore fluids. The temperature and salinity are higher than those of stage I.

3.2 Fluid Source

The primary inclusions are formed simultaneously with the host minerals during the diagenesis and mineralization, which captures the ore-forming fluids (Wang X et al., 2017; Li et al., 2013; Lu et al., 2004). Therefore, their compositions can reflect the physicochemical conditions in which the minerals were formed. Our analyses of the gas-liquid compositions of the fluid inclusions show that the Anjing Hitam stage I ore-forming fluids belong to a CO2-rich H2O-NaCl system (Table 2). The gas phase of the inclusions contains CO2, N2, CH4 and C2H6, and the H2O and CO2 contents are relatively high, resembling those of typical deep-sourced fluids (Lu et al., 2004). The enrichment of Ca2+ and CO2 in the fluid inclusions suggests that the ore-forming fluids may have influenced by the fractional crystallization of deep-lying granitic intrusion (Li et al., 2017). Cations in the inclusions include mainly Na+ and Ca2+, and the anions include mainly Cl−, with Na+/K+=9.4–13.3 (>10) and F−/Cl− of about 0 (<1). These characteristics are sim-ilar to those of SEDEXT-type deposits (Roedder, 1984), sug-gesting that the Anjing Hitam stage I ore-forming fluids were mostly likely to be derived from the exhalative sedimentary process (Zhang, 1992). Stable isotopes are wide used to identi-fy the ore-forming fluid sources (Zheng, 2001; Ohmoto and Goldhaber, 1997; Taylor, 1997; Rye and Ohmoto, 1974). There are three sources of CO2 in hydrothermal solutions: magmatic carbon, sedimentary carbon and organic carbon. Our carbon isotope analysis shows that the calcite δ13CPDB values of the stage I ores are -2.2‰ to -0.5‰, which fall between the ranges of magmatic carbon (δ13CPDB=0.8‰ to 2.0‰; Kroop-nick et al., 1972) and sedimentary carbon (δ13CPDB= -9.0‰ to -3.0‰; Hoefs, 1973). This further suggests that the stage I ore-forming fluids were sourced from both deep-sourced mag-matic rocks and exhalative sedimentary process. Similarly, oxygen isotope analysis shows that the calcite δ18OH2O values of the stage I ores are 1.1‰–4.8‰, falling between the seawater (δ18O= -1.0‰ to 1.0‰; Sheppard et al., 1971) and magmatic water (δ18O=5.5‰–9.0‰; Sheppard et al., 1971) fields. Though the Late Carboniferous–Permian granic activities weren’t found at Anjing Hitam, the Kluet Formation, which is the host rock for


the SEDEX orebodies and mainly composed of clastic rock and mafic volcanic rocks, is widely exposed in the region (Cameron et al., 1982). It indicates that the local magmatic activity may have contributed to the SEDEX mineralization.

Gaseous components of the stage II fluids include CO2, N2, CH4, CO, and the H2O and CO2 contents are high. Cations are also mainly Na+ and Ca2+, and anions are mainly Cl−, with Na+/K+=9.4–11.1 (>10) and F−/Cl−=0–0.01 (<1), which are similar to those of the stage I ore. The calcite δ13CPDB and δ18OH2O values of the stage II ores are -6.7‰ to -4.8‰ and 14.7‰ to 15.4‰, respectively, which are different from those of the stage I ore (especially in δ18OH2O values). These charac-teristics suggest that the stage II ore-forming fluids were main-ly derived from magmatic process but also inherited some iso-tope features from the stage I SEDEX-mineralization. During the Cenozoic, the Indian Plate moved eastward and subducted beneath Sumatra, forming the three back-arc basins of North Gate, Central Post and South Sumatra (Cao et al., 2005). The subduction was accompanied by intense magmatism (Ulmer and Trommsdorff, 1995), as shown by the extensive Pleisto-cene tuff deposition around the Toba crater at Sidikalang. The Pleistocene tuff is located to the northern of the Anjing Hitam area (Fig. 2). This intense magmatism may have been responsi-ble for stage II hydrothermal vein-type mineralization. There-fore, we propose that the stage II ore-forming fluids were mainly derived from magmatic rocks, and contain inheritance from the wall rocks (including stage I SEDEX ores).

3.3 Ore Deposit Type

SEDEX deposits are mostly developed on the divergent plate margins and intraplate rift (Sun et al., 2011; Betts et al., 2003; Lydon, 1996), or back-arc rift basins (Betts and Lister, 2002). This is mainly because the upper crustal permeability can be enhanced significantly under extensional environments, which would promote fluid circulation (Russell, 1983). In addi-tion, the syn-sedimentary faults resulted from the disintegration (Miall, 1984) would provide the ore-bearing fluids with migra-tion channels and space for precipitation, which are also key conditions for the SEDEX mineralization (Zhang et al., 2010). For example, the famous Lasbela-Khuzdar SEDEX Pb-Zn belt in Pakistan, which hosts the Surmai, Gunga, Dhungei, Duddar and many other Pb-Zn deposits (Leach et al., 2005; Janković, 2001; Turner, 1992; Sillitoe, 1978), is considered to have re-sulted from the rifting of the Cimmerian terrane (including Transcaucasia, Central Iran, Southern Afghanistan, Southern Pamirs, Qiangtang, Sibumasu, ect.; Ueno, 2003; Metcalfe, 1997, 1996; Şengör, 1987) from the Gondwana supercontinent. In northern Sumatra, the Kluet Formation clastic rocks are found to have decreasing grain sizes from northeast to southwest, suggesting the formation of a passive continental rift basin to the southwest (Barber and Crow, 2003; Cameron et al., 1980). This tectono-sedimentary setting in in northern Sumatra resem-bles that of the Lasbela-Khuzdar SEDEX Pb-Zn belt.

SEDEX Pb-Zn deposits commonly contain the following features: (1) metals are mainly Pb, Zn and Ag, and the ore minerals are dominated by sphalerite, galena and pyrite and Zn-rich minerals (Leach et al., 2005; Lydon, 1996); (2) strati-form orebodies hosted by marine sedimentary rocks (Leach et

al., 2010, 2005; Han and Sun, 1999) such as fine marine clastic and carbonate rocks. The sedimentary rocks are commonly folded; (3) massive or bedded ore structure; (4) orebodies are controlled by the syn-sedimentary faults; (5) most deposits were formed mostly during the Paleoproterozoic, Cambrian and Early Mesozoic (Leach et al., 2010; Goodfellow and Lydon, 2007; Laznicka, 2006); (6) ore-forming structures are mostly sedimentary and textensional-related, and the orebodies are controlled by rift-controlled the sedimentary basins (Sun et al., 2011; Betts et al., 2003; Lydon, 1996). Many of these features are present at Anjing Hitam, including: (1) ore minerals are mainly sphalerite, galena and pyrite; (2) orebodies are hosed in the Upper Carboniferous–Permian Kluet Formation marine se-dimentary rocks; (3) the deposit is bounded by the regional syn- sedimentary Balga fault; (4) during the Late Carboniferous– Permian, Sumatra was likely situated in an extensional, passive continental margin environment (Ueno, 2003; Metcalfe, 1996; Şengör, 1987). Therefore, the Anjing Hitam deposit is best classified to a modified SEDEX type.

4 CONCLUSIONS

(1) The Anjing Hitam Pb-Zn orebodies are mainly strati-form and hosted in the middle part of the Carboniferous– Permian Kluet Formation of the Tapanuli Group. According to the mineral assemblage and paragenesis, the mineralization can be divided into two stages: stage I exhalative sedimentary mi-neralization and stage II hydrothermal vein-type mineralization.

(2) The stage I ore-forming fluids were likely derived mainly from exhalative sedimentary (SEDEX) processes in-volving some deep-seated magma sourced fluids. The stage II ore-forming fluids were likely magmatic fluids with certain input from the wall rocks and the remobilization of stage I SEDEX ores.

(3) The stage I SEDEX Pb-Zn mineralization at Anjing Hitam Pb-Zn deposit was formed in a Late Carboniferous to Permian passive continental rift basin, associated with the opening of the Paleotethys. ACKNOWLEDGMENTS

We gratefully acknowledge the anonymous reviewers for their critical comments and constructive suggestions, which have improved the quality of the paper greatly. This study was financially supported by the National Basic Research Program of China (No. 2014CB440901). The final publication is available at Springer via https://doi.org/10.1007/s12583-019-0859-z. REFERENCES CITED

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