ARTICLE

Geological and isotopic evidence for magmatic-hydrothermalorigin of the Ag–Pb–Zn deposits in the Lengshuikeng District,east-central China

Changming Wang & Da Zhang & Ganguo Wu &

M. Santosh & Jing Zhang & Yigan Xu & Yaoyao Zhang

Received: 7 August 2012 /Accepted: 27 March 2014 /Published online: 8 April 2014# Springer-Verlag Berlin Heidelberg 2014

Abstract The Lengshuikeng ore district in east-central Chinahas an ore reserve of ∼43 Mt with an average grade of204.53 g/t Ag and 4.63 % Pb+Zn. Based on contrastinggeological characteristics, the mineralization in theLengshuikeng ore district can be divided into porphyry-hosted and stratabound types. The porphyry-hosted minerali-zation is distributed in and around the Lengshuikeng graniteporphyry and shows a distinct alteration zoning includingminor chloritization and sericitization in the proximal zone;sericitization, silicification, and carbonatization in the periph-eral zone; and sericitization and carbonatization in the distalzone. The stratabound mineralization occurs in volcano-sedimentary rocks at ∼100–400 m depth without obviouszoning of alterations and ore minerals. Porphyry-hosted andstratabound mineralization are both characterized by early-stage pyrite–chalcopyrite–sphalerite, middle-stage acanthite–native silver–galena–sphalerite, and late-stage pyrite–quartz–calcite. The δ34S values of pyrite, sphalerite, and galena in theores range from −3.8 to +6.9‰ with an average of +2.0‰.The C–O isotope values of siderite, calcite, and dolomiterange from −7.2 to −1.5‰ with an average of −4.4‰ (V-PDB) and from +10.9 to +19.5‰ with an average of +14.8‰

(V-SMOW), respectively. Hydrogen, oxygen, and carbon iso-topes indicate that the hydrothermal fluids were derived main-ly from meteoric water, with addition of minor amounts ofmagmatic water. Geochronology employing LA–ICP–MSanalyses of zircons from a quartz syenite porphyry yielded aweighted mean 206Pb/238U age of 136.3±0.8 Ma consideredas the emplacement age of the porphyry. Rb–Sr dating ofsphalerite from the main ore stage yielded an age of 126.9±7.1 Ma, marking the time of mineralization. TheLengshuikeng mineralization classifies as an epithermal Ag–Pb–Zn deposit.

Keywords Stable isotope . Geochemistry . Porphyry .

Stratabound . Ag–Pb–Zn . Lengshuikeng

Introduction

The Lengshuikeng ore district, located in the Jiangxi Provinceof east-central China (Fig. 1a), contains more than 50 orebodies belonging to seven deposits hosted in granite porphyry,pyroclastic, and carbonate rocks. The ore reserves inLengshuikeng have been estimated at ∼43 Mt with averagegrades of 2.11 % Pb, 2.61 % Zn, 204.53 g/t Ag, 0.08 g/t Au,and 0.01 % Cd. The ores can be grouped into two types: (1)porphyry-hosted (Yinluling, Baojia, and Yinzhushan) and (2)stratabound (Xiabao, Yinkeng, Yinglin, and Xiaoyuan). Theporphyry-hosted mineralization is distributed within andaround the Lengshuikeng granite porphyry, whereas thestratabound mineralization occurs in volcano-sedimentaryrocks at ∼100–400 m depth. The spatial distribution of theporphyry-hosted and stratabound ore bodies, their mineralconstituents, and the zoning of alteration assemblages aremarkedly different from those of typical porphyry deposits.

Editorial handling: T. Bissig and G. Beaudoin

C. Wang (*) :D. Zhang :G. Wu :M. Santosh : J. Zhang :Y. Xu :Y. ZhangState Key Laboratory of Geological Processes and MineralResources, China University of Geosciences, No. 29, Xueyuan Road,Beijing 100083, People’s Republic of Chinae-mail: wcm233@163.com

Y. XuNo. 912 Geological Surveying Team, Bureau of Geology andMineral Exploration and Development, Yingtan 334000, China

Miner Deposita (2014) 49:733–749DOI 10.1007/s00126-014-0521-8

Over the past several decades, research in the Lengshuikengore district was focused on geological characteristics, mineral-ization, wall rock alteration, fluid inclusions, and geochemistryof the porphyry-hosted deposits (Deng 1991; Meng et al. 2007;Wang et al. 2010c). Recently, stratabound Ag–Pb–Zn depositshave been found beneath the porphyry-hosted deposits, occur-ring in volcano-sedimentary rocks of the E’huling Formation.This paper reports the geologic and isotopic characteristics ofthe porphyry-hosted and stratabound ores, in combination withthose from Chinese literature. The regional and the

Lengshuikeng Ag–Pb–Zn ore district geologies, including theoccurrence of ore bodies, and associated hydrothermal alter-ation are described, followed by a discussion of the origin of theAg–Pb–Zn deposits.

Regional geological setting

The Lengshuikeng ore district is located in northeasternJiangxi Province, east-central China, close to the Shaoxing–

Fig. 1 a Location map for theLengshuikeng District. b Sketchmap showing the Late Mesozoicvolcanic-intrusive complex belt inSE China. c Sketch map showingthe regional geology of theLengshuikeng ore district andDexing ore field (modified afterJiang et al. 2011). Major faults inthe study area: Shi–HangShiwandashan–Hangzhou ascollision-induced suture zonebetween the Cathaysiaand Yangtze blocks, SJShaoxing–Jiangshan, ZDZhenghe–Dapu

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Jiangshan (SJ) fault between the Cathaysia and Yangtzeblocks (Fig. 1b). This fault represents the eastern part of theShiwandashan–Hangzhou (Shi–Hang) fault zone and is con-sidered to mark the collisional suture zone in SE China (Yaoet al. 2011). Geophysical and remote sensing data suggest thatthe SJ fault extends deep into the lower crust and upper mantle(Fig. 1c; Wang et al. 2010c). The collisional amalgamation ofthe Cathaysia and Yangtze blocks into the proto “SouthChina” Block (SCB) began in the early Qingbaikou period(∼950±50 Ma) and was completed by the end of the JinningOrogeny at ca. 850 Ma (Shu and Charvet 1996; Charvet et al.1996; Li et al. 2008, 2010; Zhang and Zheng 2013). Duringthe Sinian (ca. 850–600 Ma), the Yangtze and Cathaysiablocks were rifted. In the Caledonian (600–405 Ma), theYangtze and Cathaysia blocks collided for a second time andreunited within the SCB (Zhou et al. 2002; Wang et al. 2010a,b). During the Variscan (405–270 Ma), extension within theSCB resulted in Paleozoic intracontinental rifts. TheIndosinian collision between the South China and NorthChina blocks occurred from the Palaeozoic to LateTriassic (ca. 270–208 Ma; Wang et al. 2013a, 2014a).Magmatic activity during 208 to 180 Ma is documentedby bimodal magmatism in southeastern Hunan Provinceand the A-type granitic magmatism in southern JiangxiProvince (Zhao et al. 1998; Yu et al. 2006, 2010). FromTriassic to Early Jurassic (180–145 Ma), most areas ofthe Wuyi Mountains in the northeastern part of theCathaysia Block (Fig. 1b) were folded and upliftedbefore undergoing extensional collapse. The region ex-perienced Early Cretaceous granite magmatism (145–100Ma)and the formation of large-scale Late Cretaceous–Paleogenered bed sedimentary basins between 100 and 70 Ma (Jahn1974; Jahn et al. 1990; Zhou et al. 2006; Shu et al. 2009;Wanget al. 2014b).

The Precambrian units include greenschist faciesmetamorphic rocks dated at 1,000–800 Ma (Fig. 1c; Liet al. 1996; Shu and Charvet 1996; Zhou et al. 2002;Shu et al. 2009). The Cambrian and Ordovician rocks aremainly sandstone, mudstone, and carbonaceous mudstone.Silurian sedimentary rocks are absent. The Devonian,Carboniferous, and Permian strata comprise shallow marineto littoral facies clastic rocks, limestone, and dolomite. TheLower Triassic series consists of muddy limestone and shale.Middle Triassic strata are absent in most areas of the WuyiMountains.

The Wuyi Mountains are largely composed of LateMesozoic volcanic rocks and associated clastic strata(Fig. 1c). Lower Jurassic strata include conglomerate andcoarse arkosic sandstone, quartz sandstone, and siltstone withcarbonaceous mudstone and coal-bed intercalations. MiddleJurassic strata are composed of terrestrial clastic rocks and

bimodal volcanic rocks. Upper Jurassic strata comprise andes-ite and rhyolitic tuffs and tuffaceous siltstone (Liu 1985; Ye1987). Lower Cretaceous strata include rhyolitic welded tuffswith basalt intercalations (Yu et al. 2006). UpperCretaceous siltstone and mudstone are intercalated withgypsum-bearing layers and basalt, the latter with an ageof 105–98 Ma (Yu et al. 2001). Paleogene strata includecoarse clastic rocks, siltstone, and mudstone with inter-calated gypsum and oil-bearing shale. Neogene silt-stones locally overlie the Paleogene rocks.

Southeast China is characterized by extensive magmatism,which formed a belt of volcanic-intrusive complexes (Fig. 1b).Twomajor tectono-magmatic periods have been recognized inthe Wuyi Mountains: the Indosinian and the Yanshanian. TheIndosinian magmatic period lasted from 240 to 208 Ma (Xieet al. 2006). The Yanshanian igneous rocks formed during twomain stages of Early Yanshanian (208–145 Ma) and LateYanshanian (145–90 Ma) and are characterized by abundantrhyolitic volcanic rocks and highly aluminous granitoids (Jahnet al. 1976; Chen 1999; Li 2000; Deng et al. 2010, 2011, 2014;Zhou et al. 2006; Zhao et al. 2012).

Geology of the Lengshuikeng ore district

Deposit geology

The stratigraphic sequence in the Lengshuikeng District com-prises the Jurassic Daguding and E’huling Formations. TheDaguding Formation is composed of andesite and rhyolitictuffs and tuffaceous siltstone. The E’huling Formation iscomposed of tuffs, rhyolite, tuffaceous siltstone, sandstone,and manganese- and iron-rich carbonates, which are the mainhost of the stratabound ores.

The NE-striking F1 fault dipping toward NW (Figs. 2 and3a) comprises the northern segment of the Hushi fault. Themost prominent structural feature in the LengshuikengDistrictis F2 reverse fault (Figs. 2 and 3a). The stratabound fracturealong the manganese- and iron-rich carbonate strata (Fig. 3a)was cemented by later ore sulfide minerals and hydrothermalalteration minerals.

Middle Jurassic and Early Cretaceous magmatic rocks areexposed in the Lengshuikeng District (Fig. 2). The Jurassicigneous rocks are mainly granitic including the Yinluling,Yinzhushan, Biaojia, and Yinglin porphyries. TheYinzhushan granite porphyry has been dated as 162–159 Ma(Meng et al. 2007; Zuo et al. 2010). The Early Cretaceousrocks include quartz syenite porphyry, rhyolite porphyry,alkali-feldspar granite porphyry, and mafic dykes (Fig. 2).The quartz syenite porphyries crop out in the southeasternand northwestern parts of the Lengshikeng District (Fig. 2),

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with widely dispersed chloritization, sericitization, silicifica-tion, and carbonatization, with associated pyrite. Wang et al.(2010c) andMeng et al. (2007) reported that rhyolite porphyryand alkali-feldspar granite porphyry cut all the granite por-phyry and pyroclastic carbonate ore-hosted rocks (Fig. 3) aswell as the quartz syenite porphyry.

The least hydrothermally altered granite porphyries containphenocrysts (15–35 %) of quartz, plagioclase, K-feldspar, andbiotite in a groundmass (65–85 %) of subhedral K-feldspar,quartz, plagioclase, and minor biotite. Accessory minerals(∼1 %) are mainly magnetite, zircon, and apatite. Most quartzcrystals are xenomorphic and exhibit undulose extinction. Thequartz syenite porphyries contain phenocrysts (33–55 %) ofK-feldspar (∼20 %), biotite (∼10 %), and plagioclase (∼8 %)in a groundmass (45–67 %) of subhedral K-feldspar, biotite,and quartz. K-feldspar phenocrysts are euhedral to subhedral,have a grain size of 2–5 mm, and are locally replaced bysericite. Plagioclase phenocrysts are euhedral to subhedral,3–6 mm in size, with evidence of weak silicification andsericitization. Biotite phenocrysts are 0.5–1.0 mm in sizeand show alteration to chlorite and carbonate.

Ore bodies and wall rock alteration

Among the various ore deposits, the Baojia porphyry-hosteddeposit is the most important, accounting for 52 % of the totalore reserve in the Lengshuikeng District (Fig. 2).

The porphyry-hosted ore bodies (Fig. 3a) are associatedwith NNE-striking F2 reverse faults or comprise of fracturefillings in veins and breccias. Associated with the porphyry-hosted ore bodies is a distinct zoning of alteration and oreminerals, both vertically and laterally (Fig. 3b, c). An inner (orproximal) zone in the granite porphyry is characterized byenrichments in lead, zinc (with grade Pb+Zn >5 %) withminor disseminated chalcopyrite and pyrite, and with minorchlorite and sericite alteration. The intermediate zone surroundsthe inner zone near the contact between the granite porphyryand country rocks. This intermediate zone exhibits strongsericitization, carbonatization, and silicification, and in somecases, high-grade native silver mineralization (Ag >200 g/t),with minor galena–sphalerite vein mineralization (Fig. 4a). Theouter peripheral (or distal) zone is hosted by volcano-sedimentary country rocks to the granite porphyry and is de-fined by weakly developed silver, galena, sphalerite veins(Ag <100 g/t; Pb+Zn <2 %), and vein sericite and carbonate.

Stratabound mineralization is hosted by manganese–ironcarbonate layers of the E’huling Formation (∼5.0–33.1-mthickness) between tuffaceous sandstone and rhyolitic crystaltuff (Jiangxi Bureau of Geology and Mineral Exploration andDevelopment (JBGMED) 1982; Meng et al. 2007). Theserocks are characterized by high-grade native silver minerali-zation (Ag >200 g/t), lead, zinc (with grade Pb+Zn >5 %) asveins and breccias, with minor vein chlorite, sericite, andcarbonate (Fig. 4b, c).

Ore mineralogy and paragenesis

The mineralization in stratabound and porphyry-hosted orescan be divided into three stages (Fig. 5): stage 1, pyrite–chalcopyrite–sphalerite; stage 2, silver minerals–galena–sphalerite; and stage 3, pyrite–quartz–calcite. The mineralassemblage of stage 1 is dominantly pyrite and Fe-rich sphal-erite, with small amounts of chalcopyrite, cubanite, galena,arsenopyrite, pyrrhotite, and minor quartz (Fig. 6a–c). Stage 1mineralization was accompanied by chloritization andsericitization, replacing K-feldspar and plagioclase crystalsin rhyolitic crystal tuff and granite porphyry. Siderite isintergrown with sphalerite but occurs mostly as overgrowthson sphalerite or as monomineralic cement in breccias and thinveinlets. Stage 2 was the principal stage of silver–lead–zincmineralization. This stage is characterized by sericitizationand carbonatization, and minor chloritization. The silver–lead–zinc minerals of stage 2 fill the manganese–iron

Fig. 2 Geological map of the Lengshuikeng Ag–Pb–Zn ore district (afterJBGMED 1982). Sections a and b are shown in Fig. 3a–c

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carbonate stratabound fractures. The dominant silver mineralsare acanthite (Ag2S) and native silver, which occur in fissureswithin manganese–iron carbonate or in the intergranular spacebetween manganese–iron carbonate and early sulfides. In ad-dition, fine-grained canfieldite (Ag8SnS6), proustite (Ag3AsS3),aerosite (Ag3SbS3), Ag-bearing tetrahedrite (Cu12Sb4S13), andkustelite (Ag, Au) occur in the intergranular pores of

manganese–iron carbonate or as inclusions in galena, sphalerite,and other sulfides. The galena is euhedral and coarse-grained(Fig. 6e). Veins, veinlets, or disseminated silver minerals–gale-na–sphalerite are disseminated in the intergranular pores ofmanganese–iron carbonate (Fig. 6f–h). Stage 1 pyrite is cut bygalena and sphalerite vein (Fig. 6b), sphalerite surrounded bygalena (Fig. 4d), and sphalerite cut by ankerite–galena vein. In

Fig. 3 Geological features along sections a and b of the Baojiao deposit in the Lengshuikeng ore district (after JBGMED 1982): a relationship of orebodies, b alteration zoning, and c mineralized zone

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stage 3, ore minerals are dominated by pyrite, with lesser galena,pyrrhotite, and arsenopyrite. Calcite, quartz, and quartz–pyriteare characterized by open-space filling textures such as comb,veins, and veinlets and cut the stage 2 galena or sphalerite veins(Figs. 4e, f and 6d).

Sampling and analytical procedure for stableand radiogenic isotopes

Samples were collected from ore materials at the −80, −120,−152, and −160 m levels of underground workings, outcrops

Fig. 4 Macroscopic features of samples selected for ore mineralogy andparagenesis studies. a Porphyry-hosted ore with vein galena and withchloritization and sericitization. b Brecciated stratabound-type ore. cStratabound-type ore with vein sphalerite and galena and withchloritization, sericitization, and carbonation (Lu et al. 2012). d

Sphalerite phase (stage 1) surrounded by galena (stage 2) (Lu et al.2012). e Pyrite (stage 1) intersected by quartz vein (stage 3). gDisseminated ore intersected by pyrite vein (stage 3). Sp sphalerite, Gngalena, Py pyrite, Chl chloritization, Ser sericitization, Cbn carbonation,and Qz quartz

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(Fig. 2) at ∼160 m.s.l. elevations, and two drill holes in theLengshuikeng ore district. Pure mineral concentrates from theporphyry-hosted and stratabound ores and wallrocks wereprepared using a combination of heavy liquid and magnetic-and hand-picking techniques, and these were then checked byX-ray diffraction to ensure mineral purity.

Sulfur isotope analyses of sphalerite, galena, and pyritewere carried out at the Resource and Environment AnalysisCentre of the Geochemistry Institute, Chinese Academy ofSciences. Pyrite, galena, and sphalerite were combusted withCuO at 1,000 °C, and the sulfur isotopic compositions wasdetermined on a MAT-253 mass spectrometer. The sulfurisotopic compositions were reported relative to the CanyonDiablo Triolite (VCDT) standard. Routine analytical precisionfor standards material was ±0.2‰.

Rhodochrosite, siderite, calcite, and ankerite werehandpicked under a stereomicroscope and washed with dis-tilled water. Carbon and oxygen isotopic measurements weremade in the Environmental Isotope Geochemistry Laboratoryof the Institute of Geology and Geophysics, Chinese Academyof Science. About 150 μg was reacted with phosphoric acid at72 °C for 6 h using a GasBench II (Thermo-Finnigan). The

CO2 produced was analyzed for carbon and oxygen isotoperatios using a MAT-253 isotope ratio mass spectrometer. Thecarbon and oxygen isotope measurements have a precisionbetter than 0.1‰. Accuracy and precision were routinelychecked by running the carbonate standard NBS-19 afterevery six measurements of the samples. Carbon isotope ratiosare reported relative to Peedee belemnite (V-PDB), and oxy-gen isotope ratios are reported relative to standard mean oceanwater (V-SMOW).

Rb–Sr analyses were performed at the Laboratory forRadiogenic Isotope Geochemistry (LRIG), Institute ofGeology and Geophysics, Chinese Academy of Sciences (Liet al. 2006). Sphalerite grains in Teflon® vessels, washedultrasonically in analysis-grade alcohol and millipore water,were dissolved using 0.3 ml 3 N HNO3 and 0.1 ml HF at120 °C. Rb and Sr were separated using ion exchange col-umns. Rb and Sr concentrations were measured by isotopedilution, and a mixed 87Rb/84Sr spike solution was used.Isotopic ratios of Rb and Sr were measured on an IsoProbe-T mass spectrometer at the LRIG. Correction of mass frac-tionation for Sr isotopic ratios was based on an 88Sr/86Sr valueof 8.37521. Repeated measurements of NBS987 Sr standardsolution gave an average value of 87Sr/86Sr ratio of 0.710250±31 (2σ).

One quartz syenite porphyry sample in the LengshuikengDistrict (Fig. 2) was selected for U–Pb zircon dating by laserablation multi-collector inductively coupled plasma massspectrometry (LA–(MC)–ICP–MS) at the Tianjin Institute ofGeology and Mineral Resources, Tianjin, China (Li et al.2009). The zircon was ablated with a NUP193-FX ArFExcimer laser using a spot diameter of 35 μm, with constant13–14 J/cm2 energy density and a frequency of 8–10 Hz. Theablated material was carried in He into the plasma source of aGVI. All measurements were made in static mode, usingFaraday cups for 238U, 232Th, 208Pb, 206Pb, 207Pb, and anion-counting channel for 204Pb. A common Pb correction isachieved by using the measured 204Pb and assuming an initialPb composition from Stacey and Kramers (1975).

Analytical results

Sulfur isotope data

The δ34S values determined from 20 sulfide samples collectedin this study and δ34S data from previous works in the samearea (Meng et al. 2007; Xu et al. 2001; No 912 GeologicalSurveying Team (NGST) 1997) are listed in Table 1 andplotted in Fig. 7. The δ34S values of sulfides in ores rangefrom −3.8 to 6.9‰ with an average of 2.0‰. However, themajority of sulfide minerals have δ34S values between −1 and

Fig. 5 Mineral paragenesis of the porphyry-hosted and stratabound oresin the Lengshuikeng ore district showing mineral assemblages

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4 ‰. The ranges of δ34S values of sulfides in the porphyry-hosted and stratabound ores from −3.8 to 6.9‰ (average2.3‰) and −2.4 to 4.9‰ (average 1.7‰), respectively. Theδ34S values of pyrite in the porphyry-hosted ores in pyrite–chalcopyrite–sphalerite (stage 1) range from 2.2 to 4.9‰(average 3.9‰). However, the δ34S values of pyrite, sphaler-ite, and galena in the porphyry-hosted ores in silver minerals–

galena–sphalerite (stage 2) range from −0.4 to 3.1‰ (average2.0‰), 0.9 to 4.3‰ (average 2.8‰), and −2.4 to 2.8‰(average −0.4‰), respectively. The δ34S values of pyrite,sphalerite, and galena in the stratabound ores in pyrite–chal-copyrite–sphalerite (stage 1) range from 2.3 to 4.0‰ (average3.3‰), 3.5 to 6.9‰ (average 5.0‰), and 3.2‰, respectively.However, the δ34S values of pyrite, sphalerite, and galena in

Fig. 6 Photomicrographsshowing the salient mineralogicaland textural aspects. a Pyritedisseminated in porphyry-hostedore and replacing K-feldsparcrystals. b Granite porphyryfragments cemented by sulfideminerals with brecciated veinstructure and pyrite brecciasintersected by galena andsphalerite vein (Su 2013). cChalcopyrite, galena, andsphalerite in rhyolitic crystal tuff,with chloritization andsericitization. d Galena with“crumpled” texture and galenaand sphalerite intersected byquartz vein. e Dolomite replacedby sphalerite and sphaleritesurrounded by galena. fAggregate of acanthite in theintergranular pores offerromanganese carbonate(Lu et al. 2012). g Subhedralnative silver occurring in theintergranular pores offerromanganese carbonate(Lu et al. 2012). h Native silvervein in ferromanganese carbonate(Lu et al. 2012). Aca acanthite,Cpy chalcopyrite, Dol dolomite,Fer ferromanganese carbonate,Gn galena, Ksp K-feldspar,Py pyrite, Qz quartz, Slv nativesilver, and Sp sphalerite

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the stratabound ores in silver minerals–galena–sphalerite(stage 2) range from 2.3 to 2.8‰ (average 2.5‰), 0.9 to3.8‰ (average 2.2‰), and −3.8 to 2.4‰ (average 0.1‰),respectively.

Carbon and oxygen isotope data

The carbon and oxygen isotope values of carbonate mineralswere determined for nine hydrothermal siderite samples col-lected from the stratabound ores and crystal tuffs with weak

alteration, two calcite vein samples, five ankerite vein sam-ples, and eight manganese–iron carbonate samples (rhodo-chrosite and siderite) from the volcano-sedimentary strata.Carbon and oxygen isotopic compositions are listed inTable 2 and plotted in Fig. 8.

The δ13CPDB values in rhodochrosite and siderite samplesfrom the volcano-sedimentary strata vary from −7.0 to −2.4‰(Table 2). The δ13CPDB values of hydrothermal carbonates insiderite, calcite, and ankerite samples vary from −7.2 to−2.2‰, from −3.3 to −1.5‰, and from −3.9 to −2.0‰,

Table 1 Sulfur isotopic compositions of sulfide minerals from the Lengshuikeng Ag–Pb–Zn ore district

Sample no. Mineral Stage δ34S (‰) Sample no. Mineral Stage δ34S (‰) Sample no. Mineral Stage δ34S (‰)

Stratabound ores Stratabound ores Porphyry-hosted ores

ZK504 Py 1 3.7 PD152-4 Gn 2 1.1 ZK10412-1b Py 2 1.9

Zk13 Py 1 4.0 ZK136-1 Gn 2 −1.4 L14c Py 2 2.0

ZK410-2 Py 1 3.0 LSK-74a Gn 2 1.8 L15c Py 2 1.7

No12 Py 1 2.3 N4-8-102b Gn 2 0.1 L16c Py 2 2.4

ZK515 Py 1 3.2 S4-0-28b Gn 2 0.2 L26c Py 2 1.5

LSK-9a Py 1 3.5 LSK-101a Gn 2 2.0 126-2-1a Py 2 −0.4LSK-9-1a Py 1 3.6 LSK-102a Gn 2 2.4 130 N-4a Sp 2 4.3

LSK-41a Py 1 2.7 So-8-11b Gn 2 −1.7 130S-1a Sp 2 2.9

LSK-42a Py 1 3.6 N4-8-77b Gn 2 −0.1 L17c Sp 2 3.2

ZK136-1 Sp 1 4.3 N4-8-13b Gn 2 1.1 L18c Sp 2 2.9

PD160-6 Sp 1 5.8 N4-8-96b Gn 2 −0.9 L19c Sp 2 2.6

PD80-10 Sp 1 5.1 N8-4-20b Gn 2 0.2 L20c Sp 2 1.9

Zk197 Sp 1 3.5 So-12-23b Gn 2 −3.8 LSK-77a Sp 2 4.6

No7 Sp 1 5.2 N4-8-102b Py 2 2.7 LSK-78a Sp 2 3.6

PD152-4 Sp 1 4.6 N8-8-26b Py 2 2.3 L27c Sp 2 1.5

ZK515 Sp 1 6.9 So-8-11b Py 2 2.3 L28c Sp 2 0.9

LSK-101a Sp 1 4.6 Porphyry-hosted ores 130 N-4a Gn 2 1.2

PD80-13 Sp 1 5.0 L1c Py 1 4.9 130S-1a Gn 2 0.1

LSK-74a Sp 1 4.8 L2c Py 1 4.9 LSK-77a Gn 2 1.6

ZK515 Gn 1 3.2 L3c Py 1 4.1 L21c Gn 2 2.8

N4-8-77b Py 1 3.0 L4c Py 1 4.1 L22c Gn 2 −0.3N8-0-150b Py 1 4.0 L5c Py 1 3.6 L23c Gn 2 −0.9ZK136-1 Py 2 2.8 L6c Py 1 3.6 L24c Gn 2 −1.7So-8-11b Sp 2 2.3 L7c Py 1 2.2 L25c Gn 2 −2.3N4-8-77b Sp 2 2.8 L8c Py 2 3.1 L29c Gn 2 −0.1N4-8-102b Sp 2 1.0 L9c Py 2 3.0 L30c Gn 2 −0.2LSK-102a Sp 2 3.8 L10c Py 2 2.6 L31c Gn 2 −0.4So-12-23b Sp 2 0.9 L11c Py 2 2.5 L32c Gn 2 −0.9N4-8-77b Gn 2 −0.8 L12c Py 2 2.3 L33c Gn 2 −1.1Zk29 Gn 2 1.6 L13c Py 2 2.3 L34c Gn 2 −1.2Zk311 Gn 2 −0.1 ZK10010-718b Py 2 2.3 L35c Gn 2 −2.4Zk198-1 Gn 2 0.2 ZK10010-719b Py 2 1.4

Sp sphalerite, Gn galena, Py pyriteaMeng et al. (2007)b Xu et al. (2001)c NGST (1997)

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Fig. 7 Histogram of sulfurisotopic composition of sulfideminerals in the Lengshuikeng oredistrict. a All sulfide minerals. bSulfide minerals in porphyry-hosted ore. c Sulfide minerals instratabound ore

Table 2 Carbon and oxygen isotopic compositions of carbonate minerals from the Lengshuikeng Ag–Pb–Zn ore district. The δ18OSMOW values werecalculated from δ18OPDB values using the formula: δ18OSMOW=1.03091×δ18O+30.91 (González and Lohmann 1985)

Sampling location Sample no. Lithology Mineral δ13CPDB δ18OSMOW

∼152 m elev. PD152-3 Manganese–iron carbonate Rhodochrosite −3.3 11.6

∼160 m elev. 160-4 Manganese–iron carbonate Rhodochrosite −2.4 18.0

∼120 m elev. PD120-9 Manganese–iron carbonate Siderite −3.9 14.6

∼152 m elev. PD152-11 Manganese–iron carbonate Siderite −5.3 13.0

13703 drill hole Zk315 Manganese–iron carbonate Siderite −2.7 16.8

15150 drill hole Zk18 Manganese–iron carbonate Siderite −5.9 14.9

∼152 m elev. PD152-10 Manganese–iron carbonate Siderite −5.5 13.4

13704 drill hole Zk198-1 Manganese–iron carbonate Siderite −7.0 19.5

∼160 m elev. 160-3 Crystal tuff Hydrothermal siderite −2.2 17.9

13213 drill hole ZK513-1 Crystal tuff Hydrothermal siderite −3.9 17.5

15150 drill hole Zk32 Crystal tuff Hydrothermal siderite −4.2 13.5

∼120 m elev. PD120-5 Crystal tuff Hydrothermal siderite −5.9 17.5

∼160 m elev. 160-6 Stratabound ore Hydrothermal siderite −3.8 16.8

∼120 m elev. No5 Stratabound ore Hydrothermal siderite −5.4 13.6

∼120 m elev. PD120-6 Stratabound ore Hydrothermal siderite −5.9 13.5

∼152 m elev. PD152-4 Stratabound ore Hydrothermal siderite −3.6 13.7

13213 drill hole ZK509 Stratabound ore Hydrothermal siderite −7.2 12.8

15150 drill hole Zk33 Ankerite vein Ankerite −3.3 13.1

15150 drill hole Zk34 Ankerite vein Ankerite −2.0 13.5

15151 drill hole ZK136 Ankerite vein Ankerite −3.3 13.9

15151 drill hole Zk138-2 Ankerite vein Ankerite −3.9 11.0

13703 drill hole Zk309 Ankerite vein Ankerite −3.0 12.4

15151 drill hole ZK138-3 Calcite vein Calcite −1.5 10.9

13703 drill hole Zk313 Calcite vein Calcite −3.3 11.9

Surfacea 83 Carboniferous Limestone 0.6 19.6

a NGST (1997)

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respectively (Table 2). The δ18OSMOW values in rhodochrositeand siderite samples from the volcano-sedimentary strata varyfrom 11.6 to 19.5‰ and from 10.9 to 11.9‰, respectively(Table 2). The δ18OSMOW values of hydrothermal carbonatesin siderite, calcite, and ankerite samples vary from 12.9 to17.9‰, from 10.9 to 11.9‰, and from 11.0 to 13.9‰. OneCarboniferous limestone sample is isotopically heavy(19.6‰; NGST 1997).

Rubidium and strontium isotope data

The Rb–Sr analytical data of sphalerite are given in Table 3.The sphalerite was separated from the manganese–iron car-bonate ores in the silver minerals–galena–sphalerite stage.Data regression for isochron ages and weighted mean valueswere performed using the ISOPLOTsoftware (Ludwig 2001),with 2 % error for 87Rb/86Sr ratios and 0.05 % error for87Sr/86Sr at the 95 % confidence level. The analytical datafor sphalerite yielded an age of 126.9±7.1 Ma (Fig. 9) with aninitial 87Rb/86Sr ratio of 0.71490 (mean square weighteddeviation (MSWD)=0.94).

Zircon U–Pb geochronology

Measured 206Pb/238U ages from individual zircons are shownin Fig. 10, and the analytical results of LA–ICP–MS U–Pbdating are listed in Table 4. For the quartz syenite porphyry(sample T10), analyses from 20 spots cluster close to theconcordia, yielding a weighted mean 206Pb/238U age of136.31±0.81 Ma (2σ, MSWD=1.3; Fig. 10).

Discussion

Ages of magmatism and mineralization

The results presented in this study together with those fromprevious investigations suggest multistage magmatism in theLengshuikeng and adjacent regions. The magmatic activitytook place principally during three periods, in the Jurassic,earlier Early Cretaceous, and later Early Cretaceous.

The Jurassic magmatism in the Lengshuikeng District isrepresented by the emplacement age of the granite porphyry,

Fig. 8 Plots of calculated δ18OSMOW versus δ13CPDB from varioussamples in the Lengshuikeng ore district. Carbonate fields are fromprevious studies. The data are from four different materials includingmarine carbonate (Baker and Fallick 1989; Hoefs 1997), continentalcarbonate (Hoefs 1997), sedimentary organic matter carbon (Hodson1977; Hoefs 1997), and magma-mantle carbonate (Taylor et al. 1967;Valley 1986; Ray et al. 1999). This plot offers information about variousprocesses of CO2 and carbonate ions including meteoric water influence,

sea water penetration, sediment contamination, and high temperatureinfluence, low temperature alteration (Deines 1989; Demrny andHarangi 1996; Demeny et al. 1998; Hoernle et al. 2002), decarboxylationand oxidation (Hofmann and Bernasconi 1998), decarbonate and carbon-ate dissolution (Lorrain et al. 2003), crystallization differentiation with nosignificantly influence on the oxygen, and carbon isotopic composition(Santos and Clayton 1995; Bindeman 2008)

Table 3 Rb–Sr isotopiccompositions of sphalerite in theLengshuikeng Ag–Pb–Zn oredistrict

Sample no. Mineral Rb (μg/g) Sr (μg/g) 87Rb/86Sr 87Sr/86Sr(±2σ) Isr

PD152-7 Sphalerite 1.390 4.080 0.9891 0.716557±34 0.71435

ZK205 Sphalerite 0.096 0.972 0.2866 0.715641±38 0.71500

ZK513-1 Sphalerite 2.060 1.820 3.2726 0.720846±22 0.71354

No4 Sphalerite 0.960 3.960 0.7019 0.716056±18 0.71449

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from the whole-rock Rb–Sr age of 159Ma (Meng et al. 2007),LA–ICP–MSU–Pb zircon age of 154.3±3.0Ma to 163.6±2.1(Qiu et al. 2013) and 155.1±0.97Ma (Wang et al. 2013b), andSHRIMP zircon U–Pb age of 162.0±2 Ma (Zuo et al. 2010).Previous studies reported the ages of the Daguding Formationvolcanic rocks in the Lengshuikeng District, such as LA–ICP–MS zircon U–Pb ages of 161.0±1.0 Ma for the rhyolite tuff(Wang et al. 2013b) and 160.8±1.9Ma for the ignimbrite (Qiuet al. 2013), and a SHRIMP zircon U–Pb age of 157.6±3.2 Ma for the tuff (Di et al. 2013). These age data coincidewith the major magmatic event that took place during ca. 164–154 Ma in SE China as documented in other studies (Penget al. 2006; Yuan et al. 2008; Li et al. 2008).

The Early Cretaceous zircon U–Pb age of 136.3±0.8 Maobtained for the quartz syenite porphyry likely represents thecrystallization age of the magma. Ages for the E’hulingFormation volcanic rocks in the Lengshuikeng District inprevious studies include the LA–ICP–MS zircon U–Pb agesof 144±1 Ma for the tuff, 140±1 for the rhyolite, 137±1 Mafor the rhyolite tuff, and 129±1 Ma for the tuffite (Su 2013).

The second phase of Early Cretaceous magmatism in theLengshuikeng District is represented by rhyolite porphyry,alkali-feldspar granite porphyry, and mafic dykes. The rhyo-lite porphyry and alkali-feldspar granite porphyry yielded agesof 110 and 109.6 Ma, respectively, based on whole rock K–Ardating (JBGMED 1982; NGST 2003).

Dating of hydrothermal mineral deposits is often difficultto achieve, although the ages are critical for understanding therelationship between the timing of mineralization and othergeological events. Rb–Sr dating of sphalerite has been suc-cessfully used to directly determine the age of sulfide miner-alization and to constrain models of large-scale migration ofmineralizing fluids (e.g., Brannon et al. 1992; Nakai et al.1990, 1993; Christensen and Halliday 1995; Christensen et al.1995; Walshaw and Menuge 1998; Yin et al. 2009). Althoughsphalerite appears to yield meaningful Rb–Sr ages, the site ofRb and Sr and the factors controlling Rb/Sr fractionation insphalerite remain uncertain (Nakai et al. 1990; Schneider et al.2008). A Rb–Sr age of 126.9±7.1 Ma was obtained fromstage 2 sphalerite in the stratabound ore, which is similar tothe age of the volcano-sedimentary rocks of the E’hulingFormation (129±1 Ma; Su 2013). The sphalerite residuesdisplay no correlation between 1/Sr and 87Sr /86Sr (Table 3),suggesting that the sphalerite Rb–Sr isochron age is not apseudoisochron and has actual geological significance (e.g.,Nakai et al. 1993). Chen (2011) has reported the mineralogicalcharacteristics of sphalerite of the stratabound ore in theLengshuikeng District, indicating no clay minerals in sphal-erite. Therefore, this age is interpreted to reflect the timing ofthe Pb–Zn mineralization. Available geochronological datafor the Lengshuikeng District are summarized in Fig. 11.The K–Ar ages of 138 Ma for sericite in porphyry-hostedore (JBGMED 1982; NGST 2003) and sphalerite Rb–Sr ageof 127 Ma in stratabound ore suggest that the hydrothermalalteration and mineralization do not overlap with any of theJurassic magmatic ages. The ages for mineralization do, how-ever, overlap with the ages for the first phase of EarlyCretaceous magmatism (ca. 144 to 129 Ma; Su 2013). Theserelationships suggest that stage 2 is not genetically related tothe Jurassic magmatism, although it is still possible that heatfrom cooling intrusions associated with the formation of theE’huling Formation (ca. 144 to 129 Ma; Su 2013) drove thehydrothermal system.

Sources of metals and ore-forming fluids

The δ18OH2O values of ore fluids were calculated using thequartz–water equilibrium fractionation of Clayton et al.(1972) using the final homogenization temperatures of prima-ry fluid inclusions. The fluids of stage 1 quartz had a δ18OH2O

value of about +5.3‰ (Zuo et al. 2009; Lu 2012), slightly

Fig. 9 Rb–Sr isochron of sphalerites from the Lengshuikeng Ag–Pb–Znore district

Fig. 10 Zircon U–Pb concordia plots and calculated weighted mean206Pb/238U ages for sample T13 quartz syenite porphyry from theLengshuikeng ore district. Data are from Table 4

744 Miner Deposita (2014) 49:733–749

lower than the values of the primary magmatic water(δ18OH2O=+5.5 to +9.0‰; Taylor 1974). As the δ18OH2O

values in stage 1 are close to the range of primary magmaticwaters, a contribution of magmatic water cannot be ruled outduring this stage. The δ18OH2O values of the stage 2 fluidsrange from +1.2 to +4.5‰ (average=+4.0‰), whereas the δDvalues range from −78 to −63‰, with an average of −70‰(Zuo et al. 2009; Lu 2012). Compared to the stage 1 fluids, thestage 2 fluids clearly shift toward the composition of meteoricwater. The δ18OH2O values of stage 3 quartz are between −3.1and +4.4‰ (average −0.6‰; Zuo et al. 2009; Lu 2012),indicating that the fluids were dominated by meteoric water.The δD values in stage 3 fluids have a narrow range from −84to −53‰ (Zuo et al. 2009; Lu 2012), which are close to that ofMesozoic meteoric water in Jiangxi Province, east-centralChina (−60‰; Zhang 1989).

The range of δ34S values for sulfides in the Lengshuikengore district is close to the range (mainly −3 to 3‰) of δ34Svalues for magmatic sources (Ohmoto and Rye 1979; Wanget al. 2014a). The δ34S values of sulfides in the porphyry-hosted and stratabound ores are similar, which support acommon hydrothermal fluid forming both ore types (Fig. 7).In some samples, pyrite has high δ34S, suggesting that part ofthe sulfur was derived from the regional Precambrian base-ment rocks (δ34S average value of 5.5‰) through dissolutionand leaching, similar to the scenario reported from the Jinshandeposit, Jiangxi Province (Zeng et al. 2002). The δ34S valuesin Lengshuikeng permit the inference that the sulfur wasderived mainly from magmatic sources, with minor contribu-tions of heavy sulfur from the country rocks.

The Lengshuikeng hydrothermal carbonates are character-ized by a wide variation of δ18OSMOW from 10.9 to 17.9‰.

Table 4 LA–ICP–MS zircon U–Pb analytical data for the quartz syenite porphyry in the Lengshuikeng ore district

Spotnumber

Content(ppm)

Ratios Age (Ma)

Pb U 207Pb/206Pb 1σ 207Pb/235U 1σ 206Pb/238U 1σ 208Pb/232Th 1σ 232Th/238U 1σ 206Pb/238U 1σ

T10.1 12 498 0.0213 0.0001 0.1408 0.0050 0.0478 0.0017 0.0058 0.0001 0.89 0.0158 136 1

T10.2 8 279 0.0216 0.0002 0.1469 0.0088 0.0492 0.0029 0.0060 0.0001 1.50 0.0320 138 1

T10.4 79 3,160 0.0220 0.0001 0.1510 0.0018 0.0497 0.0006 0.0059 0.0000 0.99 0.0109 140 1

T10.5 46 1,968 0.0216 0.0001 0.1473 0.0022 0.0494 0.0007 0.0068 0.0001 0.61 0.0058 138 1

T10.6 71 2,930 0.0213 0.0001 0.1433 0.0018 0.0487 0.0006 0.0061 0.0000 0.89 0.0080 136 1

T10.7 9 390 0.0211 0.0002 0.1445 0.0074 0.0496 0.0025 0.0060 0.0001 0.81 0.0083 135 1

T10.10 32 1,336 0.0225 0.0001 0.1535 0.0023 0.0494 0.0007 0.0069 0.0000 0.60 0.0051 144 1

T10.11 26 1,110 0.0214 0.0001 0.1394 0.0025 0.0473 0.0008 0.0072 0.0001 0.58 0.0050 136 1

T10.12 48 1,954 0.0222 0.0001 0.1618 0.0022 0.0528 0.0007 0.0062 0.0000 0.84 0.0074 142 1

T10.14 61 2,349 0.0224 0.0001 0.1461 0.0020 0.0474 0.0006 0.0062 0.0000 1.00 0.0089 143 1

T10.18 40 1,606 0.0213 0.0001 0.1403 0.0021 0.0479 0.0007 0.0052 0.0000 1.22 0.0105 136 1

Fig. 11 Summary ofgeochronological data for theLengshuikeng District. All datanoted in the text

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The wide variation of the oxygen isotope composition of theLengshuikeng carbonates are considered to be related to wa-ter–rock interaction combined with the temperature depen-dence on mineral-fluid oxygen isotope fractionation (Santosand Clayton 1995; Biondi and Santos 2013). The δ18OSMOW

versus δ13CPDB plot illustrates the various processes affectingCO2 and carbonate ions in the Lengshuikeng District (Fig. 8).Except for the Carboniferous limestone sample, all the othersamples from the Lengshuikeng District plot within or nearthe fields of continental carbonates (Fig. 8). As the homoge-nization temperatures of fluid inclusions in dolomites fromprimary ores are relatively low (from 150 to 270 °C; Lu 2012),the variation of carbon and oxygen isotopic composition ofthe Lengshuikeng hydrothermal carbonates are similarwith those of the manganese–iron carbonate sedimentarycountry rocks. This feature indicates that the carbonatefrom the Lengshuikeng is dissolved from the local car-bonate country rocks.

Evolution of the Lengshuikeng District

Since the Middle Jurassic, possibly from 170 to 155 Ma, thepaleo-Pacific plate subducted underneath the SCB generatingI-type magmas (Wang et al. 2013b) along the NE-trendingcompressive faults and thrust nappe structures, especially inthe Lengshuikeng ore district (Jahn et al. 1976; Chen 1999;Jiang et al. 2011). However, the paleo-Pacific plate did notsubduct successively toward to the northwest but instead slabrollback occurred at the beginning of Late Jurassic, possiblylasting until Early Cretaceous. This was followed by theformation of an intra-arc rift along the Shihang-Hang zone.Injection of anomalously high-temperature magma into thecrustal regions may have induced partial melting of the crustalrocks, generating A-type magmas (Wang et al. 2013b).Therefore, it is likely that the southern Hunan to northernGuangxi region is part of an intra-arc rift or back-arc exten-sional zone induced by the subduction of paleo-Pacific plate.Thus, the Lengshuikeng ore district is considered to be relatedto the tectonic transition regime from a shallow-dipping com-pressional stress regime to a steep-dipping extensional stressregime during the Early Cretaceous (Mao et al. 2013).

The Lengshuikeng granite porphyry was emplaced alongNNE-striking faults at shallow depths, and subsequent hydro-thermal fluid activity led to strata- and fracture-controlled Pb,Zn, and Ag mineralization. The stratabound Ag–Pb–Zn orebodies are associated with stratabound fractures, whereas theporphyry-hosted Ag–Pb–Zn ore bodies are associated withNNE-striking F2 reverse faults. The Lengshuikeng ores aresimilar to the structurally controlled epithermal deposits suchas the Swayaerdun gold deposit in the southwestern ChineseTianshan metallogenic belt (Chen et al. 2012a). Some of thefeatures of the Lengshuikeng Ag–Pb–Zn deposits are similarto epithermal deposits, such as those in the Cerro de Pasco and

Colquijirca carbonate replacement epithermal deposits,Peru (Bendezú et al. 2003, 2007; Baumgartner andFontboté 2008; Baumgartner et al. 2009), carbonatereplacement epithermal deposits in the Kamariza oredistrict, Lavrion, Greece (Voudouris et al. 2008), andother epithermal deposits (Thiersch et al. 1997; Aramburu2008; Tassinari et al. 2008; Duuring et al. 2009a, b; Chenet al. 2012b).

The average Au/Ag ratios of pyrite–chalcopyrite (early-stage) and silver minerals–galena–sphalerite (middle-stage)assemblages in the porphyry-hosted ores are 0.02 and0.0008, respectively (Meng et al. 2007). The Au/Ag averageratios of pyrite–chalcopyrite–sphalerite (early-stage) andsilver minerals–galena–sphalerite (middle-stage) assem-blages in the stratabound ores are 0.001 and 0.0004,respectively (Meng et al. 2007). The low Au/Ag ratiosin ores in Lengshuikeng Ag–Pb–Zn deposits are similarto those of epithermal deposits, such as the range from0.0001 to 1 in the Lake City II, Summitville, RedMountain (USA), Julcani (Peru), Lepanto (Philippines),Kushikino and Hishikari (Japan), Ametistovoe and Balei(Russia) (Charoy and Gonzalez-Partida 1984; Berger andBonham 1990; Izawa et al. 1990; Nekrasova et al. 1997;Pal'yanova 2008).

Conclusions

The mineralization in the Lengshuikeng ore district is mainlyfracture-controlled epithermal type of Ag–Pb–Zn deposits.The mineralization age of 126.9±7.1 Ma is close to that ofthe volcano-sedimentary rocks of the E’huling Formation, andtherefore it is possible that heat from cooling magmas associ-ated with the formation of the E’huling Formation drove thehydrothermal system. Hydrogen, oxygen, and carbon isotopedata from porphyry-hosted and stratabound ores atLengshuikeng indicate that the ore-forming fluids were de-rived from meteoric water, whereas sulfur isotopes do notpreclude the possibility that a magmatic fluid contributionalso existed.

Acknowledgments This research is jointly supported by China Bureauof Geological Survey project (Nos. 1212011085472, 1212010533105,1212010981048), Fundamental Research Funds for the CentralUniversities (No. 2652013034), and the 111 Project (No. B07011). Thisstudy also contributes to the 1000 Talents Award to M. Santosh from theChinese Government. We thank Emmanuel John M. Carranza (JamesCook University, Australia) and Gregory A. Davis (University ofSouthern California, USA) for their valuable time, suggestions, andcomments to improve the various versions of the manuscript. We thankPaul Duuring, University of Western Australia, Australia, and HuayongChen, Guangzhou Institute of Geochemistry, CAS, China, for their crit-ical reviews and constructive comments. The authors also thank Drs.Georges Beaudoin, PatrickWilliams, Rolf Romer, and Thomas Bissig fortheir great contributions to this paper.

746 Miner Deposita (2014) 49:733–749

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