Journal of Asian Earth Sciences 156 (2018) 41–58

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Journal of Asian Earth Sciences

journal homepage: www.elsevier.com/locate/jseaes

Late Paleozoic SEDEX deposits in South China formed in a carbonate T

platform at the northern margin of Gondwana
⁎
Wenhong Johnson Qiu, Mei-Fu Zhou , Zerui Ray Liu
Department of Earth Sciences, University of Hong Kong, Hong Kong Special Administrative Region

A R T I C L E I N F O A B S T R A C T

Keywords: SEDEX sulfide deposits hosted in black shale and carbonate are common in the South China Block. The
SEDEX Dajiangping pyrite deposit is the largest of these deposits and is made up of stratiform orebodies hosted in black
Mineralization age shales. Sandstone interlayered with stratiform orebodies contains detrital zircon grains with the youngest ages of
Re-Os isochron 429 Ma. Pyrite from the orebodies has a Re-Os isochron age of 389 ± 62 Ma, indicative of formation of the
Zircon U-Pb dating
hosting strata and syngenetic pyrite ores in the mid-late Devonian. The hosting strata is a transgression sequence
Depositional environment
Tectonic setting
in a passive margin and composed of carbonaceous limestone in the lower part and black shales in the upper
part. The ore-hosting black shales have high TOC (total organic carbon), Mo, As, Pb, Zn and Cd, indicating an
anoxic-euxinic deep basin origin. The high redox proxies, V/(V + Ni) > 0.6 and V/Cr > 1, and the positive
correlations of TOC with Mo and V in black shales are also consistent with an anoxic depositional environment.
The Dajiangping deposit is located close to the NE-trending Wuchuan-Sihui fault, which was active during the
Devonian. The mid-late Devonian mineralization age and the anoxic-euxinic deep basinal condition of this de-
posit thus imply that the formation of this deposit was causally linked to hydrothermal fluid exhalation in an
anoxic fault-bounded basin that developed in a carbonate platform of the South China Block. The regional
distribution of many Devonian, stratiform, carbonaceous sediment-hosted sulfide deposits along the NE-trending
fault-bounded basins in South China, similar to the Dajiangping deposit, indicates that these deposits formed at a
basin developed in the passive margin setting of the South China Block during the Devonian. This environment
was caused by the break-up and northward migration of the South China Block from Gandwana.

1. Introduction regional rifting, the redox-state of basinal water and mineralization of

A broad carbonate platform was developed on the southern part of
the South China Block during the Devonian after it was separated away
from Gondwana (Zhao et al., 1996). The platform was crosscut by a
series of NE-trending faults in a rift setting related to the northward
migration of the South China Block (Chen et al., 2001, 2006; Zhao
et al., 1996). The rifting event not only created several fault-bounded
basins, but also led to extensive hydrothermal venting within these
basins (Chen et al., 2001, 2006; Chen and Gao, 1987; Yang et al., 1996;
Zhao et al., 1996). Numerous stratiform sulfide deposits, including the
Dajiangping, Hongyan and other stratiform pyrite deposits along the
Wuchuan-Sihui fault belt, and the Panglong Pb-Zn deposit and other
stratiform Pb-Zn deposits in the Guizhong Basin, are located along NE-
trending faults and hosted in Devonian sedimentary successions (Chen
et al., 1987; Fu, 2012; Jiang, 1987; Li, 2007; Niu et al., 2017; Pei,
1989). Although these stratiform sulfide deposits were thought to be of
sedimentary exhalative (SEDEX) origin, the relationships among
these SEDEX deposits have not been considered.
The Dajiangping deposit in the southwestern Cathaysia Block is the
largest SEDEX-type pyrite deposit in China and contains > 200 million
tons of pyrite ore (BGE723BGD, 1965). Being the most typical SEDEX
pyrite deposit (Chen et al., 1998a; Pan and Zhang, 1994; Zhang et al.,
1992, 1993, 1994), this deposit contains stratiform orebodies and
ubiquitous laminated ores. Predominantly negative δ34S values
(< -10.3‰) of pyrite in the Dajiangping deposit indicate that pyrite
was formed by the reduction of seawater sulfate by bacteria, supporting
a syngenetic origin of this deposit (Chen et al., 1998a; Zhang et al.,
1993). The investigation of depositional environment and tectonic
setting of mineralization of the Dajiangping deposit would therefore
provide a better understanding for the regional mineralization of
SEDEX-type sulfide deposits in South China. Although some studies on
the genesis and sources of the Dajiangping deposit are available in the
Chinese literature (Chen et al., 1998a, 1998b; Zhang et al., 1992, 1993,
1994), the age and tectonic setting of the mineralization of the

⁎
Corresponding author.
E-mail address: mfzhou@hku.hk (M.-F. Zhou).

https://doi.org/10.1016/j.jseaes.2018.01.006
Received 28 August 2017; Received in revised form 13 January 2018; Accepted 13 January 2018
1367-9120/ © 2018 Published by Elsevier Ltd.
W.J. Qiu et al.
Dajiangping deposit are still unknown and the genetic relations be-
tween the Dajiangping deposit and other SEDEX sulfide deposits hosted
in Devonian strata in South China are not clear. In addition, a detailed
study of the deposition of ore-hosting strata and laminated ores of this
deposit, as has been carried out for other SEDEX deposits (Goodfellow,
1987; Goodfellow and Jonasson, 1984; Large et al., 1998, 2005; Leach
et al., 2005), is still lacking.
In this study, we present the chemical compositions of ore-hosting
carbonaceous rocks in order to discuss the relationship between the
mineralization of the Dajiangping SEDEX deposit and depositional en-
vironment. We also report ages of the mineralization and hosting strata,
using detrital zircon U-Pb ages of sandstone interlayers and Re-Os
dating of laminated pyrite ores. With the new dataset, we further dis-
cuss the possible tectonic setting of mineralization in the context of
Gondwana breakup.
2. Geological background
The Dajiangping deposit is located in the Yunkai terrane of the
Cathaysia Block. The Cathaysia Block collided with the Yangtze Block
along the Jiangnan orogenic belt at around 830 Ma, forming the South
China Block (Fig. 1) (Wang et al., 2013a; Zhao et al., 2011). The
Cathaysia Block was attached to the western margin of Gondwana and
involved in the Caledonian intracontinental orogeny of South China
during the Silurian (420–460 Ma) (Charvet, 2013; Shu et al., 2014; Xu
et al., 2016). This orogenic event caused the extensive deformation,
low-grade green schist facies metamorphism and large-scale
Fig. 1. Paleogeography of the South China Block in the late Devonian, showing the location of the Dajiangping SEDEX pyrite deposit, other SEDEX pyrite and Pb-Zn-Ba deposits hosted in
Devonian strata, modified from Wang et al. (1985).
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Journal of Asian Earth Sciences 156 (2018) 41–58
emplacement of granitoids in the Cathaysia Block and developed the
pre-Devonian metamorphic basement, particularly in the Yunkai ter-
rane (Shu, 2006, 2012; Wan et al., 2010; Wang et al., 2007; Zhao and
Cawood, 2012). After this orogenic event, the South China Block se-
parated from Gondwana and the southern side of this block transferred
to a passive margin (Metcalfe, 1996a, 1996b, 2006), which is marked
by the regional unconformity between the pre-Devonian metamorphic
basement and the overlying Devonian unmetamorphosed sedimentary
sequences (Metcalfe, 2006). The South China Block was in a relatively
stable sedimentary stage and underwent progressive northeastward
transgression during Devonian, which led to the development of a
carbonate platform on the passive margin (BGMRGD, 1988). The mid-
late Devonian limestone and dolomite strata, such as the Donggangling
Group and Rongxian Group, are widely distributed in the Cathaysia
Block. Due to the northward migration of the South China Block from
Gondwana, a series of active NW and NNE-trending faults cut through
the carbonate platform of the South China Block and formed several
fault-bounded basins with deep-water sedimentary sequences, e.g. the
fault-bounded basins along the Wuchuan-Sihui deep fault zone (Fig. 1).
The late Devonian Liujiang Group, which is composed of carbonaceous
limestone in the lower part and shale-siltstone in the upper part and
shows a basinal sedimentary facies, is also exposed locally in the
Cathaysia Block (Fig. 3) (BGMRGD, 1988).
The Dajiangping pyrite deposit is composed of stratiform orebodies
that are distributed within a ∼6 km-long × ∼4 km-wide zone with
thickness of up to 170 m (Fig. 2). Stratiform orebodies are hosted by the
carbonaceous strata (BGMRGD, 1988) (Fig. 2). Based on a drill hole
W.J. Qiu et al.
Fig. 2. A simplified geologic map of the Yunfu region, showing location of the drill holes YF02 and YF04 in the Dajiangping pyrite mine district. Modified from the Yunfu Dagangshan
region 1:50,000 geological map (BGE723BGD, 1965).
(YF04) that penetrated the full mineralized sequence in the center of
the deposit, the stratiform orebodies are composed of four ore units
separated by thick black shale layers (Fig. 3), with each ore unit being
composed of laminated pyrite ores and black shales (Fig. 4a and b). The
ore strata unconformably overlies a metamorphic basement complex
(Fig. 3), which consists of mica-quartz schist and quartz schist (Fig. 4c
and d) (Chen et al., 1998a, 1998b) and is comparable to the regionally
distributed Caledonian metamorphic basement rocks in the Yunkai
terrane (Wan et al., 2010). Based on a drill hole (YF02), which extended
to a depth of 550 m and locates ca.2 km south of the deposit (Fig. 2), the
whole ore-hosting strata forms a transgression sequence and can be
divided into three units from the bottom upwards (Fig. 3). The Lower
Unit (201–152 m), overlying the metamorphic basement complex with
43
Journal of Asian Earth Sciences 156 (2018) 41–58
an unconformable boundary (Figs. 2 and 3), is composed of thick cal-
careous siltstone and limestone with a low organic concentration, in-
dicating a terrestrial-littoral facies environment (Fig. 3). The Middle
Unit (152–124 m) is dominated by carbonaceous limestone with only a
minor clastic component, indicating a carbonate platform facies
(Figs. 3 and 4e). There are thin, laminated pyrite layers intercalated
with black shale at the top of the Middle Unit (152–124 m) (Fig. 3). The
Upper Unit (124–58 m) overlying this pyrite layer is dominated by thick
black shale with a high organic content (Figs. 3 and 4f), which is
comparable to the ore-hosting black shale at the center of the deposit.
This indicates a deep sea or deep rifted basin depositional environment.
Brachiopod and crinoid fossils are distributed throughout the carbo-
naceous limestone layers of the Middle and Upper units (Fig. 4g–h).
W.J. Qiu et al.
Fig. 3. Schematic stratigraphic columns of the ore strata (drill hole YF04) and ore-hosting strata (drill hole YF02). Also shown is the stratigraphic column of the Late Devonian Liujiang
Group in the Shimen section (modified from BGMRGD, 1988).
Although the age of the ore-hosting strata is still a matter of debate, the
hosting strata in the Dajiangping region are explained to be of late
Devonian age, because lithologies are similar to those of the late De-
vonian Liujiang Group (BGMRGD, 1988), which is also composed of
limestone in the lower part and shale-siltstone in the upper part.
However, Wang et al. (1996) used Rb-Sr isotopes to date the chert in-
terlayers in the Dajiangping deposit and concluded that the ore strata
was deposited at 630 ± 7.3 Ma.
3. Samples and analytical methods
3.1. Zircon U-Pb dating by LA-MC-ICP-MS
Three sandstone samples for detrital zircon U-Pb dating were col-
lected from sandstone-siltstone interlayers in stratiform orebodies at
three different locations in the mining pit (13YF41: 22°58′4.86″N,
112°0′45.11E; 13YF43: 22°58′8.04″N, 112°0′44.10″E; 13YF47:
22°57′48.02″N, 112°0′45.54″E) (Fig. 4a). These sandstone interlayers of
stratiform orebodies belong to the Upper Unit of the ore-hosting strata.
Zircon grains were separated using standard heavy liquid and magnetic
techniques, then hand-picked and mounted in epoxy resin and polished
to half thickness. The U–Pb isotopic measurement of zircons was carried
out on a Nu Plasma HR MC-ICP-MS equipped with a Resonetics RE-
SOlution M50 laser ablation system, at the Department of Earth Sci-
ences in the University of Hong Kong. All analyses were carried out
with a beam diameter of ca. 22 μm, and a 6 Hz repetition rate for 45 s.
Helium was used as a carrier gas to efficiently transport the aerosols to
the MC-ICP-MS. We used zircon 91,500 as an external standard to
correct elemental fractionation and zircon GJ-1 as secondary reference
standard, whereas Plesovice was used for quality control. Analyses of
the zircon standard 91,500 yielded a weighted 206Pb/238U age of
1062 ± 2 Ma (MSWD = 0.2, n = 45), which is in agreement with the
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Journal of Asian Earth Sciences 156 (2018) 41–58
recommended age of 1065 Ma (Wiedenbeck et al., 1995). More detailed
instrumental settings and analytical procedures have been described by
Xia et al. (2004). Data reduction was performed off-line with ICPMS-
DataCal (Liu et al., 2009). The data were processed using the ISOPLOT
program (Ludwig, 2003).
3.2. Pyrite Re-Os isotope analyses
Representative unmetamorphosed laminated pyrite ore samples
(Fig. 4b) were taken from the stratiform orebodies in the open pit.
Pyrite grains from these samples were separated and used for Re-Os
isotope analysis. Chemical preparation and measurements were un-
dertaken at Guangzhou Institute of Geochemistry, Chinese Academy of
Sciences and detailed analytical procedures are described in Li et al.
(2010). Approximately 0.4–0.8 g sample powder was digested for 24 h
in an oven at 230 °C by 2.5 ml of concentrated HCl and 7.5 ml of con-
centrated HNO3 in a Carius tube together with a Re-Os tracer (185Re,
190
Os). Osmium was separated from sample solutions by solvent ex-
traction with bromine and purified by micro-distillation. Measurements
of Os isotopes were performed using a Triton mass spectrometer
(Thermo-Fiser). Re concentrations were analysed by Xseries-2 ICP-MS
(Thermo-Fiser). All data are corrected for isobaric oxide interferences,
spike and mass fractionation. Procedural blanks and standard deviation
for Re and Os are 10 ± 3 and 0.09 ± 0.01 picogrammes, respectively,
with an 187Os/188Os ratio of 0.40 ± 0.01. Detailed procedures are
available in previous publications (Li et al., 2010, 2011). All age cal-
culations were made using ISOPLOT version 3.0 (Ludwig, 2003).
3.3. Bulk rock major and trace elements and organic carbon
Samples of the ore-hosting strata are taken from drill hole YF02
(Fig. 3) and are mostly undeformed and unmetamorphosed. Twenty six
W.J. Qiu et al. Journal of Asian Earth Sciences 156 (2018) 41–58

Fig. 4. (a) Field photo of stratiform pyrite orebodies and sandstone interlayers that sampled for separation of detrital zircons. (b) Laminated pyrite ores interlayered with black shales. (c)
Quartz-mica schist of the metamorphic basement from the mining pit. (d) Photomicrographs of mica-quartz schist showing parallel foliation of quartz, muscovite, and biotite. (e)
Carbonaceous limestone from the mining pit. (f) Black shales and carbonaceous siltstone from the mining pit. (g) and (h) Photomicrograph of typical carbonaceous limestone composed of
calcite and organic matter with crinoid and brachiopod fossils.

samples were collected systematically at ∼8 m intervals from a depth of representative suite of samples for petrographic observation.
54–250 m (Fig. 3). The samples were crushed to powder for bulk ele- Major element abundances were determined using X-ray fluores-
mental analyses. Polished petrographic sections were prepared from a cence (XRF) on fused glass beads at the ALS Minerals/ALS Chemex Co.

45
W.J. Qiu et al.
Fig. 5. Concordia plots of LA-ICP–MS U–Pb analytical results for detrital zircons from sandstone interlayers in ore-hosting strata.
Ltd, Guangzhou, China. Accuracies of the XRF analyses are estimated to
be 2% for most major elements and 1% for SiO2. Trace elements were
analyzed by ICP-MS at the Nanjing Focums Technology Co. Ltd. Sample
powders (∼50 mg) were digested in 1 ml HF and 0.5 ml of HNO3 in
Teflon cups sealed in screw-top stainless steel bombs at 190 °C for 12 h.
The analytical precision is generally better than 5% for elements with
concentrations > 200 ppm, and 5–10% when less than 200 ppm.
Detailed description of the analytical procedure was reported in Qi
et al. (2000).
The total organic carbon (TOC) contents were measured at the ALS
Minerals/ALS Chemex Co. Ltd, Guangzhou, China, using a LECO CS-
200 analyzer. Samples were treated with hydrochloric acid (2.6 mol/L)
to remove carbonates before TOC analyze. The analytical precision of
the TOC was estimated to be < 5%.
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Journal of Asian Earth Sciences 156 (2018) 41–58
4. Analytical results
4.1. Zircon U-Pb ages
Detrital zircons were separated from three samples: 13YF41,
13YF43 and 13YF47. Detrital zircons with clearly magmatic texture of
oscillatory zoning were selected for U-Pb age dating and the analytical
results are presented in Fig. 5 and Table 1. Most analyses yield con-
cordant or nearly concordant U-Pb ages and most results are plotted on
the concordia curve (results with concordant ratio lower than 85% are
excluded) (Fig. 5). Zircons from three samples have similar 206Pb/238U
age ranges: 370–2942 Ma in sample 13YF41, 371–2645 Ma in sample
13YF43, and 371–2605 Ma in sample 13YF47 (Fig. 6). The youngest
zircon groups of these three samples show evidence of lead loss, al-
though they do produce very similar intercept ages of 447 ± 17 Ma for
W.J. Qiu et al. Journal of Asian Earth Sciences 156 (2018) 41–58

Table 1
LA-MC-ICPMS zircon U-Pb dating results for detrital zircons from the Dajiangping deposit.

Sample no. Measure ratios Corrected age (Ma)

207
Pb/206Pb 1σ 207
Pb/235U 1σ 206
Pb/238U 1σ 207
Pb/206Pb 1σ 207
Pb/235U 1σ 206
Pb/238U 1σ

13YF41
YF41-58 0.05759 0.00020 0.46967 0.00459 0.05910 0.00048 522 7 391 3 370 3
YF41-35 0.05679 0.00024 0.46731 0.00664 0.05966 0.00078 483 14 389 5 374 5
YF41-41 0.05865 0.00027 0.48458 0.00389 0.06002 0.00055 554 11 401 3 376 3
YF41-37 0.05749 0.00039 0.50515 0.00509 0.06370 0.00045 509 15 415 3 398 3
YF41-40 0.05768 0.00027 0.50687 0.00394 0.06376 0.00053 517 9 416 3 398 3
YF41-2 0.05587 0.00010 0.52766 0.00839 0.06841 0.00105 456 4 430 6 427 6
YF41-61 0.05598 0.00019 0.52794 0.00491 0.06843 0.00065 450 7 430 3 427 4
YF41-66 0.05665 0.00019 0.53546 0.00492 0.06858 0.00064 480 7 435 3 428 4
YF41-50 0.05559 0.00012 0.53942 0.00826 0.07040 0.00110 435 6 438 5 439 7
YF41-55 0.05554 0.00020 0.54202 0.00775 0.07074 0.00098 435 5 440 5 441 6
YF41-42 0.05616 0.00030 0.55372 0.01103 0.07120 0.00120 457 11 447 7 443 7
YF41-16 0.06166 0.00036 0.62726 0.00492 0.07379 0.00050 661 13 494 3 459 3
YF41-70 0.05887 0.00032 0.61797 0.00955 0.07604 0.00104 561 12 489 6 472 6
YF41-63 0.05568 0.00021 0.59065 0.00634 0.07696 0.00081 439 12 471 4 478 5
YF41-71 0.06257 0.00047 0.71853 0.00675 0.08336 0.00058 694 17 550 4 516 3
YF41-43 0.06739 0.00017 0.79046 0.00962 0.08508 0.00108 850 0 591 5 526 6
YF41-7 0.06241 0.00026 0.87226 0.00886 0.10134 0.00101 687 9 637 5 622 6
YF41-64 0.06902 0.00044 0.96597 0.00836 0.10161 0.00078 898 18 686 4 624 5
YF41-67 0.07259 0.00060 1.03384 0.01416 0.10322 0.00108 1011 17 721 7 633 6
YF41-51 0.06837 0.00023 1.00750 0.00886 0.10681 0.00085 880 7 708 4 654 5
YF41-32 0.06450 0.00024 0.96188 0.00987 0.10816 0.00111 767 7 684 5 662 6
YF41-23 0.06238 0.00016 0.97259 0.01409 0.11301 0.00158 687 6 690 7 690 9
YF41-47 0.06925 0.00060 1.15396 0.02769 0.12098 0.00276 906 18 779 13 736 16
YF41-6 0.07190 0.00017 1.20397 0.01239 0.12142 0.00131 983 −1 802 6 739 8
YF41-73 0.06983 0.00088 1.21286 0.02233 0.12628 0.00197 924 26 807 10 767 11
YF41-5 0.07431 0.00094 1.32606 0.03442 0.12826 0.00229 1050 21 857 15 778 13
YF41-54 0.06577 0.00025 1.16684 0.01310 0.12873 0.00150 798 8 785 6 781 9
YF41-29 0.06626 0.00062 1.18753 0.01401 0.12990 0.00086 815 20 795 7 787 5
YF41-21 0.06803 0.00022 1.22264 0.01167 0.13036 0.00132 878 7 811 5 790 8
YF41-15 0.07551 0.00041 1.40185 0.01049 0.13476 0.00125 1083 11 890 4 815 7
YF41-60 0.06600 0.00018 1.24142 0.01699 0.13635 0.00182 806 −194 820 8 824 10
YF41-27 0.07713 0.00038 1.45463 0.03515 0.13665 0.00313 1124 14 912 15 826 18
YF41-25 0.07290 0.00036 1.39084 0.01581 0.13835 0.00149 1011 5 885 7 835 8
YF41-26 0.07385 0.00027 1.42157 0.01113 0.13966 0.00130 1039 12 898 5 843 7
YF41-9 0.07246 0.00014 1.42198 0.01813 0.14229 0.00185 998 4 898 8 858 10
YF41-65 0.06668 0.00012 1.31731 0.01775 0.14314 0.00185 828 −1 853 8 862 10
YF41-72 0.06859 0.00013 1.36216 0.01653 0.14411 0.00182 887 8 873 7 868 10
YF41-31 0.07626 0.00062 1.55797 0.01249 0.14830 0.00090 1102 16 954 5 891 5
YF41-45 0.07406 0.00032 1.51718 0.01757 0.14859 0.00166 1043 8 937 7 893 9
YF41-24 0.07251 0.00042 1.54883 0.02682 0.15457 0.00195 1011 12 950 11 927 11
YF41-22 0.06965 0.00013 1.49966 0.01901 0.15617 0.00203 918 4 930 8 935 11
YF41-38 0.07232 0.00015 1.55854 0.01306 0.15626 0.00128 994 4 954 5 936 7
YF41-10 0.07281 0.00015 1.60357 0.01956 0.15976 0.00202 1009 4 972 8 955 11
YF41-20 0.07121 0.00012 1.56971 0.01867 0.15984 0.00194 965 4 958 7 956 11
YF41-44 0.07123 0.00012 1.60067 0.01765 0.16299 0.00184 965 4 970 7 973 10
YF41-59 0.07540 0.00055 1.70011 0.01769 0.16465 0.00212 1080 15 1009 7 983 12
YF41-36 0.07293 0.00021 1.71874 0.02756 0.17014 0.00254 1013 6 1016 10 1013 14
YF41-56 0.07660 0.00025 1.92952 0.02952 0.18326 0.00302 1111 6 1091 10 1085 16
YF41-33 0.08425 0.00019 2.17883 0.01526 0.18761 0.00141 1298 4 1174 5 1108 8
YF41-4 0.07969 0.00030 2.21031 0.01238 0.20118 0.00114 1191 7 1184 4 1182 6
YF41-12 0.09138 0.00021 2.90621 0.03251 0.23042 0.00242 1455 4 1384 8 1337 13
YF41-53 0.09837 0.00022 3.51522 0.03848 0.25903 0.00275 1594 4 1531 9 1485 14
YF41-8 0.09230 0.00013 3.30990 0.05428 0.26002 0.00430 1474 2 1483 13 1490 22
YF41-1 0.09775 0.00013 3.74227 0.03341 0.27761 0.00255 1583 −2 1580 7 1579 13
YF41-48 0.09995 0.00019 3.98800 0.05630 0.28932 0.00412 1633 4 1632 11 1638 21
YF41-3 0.11463 0.00014 5.39489 0.04963 0.34133 0.00326 1874 2 1884 8 1893 16
YF41-39 0.13672 0.00044 6.60599 0.03098 0.35030 0.00120 2187 6 2060 4 1936 6
YF41-46 0.15891 0.00033 7.73173 0.04180 0.35284 0.00224 2444 4 2200 5 1948 11
YF41-75 0.17068 0.00293 8.89019 0.25289 0.37583 0.00445 2565 29 2327 26 2057 21
YF41-17 0.17238 0.00136 10.43932 0.18834 0.43634 0.00470 2581 13 2475 17 2334 21
YF41-30 0.15598 0.00039 9.67083 0.15011 0.44797 0.00644 2413 4 2404 14 2386 29
YF41-74 0.16239 0.00027 10.63537 0.12635 0.47479 0.00556 2481 2 2492 11 2505 24
YF41-28 0.18276 0.00037 12.11334 0.19866 0.48053 0.00779 2680 3 2613 15 2530 34
YF41-49 0.17413 0.00165 11.95797 0.22036 0.49567 0.00464 2598 15 2601 17 2595 20
YF41-57 0.17941 0.00295 15.79749 1.17415 0.57857 0.02977 2647 28 2865 71 2943 122

13YF43
YF43-23 0.05646 0.00028 0.46253 0.00307 0.05936 0.00026 472 9 386 2 372 2
YF43-8 0.05587 0.00020 0.45963 0.00508 0.05957 0.00053 456 7 384 4 373 3
YF43-49 0.05503 0.00014 0.45506 0.00507 0.05998 0.00071 413 6 381 4 375 4
YF43-5 0.05537 0.00016 0.46037 0.00485 0.06027 0.00062 428 7 385 3 377 4
YF43-84 0.05544 0.00015 0.46143 0.00500 0.06034 0.00068 432 1 385 3 378 4
(continued on next page)

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W.J. Qiu et al. Journal of Asian Earth Sciences 156 (2018) 41–58

Table 1 (continued)

Sample no. Measure ratios Corrected age (Ma)

207
Pb/206Pb 1σ 207
Pb/235U 1σ 206
Pb/238U 1σ 207
Pb/206Pb 1σ 207
Pb/235U 1σ 206
Pb/238U 1σ

YF43-1 0.05579 0.00012 0.48757 0.00500 0.06337 0.00065 443 6 403 3 396 4
YF43-9 0.05662 0.00023 0.49746 0.00498 0.06393 0.00078 476 5 410 3 399 5
YF43-6 0.05529 0.00010 0.49355 0.00490 0.06474 0.00066 433 4 407 3 404 4
YF43-4 0.05510 0.00009 0.54413 0.00643 0.07160 0.00084 417 4 441 4 446 5
YF43-66 0.05945 0.00026 0.60978 0.00619 0.07467 0.00091 583 9 483 4 464 5
YF43-53 0.06550 0.00063 0.70645 0.01236 0.07804 0.00113 791 20 543 7 484 7
YF43-22 0.07256 0.00034 0.95777 0.00761 0.09575 0.00084 1011 10 682 4 589 5
YF43-88 0.07138 0.00049 0.99769 0.02031 0.10140 0.00199 969 15 703 10 623 12
YF43-78 0.07005 0.00048 0.99154 0.00738 0.10281 0.00075 931 13 700 4 631 4
YF43-20 0.06487 0.00018 0.93624 0.00705 0.10459 0.00076 770 6 671 4 641 4
YF43-3 0.07272 0.00132 1.08367 0.02380 0.10790 0.00114 1006 37 745 12 661 7
YF43-60 0.06493 0.00053 0.99662 0.01592 0.11121 0.00153 772 19 702 8 680 9
YF43-21 0.06628 0.00018 1.03180 0.00771 0.11275 0.00069 817 6 720 4 689 4
YF43-85 0.06724 0.00019 1.08018 0.01627 0.11645 0.00172 856 6 744 8 710 10
YF43-32 0.06688 0.00022 1.09114 0.01133 0.11842 0.00131 835 7 749 6 721 8
YF43-80 0.06338 0.00035 1.07728 0.08392 0.11878 0.00875 720 11 742 41 724 50
YF43-29 0.06795 0.00032 1.14996 0.00641 0.12270 0.00063 878 9 777 3 746 4
YF43-15 0.06506 0.00009 1.10948 0.01273 0.12361 0.00144 776 8 758 6 751 8
YF43-12 0.06704 0.00011 1.16045 0.01229 0.12545 0.00133 839 4 782 6 762 8
YF43-27 0.06428 0.00024 1.13256 0.01796 0.12768 0.00199 750 12 769 9 775 11
YF43-42 0.07520 0.00049 1.33767 0.01315 0.12926 0.00147 1074 13 862 6 784 8
YF43-70 0.06850 0.00036 1.29429 0.05543 0.13381 0.00524 883 11 843 25 810 30
YF43-13 0.06992 0.00015 1.29063 0.00969 0.13383 0.00106 928 5 842 4 810 6
YF43-31 0.08222 0.00074 1.53306 0.01310 0.13535 0.00078 1251 22 944 5 818 4
YF43-14 0.07685 0.00021 1.43730 0.00764 0.13563 0.00082 1117 1 905 3 820 5
YF43-40 0.07317 0.00031 1.37640 0.01578 0.13644 0.00162 1020 9 879 7 825 9
YF43-19 0.07671 0.00020 1.53963 0.01310 0.14540 0.00109 1122 6 946 5 875 6
YF43-24 0.07082 0.00031 1.43102 0.00964 0.14658 0.00125 954 9 902 4 882 7
YF43-63 0.07403 0.00035 1.51416 0.01771 0.14825 0.00159 1043 11 936 7 891 9
YF43-57 0.07474 0.00038 1.54395 0.01705 0.15035 0.00200 1061 11 948 7 903 11
YF43-18 0.07618 0.00030 1.59614 0.02056 0.15183 0.00184 1100 9 969 8 911 10
YF43-68 0.06920 0.00038 1.49152 0.02098 0.15502 0.00155 906 11 927 9 929 9
YF43-43 0.07788 0.00020 1.77112 0.02910 0.16490 0.00273 1144 6 1035 11 984 15
YF43-87 0.07596 0.00018 1.76618 0.01459 0.16856 0.00122 1094 −1 1033 5 1004 7
YF43-73 0.07341 0.00020 1.72254 0.01280 0.17013 0.00130 1026 6 1017 5 1013 7
YF43-76 0.07252 0.00015 1.72793 0.01794 0.17287 0.00186 1011 4 1019 7 1028 10
YF43-33 0.07787 0.00010 1.90149 0.01753 0.17701 0.00165 1144 2 1082 6 1051 9
YF43-86 0.07516 0.00024 1.90647 0.02268 0.18390 0.00208 1072 7 1083 8 1088 11
YF43-67 0.07660 0.00051 2.06098 0.06705 0.19003 0.00500 1111 13 1136 22 1122 27
YF43-69 0.08979 0.00039 2.50530 0.04021 0.20185 0.00276 1421 8 1274 12 1185 15
YF43-16 0.08522 0.00047 2.91925 0.13166 0.24202 0.00998 1320 11 1387 34 1397 52
YF43-28 0.08828 0.00012 2.95624 0.04324 0.24246 0.00338 1389 2 1396 11 1399 18
YF43-44 0.09258 0.00041 3.32754 0.04032 0.25971 0.00252 1480 8 1488 9 1488 13
YF43-50 0.09726 0.00025 3.71300 0.05225 0.27691 0.00396 1572 4 1574 11 1576 20
YF43-51 0.10756 0.00025 4.20267 0.05531 0.28322 0.00369 1758 4 1675 11 1608 19
YF43-48 0.12930 0.00081 5.14793 0.04219 0.28855 0.00147 2089 11 1844 7 1634 7
YF43-30 0.11647 0.00025 5.00924 0.07213 0.31122 0.00422 1903 4 1821 12 1747 21
YF43-7 0.14653 0.00031 6.35465 0.04307 0.31446 0.00243 2306 4 2026 6 1763 12
YF43-26 0.15411 0.00032 7.01006 0.08001 0.32941 0.00350 2392 3 2113 10 1836 17
YF43-64 0.11230 0.00051 5.14228 0.05331 0.33276 0.00351 1837 13 1843 9 1852 17
YF43-17 0.15750 0.00057 7.47041 0.10214 0.34331 0.00393 2429 1 2169 12 1903 19
YF43-35 0.12371 0.00063 5.94054 0.07982 0.34657 0.00324 2010 −23 1967 12 1918 16
YF43-61 0.11617 0.00072 6.15483 0.23553 0.37133 0.01186 1898 11 1998 33 2036 56
YF43-2 0.16163 0.00040 8.35669 0.12633 0.37521 0.00597 2473 4 2270 14 2054 28
YF43-37 0.16048 0.00060 8.49072 0.14944 0.38190 0.00590 2461 12 2285 16 2085 28
YF43-10 0.15969 0.00022 8.42550 0.04704 0.38248 0.00234 2454 2 2278 5 2088 11
YF43-25 0.16328 0.00025 8.65515 0.09125 0.38408 0.00395 2490 2 2302 10 2095 18
YF43-79 0.13209 0.00039 7.49853 0.21970 0.40868 0.01106 2128 5 2173 26 2209 51
YF43-34 0.15701 0.00029 9.18037 0.11774 0.42316 0.00510 2424 4 2356 12 2275 23
YF43-75 0.16669 0.00093 10.06385 0.21810 0.43522 0.00738 2525 42 2441 20 2329 33
YF43-52 0.15745 0.00035 10.10778 0.12596 0.46504 0.00560 2429 4 2445 12 2462 25
YF43-81 0.17217 0.00030 12.08534 0.25667 0.50740 0.01024 2579 4 2611 20 2646 44

13YF47
YF47-50 0.05766 0.00034 0.47094 0.00730 0.05926 0.00089 517 15 392 5 371 5
YF47-56 0.05751 0.00036 0.47579 0.00580 0.06005 0.00067 509 13 395 4 376 4
YF47-13 0.05812 0.00020 0.48354 0.00561 0.06033 0.00070 600 7 400 4 378 4
YF47-36 0.05822 0.00017 0.48609 0.00293 0.06059 0.00042 539 7 402 2 379 3
YF47-32 0.05680 0.00023 0.50294 0.00633 0.06436 0.00088 483 12 414 4 402 5
YF47-61 0.05541 0.00017 0.53735 0.00779 0.07025 0.00094 428 7 437 5 438 6
YF47-60 0.05572 0.00013 0.56521 0.00874 0.07351 0.00109 443 10 455 6 457 7
YF47-59 0.05969 0.00040 0.60475 0.00510 0.07380 0.00067 591 8 480 3 459 4
YF47-52 0.05603 0.00016 0.58048 0.00867 0.07523 0.00116 454 3 465 6 468 7
YF47-71 0.05685 0.00018 0.59344 0.00693 0.07595 0.00093 487 10 473 4 472 6
(continued on next page)

48
W.J. Qiu et al. Journal of Asian Earth Sciences 156 (2018) 41–58

Table 1 (continued)

Sample no. Measure ratios Corrected age (Ma)

207
Pb/206Pb 1σ 207
Pb/235U 1σ 206
Pb/238U 1σ 207
Pb/206Pb 1σ 207
Pb/235U 1σ 206
Pb/238U 1σ

YF47-67 0.05743 0.00019 0.60483 0.01263 0.07629 0.00154 509 7 480 8 474 9
YF47-69 0.05614 0.00012 0.59859 0.00620 0.07736 0.00080 457 4 476 4 480 5
YF47-18 0.06130 0.00031 0.78824 0.00957 0.09316 0.00089 650 11 590 5 574 5
YF47-48 0.06715 0.00097 0.89150 0.01505 0.09626 0.00080 843 30 647 8 592 5
YF47-65 0.06073 0.00017 0.83175 0.00612 0.09927 0.00064 629 1 615 3 610 4
YF47-16 0.07095 0.00066 1.10233 0.01852 0.11264 0.00151 967 20 754 9 688 9
YF47-42 0.06653 0.00041 1.03561 0.01452 0.11293 0.00152 833 13 722 7 690 9
YF47-12 0.07596 0.00098 1.19010 0.01552 0.11370 0.00077 1094 −6 796 7 694 4
YF47-58 0.06595 0.00026 1.05044 0.01713 0.11605 0.00207 806 7 729 8 708 12
YF47-17 0.06803 0.00066 1.09323 0.01936 0.11634 0.00147 878 25 750 9 709 8
YF47-70 0.06286 0.00018 1.02430 0.01335 0.11817 0.00150 702 6 716 7 720 9
YF47-34 0.07147 0.00019 1.19706 0.01479 0.12159 0.00161 972 6 799 7 740 9
YF47-7 0.07390 0.00088 1.23846 0.01630 0.12182 0.00134 1039 24 818 7 741 8
YF47-68 0.06945 0.00030 1.19265 0.02262 0.12436 0.00213 922 9 797 10 756 12
YF47-45 0.07509 0.00050 1.29245 0.01233 0.12534 0.00145 1072 13 842 5 761 8
YF47-66 0.06651 0.00027 1.18143 0.01640 0.12869 0.00164 833 9 792 8 780 9
YF47-38 0.07413 0.00040 1.34374 0.01559 0.13145 0.00136 1056 11 865 7 796 8
YF47-21 0.07721 0.00116 1.40097 0.01851 0.13275 0.00117 1128 34 889 8 804 7
YF47-15 0.06902 0.00019 1.30435 0.01726 0.13721 0.00189 898 6 848 8 829 11
YF47-55 0.06929 0.00081 1.32715 0.02655 0.13856 0.00183 907 24 858 12 837 10
YF47-75 0.07233 0.00213 1.41566 0.06426 0.14014 0.00206 994 27 896 27 845 12
YF47-40 0.07292 0.00043 1.47048 0.01872 0.14661 0.00195 1013 17 918 8 882 11
YF47-57 0.07503 0.00033 1.62189 0.02292 0.15601 0.00181 1069 9 979 9 935 10
YF47-49 0.07402 0.00022 1.59696 0.01985 0.15645 0.00190 1043 6 969 8 937 11
YF47-72 0.07240 0.00023 1.57761 0.01955 0.15783 0.00174 998 6 961 8 945 10
YF47-74 0.07060 0.00011 1.54891 0.01816 0.15914 0.00192 946 4 950 7 952 11
YF47-26 0.08277 0.00052 1.87772 0.02209 0.16472 0.00175 1265 12 1073 8 983 10
YF47-24 0.07556 0.00013 1.85356 0.02931 0.17805 0.00290 1083 4 1065 10 1056 16
YF47-43 0.09966 0.00048 3.39515 0.03345 0.24785 0.00280 1618 9 1503 8 1427 14
YF47-37 0.11959 0.00110 4.20172 0.04695 0.25459 0.00125 1950 11 1674 9 1462 6
YF47-25 0.09424 0.00020 3.45574 0.04163 0.26606 0.00322 1522 4 1517 9 1521 16
YF47-4 0.12689 0.00085 4.77392 0.04807 0.27265 0.00187 2055 17 1780 8 1554 9
YF47-53 0.08360 0.00158 3.71418 0.26903 0.27573 0.01254 1283 32 1574 58 1570 63
YF47-47 0.13856 0.00096 6.12011 0.10091 0.31968 0.00396 2209 12 1993 14 1788 19
YF47-22 0.12270 0.00025 5.64986 0.06400 0.33422 0.00394 1996 4 1924 10 1859 19
YF47-46 0.14762 0.00059 7.45841 0.14682 0.36446 0.00650 2320 2 2168 18 2003 31
YF47-39 0.16197 0.00050 8.52785 0.13910 0.38187 0.00619 2476 6 2289 15 2085 29
YF47-73 0.15785 0.00036 8.37737 0.11148 0.38442 0.00470 2433 4 2273 12 2097 22
YF47-51 0.12750 0.00201 7.47417 0.61212 0.41524 0.02512 2065 28 2170 73 2239 114
YF47-20 0.16504 0.00032 9.54891 0.13507 0.41940 0.00579 2509 9 2392 13 2258 26
YF47-62 0.16172 0.00152 9.99399 0.21339 0.45460 0.01049 2474 21 2434 20 2416 47
YF47-5 0.17090 0.00027 10.85602 0.15826 0.45995 0.00623 2566 2 2511 14 2439 27
YF47-54 0.15854 0.00080 10.08042 0.14178 0.46194 0.00659 2440 9 2442 13 2448 29
YF47-8 0.17298 0.00055 11.74993 0.13032 0.49391 0.00593 2587 5 2585 10 2588 26
YF47-19 0.17145 0.00026 11.79682 0.26655 0.49800 0.01090 2572 3 2588 21 2605 47

13YF41, 429 ± 30 Ma for 13YF43 and 437 ± 27 Ma for 13YF47

(Fig. 5). Given that the petrography indicates that these pyrite ores
were mineralized at the same time as the deposition of ore-hosting
strata, the maximum depositional age of the sandstone interlayers
constrains the mineralization age of the Dajiangping deposit as younger
than 429 Ma.

4.2. Re-Os isotopic compositions

The rhenium-osmium isotopic compositions of six pyrite samples

from banded pyrite ores are summarized in Table 2. These samples have
895 ± 25 to 5830 ± 95 ppt Re with 187Re/188Os ratios from
28.5 ± 0.4 to 237.8 ± 5.2, and 99.70 ± 0.48 to 271.93 ± 1.05 ppt
Os with 187Os/188Os ratios from 0.440 ± 0.002 to 1.849 ± 0.008.
There is a considerable scatter on the Re-Os isochron diagram and the
isochronal age is 389 ± 62 Ma (Fig. 7).

4.3. Major and trace elements

Fig. 6. U–Pb age frequency spectrum for detrital zircons from sandstone interlayers in
ore-hosting strata of the Dajiangping deposit.
Major and trace element data for rocks of ore-hosting strata col-
lected from drill hole YF02 are shown in Fig. 8 and Table 3. SiO2 and
CaO show a converse correlation, with high CaO and low SiO2

49
W.J. Qiu et al.
Table 2
Re-Os isotope analyses for pyrite from the Dajiangping deposit.
Sample no. Re (ppt) 2σ Os (ppt)
13YF05 2243 48 155.76
13YF23-2 4349 63 176.65
13YF25-3 4021 87 99.70
13YF25-7 1385 23 146.57
13YF25-8 1327 15 233.35
13YF33 2821 13 271.93
Fig. 7. Pyrite Re-Os isotopic isochron age of the Dajiangping deposit.
concentrations in the Lower Unit and Middle Unit, and high SiO2 and
low CaO concentrations in the Upper Unit (Fig. 8). Laminated pyrite
layers at the top of the Middle Unit have higher Fe2O3 and MnO con-
centrations than sedimentary rocks of the whole stratigraphy (Fig. 8).
The Lower and Middle units have low TOC concentrations, but the
whole Upper Unit has high TOC concentrations (Fig. 8). As the com-
positions of sedimentary rocks could be influenced by mineralogy and
grain size effects (Xu et al., 2014), aluminum-normalized values of
some elements (Mo/Al, As/Al, Cd/Al, Zn/Al and Tl/Al) are used in the
sediment profile (Fig. 8), in order to minimize such effects and to
evaluate the variation of these elements caused by hydrothermal fluids
or redox conditions. Ba/Al ratios exhibit a sharp increase in the Middle
Unit, a gradual decrease in the Upper Unit, but a sharp increase to high
ratios again at the top of the Upper Unit (Fig. 8). Mo/Al, As/Al, Cd/Al,
Zn/Al and Tl/Al ratios have similar variations, with low ratios in the
Lower and Middle Units and a sharp increase to high ratios in the Upper
Unit (Fig. 8).
Samples of ore-hosting strata from the Dajiangping deposit lie
on a trend from illite/muscovite to calcite-dolomite on the
(CaO + Na2O)–Al2O3–K2O diagram (McLennan et al., 1990; Nesbitt
and Young, 1984) (Fig. 9a), with samples from the Middle Unit closer to
the carbonate range and samples from the Upper Unit closer to illite/
muscovite range. All samples lie within a triangular area between
muscovite, chlorite, and carbonate on the (CaO + Na2O +
K2O)–Al2O3–(Fe2O3 + MgO) diagram (McLennan et al., 1990; Nesbitt
and Young, 1984) (Fig. 9b). Limestones and black shales lie in the
detrital portion of the Fe-Mn-Al ternary diagram (Fig. 9c) with very
limited hydrothermal input, whereas the two laminated pyrite ore
samples plot in the hydrothermal-field range. Black shale and limestone
samples show dominant detrital components with only a maximum of
∼30% hydrothermal components in the Fe/Ti vs. Al/(Al + Fe + Mn)
diagram (Fig. 9d), whereas pyrite-bearing samples exhibit a higher
hydrothermal input (40–70%).
Journal of Asian Earth Sciences 156 (2018) 41–58
187
2σ Os/188Os 2σ 187
Re/188Os 2σ Model age (Ma)
0.36 0.7834 0.0013 75.3 1.6 417.5
0.39 1.0110 0.0023 132.2 1.9 341.2
0.48 1.8486 0.0078 237.8 5.2 401.0
0.28 0.5622 0.0009 48.1 0.8 377.6
1.91 0.4401 0.0020 28.5 0.4 379.7
1.05 0.6455 0.0049 53.3 0.3 433.9
The PAAS (average Post Archean Australian Shale) normalized REE
patterns of the laminated pyrite layer and black shales in the Upper
Unit are similar and display very flat patterns without negative Ce
anomalies (Ce/Ce * ∼1) and with similar but variable Eu anomalies
(Fig. 10a) (McLennan et al., 1993). The redox-sensitive elements, Mo
(0.52–5.24 ppm), V (45–115 ppm) and Ni (13–47 ppm), in the black
shales show positive correlations with the TOC (0.3–2.89 wt%)
(Fig. 10b–d). Black shales are also plotted within the anoxic field both
in the Mn vs V/(V + Ni) (Fig. 10e) and V/(V + Ni) vs V/Cr diagrams
(Fig. 10f) (Hatch and Leventhal, 1992; Hoffman et al., 1998;
Tribovillard et al., 2006).
5. Discussion
5.1. Age and sedimentary sources of ore-hosting strata
Although previous studies have reported a whole-rock Rb-Sr iso-
chron age of 630 Ma for the Dajiangping deposit (Chen et al., 1992;
Wang et al., 1996; Xu et al., 1996), the reliability of such an age cannot
be evaluated, because the Rb-Sr isotopic system can easily be reset
during low temperature alteration (Nebel, 2013). In this study, the U-Pb
ages of detrital zircons from sandstone interlayers within the stratiform
orebodies are dominantly of early- to middle Paleazoic age, defining a
distinct age peak at ca. 520–430 Ma (Fig. 6). The maximum deposi-
tional ages of the three samples that were constrained by the intercept
ages of their youngest zircons are consistently of Devonian age, with
447 ± 17 Ma for 13YF41, 429 ± 30 Ma for 13YF43 and 437 ± 27 Ma
for 13YF47, indicating that the deposition of stratiform orebodies and
ore-hosting strata must be later than Silurian (Fig. 5). The ore-hosting
strata of this deposit are unconformably underlain by a metamorphic
basement complex, similar to that of the late Devonian Liujiang Group
(Figs. 2 and 3). This implies that the ore-hosting strata were deposited
during the mid-late Devonian, which is consistent with the age of the
regional unconformity between Devonian strata and the underlying
metamorphosed basement in the Yunkai Terrane (Wan et al., 2010;
Wang et al., 2007).
As Re-Os isotopes have a relatively high closure temperature
(500 °C), and there is a low diffusion rate within pyrite grains (Brenan
et al., 2000), the Re-Os isotopic system is more likely a closed system
within pyrite grains, making the pyrite Re-Os isochron age reliable for
sulfide deposits. Our Re-Os dating of pyrite separates from fresh, un-
metamorphosed and unaltered laminated pyrite ores in the Dajiangping
deposit yields an isochron age of 389 ± 62 Ma (Fig. 7). Although the
uncertainty is large, the isochron age is consistent broadly with de-
position during the mid-late Devonian. Such an age for the Dajiangping
deposit is similar to many syngenetic stratiform sulfide deposits hosted
by Devonian strata in South China, such as the Panglong Pb-Zn deposit
and the Hongyan pyrite deposit (Jiang, 1987; Li, 2007; Niu et al., 2017;
Pei, 1989).
In addition, the age spectrum of detrital zircon indicates that the
ore-hosting strata of this deposit is dominated by early Paleozoic and
Neoproterozoic sources with minor early Proterozoic and Neoarchean
inputs (Fig. 6). The major tectonic events in the Cathaysia Block before
Devonian include the Jiangnan Orogeny at ca. 830 Ma (Zhao et al.
2011; Wang et al., 2013a, 2013b) and the Caledonian Orogeny at ca.
50
W.J. Qiu et al. Journal of Asian Earth Sciences 156 (2018) 41–58

Fig. 8. Stratigraphic profile of SiO2, CaO, Fe2O3 (total iron), TOC (total organic carbon), Mo, As, Cb, Zn and Tl of samples from the drill hole YF02 on the margin of the Dajiangping
deposit (Table 2). Also shown is the column of various sedimentary rocks from the from the drill hole.

440–400 Ma (Wang et al. 2007). The age peaks in the age spectrum here
of 830 Ma and 440–400 Ma reveal that the Jiangnan Orogenic belt and
the metamorphic complexes in the Yunkai Terrane supplied sig-
nificantly sedimentary materials to the ore-hosting strata of the Da-
jiangping deposit. As the metamorphic basement complexes in the
Yunkai terrane contain abundant 443–430 Ma zircons (Xu et al., 2017;
Wang et al., 2013a, 2013b), our 440–400 Ma ages with a peak of
430 Ma indicate that the sedimentary materials were mostly sourced
from the metamorphic basement complexes and their associated vol-
canic and igneous rocks (Huang et al., 2013; Wan et al., 2010; Wang
et al., 1999, 2007, 2013b; Xu et al., 2017; Yao et al., 2012).
5.2. Redox evolution associated with transgression
The predominantly laminated pyrite ores of stratiform orebodies are
intercalated with black shale layers (Fig. 3), which implies ores

51
 Table 3
Major and trace elemental compositions of drill core YF02 from the Dajiangping deposit.

Sample YF02-02 YF02-03 YF02-04 YF02-05 YF02-06 YF02-07 YF02-08 YF02-09 YF02-10 YF02-11 YF02-12 YF02-13 YF02-14
W.J. Qiu et al.

Unit Upper Unit Upper Unit Upper Unit Upper Unit Upper Unit Upper Unit Upper Unit Upper Unit Upper Unit Upper Unit Upper Unit Upper Unit Upper Unit

Depth (m) 54 60 63 68 73 81 83 86 92 100 104 109 113

Major oxides and total organic carbon (wt%)

Al2O3 (%) 7.09 9.28 10.93 10.86 15.79 8.06 11.16 6.64 14.62 18.55 12.51 5.18 11.73
CaO (%) 0.06 8.75 5.51 11.66 3.85 1.83 1.42 10.89 1.78 1.01 2.06 1.33 3.60
Fe2O3 (%) 1.25 4.96 5.90 5.03 3.58 4.72 5.62 6.17 5.48 5.57 4.00 2.50 3.60
K2O (%) 1.52 2.38 2.83 2.75 4.35 1.87 3.03 1.00 4.38 5.51 3.48 1.31 3.31
MgO (%) 0.30 1.73 0.92 1.17 1.43 1.10 1.41 3.34 1.43 1.52 1.34 0.89 1.88
MnO (%) 0.01 0.06 0.03 0.12 0.08 0.05 0.06 0.25 0.06 0.02 0.04 0.04 0.09
Na2O (%) 0.08 0.09 0.10 0.17 0.21 0.09 0.09 0.03 0.12 0.13 0.10 0.04 0.09
P2O5 (%) 0.08 0.09 0.08 0.05 0.06 0.04 0.07 0.05 0.07 0.06 0.08 0.11 0.05
SiO2 (%) 86.41 59.89 63.78 53.65 62.01 75.69 69.82 60.87 63.85 60.02 70.14 82.79 68.25
TiO2 (%) 0.18 0.28 0.32 0.31 0.59 0.20 0.40 0.34 0.56 0.74 0.54 0.18 0.51
LOI (%) 2.92 12.55 9.73 14.12 7.88 6.27 6.86 10.49 7.51 6.62 5.52 5.60 6.96
TOC (%) 0.97 1.02 1.28 1.44 1.12 1.83 2.03 0.36 1.91 1.02 1.42 2.89 1.26

Trace elements (ppm)

V 70.66 57.20 69.86 83.22 97.70 72.09 106.42 45.28 114.60 107.24 96.89 87.60 87.43
Cr 27.83 31.14 35.72 46.15 69.97 28.67 56.19 33.19 69.51 76.83 62.55 31.36 55.76
Mn 54.51 447.38 276.64 926.21 700.92 358.12 479.45 1865.57 501.23 222.05 347.39 348.76 778.49
Co 172.38 61.06 54.49 50.32 51.33 114.23 84.73 43.51 58.70 69.74 200.11 84.20
Ni 39.19 27.78 29.31 38.35 32.12 35.75 43.36 13.78 40.06 46.69 36.61 41.08 35.23
Cu 66.47 52.60 49.09 75.99 19.74 17.32 23.38 47.85 42.43 33.99 25.29 11.81 66.45
Zn 26.52 27.87 24.04 19.52 17.76 557.69 32.27 125.23 1338.04 37.89 1806.79 6439.26 562.42
As 30.18 17.38 33.16 35.24 24.09 31.24 18.20 127.70 32.72 35.95 176.91 22.43 267.81

52
Y 89.22 9.10 6.83 16.26 24.36 8.12 19.14 39.10 23.71 27.78 26.62 8.04 21.66
Mo 0.52 2.33 2.19 3.51 1.34 3.87 4.64 0.72 3.81 2.67 2.19 5.24 2.04
Ag 0.35 0.34 0.33 0.45 0.47 0.23 0.69 1.39 1.03 1.44 1.41 1.29 1.62
Cd 0.08 0.16 0.08 0.14 0.11 2.34 0.16 0.72 5.88 0.27 9.67 29.90 2.92
Sb 1.87 1.23 1.93 9.12 2.18 3.28 2.67 2.05 6.62 8.47 6.16 2.30 12.00
Ba 2155.27 5510.72 6862.28 6127.77 1064.40 384.61 565.63 193.50 1152.85 997.18 686.31 550.25 798.93
La 35.11 12.86 10.15 20.04 37.20 12.95 25.87 28.91 38.18 58.08 35.09 15.03 24.33
Ce 57.84 23.67 19.93 43.07 72.45 24.89 48.47 60.67 70.67 107.43 67.07 27.17 47.52
Pr 9.52 2.73 2.18 4.28 8.54 2.80 5.78 7.41 8.24 12.38 8.01 3.19 5.71
Nd 44.49 10.41 8.22 16.52 33.74 10.91 21.68 30.30 29.69 46.52 30.29 12.99 21.96
Sm 10.52 2.01 1.55 3.35 5.66 1.98 4.26 7.90 5.30 6.44 6.28 2.70 4.85
Eu 2.08 0.46 0.39 0.55 1.20 0.28 0.76 1.13 1.05 1.09 0.96 0.44 0.65
Gd 13.02 1.74 1.33 2.97 4.79 1.63 3.95 7.49 4.53 4.52 5.61 2.48 4.51
Tb 2.27 0.27 0.20 0.47 0.76 0.26 0.60 1.17 0.71 0.79 0.85 0.33 0.70
Dy 13.90 1.49 1.07 2.59 4.20 1.44 3.24 6.48 3.86 4.63 4.60 1.57 3.83
Ho 3.00 0.31 0.23 0.55 0.86 0.28 0.65 1.32 0.80 0.99 0.93 0.28 0.78
Er 8.86 0.92 0.72 1.61 2.51 0.82 1.84 3.71 2.32 2.91 2.59 0.73 2.25
Tm 1.34 0.14 0.11 0.25 0.37 0.12 0.27 0.53 0.34 0.42 0.38 0.10 0.33
Yb 8.63 0.97 0.78 1.58 2.34 0.78 1.63 3.22 2.11 2.55 2.31 0.60 2.11
Lu 1.35 0.16 0.14 0.26 0.37 0.12 0.25 0.48 0.33 0.41 0.37 0.09 0.34
Hf 0.92 1.96 2.04 1.75 3.38 0.97 2.77 4.93 3.52 5.36 3.34 1.24 4.15
Ta 0.78 0.68 0.76 0.63 0.97 0.62 0.88 0.60 0.91 1.23 1.00 0.75 1.01
Tl 1.20 1.41 1.85 1.76 2.99 1.67 3.23 1.05 8.27 4.51 3.37 1.94 4.53
Pb 4.89 46.80 38.75 37.27 29.51 28.97 195.02 214.44 164.58 71.80 146.91 275.46 77.35
Bi 0.45 1.10 1.57 0.85 0.43 0.35 0.49 0.26 0.67 0.55 1.43 0.20 0.22
Th 4.82 9.07 10.32 10.19 17.44 5.22 11.34 11.02 15.64 21.22 15.35 5.19 13.70
U 2.98 2.08 2.62 3.08 2.94 1.24 2.32 1.98 2.77 3.89 2.96 1.45 2.90

(continued on next page)

Journal of Asian Earth Sciences 156 (2018) 41–58
 Table 3 (continued)

Sample YF02-15 YF02-16 YF02-17 YF02-18 YF02-19 YF02-20 YF02-21 YF02-25 YF02-26 YF02-27 YF02-28 YF02-29 YF02-41
Unit Upper Unit Upper Unit Middle Unit Middle Unit Middle Unit Middle Unit Lower Unit Lower Unit Lower Unit Lower Unit Basement Basement Basement
W.J. Qiu et al.

Depth (m) 120 124 129 137 145 150 153 177 182 193 210 234 500

Major oxides and total organic carbon (wt%)

Al2O3 (%) 5.77 11.65 5.60 15.12 8.42 3.28 26.27 3.17 23.61 13.86 5.70 14.27 17.04
CaO (%) 8.49 3.55 34.87 21.94 32.18 43.92 0.90 2.79 1.24 23.20 0.25 0.11 0.70
Fe2O3 (%) 25.42 17.14 2.55 6.35 2.72 3.12 7.65 1.34 6.41 4.63 1.98 3.25 5.77
K2O (%) 1.56 3.29 0.74 2.86 2.25 0.67 5.88 0.37 5.60 3.45 1.59 4.05 5.03
MgO (%) 0.96 0.68 1.63 3.95 1.53 1.20 1.86 0.41 2.27 2.12 0.38 1.18 2.29
MnO (%) 0.47 0.14 0.54 0.06 0.05 0.08 0.03 0.06 0.03 0.07 0.01 0.03 0.09
Na2O (%) 0.09 0.20 0.28 0.21 0.15 0.03 0.52 0.08 0.42 0.37 0.07 0.13 0.58
P2O5 (%) 0.03 0.04 0.11 0.18 0.06 0.09 0.11 0.04 0.08 0.18 0.05 0.07 0.09
SiO2 (%) 35.16 49.21 26.84 31.25 25.13 11.96 51.34 88.09 54.23 34.05 87.41 73.61 65.25
TiO2 (%) 0.24 0.45 0.21 0.35 0.23 0.10 0.70 0.64 0.89 0.40 0.82 0.91 0.69
LOI (%) 21.88 13.54 26.50 17.65 27.41 35.70 4.98 3.02 5.29 17.74 1.59 2.55 2.48
TOC (%) 0.66 0.85 2.09 0.48 0.45 0.37 0.10 0.16 0.28 0.16 null null null

Trace elements (ppm)

V 65.23 102.04 43.08 104.60 51.69 30.42 172.53 21.61 128.23 87.63 36.81 86.71 94.31
Cr 33.46 59.14 28.66 79.45 49.17 25.35 135.41 29.58 111.07 72.87 36.01 65.99 66.47
Mn 3976.13 1177.59 4155.47 490.33 447.79 746.11 256.26 505.44 238.42 651.26 106.45 247.11 787.71
Co 84.67 80.24 13.20 19.79 9.44 9.83 43.78 188.24 25.62 37.41 243.75 128.43 68.45
Ni 32.93 40.69 12.59 29.43 12.82 14.85 41.76 23.64 25.19 27.70 36.99 36.13 30.38
Cu 134.02 17.50 7.28 21.88 22.45 20.05 26.87 1.56 11.91 24.17 14.43 11.10 24.51
Zn 365.08 16.93 12.48 139.44 56.26 15.07 48.88 14.24 44.38 33.31 14.27 28.85 1151.45
As 55.55 42.52 15.52 2.37 1.44 1.69 4.37 2.64 2.79 2.92 21.12 4.36
Y 13.95 14.41 92.08 14.61 11.00 15.41 28.68 42.26 23.38 11.12 27.95 42.42 31.54

53
Mo 5.81 4.13 1.28 0.53 0.65 1.03 0.57 0.44 0.60 0.54 0.63 0.88 0.69
Ag 1.26 0.69 0.23 0.21 0.13 0.06 0.32 2.62 0.50 0.22 1.71 1.21 0.65
Cd 1.96 0.17 0.10 0.13 0.15 0.08 0.08 0.56 0.11 0.08 0.39 0.30 9.40
Sb 11.22 3.91 2.89 0.00 0.00 0.00 0.08 0.84 0.10 0.00 0.33 1.18 0.15
Ba 1608.16 2257.03 207.96 351.34 191.81 71.21 660.12 73.04 646.27 444.89 138.00 419.03 784.13
La 23.09 28.62 26.54 28.06 14.53 13.04 43.38 26.52 41.93 23.48 65.80 54.55 27.57
Ce 46.01 55.51 52.65 52.06 27.80 25.65 84.14 54.41 79.76 43.89 147.75 111.56 57.53
Pr 5.52 6.43 5.72 6.24 3.10 3.12 9.85 6.08 9.23 4.97 15.55 12.63 6.81
Nd 21.28 23.19 24.04 22.65 11.72 12.83 38.72 22.51 35.89 18.09 58.62 50.13 26.34
Sm 4.24 4.02 6.23 4.02 2.18 2.86 6.53 4.66 5.97 3.03 9.86 9.06 5.54
Eu 1.03 0.67 1.20 0.61 0.61 0.99 1.03 1.34 1.08 0.71 1.58 1.66 1.14
Gd 3.60 3.14 8.52 3.34 1.97 2.82 5.33 6.06 5.00 2.38 6.68 8.22 5.57
Tb 0.49 0.48 1.63 0.49 0.31 0.41 0.88 1.08 0.78 0.37 0.97 1.29 0.95
Dy 2.44 2.51 11.22 2.58 1.69 2.22 5.02 6.55 4.29 1.94 4.98 7.24 5.63
Ho 0.47 0.52 2.53 0.52 0.35 0.43 1.03 1.38 0.89 0.40 1.01 1.48 1.20
Er 1.32 1.58 7.12 1.51 1.03 1.11 2.98 3.99 2.65 1.18 2.95 4.25 3.51
Tm 0.19 0.24 0.99 0.22 0.15 0.15 0.43 0.60 0.39 0.18 0.44 0.63 0.54
Yb 1.22 1.56 5.59 1.37 0.93 0.79 2.65 3.76 2.53 1.18 2.77 3.88 3.33
Lu 0.20 0.26 0.77 0.21 0.14 0.11 0.40 0.61 0.43 0.19 0.43 0.61 0.52
Hf 1.78 2.87 1.38 1.52 1.03 0.46 2.81 21.31 4.26 1.66 12.70 10.13 4.88
Ta 0.65 0.94 0.33 0.51 0.36 0.17 1.06 0.92 1.37 0.64 1.62 1.71 1.13
Tl 25.77 32.91 1.22 0.72 0.46 0.13 1.29 0.10 0.87 0.78 0.50 1.16 2.24
Pb 169.86 153.58 28.49 26.16 21.73 15.98 11.92 4.21 18.84 28.17 14.04 6.97 33.01
Bi 0.45 0.77 0.20 0.49 0.20 0.16 0.61 0.09 0.49 0.51 0.25 0.37 2.04
Th 6.50 12.28 5.46 12.23 7.09 2.72 23.14 13.63 22.35 12.76 16.01 18.15 18.22
U 2.21 2.99 1.21 1.84 1.43 0.97 2.75 3.67 3.33 1.72 2.93 4.28 3.06
Journal of Asian Earth Sciences 156 (2018) 41–58
W.J. Qiu et al.
Fig. 9. (a) The Al2O3–(CaO + Na2O)–K2O ternary diagram of sedimentary rocks (adapted from Nesbitt, 2003). (b) The Al2O3–(CaO + Na2O + K2O)–(Fe2O3 + MgO) ternary diagram
(adapted from Nesbitt, 2003) showing the main alteration trend of sedimentary rocks, involving the illite–muscovite and the chlorite. (c) The Fe-Al-Mn ternary diagram of hydrothermal
element provenance of sedimentary rocks (Boström, 1973). (d) The Fe/Ti vs. Al/(Al + Fe + Mn) plot of sedimentary rocks (Boström, 1973). All the sedimentary rocks are from the ore-
hosting strata sampled from the drill hole YF02.
deposition in low-energy and deep water environments (Miall, 2016).
However, the rocks of the Lower and Middle Units of the ore-hosting
strata are dominated by the calcareous siltstone and carbonaceous
limestone (Fig. 3), indicating a shallow sea-water environment. Such
different sedimentary facies across the Dajiangping deposit, with black
shales of deep water facies in the center and shallow carbonate platform
facies on the margin (Fig. 3), imply that this deposit formed in a basin
within a carbonate platform (Miall, 2016). Combined with the closely
spatial relations between the Dajiangping deposit and the Wuchuan-
Sihui fault belt (Fig. 1), the lithological features imply that the basin
should be a sub-fault-bounded basin within this carbonate platform.
Such a hypothesis is consistent with the extensive development of deep,
fault-bounded basins within a carbonate platform in South China
during the Devonian (Chen et al., 2001; Zhao et al., 1996). The un-
metamorphosed Devonian laminated ores and ore-hosting strata un-
conformably overlying the metamorphic basement (Fig. 3) also provide
strong evidence that the mineralization took place at the same time as
the onset of fault-bounded basin subsidence (Miall, 2016; Zhao et al.,
1996).
Before using the geochemical proxies to discuss the paleo-redox
conditions of the basin, it is necessary to evaluate the possibility of
hydrothermal fluid contamination of ore-hosting rocks (Piercey et al.,
2016; Sáez et al., 2011). In fact, most sedimentary rocks within the ore-
hosting strata plot in a non-hydrothermal field and there is little evi-
dence of contamination of hydrothermal fluids on the Fe-Mn-Al ternary
diagram and plot of Fe/Ti vs. Al/(Al + Fe + Mn) (Fig. 9c and d). The
geochemical composition of these sedimentary rocks thus can be used
to reconstruct the paleo-redox conditions of the original basin.
The total organic carbon concentrations (TOC) of sedimentary rocks
is an important proxy for evaluating primary productivity and paleo-
54
Journal of Asian Earth Sciences 156 (2018) 41–58
redox conditions, because TOC is dependent, not only on organic
carbon delivery from primary production (photosynthesis) in surface
water to sea floor, but also on the sea-floor redox conditions that are
critical for preservation of organic matter (Arthur and Sageman, 1994;
Tribovillard et al., 2006). The organic carbon concentrations (TOC)
gradually increase from calcareous limestone-siltstone in the Lower
Unit to carbonaceous limestone in the Middle Unit, and sharply in-
crease into the black shales of the Upper Unit in the element profiles
(Fig. 8). Assuming that the primary productivity in surface water was
stable during precipitation of the ore-hosting strata, such a sharp var-
iation of TOC indicates that the redox conditions on the sea floor
changed from oxic in the shallow water carbonate platform condition to
anoxic in the deep basin floor environment (Jones and Manning, 1994;
Leventhal, 1983), as organic carbon is preferentially preserved in the
anoxic surface sediments of the deep basin with its low dissolved-
oxygen concentration.
The high Ba/Al values in the pyrite layers of the Middle Unit suggest
that such Ba enrichment was probably caused by hydrothermal fluids,
as in most SEDEX deposits (Leach et al., 2005). However, the high Ba
content in the black shale of the Upper Unit may have other origin,
given that the black shales show evidences of limited hydrothermal
contamination. More likely, it relates to the increase of productivity and
hence the influx of sinking organisms (e.g. phytoplankton), which
carried barite from sea surface to seafloor and delivered Ba to sediment
after decomposition (Tribovillard et al., 2006). The gradual decrease of
Ba/Al values in black shales in the Upper Unit also indicates that an-
oxic-euxinic basin conditions caused dissolution of barite in sediments
and prevented abundant barite precipitation (Tribovillard et al., 2006).
The rapid increase of Ba/Al values of the black shales at the top of the
Upper Unit was possibly caused by the replenishment of sea water
W.J. Qiu et al. Journal of Asian Earth Sciences 156 (2018) 41–58

Fig. 10. (a) PAAS normalized rare earth element plots for laminated ore layers of the Middle Unit and black shales of the Upper Unit (Average values of Post-Archean Australian Shale
(PAAS) from McLennan, 1989). (b) Bivariate plot of TOC vs. Mo of black shales. (c) Bivariate plot of TOC vs. V of black shales. (d) Bivariate plot of TOC vs. Ni of black shales. (e) Bivariate
plot of Mn vs. V/(V + Ni) of black shales (Piercey et al., 2016). (f) Bivariate plot of V/Cr vs. V/(V + Ni) of black shales, with limits of environmental conditions after Jones and Manning
(1994) and Hoffman et al. (1998). Laminated ores and black samples were from the drill hole YF02.

sulfate in the anoxic basin associated with an increase in barite pre-
cipitation (Goodfellow, 1987; Tribovillard et al., 2006).
Molybdenum is mainly in the form of molybdate (MoO42−) under
oxic conditions (Algeo and Tribovillard, 2009). It is preferentially re-
duced to thiomolybdate (MoOxS2− 4−x, x = 0 to 3) and precipitated in
sediments as organic thiomolybdates or inorganic Fe-Mo-S solid solu-
tion in Fe-sulfides under anoxic-euxinic conditions (Helz et al., 1996;
Tribovillard et al., 2004). The strongly positive correlation between Mo
and TOC in the black shales of the Upper Unit (Fig. 10b) indicates
euxinic depositional conditions, in which Mo was present as reactive
thiomolybdate particles and scavenged by organic matter by forming
bonds with sulfur-rich organic molecules (Helz et al., 1996). The sharp
increase of Mo/Al values from the carbonaceous limestone in the
Middle Unit to the black shale in the Upper Unit (Fig. 8), with similar
variations in TOC, therefore implies that the sedimentary condition
changed sharply from oxic to anoxic-euxinic.
Some elements, which are readily precipitated as diagenetic sulfides
or absorbed on organic matter, e.g. As, Zn, Cd and Tl, can also be used
to constrain the evolution of redox conditions (Arthur and Sageman,
1994; Calvert and Pedersen, 1993; Tribovillard et al., 2006). Zn and Cd
are nutrient elements and present as zinc-humic/fulvic acid complexes
and aqueous Cd2+ in water column respectively. They would be de-
livered to marine sediment mainly in association with organic matter
and released into interstitial waters after organic matter has decayed
(Algeo and Maynard, 2004; Calvert and Pedersen, 1993). Under euxinic
conditions, Zn and Cd would be authigenically enriched in sediment in
the form of sulfide, for example as a solid-solution phase in diagenetic
pyrite (Morford and Emerson, 1999; Piper and Perkins, 2004). As and Tl
are also commonly removed from seawater and substituted into the
lattices of early diagenetic pyrite and acid-volatile sulfides in sediments
under euxinic conditions (Lowers et al., 2007; Schaefer et al., 2017).
The Al-normalized values of these elements (Zn/Al, Cd/Al, As/Al, Tl/

55
W.J. Qiu et al.
Fig. 11. (A) A genetic model for the formation of the Dajiangping deposit in a fault-bounded basin on a passive continental margin; (B) Reconstruction of eastern Gondwana in the late
Devonian, cited from Metcalfe (2006) (NC = North China; T = Tarim; I = Indochina/East Malaya/West Sumatra; QI = Qiangtang; L = Lhasa; S = Sibumasu; WB = West Burma;
WC = Western Cimmerian Continent).
Al) show predictably similar correlation with TOC and Mo/Al, with
sharp increases from the carbonaceous limestone in the Middle Unit to
the black shale in the Upper Unit in the elemental profiles (Fig. 8). As
these elements are readily transported into sediment by absorption of
organic matter and preferentially precipitated in sediments as sulfides,
such enrichment of these elements in black shale should be caused by
rapid change of redox conditions from oxic to anoxic-euxinic during
deposition of black shale (Arthur and Sageman, 1994; Erickson and
Helz, 2000; Tribovillard et al., 2006).
Vanadium is a redox-sensitive element and present in various va-
lence states in seawater under different redox conditions. Vanadium as
V5+ forms vanadate oxyanions (HVO42−) under anoxic conditions and
would be reduced to V4+ in forms of vanadyl ion (VO2−), hydroxyl VO
(OH)3− and insoluble hydroxides VO(OH)2 under moderately reducing
conditions, which are readily removed to the sediment by surface ad-
sorption or formation of organometallic ligands. It would be further
reduced to V3+ under strongly reducing conditions and be taken up by
geoporphyrins and deposited to sediment as solid oxide V2O3 (Algeo
and Maynard, 2004; Tribovillard et al., 2006). The strong correlation
between V and TOC in black shales in the Upper Unit therefore in-
dicates that V was mainly resident in organic matter under anoxic-eu-
xinic conditions (Fig. 10b–d) (Algeo and Maynard, 2004; Tribovillard
et al., 2006).
Vanadium is more effectively fixed in sediments in association with
organic compounds in anoxic conditions than other competing metals,
such as Ni and Cr. The V/(V + Ni) and V/Cr ratios therefore have been
widely used to evaluate the prevalence of anoxic-euxinic conditions
(Calvert and Pedersen, 1993; Hoffman et al., 1998; Jones and Manning,
1994). The black shales of the Upper Unit have V/(V + Ni) ratios > 0.6
and V/Cr ratio > 1 and are plotted in the anoxic field of the V/(V + Ni)
vs. Mn and V/Cr vs. V/(V + Ni) diagrams, indicating that they pre-
cipitated in a anoxic environment (Calvert and Pedersen, 1993;
Hoffman et al., 1998; Jones and Manning, 1994) (Fig. 10e and f). The
flat REE patterns of black shales and absence of negative Ce anomalies
(Fig. 10a) further indicate anoxic conditions, as the oxic conditions
would cause adsorption of Ce into Mn oxides and nodules and lead to
pronounced negative Ce anomaly in seawater and authigenic sediments
(De Baar et al., 1988; Elderfield et al., 1988).
Based on the basin architecture reconstructed by the variations in
sedimentary facies across the deposit and the paleo-redox conditions
determined by multiple geochemical proxies, we propose that the black
shales and laminated pyrite ores formed in an anoxic-euxinic deep basin
in a carbonate platform. Such an anoxic-euxinic basin is a preferential
56
Journal of Asian Earth Sciences 156 (2018) 41–58
environment for bacteria to reduce seawater sulfate and produce H2S
(Goodfellow, 1987; Large et al., 2005; Sáez et al., 2011), which would
be fixed by Fe2+ in exhaled hydrothermal fluids and lead to pyrite
precipitation (Large et al., 2002). The organic-rich black shales of ore-
hosting strata provide a reducing condition for the preservation of
sulfide ores and prevent them from being oxidized on sea floor (Sáez
et al., 2011).
5.3. Implications for the late Paleozoic evolution of northern Gondwana
The Dajiangping deposit has many features in common with other
SEDEX sulfide deposits in the southwestern Cathaysia Block, such as the
Hongyan and Xiniu pyrite deposits, and the Panlong Pb-Zn deposits,
which are located near several NE-trending deep faults in the Cathaysia
Block and contain stratiform orebodies hosted by Devonian strata in the
anoxic deep fault-bounded basins (Jiang, 1987; Li, 2007; Niu et al.,
2017; Pei, 1989; Yang et al., 1996). The predominant ore-hosting rocks,
the black shales, in this deposit are also similar to those of other SEDEX
sulfide deposits hosted by Devonian carbonaceous sequences in South
China (Jiang, 1987; Li, 2007; Pei, 1989; Zhang et al., 1993). The
SEDEX-type sulfide deposits mostly formed in anoxic fault-bounded
basins of two broad settings: intracontinental failed rifts, and rifted
Atlantic-type continental passive margins (Large et al., 1998, 2005;
Leach et al., 2005). These Devonian SEDEX deposits, which formed in
anoxic fault-bounded basins in an carbonate platform in the Cathaysia
Block (Fig. 1) (Chen et al., 2001, 2006; Yang et al., 1996; Zhao et al.,
1996), thus require a extensional and rifting setting in a passive margin.
The Cathaysia Block, which was the southern part of the South
China Block, was attached on the western part of NE Gondwana in the
early Paleozoic (Fig. 11b) (Metcalfe, 2009). The extensive lower green-
schist facies metamorphism during the Silurian (420–460 Ma) (Charvet,
2013; Shu et al., 2014; Xu et al., 2016) and the large scale emplacement
of early Paleozoic magmatic rocks in the Cathaysia Block (Xu et al.,
2017; Wang et al., 2013a, 2013b) indicate that the Cathaysia Block was
in a contractional environment, which was caused by an in-
tracontinental orogenic event (Charvet, 2013; Shu et al., 2014; Xu et al.,
2016). The significant 440–430 Ma peak in the detrital zircon age
spectrum in our study may also be a record of such an intracontinental
orogeny in South China during the early Paleozoic (Fig. 6).
After this intracontinental orogeny, the South China Block in asso-
ciation with the North China, Tarim and Indochina Blocks, started
rifting from Gondwana after the mid-late Silurian (Metcalfe, 2009).
Lehmann et al. (2013) proposed that the South China Block separated
W.J. Qiu et al.
from Gondwana by back-arc spreading during the mid-Silurian due to
southward or eastward subduction along an active plate margin of
northeast Gondwana (Fig. 11b). This proposal was based on submarine
dacite magmatism (430 Ma) and associated VHMS mineralization in the
Simao basin in the western Yangtze Block.
After rifting from Gondwana, the South China Block migrated
northward and the Cathaysia Block was in a passive margin setting with
an extensive carbonate platform during the Devonian (Fig. 11b) (Chen
et al., 2001, 2006; Zhao et al., 1996), as suggested by the development
of a broad carbonate platform in South China (Chen et al., 2001, 2006;
Yang et al., 1996; Zhao et al., 1996). Due to northward migration
(Fig. 11b), the Cathaysia Block was in an extensional tectonic setting
and a series of NW-SE-trending normal faults and numerous high-angle
NE-SW transitional faults crosscut the carbonate platform on the pas-
sive margin and formed fault-bounded basins (Fig. 1), where numerous
SEDEX deposits were formed (Chen et al., 2001, 2006; Zhao et al.,
1996). We therefore believe that the formation of these SEDEX sulfide
deposits in the southwestern Cathaysia Block during Devonian was
closely related to break-up of the South China Block from Gondwana
and the extensional passive margin setting of the South China Block
during its northward migration.
6. Conclusions
(1) Detrital zircon U-Pb ages for sandstone and Pyrite Re-Os isotopic
isochron ages for laminated ores constrain the mineralization of the
Dajiangping deposit at mid-late Devonian.
(2) Both of the ore-hosting black shales and laminated pyrite ores of the
Dajiangping deposit formed in an anoxic-euxinic bottom water
environment of a fault-bounded basin.
(3) Late Devonian SEDEX deposits in South China formed in a passive
margin setting, in response to the northward migration of the
Cathaysia Block from Gondwana.
Acknowledgements
This study was supported by National Natural Science Foundation of
China (41673057). We would like to express our thanks to geologists of
the Yunfu Guangye Pyrite Group Limited, especially Junqiao Tu and
Yicheng Wang for their help during our field trip in the Dajiangping
deposit. Great thanks are extended to Jianfeng Gao from Institute of
Geochemistry, Chinese Academy of Sciences for his assistance with the
analyses of elemental compositions and zircon U-Pb dating.
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