Tracing mineralization history from the compositional textures of sulfide association: A case study of the Zhenzigou stratiform Zn-Pb deposit, NE China
Graphical abstract
Mineral record of the fluid property and evolution of the Zhenzigou Zn-Pb deposit. A primary fluid with origin of marine sedimentary process is overprinted by a subsequent metamorphism as well as a magmatic hydrothermal fluid with significant trace element associations; elements from two distinct fluids are fractionationed and incorporated in different sulfide phases.
Introduction
Globally, stratiform Pb-Zn deposits supply significant non-ferrous metal resources (Carne and Cathro, 1982). Such sulfide-rich and massive sulfide Pb-Zn-Cu-Ag-Au deposits commonly form sheet-like layers, which are interbedded with chert, shale, carbonate, and barite (Gustafson and Williams, 1981). Examples include those in the Selwyn Basin of Canada, the Copperbelt of central Africa, McArthur Basin in Northern Australia, the North Korean Jiande deposit, and several deposits in the Qingchengzi Orefield such as the Zhenzigou and Diannan deposits, NE China (Okita and Shanks, 1992, Goodfellow, 1987, McClay, 1991, Turner, 1992, Zhang and Yang, 1988).
The Qingchengzi Orefield is one of the major Pb-Zn polymetallic ore fields in China. More than fifty years of exploration have resulted in the discovery of over ten Pb-Zn deposits, one silver deposit and four gold deposits containing ca. 1.5 Mt of Pb and Zn metals, 2000 ton of Ag metal, and 100 ton of Au metal (103GT, 1976). A large body of research has been carried out discussing aspects of the geology, geochronology, and geochemistry of Zn-Pb mineralization in this area, aiming to determine the ore genesis. Despite such extensive work, controversies still persist on a genetic model. At an early stage both a magmatic-hydrothermal origin (103GT, 1976) and a metamorphic origin (Zhang, 1984) were proposed for the mineralizing fluids. Subsequently, a Proterozoic sea floor exhalation model (Wang et al., 1994) and a sedimentation-metamorphism-hydrothermal reworking model (Jiang, 1987, Jiang, 1988, Jiang and Wei, 1989, Ding et al., 1992) were considered to account for the mineralization. More recently, the role of Mesozoic hydrothermal fluids in mineralization has been highlighted (Liu and Ai, 2002, Xue et al., 2003). The development of in-situ isotopic analysis has been further advancing the understanding of the mineralization age (Yu et al., 2009, Duan et al., 2014, Ma et al., 2016, Xu et al., 2020) and the sources of metals and sulphur (Yu et al., 2009, Duan et al., 2017) of the Qingchengzi Orefield, providing vital knowledge to constrain the genesis of the ore field. In particular, what the findings consistently suggest is that the Pb-Zn mineralization system in the Qingchengzi Orefield, including the Zhenzigou Zn-Pb deposit, represents a distal hydrothermal mineralization type related to the Triassic magmatic activity (Duan et al., 2017). In this study, we applied a novel Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS) elemental mapping technique on an association of sulfide minerals (galena, sphalerite, pyrite, and arsenopyrite) from the Zhenzigou stratiform Zn-Pb deposit, in combination with in-situ spot analysis data, to reveal their elemental composition and distribution pattern. The compositional texture of the sulfide association carries crucial information regarding the nature and sequence of multi-stage mineralization events that are responsible for their precipitation.
The LA-ICPMS elemental mapping technique has been extensively applied on individual sulfide minerals such as sphalerite (e.g. Cave et al., 2020) and pyrite (e.g. Large et al., 2009, Zhou et al., 2019) for the discussion of ore genesis. The trace element maps of sulfide association have also been reported but not frequently, including for example, an arsenopyrite-pyrite association from an orogenic gold deposit in Australia (Cook et al., 2013), a galena-sphalerite-pyrite-chalcopyrite association from Pb-Zn deposits (George et al., 2015), and a sphalerite-pyrite-chalcopyrite association from the Sulitjelma Cu-Zn ore field (Lockington et al., 2014). Our examination of the full range of coexisting sulphide minerals (galena-sphalerite-pyrite-arsenopyrite) for the Zhenzigou Zn-Pb deposit allows a comprehensive understanding of the mineralization history in the stratiform Pb-Zn ore system. The trace element maps of the sulfide association provide key in-situ evidence reinforcing a sedimentation-metamorphism-magmatic-hydrothermal reworking model for the Zhenzigou Zn-Pb mineralization. Furthermore, by integrating the results of LA-ICPMS spot analysis, we present a full consideration of the metal partitioning behaviors among the coexisting sulfide minerals in the proposed model, which enables detailed characterization of metal paragenesis. Ultimately, our findings provide an insight into the behaviors of precious metals such as Au and energy critical metals such as In and Sn, among coexisting sulfide minerals. The approaches that we applied for this case study are applicable to address the relationship of fluid evolution and metal partitioning in a broad range of ore deposits, and the case study of the Zhenzigou Zn-Pb deposit can provides a suitable example for studying many other stratiform Pb-Zn deposits worldwide.
Section snippets
Regional geology
The Qingchengzi Orefield is located in the eastern Liaoning Province and it is tectonically situated in the Paleoproterozoic Liaodong Rift Zone (Fig. 1). This paleo rift is located on the northeastern segment of the North China Craton and extends for ca. 700 km trending NNE. It is bounded by the Tanlu fault to the west and extends to the Sea of Japan to the east. The development of the Liaodong Rift is the product of a series of tectonic events during the Palaeoproterozoic, including crustal
Deposit geology
The stratiform Zhenzigou Zn-Pb deposit is located in the east of the Qingchengzi Orefield (Fig. 2). The orebodies occur as conformable layers and lenses in interbedded fractures which are strictly restrained to the folded bedding (Fig. 3). Two stratigraphic intervals host the majority of ore bodies: the lower Dashiqiao Formation composed of graphite-bearing marble and the lower Langzishan Formation which is a graphite-bearing marble interbedded with amphibolite, and biotite schist bands.
Sampling and analysis
In order to distinguish the role of different fluids in assisting grain-scale redistribution of metals, we selected ore samples from the modified near-layer mineralization, which is the most common type of mineralization in the Zhenzigou Zn-Pb deposit. On the basis of microscopy observation, we further chose an association of sulfide phases of sphalerite-galena-arsenopyrite-pyrite from an individual thin section that represents the main mineralization stage. Due to the limited occurrence of
Mineral paragenesis
In our study of the Zhenzigou stratiform Zn-Pb deposit, evidence of macro- and micro-observation of ore texture demonstrates evident paragenesis of the sulfide association. The sharp grain boundaries between a euhedral arsenopyrite and a subhedral sphalerite, and between a euhedral pyrite and a subhedral sphalerite (Fig. 4f, g), suggest that sphalerite was precipitated at a later stage than euhedral pyrite and arsenopyrite. The penetration of mutual boundaries indicates that the fluids that
Multi-stage enrichment process
Pyrite is the most abundant of all sulfide minerals. It is commonly found in mineral deposits, in igneous and sedimentary rocks and their metamorphic equivalents. In addition, pyrite present in any given environment may have formed through more than one process at one or more separate times, and post-depositional effects may alter the composition of pyrite (e.g. Large et al., 2009). In the Zhenzigou Zn-Pb deposit, the irregular and rounded pyrite core (Py 0, Fig. 7) revealed in the trace
Conclusions and remarks
The compositional textures of a pyrite-sphalerite-galena-arsenopyrite association in the Zhenzigou stratiform Zn-Pb deposit suggest that three distinct fluids were responsible for the mineralization (Fig. 11). The earliest episode of fluids was released in an exhalative tectonic setting initiating at ca. 2052 Ma, resulting from de-watering of the Dashiqiao Formation. The fluid is low-temperature (<150 °C) and sedimentary in origin, corresponding to the formation of an early pyrite core (Py0).
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
This research was funded by the National Natural Science Foundation of China (grant no. 41702090), the National Key R&D Program of China (Grant no. 2016YFC0600109), and National Key R&D Program of China (2016YFC0600108-03). Part of the article was written during the first author’s postdoctoral fellowship funded by the Geological Survey of Ireland. The analyses were carried out as a part of collaborative project between the Institute of Geology and Geophysics, the Chinese Academy of Sciences,
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Mineralogical distribution and genetic aspects of cobalt at the active Fåvne and Loki's Castle seafloor massive sulfide deposits, Arctic Mid-Ocean Ridges
2023, Ore Geology ReviewsCitation Excerpt :Helium was used as carrier gas in the ablation cell and Ar and N2 were added at the ICP-MS interface to enhance signal sensitivity. Sets of parallel and overlapping line rasters were ablated sequentially across rectangular map areas and the laser beam size, fluence, repetition frequency, scan speed and dwell time were set according to the target sulfide grain sizes in each map (Zhou et al., 2020). The external standards MASS-1 and UQAC were measured at the beginning and at the end of each run to correct for mass bias and instrument drift.
Trace element compositions of galena in an MVT deposit from the Sichuan-Yunnan-Guizhou metallogenic province, SW China: Constraints from LA-ICP-MS spot analysis and elemental mapping
2022, Ore Geology ReviewsCitation Excerpt :Generally, Sb, Bi, Ag, Se, Tl, and Te are preferentially incorporated into galena, while Cd, Fe, Mn, Ge, Ga, Cu, and In are primarily concentrated in coexisting sphalerite (George et al., 2016, 2017; Wei et al., 2021; Zhou et al., 2020). The element partitioning between galena and associated sulfides has been attributed to intrinsic factors of the focused trace element and the host base metal sulfides (e.g., valence state, ionic radius, the availability of this element in the hydrothermal fluid, and the maximum capacity of the host mineral lattice), rather than external factors, such as physicochemical parameters (temperature, pressure, and redox conditions) during sulfide precipitation and the sources of base metals (George et al., 2016, 2017; Wei et al., 2021; Zhou et al., 2020). Trace element signatures of base metal sulfide minerals, especially sphalerite, have been widely employed to identify the genetic types of ore deposits (Frenzel et al., 2016; Yang et al., 2021; Ye et al., 2011).