Trace element geochemistry of pyrite is widely used to monitor ore-forming processes of various types of deposits, but its application to skarn mineral systems is not well constrained due to the multi-stage nature and complex associated mineral assemblages for skarn-type pyrite. The Jiguanzui skarn Au-Cu deposit in the Middle-Lower Yangtze River Valley Metallogenic Belt (Eastern China) is characterized by abundant pyrite that formed in the main-ore (Py1), late-ore (Py2), and post-ore (Py3) stages, which makes it ideal for unraveling skarn ore-fluid evolution. Specifically, Py1 is composed of quartz–pyrite (Py1a), quartz–calcite–pyrite (Py1b), quartz–sericite–pyrite (Py1c), quartz–chlorite±epidote–pyrite (Py1d), and quartz–K-feldspar–pyrite (Py1e), among which Py1a is the most widespread. Py2 comprises calcite–pyrite (Py2a) and calcite–K-feldspar–pyrite (Py2b), and Py3 comprise bird’s-eye pyrite (Py3a) and fingerprint-like pyrite (Py3b). The varying Co/Ni ratios (mostly >2) and coexistence with hydrothermal minerals (quartz, calcite, K-feldspar, chlorite, and epidote) reveal the hydrothermal origin of Py1 and Py2. The Co/Ni (0.97–7.30), Cu/Ni (8.94–186), and As/Ni (0.80–11.7) ratios, and the high trace-element contents indicate that Py3a may have been genetically linked to the waning magmatic-hydrothermal system and increasing meteoric fluid influx. Py1 generally has higher Co-Ni-Se but lower Zn-As-Mo contents than Py2. Py1 in the orebodies also has higher Cu-Au contents than Py2, consistent with the formation of Py1 during the main Au-Cu ore stage. During the ore-fluid evolution, meteoric water input and abundant galena formation in the late-ore calcite-sulfide stage may have controlled the decreasing Se-Co-Ni contents from Py1 to Py2, while the fluid cooling and pH rise (caused by acidic fluid-carbonate rock reactions) may have increased the As-Zn-Mo contents from Py1 to Py2. Py1a in the orebodies has higher As-Ag-Te, but lower Co-Ni-Se contents than Py1a in the wallrocks. The decompression and phase separation (fluid boiling) by extensive hydraulic fracturing may have caused the higher temperature, pH, and fO2 for the Py1a-forming fluids in the orebodies (than those in the wallrocks). Such fluid physicochemical differences may have been the main controlling factor on trace element spatial variations of Py1a. More importantly, the spatial variation of these trace elements in Py1a provides insights for using pyrite trace element geochemistry in skarn mineral exploration.

The origin of stratabound deposits in the Middle-Lower Yangtze River Valley Metallogenic Belt (MLYRB), Eastern China, is the subject of considerable debate. The Xinqiao Cu-Fe-Au deposit in the Tongling ore district is a typical stratabound ore body characterized by multi-stage magnetite. A total of six generations of magnetite have been identified. Mt1 is commonly replaced by porous Mt2, and both are commonly trapped in the core of Mt3, which is characterized by both core-rim textures and oscillatory zoning. Porous Mt4 commonly truncates the oscillatory zoning of Mt3, and Mt5 is characterized by 120° triple junction texture. Mt1 to Mt5 are commonly replaced by pyrite that coexists with quartz, whereas Mt6, with a fine-grained foliated and needle-like texture, commonly cuts the early pyrite as veins and is replaced by pyrite that coexists with calcite. The geochemistry of the magnetite suggests that they are hydrothermal in origin. The microporosity of Mt2 and Mt4 magnetite, their sharp contacts with Mt1 and Mt3, and lower trace-element contents (e.g., Si, Ca, Mg, and Ti) than Mt1 and Mt3 suggest that they formed via coupled dissolution and reprecipitation of the precursor Mt1 and Mt3 magnetite, respectively. This was likely caused by high-salinity fluids derived from intensive water-rock interaction between the magmatic-hydrothermal fluids associated with the Jitou stock and Late Permian metalliferous black shales. The 120° triple junction texture of Mt5 suggests it is the result of fluid-assisted recrystallization, whereas Mt6 formed by replacement of hematite as a result of fracturing. The geochemistry of the magnetite suggests that the temperature increased from Mt2 to Mt3 and implies that there were multiple pulses of fluids from a magmatic-hydrothermal system. Therefore, we propose that the Xinqiao stratiform mineralization was genetically associated with multiple influxes of magmatic hydrothermal fluids derived from the Early Cretaceous Jitou stock. This study demonstrates that detailed texture examination and in situ trace-elements analysis under robust geological and petrographic frameworks can effectively constrain the mineralization processes and ore genesis.

Quartz is one of the most abundant minerals. Used in a variety of materials, it preserves geological history and reflects alteration conditions. Data were collected (>2400 data points) from more than 40 ore deposits to understand its internal texture and geochemistry. Cathodoluminescence imaging is a technique for examining the internal texture of quartz that may reveal information about the crystal’s origin and evolution. The dominant trace elements in quartz lattice are Al, P, Li, Ti, Ge, K, and Na. These, combined with internal texture, can distinguish quartz from different origins and can differentiate between different types of ore deposits, as each type of ore deposit has its own unique CL characteristics. Therefore, Al did not correlate with cathodoluminescence (CL) in epithermal Au-Sb-Hg, Carlin-type Au, epithermal Ag, or shale-hosted Zn deposits. Epithermal base metal and porphyry-Cu-type deposits were intermediate, and Mississippi-Valley-type, epithermal Au-Ag, and porphyry Cu-Mo deposits were characterized for Al correlation with CL. Furthermore, Gigerwald, Rohdenhaus, and Westland deposits had Li/Al ratios less than one, suggesting that H (as hydroxyl substituting for oxygen) completed the charge. However, trace elements (i.e., Ge, Sb, Ti, and Al), sector zoning, and resorption surfaces were vital parameters to differentiate between magmatic and hydrothermal quartz. Additionally, titanium and aluminum were the most important trace elements. Their values could be used to differentiate between different quartz types. Among them, hydrothermal and pegmatitic quartz were characterized by lower temperatures and Ti concentrations. Rhyolitic quartz was characterized by the lowest Al, the highest temperatures, and lower Al/Ti ratios. Aluminum, Li, and H were most important in hydrothermal and metamorphic quartz, but magmatic quartz was generally enriched with Ti.

The Zhengchong gold deposit is located in the central segment of the Jiangnan Orogen in northeastern Hunan Province, South China. The host rocks of this deposit are the Neoproterozoic slates of the Lengjiaxi Group and granodiorite. The structures in the Zhengchong gold deposit are dominated by NE-trending reverse faults, which control the gold-bearing veins. The orebody consists of NE-trending laminated quartz veins and NW-trending quartz veins. The alteration styles include silicification, carbonatization, sulfidation, sericitization and chloritization. The Zhengchong gold mineralization can be divided into four stages: Quartz-pyrite (stage I), quartz-pyrite-arsenopyrite (stage II), quartz-polysulfide (stage III) and quartz-carbonate (stage IV). Three generations of hydrothermal pyrite were identified: Disseminated euhedral to subhedral cubes in altered wall-rock (PyI), euhedral to subhedral cubes inter-grown with arsenopyrite and tetrahedrite in quartz veins and wall-rock (PyII), and euhedral cubes with microinclusions (native gold, galena, sphalerite, chalcopyrite, tetrahedrite, and pyrrhotite) or metasomatic textures in sulfide-rich veins or veinlets (PyIII). PyII and PyIII are arsenian pyrite and represent the main Au-bearing minerals. PyI records the lowest concentrations of Au; PyII and PyIII record similar amounts of Au, Cu, Pb, Zn, and Bi, but PyIII is more enriched in Co, Ni, Te, and Se. The substitution of As, Se and Te for S and that of Co and Ni for Fe occurs by direct-ion exchange. Invisible gold is uniformly distributed within the arsenian pyrite, and visible gold fills microfractures in PyII or occurs as inclusions in PyIII. Co, Ni, Cu exhibit positive correlations with Au and a negative correlation between Au + Cu + Co + Ni and Fe reflect that Fe vacancies may have been a major cause of the precipitation of invisible Au and other metal elements in pyrite structure. There are systematic trace element differences between the three generations of pyrite (PyI, PyII, PyIII). The more Co, Ni and Se, Te substitution that occurred for Fe and S, respectively, the greater the increase in the Co/Ni ratio (<1) and the decrease in the Se/Te ratio (<10) in stage III, indicating that a more reduced, lower-temperature metamorphic hydrothermal fluid was present in stage III.