Trace Element Composition Of Pyrite Research Articles

Application of pyrite trace-metal and S and Ni isotope signatures to distinguish sulfate- versus iron-driven anaerobic oxidation of methane

The formation of authigenic pyrite in marine sediments involves multiple reactions between ferrous iron (Fe2+) and hydrogen sulfide (H2S). Ferrous iron is commonly provided through the reductive dissolution of Fe-(oxyhydr)oxides by organic matter (i.e., dissimilatory Fe reduction), dissolved sulfide (i.e., abiotic Fe reduction) or methane (i.e., Fe-AOM), whereas sulfide is supplied by organoclastic sulfate reduction (OSR) or sulfate-driven anaerobic oxidation of methane (SD-AOM). Since Rayleigh-type distillation operates widely in sediments of gas-hydrate-bearing zones, sulfur and nickel isotope compositions (i.e., δ34S and δ60Ni) cannot readily distinguish OSR- from SD-AOM-associated pyrite. However, these microbial pathways may yield different patterns of trace-element enrichment in pyrite. To better understand the linkage of trace-element patterns to specific microbial pathways (i.e., Fe reduction, Fe-AOM, OSR and SD-AOM), and to evaluate the use of S and Ni isotopic signatures as tracers for pyrite formation pathways in methane-rich sediments, we report pyrite-associated trace element and δ34S and δ60Ni isotope analyses of sediments from a gas hydrate borehole (Site GMGS4-SC-03) from the Shenhu area, Pearl River Mouth Basin, South China Sea. Pyrite formed in conjunction with Fe- and/or SD-AOM exhibits abundant framboidal overgrowths and extremely high δ34S (up to +142.8‰) and δ60Ni (up to +2.72‰), representing the highest stable S and Ni isotopic compositions of pyrite reported to date. These pyrite morphologies are enriched in Co and Ni, which may be a diagnostic signature of an SD-AOM pathway. By contrast, OSR-associated pyrite is enriched in Cu and Zn due to OSR-induced release of trace elements from decaying organic matter. In addition, the relationship of As to Cu and/or Zn can distinguish microbial Fe/Mn reduction from Fe/Mn-AOM, because microbial Fe/Mn reduction releases trace elements from both Fe/Mn-(oxyhydr)oxides (i.e., As) and organic matter (i.e., Cu and Zn), whereas Fe/Mn-AOM only releases trace elements from Fe/Mn-(oxyhydr)oxides. Furthermore, an observed covariation between As and either Co or Ni in most pyrite with high δ34S, indicates that this pyrite captured both As released during Fe/Mn-AOM and Co and Ni from SD-AOM. Thus, the high nickel isotope values measured in this study likely dominantly reflect release of isotopically heavy Ni from Fe- and Mn-(oxyhydr)oxides. Our results demonstrate that the trace-element composition of pyrite in gas-hydrate-bearing sediments can record the geochemical signature of the dominant microbial processes.

Ore-forming material sources of the Pakbeng gold deposit, Laos: Evidence from fluid inclusions, H-O-S isotopes, and trace elements

The Pakbeng gold deposit, located at the junction of the eastern Tethys and western Pacific tectonic domains, is part of the Phôngsali-Luang Prabang-Sayaboury polymetallic metallogenic belt. Its gold ore bodies are predominantly governed by fault structures, being vein-like and short-axis-veined in shape. The Pakbeng gold deposit primarily exhibits two types of mineralized alterations: the quartz-vein type and the schistositized altered rock type. The ore bodies are primarily distributed within cataclastic granites and altered andesite plutons, near their contact zone. The ore-forming process can be divided into four stages: quartz + rutile + pyrite (stage I), quartz + pyrite + coarse-grained arsenopyrite (stage II), quartz + polymetallic sulfides + native gold (stage III), and calcite + quartz (stage IV). Native gold primarily occurs as invisible gold in the quartz and pyrite of stages I and II, and as enclosed, intergranular, and interstitial gold within the quartz, pyrite, and other metal sulfides of stage III. The ore-forming materials of the Pakbeng gold deposit primarily originate from plagioclase granites and altered andesites, as indicated by investigations of gold-bearing quartz fluid inclusions, hydrogen and oxygen isotopes, the trace-element composition of pyrite, and in situ sulfur isotopes. The sulfur in the deposit is mainly derived from metamorphic sources, supplemented by late magmatic sulfur. The ore-forming fluids in the deposit were dominated by metamorphic fluids in the early stage, with magmatic fluids participating in the late stage. While ascending, the temperature of the ore-forming fluids decreased due to fluid boiling and mixing, but their salinity increased slightly. The ore-forming fluids exhibited a consistent decrease in homogenization temperatures from stages I to IV, with salinity initially increasing and then decreasing. This suggests that the ore-forming fluids are low-temperature, medium to low-salinity and low-density fluids.

Trace element compositions of pyrite and stibnite: implications for the genesis of antimony mineralization in the Yangla Cu skarn deposit, Northwestern Yunnan, China

Trace element compositions of pyrite and stibnite: implications for the genesis of antimony mineralization in the Yangla Cu skarn deposit, Northwestern Yunnan, China

Geology and Geochemistry of K‐feldspar Veins in Lamprophyre at the Zhenyuan Gold Deposit, Yunnan, Southwest China: Implications for Gold Mineralization

AbstractLamprophyres typically appear in hydrothermal gold deposits. The relationship between lamprophyres and gold deposits is investigated widely. Some researchers suggest that the emplacement of lamprophyres triggers gold mineralization, whereas others hypothesize that the formation of lamprophyres increases the fertility of mantle sources and ore‐forming fluids. K‐feldspar veins, with ages between those of lamprophyres and gold deposits, appear in lamprophyres in Zhenyuan. Therefore, K‐feldspar veins are ideal for investigating the relationship between lamprophyres and gold deposits. Phlogopite in K‐feldspar veins has lower Mg#, Ni, and Cr contents and higher TiO2, Li, Ba, Sr, Sc, Zr, Nb, and Cs contents than phlogopite in lamprophyres. The in‐situ Sr isotopic values of apatites (0.7063–0.7066) in K‐feldspar veins are within the range for apatites (0.7064–0.7078) from lamprophyres. High large‐ion lithophile element concentrations and low Nb and Ta concentrations in phlogopite from lamprophyres, in addition to high (87Sr/86Sr)i values of apatite (0.7064–0.7078), indicate that the magma parental to these phlogopite and apatite crystals is derived from an enriched mantle. K‐feldspar veins are genetically correlated with lamprophyres, whereas sulfide mineral assemblage and trace element compositions of pyrite in K‐feldspar veins suggest that K‐feldspar veins in lamprophyres are not directly related to gold mineralization of the Zhenyuan deposit.

Microfabrics, In Situ Trace Element Compositions of Pyrite, and the Sulfur Isotope Chemistry of Sulfides from the Xitieshan Pb-Zn Deposit, Qinghai Province, Northwest China: Analysis and Implications

The Xitieshan deposit, located in the central segment of the northern margin of the Qaidam Basin, is among the largest massive Pb-Zn sulfide deposits in China. This deposit, along with its ore-bearing rock series known as the Tanjianshan Group, underwent greenschist facies metamorphism due to subsequent orogeny. We investigated the in situ sulfur isotopes of sulfides with different occurrences to define the origin of ore-forming fluids. The δ34S values of sulfides from stratiform ores, massive ores in schist, stockwork ores in marble, schist and discolored altered rocks that constitute a typical double-mineralization structure range from −5.3‰ to +5.6‰ and from −1.7‰ to +32‰, respectively, indicating distinct biological and thermochemical reductions in seawater sulfates. These are similar to the sulfur isotopic characteristics of VSHMS deposits. Pyrite, whose LA-ICP-MS trace element compositions can provide significant information about metallogenic evolution and deposit genesis, is ubiquitous throughout the whole mineralization process. In these stratiform, massive and stockwork ores, three pyrite types were identified: colloform pyrite (Py0), fine-grained anhedral spongy pyrite (Py1) and coarse-grained euhedral pyrite (Py2). The contents of most metallogenic elements, such as Cu, Pb, Zn, Ag, Mo, Mn and Sn, decrease from Py0 to Py2 with the enhancement of metamorphic recrystallization. This suggests that the expelled elements appear as inclusions in primitive pyrite, contributing to the precipitation of new sulfide phases, such as sphalerite and galena. Orogenic metamorphism played an important role in controlling further Pb-Zn enrichment of the Xitieshan deposit. Moreover, there is another mineralization type, primarily occurring as sulfide veins in the undeformed Formation C siltstones of the Tanjianshan Group, which also crosscut early-formed sulfides, showing close-to-zero S isotopic compositions. In this mineralization type, pyrite (Py3) displays high Se/Tl (>10) and Co/Ni (>2.2) ratios, both indicating a minor superimposed post-orogenic magmatic–hydrothermal event.

Mineral exploration using trace element composition of pyrite grains from till: A case study from the Petäjäselkä Au occurrence, northern Finland

Geochemical anomalies and indicator mineral studies in glacial sediments are commonly used to define mineral exploration targets in glaciated areas. Trace element composition of sediment-hosted heavy minerals, such as pyrite and chalcopyrite, can be potentially used to fingerprint mineral deposits. This study presents results from trace element compositions of pyrite in the heavy mineral concentrates of till and mineralized bedrock samples from the orogenic gold ore occurrences in the Petäjäselkä area, Central Lapland belt, northern Finland.The trace element contents of pyrite grains were evaluated by using a robust compositional data analysis workflow, including symmetric pivot coordinates and robust principal component analysis (PCA). Four different pyrite textures (A-D) were identified from the gold ore occurrences. Compositional data analysis showed that the heavy mineral pyrite correlated with Pyrite D in the ore occurrence and confirmed the discrimination power of pyrite in the heavy mineral grains as a tool for source characterization of transported sedimentary material. The study also discusses the difficulties of finding suitable grains for the LA-ICP-MS, highlighting the importance of proper heavy mineral grain recovery procedures and the factors of oxidization and weathering processes influencing the geochemical compositions of the pyrite grains.

Trace Element Composition of Pyrite from Selected Black Shale and Chert Exposures in the Central Belt of Peninsular Malaysia: Implications for Mineral Exploration

Sedimentary and hydrothermal pyrites contained in selected Malaysian black shale and cherts have been analysed using laser ablation inductively coupled plasma (LA ICP-MS) and electron probe microanalysis (EPMA) at the University of Tasmania, Australia. This study shows that gold is concentrated in sedimentary and hydrothermal pyrite in the Middle Permian to Late Triassic black shales and Devonian cherts. According to LA ICP-MS analysis, gold contents in pyrite varied from 0.5 to 0.8 ppm Au in the Permo-Triassic black shale and between 0.2 and 0.8 ppm Au in the Devonian cherts. The lowest level of gold (0.3 ppm Au) was observed in the Permo-Triassic black shale that crops out at the Selinsing gold mine. In the Permo-Triassic period, the selenium contents display one peak (average range: 63.4–103.4 ppm Se) that is far from any gold deposit and one lowest point (average: 5.3 ppm Se) at the Selinsing gold deposit. In the Devonian period, the selenium content in sedimentary pyrite shows a peak (72.6–243.8 ppm Se) in the cherts. EPMA and LA ICP-MS data show consistent Se content variation in the Devonian and Permo-Triassic periods. Using selenium as a proxy for atmospheric oxygenation, the lowest level of Se content in the Permo-Triassic period is believed to decrease atmospheric oxygenation, as recorded in sedimentary pyrite found in black shale from the Selinsing gold deposit. The two peaks of selenium contents are interpreted as periods of increased atmospheric oxygenation. From an exploration perspective, the concentration of gold in sedimentary pyrites makes them sources for gold in the central sedimentary basin of Peninsular Malaysia. Therefore, the two maximum levels of Se and gold content during Permo-Triassic and Devonian times correspond to two stratigraphic levels of potential for orogenic gold mineralisation in the district. The EPMA data show significant values of Co over Ni in pyrite from the Gua Musang, Semantan, and Karak formation black shales, indicating a volcanic contribution of Co during the formation of sedimentary pyrite. Based on the current study’s findings, gold exploration should not be restricted to areas in and around the Selinsing gold mine, Buffalo Reef, Penjom mine, Tersang mine, and Bukit Koman mine but can be extended to BRSZ Units 1 and 2, Gua Musang, and Karak formations in the central belt of Peninsular Malaysia.

U-Pb Dating, Lead Isotopes, and Trace Element Composition of Pyrite Hosted in Black Shale and Magmatic Rocks, Malaysia: Implications for Orogenic Gold Mineralization and Exploration

Several orogenic/sediment-hosted gold deposits are widely distributed in the Central Belt of Peninsular Malaysia. This study combines U-Pb dating with the isotope composition of lead as well as gold content in ore and magmatic rock-hosted pyrite. It aims to investigate the age of gold mineralization and possibly establish a link between gold mineralization and magmatic intrusion in the district. The results show that the S-type magmatic rocks yield crystallisation ages ranging from 204.1 ± 4.7 Ma to 223 ± 3.2 Ma with low magnetic susceptibility measurements below 3 × 10−3 SI unit. These ages fit within the 200–250 Ma Pb-Pb model age of the Pb isotopic composition of K-feldspars. Pyrite trace element mapping has shown that gold and lead show zoning patterns occurring at the same time in pyrite. The Pb isotope composition of the cores of pyrite grains indicate that the approximate model age of gold mineralization is 200 Ma. This age is close to 197–199 Ma (Early Jurassic), previously determined by K-Ar dating of sericite which was interpreted to be the age of gold mineralization. In this study, gold content varies up to 793 ppb in the analysed magmatic rock-hosted pyrites, indicative of a likely magmatic contribution to gold mineralization.

Genesis and prospecting significance of the Buziwannan gold-polymetallic ore deposit in the West Kunlun Orogen Belt, China: Constraints from mineral geochemistry and in situ S–Pb isotope analyses of sulfides

The Buziwannan gold-polymetallic deposit is located in Northwest China's West Kunlun Orogen Belt (WKOB). There are two metallogenic stages that have been identified: skarn and hydrothermal. In this research study, in situ mineral geochemistry and sulfur–lead isotopes are used to precisely constrain the genesis and ore-forming process.Pyrite is the most dominant sulfide, and four types have been identified. Py0 is a sedimentary euhedral crystal; Py1 is a subhedral grain occurring in skarn ores, and coexists with Po1, Apy1, Ccp1 and Gn1; Py2, which coexists with Apy2, Po2 and Ccp2, is a subhedral to irregular crystal; and Py3 is a colloform crystal. Gn2 is the most recent sulfide. Magnetite and Ccp1 LA–ICMPS analyses indicate a skarn origin. Py0 and Py1 have the highest Co/Ni ratios and Ni contents, respectively, and Au has positive correlations with Pb, Ag and As, according to the trace element compositions of pyrite (LA–ICPMS). With the exception of four spots, most pyrites have Au (0.01–30.23 ppm) and As (1.47–15,709 ppm) concentrations below the Au saturation line, indicating that the majority of gold is present as lattice bound Au+. Py3 has clearly higher Sb contents indicating that Sb-rich fluids were added.The δ34S values of sulfides show that the sedimentary Py0 and skarn sulfides have the highest and lowest δ34S values of +13.30 to +14.67 ‰ and +4.48 to +7.77 ‰, respectively, and other sulfides possess δ34S values that fall between the two members, indicating a mixed source of magmatic and sedimentary. The lead isotope values also indicate that the sulfides from the hydrothermal stage have a mixed Pb source of magmatic and sedimentary.The skarn ores are spatially and genetically related to the Triassic granodiorite, indicating a Triassic age for ore formation. The Triassic magmatic intrusions hold the potential for future gold deposit exploration in the WKOB.

Trace-element composition of pyrite in the Baoshan Cu–Mo–Pb–Zn deposit, southern Hunan Province, China: Insights into the ore genesis

The southern Hunan Province in southeastern China is the site of extensive Mesozoic magmatism and the formation of associated polymetallic deposits, among which, the studies for Cu–Pb–Zn mineralization are relatively rare compared with the W–Sn polymetallic deposits. In this study, the Baoshan skarn Cu–Mo–Pb–Zn deposit is investigated as a typical example with sulfide ores hosted in the distal carbonate. By presenting in situ laser ablation–inductively coupled plasma–mass spectrometry trace-element compositions of the ubiquitous pyrite, as well as arsenopyrite, sphalerite, and chalcopyrite, from carbonate strata, granodiorite porphyry, early disseminated and massive Cu–Mo–Pb–Zn ores, and late brecciated Cu ores, we aim to elucidate the relationships between the proximal skarn Cu–Mo and the distal carbonate hosted Pb–Zn mineralization in this deposit. Together with the geological characteristics, our results suggest that the pyrite trace-element compositions can be used to infer the precipitation environment. The pyrite from the early disseminated and massive Cu–Mo–Pb–Zn ores has high As/Sb and low Ni/As ratios, indicating that the ore-forming fluids and materials directly separated from the granodioritic magmas have dominated the sulfide mineralization in this stage, with minor contributions from the carbonate; the Pb–Zn mineralization is most likely precipitated from the same hydrothermal system with the early Cu–Mo mineralization, despite of the distal locations. On the contrary, the pyrite from the late brecciated Cu ores is characterized by low As/Sb and high Ni/As ratios, indicating that the ore-bearing fluids have circulated through the basements beneath the mining area, which should have also leached the ore-forming materials for the subsequent Cu mineralization. In addition to the direct contributions from the magmas and carbonate strata, this study emphasizes the substantial contributions from the basements to the Cu–Mo–Pb–Zn mineralization at Baoshan. This also indicates that the deep locations or the adjacent areas with well-developed fractures can be the potential targets for further exploration.

Phase separation and fluid mixing revealed by trace element signatures in pyrite from porphyry systems

Porphyry deposits host various trace elements in economic amounts, but the hydrothermal processes causing their fractionation and enrichment are still not fully understood, but vital to target the most prospective mineralisation. We present the first micro-analytical study on the trace element composition of pyrite from the Koloula Cu-Au porphyry in the young and thin (<25 km) Solomon Islands arc. A statistical evaluation of the trace element data of pyrite indicates that mineral inclusions obscure the chemical signature of the mineralisation processes. The filtered pyrite data, from which the inclusions were excluded, correlate with variations in temperature and salinity, as defined by fluid inclusions from several alteration zones. Trace element ratios in pyrite show systematic variations with fluid temperature and salinity (Co/Ni, Se/Te), phase separation (Co/Ni, Co/As) and mixing of magmatic fluids and meteoric waters (Se/Ge). The mineralisation in the potassic alteration zone was controlled by the formation of a hypersaline liquid (Co/As > 1, Co/Ni > 50) from a magma-derived fluid (Se/Ge ~ 100) at lithostatic pressure conditions and temperatures of up to 700 °C (Se/Te > 50). This was followed by a transition to hydrostatic pressure conditions due to open-fracture continuity towards the paleo-surface, marking the onset of boiling in the chlorite-sericite to sericitic alteration zone (Co/As < 1), where minor proportions of meteoric water were involved (Se/Ge < 100). The shallowest part of the mineralisation is controlled by lower temperature (<300 °C, Se/Te < 50) vapour-rich fluids (Co/As < 1) that condensed into meteoric waters in an epithermal transition zone (Co/Ni < 50, Se/Ge < 100). Trace element systematics in pyrite from progressive alteration zones therefore preserve the time-space evolution of porphyry (-epithermal) systems in young and thin oceanic island arcs.

Genesis of the Mianhuakeng uranium deposit, South China: Constraints from in-situ sulfur isotopes and trace elements of pyrite

The Mianhuakeng U deposit is the largest granite-type deposit in South China, ore bodies commonly occur in fault zones of Youdong and Changjiang geanites. However, the genesis and mineralization processes remain poorly understood. The main metal sulfide in this deposit is pyrite, which can be classified into four stages based on its mineral assemblages and textures: pre-ore stage (Py Ⅰ), early-syn-ore stage (Py Ⅱa), syn-ore stage (Py Ⅱb), and post-ore stage (Py Ⅲ). In this study, we present in-situ sulfur isotopic and trace element compositions of different stages of pyrite, obtained using laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-(MC)-ICP-MS), to reveal the evolution of the ore-forming fluid and ore genesis. The δ34S values of pyrite ranged from −18.5‰ to −6.8‰, with peaks at −8‰ to −10‰, similar to the δ34S values of the host rock. The large range variations in δ34S values result from the mixing of ore-forming fluid and meteoric water. The U and W contents of all pyrite showed a strong positive linear relationship with their concentrations, indicating that the host granites were likely the main source of metal for U mineralization. From the pre-ore to the syn-ore stage, the contents of Co and Ni decreased, and those of Cu and As increased, while Ni/Se ratios decreased, suggesting that the temperature and oxygen fugacity of the ore-forming fluids decreased. There are significant vertical variations in δ34S values and trace element compositions of pyrite in the ore body of the Mianhuakeng deposit. From the bottom to the top, the oxygen fugacity and temperature of the ore-forming fluids increased and decreased, respectively. These results, combined with published data, suggest that the initial hydrothermal fluids likely originated from meteoric water and mixed with mantle-derived CO2 circulating within host granites and leached U and other metals (e.g., W) to form ore-forming fluids. As the temperature, oxygen fugacity, and pressure decreased, the hydrothermal solution outgassed and released CO2 while U6+ was reduced to U4+ and precipitated as pitchblende, resulting in U mineralization. Thus, the combined effect of temperature, pressure, and oxygen fugacity controlled U mineralization in the Mianhuakeng deposit. In particular, change in oxygen fugacity acted as an important factor affecting uranium mineralization.

Geology, U-Pb geochronology and stable isotope geochemistry of the Heihaibei gold deposit in the southern part of the Eastern Kunlun Orogenic Belt, China: A granitic intrusion-related gold deposit?

The Heihaibei gold deposit is a newly discovered gold deposit in the southern part of the Eastern Kunlun Orogenic Belt. Its most distinctive features are that the gold mineralization is hosted in monzogranite, and that the presence of pre-ore (possibly syn-ore) monzogranite and post-ore gabbro allows to constrain the mineralization’s formation age. Zircons from the monzogranites yield U-Pb ages of 454 ± 3 Ma, while zircons separated from the gabbro dikes cutting the monzogranites and gold mineralized body yield U-Pb ages of 439 ± 3 Ma, which is interpreted to be the minimum age of the Au mineralizing event. Combined with the regional geological background, we proposed that the Heihaibei Au mineralization occurred during the subduction stage of the Early Paleozoic Proto-Tethys ocean.The ore assemblage is dominated by pyrite, arsenopyrite and native gold. The hydrothermal alteration that has led to the peculiar enrichment of Au is not systematically distributed and displays no clear concentric zoning pattern. The main mineralization formed during three stages: the K-feldspar-quartz-pyrite (Py1)-arsenopyrite-sericite-epidote stage (I), the quartz-pyrite (Py2)-native gold-chlorite stage (Ⅱ), and the quartz-carbonate stage (III). The main gold mineralization occurred during stage Ⅱ. Fluid inclusion homogenization temperature and salinities decrease from stage I (Th., 268–412 °C; W., 6.87–16.63 wt% NaCl equiv.) to stage Ⅱ (Th., 183–288 °C; W., 3.69–14.84 wt% NaCl equiv.). The δ18O and δD values (δ18OH2O = 4.9 to 9.7‰; δDV-SMOW = -84.1‰ to −81.1‰) of quartz samples from stage I and stage Ⅱ are comparable to a magmatic-hydrothermal ore-forming fluid that possibly underwent fluid-rock interaction with the Nachitai Group metamorphic rocks during the early ore-forming stage. The relatively uniform δ34S values (δ34SV-CDT = 7.7 to 8.5‰) are slightly elevated compared to magmatic δ34S values, but could be derived from a magma if a significant crustal melt component is present. Moreover, the δ34S values are within the S isotopic composition range of a granitic reservoir, suggesting that they are probably inherited from the Heihaibei monzogranites. The Pb and Hf isotope compositions imply a close genetic association between the gold mineralization and granitic magmatism, which are both the products of the mixing of crustal and mantle sources. The trace element compositions of pyrite provide additional evidence that the gold mineralization in the Heihaibei deposit was related to the magmatism. Compared with the typical characteristics of orogenic gold and intrusion-related gold systems (IRGS) deposits, the Heihaibei gold deposit may instead be classified as a granitic intrusion-related gold deposit.

Mineralogy, Fluid Inclusions, and Isotopic Study of the Kargah Cu-Pb Polymetallic Vein-Type Deposit, Kohistan Island Arc, Northern Pakistan: Implication for Ore Genesis

The Kargah Cu-Pb polymetallic deposit is a newly discovered ore deposit from the Gilgit-Baltistan region, located in the Kohistan Island Arc, northern Pakistan. However, this area is poorly researched on the ore genesis, and its origin and the evolution of its magmatic-hydrothermal system remain unclear. Three stages of mineralization were identified, including quartz-pyrite, quartz-sulfide, and carbonate representing early, middle, and late stages, respectively. The major ore minerals are pyrite, chalcopyrite, galena, and zincian tetrahedrite with minor native silver, and native gold mainly distributed in pyrite. Here, we present a systematic study on ore geology, hydrothermal alterations, trace element composition of pyrite, fluid inclusions, and isotopes (S and Pb) characteristics to gain insights into the nature of the ore-forming fluids, types of unknown deposits, and hydrothermal fluid evolution. The high Co/Ni ratio (1.3–16.4) and Co content (average 1201 ppm), the low Mo/Ni ratio (0.43–0.94) and Mo contents (average 108 ppm) of both Py-I and Py-II suggest a mafic source for the mineralization. The Au-Ni plots, Co-As-Ni correlation, and the δ34S values range from −2.8 to 6.4‰ (average of 3.4‰) indicating the affiliation of the mineralization with a mantle-derived magmatic-hydrothermal provenance. The Pb isotope data showing the narrow variations in 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values suggest a single lead source from crustal-derived materials. The microthermometry data suggest that the dominant mechanisms are fluid boiling and mixing for mineral precipitation at temperatures ranging between 155 and 555 °C, and represent an intrusion-related magmatic-hydrothermal environment for the Kargah Cu-Pb polymetallic deposit.

Evidence of fluid evolution of Baoshan Cu−Pb−Zn polymetallic deposit: Constraints from in-situ sulfur isotope and trace element compositions of pyrite

In-situ LA-ICP-MS and S isotopes of pyrite from the Baoshan Cu polymetallic deposit were conducted to investigate the ore-forming process and the enrichment mechanism of elements. Three generations of pyrite (Py I, Py II, and Py III) in the skarn-type ores and pyrite in the carbonate-hosted sulfide ores from central, western, and northern (C_Py, W_Py, and N_Py) mining districts are selected for comparison. Compared with Py I and Py III, the contents of most elements in Py II are apparently higher. The As and Se contents are high within a wide range and are decoupled in the growth band of the C_Py. The highest As, Se, and Pb contents were found in W_Py and N_Py. These results indicate the drastic changes in the temperature and fluid mixing during the mineralization. The occurrence of fluctuation and change in temperature and f(O2) was triggered by intermittent pulses of magmatic-hydrothermal fluids, mixing with meteoric water, and water−rock interactions. The sulfur isotopes of all species of pyrite indicated the magmatic source. The change in the f(O2) conditions caused slight differences in the sulfur isotope compositions. Consequently, a metallogenic model was proposed to explain the ore-forming processes.

Fingerprinting fluid evolution by trace elements in epithermal pyrite, Vatukoula Au-Te deposit, Fiji

Tellurium (Te) is an important element for green technologies, including thin film photovoltaic panels. Stagnating supply caused by its by-product dependency together with an increasing demand will likely lead to a shortage in the near future. Pyrite may represent a potential target for the direct recovery of Te, since the concentrations of Te can reach weight percent levels under specific, but poorly constrained hydrothermal conditions. The Vatukoula (formerly Emperor) epithermal Au-Te deposit is currently mined for Au and ~ 75% are recovered from Au-tellurides and pyrite. Tellurium has been processed in the past, but is now sent to tailings despite of concentrations reaching 1.4 wt. % in pyrite, which makes this system a natural laboratory to investigate key Te enrichment processes.The epithermal mineralisation at Vatukoula consists of an early low-grade disseminated host-rock and a later high-grade Ag-Au-Te vein-type stage. Pyrite occurs in both ore-types with diverse As contents including concentrations < 0.5 wt. % in pure pyrite, 0.5 to 13 wt. % in low-As and 23 to 43 wt. % in high-As pyrite, reflecting increasing fluid As with system evolution towards the high-grade mineralisation. Tellurium contents in pyrite increase from pure pyrite (up to 220 ppm) to low-As pyrite (up to 1.4 wt. %), but with a decrease towards high-As pyrite (up to 185 ppm). This is a yet unknown relation, since trace element incorporation in pyrite is usually facilitated by increasing As. Instead, the presented results suggest a threshold between 13 and 23 wt. % As, above which the incorporation of Te and related elements (e.g., Ag, Au) may be less favourable. Mineral stabilities, trace element ratios (e.g., Sb/Pb, Tl/Pb) and LA-ICP-MS mapping of texturally distinct pyrite indicate that fluid boiling was a critical process for the Ag, Au and Te enrichment in the Vatukoula epithermal system. Fluid sulphidation states decreased with proceeding evolution of the epithermal system from initially intermediate- to late low-sulphidation conditions, which led to the diverse chemical character of pyrite. Early pure pyrite primarily formed as a replacement product of magnetite in the altered host rocks, whereas low- and high-As pyrite precipitated in the direct vicinity of Ag-Au-telluride veins, from which most of the As, Ag, Te and Au hosted in pyrite was derived from. Consequently, the trace element composition of pyrite allows the fingerprinting of the fluid evolution of Te-rich ore-forming systems like Vatukoula, Fiji.

LA-ICPMS trace elements of pyrite from the super-large Dulong Sn-Zn polymetallic deposit, southeastern Yunnan, China

滇东南马关都龙是一个以锡锌为主，共-伴生铟、铜、铅、钨、铁、银等多种元素的锡锌多金属超大型矿床。虽然前人从矿物学、矿床地球化学、年代学等不同角度开展了较多的研究，该矿床锡锌多金属矿化为燕山晚期岩浆热液活动的产物已是不争的事实，但关于该矿床是否存在热水沉积作用及其与锡锌多金属成矿作用的关系依然存在较大争议。本文选取都龙矿区广泛存在的黄铁矿作为主要研究对象，在矿相学基础上利用LA-ICPMS对不同阶段黄铁矿的微量元素组成开展了系统的研究。野外及显微鉴定结果表明，矿区存在四种类型（期次）的黄铁矿，即：鲕状黄铁矿Py1；穿切或交代Py1的细脉状黄铁矿Py2；与闪锌矿等硫化物共生的自形黄铁矿Py3；包裹早期黄铁矿或闪锌矿等硫化物的他形黄铁矿Py4。LA-ICPMS分析结果表明，该矿床黄铁矿中富集多种微量元素，其中Co、Ni、As、Ge等元素以类质同象的形式存在黄铁矿晶格中，而其余元素多以显微矿物包体形式赋存于黄铁矿中。上述四期黄铁矿微量元素组成存在较大差别，Py1相对富集Zn和As，而其余微量元素含量较低，Co与Ni含量较低，Co/Ni比值远低于1.00，其微量元素组成与典型沉积作用形成黄铁矿基本一致；Py2与Py1具有相似的微量元素组成特征，其Co/Ni比值接近Py1变化范围；Py3和Py4除富集Zn、As外，Mn、Co、Ni、Cu、Sb、Pb、Bi元素含量也相对较高，其Co/Ni比值相对较高，多大于1，与典型岩浆热液型黄铁矿微量元素组成相似，而与沉积型黄铁矿差异明显。结合各阶段黄铁矿产出地质特征，对比不同类型黄铁矿微量元素组成，本研究认为：Py1鲕状黄铁矿为热水沉积作用形成；Py2为Py1变质改造形成的细脉状黄铁矿，其微量元素继承了Py1；Py3为岩浆热液活动形成的自形黄铁矿；Py4为岩浆热液活动晚期形成的他形黄铁矿，Ag和Bi组成作为区分不同成因类型黄铁矿的化学指标的潜力。矿区早期沉积作用形成鲕状黄铁矿过程可能为后期成矿作用提供了部分硫源及少量Zn等成矿物质，海西-印支期区域变质改造作用对矿区成矿作用影响不大，而燕山晚期岩浆热液活动才是矿区锡多金属大规模成矿作用的主导因素。;The Dulong Sn-Zn polymetallic deposit, located in the southeastern Yunnan Province, is a super-large Sn-Zn polymetallic deposit with by-products of In, Cu, Pb, W, Fe, Ag, etc. Many studies on mineralogy, ore deposit geochemistry and chronology have been carried out on this deposit, confirming a genetical relationship of its Sn-Zn mineralization to the Late Yanshanian magmatic activity. However, whether the deposit underwent exhalative sedimentary Sn-Zn mineralization is still controversial. Based on detailed petrographic observation, the LA-ICPMS trace element compositions of pyrite that widely occur in the Dulong deposit are investigated systematically in this paper. Field and microscopic observations show that four types of pyrite have been identified in Dulong, including the oolitic pyrite (Py1), fine vein pyrite (Py2) crosscutting and/or replacing Py1, euhedral pyrite (Py3) coexisting with sphalerite and other sulfides, anhedral pyrite (Py4) enclosing early generated pyrite and sphalerite. LA-ICPMS analysis results suggest that pyrite is enriched in Co, Ni, As and Ge, which are mainly incorporated into the pyrite lattice in the form of isomorphism. Other elements occur mostly as mineral micro-inclusions in pyrite. The trace element compositions of the four types' pyrite exhibit significant difference from each other: Py1 is enriched in Zn and As but depleted in Co, Ni and Cu with low Co/Ni ratios (<1.0), which share similar features with typical sedimentary pyrite; Py2 is similar in its trace element compositions and Co/Ni ratios to those in Py1; while Py3 and Py4 have elevated Zn, As, Mn, Co, Ni, Cu, Sb, Pb and Bi contents with high Co/Ni ratios (mostly >1.0), which is consistent with that of euhedral pyrite formed by magmatic-hydrothermal activity rather than sedimentary pyrite. Comparing with the trace element compositions of pyrite in different types, we consider that Py1 is of sedimentary origin, Py2 that inherits the trace element features of Py1 is formed by metamorphic reworking of Py1, while Py3 and Py4 are formed by late magmatic-hydrothermal activity. Ag and Bi in pyrite display potential probobilities as a geochemical indicator to distinguish pyrite of different genetic types. Oolitic pyrite formed in the depositional diagenesis stage may provide some sulfur and a small amount of Zn for the later Sn-Zn mineralization. The regional metamorphic reworking in the Hercynian to Indosinian displays a limited effect on the Sn-Zn mineralization, while Late Yanshanian magmatic-hydrothermal activity is the controlling factor for the formation of the super-large scale Dulong Sn-Zn polymetallic deposit.

Paragenetic relationships between low- and high-grade gold mineralization in the Cripple Creek Au-Te deposit, Colorado: Trace element studies of pyrite

The Cripple Creek alkaline igneous rock-related low-sulfidation epithermal gold telluride deposit is hosted in a 10 km wide Oligocene alkaline volcanic diatreme in Proterozoic rocks. Periods of phreatic eruptions and progressively more mafic alkaline magma emplacement created the diatreme and breccias that host the gold ore, followed by breccia pipe creation, and later by the emplacement of phonolite and later lamprophyre dikes throughout the diatreme. Pervasive potassic alteration affected much of the diatreme, and is spatially related to the late-stage veins containing native gold and precious metal tellurides. Previous studies have mainly focused on the high-grade gold veins primarily located toward the center of the diatreme. The current study evaluates the mineralogy and paragenesis of low-grade mineralization in the currently mined Wild Horse Extension (WHEX), Globe Hill, and Schist Island pits, and the Galena Embayment along the margin of the diatreme next to the WHEX pit, as well as high-grade mineralization in the WHEX and Cresson pits. Given the variable paragenesis of mineralizing stages in different locations in the Cripple Creek deposit, a simplified three stage paragenesis (stages 1, 2, and 3) is recognized here involving low- and high-grade gold mineralization.Scanning electron microscopy, electron microprobe, and laser ablation-inductively coupled plasma-mass spectrometry analyses are used to compare the trace element compositions of pyrite in low- and high-grade gold mineralization. These analyses reveal a complex trace element pattern with variability in Ag, As, Au, Co, Ni, Sb, and Te in the rims, cores, and zones (area between the core and the rim) of stages 2 (Py2) and 3 pyrite (Py3) and spatially between the pits currently being mined. Trace element concentrations in stage 1 pyrite (Py1) are lower than those in Py2 and Py3 and the patterns are uniform. Trace elements reside within the lattice structure of pyrite and as micro- and nano-inclusions (e.g., up to 48,220 ppm As, 6983 ppm Co, 12,250 ppm Ni, and 10,860 ppm Sb). The trace element patterns from the final stage of pyrite growth in high-grade gold telluride veins indicate enrichment in Ag, As, Au, Cu, Pb, Sb, and Te.The paragenesis and compositional zoning of pyrite associated with high-grade ore contrast with those associated with pyrite from low-grade ore, which preceded the formation of high-grade gold telluride veins. This suggests that metallic mineralization occurred in multiple episodes and that low-grade ore did not form from the same hydrothermal fluids that precipitated the high-grade ore. Early pyrite formed under passive, non-boiling conditions, followed by a transition to vigorous boiling in Py2 and Py3, ending with non-boiling conditions recorded in the Au and As-rich rims of Py3. This enrichment in Au and As on the rims of pyrite is consistent with other alkaline igneous rock-related epithermal Au deposits, as are the concentrations of trace elements throughout the pyrite grains. The presence of As, Ag, Co, Cu, Mo, Ni, Sb, Te, and Tl in pyrite are considered vectors to high-grade Au ore in the Cripple Creek deposit.

Deconvolution of the composition of fine-grained pyrite in sedimentary matrix by regression of time-resolved LA-ICP-MS data

Abstract Pyrite is a common mineral in sedimentary rocks and is the major host for many chalcophile trace elements utilized as important tracers of the evolution of the ancient hydrosphere. Measurement of trace element composition of pyrite in sedimentary rocks is challenging due to fine-grain size and intergrowth with silicate matrix and other sulfide minerals. In this contribution, we describe a method for calculation of trace element composition of sedimentary pyrite from time-resolved LA-ICP-MS data. The method involves an analysis of both pyrite and pyrite-free sediment matrix, segmentation of LA-ICP-MS spectra, normalization to total, regression analysis of dependencies between the elements, and calculation of normalized composition of the mineral. Sulfur is chosen as an explanatory variable, relative to which all regressions are calculated. The S content value used for calculation of element concentrations from the regressions is calculated from the total, eliminating the need for independent constraints. The algorithm allows efficient measurement of concentrations of multiple chalcophile trace elements in pyrite in a wide range of samples, including quantification of detection limits and uncertainties while excluding operator bias. The data suggest that the main sources of uncertainties in pyrite composition are sample heterogeneity and counting statistics for elements of low abundance. The analysis of regression data of time-resolved LA-ICP-MS measurements could provide new insights into the geochemistry of the sedimentary rocks and minerals. It allows quantification of ratios of elements that do not have reference material available (such as Hg) and provides estimates on the content of non-sulfidic Fe in the silicate matrix. Regression analysis of the mixed LA-ICP-MS signal could be a powerful technique for deconvolution of phase compositions in complex multicomponent samples.

Genesis of the Bangbu gold deposit in the southern Tibet: Evidenced from in-situ sulfur isotopes and trace element compositions of pyrite

The Bangbu orogenic gold deposit in the North Himalaya of the southern Tibet contains more than 40 t Au at an average grade of 7.0 g/t. In this deposits, gold-bearing quartz veins were controlled by nearly E-trending Qusong-Cuogu-Zhemulang shear zone and occurred within the secondary faults which crosscut Late Triassic greenschist- facies rocks. To further understand the sulfur source and ore-forming process, we have conducted a compressive study of in-situ SIMS sulfur isotopes and LA-ICP-MS trace element compositions of two stages of pyrite at Bangbu. Early-stage pyrite (Py1) is coarse-grained (mostly 0.2–2 mm) and euhedral, and has gold concentrations of less than 0.3–54 ppm (mean of 20 ppm) and δ34S values of 1.6–5.1‰ (mean of 3.2‰). Late-stage pyrite (Py2) is generally fine-grained (mostly <50 μm to 1 mm) and subhedral to anhedral, and has gold concentrations of 3.6–115 ppm (mean of 30 ppm) and δ34S values of 0.9–5.2‰ (mean of 2.7‰). Gold occurs mainly as invisible refractory within Py1 and Py2, and to a lesser extent as native gold within quartz, pyrite, arsenopyrite and sphalerite. Sulfur for Bangbu gold mineralization was probably sourced from the Greater Himalayan crystalline complex. Release of ore-forming fluids was likely related to amphibolite-facies metamorphism during ~50–45 Ma. Ore fluids deposited Au-rich pyrite during early and late mineralization stage and precipitation of native gold was probably related to fluid boiling and/or remobilization of invisible gold within pyrite.