Trace Element Content Of Pyrite Research Articles

A synproportionation-controlled hybrid hydrothermal mineralization system in the Okinawa Trough

Hybrid hydrothermal systems, in which both water-rock reactions and magmatic fluids contribute to sulfide mineralization, have recently been reported in some submarine arcs and mature back-arc basins. Owing to their high mineralization efficiency, hybrid hydrothermal systems have attracted significant attention from geologists. This study provides first clues for the identification of a novel hybrid hydrothermal system (synproportionation-controlled instead of the more common disproportionation-controlled) in the Tangyin field, Southern Okinawa Trough. The studied samples are native sulfur-type precipitates, primarily composed of elemental sulfur with minor sulfide disseminations. The distinct crystallization conditions and S isotope compositions of elemental sulfur and sulfide disseminations indicate their different genesis. The S in sulfide disseminations (δ34S = −2.7 to 1.6 ‰) is derived from water-rock reaction and subsequently influenced by fluid phase separation, which is further demonstrated by the trace element contents of pyrite (low Tl/Pb, Sb/Pb, Te/As, Te/Sb ratios). In contrast, the elemental sulfur (δ34S = 3.9 to 4.3 ‰) is formed by the synproportionation of magmatic SO2 and hydrothermal H2S from the boiled liquid. A simple two-component mixing calculation indicated that the contributions of the water-rock reactions and magmatic fluids to the Tangyin hydrothermal system were approximately equal. The higher temperature (> 350 °C) and oxygen fugacity conditions may be the key factors for the development of a synproportionation-controlled hybrid hydrothermal system in the Tangyin field. Hydrothermal systems in back-arc basins exhibit higher sulfide accumulation rates than those in mid-ocean ridges; this may be attributed to the prevalence of hybrid hydrothermal vents in back-arc settings.

Big data analytics for mining geochemistry of gold mineralization: The Gandy gold deposit, the Toroud-Chah Shirin (TCS) belt, north Iran

Due to the complexity of the gold element, the mineralogical and geochemical investigations are significant to trace the gold behavior in sedimentary, metamorphic, magmatic, and post-magmatic processes and to identify the physicochemical conditions (i.e., pH, Eh, temperature, pressure) of concentration in the ore bodies. The trace elements may be concentrated as the primary or secondary haloes in endogenic and exogenic deposits with multi-formational types. Identification and separation of multi-formational geochemical halos associated with ore bodies have been the most significant challenge of gold deposits. Mining Geochemistry and Big Data analytics have become essential to identify the multi-formational geochemical anomalies for gold exploration in the Commonwealth of Independent States (CIS) countries. During the last three decades, pattern recognition techniques such as Bayesian and Geochemical spectra have been used to determine mineralogical and geochemical types of multi-formational anomalies. Big Data analytics has been used for integrating multi-type geoscience data and pattern recognition techniques to assess geochemical anomalies. In this study, Big Data analytics were used to generate the mineralogical and geochemical type (MGT) quantitative models based on the Bayesian, geochemical spectrum and hybrid methods for investigating the distribution of trace element contents of pyrite, galena, and sphalerite in the Gandy Gold Deposit, the Toroud-Chah Shirin (TCS) belt, north Iran. The multi-formational geochemical anomalies associated with gold mineralization in the Gandy deposit indicated a multi-MGT anomaly superposition, which is a combination of two MGTs: Au + Polymetals and Au + sulfide. The results of this study demonstrated a new perspective on the distribution of geochemical anomalies and the multi-MGT geochemical modeling for gold exploration in the TCS belt. Consequently, the instigated approach is greatly conceivable and applicable to reveal contrasting near-ore multi-formational geochemical haloes for gold exploration in many other metallogenic provinces.

Effects of sulfate reduction processes on the trace element geochemistry of sedimentary pyrite in modern seep environments

Although it has been suggested that the trace element patterns of sedimentary pyrite can be affected by early diagenesis, detailed studies on modern marine environments addressing this hypothesis are scarce. Organoclastic sulfate reduction (OSR) and sulfate-driven anaerobic oxidation of methane (SD-AOM) are the dominant sulfate reduction processes in organic-rich and methane-rich marine sediments, and commonly result in the formation of authigenic pyrite. To better understand how OSR and SD-AOM affect the trace element geochemistry of pyrite, we applied laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) to analyze trace element contents of pyrite from two methane-seep sites (DH-CL11 and HS148) of the South China Sea. The trace element data are complemented by the measurement of iron isotope compositions of authigenic pyrite. This new data set, supplemented by published sulfur isotope data, improves our understanding of the diagenetic processes during early diagenetic pyrite formation. High δ56Fe and δ34S values of pyrite reflect the dominance of SD-AOM within sulfate-methane transition zones (SMTZs) at both sites (i.e., from 705 to 767 cm below seafloor at site DH-CL11 and from 490 to 690 cm below seafloor at site HS148), whereas pyrite from shallow depth characterized by low δ56Fe values points to early OSR processes. Within the SMTZs, pyrite exhibits highly variable but overall high manganese (Mn) contents (12 to 732 mg/kg at site DH-CL11; 12 to 1145 mg/kg at site HS148), compared to OSR-derived pyrite from shallow depth. Similar to this pattern, pyrite formed at the SMTZ shows higher lead (Pb), zinc (Zn), copper (Cu), and vanadium (V) contents than pyrite formed at shallower depths above the SMTZ. Enrichments of these metals in pyrite forming at the SMTZ are best explained by enhanced reductive dissolution of iron and manganese (oxyhydr)oxides under sulfidic conditions induced by SD-AOM, and subsequent trace element incorporation into pyrite. Arsenic (As), molybdenum (Mo), and antimony (Sb) distributions in pyrite vary between the two study sites. Pyrite from shallow depth of site HS148 has high contents of all three elements, indicating effective immobilization of dissolved As, Mo, and Sb during pronounced OSR. In contrast, apparently less intense OSR at shallow depth of site DH-CL11 allowed for more dissolved As, Mo, and Sb to diffuse downward to greater depth, resulting in the enrichments of these elements in pyrite formed at or close to the SMTZ. Positive correlations between As and cobalt (Co), and between As and nickel (Ni) typify pyrite derived from both OSR and SD-AOM for both study sites, and As-rich pyrite from site DH-CL11 is characterized by a distinctly high Co/Ni ratio. Both patterns suggest that the presence of As affects the uptake of Co and Ni into pyrite. Our study documents that pyrite element contents in methane-rich environments are significantly influenced by different sulfate reduction processes during early diagenesis, allowing the differentiation of OSR-derived pyrite from SD-AOM-derived pyrite by means of trace element geochemistry.

Enrichment of rare earth elements in the early Cambrian Zhijin phosphorite deposit, SW China: Evidence from francolite micro-petrography and geochemistry

The Zhijin phosphorite deposit is a giant early Cambrian rare earth element (REE) deposit, with particular enrichment in heavy REEs, and is of high economic significance. The REEs of the deposit occur almost entirely in apatite, which, on the basis of petrographic characteristics, can be divided into francolite grains (90%), amorphous apatite, and phosphate fossils. In this paper, we report an investigation into francolite grains in different types of phosphorite from ore sections of the Zhijin deposit. Detailed petrographic and transmission electron microscopy observations reveal that the francolite grains are composed of nano-apatite crystals measuring 120–160 nm long. Trace-element contents of pyrite and whole-rock geochemical indicators (such as Cr/Zr and V/Ni ratios and Th/U–Co/Ni plots) suggest that the Zhijin phosphorite formed in an anoxic hydrothermal sedimentary environment. However, the negative Ce/Ce* and Eu/Eu* anomalies indicate that the diagenetic environment of the francolite grains was oxidic. Different diagenetic redox environments and the presence of transportation fractures in francolite grains identified under back-scattered electron imaging reveal that the francolite grains underwent prolonged abrasion and transportation in seawater before sedimentation. Petrographic observations and laser ablation–mass spectrometry element surface scanning analyses indicate that the REEs are uniformly distributed in nano-apatite in isomorphic form, and no nano-inclusions or REE minerals were found, implying that late mineralization was not the cause of REE enrichment. The higher (La/Yb)N ratios of francolite grains relative to seawater indicate that the francolite grains captured abundant REEs during the early diagenetic stage. We infer that prolonged exposure to seawater and the high specific surface area of francolite grains are the key factors that led to the enrichment in REEs. Combining the timing of the metallogenic epoch (543 Ma), Sr–Nd isotopic data, and the Y/Ho ratio, which is close to those of modern seawater, indicates that the REEs were sourced from paleo-seawater. Paleogeographic information suggests that during the early Cambrian, extensive continental collisions caused great amounts of continental weathering products to enter the paleo-ocean, leading to the production of abundant amounts of hydrothermal–sedimentary phosphorus and REEs in shallow seas, thus forming an ideal sedimentary environment for generating the REE resources of the Zhijin phosphorite deposit.

Mineralogical and geochemical features of pyrite nodules of sulfide turbidites from the Talgan Cu–Zn massive sulfide deposit (South Urals)

Pyrite nodules were found in thin-layered sulfide ores localized at the flanks of the Talgan Cu‒Zn massive sulfide deposit (South Urals). The nodules consist of (1) an inner core of microgranular pyrite with inclusions of authigenic sulfides and host rock minerals, (2) an intermediate zone of anhedral and subhedral pyrite metacrystals, (3) an outer zone formed by parallel subhedral pyrite crystals and (4) dioctahedral chlorite rimming the pyrite crystals of zone 3. Each zone exhibits specific trace element association, which is identified using LA ICP-MS micromapping. The trace element content of pyrite significantly (by 13 orders of magnitude) decreases in a range of microgranular pyrite of the core an- and subhedral pyrite crystals of the intermediate zone subhedral pyrite crystals of the outer zone (average values, ppm): 131069 Zn, 241001783 Pb, 1323134 As, 10271.81 Co, 4564 Ni, 39038 Ag, 0.10.01 Au, 550.6 Te, 9.80.6 Bi. The subhedral pyrite crystals of the outer zone are enriched (ppm, up to) in Cu (8367), Sb (1627) and Mn (734) relative to microgranular pyrite of the core. The extremely high trace element contents are related to the inclusions of authigenic chalcopyrite, sphalerite, fahlore, gold and silver minerals. The host rock components of the nodules include quartz, calcite, chlorite, illite and REE minerals. The ore clasts of distal sulfide turbidites mixed with hyaloclastites, which were altered during dia- and anadiagenesis, were the source of ore material for the nodules.

Distinguishing Ore Deposit Type and Barren Sedimentary Pyrite Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Trace Element Data and Statistical Analysis of Large Data Sets

Faced with ongoing depletion of near-surface ore deposits, geologists are increasingly required to explore for deep deposits or those lying beneath surface cover. The result is increased drilling costs and a need to maximize the value of the drill hole samples collected. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis of pyrite is one tool that is showing promise in deep exploration. Since the trace element content of pyrite approximates the composition of the fluid from which it precipitated and the crystallization mechanism, the trace element characteristics can be used to predict the type of deposit with which a pyritic sample is associated. This possibility, however, is complicated by overlapping trace element abundances for many deposit types. The solution lies with simultaneous comparison of multiple trace elements through rigorous statistical analysis. Specifically, we used LA-ICP-MS pyrite trace element data and Random Forests, an ensemble machine learning supervised classifier, to distinguish barren sedimentary pyrite and five ore deposit categories: iron oxide copper-gold (IOCG), orogenic Au, porphyry Cu, sedimentary exhalative (SEDEX), and volcanic-hosted massive sulfide (VHMS) deposits. The preferred classifier utilizes in situ Co, Ni, Cu, Zn, As, Mo, Ag, Sb, Te, Tl, and Pb measurements to train the Random Forests. Testing of the Random Forests classifier using additional data from the same deposits and sedimentary basins (test data set) yielded an overall accuracy of 91.4% (94.9% for IOCG, 78.8% for orogenic Au, 81.1% for porphyry Cu, 93.6% for SEDEX, 97.2% for sedimentary pyrite, 91.8% for VHMS). Similarly, testing of the Random Forests classifier using data from deposits and sedimentary basins that did not have analyses in the training data set yielded an overall accuracy of 88.0% (81.4% for orogenic Au, 95.5% for SEDEX, 90.0% for sedimentary pyrite, 73.9% for VHMS; insufficient data was available to perform a blind test on porphyry Cu and IOCG). The performance of the classifier was further improved by instituting criteria (at least 40% of total votes from the Random Forests needed for a conclusive identification) to remove uncertain or inconclusive classifications, increasing the classifier’s accuracy to 94.5% for the test data (94.6% for IOCG, 85.8% for orogenic Au, 87.8% for porphyry Cu, 95.4% for SEDEX, 98.5% for sedimentary pyrite, 94.6% for VHMS) and 93.9% for the blind test data (85.5% for orogenic Au, 96.9% for SEDEX, 96.7% for sedimentary pyrite, 84.6% for VHMS). The Random Forests classification models for pyrite trace element data can be used as a predictive modeling tool in greenfield terrains by providing an accurate indication of ore deposit type. This advance will assist mineral explorers by allowing early implementation of predictive ore deposit models when prospecting for ore deposits. Furthermore, the ability of the classifier to accurately identify pyrite of sedimentary origin will allow researchers interested in paleoenvironmental conditions of ancient oceans to effectively screen prospective samples that are affected by a hydrothermal overprint.

In-situ sulfur isotope and trace element analysis of pyrite from the Xiwang uranium ore deposit in South China: Implication for ore genesis

The Xiwang uranium ore deposit is one large-scale granite-hosted U deposit in the Xiazhuang U orefield in South China. Uranium orebodies occur as thin veins along the fracture zones within the Maofeng granitic pluton. Pyrite is the main sulfide mineral in the ores. Textural observation suggested that formation of hydrothermal pyrite can be divided into three stages: pre-mineralization stage pyrite (Py I), mineralization stage pyrite (Py II) accompanying with U-minerals, post-mineralization stage pyrite (Py III). In this study, in-situ sulfur isotopic compositions and trace element contents of pyrite from different stages were analyzed by laser ablation (MC-) ICP-MS methods. The δ34S values of Py I vary from −28.5‰ to −12.0‰ with an average value of −18.4‰, Py II from −15.9‰ to −10.2‰ with an average value of −12.5‰ and Py III from −22.3‰ to −14.8‰ with an average value of −19.4‰. The variations of sulfur isotopic compositions of pyrites were caused by the changes of oxygen fugacity of hydrothermal fluids. The hydrothermal fluids at the pre-mineralization stage had relatively higher oxygen fugacity (ƒO2 > 10−34). The decreasing of oxygen fugacity (to 10−36–10−35) at the mineralization stage might promote the precipitation of uraninite. The mineralization was terminated as the increasing of oxygen fugacity of hydrothermal fluids back to 10−35. Pyrite from the Xiwang deposit generally contains high U contents (up to ten thousand ppm) and very low Th contents (mostly <0.1 ppm). U and W contents in pyrite show good positive linear relationship, indicating that both U and W came from the hosting granite. Py II shows higher Mo and V contents than Py I, also suggesting more reduced environment at the U mineralization stage. Such high oxygen fugacity for initial hydrothermal fluids supports that the ore-forming fluids should be originated from meteoric water. The circulating meteoric water can leach U and other metals from the hosting granite to form U-rich hydrothermal fluids. In fracture zones and under reduced conditions, U6+ in the fluids can be reduced to precipitate uraninite (UO2). Thus, U-rich granites, circuiting meteoric water and reduced agents are pre-requisites for the formation of the granite-hosted U deposits in South China.

Whole rock and discrete pyrite geochemistry as complementary tracers of ancient ocean chemistry: An example from the Neoproterozoic Doushantuo Formation, China

The trace element content of pyrite is a recently developed proxy for metal abundance in paleo-oceans. Previous studies have shown that the results broadly match those of whole rock studies through geologic time. However, no detailed study has evaluated the more traditional proxies for ocean chemistry for comparison to pyrite trace element data from the same samples. In this study we compare pyrite trace element data from 14 samples from the Wuhe section of the Ediacaran-age Doushantuo Formation, south China, measured by laser ablation inductively coupled plasma mass spectrometry with new and existing whole rock trace element concentrations; total organic carbon; Fe mineral speciation; S isotope ratios; and pyrite textural relationships. This approach allows for comparison of data for individual trace elements within the broader environmental context defined by the other chemical parameters. The results for discrete pyrite analyses show that several chalcophile and siderophile elements (Ag, Sb, Se, Pb, Cd, Te, Bi, Mo, Ni, and Au) vary among the samples with patterns that mirror those of the independent whole rock data. A comparison with existing databases for sedimentary and hydrothermal pyrite allows us to discriminate between signatures of changing ocean conditions and those of known hydrothermal sources. In the case of the Wuhe samples, the observed patterns for trace element variation point to primary marine controls rather than higher temperature processes. Specifically, our new data are consistent with previous arguments for pulses of redox sensitive trace elements interpreted to be due to marine oxygenation against a backdrop of mostly O2-poor conditions in the Ediacaran ocean—with important implications for the availability of bioessential elements. The agreement between the pyrite and whole rock data supports the use of trace element content of pyrite as a tracer of ocean chemistry in ways that complement existing approaches, while also opening additional windows of opportunity. For example, unlike the potential vulnerability of whole rock data to secondary alteration, the pyrite record may survive greenschist facies metamorphism. Furthermore, early-formed pyrite can be identified through textural relationships as a proxy of primary marine chemistry even in the presence of hydrothermal overprints on whole rock chemistry via secondary fluids. Finally, pyrite analyses may allow for the possibility of more quantitative interpretations of the ancient ocean once the elemental partitioning between the mineral and host fluids are better constrained. Collectively, these advances can greatly increase the number of basins that may be investigated for early ocean chemistry, especially those of Precambrian age.

Simultaneous determination of sulfur isotopes and trace elements in pyrite with a NanoSIMS 50L

In this paper, we established simultaneous and quantitative analyses of 34S/32S ratios and trace element contents of pyrite using nanometer-scale secondary ion mass spectrometry (NanoSIMS).

Trace Element Content of Pyrite from the Kapai Slate, St. Ives Gold District, Western Australia

The Kapai Slate is a continuous, pyrite-rich carbonaceous shale horizon within the St. Ives Au district that is spatially related to high-grade Au mineralization. In situ laser ablation-inductively coupled mass spectrometry (LA-ICPMS) trace element analyses, in situ sensitive high resolution ion microprobe, stable isotope (SHRIMP-SI) S isotope analyses, and optical microscopy pyrite texture analyses were used to examine the different pyrite types in the Kapai Slate and Au deposits. These data were also used to confirm that the trace element signature of sedimentary pyrite can be preserved in rocks that underwent upper to mid-greenschist facies metamorphism and significant hydrothermal overprint. The data were further utilized to gain a more detailed understanding of the ocean conditions during deposition of the Kapai Slate and determine whether some of the Au and S in the St. Ives district could have been sourced from the Kapai Slate. Seven different types of pyrite were identified: fine-grained sedimentary pyrite (Py 1 ), nodular sedimentary pyrite (Py 2 ), remobilized sedimentary pyrite (Py 3 ), coarse-grained, inclusions poor late pyrite (Py 4 ), inclusion-rich magnetite series pyrite (Py 5 ), ore stage pyrite (Py 6 ), and pyrite associated with the mafic units (Py 7 ). Each type of pyrite was found to have distinctive trace element compositions and S isotope signatures. The results of the LA-ICPMS analyses provide evidence for early trace element enrichment in the Kapai Slate sedimentary pyrite (median values of 158 ppm Ni, 387 ppm Co, 82 ppm Cu, 727 ppm As, 1.91 ppm Mo, 13 ppm Se, 0.25 ppm Au, 7.72 ppm Te and 3.36 ppm Ag for Py 1 and 223 ppm Ni, 158 ppm Co, 99 ppm Cu, 856 ppm As, 1.27 ppm Mo, 10.2 ppm Se, 0.57 ppm Au, 10.09 ppm Te, and 6.62 ppm Ag for Py 2 ). Concentrations of Ni and Co are low, relative to other late Archean sedimentary pyrite (median of 813 and 465 ppm, respectively) and Mo levels are near that of the euxinic shales of the similar-aged Jeerinah Formation in the Hamersley Basin, Western Australia. These data suggest that the Kapai Slate was deposited in an anoxic to euxinic basin with relatively low biological productivity. The Δ 33 S and δ 34 S signatures of the sedimentary pyrite suggest two different sources of S. Positive δ 34 S and negative Δ 33 S signatures indicate bacterial reduction of SO 4 2− from seawater, whereas positive δ 34 S and positive Δ 33 S signatures indicate an elemental S 8 source, indicating the pyrite formed later during diagenesis. This S isotope signature is consistent with a transition between a near-sediment environment to a more distal environment source. Analyses of the ore-phase pyrite yield weakly positive Δ 33 S values. This suggests there was a minor contribution of sedimentary S to the more significant oxidized ore-forming fluids, which is consistent with a small contribution of Au from a sedimentary source. Approximations of the degree of sedimentary pyrite destruction in the pyrrhotite/pyrite dominated zones and pyrrhotite/magnetite/pyrite zones of the northern part of the St. Ives district were used to calculate the amount of Au released from the early sedimentary pyrite. The calculation suggests that a minor, though possibly locally significant, amount of Au could have been sourced from the Kapai Slate.

Sulfur isotope and trace element systematics of zoned pyrite crystals from the El Indio Au–Cu–Ag deposit, Chile

We present a comparative study between early, massive pyrite preceding (Cu–Ag) sulfosalt mineralization in high-temperature feeder zones (‘early pyrite’) and late pyrite that formed during silicic alteration associated with Au deposition (‘late pyrite’) at the El Indio high-sulfidation Au–Ag–Cu deposit, Chile. We use coupled in situ sulfur isotope and trace element analyses to chronologically assess geochemical variations across growth zones in these pyrite crystals. Early pyrite that formed in high-temperature feeder zones shows intricate oscillatory zonation of Cu, with individual laminae containing up to 1.15 wt% Cu and trace Co, As, Bi, Ni, Zn, Se, Ag, Sb, Te, Au, Pb and Bi. Late pyrite formed after (Cu–Ag) sulfosalt mineralization. It contains up to 1.14 wt% As with trace Cu, Zn, Pb, V, Mn, Co, Ni, Ge, Se, Ag, Sb, Te, Pb and Bi, as well as colloform Cu-rich growth bands containing vugs toward the outer edges of some crystals. Plotting the trace element data in chronological order (i.e., from core to rim) revealed that Co and Ni were the only elements to consistently co-vary across growth zones. Other trace elements were coupled in specific growth zones, but did not consistently co-vary across any individual crystal. The δ34S of early pyrite crystals in high-temperature feeder zones range from −3.19 to 1.88 ‰ (±0.5 ‰), consistent with sublimation directly from a high-temperature magmatic vapor phase. Late pyrite crystals are distinctly more enriched in δ34S than early pyrite (δ34S = 0.05–4.77 ‰, ±0.5 ‰), as a consequence of deposition from a liquid phase at lower temperatures. It is unclear whether the late pyrite was deposited from a small volume of liquid condensate, or a larger volume of hydrothermal fluid. Both types of pyrite exhibit intracrystalline δ34S variation, with a range of up to 3.31 ‰ recorded in an early pyrite crystal and up to 4.48 ‰ in a late pyrite crystal. Variations in δ34Spyrite at El Indio did not correspond with changes in trace element geochemistry. The lack of correlation between trace elements and δ34S, as well as the abundance of microscale mineral inclusions and vugs in El Indio pyrite indicate that the trace element content of pyrite at El Indio is largely controlled by nanoscale, syn-depositional mineral inclusions. Co and Ni were the only elements partitioned within the crystal structure of pyrite. Cu-rich oscillatory zones in early pyrite likely formed by nanoscale inclusions of Cu-rich sulfosalts or chalcopyrite, evidence of deposition from a fluid cyclically saturated in ore metals. This process may be restricted to polymetallic high-sulfidation-like deposits.

Trace element systematics of pyrite from submarine hydrothermal vents

Submarine hydrothermal sulfide ores occur at mid-ocean ridges, intra-oceanic arcs and in back-arc basins associated with host rocks of highly variable composition. Pyrite is the dominant sulfide mineral in most samples presented within this study, and thus the trace element composition of pyrite may reflect the different metal sources and precipitation processes. Here, we report on a systematic study of minor and trace element contents in pyrite from active and inactive submarine hydrothermal vent fields at different plate-tectonic settings including the Indian and Mid-Atlantic Ridges, the Tonga–Kermadec intra-oceanic arc, the Lau back-arc and the central Okinawa Trough. Our results show that the trace element contents of pyrite from different locations vary significantly but for most elements without any systematic correlation to the concentration in the magmatic host rocks. Only As appears to be depleted in pyrite from ultramafic-hosted vent systems that are affected by serpentinization. These As depleted pyrites preferentially host Au 0 micro- or nano-particles. Bismuth is enriched in pyrite from hydrothermal systems that contain a sedimentary component and micro-inclusions of sphalerite are either due to fluid–sediment interaction or phase-separated fluid venting. Pyrites from individual locations have highly variable concentrations of elements like Au, Co, Cu, Se, Mo, Ag and Sb that are most likely related to fluid evolution and changes in fluid composition. Sub-seafloor hydrothermal fluid–seawater mixing influences the distribution of Au, Co, Cu, Se and Mo in pyrite. Elements like Au, Ag, Sb and Pb often have a characteristic affinity to As, while Cd correlates closely with Zn. A magmatic volatile contribution to the Hine Hina hydrothermal system may result in the precipitation of Cu-enriched pyrite. Our results show that the concentrations of most trace metals in pyrite are a function of the physicochemical parameters of the fluid phase rather than a reflection of the magmatic host rock composition.

The chemical conditions of the late Archean Hamersley basin inferred from whole rock and pyrite geochemistry with Δ33S and δ34S isotope analyses

The well-preserved late Archean sedimentary rocks of the Fortescue and Hamersley Basins in Western Australia offer fascinating insights into early earth ocean chemistry prior to the Great Oxidation Event (GOE). In this study, we use a combination of whole rock geochemistry, LA-ICPMS trace element analysis of sedimentary pyrite and pyrrhotite and SHRIMP-SI sulfur isotope analyses to elucidate the chemical changes in these sedimentary rocks. These proxies are used to examine chemical conditions of the ocean during the late Archean. Two to three periods of oxygen enrichment prior to the deposition of banded iron formations (BIF) can be identified. One minor stage of general increase in whole rock enrichment factors and trace element content of pyrite is observed up stratigraphy in the Jeerinah Formation, Fortescue Basin and a more substantial stage is present in the Paraburdoo and Bee Gorge Members of the Wittenoom Formation, Hamersley Basin. Some of the trace element enrichments indicate organic matter burial flux (Ni, Cr, Zn, Co and Cu) which suggests an increase in biological productivity. If the increased biological activity reflects an increase in cyanobacteria activity then an associated increase in oxygen is likely to have occurred during the deposition of the Bee Gorge Member. An increase in atmospheric oxygen would result in continental weathering of sulfide and other minerals, increasing the trace element content of the water column via erosion and avoiding excessive depletion of trace elements due to drawdown in seawater. Since some of these trace elements may also be limiting nutrients (such as Mo and Se) for the cyanobacteria, the degree of biological productivity may have further increased due to the increasing amount of trace elements introduced by oxygenation in a positive feedback loop. These periods of increased productivity and oxygen rise stopped prior to the onset of BIF deposition in the Hamersley Basin. This may be due to the ocean reaching an oxidation threshold, enabling the precipitation of hematite and magnetite BIF. The BIF deposition caused depletion of ocean nutrients such as phosphate, severely limiting the growth of cyanobacteria, and thus limiting further oxygen production.

The origin of sulfide mineralization in arenaceous rocks beneath carbonaceous horizons in fluvial depositions of late Paleozoic through Cenozoic age (SE Germany)

Sulfide mineralization in clastic rocks from SE Germany were mineralogically and chemically investigated in relation to host-rock lithology and their environment of deposition. The S isotopes and trace-element contents of pyrite were determined to decipher the origin of sulfur concentration in arenaceous rocks beneath carbonaceous horizons. Two principal types of CS distribution may be defined in these fluvial depositions. Type I may be encountered in meandering stream depositions and is of syn(dia)genetic origin. Type II was found in sediments laid down by braided streams and is likely to have been overprinted by an epigenetic pyritization. The sulfur of sulfides probably derived from evaporites. There is no evidence for these swamp environments to have been flooded by marine ingressions. The organic matter originated from higher-plant material and to a varying amount from algae and bacteria. Sedimentation did not occur in a strongly reducing environment. Biogenic reduction controlled by the humic matter preferentially removed 32S from the sulfate of intrastratal solutions and conduced to negative δ 34S-values at the top and increasingly more positive values with depth. Sulfate reduction commenced in an open system and later converted into a more or less closed system. Concluding from the data of organic chemistry the organic matter of type-I sediments may be categorized as “gas prone”. However, the clastic rocks of type II show small-scale hydrocarbon migration along with sulfidization. Their C isotopes attest to a slight change in the composition of kerogenous matter, owing to the shift of δ 13C-values plotted as a function of host-rock stratigraphy.