Pyrite Grains Research Articles

SEM-EDS and water chemistry characteristics at the early stages of glacier recession reveal biogeochemical coupling between proglacial sediments and meltwater

Most glaciers worldwide are undergoing climate-forced recession, but the impact of glacier changes on biogeochemical cycles is unclear. This study examines the influence of proglacial sediment weathering on meltwater chemistry at the early stages of glacier recession in the High Arctic of Svalbard. Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) in combination with a wide range of geochemical analyses were used in this study. The SEM-EDS analyses of sediments collected in front of Werenskioldbreen show general degradation of pyrite and carbonate grains with age. The outer parts of pyrite grains have a gradual decrease in sulphur and gradual increase in iron oxides due to pyrite oxidation. This process was less advanced in the proglacial zone younger than 100 years compared to older sites such as the terminal moraine from the Little Ice Age. In both the proglacial zone and the terminal moraine, physical weathering of mineral grains, including formation of microcracks and microfractures, clearly enhanced pyrite oxidation. A consequence of proglacial sediment weathering is that the river chemistry is strongly affected by carbonate dissolution driven by sulphuric acid from sulphide oxidation. Also, reactive iron oxides, a product of sulphide oxidation, are mobilized in the proglacial zone. The results of this study show that proglacial weathering in the High Arctic of Svalbard is strongly coupled to river geochemistry, especially during the early stages of proglacial exposure after glacier recession.

Sulfur- and Iron-Rich Mineralogical Features Preserved in Permafrost in the Canadian High Arctic: Analogs for the Astrobiological Exploration of Mars

Elliptical sulfate-rich features, stained red by the presence of iron oxides, are set within permafrost and carbonate rock at Borup Fiord Pass in the Canadian High Arctic. These features, which vary in diameter from ∼0.5 to 3 m, exhibit the co-localization of sulfur (S) and iron (Fe) minerals, with S and Fe both preserved in multiple oxidation states. Through application of x-ray diffraction (XRD) and Raman microspectroscopy, we find that these features appear to encapsulate central cores with abundant pyrite while S0, gypsum, and iron-bearing secondary minerals such as jarosite, goethite, and hematite have formed from oxidative weathering of the pyrite. These features appear similar to terrestrial gossans, mineral features representative of weathered sulfide ores in the near-surface. We use Raman microspectroscopy and scanning transmission x-ray microscopy (STXM) to show that organic carbon is associated with the minerals within these features. The origin of this carbon remains enigmatic; however, we consider the possibility that this carbon, along with etching of the pyrite grains and accumulation of encrusted filaments detected in the features, may be indicative of preserved biological activity during alteration of the pyrite. We also consider how such geological sulfide emplacements and their weathered surface expressions may provide a target for future surface and remote sensing studies of Mars and in the search for extraterrestrial life.

Nanoscale trace-element zoning in pyrite framboids and implications for paleoproxy applications

Abstract Pyrite framboids (spherical masses of nanoscale pyrite) are among the earliest textures of pyrite to form in sediments. It has been proposed that their trace-element (TE) contents can be used to track the TE composition of the water column in which they formed. However, it is not clear how these TEs are associated with the framboidal pyrite grains. For instance, it is important to know whether they are incorporated uniformly or are enriched in different regions of the framboid. We used high-resolution scanning transmission electron microscopy to identify chemical zoning within pyrite framboids. We found that initial, nanoscale pyrite euhedral crystals, which make up the volumetric majority of the framboids, are covered/infilled by later pyrite that templates on the earlier pyrite. Further, this later pyrite is enriched in TEs, suggesting that many TEs are incorporated in pyrite relatively late (during early diagenesis; not in the water column). This observation suggests that although chemical analyses of pyrite framboids may provide ocean-water chemistry trends through time, the details are complex. Specifically, the TEs found in pyrite may be linked to adsorption onto organic matter, detrital material, and authigenic minerals such as Fe- and Mn-oxide phases followed by desorption in the sediments or release via dissolution and incorporation into pyrite as overgrowths on the initial nanoscale euhedral crystals that make up framboids. While the use of pyrite chemistry to understand past ocean conditions remains promising, and even diagenetic additions may not preclude the utility of pyrite for reconstructing ancient ocean conditions, care must be taken in interpretations because the end concentration may be influenced by diagenesis.

Carbonate shutdown, phosphogenesis and the variable style of marine anoxia in the late Famennian (Late Devonian) in western Laurentia

The shutdown of carbonate productivity and its replacement by black shale deposition is often observed in the geological record and yet the factors driving such a change are debated. The latest Famennian of western Laurentia (present day North America) provides a good example of a limestone – black shale transition that is roughly contemporaneous with the global Hangenberg Crisis – a series of environmental and biotic changes associated with the widespread development of black shale deposition. However, in western Laurentia limestone deposition ceased and black shale deposition began prior to this crisis. Examining the type section of the Exshaw Formation at Jura Creek (Alberta) reveals that declining seafloor oxygen levels were likely responsible for the loss of carbonate productivity, followed by phosphogenesis of the youngest carbonates. The top surface of the limestone is a hard ground that was reworked, possibly by internal wave action, producing a lag of phosphatic clasts and pyrite grains including giant framboids (reaching 100 μm diameter) and polyframboids. The subsequent redox history of the lower Exshaw Formation shows substantial variations. Initially, the occurrence of small framboids, and elevated FeHR/FeT and Fepy/FeHR combined with enhanced U, Mo and Re concentrations indicates intense euxinia in the water column. These conditions were replaced by ferruginous anoxic conditions recorded in radiolarian-rich black shales that have moderate concentrations of trace metals, and low pyrite content, as confirmed both by low Fepy/FeHR ratios and scanning electron microscope (SEM) observation. Mo-U covariation trends suggest that Mo enrichment under ferruginous conditions was promoted by drawdown in association with Fe minerals precipitated in the water column. The return of better ventilated conditions around the Devonian/Carboniferous boundary is marked by a decrease in trace metal content and the loss of syngenetic pyrite. The Hangenberg Crisis is thus marked by an improvement in ventilation, from euxinic to ferruginous conditions in our study, and evidence from other basins in western North America suggests an even greater increase in oxygenation at this time.

Deciphering multiple ore-forming processes of the Shuangqishan orogenic gold deposit, Southeast China by in situ analysis of pyrite

Gold deposits are characteristically formed via multiple mineralization and remobilization events. Inferences on the complex formation history of such deposits from ore textures can be ambiguous in the lack of chemical and isotopic evidence as exemplified by the Shuangqishan orogenic gold deposit in Southeast China. We, therefore, conducted LA-ICP-MS spot analysis coupled with LA-MC-ICP-MS sulfur and lead isotope analysis on texturally complex gold-bearing pyrite from the Shuangqishan deposit. Gold distribution in different syn- to late-ore pyrite generations indicate initial evenly deposition of nano- to micro-inclusions of Au-Ag-Pb-Bi tellurides within pyrite grains and subsequent Au remobilization following brittle deformation and fluid-mediated coupled dissolution-reprecipitation (CDR) reactions. Gold dissolved from the pyrite during the reworking event became re-concentrated and re-precipitated as visible gold either as inclusions in pyrite or larger free gold grains within microfractures of pyrite. The distribution of Bi-Te-Pb-Ag assemblage is comparable to that of Au, illustrating that these trace metals became redistributed in a similar fashion. Early, undeformed pyrite has the least radiogenic Pb isotopic compositions. Late, porous and inclusion-rich pyrite, brecciated pyrite, and recrystallized Te-Bi minerals have variable but in general more radiogenic Pb isotope ratios (higher 206Pb/204Pb and 207Pb/204Pb ratios), which are attributed to modification and precipitation from a more evolved crustal fluid during the re-precipitation of native gold. The Pb isotopic signature of the younger pyrite generations was likely inherited from Pb released during modification of earlier proto-pyrite and a second, crustal lead source that was involved in the hydrothermal system during later remobilization. The δ34S values for the early proto-pyrite and the reworked pyrite generations within the individual vein stage are broadly similar. The variations in sulfur isotope compositions reflect the change in physicochemical conditions (temperature and oxygen fugacity) during proto-ore formation. Our study highlights the importance of metal recycling from early proto-auriferous pyrite during later reworking and gold remobilization, which led to visible gold and high-grade ore shoot formation. The extensive variations of trace element concentrations and S-Pb isotope compositions of proto and reworked pyrites record the complicated Au mobilization and deposition processes and help to understand how gold ores evolved.

A metamorphic devolatilization model for the genesis of the Baiyun gold deposit in the North China Craton: A novel Fe-S isotopes perspective

The Mesozoic gold deposits in the North China Craton (NCC) were hosted by the Precambrian basement and Mesozoic intrusions. Thus, most researchers consider that these gold deposits were genetically linked to the Mesozoic intrusions. However, we suggest that a metamorphic devolatilization model provides an alternative based on a combined Fe and in-situ S isotopes study on auriferous pyrites from the Baiyun gold deposit in the NCC. The Triassic Baiyun gold deposit contains the quartz vein and altered rock ores that were developed in the Paleoproterozoic metavolcanic-sedimentary rocks (the Liaohe Group). Our in-situ S isotopic analyses show that pyrites from the quartz vein ores are characterized by negative δ34S values (-10.7 ∼ -5.5‰), while those from the altered rock ores have two distinct groups of δ34S values, one being positive (+13.5 ∼ +16.2‰) and the other negative (-10.6 ∼ -3.0‰). We suggest that pyrite grains with positive δ34S values should be relicts from the host rocks, because they show comparable δ34S values with those from the host rocks schists (+3.3 ∼ +16.1‰). Thus, only the negative δ34S values of pyrites in ores (-10.7 ∼ -3.0‰) and the Fe isotopes of the quartz vein ores (δ56Fe = +0.30 ∼ +0.48‰) can represent the isotopic characteristics of ore-forming fluids at Baiyun. Our study shows that the sulfur were probably from the pyritic volcanic-sedimentary sequences of the Liaohe Group, rather than from magmas. The calculated δ56Fe values of the ore-forming fluids (-0.78 ∼ -0.37‰; pyrite-fluid isotope fractionation) could be modelled in a metamorphic devolatilization model with Fe-species (pyrite&magnetite) of the Liaohe Group as sources. Therefore, our combined S- and Fe- isotope data indicate that the metamorphic devolatilization of the Liaohe Group could account for the genesis of the Baiyun gold deposit.

Au-rich bimodal-mafic type volcanogenic massive sulphide deposit associated with Jurassic arc volcanism from the Central Pontide (Kastamonu, Turkey)

The central part of the Pontide Orogenic Belt, located in northern Anatolia, is a segment of the Alpine-Himalayan orogeny. Çangaldağ Metamorphic Complex (CMC) occurs within this segment which consists of ensimatic island arc volcanics and deep sea sediments which occasionally cut cross by mafic sills/dykes. They were exposed to metamorphism under the greenschist facies conditions and remain in tectonic contact with each other. The Say yayla mineralization is one of the recently discovered volcanogenic massive sulfide (VMS) deposits in the CMC with a remarkable Au content. The mafic and felsic metavolcanic rocks are the host-rocks of the Say Yayla mineralization and the ages determined by U-Pb zircon grains of these felsic volcanic rocks range from 170 Ma to 165 Ma indicating Middle Jurassic time.At the 0.1% cut-off grade, 7.5 million tons of resource has been calculated with 0.75 ppm Au, 0.65 wt% Cu, and 0.35 wt% Zn grades. The Say Yayla mineralization consists of massive and semi-massive sulfide minerals and a mineral assemblage represented by predominantly pyrite and chalcopyrite and trace amounts of sphalerite, tennantite and galena. Average base and precious metal grades of the zones occur with >1 wt% Cu are 2 wt% for Cu, 0.7 wt% for Zn, 0.04 wt% for Pb and 1.5 g/t for Au.The sulfur isotope values (δ34S VCDT) range from 4.9‰ to 6.7‰ for pyrite grains and 4.2‰ was obtained from the one sphalerite sample. δ18O values for the quartz from quartz-rich ore samples were 10.6 ‰ and 11.7‰ δ18O (VSMOW)qtz. δ18O (VSMOW)fluid values for the ore-forming fluids vary between 0‰ and 2.4‰. Lead isotope compositions of the pyrite minerals were 18.148–18.150 (206Pb/204Pb), 15.548–15.550 (207Pb/204Pb) and 38.078–38.083 (208Pb/204Pb)The geological, geochemical, and isotopic data of the ore and host-rocks reveal that the mineralization is a bimodal-mafic type (Noranda type), which is classified into Cu-Zn group of volcanogenic massive sulfides. Geochemical and geochronological data from the wall rocks further show that mineralization was developed within an ensimatic island arc environment during the Middle Jurassic.

Complementary Textural, Trace Element, and Isotopic Analyses of Sulfides Constrain Ore-Forming Processes for the Slate-Hosted Yuhengtang Au Deposit, South China

Abstract Yuhengtang is a representative slate-hosted Au deposit in the Jiangnan orogenic belt, South China, with a reserve of ~55 t Au and an average grade of ~3.9 g/t. Gold mineralization is characterized by veinlet and disseminated ores comprising native gold, auriferous pyrite, and arsenopyrite. Paragenesis of the Yuhengtang deposit can be divided into three stages. Pre-ore stage 1 is composed of bedding-parallel layers of pyrite in slate of the Neoproterozoic Banxi Group. Main ore stage 2 represents the Au mineralization stage, and two distinct types of mineralization can be distinguished: visible Au-arsenopyrite-pyrite in quartz veinlets and auriferous arsenopyrite-pyrite disseminated within altered slate. Post-ore stage 3 consists of quartz-pyrite-calcite-ankerite veins. In this study, we integrate electron microprobe, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and high-resolution ion microprobe (SHRIMP) analyses to document textural, isotopic, and compositional variation among texturally complex pyrite and arsenopyrite assemblages in veinlet and disseminated ores. Additionally, LA-ICP-MS sulfur isotope mapping of pyrite highlights the covariation behavior between trace elements and sulfur isotopes at the grain scale, thus allowing the factors controlling sulfur isotope fractionation in hydrothermal Au deposits to be constrained. Pyrite, of sedimentary origin (stage 1), hosts negligible Au (<1.6 ppm) but is enriched in δ34S (15.6–25.8‰). Pyrite and arsenopyrite from stage 2 veinlet mineralization both display porous and dissolution-reprecipitation textures, have low Au concentrations (<4 and <78 ppm, respectively), and show a large variation in δ34S (–2.7 to 14.7‰ and –10.3 to 12.1‰, respectively). Pyrite and arsenopyrite from disseminated mineralization are, in contrast, characterized by oscillatory zoning textures and homogeneous appearance in backscattered electron (BSE) images, respectively, and are obvious by their relatively high contents of invisible Au (up to 90 and 263 ppm, respectively) and restricted range of δ34S values (0–5.3‰). These data suggest that magmatic-hydrothermal fluids contribute most of the Au and S budget in the Yuhengtang Au deposit. The major differences between veinlet and disseminated mineralization in terms of texture, trace element concentrations, and δ34S signatures of pyrite and arsenopyrite reflect contrasting mechanisms of Au precipitation and an evolution of physicochemical parameters of the ore-forming processes, particularly fO2 and the intensity of fluid-rock interaction. Pyrite from stage 3 appears homogeneous in BSE images yet displays a wide variation in δ34S values (1.2–31.4‰), further highlighting the controlling role played by physicochemical condition (i.e., pressure) on the δ34S signature of sulfides. Results of the coupled LA-ICP-MS sulfur and trace element mapping reveal that some zoned pyrite grains from stage 2 formed via overgrowth of Au-rich, light δ34S (2.4‰) hydrothermal rims onto Au-poor, heavy δ34S (18.1–18.5‰) sedimentary cores. All results support that multiple depositional mechanisms within a dynamic mineral system were responsible for Au concentration and define the specific textural, compositional, and sulfur isotope signatures of sulfides in coexisting vein/veinlet and disseminated mineralization. The new data highlight the ore-forming processes-based interpretation for ore genesis and underpin the importance of performing complementary in situ mineralogical analyses to elucidate the source and evolution of ore-forming fluids and enable correct interpretation of the architecture of the hydrothermal Au system.

Extreme-resolution synchrotron X-Ray fluorescence mapping of ore samples

In order to maximise profit and sustainability of a mining operation, knowledge of the chemistry, mineralogy, texture, and structure of the ore is essential. Continuous advancements in analytical techniques enable studying these features with increasing detail. Synchrotron radiation X-ray fluorescence is unparalleled in its simultaneously high spatial resolution and detection range. Yet, its application in ore geology research and the mining industry is still in its infancy. This study investigated opportunities of extreme-resolution synchrotron X-ray fluorescence mapping of ore samples. Analysis was performed at the NanoMAX beamline at the MAX IV synchrotron facility in Lund, Sweden. The samples investigated are from the Liikavaara Östra Cu-(W-Au) deposit, northern Sweden. Analysis covered areas of several hundreds of μm2 in grains of molybdenite, pyrite, and native Bi. Key results included successful mapping of the lattice-bound distribution of Re, Se, and W in molybdenite at 200 nm spot/step size and detection of nanometre inclusions of Au in native Bi at 50 nm spot/step size. Challenges were encountered concerning data acquisition and processing. In order to achieve satisfactory resolution of both light and heavy elements and to limit mapping artefacts, repeated scans of the same area with varied experimental parameters and very thin (quasi-2d) samples are required. For complex geological samples, the software used for analysing spectral data (PyMCA) requires a considerable degree of human examination, which may be a source of error. Overall, synchrotron X-ray fluorescence mapping has a strong analytical potential for ore geology research, in analysing and imaging trace elements that would constitute potential by-products in mining operations. Detailed knowledge of how trace elements occur in the ores will inform the development of appropriate metal extraction programs thus ensuring that a larger part of the ore may then be utilized.

Genesis and mineralization style of gold occurrences of the Lower Lom Belt, Bétaré Oya district, eastern Cameroon

The Bétaré Oya district has a substrate composed of the Neoproterozoic metavolcanic-metasedimentary rocks of the Lom Belt in eastern Cameroon. The district is well-known for alluvial gold mining activities, however, the primary gold mineralization has received little attention. In the current study, we newly report geological, ore mineralogy, fluid inclusion microthermometric, laser Raman spectroscopy, and stable isotope data from auriferous veins of the Lom Belt to characterize the style of gold mineralization and to constrain the origin of the ore-forming fluids. The auriferous quartz veins are laminated, fractured, N- to NE-trending, and spatially associated with the Bétaré Oya Shear Zone. Fieldwork coupled with microscopic examination and the textural relationships of ore minerals revealed two stages of mineralization. The first stage is characterized by the presence of pyrite, sphalerite, galena, chalcopyrite, pyrrhotite, hematite, petzite, hessite, wolframite, electrum, and gold, while the second stage is characterized by the presence of a later deposition of galena and pyrite, as well as minor greenockite. The gangue minerals are quartz, sericite, muscovite, chlorite, calcite, ankerite, and barite, whereas the supergene assemblage (stage 3) includes goethite, hematite, covellite, and enargite. Two fluid inclusion assemblages containing three types of inclusions are identified in mineralized quartz veins. Assemblage 1 consists of gold-related types 1 and 2 with daughter minerals consisting of nahcolite, magnesite, and arsenolamprite (black native arsenic), whereas assemblage 2 consists of post-gold type 3 fluid inclusions. Type 1 has H2O-NaCl-CO2 ± N2 ± CH4 primary fluid inclusions (FI), with a TmCO2 ranging from −59.8 to −56.6 °C, salinities from 0.5 to 10.8 wt% NaCl eq., densities from 0.87 to 1.00 g.cm−3, and total homogenization temperatures between 280 and 360 °C. Type 2 contains CO2 (±H2O-NaCl) ± N2 ± CH4 FI that exhibit TmCO2 ranging between −60.0 and −56.7 °C, ThCO2 from 13 to 25 °C, and densities between 0.73 and 0.85 g.cm−3. Type 3 shows H2O-NaCl FI with salinities between 0.2 and 10.1 wt% NaCl eq., densities between 0.82 and 0.98 g.cm−3, and total homogenization temperatures from 160 to 235 °C. Measured δ18O for gold-bearing quartz (+11.5 to +16.0‰), δD from FI (−50.6 to −21.8‰), δ13C from FI (−5.8 to −5.5‰), and δ34S from galena and pyrite grains (+5.3‰ and +8.2‰, respectively) suggest a metamorphic source as most likely for the ore-forming fluids and sulfur, although a mantle CO2 contribution cannot be ruled out.The gold deposition probably took place by fluid-rock interaction and fluid unmixing at ∼310 °C and at a depth of about 6–9 km. The ore-forming fluid was a low salinity (∼6.2 wt% NaCl eq.) H2O-NaCl-CO2 ± N2 ± CH4 solution. These data revealed that the Lom Belt gold mineralization is best classified as a mesozonal orogenic gold deposit.

Origin of Fe–Ni–Cu (Co) sulfide and Fe–Ti oxide minerals in the c. 1.77 Ga dolerite dyke, Singhbhum Craton (eastern India)

Abstract Dolerite dyke swarms are widespread within the Singhbhum Craton (eastern India) that emplaced from the Neoarchean to Paleoproterozoic era just after the stabilization of crust before c. 3 Ga. These dyke swarms are oriented in NE–SW to NNE–SSW, NW–SE to WNW–ESE, east–west and north–south directions. The WNW–ESE-trending c. 1.77 Ga Pipilia dyke swarm is sampled from the Satkosia area of Orissa state. The dyke shows a noticeable disparity in terms of the modal proportion and grain size of pyroxenes, plagioclase, Fe–Ti oxide minerals and texture across the trend. In places the primary silicates are altered to secondary hydrated mineral assemblages of amphibole, chlorite and sericite. The primary silicates are clinopyroxene (augite – Mg# = 65.7–82.6; En 37–48 Fs 11–17 Wo 36–41 ), orthopyroxene (clinoenstatite – Mg# = 68.5–78; En 63–70 Fs 20–29 Wo 4–5 ) and plagioclase (An 11–39 Ab 44–82 Or 1–7 ) and the Fe–Ti oxides are titanomagnetite (FeO, 34.38–39.50 wt%; Fe 2 O 3 , 48.26–56.21 wt%; TiO 2 , 5.05–9.60 wt%) and ilmenite (FeO, 40.75–43.79 wt%; Fe 2 O 3 , 3.54–10.03 wt%; TiO 2 , 47.82–50.87 wt%). Application of two-pyroxene thermometry yields an equilibration temperature range of 1065–978°C, and coexisting titanomagnetite–ilmenite pairs reveal 731.39–573.37°C under the oxygen fugacity ( f O 2 ) condition NNO + 0.3 to FMQ − 1.03. The dyke contains disseminated sulfides at the interstices of Fe–Ti oxides and silicates. Major sulfide minerals are pyrite, chalcopyrite and vaesite; pyrite–vaesite assemblages occur in association with secondary silicate minerals. Pyrite grains contain variable concentrations of Co (0.01–5.70 wt%) and Ni (0.02–1.95 wt%). Coexisting vaesite contains Co (2.42–10.44 wt%), Ni (26.40–47.88 wt%) and Fe (7.32–26.55 wt%). Texture, sulfide–silicate assemblage and the presence of low metal/S sulfides such as the pyrite–vaesite assemblage indicate that primary Fe–Ni sulfides (pyrrhotite–pentlandite) that segregated from immiscible sulfide liquid at high temperature are modified by late magmatic/hydrothermal fluid activities. Numerous sulfide-bearing deposits hosted in ultramafic–mafic intrusions of Paleoproterozoic age have been recorded globally and the occurrence of Fe–Ni sulfides in the c. 1.77 Ga Pipilia dyke swarm in the Singhbhum Craton enhances the exploration potential of this craton in eastern India.

Mineralogical and geochemical research on Pengyang deposit: A peculiar eolian sandstone-hosted uranium deposit in the southwest of Ordos Basin

The newly discovered Pengyang uranium prospect area in the southwest of the Ordos Basin is the world's first uranium deposit hosted in eolian sandstone, which overturned the conventional view of uranium mineralization in fluvial-delta sedimentary strata. Uranium ore body occurring as tabular or lens-shaped is hosted in the gray-green reductive eolian sandstone of Lower Cretaceous Luohe Formation at depths ranging from 700 m to 3000 m. The host eolian sandstone is characterized by the typical high angle cross-bedding, wind sand ripple and grainflow strata. In this study, we conducted borehole log, petrographic observation, whole rock geochemistry analysis, geochemical and mineralogical study of uranium occurrence (SEM), element mapping of uranium minerals and in-situ sulfur isotope determination of pyrite by LA-MC-ICP-MS to reveal the uranium enrichment mechanism. The observations by SEM show that the predominant uranium mineral is pitchblende, primarily occurring as aggregates of nano to micro crystals absorbed on amorphous TiO2 or as colloform replacing the detritus Fe-Ti oxide minerals, both demonstrating the excellent absorption property of small particles of anatase. The contents of altered minerals such as chlorite and pyrite in gray-green sandstone increased significantly under scanning electron microscope (SEM). Whole rock geochemistry analysis data of sandstone samples collected in the target layers display the strong positive correlation between U and S. Whereas, in the elements mapping images, uranium enrichments display complete dissociation with pyrite as the uranium contents adjacent to or around the pyrite grains are under detection limit, demonstrating that uranium precipitation likely occurred earlier than the sulfuration of red eolian sandstone. Sulfur isotope of the two morphological types of pyrite are both characterized by a relatively light signature, ranging from − 19.23 to − 27.22 ‰ and from − 21.60 to − 29.64‰ respectively, implying that they are generated from bacterial sulfate reduction in the open systems with an adequate supply of sulfate. Anaerobic sulfate-reducing bacteria use the hydrocarbon transferred along faults to the sandstone as energy to reduce sulfate (SO42−) to H2S. In addition to the typical vertical red - yellow - gray color zonation, we also observed distinct reverse color zonation of sandstone, which can hardly be interpreted by traditional interlayer-oxidation-zone theory. We attribute the uranium reduction to the encounter of downward penetrating oxygenated groundwater with the upward migrating oil and gas conducted by thrust faults, which are widespread distributed in the west margin of the Ordos Basin. This study gives a new insight into uranium metallogenic mechanism in eolian sandstone and underpins an effective vector for the exploration of sandstone-type uranium deposits in the western of the Ordos Basin.

Post-depositional modification of carbonate ooids by sulfate-reducing bacteria: Evidence from the Lower–Middle Jurassic, Tethyan Himalayas of southern Tibet

The role of microbial vs. abiotic processes in ooid formation has been a controversial topic for over a century. Recent sedimentological, geochemical and biomarker data indicate that microbes make an important contribution to the construction, destruction and modification of ooids. Here, we present a detailed petrographic and chemical investigation of well-preserved red oolites from the Lower–Middle Jurassic Nieniexiongla Formation in the Tethyan Himalaya of southern Tibet. Petrographic studies and electron probe microanalysis indicate that the red coloration is due to the presence of hematite minerals. The hematites show euhedral and amorphous spheroidal morphology and residual elemental sulfur was detected within minerals. The δ34S values in the leachate (δ34SNaCl) and in carbonate associated sulfate (δ34SCAS) of red oolites are lower than gray oolites and micritic limestones. Moreover, δ34SNaCl and δ34SCAS values are lowest in samples with the highest content of hematitic ooids. Together, these observations suggest that the hematites are transformed from pyrite. The Fe2+ (and possibly SO42−) provided by pore-water combined with degradation of syn-depositional organic matter within ooids produced anoxic microenvironments that facilitated local pyrite precipitation. Some spheroidal pyrites were subsequently transformed to euhedral crystals through continuous growth of the constituent microcrystals. This study demonstrates that organomineralization mediated by sulfate-reducing bacteria can produce pyrite grains within carbonate ooids. The results emphasize the important role that microbial communities play in the deposition and modifications of ooids.

Enrichment and distribution of elements in the middle Miocene coal seams in the Orhaneli coalfield (NW Turkey)

This study focuses on ascertaining controlling factors and differences on mineralogical and elemental contents for reconstructing palaeoenvironmental conditions of both seams applying standard coal characteristics, mineralogical, coal-petrologic, and elemental data of the Orhaneli coalfield. The studied coalfield, one of the important coalfields in NW Turkey, includes two workable coal seams, the lower with 0.5–2 m and the upper with 5–6 m in thickness, which are separated by 2–5 m thick, grayish-green limnic claystone. The floor rocks of the both seams are limnic claystones, whereas the roof rock of the upper seam is the tuffite layers-bearing lacustrine marls. Matrix and xylite-rich lithotypes are common in the upper seam, while alternations of xylite-clayey bands (detro-xylite and xylo-detritic) are common in the lower seam. The lower seam is also characterized with the presence of altered tuff layers, while freshwater gastropod shell-bearing bands were identified from the upper seam. Even though the banding character and maceral composition of the coals were invariant between the seams, there are distinct differences in mineralogy and elemental composition, that can be related to the nature of the clastic sediment influx and contemporary volcanic inputs into freshwater forested mires.The lower seam is characterized by high ash yields (%44.2–64.3, d) and relatively high concentrations of aluminosilicate-affiliated elements and REY (rare earth elements and Y). In contrast, the upper seam has relatively low ash yield, and is slightly enriched B concentration. The B enrichment in the upper seam is presumably controlled by the presence of clay mineral (e.g., illite) and clastic volcanogenic accessory minerals (e.g., apatite). Arsenic is the only enriched element in both seams due to development of anoxic conditions. Although no traceable As was detected from syngenetic framboidal pyrite grains, the contemporary volcanic inputs (e.g., air-fall ash/tephra) along with leached surface waters into palaeomires might be source for As, while the development of anoxic conditions palaeomires could cause formation of syngenetic pyrite grains. Thus, the As concentrations of the studied samples are elevated. Nevertheless, the difference on ash yields and mineralogical compositions between studied seams might be related with different clastic influx ratios and contemporary volcanic inputs, in turn, aluminosilicate affiliated elements display different concentration coefficients (CC) values in the studied seams, and high B concentrations that are not expectable for a limnic coal Besides, enrichment of Cr, V and Ni in the upper seam are controlled by clastic V-bearing chromite grains from Orhaneli chromite deposit in the adjacent area. Furthermore, the contemporary volcanic inputs into the palaeomire of the lower seam, and their alteration under anoxic conditions caused REY enrichment and the formation of kaolinite and smectite matrices of clay aggregates in coal and altered tuff layers in this seam.

Modelling pyrite oxidation in a refractory gold ore stockpile to estimate the gold recovery via direct cyanide leaching – A case study

This paper presents a case study of the modelling of the natural oxidation of pyrite in a refractory gold ore stockpile at a mine on the island of Aniolam in Papua New Guinea to predict the gold recovery through direct cyanide leaching. The stockpile comprises low-grade material that was mined twenty years ago to access the orebody. The value of this low-grade resource could be increased if the processing cost could be reduced. The natural oxidation of the gold-bearing pyrite in the stockpile may reduce the processing cost by reducing or eliminating the need for pre-treatment of the material and enable gold recovery via direct cyanide leaching. Depending on the oxidation level and the gold recovery that could be achieved by direct cyanide leaching, reclamation of the stockpile may be more profitable if the pyrite oxidation stage could be fully or partially bypassed. In this paper, we describe the modelling of the pyrite oxidation level in the stockpile using the numerical model reported in our previous work. The characteristics of the stockpile used in the model are the stockpile geometry, the geothermal heat underneath the stockpile, and the properties of the different types of material, including the acid neutralization capacity, rock particle size distribution and pyrite grain size distribution. Limited onsite test results were used to calibrate the model and the final oxidation level over the stockpile was estimated using the calibrated model. Based on the simulation results, it was found that the accessibility to oxygen is the limiting factor for the level of pyrite oxidation when diffusion is the dominant mechanism for oxygen transport within the stockpile. However, experimental tests on samples showed that sufficient oxygen resupply should have been available in the stockpile and therefore there may be air movement mechanisms other than diffusion and thermal-induced air convection onsite. This study also demonstrates that the numerical model can be used to estimate the gold recovery via direct cyanide leaching from the simulated oxidation profile together with the gold distribution in pyrite grains and gold fractions in pyrite of different sizes.

Paleoredox conditions, hydrothermal history, and target vectoring in the Macmillan Pass base-metal district, Yukon, Canada: 2 – Pyrite paragenesis and mineral chemistry

ABSTRACTThe MacMillan Pass district in Yukon, Canada, hosts the Tom and Jason clastic sediment-hosted Zn-Pb-Ag-(Ba) deposits. Pyrite-bearing drill core samples were collected from seven drill holes that intersected sulfide mineralization and time-stratigraphically equivalent rocks at varied spatial distances extending up to 3 km away from the deposits to assess the relative timing of pyrite mineralization and the chemistry of pyrite paragenesis. There are four pyrite morphologies: framboids and polyframboids (Py1), subhedral to euhedral inclusion-free crystals (Py2a), silicate inclusion-bearing nodules with serrated edges (Py2b), and euhedral idiomorphic overgrowths on preexisting pyrite morphologies (Py3). These morphological varieties correspond in time from syngenetic to earliest diagenetic growth (Py1), early to late diagenetic growth (Py2a, Py2b), and metamorphic crystallization and/or recrystallization of previous textural varieties (Py3). A representative subset of pyrite grains was analyzed for trace element contents and distributions by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Analyses by LA-ICP-MS reveal that each textural variety of pyrite has a distinct trace element composition that also varies depending on stratigraphic unit. A suite of clastic sediment-hosted sulfide mineralization-related elements was incorporated into Py2 within sulfide mineralized units at greater abundances than that in unmineralized units (e.g., Zn, As, Pb, Tl, Bi). Lead abundances and Pb/Se and As/Mo values in pyrite are the most robust vectoring tools documented. The timing for clastic sediment-hosted Zn-Pb mineralization was syn and/or post late diagenesis (Py2b).A Ba-enriched horizon was identified in rocks and this is interpreted to be the distal time-stratigraphic equivalent unit to Zn-Pb mineralization. The Ba-enriched horizon contains Py2 with anomalous metal (Tl, Co, Mn, Cd, Zn, Sb) contents and abundant macroscopic baryte, and it is interpreted to represent the distal expression of sulfide mineralization-forming hydrothermal activity. Four genetic models for mineralization are reviewed; however, the only model that is consistent with our whole rock and pyrite geochemistry involves venting of buoyant hydrothermal fluid, mixing with ambient seawater, and remaining or sinking into unconsolidated sediments, with lateral migration up to 2–3 km from the vent source.

A Magnetic Geothermometer in Moderately Buried Shales

Shales contain magnetic minerals generally at very low concentrations. In the early stages of diagenesis, the inherited magnetic minerals are altered, while magnetic nanominerals are formed. In this study, we proposed a study of shales over a stratigraphic thickness of 1.3 km from a borehole in the Paris basin (Borehole EST 433, France), and shales from the same formation (Opalinus Clay) collected in seven boreholes in the Jura molasse basin (Swiss). Magnetic measurements at experimental temperatures <30 K allowed the formation of a proxy of magnetite nanograins named PM. We showed that some of these nanograins formed around the pyrite grains, probably under the action of temperature and organic matter. PM was then compared to the maturity values of the organic matter. We found a correlation between PM and the percentage of reflectance of vitrinite. The shales from both Paris and molassic Swiss basins showed very comparable magnetic characteristics for a given maturity level. The magnetic study therefore provided constraints on the maturity level of the shales in the oil window area. Our study showed that PM can be used as a geothermometer in shales in which CaCO3 is lower than 60%.

Extreme iron isotope variation of pyrite in the Muping gold deposit, Jiaodong: Implication for tracing metal origin

Pyrite has complicated iron isotope fractionation behavior in the hydrothermal condition. Here we present a detailed in-situ iron isotope analyses of different generation pyrite from the Muping gold deposit, eastern China. δ56Fe values of pyrite investigated range from −4.25‰ to +1.78‰, unlike previous bulk analytic data (−0.78‰ to +0.79‰). Iron isotopic homogeneity of single pyrite grain, which can be verified by in-situ analysis, was recommended as the preferred and reliable criterion to judge the isotopic fractionation condition in the hydrothermal gold deposit. Inter-grain variations in Fe isotopic composition suggest occurrence of both kinetic and equilibrium fractionation for pyrite at Muping. Electron backscattered diffraction analysis shows that the replacement likely occurred via dissolution-reprecipitation pathway. The replacement process resulted in obvious kinetic isotope effect, in which pyrites are possessed in extreme negative Fe isotopic composition (~−4‰). Maximum δ56Fe of pyrite up to +1.78‰ implied that kinetic isotopic effect also play a significant role in increasing the Fe isotopic composition of ore-forming fluids in the Muping gold deposit. Further model calculations suggested the kinetic isotopic effect was dominated by pyrite fast precipitation rather than pyrrhotite precipitation or pyrite precipitation via “FeS” pathway. This kinetic isotope effect ultimately will be partly or completely erased due to fast isotope exchange rate at medium–high temperature condition. Pyrite with homogeneous Fe isotopic composition can be used to trace iron source of hydrothermal gold deposit but be cautious.

Desaturation effects of pyrite–sand mixtures on induced polarization signals

SUMMARY Induced polarization (IP) is an acknowledged method in ore exploration and can be applied to evaluate the metal content in dumps containing the residues of ore processing facilities. Existing models explain the relationships between ore content and grain size of the ore particles with IP parameters. However, the models assume full water saturation of the ore containing samples, which is often not the case in field conditions at dump sites. Hence, our study investigates the effect of desaturation on the resulting IP signal. We used six different sand–pyrite mixtures with varying amount and grain sizes of the pyrite particles. Evaporative drying desaturated the samples. Complex conductivity spectra were recorded in the frequency range between 0.02 and 1000 Hz at certain saturation levels. The resulting spectra indicate an decrease of the conductivity amplitude with progressing desaturation. This effect agrees with the second empirical Archie equation. The saturation exponent of the conductivity amplitude shows values slightly larger than one. The measured spectra were processed by a Debye decomposition. We observe a nearly constant total chargeability during desaturation. This finding is in agreement with existing models that relate the total chargeability to the metal content in the sample. However, the mean relaxation time decreases remarkably during the drying process, whereas the normalized relaxation time, which considers the ratio between the mean relaxation time and the resistivity of the embedding material, does not indicate any dependence on water saturation. This behaviour contradicts existing models that predict a decreasing relaxation time with increasing water salinity, which results from evaporative drying. In order to explain the observed effects, we propose a conceptional model that compares a mixture of pyrite particles in an embedding material (sand, water and air) with an electrical RC circuit. The pyrite grains behave as small condensers that are charged and discharged via the conductive background material. According to this simple physical model, the relaxation time is proportional to the resistivity of the embedding material. A resistivity increase while desaturation causes an increase of relaxation time as observed in our experiments. This conceptional model is in good agreement with other experiments that change the resistivity in the background material by varying water salinity or clay content. The capacitive behaviour of the dispersed particles is characterized by the normalized relaxation time that depends on the grain size and the volume content of the pyrite particles.

Constraints on fluid evolution and growth processes of black smoker chimneys by pyrite geochemistry: A case study of the Tongguan hydrothermal field, South Mid-Atlantic Ridge

Up to now, the Tongguan hydrothermal field is the southernmost-distributed modern submarine massive sulfide discovered on the South Mid-Atlantic Ridge. A well-preserved black smoker chimney which contains three distinct concentric zones was collected from the active vent field. The external outer wall of the chimney contains mainly pyrite with minor sphalerite, chalcopyrite and galena. The sulfides within the internal middle layer consist of predominant pyrite, with lesser amounts of marcasite. The axial conduit is dominated by chalcopyrite, with minor pyrite. To clarify the ore-forming fluid evolution during the black smoker chimney growth, we performed detailed petrographic and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICPMS) studies on pyrite grains from the chimney. Seven types of pyrite: framboidal, relict, colloform, dendritic, massive, euhedral and lined pyrites, are identified from exterior to interior of the chimney.As shown by the results of LA-ICPMS, geochemical compositions of pyrite vary across the chimney. Generally, low-temperature elements (Mg, V, Mn, Pb, Zn, Ag and Tl) are enriched in pyrite in the outer wall of the chimney and decrease toward the interior zones. Elements indicative of high temperature conditions, such as Se and Te, show opposite trends and are enriched in pyrite within the inner zones of the chimney. Framboidal, relict, colloform and dendritic pyrites precipitate from low to mid temperature fluids (<250 °C), while massive and euhedral pyrites are products of ore-forming fluids characterized by mid to high temperature (250 to > 335 °C). Relict and lined pyrites have the same chemical signatures, suggesting that they precipitated under similar physicochemical conditions. The observed patterns are resulted from the changes in temperature and fluid chemistry caused by interactions of between seawater and hydrothermal fluids with each other in the chimney.Cobalt concentrations in pyrite from the modern black smoker chimneys located on the mid-ocean ridge apparently vary systematically in response to salinity change of vent fluids. The low Co contents (average 0.32 ppm) in pyrite suggest that the hydrothermal fluids vented from the black smoker chimney are Cl-depleted compared to seawater, most likely caused by phase separation. The systematic variations in geochemistry and morphology of the pyrite across the chimney reflect multiple stages of mineralization. Different degrees of fluid-seawater mixing and phase separation are the main controlling factors during the chimney formation.