Framboidal Pyrite Research Articles

Mapping hydrothermal alteration in regolith using white micas and chlorite as vectors towards gold mineralization

Mineral exploration through regolith-dominated terrains poses a significant challenge to cost-effective exploration techniques. Due to missing surface expression, undercover mineral exploration relies on understanding ore-forming processes and characterizing alteration regimes to decipher suitable vectors towards ore deposits. The work presented focuses on the Archean granite-greenstones of the Yilgarn Craton, east of the Meekatharra area in Western Australia, and characterizes the weathering profiles by understanding metal dispersion mechanisms and identifying mineralogical vectors towards gold mineralization within regolith. Mineral mapping of gold mineralization using TESCAN Integrated Mineral Analyzer and laser ablation ICP-MS shows gold is associated with multiple generations of pyrite, and base metal sulfides and sulfosalts hosted in felsic to intermediate volcanics and volcaniclastics. Intensive weathering generated a thick regolith profile dominated by a leached zone of kaolinitic and micaceous saprolite underlain by a supergene Au-Cu deposit blanket at the base. The supergene deposit is dominated by colloform and framboidal pyrite, with pure microcrystalline Au, chalcocite, bornite, malachite, and alunite. Hyperspectral analyses were used to trace the composition and abundance of chlorite and white mica variations in the host rock and the weathering profile. The mineral assemblage in the hydrothermal alteration halo proximal to and intersecting gold mineralization is dominated by Fe-rich chlorite and Na-rich white mica (paragonite). Fe-rich chlorite and paragonite are spatially tied to elevated Au concentration and trends to Fe-Mg-rich chlorite and K-rich white mica (muscovite) distal to the alteration. The variations in chlorite chemistry were detected mainly in bedrock and saprock. Conversely, the white mica chemistry variations were detected in bedrock and the regolith profile, in which white micas resist intensive weathering. The spectral signatures identified through short-wave and thermal infrared data are verified through X-ray diffraction, mineral chemistry, and bulk geochemical analyses. This distinctive spectral signature of white mica and chlorite is a cost-effective exploration method for regional mapping of mineral systems to identify hydrothermal alteration footprints in the regolith developed over felsic and intermediate rocks.

In-situ trace element and sulfur isotope compositions of Multi-Stage sulfides in the Buzhu orogenic gold (Antimony) Deposit, southern Tibet: Implications for the metallogenic process

The Buzhu gold (antimony) deposit, located within the gold-antimony polymetallic belt of southern Tibet in the Tethys Himalayan belt, is a recently discovered medium-sized gold polymetallic deposit. The orebody consists primarily of gold-bearing quartz sulfide veins. Currently, the metallogenic mechanism of the deposit remains largely unexplored. Utilizing results from the mineralogical observation of principal ore minerals, LA-ICP-MS trace element analysis, and in-situ sulfur isotope analysis of pyrite, investigations reconstruct the evolution process of pyrite-arsenopyrite and constrain the metallogenic process of the Buzhu gold (antimony) deposit. It has been discovered that the gold-bearing sulfides in the Buzhu gold (antimony) deposit are primarily pyrite and arsenopyrite. Pyrite can be categorized into six generations: framboidal pyrite Py0, dissolution cavity pyrite Py1a (some exhibiting oscillatory zoning), disseminated pyrite Py1b, euhedral pyrite Py2a, irregular pyrite Py2b, and Py3. Arsenopyrite, on the other hand, can be classified into three generations: early arsenopyrite Apy0, disseminated arsenopyrite Apy1, and euhedral Apy2. The analysis of δ34S in pyrite throughout the ore-forming process indicates sulfur derives from multiple sources, with Py0 indicative of a biological sulfur source. The evolutionary process of pyrite, supported by trace element analysis, suggests that the remaining pyrite derives from sedimentary fluid transformation, with sulfur primarily sourced from metamorphic sediments. Elemental spectrum analysis and BSE observations indicate that the Buzhu gold (antimony) deposit primarily undergoes two distinct stages of mineralization: the initial stage is the gold-antimony mineralization phase, during which antimony precipitates in the fissures of Py1a as stibnite, while gold is primarily found in Py1-Apy1 as invisible gold, with the highest gold content in Apy1 (28.20–60.13 ppm, average 40.51 ppm). The subsequent stage of mineralization is characterized by gold mineralization, with gold primarily residing in the internal fissures of Apy2 as micron silver gold ore. The evolution characteristics of gold-bearing sulphide and the solubility curve of Au indicate that gold mainly derives from gold-bearing unsaturated fluid, rather than from early framboidal pyrite Py0 (0.52–1.06 ppm, average 0.79 ppm). Only a minor fraction of gold (originating from early sediments) in Py0 was liberated and integrated into subsequent pyrites. The content of antimony in Py0 significantly reduces after dissolution, suggesting that antimony predominantly originates from Py0 (206–440 ppm, average 335 ppm). Throughout the genesis of the Buzhu gold (antimony) deposit, the gold constituent underwent a sequence of pre-enrichment, re-enrichment, liberation, and precipitation. The processes of coupled dissolution-reprecipitation (CDR) and boiling fostered the reactivation and reenrichment of gold. The recrystallization into cubic pyrite led to the expulsion of gold from the pyrite lattice, and fluid oxidation resulting from multistage fluid boiling, coupled with a decrease in sulfur fugacity, led to gold precipitation.

Geochemical characterization of trace fossil assemblages in spotted marls and limestones of the Lower Jurassic of the Western Carpathians: environmental implications

AbstractThe trace fossils of the spotted limestones and marls from upper Pliensbachian of the Skladaná Skala section, Western Carpathians (Slovakia), are characteristic of Zoophycos ichnofacies preserved in outer shelf deposits. The ichnoassociation is dominated by Lamellaeichnus and Chondrites, while Palaeophycus, Planolites, Teichichnus, Thalassinoides, Trichichnus, and Zoophycos, are less abundant. The presence of relatively large sized traces (reaching a decimetre in horizontal dimension for Thalassinoides and Zoophycos) and continuously well bioturbated deposits point to well oxygenated shallow zone (mixed layer) and deeper part of stiffed substrate of the transitional layer of bottom substrate up to the first tens of centimetres to depth. A first tier (tier I) corresponds to the shallowest sediment occupied by Bathysiphon tests and other epifaunal body fossils. The tier II is characterized by shallow infaunal burrows of deposit feeders (Planolites) and permanent dwelling, open burrows (Palaeophycus, Thalassinoides) located in a Ca-rich sediment (corresponding to CaCO3). The tier III is dominated by deposit feeders (Lamellaeichnus, Teichichnus) that burrowed stiff Ca-rich sediment below the redox boundary. Trace fossils of tier III are rich in fine siliciclastics (high content in Si, Al, K mainly associated to clays) and pyrite framboids (enrichment in Fe, S and Co). The deposit-feeders of tier III maintain connection to the sediment-water interface. Tier IV (Zoophycos, Teichichnus and large Chondrites), and deepest infaunal forms of the tier V. (Trichichnus, Pilichnus and tiny forms of Chondrites) comprises trace fossils commonly rich in pyrite framboids with relatively high content of Fe, S, and Co, congruent with chemosymbiotic behaviour commonly inferred for Chondrites, Trichichnus, and the organic-matter storage of Zoophycos.

Occurrence characteristics of authigenic pyrite in the deep-sea environment and its paleoceanographic implications based on core sediments from IODP Expedition 342 Site U1406

Although authigenic pyrite (FeS2) in marine sediment is an important proxy for oxygen conditions and microbial activities at its formation site, very little is known about its morphological characteristics in the deep-sea (> 3500 m) environment and their paleoceanographic implications. Here, we report the occurrence characteristics of authigenic pyrite including texture, size distribution, and relative content in North Atlantic deep-sea sediments from Integrated Ocean Drilling Program (IODP) Expedition 342 Site U1406. The results of electron microscopy show octahedral pyrite microcrystals of 1.5–4.0 μm, the spherical texture of greigite (Fe3S4), and large pyrite framboids (average, 25 μm) relative to those of the continental margin. These features may demonstrate an unchanged supersaturation level of the pore water for octahedral pyrite after its initial formation, replacement of the precursor greigite by pyrite, and an expanded pyrite framboid formation zone with a low sulfate reduction rate in deep-sea sediments, respectively. Although the size distribution of pyrite framboids measured in this study falls into the range of pyrites formed in the sulfate–methane transition zone, based on onboard geochemical data and previous research, these pyrites most likely formed through organoclastic sulfate reduction during diagenesis. We assessed the implications of these findings for paleoceanographic changes, as the formation of diagenetic pyrite is controlled by the supply rate and reactivity of organic matter, which are closely related to ocean productivity and circulation. A comparison between the profiles of relative pyrite content and benthic foraminiferal oxygen isotope (δ18Obf) values indicated that these factors were anti-phased during the late Oligocene. Based on our results, we conclude that the formation of diagenetic pyrite was favored during interglacial periods due to increases in the amount and reactivity of organic matter driven by more energetic formation of proto-North Atlantic Deep Water. Our findings provide new insights into the formation of authigenic pyrite in deep-sea environments and its potential as a paleoceanographic proxy.

Framboidal pyrite in Dongsheng sandstone-hosted uranium deposit, northern Ordos Basin: Implications for fluid evolution and uranium mineralization

Occurrence characteristics, internal morphology patterns, size variations and trace elements contents for framboidal pyrite in the sandstone of middle Jurassic Zhiluo Formation hosting U deposit in the northern Ordos Basin collectively demonstrate three types of framboids: (i) Py1 is the synsedimentary origin, characterized by the close association with clay minerals, equal-sized microcrystals with globular or octahedral shape, the diameter of framboids and microcrystals ranging from 2.1 to 9.3 µm (mean = 5.9 µm) and from 0.1 to 1.4 µm (mean = 0.5 µm), respectively, and relatively low trace element contents (mean = 0.83 wt% of Co, Ni, As, Mo in total); (ii) Py2 is the early diagenetic origin, characterized by equal-sized pyritohedral microcrystals while other substance also occurs within the framboid, or non-uniform size and morphology of microcrystals with the diameter of framboids and microcrystals ranging from 7.3 to 26.3 µm (mean = 11.8 µm) and from 0.3 to 1.9 µm (mean = 0.8 µm), respectively, and similar trace element compositions with Py1; and (iii) Py3 is the U ore-stage origin, characterized by equal-sized cubic microcrystals in the loosely packed pattern with U-bearing minerals filling between microcrystals, the diameter of framboids and microcrystals ranging from 7.6 to 27.4 µm (mean = 15.9 µm) and from 0.7 to 3.2 µm (mean = 1.5 µm), respectively, and the highest trace element contents (mean = 1.07 wt% of Co, Ni, As, Mo and Se in total). During mineralization, Py1 and Py2 are dissolved by the interlayer oxidation fluid, providing S source and trace elements for the precipitation of Py3 with larger diameter. Its strong reducing ability, large specific surface area and abundant internal porosity facilitate the fixation of U in the interstices of Py3 through reduction or adsorption. Negative sulfur isotope compositions suggest biogenic redox processes for U mineralization. The formation and transformation relationship of different stages of framboidal pyrite indicates the complex evolution process of synsedimentary, early diagenetic and U ore-forming fluids.

Similar sources but distinct δ13C signatures in adjacent low-temperature travertines from Laguna Amarga (Southern Patagonian Andes)

This study examined the waters and carbonates from two cold spring travertines (ca. 13 °C) located on the sun-exposed (north-facing travertine) and sun-shaded (south-facing travertine) margins of Laguna Amarga, an alkaline lake from the semiarid region of the eastern Patagonian Andes (51°S).The travertines are composed of calcite + low-Mg calcite ± aragonite. Both exhibit similar sedimentological transitions along their longitudinal profiles. In the proximal zones, biologically-influenced carbonates form in wetland-like environments. Spherulitic calcite precipitates in association with extracellular polymeric substances in microbial biofilms containing cyanobacteria-like molds at the vent of the south-facing travertine, while aragonite spherulite formation at the north-facing travertine vent also involves sulfate-reducing bacteria, as indicated by their close association with framboidal pyrite. Downstream, in the intermediate and distal zones, crystalline dendrites predominantly precipitate due to increased turbulence-induced CO2 degassing.Both travertines share a similar range of carbonate 87Sr/86Sr composition (0.70720–0.70740) and isotopic signatures of the spring waters, including δ2H (ca. -110 ‰ VSMOW), δ18Owater (ca. -14 ‰ VSMOW) and δ13C-DIC (ca. -5 ‰ VPDB), suggesting common sources and processes influencing fluid composition. This points to the dissolution of carbonates from mudstone-rich marine units of the Lower Cretaceous (δ13C ca. -1 ‰ VPDB) and Upper Cretaceous (δ13C ca. -10 ‰ VPDB) during shallow subsurface circulation of meteoric waters through the bedrock. The carbon isotopic composition of the deposits resembles those of endogenic travertines (δ13Ctrav − 1.2 to 5.3 ‰ VPDB), with the highest δ13Ctrav values associated with carbonates from the vents. However, the involvement of deep CO2 sources is unclear and epigenic processes capable of producing the observed 13C enrichments are discussed.Despite their common sources, similar sedimentological features and δ18Otrav compositional range (−12.4 to −10.1 ‰ VPDB), the δ13Ctrav values are lower in the south-facing travertine (−1.2 to 1.9 ‰ VPDB) compared to the north-facing travertine (1.8 to 5.3 ‰ VPDB). This disparity is inferred to result from variations in local environmental conditions due to different levels of insolation, which favored the incorporation of soil-derived CO2 in the south-facing travertine and likely increased photosynthetic productivity in the north-facing travertine, thereby shifting their δ13Ctrav signatures to lower and higher values, respectively. These relationships highlight the sensitivity of low-temperature spring carbonates to subtle environmental changes at basin scales.

Re‐Evaluating Water Column Reoxygenation During the End Permian Mass Extinction

AbstractOcean anoxia is considered a key driver of the end‐Permian mass extinction (EPME). However, it is much debated whether there was an ocean reoxygenation phase during, and in the aftermath, of the EPME. Evidence for ocean reoxygenation is often inferred from the absence of framboidal pyrite in some boundary marine sediments (termed the “framboid gap”). To reconstruct ocean redox evolution across the EPME, we investigated the carbon isotopic, sedimentological, and redox records of the Ruichang and Ehtan sections in South China. These documents two negative δ13Ccarb excursions and the development of anoxia associated with deepening leading up to the Permian‐Triassic boundary. Above the level at which most siliceous organisms became extinct, pyrite framboid and iron proxies indicate that water column redox conditions were predominantly oxygenated but sporadically anoxic/ferruginous [non‐sulfidic, free Fe(II) in the water] at Ruichang, while ferruginous conditions were more widely developed at Ehtan. These contrasting redox states are characteristic of a dynamic ocean redox landscape in the extinction interval. The “framboid gap” is seen in strata deposited under both oxic and ferruginous conditions, suggesting that the availability of decomposable organic matter for sulfate reduction additionally controlled framboid genesis. Our data confirm that oxygenated conditions were developed in some deep water basins during the EPME.

Sedimentary Expressions of the Early Jurassic Jenkyns Event in an Inland Lacustrine System in the Yin'gen–Ejinaqi Basin, North China

AbstractThe Jenkyns Event, more widely known as the Toarcian Oceanic Anoxic Event (T‐OAE), is marked by globally distributed negative carbon‐isotope excursions, widespread oxygen depletion, and large‐scale organic carbon burial, which indicate major climate/environmental perturbations in Earth's surface systems during the Early Jurassic. Although extensive research has been conducted in European continental settings, particularly in the western peri‐Tethys regions, the impacts of this event beyond Europe remains largely unexplored. Here, a multiapproach study including investigations into the spore‐pollen assemblages, pyrite framboids, clay minerals, total organic carbon (TOC) levels, and organic carbon isotope (δ13Corg) levels in a lacustrine borehole section (MED1) from the Yin'gen–Ejinaqi Basin, North China, provides evidence of the occurrence of the Jenkyns Event and its extensive sedimentary responses in the eastern Tethys terrestrial systems. Two distinct spore‐pollen assemblages have been identified in MED1 (drilling depth: 982.4 m to 1267.5 m), with the Cycadopites–Protopinus–Osmundacidites assemblage in the lower part (1267.5 m to 1132.9 m) indicating a middle Early Jurassic age and the Classopollis assemblage in the upper part (1132.9 m to 985.7 m) suggesting a Toarcian age. Framboidal pyrite data suggest more anoxic conditions during the deposition of black mudstone and shale intercalations in the lower part of the Classopollis assemblage (1132.9 m to 1066.9 m), which combined with organic carbon enrichment and negative δ13Corg excursions, are considered the paleoenvironmental response to the Jenkyns Event in the study area. Furthermore, the evolution of vegetation groups changed from plant groups characterized by bisaccate and cycad pollen, as well as fern spores, to vegetation groups represented by Cheirolepidiaceae pollen across the Jenkyns Event, as evidenced by spore‐pollen data, together with the clay mineral assemblage change characterized by a notable increase in illite at the expense of kaolinite, suggests that while a subtropical‐temperate climate persisted, a change toward warmer and drier conditions most likely occurred in the early Toarcian in the study area. In contrast to the humidification evidenced in many coastal settings, this aridification trend in the Yin'gen–Ejinaqi Basin aligns with the conditions in many inland areas. It is hypothesized that the underlying cause of these divergent changes may be linked to certain patterns of spatially variable water availability on land, potentially driven by extremified hydrological conditions.

Geochemical Evidence of Ore-Forming Processes in the Shuiyindong Gold Deposit of Southwest Guizhou Province, China.

The Shuiyindong deposit is one of the ultralarge Carlin-type gold deposits in Southwest Guizhou Province, China. Gold mineralization mainly occurs in the Permian Longtan Formation and the early Triassic Yelang Formation. It is controlled by both strata and faults. Detailed studies of the mineralogy and geochemistry characteristics of the Shuiyindong deposit are conducted to investigate the ore-forming process. Arsenian pyrite and arsenopyrite are the main Au-hosting minerals. Three types of pyrite can be recognized, including euhedral and subhedral pyrite, framboidal pyrite, and bioclastic pyrite. The euhedral and subhedral pyrite is the main Au-hosting type. The Au appears as a solid solution (Au+) and natural nanoscale gold (Au0) in the sulfide minerals. The Co/Ni ratios of sulfides (0.07-3.13) reveal that the ore-forming fluids were mainly affected by hydrothermal activity, but magmatic activity cannot be excluded. Organic matter in the ores is abundant (0.11-3.04%), which might provide sulfur for pyrite and favor an increase in the porosity and permeability of the host rocks by releasing organic acids. The REE and trace element results suggest that halogens (F and Cl) were contained in the reducing magmatic hydrothermal fluids. The sulfur isotopic data (from -8.64‰ to 27.17‰) suggest that the source of sulfur is complicated and is probably a combination of a magmatic source, the reduction of marine sulfate, and bacterial sulfate reduction. The Pb isotopic data of the sulfides indicate that Pb is from a mixture of crust and mantle sources. The obvious enrichment zones exist along the boundary faults in the geochemical map of As, implying that As may originate from the deep crust and then move to the strata with basinal fluids. By combining these results, it can be inferred that the ore-forming fluids were a mixture of basinal and deep source fluids. A probable ore-forming model of the Shuiyindong gold deposit is established.

Potential effects of the Emeishan large igneous province on Capitanian marine anoxia in the Upper Yangtze region

The widespread Capitanian (late Guadalupian) marine anoxia/euxinia has long been regarded as a key driver of the end-Guadalupian (middle Permian) biotic crisis. However, the cause of this marine anoxia is debated, particularly regarding the influence of the Emeishan large igneous province (ELIP). To investigate the contribution of the ELIP to marine anoxia and the possible causal mechanisms, we undertook a conodont biostratigraphic and geochemical study of the middle Permian Maokou Formation in a platform-to-trough transect in the Upper Yangtze region, South China. Our results show that the depositional facies of the Maokou Formation changed from a carbonate ramp to an intra-platform trough within the Jinogondolella (J.) altudaensis zone in the northwestern Yangtze region, which can be attributed to the initial activity of the ELIP. Mantle-derived Sr inputs in the initial and main stages of the ELIP led to two decreases in 87Sr/86Sr during the Capitanian, in the J. shannoni–J. altudaensis and J. prexuanhanensis–J. xuanhanensis zones. The elevated 87Sr/86Sr values during the late Capitanian may have been due to enhanced continental weathering caused by rapid climate warming in response to subaerial eruptions of the ELIP. The deep-water anoxia–euxinia expanded during the middle Capitanian, as indicated by increased MoEF/UEF and V/(V + Ni) values, along with the disappearance of burrows and appearance of small pyrite framboids in the J. altudaensis zone in the Cheng 20 well. However, shallow-water anoxia occurred during the late Capitanian (i.e., J. prexuanhanensis–J. xuanhanensis zone), as evidenced by positive Ce anomalies and losses of aerobic benthic species in the Erya section. Importantly, marine anoxia and negative δ13Ccarb excursions occurred synchronously, but earlier in deep water than in shallow water, potentially indicating an expansion of the oxygen minimum zone (OMZ). The deep-water anoxia corresponded to a decrease in 87Sr/86Sr ratios and the appearance of an intra-platform trough in the J. altudaensis zone, whereas the shallow-water anoxia in the late Capitanian coincided with elevated 87Sr/86Sr ratios. This suggests that the initial activity of the ELIP promoted the development of the OMZ in deep waters during the middle Capitanian, while the subaerial eruptions of the ELIP drove climate warming that led to the expansion of the OMZ into shallow-water platforms during the late Capitanian.

Volcanism and turbidity current events as drivers of the evolution of benthic redox conditions: Organic matter enrichment in the Chang 7 member, Upper Triassic Yanchang formation, Ordos Basin, North China

Depositional events have a significant impact on the terrestrial redox conditions and provide evidence for studying the organic matter enrichment. The objective of this study was to evaluate the influence of volcanic and turbidity current events on benthic redox conditions during the Upper Triassic Chang 7 member (Ch7) of the Ordos Basin. To address these issues, the varying sedimentological settings, paleoredox conditions, and relationships between the redox environment and depositional events were investigated via sedimentary analysis of the profiles, microscopic analysis, organic geochemical analysis, and elemental geochemical data. The fine-grained sediments in the Chang 73 submember (Ch73) consist of abundant organic matter, collophanite, and framboidal pyrite. However, in the upper part of the Ch7 member, there was a decrease in organic matter, a decrease in the number of microorganisms, and an increase in pyrite size, indicating that the oxic environment is not favorable for organic matter enrichment. The element and geochemical proxies show similar vertical variations and redox changes. Volcanic activity can bring substantial amounts of material or elements to the basin. The enrichment of Hg and S exhibited considerable variation, ranging from 8.7 to 274.4 ppb and from 0.16 to 4.53 wt%, respectively, which influenced the organic matter accumulation through the flourishing and death of microorganisms and redox changes in the benthic environment of the terrestrial basin. As the lake basin shrinks, the Ti and Al contents increase with increasing frequency of turbidity current events, and the terrestrial debris transported to the lake basin gradually increases while carrying large amounts of oxygen and affecting sedimentation rates, contributing to the destruction of the reducing conditions of the benthic environment, subsequently, influencing organic matter accumulation. These results will be helpful in understanding the effect of multiple depositional events on organic matter enrichment in lacustrine basins.

A refined model for the mechanisms of Precambrian phosphorite formation

Despite the economic and scientific importance of Precambrian phosphorites, our understanding of the mechanism leading to their formation remains limited, including for the largest phosphogenic episode in the late Neoproterozoic. To improve our understanding of Precambrian phosphorite formation, we combined sedimentology, petrography, and elemental, and Fe-C isotopic analyses to study the two main phosphorite beds (the lower and upper phosphorite beds) in the Ediacaran Doushantuo Formation, Zhangcunping area, South China. The phosphorites consist mainly of granular textures characterized by densely packed grains, some of which are coated with secondary phosphate growth. However, there are notable differences in the mineralogy, microfossil assemblages, and elemental contents of the two beds. The lower phosphorites have no Ce anomaly, and relatively low Y/Ho ratios and positive δ56Fe values (0.04–0.30 ‰, average of 0.19 ‰). In contrast, the upper phosphorites have negative Ce anomalies and higher Y/Ho ratios and near-zero δ56Fe values (−0.29–0.19 ‰ (average of −0.01 ‰). These observations suggest that the lower phosphorites formed in anoxic-suboxic environments, whereas the upper phosphorites formed in relatively oxygenated environments. The δ13Ccarb values of the phosphorites range from −3.97 ‰ to 1.71 ‰ (average of −1.56 ‰), and are lighter than values in dolostones (−0.52 ‰ to 4.39 ‰, average of 2.02 ‰). This suggesting that formation of the Doushantuo phosphorites was influenced by degradation of organic matter in an ocean with high primary productivity. The lower phosphorites, which were also regulated by Fe redox pumping, have positive δ56Fe values, along with the presence of pyrite framboids and iron oxides, suggesting deposition near the Fe-redox boundary where extensive Fe cycling. The upper phosphorites show positive correlations between Mn and Fe, and Mn/Fe and P2O5, suggesting formation near the Mn boundary with extensive Mn cycling, primarily mediated by Mn redox pumping. Sedimentological observation indicate that primary phosphates were concentrated into granular phosphorites by winnowing processes following primary precipitation. Accordingly, we propose a refined model for Precambrian phosphorite formation in which degradation of organic matter, Fe and Mn pumping, and physical reworking of deposits co-evolve and interact within a dynamic Precambrian redox environment. Our model provides a reasonable explanation for the distribution of global phosphorite deposits throughout geological history.

Study of the Geological Context of the 7th–6th Century BC Phoenician Era Shipwreck “Mazarrón 2” (Murcia, Spain)

The Mazarrón 2 shipwreck was found in 1994 on the beach of Playa de la Isla (Mazarrón, Murcia, Spain). This finding is extremely important because the boat and its lead cargo were still in a reasonable conservation state and, therefore, provided new data on naval construction, commercial goods, navigation routes, and the relationships between the Phoenicians and the local population in the 7th–6th century BC. Currently, the shipwreck remains underwater, protected by a metallic coffer. In the last 2 years, a Preliminary Studies Project has been carried out, supported by national and regional public institutions. This research aims to know the shipwreck’s conservation state and to determine the extraction and conservation methods at the Museo Nacional de Arqueología Subacuática ARQVA (Cartagena, Spain), where the conservation and restoration treatment will be conducted. The sampling strategy and analytical study included not only wood and other materials from the shipwreck and its cargo but also the seawater and the seabed materials in the vicinity of the shipwreck. This paper presents the results of the geochemical study of the archeological site. The applied methodology included physico-chemical tests, X-ray diffraction, optical microscopy, FTIR spectroscopy, field-emission scanning electron microscopy coupled with X-ray microanalysis, and X-ray microscopy. The results indicated that, despite the wreck being buried at a shallow depth (less than 50 cm) in a marine environment with a water column of 2–2.5 m, influenced by complex coastal dynamics that favor an oxic environment, early diagenetic processes like the formation of pyrite framboids are particularly intense in the pores and internal channels of the wreck’s wood, where a different dysoxic–anoxic environment prevails. These processes have been the main mechanisms to have affected the wreck and are related to the biogeochemistry of sediments. The sediments have been confirmed to be closely related to the geological context of the Mazarrón region. The conducted study found no significant evidence of pollution due to the lead cargo.

Decoding paleomire conditions of paleogene superhigh-organic-sulfur coals

Superhigh-organic‑sulfur (SHOS) coals (coals with organic sulfur content >4 wt%) are unique coal deposits found at a few notable locations in the world. Specific peat accumulation and preservation conditions must be met to form SHOS coals. Organic sulfur is a major constituent of such coals, and it may have various sources depending on the prevailing paleomire conditions. Understanding such paleomire conditions sheds light on the formation mechanisms of SHOS coals. This investigation decodes the paleomire conditions of the Paleogene SHOS coals from Meghalaya, India, using sulfur isotopic compositions (δ34S) of organic sulfur (δ34SOS) and pyritic sulfur (δ34SPy) along with organic petrography, pyrite morphology and trace element ratios. Thirty coal samples were collected from the Jaintia Hills in the east, Khasi Hills in the middle, and Garo Hills in the west of Meghalaya. The organic sulfur content in the Garo, Khasi, and Jaintia coals varies from 1.0 to 3.3 wt%, 1.4 to 13.8 wt%, and 1.0 to 7.2 wt%, respectively. Further, after separation from pyritic sulfur and sulfate sulfur phases, the organic sulfur content ranges from 54.4 to 69.2%, 63.8 to 79.9%, and 59.3 to 73.8%, in the Garo, Khasi, and Jaintia Hills, respectively, suggesting the SHOS nature of these coal samples. The δ34SPy varies from −29.3 ‰ to +5.7 ‰, −21.3 ‰ to +27.3 ‰, and −12.1 ‰ to −4.3 ‰, in the Jaintia, Khasi, and Garo Hills, respectively, while the δ34SOS fluctuates from −4.6 ‰ to +3.7 ‰, −9.3 ‰ to +7.8 ‰, and − 9.0 ‰ to −5.0 ‰, respectively. The δ34S values of pyrite and organic sulfur (OS) in Jaintia coals are 34S depleted compared to seawater sulfate (+22 ‰), leading to fractionations in the range of −51.3 ‰ to −16.3 ‰ (mean − 31.6 ‰) and − 26.6 ‰ to −18.3 ‰ (mean − 23.1 ‰) for pyritic and organic sulfur (OS), respectively. Pyrite in Khasi coals show a relatively heavier δ34S composition averaging at −20.5 ‰, whereas organic sulfur (OS) isotope compositions range from −31.3 ‰ to −14.2 ‰ with a mean of −22.6 ‰. Pyrite and OS in the Garo coals are depleted compared to seawater sulfate. Isotope variations in the Jaintia, Khasi, and Garo coals indicate microbial sulfate reduction (MSR) of seawater sulfate. Large isotopic fractionations between Eocene seawater sulfate and pyritic sulfur (Δ34SSO4Eocene – pyrite = up to −51.3 ‰; mean − 31.6 ‰) in Jaintia coals indicate their possible formation in the water column/near the sediment-seawater interface (open system) and also hint toward dissimilatory sulfate reduction pathways that prevailed under anoxic redox conditions. However, mean values of Δ34SSO4Eocene – pyrite (−20.5 ‰) in the Khasi coals imply pyrite formation deeper in the sediments (more closed system) under dysoxic conditions. The dominance of OS over pyritic sulfur, framboidal pyrite, and its microcrystal size distributions in Jaintia coals may suggest syngenetic pyrite formation in open water reducing/anoxic conditions under paralic environments. Elevated Sr/Ba and U/Th values in these coals further confirm the anoxic conditions. Nevertheless, the presence of euhedral pyrite with the alleviated pyrite framboids in the Khasi coals and their complete absence in the Garo coals may suggest dysoxic-suboxic and suboxic-oxic depositional conditions, respectively. The isotopic signatures of the Garo coals suggest sulfur contribution from the parent paleobiota and MSR under a freshwater-oxic environment. Insignificant fractionations between δ34SPy and δ34SOS indicate limited iron and sulfate availability for additional sulfur cycling and disproportionation reactions, typical of oxic conditions. The absence of framboidal pyrite, elevated sulfate concentration, and mean Sr/Ba and U/Th values of 0.5 and 0.3, respectively, further suggest the freshwater peat deposition in the Garo Hills under limnotelmatic to telmatic freshwater conditions. Moreover, high inertinite content (Immf = 9.77–33.16 vol%), possibly induced by atmospheric peat exposure, supports the interpretation of suboxic-oxic paleomire conditions in Garo Hills. Gradually decreasing mineral matter content from Jaintia (mean 13.6 vol%) to Garo coals (mean 7.4 vol%) additionally projects a transition from mesotrophic brackish to freshwater limnotelmatic environment, complementing the shift in the paleomire condition from eastern (Jaintia) to western (Garo) Meghalayan Hills.

Barite Replacement as a Key Factor in the Genesis of Sediment-Hosted Zn-Pb±Ba and Barite-Sulfide Deposits: Ore Fluids and Isotope (S and Sr) Signatures from Sediment-Hosted Zn-Pb±Ba Deposits of Iran

Iran hosts more than 350 Precambrian to Cenozoic sediment-hosted Zn-Pb±Ba and barite-sulfide deposits, including shale-hosted massive sulfide (SHMS, also called SEDEX) and Irish-type and Mississippi Valley-type (MVT) mineralization, and barite is a common mineral in these deposits. In the SHMS deposits, barite is typically found as fine-grained disseminations in thin laminae. In these deposits, the sulfide laminae often occur as diagenetic replacements and as bands containing authigenic and diagenetic barite and pyrite framboids. In the Irish-type Zn-Pb-Ba and stratabound barite-sulfide deposits, barite exhibits various textures, including fine-grained disseminated barite, banded zebra textures, veins, and massive barite lenses. In some of the giant Irish-type deposits, as well as in the stratabound barite-sulfide mineralization, the main stratabound sulfide ore is developed within a barite envelope and is characterized by the replacement of barite and pyrite by chalcopyrite, galena, and sphalerite. In the MVT deposits, the formation of barite is often related to dolomitization, and sulfide mineralization involves the replacement of the dolomitized carbonate rocks, as well as associated barite. Fluid inclusion studies on the Irish-type deposits indicate that the temperatures and salinities of the sulfide-forming fluids are higher compared to those of the barite-forming fluids. Fluid inclusion analyses of coarse-grained barites from Irish and MVT deposits reveal their hydrothermal origin. The δ3⁴S values of sulfide minerals (pyrite, sphalerite, and galena) in Irish-type deposits exhibit a broad range of low values (mostly −28 to +5‰), primarily revealing a process of bacterial sulfate reduction (BSR). However, the textures (replacement, colloform, and banded) and more positive sulfur isotope values (+1 to +36‰) in the SHMS Zn-Pb deposits suggest that bacterial sulfate reduction (BSR) plays a less significant role. We suggest that thermochemical sulfate reduction (TSR) connected to the direct replacement of barite plays a more relevant role in providing sulfur for the sulfide mineralization in the SHMS, barite-sulfide, and MVT deposits. Based on the textual evidence, sulfur isotopic data, and fluid inclusion studies, barite has been identified as a key controller for the subsequent Zn-Pb mineralization by providing a suitable host and significant sulfur contribution in the sediment-hosted Zn-Pb and stratabound barite-sulfide deposits. This implies that diagenetic barite might be a precursor to all types of sediment-hosted Zn-Pb mineralization.

SEM/Raman spectroscopy of clathrites as analogs of authigenic carbonates in ocean worlds

AbstractThere is evidence from the near‐infrared observations of space missions of the presence of carbonates on the surface of several ocean worlds. However, their genesis remains unresolved. We investigate the hypothesis that these carbonates may be in the form of clathrites assuming that clathrate hydrates are stable phases in the crust and ocean of these ocean worlds. In order to support this, we studied a sample of a potential clathrite from the Hydrate Ridge cold seep (Cascadia Subduction Zone), the carbonate rock fossil of clathrate hydrates, as a terrestrial analogue. We characterised the mineralogy and texture of the sample by using a coupled confocal Raman microscope and scanning electron microscopy instrument with the aim of identifying possible geo‐ and biosignatures, which could be relevant for future missions of exploration to ocean worlds and Mars. Our results show that aragonite is the dominant mineral phase in the clathrite sample, but Mg‐calcite and dolomite were also identified. These three carbonates constitute a pattern related to clathrate hydrate formation and dissociation processes. Dolomite was defined as a biosignature of gas hydrate microbiomes because it was integrated within Mg‐calcite grains precipitated after clathrate hydrate dissociation. Nevertheless, no spectral changes were observed in Raman bands of carbonate minerals that would indicate the influence of clathrate hydrates in their genesis. We also observed that Raman band positions of the associated framboidal pyrites are a characteristic signature of the associated framboid‐like texture because its potential as biosignature may only be attributed by biochemical analysis.

Tracing the evolution of the world's first mined bauxite from palaeotopography to pyritization: Insights from Minjera deposits, Istria, Croatia

The Minjera bauxites are the first analysed and mined bauxites in the world. They are a group of pyritised bauxites situated in northern Istria, developed during the subaerial exposure phase which marked a major part of the Late Cretaceous and Palaeocene in northern Istria. In this study, the morphology, petrography, mineralogy, geochemistry as well as stable sulphur isotopes of the D-1 and D-15 deposits from Minjera were studied, as well as the evolution of their bedrock and cover. This study found that those two deposits differ in morphology, mineralogy and geochemistry as a consequence of their different palaeotopographical positions, with the D-1 deposit located at a higher position at the time of its formation compared to D-15, which led to the higher degree of leaching and desilicification in the D-1 deposit. The pyritisation in the studied deposits was a multi-phase process, which began with the deposition of framboidal pyrite and micrometre-sized anhedral pyrite, over which colloform pyrite was precipitated. This indicates that the solutions were initially supersaturated with iron sulphide, saturation of which subsequently changed, as finally euhedral, dendritic and acicular pyrite were deposited, indicating undersaturated conditions. The final stage was marked by deposition of pyrite veins. This formational sequence of pyrites is also supported by stable sulphur isotopes, as the δ34S values exhibit a wide range from -40.86 to 2.32 ‰, where lower values indicate an open system with an unrestricted sulphate supply in which supersaturated conditions could have been achieved, while the higher values indicate a change towards a closed system with limited sulphate supply. The organic matter necessary for microbial sulphate reduction was derived from the marshy environment established atop of the bauxite. The initial flooding started in the Palaeocene, with the first part of the sequence being deposited under lacustrine conditions, which changed towards fully marine with the deposition of Foraminiferal limestones.

Hydrocarbon‐derived thrombolites from the Outer Carpathians (Lower Cretaceous, Poland)

AbstractShallow marine thrombolites from a newly discovered Lower Cretaceous cold seep in the Outer Carpathians (Poland) were analysed in order to untangle the complex sedimentological and biogeochemical processes involved in their formation and their diagenetic modifications. The studied thrombolites are made of two components: (i) microcrystalline mesoclots; and (ii) spar‐filled framework cavities. These components are dominated by calcite and show a complex spatial relationship, resulting in a heterogeneous, clotted fabric. The mesoclots exhibit digitate structures, often concentrically‐laminated, and are chiefly composed of microcrystalline material with δ13C values from −34.8 to −19.4‰ PeeDee Belemnite. Biomarkers analyses show the presence of 2, 6, 10, 15, 19‐pentamethylicosane within the mesoclots. The mesoclots host <5 mm wide microtubes filled with isopachous calcite recording even lower δ13C values (from −39.0 to −20.5‰ PeeDee Belemnite). The morphology of the mesoclots relative to their internal lamination and their geochemistry indicates that their growth was linked to anaerobic oxidation of methane while the microtubes acted as conduits for hydrocarbon‐charged fluids. The framework cavities are internally lined with framboidal pyrite, and are cemented by calcite spar with relatively high δ13C (−15.1 to −7.3‰ PeeDee Belemnite) and low δ18O values (−9.3 to −4.4‰ PeeDee Belemnite). Carbonate precipitation within the framework cavities is interpreted to have been related to bacterial sulphate reduction. U‐shaped trace fossils attributed to the ichnogenus Balanoglossites cross‐cut both mesoclots and framework cavities. The mechanisms involved in the formation and diagenesis of thrombolites at cold seeps are yet to be fully understood, and this work provides new insights on these complex biogeochemical and sedimentological processes.

Discovery of Late Carboniferous high-grade carbonate-hosted manganese mineralization in the Maerkansu area of the Western Kunlun Orogen, Northwest China

The Aoertuokanashi deposit located in the Western Kunlun Orogen is the first known Late Carboniferous large high-grade carbonate-hosted Mn deposit in the world and it has been mined since 2018. The deposit is considered to have formed in a back-arc basin developed during the northward subduction of the Paleo-Tethys Ocean beneath the Tarim Block. The Re-Os isotope isochron age of Mn ore at the Aoertuokanashi deposit is 302 ± 9 Ma. The minimum initial 187Os/188Os values obtained from the deposit is 0.28, which indicates the presence of a mantle source for the mineralization. The Aoertuokanashi deposit is similar in age to the 301 ± 5 Ma Wajilitag kimberlite in the Tarim Block, which is considered to be the initial magmatic pulse triggered by the Tarim mantle plume. The Late Carboniferous Aoertuokanashi Mn deposit was likely promoted by igneous activity from the Tarim mantle plume.The Aoertuokanashi deposit shows geochemical characteristics of hot water activity in a back-arc basin. The Mn mineralization is hosted in the restricted platform facies. Framboidal pyrite, typical biomat, and authigenic quartz are observed in the Mn deposit, indicating the influence of microbial processes. The sedimentary facies show a starving basin feature that can enhance microbial mediation. The δ13CV-PDB values of mineralized rocks (from −19.5 to −8.2 ‰) are more negative than those of wall rocks (from −5.3 to + 4.2 ‰), whereas the δ13CV-PDB values (around −29 ‰) of kerogen for the Mn ore are significantly lower than those of the whole rock. These compositions indicate that the reducing function of organic matter played an important role in Mn mineralization. In the inferred extensional tectonic environment, under the influence of a mantle plume, the stratum with strong hot water activities and a large amount of organic matter becomes the focal point for the formation of carbonate type manganese ore deposit.

Organic petrographic and mineralogical composition of the No. 6 coal seam of the Soutpansberg Coalfield, South Africa: Insights into paleovegetation and depositional environment

This study investigates the paleodepositional conditions of the No. 6 Seam of the Madzaringwe Formation in Makhado and Voorburg south area of the Soutpansberg Coalfield (Limpopo Province, South Africa) utilizing organic petrography and inorganic geochemical proxies. The coals are predominantly high-volatile bituminous B-A rank with high ash yields (avg. 36.1 wt%), characterized by high-vitrinite (~ 41.5 vol%), moderate-to-high inertinite (9.8 vol%–33.7 vol%) and low liptinite (~ 2.3 vol%). The distribution of inertinite varies among different coal horizons (from bottom-lower to middle-upper), suggesting differential oxidation conditions and/or paleofire occurrence. Vitrinite-to-inertinite (V/I) ratio, tissue preservation–gelification index (TPI–GI), and groundwater–vegetation index (GWI–VI) plots, indicate that the peat-forming forest-swamp vegetation accumulated under mesotrophic-to-rheotrophic hydrological conditions. The presence of structured macerals (i.e., telinite, collotelinite, fusinite, and semifusinite) suggests well-preserved plant tissues, whereas framboidal pyrite and sulphur content (0.24 wt%–2.16 wt%) point to brackish-water influence at the peat stage. The coals contain quartz, kaolinite, siderite, muscovite, dolomite, calcite, and pyrite minerals, most of which were likely sourced from felsic igneous rocks. The Al/(Al+Fe+Mn) and (Fe+Mn)/Ti ratios for the studied samples range between 0.24–0.97 and 0.57–70.10, respectively. The ratios, Al–Fe–Mn plot, and presence of massive botryoidal-type pyrite imply some influence of meteoric waters or fluids from hydrothermal activity post-deposition. Moreover, the chemical index of alteration (CIA: 98.25–99.67), chemical index of weathering (CIW: 92.04–97.66), and A–CN–K ternary diagram suggest inorganic matter suffered strong chemical weathering, indicating warm paleoclimatic conditions during the coal formation.