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Variable partitioning of lithium in rhyolitic melt during decompression and ascent

The partitioning behavior of Li in magmatic systems is increasingly being investigated due to the economic importance of Li in the transition to sustainable energy resources (e.g., batteries). However, at upper crustal pressures, it remains uncertain whether Li preferentially partitions into the vapor or liquid (brine) phase or remains in the silicate melt. This complicates our ability to determine where Li resides—silicate melt, minerals, or fluid phase—upon eruption, a crucial factor for understanding its postdepositional movement and concentration into a brine or volcano-sedimentary deposit. Here, we present a novel investigation into the behavior of Li within natural evolved melts during continuous magma decompression and ascent using melt embayments (open melt inclusions). Mineral-hosted melt embayments preserve records of the evolving composition of the exterior melt, including degassing pathways and ascent timescales, when paired with appropriate diffusion coefficients. Lithium concentration profiles were measured in quartz-hosted melt embayments from the rapidly quenched eruptive phases of five rhyolitic, caldera-forming eruptions to investigate the behavior of Li during magma decompression and ascent, where vapor partitioning and ascent dynamics were previously established by investigating H 2 O and CO 2 profiles. We find that in four systems, embayments contain lower interior Li concentrations than the coerupted melt inclusions; the fifth system contains the same Li concentrations in embayments and melt inclusions. However, many of these embayments contain gradients, with 84 % preserving Li enrichment near the melt-bubble interface, as compared to their interior concentration. We interpret these characteristics to represent two distinct stages of Li partitioning during magma decompression and ascent, in contrast to existing literature that proposes only one type of partitioning behavior. The first stage is interpreted as melt depletion of Li, likely driven by partitioning into an exsolved supercritical fluid phase, supported by the strong correlation between the extent of Li depletion and Cl concentration in the melt, as well as the decompression rate. This behavior then fundamentally shifts, where Li reenriches in the melt, postulated to be driven by the unmixing of the supercritical fluid phase at shallow pressures. For the one system that did not develop Li gradients through decompression, we attribute this to the lower values of Na and Cl in the melt, potentially inhibiting the partitioning of Li into a fluid phase. Importantly, the behavior of Li during decompression is not consistent within or between volcanic centers, highlighting the need for systematic experimental investigation in variable composition melts at pressures relevant to conduit dynamics. This knowledge would improve our ability to model Li profiles to understand magma decompression, and predict where Li resides (e.g., stored in volcanic glass, gas, or crystals) upon eruption prior to any later extraction.

Economic Geology

Widespread abyssal turbidites record megathrust earthquake-triggered landslides and coseismic deformation in the Cascadia subduction zone

Abyssal marine turbidites provide some of the longest and most spatially extensive records of subduction zone earthquake recurrence globally; however, correlation of these deposits over long distances and interpretation of synchronous emplacement requires both an understanding of the turbidite generating systems and precise dating. Here, we present an integrated suite of high-resolution bathymetry, subbottom profiles, and sediment cores from combined autonomous underwater vehicle, remotely operated vehicle, and ship-based studies at a key paleoseismic site in the southern Cascadia subduction zone. We demonstrate how widespread, earthquake-triggered landslides on the lower slope deposit discrete, proximal mass transport deposits (MTDs) that grade offshore into complex, interfingered abyssal turbidites, which correspond to records of megathrust earthquake history. We propose accretion and oversteepening of thrust folds on the lower slope both preconditions the slope to fail and provides a perpetual source of unstable material to fail during every earthquake cycle. Furthermore, we suggest the periodic and pervasive landsliding indicates coseismic deformation of the outer accretionary wedge during megathrust rupture.

California, Oregon

A diatom-based quantitative sea-ice proxy for the Bering and Chukchi seas

Sea ice affects Earth's climate system on both regional and global scales. Its incorporation into climate can be used to achieve more accurate predictions of future climate. However, instrumental records of sea-ice concentration do not extend earlier than 1978. In an effort to extend this record, we constructed a proxy using the generalized additive model based on relative abundances of five easy-to-identify diatom species found in sediment samples across the Bering and Chukchi seas. Here we present the first quantitative diatom-based sea-ice proxy developed for Beringia. The developed proxy has been applied to two sediment cores in the Bering Sea ranging from 0 to 25.7 ka (HLY0204 51JPC) and 369 to 430 ka (IODP Exp 323 Site U1345) and one in the Chukchi Sea ranging from 2.7 to 10 ka (HLY0204 24JPC). The obtained reconstructions of sea-ice concentrations are similar, but not identical to previously published qualitative and nearby records based on other proxies. Because our results are quantitative, they can be incorporated into regional climate models. The proxy is publicly available as an R Shiny application (app) and can be applied to any diatom count from marine sediments in the region.

Bering Sea, Chukchi Sea

Turbidite correlation for paleoseismology

Marine turbidite paleoseismology relies on the assumption of synchronous triggering of turbidity currents by earthquake shaking to infer rupture extent and recurrence. Such inference commonly depends on age dating and correlation of the physical stratigraphy of deposits carried by turbidity currents (i.e., turbidites) across great distances. Along the Cascadia subduction zone, which lies offshore the Pacific Northwest, USA, turbidite facies in core photographs, X-ray computed tomography images, and magnetic susceptibility (MS) data exhibit differences in character over relatively short distances, which implies that not all deposits can be correlated with confidence. Thus, subjective correlation based on expected similarity over great distances and weak age constraints does not independently support paleoseismic models. We present a new method for correlating turbidites along the Cascadia margin that can yield a more objective and repeatable stratigraphic framework to underpin earthquake recurrence. We use dynamic time warping to correlate MS logs and measure correlation coefficients of core pairs to evaluate correlation strength. We then compare these measures to a distribution of correlation coefficients of randomly generated turbidite sequences and find that only a small number of core pairs can be correlated more confidently than randomly stacked turbidites. This methodology promises a more robust correlation strategy for future stratigraphic studies.

Oregon, Washington

Shallow faulting and folding beneath south‐central Seattle, Washington State, from land‐based high‐resolution seismic‐reflection imaging

The geologic framework of the Seattle fault zone (SFZ) has been extensively studied, but the structure and fault strand locations in the central portion of the fault zone through the city of Seattle have remained controversial. Much of what is known about the SFZ has come from light detection and ranging (lidar)‐topographic surveys and paleoseismic investigations of fault scarps primarily west of Puget Sound, regional gravity and aeromagnetic modeling, and multiscale marine seismic imaging in waters both west and east of Seattle. We analyze ∼24 km of land‐based P ‐wave seismic‐reflection data that fill in a critical gap in our understanding of the SFZ beneath the urban areas of West Seattle, south‐central Seattle, and Mercer Island. These data image deformed strata in the upper 1 km, including upwarped Tertiary rock and younger sediments. Collectively, these data provide evidence for multiple Quaternary‐active thrust faults, back thrusts, and sub‐basins within the SFZ beneath the city of Seattle. The results indicate that multiple and potentially active back thrusts in the upper ∼500 m extend across the length of the SFZ and the entire urban corridor that may be analogous to those on Bainbridge Island west of Puget Sound.

Washington

Classification of lakebed geologic substrate in autonomously collected benthic imagery using machine learning

Mapping benthic habitats with bathymetric, acoustic, and spectral data requires georeferenced ground-truth information about habitat types and characteristics. New technologies like autonomous underwater vehicles (AUVs) collect tens of thousands of images per mission making image-based ground truthing particularly attractive. Two types of machine learning (ML) models, random forest (RF) and deep neural network (DNN), were tested to determine whether ML models could serve as an accurate substitute for manual classification of AUV images for substrate type interpretation. RF models were trained to predict substrate class as a function of texture, edge, and intensity metrics (i.e., features) calculated for each image. Models were tested using a manually classified image dataset with 9-, 6-, and 2-class schemes based on the Coastal and Marine Ecological Classification Standard (CMECS). Results suggest that both RF and DNN models achieve comparable accuracies, with the 9-class models being least accurate (~73–78%) and the 2-class models being the most accurate (~95–96%). However, the DNN models were more efficient to train and apply because they did not require feature estimation before training or classification. Integrating ML models into benthic habitat mapping process can improve our ability to efficiently and accurately ground-truth large areas of benthic habitat using AUV or similar images.

Michigan, Wisconsin

As above, so below? A framework for integrating long-term water quantity trends reveals divergent patterns in groundwater and low streamflow across the United States

Climate, land-use, and disturbance drive long-term global trends in groundwater levels and streamflow. At large scales, these trends are typically considered separately, despite the well-established concept that groundwater and surface water comprise a single resource. Joint trend assessment at national scales is challenging because it requires pairing and aggregating data from spatially disparate streamflow and groundwater monitoring sites for which no established framework exists. Here, we evaluate alternative approaches for integrating groundwater and streamflow data to enable joint trend analysis—a critical step toward understanding how water-budget components respond concurrently and interactively to environmental drivers. Mann–Kendall trends were computed for individual groundwater (annual mean depth) and streamflow (annual low of 7 d averages) sites across the U.S over 21- (2000–2020), 31- (1990–2020), and 41-year (1980–2020) periods. Regional Kendall trends were calculated using five spatially contiguous and noncontiguous regional classifications for aggregation based on subsurface (e.g. aquifer, geology) and surface (e.g. watershed, landscape) characteristics. Site-level results revealed contrasting trends, with tendencies toward increasing low flows (wetting) and increasing groundwater depths (drying). Agreement between streamflow and groundwater trends increased with regional aggregation and longer timeframes, though persistent skew toward streamflow wetting and groundwater drying remained. Results varied by region and trend period, with notable consistencies: unified drying in the West/Southwest and wetting in the Upper Midwest. Directional mismatches in long-term trends were prominent in the High Plains and Mississippi Alluvial Plain, whereas near-term mismatches were most evident in the Northwest. Aggregation by hydrologic landscape regions (HLR) yielded the greatest agreement between groundwater and streamflow trends. These findings indicate that coupled responses may represent combined influences of climate, relief, and geology, as captured by HLR, more strongly than geography or geology alone. Integrated water availability assessments may benefit from a multi-characteristic classification framework to treat groundwater and surface water as a unified resource.

Environmental Research: Water

The projected exposure and response of a natural barrier island system to climate-driven coastal hazards

Accelerating sea level rise (SLR) and changing storm patterns will increasingly expose barrier islands to coastal hazards, including flooding, erosion, and rising groundwater tables. We assess the exposure of Cape Lookout National Seashore, a barrier island system in North Carolina (USA), to projected SLR and storm hazards over the twenty-first century. We estimate that with 0.5 m of SLR, 47% of current subaerial barrier island area would be flooded daily, and the 1-year return period storm would flood 74%. For 20-year return period storms, over 85% is projected to be flooded for any SLR. The modelled groundwater table is already shallow (< 2 m deep), and while projected to shoal to the land surface with SLR, marine flooding is projected to overtake areas with emergent groundwater. Projected shoreline retreat reaches an average of 178 m with 1 m of SLR and no interventions, which is over 60% of the current island width at narrower locations. Compounding these hazards is subsidence, with one-third of the study area currently lowering at > 2 mm/yr. Our results demonstrate the difficulty of managing natural barrier systems such as those managed by federal park systems tasked with maintaining natural ecosystems and protecting cultural resources.

North Carolina

Oblique contraction along the fastest ocean-continent transform plate boundary focuses rock uplift west of the Fairweather fault, southeast Alaska

Contraction along the Yakutat–North America plate boundary drives 4.6–9.0 mm/year Holocene rock uplift rates along Earth's fastest slipping (≥49 mm/year) ocean–continent transform fault, the Fairweather Fault. Between Icy Point and Lituya Bay, the near-vertical Fairweather fault focuses rock uplift and rapid right-lateral slip by accommodating both vertical and fault-parallel strain during oblique-slip and separate, predominantly strike-slip ruptures. Unusually high uplift rates, indicated by radiocarbon and luminescence dating, result from a 10-km-wide, asymmetric, positive flower structure along a 20°, ∼30-km-long restraining double bend in the Fairweather fault. The principal reverse fault in the flower structure, the offshore, blind Icy Point–Lituya Bay fault, ruptures no more than every 460–1040 years evidenced by uplifted Holocene shorelines. Maximum 3–5 m coseismic uplifts imply 3.1–10 m dip slip per event and earthquake magnitudes of M w 7.0–7.5. The Yakutat block collides obliquely into North America, and our model entails oblique slip on the Fairweather fault with and without corupture on the reverse fault. Oblique slip is evident by vertically offset (&gt;25 m) fluvial and marine terraces and by the primary Fairweather fault strand that strikes &gt;20° to the west of plate-boundary motion.

Alaska

‘The fish that stop’: Drivers of historical decline for Pacific cod and implications for modern management in an era of rapidly changing climate

n the Gulf of Alaska, a series of marine heat waves depleted Pacific cod ( Gadus macrocephalus ) biomass to the lowest abundance ever recorded and led to the fishery’s closure in 2020. Although the fishery has been productive for decades, this collapse may have historical precedents. Traditional knowledge holders refer to cod as ‘the fish that stop’, and there is a suggested period of decline in the 1930s. Here we conduct a catch reconstruction of the early commercial fishery (1864–1950), confirming a rapid catch decline in the 1920s and 1930s. Next, we evaluate evidence for possible drivers. We document changes to demand and technology that contributed to declining catch. However, we also find both qualitative and quantitative evidence of depletion, suggesting catch declines were not driven entirely by social factors. Overfishing may have contributed to localized catch declines as evidenced by declining catch rates in heavily fished localities. We also find evidence for climate as a driver of regional decline, with the period of catch decline characterized by up to 2°C higher temperatures as compared to the earlier period of high fisheries production. Our analysis underscores the importance of understanding long-term drivers of fisheries productivity and the value of linking fisheries and climate histories.

Alaska

Bedrock geologic map of the Bellows Falls 7.5- x 15-minute quadrangle, Windham and Windsor Counties, Vermont, and Sullivan and Cheshire Counties, New Hampshire

Introduction The bedrock geology of the Bellows Falls 7.5- x 15-minute quadrangle, Vermont and New Hampshire, consists of polydeformed Ordovician to Devonian metasedimentary, metavolcanic, and metaplutonic rocks of the Connecticut Valley trough, Bronson Hill anticlinorium (or Bronson Hill terrane), and the Central Maine terrane. Previous work in this area includes a 1:62,500-scale published map and text (1946), State geologic maps of New Hampshire (1997) and Vermont (2011), and various maps and reports presented largely as parts of field trip guidebooks. A provisional open-file map of the geology of the Vermont part of the Bellows Falls 7.5- x 15-minute quadrangle, completed in 1997, is incorporated and revised on this map based on additional fieldwork. This study recognizes three major structural levels from west to east and from lowest to highest: (1) autochthonous rocks of the Connecticut Valley trough; (2) allochthonous rocks of the New Hampshire sequence and Bronson Hill arc in the Monroe thrust sheet (or nappe), including the Skitchewaug nappe; and (3) allochthonous rocks of the Fall Mountain thrust sheet or nappe.

New Hampshire, Vermont

Repeated coseismic uplift of coastal lagoons above the Patton Bay Splay Fault System, Montague Island, Alaska, USA

Coseismic slip on the Patton Bay splay fault system during the 1964 M w 9.2 Great Alaska Earthquake contributed to local tsunami generation and vertically uplifted shorelines as much as 11 m on Montague Island in Prince William Sound (PWS). Sudden uplift of 3.7–4.3 m caused coastal lagoons along the island's northwestern coast to gradually drain. The resulting change in depositional environment from marine lagoon to freshwater muskeg created a sharp, laterally continuous stratigraphic contact between silt and overlying peat. Here, we characterize the geomorphology, sedimentology, and diatom ecology across the 1964 earthquake contact and three similar prehistoric contacts within the stratigraphy of the Hidden Lagoons locality. We find that the contacts signal instances of abrupt coastal uplift that, within error, overlap the timing of independently constrained megathrust earthquakes in PWS—1964 Common Era, 760–870 yr BP, 2500–2700 yr BP, and 4120–4500 yr BP. Changes in fossil diatom assemblages across the inferred prehistoric earthquake contacts reflect ecological shifts consistent with repeated draining of a lagoon system caused by >3 m of coseismic uplift. Our observations provide evidence for four instances of combined megathrust-splay fault ruptures that have occurred in the past ∼4,200 years in PWS. The possibility that 1964-style combined megathrust-splay fault ruptures may have repeated in the past warrants their consideration in future seismic and tsunami hazards assessments.

Alaska

Depth of magma crystallization and fluid exsolution beneath the porphyry-skarn Cu deposits at Santa Rita and Hanover-Fierro, New Mexico, USA

The depth level at which porphyry Cu–forming magmas fractionated and exsolved mineralizing fluids is actively debated. In the classic model, extensive magma fractionation occurs in large, upper crustal magma chambers, and concomitant fluid exsolution leads to forceful expulsion of residual magmas in the form of porphyry dikes, stocks, and breccia pipes, which subsequently serve as pathways for the mineralizing fluids. In contrast, some recent studies highlighting the role of deep crustal magma fractionation in the production of fertile magmas essentially deny the existence of upper crustal magma chambers at the time of mineralization. To address this, we conducted a detailed thermobarometric investigation of 13 intermediate to felsic, porphyritic intrusive rocks related to porphyry-skarn Cu mineralization at Santa Rita and Hanover-Fierro, New Mexico, United States, representing two premineralization magmas (61–60 Ma), seven synmineralization magmas (60–58 Ma), and four late- to postmineralization magmas (58–57 Ma). For each sample, the pressure of last magma crystallization before final magma ascent to the current exposure level was reconstructed based on Al-in-hornblende barometry of small hornblende inclusions trapped within quartz phenocrysts and through titanium-in-quartz (TitaniQ) thermobarometry of the host quartz phenocrysts themselves. Since quartz is one of the last crystallizing magmatic minerals, and no significant phenocryst growth could have occurred in small dikes and stocks after final magma emplacement, quartz phenocrysts and their contained hornblende inclusions record the depth of last magma crystallization before final magma ascent. When present, hornblende phenocrysts and hornblende inclusions within other major phenocrysts were also analyzed. Both quartz and hornblende barometers return consistent average pressures of 3.2 ± 0.4 kbar for the entire suite of pre- to postmineralization magmas, corresponding to depths of 11 to 14 km. The synmineralization magmas return even more consistent average pressures of 3.1 ± 0.2 kbar, corresponding to a depth of 12 ± 1 km. The volume of the mineralizing porphyry dikes and stocks at the emplacement level is far too small to have provided all the fluids and metals required to form the observed ore deposits. Therefore, the majority of the ore-forming fluids must have originated from the magmas that crystallized at 12 ± 1 km depth. The ore deposits, conversely, formed at ~5-km paleodepth. This implies that most of the mineralizing fluids traveled an average vertical distance of ~7 km from their magmatic source to the eventual site of ore precipitation. The relatively unaltered nature and low veining degree of deeper parts of mineralized porphyry dikes and stocks suggest that the fluid transport through these intrusive bodies occurred mostly at near-solidus conditions by means of fluid percolation along grain boundaries. In summary, our results suggest that (1) a large, upper crustal pluton exists ~7 km beneath the Santa Rita and Hanover-Fierro deposits; (2) abundant phenocryst crystallization occurred at this depth level; and (3) this pluton was the main source for the exsolution of ore-forming fluids. However, the investigated rocks have elevated whole-rock Sr/Y ratios, indicating magma fractionation at deep crustal levels. As a result, our preferred model is a combination of the two end-member models introduced above, with most magma fractionation having occurred in the deep crust and with residual, intermediate to felsic melts having ascended and accumulated at 11 to 14 km paleodepth, where they continued to crystallize with comparatively little crystal-liquid separation, before some of these magmas ascended further to shallow levels and quenched to porphyries.

New Mexico

Reduction of red bed sedimentary rocks in connection with energy metal ore formation: A case study from the Sinbad seep, Mesa County, Colorado

The Paradox Basin’s Sinbad seep is a modern analog for ancient bleaching of red bed sediments by introduced alkaline, reducing brines. This bleaching, involving reductive alteration of former red beds, is essential ground preparation that enables the altered rocks to trap Cu, U, and V from later oxidized fluids, forming ore deposits. Study of Sinbad thus offers insights into these metallic mineralization processes in the Paradox and other sedimentary basins. The Sinbad seep occurs where shallow groundwater interacts with organic-rich petroleum source rocks, flows up a fault, and discharges into Salt Creek. Ratios of Na/Cl, Na/Br, and Cl/Br, plus high sulfate concentrations, indicate that the salinity of the seep water originated from dissolution of halite and gypsum during topographically driven flow of meteoric water across a diapir of the Pennsylvanian Paradox Formation, rather than from deep basinal brines. In contact with the organic-rich shales of the Paradox, these SO 4 -rich waters become reduced through bacterial reduction, producing H 2 S. The waters react with red beds of the Permian Cutler Formation, causing pervasive bleaching. The bleaching at Sinbad is characterized by iron-conservative reduction of ferric iron in diagenetic hematite and detrital ilmenite and magnetite to Fe sulfides. The ferrous iron is retained in these sulfides likely as sorbed Fe. Associated alteration includes precipitation of quartz and feldspar overgrowths, partial dissolution of detrital quartz and feldspar caused by pressure solution, formation of clay and authigenic rutile, and precipitation of carbonate and gypsum. The Fe sulfides rapidly degenerate to a mixture of jarosite and iron oxides on weathering at the surface. Among the major-oxide elements and most trace elements, there is no statistical difference between unbleached and bleached samples. The exceptions are uranium and sulfur, which are somewhat greater in bleached samples. Fission track radiography illuminates that uranium is preferentially concentrated in iron oxide cements, iron sorbed into detrital clasts, and finely disseminated iron oxide in illite cement in bleached samples. A leaching experiment suggests that uranium may be more easily available for mobilization from rocks that have undergone bleaching alteration, making them potential U sources. In addition, bleached rocks form effective traps for U, V, and some Cu mineralization.

Colorado

Surficial geologic map of the Owlshead Mountains 30' x 60' quadrangle, Inyo and San Bernardino Counties, California

The surficial geologic map of the Owlshead Mountains 30' x 60' quadrangle depicts the distribution and characteristics of surficial-deposit materials and neotectonic deformation for an area of approximately 5,000 square kilometers (km 2 ) located in the western Basin and Range Province of eastern California. The map represents a new compilation of the surficial geology that encompasses deposits within the late Pliocene to Quaternary. The map is based primarily on new mapping conducted between 2001 and 2009. Map compilation was supported by field observations distributed across the map area, combined with reference to several published and unpublished mapping sources that mostly emphasized neotectonic deformation. The surficial-deposit units included in the map follow a classification scheme that systematically denotes depositional process, relative age, and any secondary sedimentologic or morphologic characteristics. Identification, correlation, and age estimation of map units are based primarily on the relative degree of development of certain time-dependent characteristics such as surface morphology, including local dissection and surface preservation, surface clast modification, and degree of soil development; these characteristics are implicitly incorporated into unit designations. The map represents a detailed and regionally uniform synthesis of the late Neogene geology for this large area that provides a framework applicable to many interpretative studies, such as regional patterns of deposition and dissection; surface drainage development and evolution; and the distribution, style, and timing of neotectonic deformation.

California

Beyond the mangroves: A global synthesis of tidal forested wetland types, drivers and future information opportunities

There is increasing awareness of the global diversity of tidal forested wetlands (TFWs) and their significance in the provision of ecosystem services. These ecosystems, including mangrove forests, tidal freshwater forested wetlands, supratidal forests and transitional forests together span multiple climatic zones, geomorphic settings, and inundation and salinity regimes. We utilise case studies across five continents to demonstrate the state of knowledge among TFWs. Intertidal mangroves are the best-defined of the TFWs thanks to decades of research on their geomorphology, hydrology and ecology across their broad distribution. Non-mangrove forest settings, however, demonstrate more diverse hydrological, biochemical and vegetation conditions. In many cases, non-mangrove forests are situated at upper intertidal or supratidal elevations, where surface waters and groundwater are subject to interactions between tides freshwater inputs. Salinity datasets show variations ranging from tidal freshwater forested wetlands and ‘low-salinity mangroves’ to mesohaline or marine salinities, often with high temporal variability. While the floristic composition of non-mangrove forests vary among biogeographic regions, locally dominant TFW species are commonly distributed beyond the tidal niche into non-tidal wetland and upland forests. This presents challenges for traditional remote sensing approaches to ecosystem mapping, which are mostly lacking for non-mangrove forests. Geomorphic approaches and developments in machine learning offer opportunities to address this.

Preprint

Reaction kinetics and accelerant effects of sulfides in early mature hydrocarbon generation using hydrous pyrolysis

Hydrocarbon generation in organic-rich sediments is influenced by the molecular organic composition and relative abundance of associated minerals. Certain mineral-derived elements act as catalysts and reaction intermediaries, facilitating early-stage hydrocarbon formation in potential source rocks. This study investigated the role of sulfur contributed from pyrite as an accelerant in thermal reaction, focusing on its effects on early maturation and consequent hydrocarbon generation from gilsonite (low-sulfur solid petroleum). Hydrous pyrolysis (HP) experiments were conducted on mixtures of gilsonite and pyrite in varying ratios (1:0.1, 1:0.5, 1:1, 1:2, and 1:10 w/w gilsonite:pyrite) at 320, 350, and 370 °C for 72 h. Untreated and thermally altered residues were analyzed using solid bitumen reflectance (BR o , %), total organic carbon (TOC) content, programmed temperature pyrolysis, scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), and X-ray diffraction (XRD) to evaluate the potential accelerant role of pyritic sulfur in hydrocarbon formation. The results show HP residues at 320 and 350 °C with greater pyrite concentrations had higher BR o , while reflectance values were similar in the 370 °C residues, regardless of pyrite concentration, suggesting enhanced reaction at lower thermal conditions. Increasing pyrite content systematically decreased hydrogen index (HI) values while increasing the transformation ratio (TR) and production index (PI), indicating enhanced conversion of organic matter to hydrocarbons with increasing pyrite concentrations. Gas yields increased with pyrite addition, particularly at 350 °C, confirming secondary cracking effects. However, gas production stabilized or declined at higher pyrite loadings (1:10), suggesting alternative reaction pathways such as coke formation. Our data indicate the presence of pyrite lowers the activation energy for thermal cracking, shifting peak experimental hydrocarbon generation temperatures downward by 20–30 °C, with the most pronounced accelerant effects observed at moderate pyrite concentrations (1:0.5 and 1:1). The thermodynamic framework reveals that pyrite stability is influenced by experimental conditions, with pyrrhotite formation favored in the presence of gilsonite due to reduced oxygen fugacity. Pyrite transformation to pyrrhotite, as observed through XRD, SEM-EDS, and predicted by thermodynamic data, further supports the accelerant role of S, as pyrrhotite exhibits a higher hydrogen transfer potential, promoting early oil generation. These findings highlight the importance of pyrite in modulating hydrocarbon generation pathways in organic-rich systems.

Journal of Analytical and Applied Pyrolysis