Geochemical Modeling Research Articles

Regional potential of coastal ocean alkalinisation with olivine within 100 years

Abstract The spreading of crushed olivine-rich rocks in coastal seas to accelerate weathering reactions sequesters atmospheric CO2 and reduces atmospheric CO2 concentrations. Their weathering rates depend on different factors, including temperature and the reaction surface area. Therefore, this study investigates the variations in olivine-based enhanced weathering rates across 13 regional coasts worldwide. In addition, it assesses the CO2 sequestration within 100 years and evaluates the maximum net-sequestration potential based on varying environmental conditions. Simulations were conducted using the geochemical thermodynamic equilibrium modeling software PHREEQC. A sensitivity analysis was performed, exploring various combinations of influencing parameters, including grain size, seawater temperature, and chemistry. The findings reveal significant variation in CO2 sequestration, ranging from 0.13 to 0.94 metric tons (t) of CO2 per ton of distributed olivine-rich rocks over 100 years. Warmer coastal regions exhibit higher CO2 sequestration capacities than temperate regions, with a difference of 0.4 t CO2/ t olivine distributed. Sensitivity analysis shows that smaller grain sizes (10 µm) exhibit higher net CO2 sequestration rates (0.87 t/t) in olivine-based enhanced weathering across all conditions, attributed to their larger reactive surface area. However, in warmer seawater temperatures, olivine with slightly larger grain sizes (50 and 100 µm) displays still larger net CO2 removal rates (0.97 and 0.92 t/t), optimizing the efficiency of CO2 sequestration while reducing grinding energy requirements. While relying on a simplified sensitivity analysis that does not capture the full complexity of real-world environmental dynamics, this study contributes to understanding the variability and optimization of enhanced weathering for CO2 sequestration, supporting its potential as a sustainable CO2 removal strategy.

Fluid geochemistry of the Cerro Galán geothermal system (Southern Puna, Argentina): Implications for the geothermal potential of one of the youngest giant calderas in the Andes

The exploration of novel geothermal systems, particularly those promising for electrical power generation, plays a fundamental role in incorporating new renewable sources into the energy matrix. Geothermal systems associated with volcanic calderas are considered ideal targets for exploration. This study focuses on the geochemical features of fluids from the Cerro Galán hydrothermal system, which is hosted within a major resurgent caldera with >3.5 Myr of magmatic evolution situated on the Southern Puna (Central Volcanic Zone of the Andes, NW Argentina). The main aim is constructing the first geochemical conceptual model and provide information on the geothermal potential of this interesting resource. The main hydrothermal reservoir consists of a NaCl aquifer with estimated temperatures up to 187 °C at depth. This reservoir is likely hosted within the fractured pre-caldera basement rocks, mainly including Miocene-Pliocene volcanic rocks and Proterozoic-Cambrian igneous and metamorphic rocks. The confinement of the deep reservoir is attributed to the deposits of the Toconquis Group and Cueva Negra Ignimbrite, along with the basal section of the Cerro Galán Ignimbrite, which exhibit low permeability due to hydrothermal alteration. The presence of a phreatic explosion crater near one of the hot spring-rich areas is likely indicating past over-pressurization of the hydrothermal aquifer, resulting from efficient sealing. Furthermore, the absence of anomalous soil CO2 flux values on the top of the reservoir, except where the thermal spring discharges are located, can be explained by an effective cap-rock layer. Deep circulation of meteoric water, enriched with atmospheric gases, receives inputs of magmatic fluids (~11% of primordial helium), leading to the development of the hydrothermal NaCl aquifer. However, this deep fluid contribution might be underestimated due to significant crustal assimilation (up to 50%) involved in the magma genesis of the Cerro Galán Volcanic Complex, a process which modifies the He isotopic signature of the magmatic endmember. The hot springs, characterized by high flow rate (up to 459 m3/h) are positioned at the intersection between the caldera margins and the NNE-SSW oriented tectonic structures, suggesting favorable permeability conditions. The preliminary geothermal gradient for the Cerro Galán area is estimated at around 98–101 °C/km. Such a high gradient can be attributed to the considerable heat flux generated by the transcrustal plumbing system of the Cerro Galán caldera, which includes the shallow crystal mush reservoir (<4 km depth). The preliminary geothermal potential of this giant caldera was performed using the volumetric method along with Monte Carlo simulations. The results indicate a probable power production capacity of 2.09 MWe and 10.85 MWe at 90 and 50% confidence level, respectively. The results presented in this work constitute a foundational knowledge base to promote a more advanced exploration phase for the geothermal resource. Additionally to the local energy demand, lithium and other metal mining operations, which are operating independently from the National Interconnected System, could potentially be interested in power generation through binary cycles.

Slab failure‐related magmatism in the Pinheiro Machado Complex, southern Dom Feliciano Belt, Brazil

In the Dom Feliciano Belt, Brazil, the Pinheiro Machado Complex (PMC) includes diorites, tonalites, granodiorites, syenogranites and granites, whose evolution is related to several magmatic pulses and complex petrogenetic processes. Two magmatic stages were identified (early and late), resulting in different rock subgroups. The geochemical data showed that the early magmatism was chemically affected by partial melting. Geochemical modelling results suggest that fractional crystallization processes with assimilation of around 40% from the crustal basement and the decoupling of assimilated magma are crucial for the PMC rocks' genesis. Geochemical data also show that during the early magmatism, the subsequent process of early diorite anatexis developed by heating and continuous activity of the underlying magma chamber possibly occurred at a melting rate of 5%–10%. The hybrid rocks have contributions from the mixing process related to early terms, showing geochemical correlations in the major element curves, for the early diorite and syenogranitic melt members, at 60%–50% and 50%–40%, respectively. Slab failure tectonic context is related to the multi‐intrusive events dynamics recorded in the studied rocks. Recharge and melting events of the recently formed crust due to the constant heating of new pulses of deep slab melting would explain the magmatic interactions observed in the Complex. The results demonstrate that the studied rocks crystallized in an open system, including mixing processes to form hybrid rocks, physical disaggregation and assimilation of early intrusions, truncation, dragging and erosion of early mushes by younger pulses.

Geochemical Modeling and Hydrocarbon Generation Potentiality of Source Rocks of the Oligocene to Miocene Succession in the Temsah Area, Eastern Nile Delta, Egypt

Geochemical investigation of the Temsah-4 well (T-4) in Temsah gas fields at the eastern offshore Nile Delta differentiate into two categories of OM (organic matter) which are kerogen types II and III within the boreholes penetrated Oligocene-Miocene source rocks. The geochemical and lithological characteristics of the OM-bearing formations in the investigated borehole recognized four thick organic matter-rich intervals (OMRI) in well T-4. The OMRI considers a part of formations that are believed to be considered a real source rock that comprises approximately 66.68% of the Wakar, 65.17% of Sidi-Salem, and 100% of Qantara Fms in the T-4 well. They comprised intervals depths of 3120m-3150m and 3300m-3559.4m belonging to Wakar Fm, from 3580m- 3870m belonging to Sidi-Salem Fm and from 3977m- 4170m belonging to Qantara Fm. The geochemical data reveals that Wakar Fm in the T-4 well considers immature source rock. While mature OMRI within Sidi-Salem and Qantara Fms in the T-4 well represented as effective mature source rocks. Construction of a TOC map in two dimensions throughout the studied areas shows a trend of increasing the quantity of OM eastward during the deposition of Sidi-Salem and Wakar Fms. The improvements of the richness (relatively high TOC) toward the eastward suggested a favorable condition for preservation and accumulation of OM toward the east than the west drilled boreholes. Based on the relative hydrocarbon potential (RHP) the suggested expulsion threshold depths appear to be shallower at 3700m in T-4. Burial history diagrams of studied T-4 wells based on geochemical results postulate that Tineh Fm enters the early mature stage at 2.8Ma. The maturity continues till the recent periods to enter the Qantara and most of Sidi-Salem Fms the same main-oil window at the T-4 area.

Changes in soil bacterial community structure in a short-term trial with different silicate rock powders

BackgroundThe use of rock powders in soil has emerged as a nature-based technology to improve soil properties relevant to crop development and for atmospheric carbon dioxide removal (CDR) via enhanced rock weathering (ERW). Although modeling this process is crucial, the soil microbiome has been identified as the main reason why several experimental and field results do not fit the geochemical and kinetic theoretical models. Here, the hypothesis that the bacterial community structure is modulated by the application of different silicate rock powders was tested. One phonolite, three basalt variations and one granite, as well as KCl treatments, were applied to a Ferralsol cultivated with Brachiaria in short-term pedogeochemical experiments and assessed after 1 (1M), 4 (4M) and 8 (8M) months.ResultsThe main changes in soil bacterial structure were observed at 8M and found to be modulated according to rock type, with petrochemistry and mineralogy acting as the main drivers. The content of microbial biomass carbon tended to decrease over time in the Control and KCl treatments, especially at 4M, while the rock treatments showed constant behavior. The sampling time and treatment affected the richness and diversity indices. The Si, Ca and Fe from mafic minerals were the main chemical elements related to the soil bacterial changes at 8M.ConclusionsThe type (acidity) of silicate rock powder modulated the soil bacterial community (SBC) in a pot experiment with tropical soil. The specificity of the SBC for each rock type increased with time until the end of the experiment at 8 months (8M). The carbon content in the microbial biomass was lower in the rock powder treatments in the first month (1 M) than in the control and KCl treatments and was equal to or higher than that in the 8 M treatment. This result illustrates the challenge of modeling rock powder dissolution in soil since the soil medium is not inert but changes concurrently with the dissolution of the rock.Graphical

Influence of Organic Matter Thermal Maturity on Rare Earth Element Distribution: A Study of Middle Devonian Black Shales from the Appalachian Basin, USA

This study focuses on understanding the association of rare earth elements (REE; lanthanides + yttrium + scandium) with organic matter from the Middle Devonian black shales of the Appalachian Basin. Developing a better understanding of the role of organic matter (OM) and thermal maturity in REE partitioning may help improve current geochemical models of REE enrichment in a wide range of black shales. We studied relationships between whole rock REE content and total organic carbon (TOC) and compared the correlations with a suite of global oil shales that contain TOC as high as 60 wt.%. The sequential leaching of the Appalachian shale samples was conducted to evaluate the REE content associated with carbonates, Fe–Mn oxyhydroxides, sulfides, and organics. Finally, the residue from the leaching experiment was analyzed to assess the mineralogical changes and REE extraction efficiency. Our results show that heavier REE (HREE) have a positive correlation with TOC in our Appalachian core samples. However, data from the global oil shales display an opposite trend. We propose that although TOC controls REE enrichment, thermal maturation likely plays a critical role in HREE partitioning into refractory organic phases, such as pyrobitumen. The REE inventory from a core in the Appalachian Basin shows that (1) the total REE ranges between 180 and 270 ppm and the OM-rich samples tend to contain more REE than the calcareous shales; (2) there is a relatively higher abundance of middle REE (MREE) to HREE than lighter REE (LREE); (3) there is a disproportionate increase in Y and Tb with TOC likely due to the rocks being over-mature; and (4) the REE extraction demonstrates that although the OM has higher HREE concentration, the organic leachates contain more LREE, suggesting it is more challenging to extract HREE from OM than using traditional leaching techniques.

Environmental assessment of phosphogypsum: A comprehensive geochemical modeling and leaching behavior study

Understanding the variations in the geochemical composition of phosphogypsum (PG) destined for storage or valorization is crucial for assessing the safety and operational efficacy of waste management. The present study aimed to investigate the environmental behavior of PG using different leaching tests and to evaluate its geochemical behavior using geochemical modeling. Regarding the chemical characterization, the PG samples were predominantly composed of Ca (23.03–23.35 wt%), S (17.65–17.71 wt%), and Si (0.75–0.82 wt%). Mineralogically, the PG samples were primarily composed of gypsum (94.2–95.9 wt%) and quartz (1.67–1.76 wt%). Moreover, the automated mineralogy revealed the presence of apatite, fluorine and malladrite phases. The overall findings of the leaching tests showed that PG could be considered as non-hazardous material according to US Environmental Protection Agency limitations. However, a high leachability of elements at a L/S of 2 under acidic conditions ([Ca] = 166.52–199.87 mg/L, [S] = 207.9–233.59 mg/L, [F] = 248.62–286.65 mg/L) is observed. The weathering cell test revealed a considerable cumulative concentration over 90 days indicating potential adverse effects on the nearby environment (S: 8000 mg/kg, F: 3000 mg/kg, P: 700 mg/kg). Based on these results, it could be estimated that the surface storage of PG could have a serious impact on the environment. In this context, a simulation model was developed based on weathering cell results showed encouraging results for treating PG leachate using CaO before its disposal. Additionally, PHREEQC was used to analyze the speciation of major elements and calculate mineral phase saturation indices in PG leaching solutions. The findings revealed pH-dependent speciation for Ca, S, P, and F. The study identified gypsum, anhydrite, and bassanite as the key phases governing the dissolution of these elements.

A PHREEQC-Based Tool for Planning and Control of In Situ Chemical Oxidation Treatment

This article describes a tool that can be used to improve the effectiveness of the ISCO (in situ chemical oxidation) method. It is an Excel-based application that uses Visual Basic, PHREEQC, and Python. The main functions are feedback control solutions. There are several ideas that can optimise ISCO treatment when using the geochemical model: (i) looping real-time data into the geochemical model and using them to estimate the actual rate, (ii) using spatial distribution maps for delineating zones that are susceptible or resistant to oxidation, (iii) visualising the permanganate consumption that could indicate the right time for further action, and (iv) using alarm reports of the abnormal physico-chemical conditions that jeopardise successful injection.

Mantle Sources and Geochemical Evolution of the Picture Gorge Basalt, Columbia River Basalt Group

The Columbia River Basalt Group (CRBG) is the youngest continental flood basalt province, proposed to be sourced from the deep-seated plume that currently resides underneath Yellowstone National Park. If so, the earliest erupted basalts from this province, such as those in the Picture Gorge Basalt (PGB), aid in understanding and modeling plume impingement and the subsequent evolution of basaltic volcanism. Using geochemical and isotopic data, this study explores potential mantle sources and magma evolution of the PGB. Long known geochemical signatures of the PGB include overall large ion lithophile element (LILE) enrichment and relative depletion of high field strength elements (HFSE) typical of other CRBG main-phase units. Basaltic samples of the PGB have 87Sr/86Sr ratios on the low end of the range displayed by other CRBG lavas and mantle-like δ18O values. The relatively strong enrichment of LILE and depletion of HFSE coupled with depleted isotopic signatures suggest a metasomatized upper mantle as the most likely magmatic source for the PGB. Previous geochemical modeling of the PGB utilized the composition of two high-MgO primitive dikes exposed in the northern portion of the Monument Dike swarm as parental melt. However, fractionation of these dike compositions cannot generate the compositional variability illustrated by basaltic lavas and dikes of the PGB. This study identifies a second potential parental PGB composition best represented by basaltic flows in the extended spatial distribution of the PGB. This composition also better reflects the lowest stratigraphic flows identified in the previously mapped extent of the PGB. Age data reveal that PGB lavas erupted first and throughout eruptions of main-phase CRBG units (Steens, Imnaha, Grande Ronde Basalt). Combining geochemical signals with these age data indicates cyclical patterns in the amounts of contributing mantle components. Eruption of PGB material occurred in two pulses, demonstrated by a ~0.4 Ma temporal gap in reported ages, 16.62 to 16.23 Ma. Coupling ages with observed geochemical signals, including relative elemental abundances of LILE, indicates increased influence of a more primitive, potentially plume-like source with time.

Major, trace and platinum-group element geochemistry of Mesoarchean komatiites from the Banasandra greenstone belt, Western Dharwar Craton (southern India): implications for multi-stage plume magmatism in generating compositionally diverse komatiites

ABSTRACT The early Archean Al-undepleted komatiites (AUK) from two locations (Kunikenahalli, Kodihalli) of the Banasandra greenstone belt in the Western Dharwar Craton are studied for understanding their petrogenesis. The field distribution, mineralogy and geochemistry indicate their cogenetic nature. The samples are mainly cumulates (MgO: 37–45 wt%), now completely serpentinized, while the spinifex zone is obscure. Using geochemical modelling, the MgO content of the primary undifferentiated magma is estimated to be nearly 25 wt%. The depleted LREE values from this study, and the positive εNd values from previous studies suggest that the komatiites are derived from a depleted mantle source. Trace-element and PGE geochemistry eliminate the possibility of crustal contamination and sulphide-saturation in these komatiites after emplacement. Modelling results estimated in this study suggest ~45% melting of a deeper mantle (~6 GPa) to generate the komatiites. Fractionation of olivine (Fo94) from the parental melt and their accumulation formed the mesocumulates in Kodihalli, and the more fractionated orthocumulates in Kunikenahalli. The compositional spectrum from AUK through Al-depleted (ADK) to Al-enriched (AEK) varieties in the Banasandra greenstone belt reported in this study and others, are proposed to be a product of melting of a single mantle plume at different depths.

Characterization of Surfactant Adsorption Profile in Carbonates Under Severe Reservoir Conditions With Geochemical Modeling Approach

Abstract Chemical flooding has gained ample popularity as an effective technique to increase oil displacement and sweep efficiencies. However, very limited numerical applications of chemical flooding (surfactant and polymer) in carbonates are reported in the literature. Therefore, a geochemical-based surface complexation model is developed to characterize the adsorption profile of surfactants for the first time across the length of a core/reservoir. The proposed model is validated with various zeta-potential measurements and also with a recently conducted chemical flooding study. Additionally, sensitivity analysis of various parameters is performed, and it is found that surfactant effluent concentration decreases with the increase in flood temperature. It is observed that salinity reduction decreases the surfactant adsorption, increases the ionic repulsion amid the rock surface charge and the chemical species polarity. Similarly, when the concentration of surfactant is increased, the adsorption of surfactant concentration increases. However, the increase in surfactant adsorption is insignificant. The effect of sulfate spiking in chemical flooding is also investigated and it is found that an increase in sulfate concentration reduces the adsorption of surfactant across the reservoir. Moreover, the lowermost surfactant adsorption level is achieved through the injection of diluted water (&amp;lt;0.1 mg/g).

Iron silicate perovskite and postperovskite in the deep lower mantle

Ferromagnesian silicates are the dominant constituents of the Earth's mantle, which comprise more than 80% of our planet by volume. To interpret the low shear-velocity anomalies in the lower mantle, we need to construct a reliable transformation diagram of ferromagnesian silicates over a wide pressure-temperature (P-T) range. While MgSiO3 in the perovskite structure has been extensively studied due to its dominance on Earth, phase transformations of iron silicates under the lower mantle conditions remain unresolved. In this study, we have obtained an iron silicate phase in the perovskite (Pv) structure using synthetic fayalite (Fe2SiO4) as the starting material under P-T conditions of the lower mantle. Chemical analyses revealed an unexpectedly high Fe/Si ratio of 1.72(3) for the Pv phase in coexistence with metallic iron particles, indicating incorporation of about 25 mol% Fe2O3 in the Pv phase with an approximate chemical formula (Fe2+0.75Fe3+0.25)(Fe3+0.25Si0.75)O3. We further obtained an iron silicate phase in the postperovskite (PPv) structure above 95 GPa. The calculated curves of compressional (VP) and shear velocity (VS) of iron silicate Pv and PPv as a function of pressure are nearly parallel to those of MgSiO3, respectively. To the best of our knowledge, the iron silicate Pv and PPv are the densest phases among all the reported silicates stable at P-T conditions of the lower mantle. The high ferric iron content in the silicate phase and the spin-crossover of ferric iron at the Si-site above ~55 GPa should be taken into account in order to interpret the seismic observations. Our results would provide crucial information for constraining the geophysical and geochemical models of the lower mantle.

Quantifying the mitigating effect of organic matter on heavy metal availability in soils with different manure applications: A geochemical modelling study

Manure is one of the main sources of heavy metal (HM) pollution on farmlands. It has become the focus of global ecological research because of its potential threat to human health and the sustainability of food systems. Soil pH and organic matter are improved by manure and play pivotal roles in determining soil HM behavior. Geochemical modeling has been widely used to assess and predict the behavior of soil HMs; however, there remains a research gap in manure applications. In this study, a geochemical model (LeachXS) coupled with a pH-dependent leaching test with continuously simulations over a broad pH range was used to determine the effects and pollution risks of pig or cattle manure separate application on soil HMs distribution. Both pig and cattle manure applications led to soil pH reduction in alkaline soils and increased organic matter content. Pig manure application resulted in a potential 90.5–156.0 % increase in soil HM content. Cattle manure did not cause significant HM contamination. The leaching trend of soil HMs across treatments exhibited a V-shaped change, with the lowest concentration at pH = 7, gradually increasing toward strong acids and bases. The dissolved organic matter-bound HM content directly increased the HM availability, especially for Cu (up to 8.4 %) after pig manure application. However, more HMs (Cr, Cu, Zn, Ni) were in the particulate organic matter-bound state than in other solid phases (e.g., Fe-Al(hydr) oxides, clay minerals), which inhibited the HMs leaching by more than 19.3 % after cattle manure application. Despite these variations, high HM concentrations introduced by pig manure raised the soil contamination risk, potentially exceeding 40 times at pH ±1. When manure is returned to the field, reducing its HM content and mitigating possible pollution is necessary to realize the healthy and sustainable development of circular agriculture.

Macroscale Modeling of Geochemistry Influence on Polymer and Low-Salinity Waterflooding in Carbonate Oil Reservoirs.

The enhancement of oil recovery (EOR) through low-salinity waterflooding (LSWF) and the emerging hybrid with a polymer (LSP) has proven to be effective at microscale investigations and cost-effective with ease of operation at field-scale tests. Their application in carbonate oil reservoirs, which typically occur oil-wet, presents a particularly essential capacity given that over half of the global oil reserves are hosted in carbonate formation. However, modeling the mechanisms involved to predict and evaluate the performance of low salinity-based EOR at a large scale is complex and requires the integration of geochemistry in reservoir simulation to upscale the interfacial interactions of crude oil, brine, and rock observed at the micrometer scale. This study presents an integrated approach that combines MRST's polymer model with PHREEQC geochemical modeling to simulate LSWF at the reservoir scale. Using single-phase and multiphase experimental flooding data for validation, the coupled model was shown to accurately predict effluent ionic and oil recovery profiles. The simulation of LSWF and LSP both exhibited additional tertiary oil recovery, with LSWF and LSP showing 3 and 2%, respectively, which are consistent with previously reported field and core flooding results. Furthermore, the sequential application of formation water (FW), LSWF, and LSP flooding in secondary mode showed a high increase in oil recovery, with oil recovery percentages of 61, 20, and 19%, respectively. However, the FW results were 50% lower compared to regular core flooding due to upscaling limitations. The modeling of vertical and anisotropic permeability heterogeneity effects showed a positive synergy with low-salinity floodings, resulting in a 4% drop and 3 and 1% increase in FW, LSWF, and LSP, respectively. These findings demonstrate the potential of the coupled MRST-PHREEQC model in accurately simulating hydrogeochemical interactions during LSWF/LSP at the reservoir scale, providing valuable insights for the optimization of low salinity-based EOR strategies in carbonate reservoirs.

The felsic volcanism associated BIF-like iron formations: Their origin and implication for BIFs

The Banded Iron Formations (BIFs) have been invaluable archives for the Precambrian eons, providing evidence for the paleoenvironment conditions, including the atmospheric oxygen levels. This study explores the geological origin and depositional mechanism of BIF-like Carboniferous Heiyingshan (HYS) and Mesoproterozoic Pilot Knob hematite (PKH) formations, characterized by hematite-rich (Fe-rich) layer and quartz-rich (Si-rich) jasper layer alternations within felsic volcanic rocks. Through comprehensive mineralogical analyses and geochemical modeling, we present evidence supporting their formation in intra-caldera hot spring lakes, where episodic inputs of Fe(H3SiO4)2-bearing fluids mixed with ambient lake water. Experimental simulations and PHREEQC modeling corroborate a mechanism where ferrihydrite and amorphous silica precursors sequentially precipitate, possibly driven by the oxidation and decomposition rates of Fe(H3SiO4)2 complexes. The sharp or gradational change in the Fe- and Si-rich layering transition can be caused by varying atmospheric oxygen levels. The Carboniferous HYS specimen exhibits a sharp FeSi boundary that is in accordance with modeling under high atmospheric O2 condition. In contrast, the Mesoproterozoic PKH sample contains both sharp and gradual change in the FeSi transition, implying the pO2 lies between 10−3 and 10−5. This chemical precipitation model of BIF-like iron formations could provide insights into the FeSi source and banding mechanism of BIFs, and Precambrian pO2 levels.

Acceleration of Deep Subsurface Fluid Fluxes in the Anthropocene

AbstractThe Anthropocene has been framed around humanity's impact on atmospheric, biologic, and near‐surface processes, such as land use and vegetation change, greenhouse gas emissions, and the above‐ground hydrologic cycle. Groundwater extraction has lowered water tables in many key aquifers but comparatively little attention has been given to the impacts in the deeper subsurface. Here, we show that fluid fluxes from the extraction and injection of fluids associated with oil and gas production and inflow of water into mines likely exceed background flow rates in deep (&gt;500 m) groundwater systems at a global scale. Projected carbon capture and sequestration (CCS), geothermal energy production, and lithium extraction to facilitate the energy transition will require fluid production rates exceeding current oil and co‐produced water extraction. Natural analogs and geochemical modeling indicate that subsurface fluid manipulation in the Anthropocene will likely appear in the rock record. The magnitude and importance of these changes are unclear, due to a lack of understanding of how deep subsurface hydrologic and geochemical cycles and associated microbial life interact with the rest of the Earth system.

Spectrometric borehole logging in mineral exploration and mining

Borehole logging tools based on pulsed neutron technology are used to infer geophysical parameters such as bulk density. If fitted with a gamma-ray spectrometer, they may also measure elemental mass fractions of a variety of formation elements. Spectrometric borehole logging tools of this kind are established in the oil and gas industry. With the demand for mineral resources surging, cost- and time-efficient measurement techniques are increasingly needed in mineral exploration. Their ability to detect multiple elements that are building blocks of minerals makes spectrometric borehole logging tools popular in mineral exploration and mining grade control. In this article, the potential of the OreLog pulsed neutron gamma spectrometric downhole logging tool is demonstrated at Erzberg Mountain (Styria, Austria). Erzberg hosts the largest known siderite deposit in the world, and open-pit mining is used to extract iron ore. The aim was to obtain a more detailed and faster geochemical characterization of iron ore deposits prior to blasting. Elemental logs were acquired with highest accuracies for Fe, Ca, and Mn, followed by Si, Mg, K, and S. The tool mapped a 2D cross section of formation element concentration within a few hours, which agrees with orogenetic fault and geologic contact lines. Mineralogical information retrieved from elemental logs confirmed the interlaced mineralogy of the site. It is dominated by a carbonate body, hosting an intergrowth of Mg-rich siderite (sideroplesite) and a solid solution of dolomite/ankerite/kutnohorite. In addition to the tool's potential for enhanced real-time mining control, the benefit of continuous depth-resolved elemental logs is seen in the possibility to deduce a more refined and reliable geochemical and mineralogical model of the deposit. The information-rich data stream opens applications beyond grade control and exploration, such as data assimilation with gravity models or geologic model building.

Sulfide saturation and resorption modulates sulfur and metal availability during the 2014–15 Holuhraun eruption, Iceland

Mafic magmas may experience multiple stages of sulfide saturation and resorption during ascent and differentiation. Quenched tephra erupted during the 2014–15 Holuhraun eruption preserve abundant evidence for sulfide resorption, offering a rare opportunity to explore the sulfide life cycle from nucleation to resorption. Specifically, we combine detailed textural and chemical analyses of sulfides and silicate melts with geochemical models of sulfide saturation and degassing. This integrative approach demonstrates that sulfides began nucleating in melts with ~8 wt% MgO, persisted during fractionation to 6.5 wt% MgO, before resorbing heterogeneously in response to sulfur degassing. Sulfides are preserved preferentially in confined geometries within and between crystals, suggesting that kinetic effects impeded sulfur loss from the melt and maintained local sulfide saturation on eruption. The proportion of sulfides exhibiting breakdown textures increases throughout the eruption, coincident with decreasing magma discharge, indicating that sulfide resorption and degassing are kinetically limited. Sulfides likely modulate the emission of sulfur and chalcophile elements to the atmosphere and surface environment, with implications for assessing the environmental impacts and societal hazards of basaltic fissure eruptions.

Recycling of crustal Os in nascent subduction zones revealed by ophiolitic boninites

Olivine-rich lavas in the Margi area, Cyprus, are part of the boninitic Upper Pillow Lava series of the Troodos ophiolite. Re-Os isotope compositions of both whole rock and olivine phenocrysts of these lavas have been measured to determine the initial 187Os/188Os isotope compositions of the primary boninitic magma. The Margi lavas have high and variable whole rock Re-Os isotope compositions (187Re/188Os: 1.060–8.613; 187Os/188Os: 0.1307–0.1599), with (87Sr/88Sr)90Ma (0.705936 ± 0.001021), εNd(90 Ma) (5.6 ± 2.5), and δ18O (8.59 ± 0.38 ‰). In contrast, olivine phenocrysts, which host spinel and melt inclusions, have low and constant 187Os/188Os from 0.1301 to 0.1336 and low 187Re/188Os from 0.1350 to 1.557. Initial 187Os/188Os of these olivine phenocrysts (0.1300 ± 0.0041) is lower than that of whole rock (0.1373 ± 0.0135). These facts indicate that the olivine phenocrysts faithfully record initial 187Os/188Os of the primary boninitic magmas, which are comparable to the 187Os/188Os of primitive mantle, whereas whole rock Re-Os isotopes have been affected by secondary processes after olivine crystallization. Further geochemical modeling indicates that, although Os can be mobilized during slab dehydration, the contribution of crustal Os is insufficient to significantly raise the 187Os/188Os of the mantle wedge in a nascent subduction zone. Overall, our findings provide new insights about Os recycling in the early stages of subduction.

Genesis of Fe-Ti oxide-bearing ultramafic intrusions in the Duluth Complex, Minnesota, USA

Abstract The Duluth Complex is a large mafic intrusive system located in northeastern Minnesota emplaced as part of the 1.1 Ga Midcontinent Rift. Several Fe-Ti oxide-bearing ultramafic intrusions are hosted along the Western Margin of the Duluth Complex, and are discordant bodies present in a variety of geometries, hosted in multiple rock types, and dominated by peridotite, pyroxenite, and semi-massive to massive Fe-Ti oxide rock types. Their origin has been debated, and here we present geochemical evidence and modeling that supports a purely magmatic origin for the Titac and Longnose Fe-Ti oxide-bearing ultramafic intrusions. Ilmenite and titanomagnetite textures indicate a protracted cooling process, and δ34S values of sulfides reveal little assimilation of the footwall Virginia Formation, a fine-grained pelitic unit that contains sulfide-rich bands. We model the crystallization of a hypothetical parental magma composition to the host intrusion of Longnose using Rhyolite-MELTS and demonstrate that the accumulation of Fe-Ti oxides in the discordant intrusions cannot be explained by density-driven segregation of crystallized Fe-Ti oxides. Instead, we show that the development of silicate liquid immiscibility, occurring by the unmixing of the silicate melt into conjugate Si- and Fe-rich melts, can result in the effective segregation and transportation of the Fe-rich melt. The Fe-rich melt is ~2 orders of magnitude less viscous than the Si-rich melt, allowing the Fe-rich melt to be more effectively segregated and transported in the mush regime (crystallinities &amp;gt; 50%). This suggests that viscosity, in addition to density, plays a significant role in forming the discordant Fe-Ti oxide-bearing ultramafic intrusions. We propose a genetic model that could also be responsible for the Fe-Ti oxide-rich layers or bands that are hosted within the igneous stratigraphy of mafic intrusions of the Duluth Complex.