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Stable isotope composition and geochemistry of calcite and dolomite in the Mountain Pass carbonatite: A lens into petrogenesis

Carbonatites host most of the global rare earth element (REE) deposits. The petrogenesis of these rocks, including magmatic and post-magmatic processes, are poorly understood but critical in forming and upgrading these deposits. The Mountain Pass carbonatite, which hosts the only active REE mine in North America, is lithologically variable but consistently contains >50% calcite and/or dolomite. Multiple generations of carbonates are evident, suggesting bulk analysis of carbonate minerals would generate a mixed isotopic and geochemical signature. In-situ stable carbon and oxygen isotopes, combined with geochemical analysis and petrography, distinguish carbonate generations, trace the source region of the carbonatite magma, and link carbonate genesis to REE mineralization throughout the intrusion. Primary carbon and oxygen isotope values outside the accepted mantle range may suggest a subduction-related carbon and oxygen source in the mantle. Deformation textures in primary calcite indicate syn- or post-crystallization ductile flow. Carbonates with secondary textures and heavy δ 13 C and δ 18 O values are associated with ore mineralization, suggesting fluid mobilization was important in concentrating REE and upgrading of the Mountain Pass deposit.

California

A multidisciplinary approach that considers occurrence, geochemistry, bioavailability, and toxicity to prioritize critical minerals for environmental research

Critical minerals (or critical elements) are minerals or elements that are essential to global security and development and have supply chains vulnerable to disruption. In general, knowledge of the environmental behavior and health effects of critical elements is needed to support the development of safe and environmentally responsible supplies. This knowledge includes identifying potential consequences of increased critical element production and use, alternative critical element sources such as mine wastes, and adverse effects of critical elements on ecosystem condition and organismal health. Here we identify significant data gaps in the understanding of critical elements in surficial and aquatic environments, and the need, given the large number of commodities (50) identified on the 2022 critical minerals list for the United States, for an approach to prioritize them for study of their environmental fate and effects. We propose a multidisciplinary approach for this prioritization, considering measures of occurrence, geochemistry, bioavailability, and toxicity. We describe relatively easy-to-obtain metrics for each of these topic areas and demonstrate the utility of this integrated prioritization approach using indium and zinc as examples. This approach facilitates prioritizing research with a focus on those critical elements that are most mobile in the environment, bioavailable, toxic, or simply lacking data in these categories.

Environmental Science & Technology

Integrating detrital magnetite geochemistry and (U-Th)/He chronometry as a sediment provenance tool in geologic and metallogenic terranes

Magnetite is ubiquitous in porphyry Cu systems and in sediment sourcing both barren and mineralized regions, with potential as an indicator mineral in concealed and coarsely-mapped terranes. We develop and test a workflow for integrated geochemistry and (U–Th)/He (He) dating for inferring detrital magnetite (DMt) provenance in these settings. The ca. 70 Ma Taurus porphyry Cu–Mo(–Au) district in eastern interior Alaska serves as a test case. DMt from streams draining porphyry-related mineralization was characterized by geochemistry and mineral inclusion and microstructure observations, complemented by similar data for potential porphyry and host rock sources. Principal component analysis and clustering of DMt geochemical data resolve multiple populations in our samples geochemically and texturally compatible with derivation from metamorphic, porphyry-related hydrothermal, and igneous sources. Hydrothermal magnetite comprises ∼16–50% of DMt nearest porphyry mineralization but diminishes to ∼4% ∼15 km downstream. Subsampled grains within populations yield ∼160–110 Ma, ∼70 Ma, ∼55 Ma, and ∼20 Ma magnetite He date modes. Combined with provenance, He dates capture Early Cretaceous regional exhumation of metamorphic host rock and Late Cretaceous porphyry Cu mineralization. DMt grains showing partial hematite replacement yield ca. 55–20 Ma dates regardless of source, overlapping regional warm/wet climatic intervals. We interpret Cenozoic dates to reflect exhumation to near-surface oxidizing conditions and(or) supergene weathering. Magnetite is thus a promising target phase for (1) tracking the spatiotemporal distribution of porphyry systems, and (2) linking the formation and exhumation of these systems to a regional geologic history, both in Alaska and globally.

Alaska, Yukon

Geology and geochemistry of Jurassic plutonic rocks, Baboquivari Mountains, south-central Arizona

Among the plutons of the Jurassic magmatic arc segment in southern Arizona, northern Sonora, and southern California, two distinctive rock types dominate, occurring together in numerous mountain ranges: porphyritic, titanite-bearing hornblende-biotite granodiorite; and biotite leucogranite. These characteristic rocks are particularly well preserved and well exposed around Kitt Peak, in the Baboquivari Mountains, southern Arizona. The Middle to early Late Jurassic Kitt Peak Plutonic Suite (KPPS) comprises three units: Aguirre Peak Quartz Diorite (APQD;<170 Ma, >=165 Ma, U-Pb), chiefly hornblende mesodiorite; Kitt Peak Granodiorite (KPGD; 165 Ma), hornblende-biotite granodiorite and monzogranite; and Pavo Kug Granite (PKG; 159 Ma), equigranular biotite leucogranite. This range also hosts a fourth, regionally unusual, Jurassic plutonic unit: the Baboquivari Peak Perthite Granite, related to post-arc, Late Jurassic crustal extension. Binary variation diagrams, incompatible element patterns, and REE spectra indicate APQD and KPGD are consanguineous. APQD basaltic mesodiorite evidently approximates the parental magma for the APQD–KPGD series. More evolved rocks of this series evidently formed by combinations of fractional crystallization and mixing with or assimilation of crustal material. PKG is less directly related to APQD and KPGD than these two are to one another.

Arizona, Sonora

Top-down targeted network analysis of critical mineral commodities applied to international geochemistry database

The global demand for critical mineral commodities is rapidly increasing, making domestic production an important factor in supporting the economy and national security. Large scale, publicly available geochemical databases allow for the application of data informatics methods to interrogate critical mineral commodities data for correlations in deposit formation and distribution, particularly for identifying enrichment of multiple critical mineral commodities at the same deposit. In this study, we applied network analysis to the Critical Minerals Mapping Initiative (CMMI) ore geochemistry (Critical Minerals in Ores, CMiO) database to identify the high concentration (defined as 10× bulk crustal abundance) co-occurrence of different critical mineral commodities across a mineral system hierarchy from deposit environments to individual deposits. Identifying patterns or unique outliers in enrichment in network communities will allow for the location of secondary critical mineral commodity resources from under-utilized deposits. We find trends in the enrichment of critical mineral commodities in network-communities between the elements praseodymium (Pr), neodymium (Nd), terbium (Tb), and dysprosium (Dy) across multiple CMiO database deposit environments and groups down to specific deposit types and sites. A separate trend in network community deposition is observed as well between iridium (Ir) and platinum (Pt) in deposit environments, groups, types, and sites. Network analysis focused on critical minerals in magmatic-hydrothermal deposits identified multiple deposit sites from different deposit types within the CMiO database with concentrations of Dy, Nd, Tb, Pr, Ir, and Pt that are at least ten times greater than the crustal average. This approach can be applied to any target element(s) or deposit(s) of interest, allowing broad investigation of co-enriched critical mineral commodities.

Journal of Geochemical Exploration

Apatite and monazite geochemistry record magmatic and metasomatic processes in rare earth element mineralization at Mountain Pass, California

The largest rare earth element (REE) deposit in the United States is a carbonatite intrusion at Mountain Pass in the Mojave Desert, California. Despite a clear spatiotemporal association of alkaline silicate and carbonatite intrusions at Mountain Pass, a genetic model of their mutual formation has not been resolved. The Mountain Pass carbonatite has long been upheld as an example of a primary magmatic body, but recent work has suggested it could be fluid-derived. This study investigates the geochemistry of apatite and monazite grains from the alkaline silicate and carbonatite stocks and dikes of the Mountain Pass district, to elucidate the magmatic history of the intrusive suite and identify the role of fluids in rare earth element mineralization. Three apatite populations are identified in the alkaline silicate rocks. A primary magmatic apatite group supports intrusion of the stocks as separate pulses of magma derived from a spatially extensive metasomatized mantle source region. The second group implicates the role of a regional fluid that mobilized light rare earth elements from apatite grains. A minor group of inherited apatite cores, identified by low Sr and negative Eu anomalies, supports assimilation of crustal material in the formation of the intrusive suite. Analyses of monazite and apatite grains from the carbonatite orebody also reveal a mix of primary magmatic and metasomatic (fluid-related) minerals. Compositional similarities between primary phosphates in the carbonatite and alkaline silicate rocks support a genetic link between the intrusive suites. The presence of fluids regionally and within the carbonatite orebody indicates the Mountain Pass carbonatite should not be classified as a purely magmatic REE deposit.

Arizona, California, Nevada

Produced water geochemistry from hydraulically stimulated Niobrara Formation petroleum wells: Origin of salinity and temporal perspectives on treatment and reuse

Produced water (i.e., a mixture of returned injection fluids and geologic formation brines) represents the largest volumetric waste stream associated with petroleum production in the United States. As such, produced water has been the focus of intense study with emphasis on understanding the geologic origin of the fluids, environmental impacts of unintended or intentional release, disposal concerns, and their commodity (e.g., lithium) potential. However, produced water geochemistry from many active petroleum plays remain poorly constrained leading to knowledge gaps associated with the origin of brine salinity and parameters (e.g., radium levels) that can impact treatment, disposal, and possible reuse. Here we evaluate the major ion geochemistry, radium concentrations, and stable water isotope composition of ~120 produced water samples collected from 17 producing unconventional petroleum wells in Weld County, Colorado from the Late Cretaceous Niobrara Formation. This sample set encompasses eight produced water time series from four new wells across production days 0 to ~365 and from four established wells across production days ~1000 to ~1700. Additionally, produced water from nine other established Niobrara Formation wells were sampled at discrete time points ranging from day 458 to day 2256, as well as hydraulic fracturing input fluids. These results expand the available Niobrara Formation produced water geochemical data, previously limited to few wells sampled within the first year of production, allowing for the heterogeneity of major ions and radium to be evaluated. Furthermore, we explore the geochemical relationships between major ion ratios and stable water isotope composition to understand the origin of salinity in Niobrara Formation brines from the Denver-Julesburg Basin. These findings are discussed with perspective toward potential treatment and reuse of Niobrara produced water prior to disposal.

Colorado, Nebraska, Wyoming

Characterization of the hydrogeologic framework, groundwater-flow system, geochemistry, and aquifer hydraulic properties of the shallow groundwater system in the Wilcox and Lorraine process areas of the Wilcox Oil Company Superfund site near Bristow, Oklahoma, 2022

The Wilcox Oil Company Superfund site (hereinafter referred to as “the site”) was formerly an oil refinery northeast of Bristow in Creek County, Oklahoma. Historical refinery operations contaminated the soil, surface water, streambed sediments, alluvium, and groundwater with refined and stored products at the site. The Wilcox and Lorraine process areas are where the highest concentrations of volatile organic compounds, semivolatile organic compounds, polycyclic aromatic hydrocarbons, and trace elements (including metals) (collectively hereinafter referred to as “contaminants”) were measured in a local shallow perched groundwater system within the alluvium (hereinafter referred to as the “alluvial aquifer”) at the site during previous site assessments. In order to understand the potential migration of contaminants through the soil and groundwater in these areas, the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, investigated aquifer characteristics of the alluvial aquifer in the Wilcox and Lorraine process areas of the site to (1) document hydraulic conductivity and other aquifer characteristics of the alluvial aquifer that govern contaminant fate and transport, (2) describe the geospatial extent and concentration of the contaminants in the alluvial aquifer in the Wilcox and Lorraine process areas, and (3) describe the geochemical controls pertaining to oxidation and reduction governing the fate and transport and the degradation potential of contaminants in the groundwater. Various data were compiled and collected to evaluate the aquifer characteristics at the site including the hydrogeologic framework, groundwater-flow system, geochemistry, and hydraulic properties of the aquifer. A total of 20 new (2022) groundwater monitoring wells were installed at the site to collect data used to supplement groundwater-level altitude and groundwater-quality data collected from older, existing groundwater monitoring wells and piezometers. Data compiled and collected for the study were used to evaluate the characteristics of the alluvial aquifer at the site. These aquifer characteristics are defined by the hydrogeologic framework, groundwater-flow system, geochemistry, and hydraulic properties of the aquifer.

Oklahoma

Geochemistry of and radioactivity in ground water of the Highland Rim and Central Basin aquifer systems, Hickman and Maury counties, Tennessee

A reconnaissance of the geochemistry of and radioactivity in ground water from the Highland Rim and Central Basin aquifer systems in Hickman and Maury Counties, Tennessee, was conducted in 1989. Water in both aquifer systems typically is of the calcium or calcium magnesium bicarbonate type, but concentrations of calcium, magnesium, sodium, potassium, chloride, and sulfate are greater in water of the Central Basin system; differences in the concentrations are statistically significant. Dissolution of calcite, magnesium-calcite, dolomite, and gypsum are the primary geochemical processes controlling ground-water chemistry in both aquifer systems. Saturation-state calculations using the computer code WATEQF indicated that ground water from the Central Basin system is more saturated with respect to calcite, dolomite, and gypsum than water from the Highland Rim system. Geochemical environments within each aquifer system are somewhat different with respect to dissolution of magnesium-bearing minerals. Water samples from the Highland Rim system had a fairly constant calcium to magnesium molar ratio, implying congruent dissolution of magnesium-bearing minerals, whereas water samples from the Central Basin system had highly variable ratios, implying either incongruent dissolution or heterogeneity in soluble constituents of the aquifer matrix. Concentrations of radionuclides in water were low and not greatly different between aquifer systems. Median gross alpha activities were 0.54 picocuries per liter in water from each system; median gross beta activities were 1.1 and 2.3 picocuries per liter in water from the Highland Rim and Central Basin systems, respectively. Radon-222 concentrations were 559 and 422 picocuries per liter, respectively. Concentrations of gross alpha and radium in all samples were substantially less than Tennessee’s maximum permissible levels for community water-supply systems. The data indicated no relations between concentrations of dissolved radionuclides (uranium, radium-226, radium-228, radon-222, gross alpha, and gross beta) and any key indicators of water chemistry, except in water from the Highland Rim system, in which radon-222 was moderately related to pH and weakly related to dissolved magnesium. The only relation among radiochemical constituents indicated by the data was between radium-226 and gross alpha activity; this relation was indicated for water from both aquifer systems.

Tennessee

The Sedimentary Geochemistry and Paleoenvironments Project Phase 2 data release: An open data resource for the study of Earth's environmental history

Geochemical data from sedimentary rocks are the primary source of information regarding Earth's surface evolution through time, including its air and water envelopes and interactions with life and deep Earth processes. The Sedimentary Geochemistry and Paleoenvironments Project (SGP) is a scientific consortium centered around open data and community-driven development of cyberinfrastructure tools and resources for sedimentary geochemistry and Earth history. Here we describe the SGP Phase 2 data release, which focused on incorporating Paleoproterozoic and Mesoproterozoic (2500–1000 million years ago) data and better accommodating carbonate data. This data release was built through the involvement of >200 researchers worldwide in academia, government, and industry, and provides the largest available public data resource for our user community in the academic fields of geochemistry, sedimentology, tectonics, paleontology, Earth history, and paleoclimate, as well as the petroleum and minerals industries. The dataset now encompasses 126,006 samples and 4,132,371 geochemical analyses. In addition to direct entry by SGP Team Members, we have ingested and incorporated datasets from the Geoscience Australia OZCHEM database, the Alberta Geological Survey, and the Deep-Time Marine Sedimentary Element Database (DM-SED) compilation. This paper details sampling in the Phase 2 dataset with respect to age, geography, lithology, and other geological characteristics, documents access via our search website and API, discusses possible issues and/or biases in the dataset that could impact analyses, describes plans for governance and stewardship of data from Indigenous lands, and serves as the citable reference paper for the data release.

Chemical Geology

Characterizing Meteor Crater impact melts through geochemistry and textural analysis

The U.S. Geological Survey Astrogeology Science Center houses the Meteor Crater sample collection, an assemblage of over 2,500 meters of cuttings from 161 drill holes into Meteor Crater’s rim, flanks, and ejecta blanket. We have utilized this unique collection to study the composition and spatial distribution of impact-generated materials from within the ejecta blanket. Meteor Crater has historically been known to have generated only a relatively small amount of impact melt compared to other terrestrial craters of similar size. A detailed compositional and textural dataset of impact-derived melts from this impact can therefore be a useful asset in improving our understanding of crater formation, and in particular impact melt formation. We have characterized 42 impact-melt particles from Meteor Crater using a scanning electron microscope and an electron microprobe for textural and compositional analysis. We analyzed samples from six drill holes in the ejecta blanket, situated to the northwest, southeast, south, and southwest of the crater (ejecta northeast of the crater is devoid of impact melts). Impact melts were collected from drill cuttings at various depths within the ejecta blanket, ranging from a few centimeters below the surface down to ~6.5 meters. Backscattered electron (BSE) images were acquired for each analyzed impact-melt particle. To characterize the various textures and phases present in each impact melt, we also took many detailed BSE images. Our geochemical analyses include full spectral profiles using energy dispersive X-ray spectrometry and well-calibrated wavelength dispersive spectrometry for a number of phases, including minerals (olivine, pyroxene, and so on), pristine glass, and metallic inclusions. The full dataset is available in ScienceBase as a data release (Gullikson and others, 2024), accessible at https://doi.org/10.5066/P9OGAJ8P . Our goal for this Open-File Report is to provide a summary of this immense dataset, details on data collection, descriptions of the different phases observed within impact-melt particles (both geochemically and texturally), and observable trends.

Arizona

Insights into Mountain Pass carbonatite formation from in-situ sulfur isotopes and geochemistry of sulfate and sulfide minerals

The Mountain Pass carbonatite stock hosts a world-class rare earth element deposit and may be classified as a carbonate-sulfate igneous rock, as it contains on average > 50 volume percent carbonate minerals and 20 to 30 volume percent sulfate minerals. The sulfates range in composition from barite to celestine and locally occur with sparse sulfide minerals. We investigate the origin of sulfur enrichment and the occurrence of sulfur-bearing minerals in the Mountain Pass carbonatite with in-situ sulfur isotope and mineral chemistry. Barite cores with δ 34 S of 1 to 3‰ do not coexist with sulfides, whereas celestine rims with δ 34 S of > 3‰ are associated with sulfides with δ 34 S < -10‰. We propose a model in which sulfur-bearing sediments were subducted during episodes of plate convergence in the Mojave Province that preceded Mountain Pass magmatism. Metasomatism of the overlying mantle by melts derived from the subducted sediments generated an unusually carbon- and sulfur-rich source to yield carbonatite magmas. Sulfur from primary carbonatite magmas and ~ 1 to 7% sulfur from subducted sediment melts yielded a slightly enriched δ 34 S composition (relative to depleted mantle δ 34 S of -1‰) for early crystallizing barite. Celestine rims on magmatic barite cores formed at low, hydrothermal temperatures (< 350 °C) based on S isotope thermometry for equilibrium celestine-galena and celestine-pyrite pairs. The sparse sulfides in the carbonatite stock are not in equilibrium with the primary barite cores and therefore do not permit S isotope thermometry estimates of magmatic temperatures. The S/Se ratios of sulfide minerals (> 3,400) typically exceed primitive mantle values (S/Se of 3,340), also consistent with their derivation from hydrothermal fluids. Trace occurrences of sulfide and sulfate minerals in alkaline silicate stocks related to the carbonatite stock have similar δ 34 S compositions and yield similarly low formation temperatures, suggesting regionally extensive and chemically similar sulfur-bearing hydrothermal fluids that imparted lithologically diverse rocks with a consistent sulfur isotope fingerprint.

California, Nevada

Geochemistry and radiogenic isotopes constrain the mantle source region of the Mountain Pass Intrusive Suite, California

The Mountain Pass carbonatite stock is the largest rare earth element (REE) deposit and only active REE mine in the United States. The carbonatite intrusion and spatially associated alkaline silicate intrusions constitute the Mountain Pass Intrusive Suite, which is located within the Mojave Province in California. Both the carbonatite and the alkaline silicate rocks are enriched in large ion lithophile elements and light REEs, and less enriched to depleted in high field strength elements, indicating the mantle source region was metasomatically enriched in incompatible trace elements. The cause of this metasomatic mantle enrichment and the genetic relationship between the carbonatite and the alkaline silicate stocks are poorly understood. In this study, major and trace element geochemical data and isotopic (Rb-Sr, Sm-Nd, and Lu-Hf) data are presented to constrain genesis of the Mountain Pass Intrusive Suite, from mantle source region to the intrusion of the stocks. Our geochemical data are consistent with derivation of the alkaline silicate and carbonatite melts through partial melting from a shared mantle source region rather than through liquid immiscibility or fractional crystallization and separation of a carbothermal fluid. Although the Rb-Sr isotopic system in the Mountain Pass Intrusive Suite is disturbed at the whole-rock scale, the isotopic systems for whole-rock Sm-Nd (εNd i = ‐2.2 ± 0.8) and zircon Lu-Hf (εHf i = 0.1 ± 1.1) are robust and support mantle derivation of the magmas. Geochemical modeling using experimentally derived partition coefficients was used to identify possible causes of enrichment in incompatible elements through metasomatism in the mantle source region. Modeling of metasomatism by melts derived by partial melting of deeply subducted carbonated sediments approximates observed Mountain Pass Intrusive Suite trace element chemistry. Scattered εHf i in inherited zircon (2.8 ± 2.6) is consistent with derivation from an arc-related environment with substantial crustal contamination. Paleotectonic studies in the Mojave Province indicate that regional subduction preceded emplacement of the Mountain Pass Intrusive Suite by ∼300 Ma. Melting of the Mountain Pass source region may have been caused by post-collisional thermal relaxation and extension.

California

The Hardscrabble Creek complex: A newly discovered, mostly buried, Mesoproterozoic mafic-ultramafic pluton in the Wet Mountains, Colorado, USA

The origin of prolific ca. 1.4 Ga ferroan magmatism between the southwestern USA and eastern Canada is enigmatic and has been explained by various models, including extensional, mantle plume, and convergent plate-margin models. Rare mafic plutons are associated with the ferroan plutons, which may help constrain their mantle source and tectonic setting. In the southwestern USA, only two such mafic plutons are known to exist. We present the first evidence for a third, mostly buried, potentially layered, mafic-ultramafic Mesoproterozoic pluton, informally referred to as the Hardscrabble Creek complex, in the central Wet Mountains of Colorado, USA. Recent geophysical data show an elliptical magnetic and gravity high spatially coincident with local gabbroic outcrops. New field and petrographic analyses of these exposed rocks reveal that they consist of ultramafic to mafic cumulates, including orthopyroxenite, olivine norite, norite, and anorthosite. High-precision U-Pb dating of zircon from orthopyroxenite and norite yield weighted mean 206 Pb/ 238 U dates of 1352.36 ± 1.60 Ma and 1352.37 ± 1.71 Ma, respectively. These dates indicate that the complex formed over a narrow timeframe, after the adjacent 1362 ± 7 Ma ferroan San Isabel Granite, and during the waning stages of the regional ca. 1.4 Ga ferroan magmatism. Whole-rock geochemistry and Nd-Sr-Pb isotope compositions of samples from the Hardscrabble Creek complex are similar to those of the San Isabel Granite, suggesting that they were derived from the same or a similar mantle source. The mineral chemistry of the samples is comparable to Proterozoic massif-type anorthosites and related mafic intrusions, indicating that the Hardscrabble Creek complex and San Isabel Granite together represent a rare anorthosite-mangerite-charnockite-granite (AMCG) suite in the southwestern USA. The Hardscrabble Creek complex is unique because it formed ~80 m.y. after the other few mafic plutons in the southwestern USA, and it contains an ultramafic section that is absent from these plutons and rare to the AMCG suite in general. A combination of arc-like whole-rock geochemistry, chondrite uniform reservoir-like Nd-Sr-Pb isotopes, and ocean island basalt (OIB)-like zircon trace element chemistry suggests that the complex was derived from a partial melt of OIB-like mantle and interacted with metasomatically enriched lithospheric mantle. The enriched lithospheric mantle signature, combined with the long ~160 m.y. duration of magmatism in the region, is consistent with a period of protracted convergent tectonism.

Colorado

Understanding the resource potential of natural hydrogen on Earth: Scientific gaps, uncertainties and recommendations

A comprehensive scientific research roadmap is essential to bridge knowledge gaps and deepen the understanding of key geological, geochemical, and geophysical aspects of natural hydrogen (H 2 ) as a potential new energy resource. This paper reviews major scientific uncertainties on natural H 2 , suggesting research priorities, as a guide for defining exploration strategies, techniques, and data interpretation. The uncertainties concern all phases of the natural H 2 cycle, from generation (source rocks) through migration (advection and diffusion) and accumulation (reservoir and cap rocks) to the application and interpretation of subsurface and surface geochemical and geophysical exploration techniques. Understanding H 2 sources and generation rates (the amount of H 2 generated by a given volume of rock over time) is crucial for determining whether a geological H 2 system operates as a short-term dynamic system with rapid H 2 production and release, or as a conventional gas system with long-term accumulations, analogous to petroleum reservoirs. Preliminary estimates for serpentinisation, radiolysis, and organic matter degradation suggest that H 2 generation is not inherently fast, especially for non-hydrothermal continental systems (crystalline basement of shields, ophiolites, peridotite massifs, sedimentary basins), and long-term accumulations, like those of fossil natural gas systems, represent the most likely scenario. The mechanisms of H 2 migration through geological formations require application of fundamental principles of fluid-flow physics, distinguishing advection and diffusion, as well as their forms (from gas-phase, bubble flows to aqueous solutions). Additional studies of H 2 accumulation and retention in subsurface reservoirs could improve understanding of mechanisms of H 2 migration by focusing on the rock fluid-bearing properties and the factors affecting H 2 preservation, such as the presence of cap rocks impermeable to H 2 , pressure conditions, residence times, and microbial or abiotic consumption. Advanced techniques, including reservoir modelling, flow simulations, 3D imaging (micro-CT) of H 2 -bearing rocks, and extraction and analysis of gas occluded in rocks, can provide insights into the stability and potential recoverability of H 2 accumulations. The interpretation of surface exploration techniques, including gas geochemistry, geophysics, and remote sensing, long employed in mineral and energy resource exploration, is now being adapted for natural H 2 studies, but challenges remain in the data interpretation. Distinguishing H 2 seepage due to geological degassing from H 2 produced near the surface by modern microbial processes or artificial sources, such as hammering or drilling for soil-gas sampling, drilling into aquifers, and corrosion in boreholes, is an essential step in exploration. The simple detection of H 2 in soils, even in morphological structures like sub-circular depressions or “fairy circles”, cannot be cursorily interpreted as a signal of natural H 2 seepage from a deep source. A holistic geochemical approach, including isotopic analyses of gases associated with H 2 , is recommended to distinguish among the variety of possible H 2 origins. Observations of H 2 in wells should be interrogated to rule out possible artifacts such as corrosion and drill bit metamorphism. The integration of multiple geophysical methods, including seismic, gravimetric, magnetic, and electro-magnetic surveys, is recommended to mitigate interpretation ambiguities regarding the structure of a subsurface H 2 system (source and reservoir rocks, including fluid and gas storage), due to the non-uniqueness of rock-specific physical properties.

Earth-Science Reviews

Geochemical processes related to mined, milled, or natural metal deposits in a rapidly changing global environment

The demand for metals and raw materials, such as nickel and copper, has been projected to expand in the coming decades, driven by the global energy transition, the need for green technologies, and expanding infrastructure. Consequently, the increasing extraction and production of mining waste can have adverse impacts on surrounding environments and human health. The aim of this thematic collection is to fill critical knowledge gaps in the present-day cycles of metal(loid)s from source to larger sinks, and the effect of environmental management, anthropogenic development, and climate change. Altogether, the studies have been conducted in different natural settings around the world and comprise investigations in laterites, a soil-medicinal plant system, watersheds, and banded iron formations, among others. The geochemical applications in tracing mineralization, its secondary products, and/or potential impact on the immediate environment are highly diverse with applied tools ranging from isotope tracers to major and trace element systematics. Particularly the use of rare earth elements, their patterns and anomalies are methods employed by several studies in this collection. We summarize the findings to offer a potential future direction for the use of geochemical tracing techniques in resource exploration in the context of climate change and environmental challenges.

Geochemistry: Exploration, Environment, Analysis

Melt generation sources and conditions in the wake of a migrating slab window: Geochemistry and petrology of the million-year history of primitive volcanism at Clear Lake volcanic field, California

Clear Lake volcanic field (CLVF) is the northernmost and youngest (~2.2 Ma to 8 ka) of the volcanic centers distributed along the San Andreas transform fault in western California. The initial phase of CLVF volcanism (interval one) occurred between ~2.2 and 1.3 Ma and extends ~35 km southeast of Clear Lake, forming a semi-continuous upland plateau capped by lava flows, with isolated volcanic remnants on the periphery. This volcanism is broadly characterized by geochemically primitive compositions that reflect three source compositions and conditions of melt generation. (1) Partial melting of upwelling asthenospheric mantle lherzolite at moderate pressures (1.2–1.4 GPa) and temperatures (1297–1329 °C) produced high-CaO (9.8–11.3 wt %) basalts with high Al 2 O 3 (16.8–17.6 wt %), Mg#s (66–70), MgO (8–10 wt %), Ni (103–262 μg/g), and Cr (284–609 μg/g). These high-CaO basalts contain olivine (Fo 87–91 ) phenocrysts with Cr-spinel inclusions ± subordinate plagioclase and crop out only in the southern part of the CLVF. (2) Partial melting of depleted sub-continental lithospheric mantle harzburgite at variable pressures (0.7–1.5 GPa) and temperatures (1097–1299 °C) produced a compositional continuum of med-K 2 O, calc-alkaline, high-MgO basalts through high-MgO andesites with high Mg#s (67–77), MgO (8–14 wt %) and high Ni and Cr abundances (154–439 and 340–1124 μg/g, respectively). Mineral assemblages are olivine (Fo 88–93 ) with Cr-spinel inclusions ± subordinate clinopyroxene, orthopyroxene and plagioclase. Small (<2.5 cm) mantle harzburgite xenoliths and mantle olivine xenocrysts are also found in several of these samples. These high-MgO basalts through andesites represent the largest volume of primitive compositions and have erupted predominantly along the main, fault-controlled northwest-southeast trending axis of volcanism with peripheral outcrops to the north, west, and east. (3) Partial melting of the Gorda eclogite slab edge produced adakitic silicic slab melts with strong depletion in the heavy rare earth elements (Yb = 0.6 μg/g). Subsequent reaction of those melts with depleted ultramafic rocks during ascent imprinted the adakitic dacites with high Mg#s (65–78) and elevated Ni (117–210 μg/g) and Cr (191–283 μg/g). Phenocrysts of orthopyroxene (En 87–94 ) with spinel inclusions (Cr# = 80–88) and extremely Ni-rich (9483 μg/g) olivine cores (Fo 84–93 ) record those reactions. Small-volume outcrops of the adakites on the eastern periphery of the CLVF track the passing slab edge. The trio of melting sources recorded by early CLVF magmatism reflect the tectonically complex environment and the hot (1097–1329 °C), shallow (0.7–1.5 GPa) melting conditions for these primitive compositions and provide estimates of the heat delivered to the crust. Over time, this flux led to maturation of the CLVF magmatic system toward the more voluminous and silicic volcanism that characterizes the balance of its subsequent volcanic history and maintains the present-day anomalously high heat flow in the region. The current interval (interval four) of volcanic activity at CLVF is characterized by low-volume, fault-controlled eruptions of basaltic andesite and andesite suggestive of mantle magma and heat delivery to the crust, similar to interval one. This analogous activity provides motivation for the current study and begs the question of whether the system is undergoing thermal priming for renewed silicic volcanism.

California

Land-use interactions, Oil-Field infrastructure, and natural processes control hydrocarbon and arsenic concentrations in groundwater, Poso Creek Oil Field, California, USA

Like many hydrocarbon production areas in the U.S., the Poso Creek Oil Field in California includes and is adjacent to other land uses (agricultural and other developed lands) that affect the hydrology and geochemistry of the aquifer overlying and adjacent to oil development. We hypothesize that the distributions of hydrocarbons and arsenic in groundwater in such areas will be controlled by complex interactions between mixed land uses, oil-field infrastructure, and natural processes. In 2020–2021, samples of groundwater and surface water were collected and analyzed for a large suite of inorganic and organic chemicals and isotope and gas tracers to test this hypothesis. Those data are supplemented with ancillary data on historical geochemistry, hydrology, geology, and oil-field infrastructure. Hydrocarbons in groundwater (e.g., methane through pentane gases and benzene) are associated with natural processes (e.g., fault offsets or transition in sediment depositional environment) and oil-field infrastructure (e.g., fluid-migration pathways associated with uncemented annulus in oil wells or unlined pits). Arsenic concentrations >10 μg per liter (μg/L; maximum concentration 12.9 μg/L) are associated with natural processes in old, high-pH groundwater, and more recent recharge of water from natural and/or engineered recharge processes. Along the southwest margin of the oil field, pumping for drinking-water and irrigation supplies in combination with engineered groundwater recharge produce a depression in groundwater elevations where groundwater with elevated sulfate concentrations from agricultural areas and groundwater with hydrocarbons from the oil field mix to produce a zone of sulfate reduction that removes hydrocarbons and arsenic from groundwater but produces elevated sulfide (S 2- ) concentrations (maximum concentration 29 mg per liter, mg/L). In this study, multiple approaches were required to resolve the overlapping effects of land uses, oil-field infrastructure, and natural processes on the distributions of hydrocarbons and arsenic in groundwater. The combined use of geographic, historical, physical, chemical, isotopic, and other information to constrain processes could be a useful approach for studies in other hydrocarbon-production areas. This is particularly important where land uses affect aquifer hydrology to an extent that causes mixing of groundwaters with different chemical compositions.

California