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Radionuclide transport in smectite clay barrier systems used for nuclear waste disposal is controlled by diffusion, with adsorption significantly retarding transport rates. While a relatively minor component of spent nuclear fuel, 79Se is a major driver of the safety case for spent fuel disposal due to its long half-life (3.3 × 105 yr) and its low adsorption to clay (KD < 10 L/kg), thus a thorough understanding of Se diffusion through clay is critical for understanding the long-term safety of spent fuel disposal systems. Through-diffusion experiments with tritiated water (HTO, conservative tracer) and Se(VI) were conducted with a well-characterized, purified montmorillonite source clay (SWy-2) under a constant ionic strength (0.1 M) and three different electrolyte compositions: Na+, Ca2+, and a Na + -Ca2+ mixture at pH 6.5 in order to probe the effects of electrolyte composition and interlayer cation composition on clay microstructure, Se(VI) aqueous speciation, and ultimately diffusion. The results were modeled using a reactive transport modeling approach to determine values of porosity (ε), De (effective diffusion coefficient), and KD (distribution coefficient for adsorption). HTO diffusive flux was higher in Ca-montmorillonite (De = 1.68 × 10−10 m2 s−1) compared to Na-montmorillonite (De = 7.83 × 10−11 m2 s−1). This increase in flux is likely due to a greater degree of clay layer stacking in the presence of Ca2+ compared to Na+, which leads to larger inter-particle pores. Overall, the Se(VI) flux was much lower than the HTO flux due to anion exclusion, with Se(VI) flux following the order Ca (De = 1.03 × 10−11 m2 s−1) > Na–Ca (De = 2.12 × 10−12 m2 s−1) > Na (De = 1.28 × 10−12 m2 s−1). These differences in Se(VI) flux are due to a combination of factors, including (1) larger accessible porosity in Ca-montmorillonite due to clay layer stacking and smaller electrostatic effects compared to Na-montmorillonite, (2) larger accessible porosity for neutral-charge CaSeO4 species which makes up 32% of aqueous Se(VI) in the pure Ca system, and (3) possibly higher Se(VI) adsorption for Ca-montmorillonite. Through a combination of experimental and modeling work, this study highlights the compounding effects that electrolyte and counterion compositions can have on radionuclide transport through clay. Diffusion models that neglect these effects are not transferable from laboratory experimental conditions to in situ repository conditions.

Abstract: The formation of Lau Basin records an extreme event of plate tectonics, with the associated Tonga trench exhibiting the fastest retreat in the world (16 cm/yr). Yet paleogeographic reconstructions suggest that seafloor spreading in the Lau Basin only initiated around 6 Ma. This kinematics is difficult to reconcile with our present understanding of how subduction drives plate motions. Using numerical models, we propose that eastward migration of the Lau Ridge concurrent with trench retreat explains both the narrow width and thickened crust of the Lau Basin. To match the slab geometry and basin width along the Tonga‐Kermadec trench, our models suggest that fast trench retreat rate of 16 cm/yr might start ~15 Ma. Tonga slab rollback induced vigorous mantle flow underneath the South Fiji Basin which is driving the extension and thinning of the basin and contributing to its observed deeper bathymetry compared to neighboring basins.

We introduce a new isotope chronological model in which the natural mass-dependent isotopic fractionation effects of the radioactive (“parent”) and radiogenic (“daughter”) elements are systematically and rigorously considered. Using this model, we show that internally-normalized radiogenic isotopic ratios, commonly determined for daughter elements such as Sr, Nd, Cr, Ni, Hf, W, and Os, are dependent on the extent of natural isotopic fractionation of the daughter and parent elements at the time of system closure. This dependence indicates that (1) in two samples derived from the same isotopically homogeneous source at the same time and with identical radiogenic ingrowth over time, the present-day internally-normalized radiogenic isotope ratios would be different if they were initially fractionated to different degrees, and (2) if different internally-normalized radiogenic isotopic ratios are observed for two co-genetic objects, the difference between them would include contributions from both radiogenic ingrowth and natural isotopic fractionation. Consequently, the isochron dating equations employed in traditional chronological studies will yield inaccurate results when significant natural isotopic fractionation is present among the studied samples. Modified isochron equations that can be used to retrieve correct chronological information from isotopically-fractionated samples are presented. These theoretical considerations are applied to the 87Rb–87Sr, 147Sm–143Nd, and 146Sm–142Nd isotope systems of calcium–aluminium-rich inclusions (CAIs), a set of samples that have undergone significant natural Sr, Nd, and Sm isotope fractionation during their formation. The large natural Sr isotope fractionation (up to ca. 5.3 ‰ for 88Sr/86Sr) in fine-grained CAIs can generate analytically well-resolvable biases (>120 ppm) in the internally-normalized 87Sr/86Sr ratios and lead to significant scatters of their 87Rb–87Sr isochron (in conjunction with scatters induced by open-system disturbances). The 87Rb–87Sr systems of coarse-grained CAIs, on the contrary, are essentially not affected by natural Sr isotopic fractionation due to their much subdued fractionation degrees, resulting in a more robust isochron. Similarly, the large natural Nd (up to ca. 4.0 ‰ for 146Nd/144Nd) and Sm (up to ca. 7.1 ‰ for 152Sm/148Sm) isotopic fractionation in fine-grained CAIs can induce significant scatters of the 147Sm–143Nd isochron if the natural fractionation followed the kinetic or power law, and 146Sm–142Nd isochron if the natural fractionation followed the equilibrium, Rayleigh, or power law. This implies that when studying radioactive isotope systems in objects whose daughter and parent elements can undergo significant isotope fractionation in nature, accompanying stable isotope analyses are necessary for accurate chronological interpretations.

Abstract: The upper mantle under the Afar Depression in the East African Rift displays some of the slowest seismic wave speeds observed globally. Despite the extreme nature of the geophysical anomaly, lavas that erupted along the East African Rift record modest thermal anomalies. We present measurements of major elements, H2O, S, and CO2, and Fe3+/ΣFe and S6+/ΣS in submarine glasses from the Gulf of Aden seafloor spreading center and olivine‐, plagioclase‐, and pyroxene‐hosted melt inclusions from Erta Ale volcano in the Afar Depression. We combine these measurements with literature data to place constraints on the temperature, H2O, and fO2 of the mantle sources of these lavas as well as the initial and final pressures of melting. The Afar mantle plume is C/FOZO/PHEM in isotopic composition, and we suggest that this mantle component is damp, with 852 ± 167 ppm H2O, not elevated in fO2 compared to the depleted MORB mantle, and has temperatures of ∼1401–1458°C. This is similar in fO2 and H2O to the estimates of C/FOZO/PHEM in other locations. Using the moderate H2O contents of the mantle together with the moderate thermal anomaly, we find that melting begins at around 93 km depth and ceases at around 63 km depth under the Afar Depression and at around 37 km depth under the Gulf of Aden, and that ∼1%–29% partial melts of the mantle can be generated under these conditions. We speculate that the presence of melt, and not elevated temperatures or high H2O contents, are the cause for the prominent geophysical anomaly observed in this region.

Abstract: Serpentinization has been widely documented and investigated at mid-ocean ridges (MOR) and subduction zones. In contrast, at magma-poor rifted margins serpentinization has received much less attention, despite its importance in controlling rheology and mass fluxes during breakup and establishing of a steady-state MOR. In this study, we present new petrological and geochemical data on subcontinental exhumed serpentinized peridotites from the spectacularly exposed Platta, Tasna and Totalp nappes in the Eastern Central Alps in SE Switzerland, belonging to the Alpine Tethys Ocean Continent Transition (OCT). The results testify of a complex history of fluid–rock interactions recorded by several serpentinization events starting with lizardite mesh and bastite textures (S1), subsequently followed by a succession of serpentine-filling veins with distinct textures and serpentine polysomes that include spherical polyhedral serpentine (S2); chrysotile ± polygonal ± lizardite banded veins (S3); lamellar antigorite veins and patches (S4) and chrysotile crack-seal (S5). The serpentinization sequence differs at proximal (i.e. continentwards) and distal (i.e. oceanwards) domains of the OCT. At proximal domains of the OCT (Upper Platta, Tasna) serpentinites record the complete serpentinization sequence (S1 to S5), whereas at distal domains (Lower Platta) serpentinization is restricted to pseudomorphic mesh and bastite (S1) and chrysotile crack-seal (S5). We attribute this discrepancy to contrasted mechanisms of mantle exhumation along the OCT. While at proximal domains mantle is unroofed along continuous and single large offset detachment faults allowing for the formation of all serpentine generations, mantle exhumation at distal domains is a more discontinuous process, controlled by sequential out-of-sequence detachment and flip-flop faults preventing the full development of all serpentine generations. In this frame, the nature and order of formation of the serpentine polysomes are directly controlled by the conditions of serpentinization (i.e. temperature, mantle composition and fluid/rock ratio). We propose that this new conceptual model can be extrapolated to serpentinization at slow to ultra-slow MORs, where close similarities in the serpentinization sequences have been recently reported.

Abstract: Magmatic systems below volcanoes are often dominated by partially crystalline magma over the long term. Rejuvenation of these systems during eruptive events can impact lava composition and eruption style—sometimes resulting in more violent or explosive activity than would be expected, as was the case at Fissure 17 during Kīlauea’s 2018 eruption. Here, we explore how the crystallinity of unerupted intrusion magmas affect hybrid magma compositions and petrological signatures by constructing phase-equilibria models to evaluate mineral and melt compositions of low-MgO lavas erupted along the East Rift Zone of Kīlauea volcano on 30 to 31 January 1997 (Episode 54, Fissures A-F). We then compare calculated mixing proportions and petrologically derived magma volumes to GPS-based geodetic inversions of ground deformation and intrusion growth in an attempt to reconcile geodetic and petrologically estimated magma volumes. Open-system phase-equilibria thermodynamic models were used to constrain the composition, degree of differentiation, and thermodynamic state of a rift-stored, two pyroxene + plagioclase saturated low-MgO magma body immediately preceding its mixing with high-MgO recharge and degassed drainback (lava lake) magma from Pu‘u‘ō‘ō‘, shortly before fissure activity within Nāpau Crater began on 29 January 1997. Mixing models constructed using the Magma Chamber Simulator reproduce the mineralogy and compositions of Episode 54 lavas within uncertainties and suggest that the identity of the low-MgO magma body may be either variably differentiated remnants of un-erupted magmas intruded into Nāpau Crater in October 1968, or another spatially and compositionally similar magma body. We find that magmas derived from a single, compositionally stratified magma emplaced beneath Nāpau Crater in 1968 can mix with mafic Kīlauea magmas to reproduce average Episode 54 bulk lava, mineralogy and mineral compositions without necessitating the interaction of multiple, low-MgO rift-stored magma bodies to produce Episode 54 lava compositions. Further, by constructing phase equilibria-based mixing models of Episode 54, we can better define the pre-eruptive state of the magmatic system. The resultant mineral assemblages and compositions are consistent with the possibility that the now-fractionated, rift-stored magma body was compositionally stratified and ~ 40% to 50% crystalline at the time of mixing. Finally, we estimate the volume of the low-MgO magma body to be ~7.51 Mm3. Phase-equilibria model results corroborate field and geochemical relationships demonstrating how shallow intrusions at intraplate shield volcanoes can crystallize, evolve, and then be remobilized by new, later batches of mafic magma. Most notably, our MCS models demonstrate that the pre-eruptive conditions of an intrusive body may be recovered by examining mineral compositions within mixed lavas. Discrepancies between the geodetic constraints on volumes of stored rift versus newly intruded (recharge) magma and our best-fit results produced by MCS mixing models (which respectively are mmafic:mlow-MgO ≈ 2 vs. mmafic:mlow-MgO ≈ 0.75) are interpreted to highlight the complex nature of incomplete mixing on more localized scales as reflected in erupted lavas, compared to geodetically constrained volumes that likely reflect large spatial scale contributions to a magmatic system. These dissimilar volume relationships may also help to constrain eruptive versus unerupted volumes in magmatic systems undergoing mixing. By demonstrating the usefulness of MCS in modeling past eruptions, we highlight the potential to use it as a tool to aid in petrologic monitoring of ongoing activity.

Abstract: The biological carbon pump is a key controller of how much carbon is stored within the global ocean. This pathway is influenced by food web interactions between zooplankton and their prey. In global biogeochemical models, Holling Type functional responses are frequently used to represent grazing interactions. How these responses are parameterized greatly influences biomass and subsequent carbon export estimates. The half‐saturation constant, or k value, is central to the Holling functional response. Empirical studies show k can vary over three orders of magnitude, however, this variation is poorly represented in global models. This study derives zooplankton grazing dynamics from remote sensing products of phytoplankton biomass, resulting in global distribution maps of the grazing parameter k. The impact of these spatially varying k values on model skill and carbon export flux estimates is then considered. This study finds large spatial variation in k values across the global ocean, with distinct distributions for micro‐ and mesozooplankton. High half‐saturation constants, which drive slower grazing, are generally associated with areas of high productivity. Grazing rate parameterization is found to be critical in reproducing satellite‐derived distributions of small phytoplankton biomass, highlighting the importance of top‐down drivers for this size class. Spatially varying grazing dynamics decrease mean total carbon export by >17% compared to globally homogeneous dynamics, with increases in fecal pellet export and decreases in export from algal aggregates. This study highlights the importance of grazing dynamics to both community structure and carbon export, with implications for modeling marine carbon sequestration under future climate scenarios.

Access to synchrotron X-ray facilities has become an important aspect for many disciplines in experimental Earth science. This is especially important for studies that rely on probing samples in situ under natural conditions different from the ones found at the surface of the Earth. The non-ambient condition Earth science program at the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory, offers a variety of tools utilizing the infra-red and hard X-ray spectrum that allow Earth scientists to probe Earth and environmental materials at variable conditions of pressure, stress, temperature, atmospheric composition, and humidity. These facilities are important tools for the user community in that they offer not only considerable capacity (non-ambient condition diffraction) but also complementary (IR spectroscopy, microtomography), and in some cases unique (Laue microdiffraction) instruments. The availability of the ALS’ in situ probes to the Earth science community grows especially critical during the ongoing dark time of the Advanced Photon Source in Chicago, which massively reduces available in situ synchrotron user time in North America.

Magma ascent and eruption are driven by a set of internally and externally generated stresses that act upon the magma. We present microstructural maps around melt inclusions in quartz crystals from six large rhyolitic eruptions using synchrotron Laue X-ray microdiffraction to quantify elastic residual strain and stress. We measure plastic strain using average diffraction peak width and lattice misorientation, highlighting dislocations and subgrain boundaries. Quartz crystals across studied magma systems preserve similar and relatively small magnitudes of elastic residual stress (mean 53–135 MPa, median 46–116 MPa) in comparison to the strength of quartz (~ 10 GPa). However, the distribution of strain in the lattice around inclusions varies between samples. We hypothesize that dislocation and twin systems may be established during compaction of crystal-rich magma, which affects the magnitude and distribution of preserved elastic strains. Given the lack of stress-free haloes around faceted inclusions, we conclude that most residual strain and stress was imparted after inclusion faceting. Fragmentation may be one of the final strain events that superimposes stresses of ~ 100 MPa across all studied crystals. Overall, volcanic quartz crystals preserve complex, overprinted deformation textures indicating that quartz crystals have prolonged deformation histories throughout storage, fragmentation, and eruption.

The chemical and isotopic characteristics of a solidified pluton represent the integration of magmatic and sub-solidus processes operating across a range of spatial and temporal scales during pluton construction, crystallization, and cooling. Disentangling these processes and understanding where chemical and isotopic signatures were acquired requires the combination of multiple tools tracing processes at different time and length scales. We combine whole-rock oxygen and Sr-Nd isotopes, zircon oxygen isotopes and trace elements, and mineral compositions with published high-precision U-Pb zircon geochronology to evaluate differentiation within the bimodal Guadalupe Igneous Complex, Sierra Nevada, California (USA). The complex was constructed in ~300 k.y. between 149 and 150 Ma. Felsic magmas crystallized as centimeter- to meter-sized segregations in gabbros in the lower part of the complex and as granites and granophyres structurally above the gabbros. A central mingling zone separates the mafic and felsic units. Pluton-wide δ18O(whole-rock), δ18O(zircon), and Sr-Nd isotopic ranges are too large to be explained by in situ, closed-system differentiation, instead requiring open-system behavior at all scales. Low δ18O(whole-rock) and δ18O(zircon) values indicate assimilation of hydrothermally altered marine host rocks during ascent and/or emplacement. In situ differentiation processes operated on a smaller scale (meters to tens of meters) for at least ~200 k.y. via (1) percolation and segregation of chemically and isotopically diverse silicic interstitial melt from a heterogeneous gabbro mush; (2) crystal accumulation; and (3) sub-solidus, high-temperature, hydrothermal alteration at the shallow roof of the complex to modify the chemical and isotopic characteristics. Whole-rock and mineral chemistry in combination with geochronology allows deciphering open-system differentiation processes at the outcrop to pluton scale from magmatic to sub-solidus temperatures over time scales of hundreds of thousands to millions of years.

Redox processes, aqueous and solid-phase chemistry, and pH dynamics are key drivers of subsurface biogeochemical cycling and methanogenesis in terrestrial and wetland ecosystems but are typically not included in terrestrial carbon cycle models. These omissions may introduce errors when simulating systems where redox interactions and pH fluctuations are important, such as wetlands where saturation of soils can produce anoxic conditions and coastal systems where sulfate inputs from seawater can influence biogeochemistry. Integrating cycling of redox-sensitive elements could therefore allow models to better represent key elements of carbon cycling and greenhouse gas production. We describe a model framework that couples the Energy Exascale Earth System Model (E3SM) Land Model (ELM) with PFLOTRAN biogeochemistry, allowing geochemical processes and redox interactions to be integrated with land surface model simulations. We implemented a reaction network including aerobic decomposition, fermentation, sulfate reduction, sulfide oxidation, methanogenesis, and methanotrophy as well as pH dynamics along with iron oxide and iron sulfide mineral precipitation and dissolution. We simulated biogeochemical cycling in tidal wetlands subject to either saltwater or freshwater inputs driven by tidal hydrological dynamics. In simulations with saltwater tidal inputs, sulfate reduction led to accumulation of sulfide, higher dissolved inorganic carbon concentrations, lower dissolved organic carbon concentrations, and lower methane emissions than simulations with freshwater tidal inputs. Model simulations compared well with measured porewater concentrations and surface gas emissions from coastal wetlands in the Northeastern United States. These results demonstrate how simulating geochemical reaction networks can improve land surface model simulations of subsurface biogeochemistry and carbon cycling.

The past decades have witnessed the increased applications of induced polarization (IP) method in the critical zone studies with ubiquitous clay minerals. Although IP outperforms traditional electrical and electromagnetic methods through its unique ability to measure quadrature conductivity, the nonlinearity that quadrature conductivity behaves with salinities and frequencies greatly tortures IP practitioners, as (a) salinity-dependency makes the quadrature conductivity a varyingly unstable parameter to quantitatively estimate hydraulic properties and clay content; (b) frequency-dependent Cole-Cole and Debye/Warburg decomposition models, although mathematically sound, physically mingle the properties of pore water and clay minerals and are empirical in nature. From basic principles, we demonstrate that quadrature conductivity remains a hybrid property involving both clay and water, and develop relevant models to distinguish them. Our models are validated by theories, experiments, simulations, and comparisons, all of which proclaim considerable advantages over previous models and offer the prospect of quantitative applications.

Abstract: The crystal structure and bonding environment of K2Ca(CO3)2 bütschliite were probed under isothermal compression via Raman spectroscopy to 95 GPa and single crystal and powder X-ray diffraction to 12 and 68 GPa, respectively. A second order Birch-Murnaghan equation of state fit to the X-ray data yields a bulk modulus, $${K}_{0}=46.9$$ K 0 = 46.9 GPa with an imposed value of $${K}_{0}^{\prime}= 4$$ K 0 ′ = 4 for the ambient pressure phase. Compression of bütschliite is highly anisotropic, with contraction along the c-axis accounting for most of the volume change. Bütschliite undergoes a phase transition to a monoclinic C2/m structure at around 6 GPa, mirroring polymorphism within isostructural borates. A fit to the compression data of the monoclinic phase yields $${V}_{0}=322.2$$ V 0 = 322.2  Å3$$,$$ , $${K}_{0}=24.8$$ K 0 = 24.8 GPa and $${K}_{0}^{\prime}=4.0$$ K 0 ′ = 4.0 using a third order fit; the ability to access different compression mechanisms gives rise to a more compressible material than the low-pressure phase. In particular, compression of the C2/m phase involves interlayer displacement and twisting of the [CO3] units, and an increase in coordination number of the K+ ion. Three more phase transitions, at ~ 28, 34, and 37 GPa occur based on the Raman spectra and powder diffraction data: these give rise to new [CO3] bonding environments within the structure.

Sedimentary basins provide a deep time archive of tectonic and Earth-surface processes that can be leveraged by detrital mineral U-Pb dating and geochemistry to track paleogeography, magmatism, and crustal evolution. Zircon preserves the long-term (billions of years) record of supercontinent cycles; however, it is biased toward preserving felsic crustal records. Detrital rutile complements the detrital zircon record by providing constraints on the time and temperature of rifting and mafic magmatism, metamorphism, exhumation of the middle and lower crust, subduction, and amagmatic orogenesis. We use detrital zircon U-Pb and detrital rutile U-Pb geochronology and trace element analysis of Permian to Eocene siliciclastic rocks in the southern Pyrenees to capture supercontinent cycles of ocean basins opening and closing. Detrital rutile age spectra show peaks at ca. 100 Ma associated with rifting and hyperextension in the Pyrenean realm, 200 Ma associated with the Central Atlantic Magmatic Province, and 330 Ma, 375 Ma, and 400 Ma associated with subduction and Rheic Ocean crust formation. Zr-in-rutile thermometry and rutile Cr-Nb systematics provide further insight into metamorphic facies (peak metamorphic temperatures) and source rock lithology (mafic versus felsic affinity). Detrital zircon age spectra have peaks at ca. 300 Ma, 450 Ma, and 600 Ma associated with major orogenic events and felsic magmatism, and Th/U ratios provide information on relative zircon formation temperatures. Comparison of these independent records shows that detrital rutile reflects rifting, magma-poor orogenesis, and oceanic lithospheric processes, while detrital zircon detects continental lithospheric processes. Integrated detrital zircon and rutile data sets archive past geological events across multiple Wilson cycles.

The paleogeography of Laurentia throughout the Neoproterozoic is critical for reconstructing global paleogeography due to its central position in the supercontinent Rodinia. We develop a new paleomagnetic pole from red siltstones and fine-grained sandstones of the early Neoproterozoic Jacobsville Formation which is now constrained to be ca. 990 Ma in age. High-resolution thermal demagnetization experiments resolve detrital remanent magnetizations held by hematite. These directions were reoriented within siltstone intraclasts and pass intraformational conglomerate tests—giving confidence that the magnetization is detrital and primary. An inclination-corrected mean paleomagnetic pole position for the Jacobsville Formation indicates that Laurentia's motion slowed down significantly following the onset of the Grenvillian orogeny. Prior rapid plate motion associated with closure of the Unimos Ocean between 1,110 and 1,090 Ma transitioned to slow drift of Laurentia across the equator in the late Mesoproterozoic to early Neoproterozoic. We interpret the distinct position of this well-dated pole from those in the Grenville orogen that have been assigned a similar age to indicate that the ages of the poles associated with the Grenville Loop likely need to be revised to be younger due to prolonged exhumation.

Miocene strata of the Claremont, Orinda, and Moraga formations of the Berkeley Hills (California Coast Ranges, USA) record sedimentation and volcanism during the passage of the Mendocino triple junction and early evolution of the San Andreas fault system. Detrital zircon laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) age spectra indicate a change in sedimentary prove nance between the marine Claremont formation (Monterey Group) and the terrestrial Orinda and Moraga Formations associated with uplift of Franciscan Complex lithologies. A sandstone from the Claremont formation produced a detrital zircon chemical abrasion–isotope dilution–thermal ionization mass spec trometry (CA-ID-TIMS) maximum depositional age of 13.298 ± 0.046 Ma, indicating younger Claremont deposition than previously interpreted. A trachydacite tuff clast within the uppermost Orinda Formation yielded a CA-ID-TIMS U-Pb zircon date of 10.094 ± 0.018 Ma, and a dacitic tuff within the Moraga Formation produced a CA-ID-TIMS U-Pb zircon date of 9.974 ± 0.014 Ma. These results indicate rapid progression from subsidence in which deep-water siliceous sediments of the Claremont formation were deposited to uplift that was followed by subsidence during deposition of terrestrial sediments of the Orinda Forma tion and subsequent eruption of the Moraga Formation volcanics. We associate the Orinda tuff clast and Moraga volcanics with slab-gap volcanism that followed the passage of the Mendocino triple junction. Given the necessary time lag between triple junction passage and the removal of the slab that led to this volcanism, subsidence associated with ca. 13 Ma Claremont sedimentation and subsequent Orinda to Moraga deposition can be attributed to basin formation along the newly arrived transform boundary.

The Snake River Plain (SRP) volcanic province overlies the track of the Yellowstone hotspot, a thermal anomaly that extends deep into the mantle. Most of the area is underlain by a basaltic volcanic province that overlies a mid-crustal intrusive complex, which in turn provides the long-term heat flux needed to sustain geothermal systems. Previous studies have identified several known geothermal resource areas within the SRP. For the geothermal study presented herein, our goals were to: (1) adapt the methodology of Play Fairway Analysis (PFA) for geothermal exploration to create a formal basis for its application to geothermal systems, (2) assemble relevant data for the SRP from publicly available and private sources, and (3) build a geothermal PFA model for the SRP and identify the most promising plays, using GIS-based software tools that are standard in the petroleum industry. The study focused on identifying three critical resource parameters for exploitable hydrothermal systems in the SRP: heat source, reservoir and recharge permeability, and cap or seal. Data included in the compilation for heat source were heat flow, distribution and ages of volcanic vents, groundwater temperatures, thermal springs and wells, helium isotope anomalies, and reservoir temperatures estimated using geothermometry. Reservoir and recharge permeability was inferred from the analysis of stress orientations and magnitudes, post-Miocene faults, and subsurface structural lineaments based on magnetics and gravity data. Data for cap or seal included the distribution of impermeable lake sediments and clay-seal associated with hydrothermal alteration below the regional aquifer. These data were used to compile Common Risk Segment maps for heat, permeability, and seal, which were combined to create a Composite Common Risk Segment map for all southern Idaho that reflects the risk associated with geothermal resource exploration and identifies favorable resource tracks. Our regional assessment indicated that undiscovered geothermal resources may be located in several areas of the SRP. Two of these areas, the western SRP and Camas Prairie, were selected for more detailed assessment, during which heat, permeability, and seal were evaluated using newly collected field data and smaller grid parameters to refine the location of potential resources. These higher resolution assessments illustrate the flexibility of our approach over a range of scales.

Cave carbonate minerals are an important terrestrial paleoclimate archive. A few studies have explored the potential for applying carbonate clumped isotope thermometry to speleothems as a tool for constraining past temperatures. To date, most papers utilizing this method have focused on mass-47 clumped isotope values (Δ47) at a single location and reported that cave carbonate minerals rarely achieve isotopic equilibrium, with kinetic isotope effects (KIEs) attributed to CO2 degassing. More recently, studies have shown that mass-47 and mass-48 CO2 from acid digested carbonate minerals (Δ47 and Δ48) can be used together to assess equilibrium and probe KIEs. Here, we examined 44 natural and synthetic modern cave carbonate mineral samples from 13 localities with varying environmental conditions (ventilation, water level, pCO2, temperature) for (dis)equilibrium using Δ47-Δ48 values, in concert with traditional stable carbon (δ13C) and oxygen (δ18O) isotope ratios. Data showed that 19 of 44 samples exhibited Δ47-Δ48 values indistinguishable from isotopic equilibrium, and 18 (95 %) of these samples yield Δ47-predicted temperatures within error of measured modern temperatures. Conversely, 25 samples exhibited isotopic disequilibria, 13 of which yield erroneous temperature estimates. Within some speleothem samples, we find Δ47-Δ48 values consistent with CO2 degassing effects, however, the majority of samples with KIEs are consistent with other processes being dominant. We hypothesize that these values reflect isotopic buffering effects on clumped isotopes that can be considerable and cannot be overlooked. Using a Raleigh Distillation Model, we examined carbon and oxygen isotope exchange trajectories and their relationships with dual clumped isotope disequilibria. Carbon isotope exchange is associated with depletion of both Δ47 and Δ48 relative to equilibrium, while oxygen isotope exchange is associated with enrichment of both Δ47 and Δ48 relative to equilibrium. Cave rafts collected from proximate locations in Mexico exhibit the largest average departures from equilibrium (ΔΔ47¯ = −0.032 ± 0.007, ΔΔ48¯ = −0.104 ± 0.035, where ΔΔi is the measured value – the equilibrium value). This study shows how the Δ47-Δ48 dual carbonate clumped isotope framework can be applied to a variety of tcave carbonate mineral samples, enabling identification of isotopic equilibria and therefore quantitative application of clumped isotope thermometry for paleoclimate reconstruction, or alternatively, constraining the mechanisms of kinetic effects.

Abstract: Foraminifera are unicellular organisms that inhabit the oceans. They play an important role in the global carbon cycle and record valuable paleoclimate information through the uptake of trace elements such as strontium into their calcitic shells. Understanding how foraminifera control their internal fluid composition to make calcite is important for predicting their response to ocean acidification and for reliably interpreting the chemical and isotopic compositions of their shells. Here, we model foraminiferal calcification and strontium partitioning in the benthic foraminifera Cibicides wuellerstorfi and Cibicidoides mundulus based on insights from inorganic calcite experiments. The numerical model reconciles inter-ocean and taxonomic differences in benthic foraminifer strontium partitioning relationships and enables us to reconstruct the composition of the calcifying fluid. We find that strontium partitioning and mineral growth rates of foraminiferal calcite are not strongly affected by changes in external seawater pH (within 7.8–8.1) and dissolved inorganic carbon (DIC, within 2100–2300 μmol/kg) due to a regulated calcite saturation state at the site of shell formation.

Abstract: The westernmost Nankai Trough, southwest Japan, exhibits a rapid along-strike reduction in plate coupling in the proximity to the subducting Kyushu-Palau ridge. Yet how and to what extent the ridge subduction impacts physical properties at the megathrust have not been investigated. Here we present high-resolution seismic P-wave velocity models along the forearc wedge in the western Nankai Trough derived from full-waveform inversion analyses of seismic refraction data. The velocity models show that where the plate coupling is weak and the plate boundary presumably hosts slow earthquakes, the upper plate exhibits lower seismic velocities indicating higher degree of fracturing over a ~ 100 km length along trough. Intriguingly, the extent of the upper-plate low-velocity features is significantly larger than the surficial width of the Kyushu-Palau ridge, and this low-velocity zone is underthrust by the slab with increased crustal thickness by 2–4 km. Seismic reflection images consistently reveal that the thicker slab crust has appreciable basement roughness extending ~ 60 km from the eastern margin of the Kyushu-Palau ridge beneath the western Shikoku basin. We suggest that such a thicker and rugged slab crust, together with the main body of the Kyushu-Palau ridge, can cause significant fracture zones in the overriding plate, decrease the interplate coupling and produce preferable conditions for shallow slow earthquakes to occur when subducted. The results may also provide structural constraints on the western limit of future megathrust earthquakes in the Nankai Trough. Graphical Abstract

Drier and hotter conditions linked with anthropogenic climate change can increase wildfire frequency and severity, influencing terrestrial and aquatic carbon cycles at broad spatial and temporal scales. The impacts of wildfire are complex and dependent on several factors that may increase terrestrial deposition and the influx of dissolved organic matter (DOM) from plants into nearby aquatic systems, resulting in the darkening of water color. We tested the effects of plant biomass quantity and its interaction with fire (burned vs. unburned plant biomass) on dissolved organic carbon (DOC) concentration and degradation (biological vs. photochemical) and DOM composition in 400 L freshwater ponds using a gradient experimental design. DOC concentration increased nonlinearly with plant biomass loading in both treatments, with overall higher concentrations (>56 mg/L) in the unburned treatment shortly after plant addition. We also observed nonlinear trends in fluorescence and UV-visible absorbance spectroscopic indices as a function of fire treatment and plant biomass, such as greater humification and specific UV absorbance at 254 nm (a proxy for aromatic DOM) over time. DOM humification occurred gradually over time with less humification in the burned treatment compared to the unburned treatment. Both burned and unburned biomass released noncolored, low molecular weight carbon compounds that were rapidly consumed by microbes. DOC decomposition exhibited a unimodal relationship with plant biomass, with microbes contributing more to DOC loss than photodegradation at intermediate biomass levels (100-300 g). Our findings demonstrate that the quantity of plant biomass leads to nonlinear responses in the dynamics and composition of DOM in experimental ponds that are altered by fire, indicating how disturbances interactively affect DOM processing and its role in aquatic environments.

Global trends of ocean warming, deoxygenation, and acidification are not easily extrapolated to coastal environments. Local factors, including intricate hydrodynamics, high primary productivity, freshwater inputs, and pollution, can exacerbate or attenuate global trends and produce complex mosaics of physiologically stressful or favorable conditions for organisms. In the California Current System (CCS), coastal oceanographic monitoring programs document some of this complexity; however, data fragmentation and limited data availability constrain our understanding of when and where intersecting stressful temperatures, carbonate system conditions, and reduced oxygen availability manifest. Here, we undertake a large data synthesis to compile, format, and quality-control publicly available oceanographic data from the US West Coast to create an accessible database for coastal CCS climate risk mapping, available from the National Centers for Environmental Information (accession 0277984) at 10.25921/2vve-fh39 (Kennedy et al., 2023). With this synthesis, we combine publicly available observations and data contributed by the author team from synoptic oceanographic cruises, autonomous sensors, and shore samples with relevance to coastal ocean acidification and hypoxia (OAH) risk. This large-scale compilation includes 13.7 million observations from 66 sources and spans 1949 to 2020. Here, we discuss the quality and composition of the synthesized dataset, the spatial and temporal distribution of available data, and examples of potential analyses. This dataset will provide a valuable tool for scientists supporting policy- and management-relevant investigations including assessing regional and local climate risk, evaluating the efficacy and completeness of CCS monitoring efforts, and elucidating spatiotemporal scales of coastal oceanographic variability.

Right-lateral transform motion associated with the Pacific-North American plate boundary in the modern-day San Francisco Bay Area occurs across a series of sub-parallel fault zones. Much of this motion is accommodated east of the San Andreas Fault by the faults of the East Bay fault system. A major tool for reconstructing the spatial and temporal history of fault motion is the correlation of offset Neogene volcanic rocks. These Neogene volcanics within the California Coast Ranges formed in association with the slab gap that grew as the Mendocino Triple Junction migrated northward. Some of the volcanic centres have been variably offset by subsequent strike-slip faulting. A felsic volcanic unit exposed in Berkeley, CA, known as the Northbrae rhyolite has variably been interpreted to be one of these Neogene volcanic units or to be a Mesozoic volcanic unit associated with the Coast Range ophiolite. A new U-Pb zircon date of 11.10 (Formula presented.) 0.09 Ma confirms the Neogene volcanic interpretation. This date is indistinguishable from previously published Ar/Ar dates from the Burdell Mountain volcanics of the North Bay region as well as a new U-Pb zircon date of 11.07 (Formula presented.) 0.10 Ma. In addition to the indistinguishable ages, similarities in bulk lithology, zircon crystallization/dissolution textures, and zircon trace element geochemistry are consistent with these rhyolites being associated with the same volcanic centre. This correlation implies that 40 (Formula presented.) 5 km of right-lateral offset occurred to the west of the modern-day position of the Hayward-Rodgers Creek fault zone. This offset represents (Formula presented.) 20% of the total offset along the East Bay fault system. A proto-Hayward Fault with a different geometry than that of the present-day played a significant role in the evolution of the fault system. This result highlights the dynamic spatiotemporal variability of strike-slip faults along transform margins.

The long-standing assumption that aboveground plant litter inputs have a substantial influence on soil organic carbon storage (SOC) and dynamics has been challenged by a new paradigm for SOC formation and persistence. We tested the importance of plant litter chemistry on SOC storage, distribution, composition, and age by comparing two highly contrasting ecosystems: an old-growth coast redwood (Sequoia sempervirens) forest, with highly aromatic litter, and an adjacent coastal prairie, with more easily decomposed litter. We hypothesized that if plant litter chemistry was the primary driver, redwood would store more and older SOC that was less microbially processed than prairie. Total soil carbon stocks to 110 cm depth were higher in prairie (35 kg C m-2) than redwood (28 kg C m-2). Radiocarbon values indicated shorter SOC residence times in redwood than prairie throughout the profile. Higher amounts of pyrogenic carbon and a higher degree of microbial processing of SOC appear to be instrumental for soil carbon storage and persistence in prairie, while differences in fine-root carbon inputs likely contribute to younger SOC in redwood. We conclude that at these sites fire residues, root inputs, and soil properties influence soil carbon dynamics to a greater degree than the properties of aboveground litter.

In this paper, sedimentological and geochemical data from six cores are presented and discussed in order to better understand the Holocene palaeoenvironmental evolution of the coastal plains of the Pecora and Cornia Rivers (southern Tuscany, Italy). Overall, the stratigraphies show a general upward trend in the evolution of the sedimentary succession of lagoonal environments (low Zr/Rb, high EC values) connected or partially connected to the sea (low EC values), to a seaward progradation of marshy-swampy environments (Mn/Ti, high TOC values) and finally to continental environments with the progradation of distal alluvial plains (high Zr/Rb, low EC values) influenced by runoff phenomena or local water stagnation. This trend is closely related to the increasing input of sediments from inland due to soil erosion processes and, especially in the last two centuries, land reclamation works. In the Cornia coastal plain, the chronologies indicate that lagoonal environments were already present before ca. 8.2ka BC and started receding seaward at around 3.7ka BC. On the other hand, chronologies from ca. 0.5ka BC to ca. 0.6ka AD point to a persistence of lagoonal environments only in areas very close to those already identified as such in historical cartography. In the Pecora coastal plain, the chronologies show that the lagoon environments had already disappeared before ca. 3.3ka BC, whilst the peripheral environments were characterised by abundant vegetation. The latter gradually degraded in favour of the development of shallow to very deep, unvegetated marshlands, which persisted until ca. 1ka AD. [ABSTRACT FROM AUTHOR]

Antecedent hydrological conditions are recorded through the evolution of dissolved lithium isotope signatures (δ7 ${\delta }^{7}$Li) by juxtaposing two storm events in an upland watershed subject to a Mediterranean climate. Discharge and δ7 ${\delta }^{7}$Li are negatively correlated in both events, but mean δ7 ${\delta }^{7}$Li ratios and associated ranges of variation are distinct between them. We apply a previously developed reactive transport model (RTM) for the site to these event‐scale flow perturbations, but observed shifts in stream δ7 ${\delta }^{7}$Li are not reproduced. To reconcile the stability of the subsurface solute weathering profile with our observations of dynamic stream δ7 ${\delta }^{7}$Li signatures, we couple the RTM to a distribution of fluid transit times that evolve based on storm hydrographs. The approach guides appropriate flux‐weighting of fluid from the RTM over a range of flow path lengths, or equivalently fluid residence times. This flux‐weighted RTM approach accurately reproduces dynamic storm δ7 ${\delta }^{7}$Li‐discharge patterns distinguished by the antecedent conditions of the watershed. Plain Language Summary: Storm events often cause characteristic shifts in stream solute chemistry. Interpreting these signals offers insight into the water‐rock interactions occurring within watersheds. Here, we use lithium stable isotopes and reactive transport modeling to relate how long water spends in a catchment, or how deep water infiltrates through a catchment, to the extent of chemical weathering. We show that the first significant storm after a dry season exports more chemically evolved water, while a wet season storm releases less evolved, shallower, and younger water. Our results indicate that stream flow δ7 ${\delta }^{7}$Li in small watersheds offers a sensitive record of hydrological conditions prior to the storm, reflecting subtle shifts in the efficiency of the Critical Zone to generate, transport, and ultimately export solutes. Key Points: Stream lithium stable isotope ratios (δ7Li) recorded at high frequency over storm events are sensitive to antecedent conditionsA reactive transport model cannot produce observed shifts in stream chemistry through variations in flow rate aloneFlux‐weighting of model fluid outputs based on time‐varying fluid transit time distributions describes stream δ7Li over storm hydrographs [ABSTRACT FROM AUTHOR]

The El Salvador plutonic complex is a 9.2 km2 circular body within the Sierra de Tamaulipas, part of the Eastern Mexican Alkaline Province (EMAP). Three alkaline magmatic suites were identified from El Salvador from the geochemical analysis of 20 samples. Suite A (SiO2 = 58.3–65.3 wt.%) is ferroan (Fe* = 0.761–0.873) and alkalic (MALI = 4.83–9.89). In contrast, Suites B (SiO2 = 52.5–60.8 wt.%; Fe* = 0.680–0.756) and C (SiO2 = 50.5–67.1 wt.%; Fe* = 0.616–0.749) are magnesian. Suite B is alkali-calcic (MALI = -2.18–4.64), while Suite C is alkalic (MALI = 4.48–8.59). All suites display arc-related signatures. U-Pb and fission-track geochronology data reveal two uplift episodes during the cooling history of Suite A. One in the Late Eocene was based on U-Pb zircon (38.42 ± 0.21 Ma) and titanite ages (35.54 ± 3.77 Ma). The other was during the Oligocene from U-Pb apatite (29.9 ± 6.54 Ma) and fission-track titanite (30.2 ± 5.53 Ma) and apatite ages (32.7 ± 7.06 Ma). Integrating the arc-related signatures of El Salvador rocks with the well-documented Palaeogene arc magmatism of the Sierra Madre del Sur, we propose that the mantle beneath the EMAP experienced metasomatism during the Early Permian (and possibly the Early Jurassic) but not after the Late Cretaceous, ruling out Cenozoic slab subduction in eastern Mexico. In the absence of a slab to explain the El Salvador magmatism, we suggest a long-lasting, widespread mantle upwelling beneath Mexico's northern half in response to the Farallon slab's break-up. Under this context, the westward drift of the North American plate led to the Mexican Foreland Basin lithosphere reaching this massive mantle upwelling in late Eocene times to produce the EMAP magmatism. [ABSTRACT FROM AUTHOR]

The Araba and Naqus formations in Ras Milan, Sinai, constitute part of the major continuous Paleozoic clastic belt stretching across northern Gondwana. They are sandstone-dominated successions, resting on Precambrian granitic basement, with lowermost thin basal polymictic conglomerate deposits (1–2 m), marking the unconformity. The Araba Formation section is composed mainly of varicoloured violet to reddish brown, fine to coarse-grained laminated and planner and overturned cross-bedded sandstones, while the overlying Naqus Formation is characterized by chaotically distributed poorly sorted quartz pebbles to cobbles within a moderately-sorted coarse- to medium-grained quartz arenite and by abundance and variety of large-scale tabular and trough cross bedding. Modal QFL classification of Araba and Naqus formation sandstones revealed that they are merely quartzose sandstones (quartz arenites). Geochemistry of the succession shows extremely wide compositional ranges for almost all major elements, but the Araba Formation is relatively enriched in SiO2, TiO2, Fe2O3*, Na2O, P2O5, and depleted in Al2O3, MgO, CaO and K2O relative to Naqus Formation. Only the Araba Formation samples are depleted in the transition elements Ni, Cr and Co and oppositely possess extreme enrichment in the HFSEs (i.e. Zr, Hf, Y, Nb, Ta, Th, U), whereas both formations show variable depletion in the LILE Rb, K and Ba, and excessive REE abundances relative to the PAAS and UCC, and LREE-enriched patterns with marked negative Eu anomalies. The provenance of the Naqus and Araba formations could be an earlier felsic magmatic source, which has undergone extensive sedimentary recycling. They possess high compositional maturity and were subjected to intensive to moderate weathering during humid climatic conditions. Passive margin tectonic setting is implied which denotes the derivation of Araba and Naqus formation siliciclastics from stable continental regions or plate interiors and deposition in intracratonic basins. [ABSTRACT FROM AUTHOR]

A combined study of whole-rock geochemical and Sr-Nd isotopic data, and zircon U-Pb geochronological and Hf isotopes has been carried out for several Neoproterozoic intrusions, including the Lung Thang, Posen and Sin Quyen in the Phan Si Pan Zone, northwest Vietnam to constrain their age, petrogenesis and tectonic implications. The Lung Thang and Posen intrusions, mainly composed of granodiorite, were formed at 803–777 Ma and are characterized by moderate SiO2 (64.43–66.65 wt.%), and K2O (4.05–4.89 wt.%), with A/CNK and A/NK values of (0.94–1.03) and (1.72–2.11), respectively. They have negative whole-rock εNd(t) (−6.16 to −3.73) and zircon εHf(t) values (−7.9 to −4.1), which suggest that the Lung Thang and Posen intrusions were generated by partial melting of ancient, K-rich crustal rocks. The Sin Quyen intrusion, occurring as dykes, is composed of monzodiorite and was emplaced at 742 ± 3 Ma. The Sin Quyen intrusion has high alkalies (K2O+Na2O = 7.42–7.47 wt.%), and low MgO (<1.31 wt.%) and Ni (6.55–6.93 ppm), with A/CNK and A/NK values of (0.67–0.68) and (1.64–1.68), respectively. Their whole-rock εNd(t) and zircon εHf(t) values are −6.15 to −5.92 and −5.8 to + 8, respectively. These geochemical characteristics suggest that the Sin Quyen intrusion was produced by the partial melting of ancient crustal sources mingled with mantle-derived components. Geochemically, the Lung Thang, Posen and Sin Quyen intrusions are medium- to high-K, calc-alkaline in nature and show enrichment in LILE (Th, U, K, Rb) and LREE, and strong negative anomalies of Nb, Ta, and Ti. Such geochemical characteristics suggest that they formed in a subduction-related tectonic environment. The geochronological and geochemical correlation of these intrusions with those along the southwestern margin of the Yangtze Block in South China suggests that the Phan Si Pan zone in northwestern Vietnam is a constituent of the SW Yangtze Block. Additionally, these intrusions show a significant correlation with other contemporaneous magmatic rocks in the northeast Indochina Block, Lhasa Block, the northwestern margin of Greater India as well as those in Seychelles and northern Madagascar. This correlation suggests a similar history and synchronous episode of crustal growth/recycling in an Andean-type arc system along the western and northern margin of the Rodinia supercontinent during the Neoproterozoic. [ABSTRACT FROM AUTHOR]

The 72‐foot sailing yacht Eugen Seibold is a new research platform for contamination‐free sampling of the water column and atmosphere for biological, chemical, and physical properties, and the exchange processes between the two realms. Ultimate goal of the project is a better understanding of the modern and past ocean and climate. Operations started in 2019 in the Northeast Atlantic, and will focus on the Tropical Eastern Pacific from 2023 until 2025. Laboratories for air and seawater analyses are equipped with down‐sized and automated state‐of‐the‐art technology for a comprehensive description of the marine carbon system including CO2 concentration in the air and sea surface, pH, macro‐, and micro‐nutrient concentration (e.g., Fe, Cd), trace metals, and calcareous plankton. Air samples are obtained from ca. 13 m above sea surface and analyzed for particles (incl. black carbon and aerosols) and greenhouse gases. Plankton nets and seawater probes are deployed over the custom‐made A‐frame at the stern of the boat. Near Real‐Time Transfer of underway data via satellite connection allows dynamic expedition planning to maximize gain of information. Data and samples are analyzed in collaboration with the international expert research community. Quality controlled data are published for open access. The entire suite of data facilitates refined proxy calibration of paleoceanographic and paleoclimate archives at high temporal and spatial resolution in relation to seawater and atmospheric parameters. Plain Language Summary: The new research sailing yacht Eugen Seibold (ES) enables clean, contamination‐free sampling of air and seawater to better understand the interactions between ocean and climate. For example, the oceans remove increasingly less carbon dioxide (CO2) from the atmosphere the more saturated they are with CO2 (ocean acidification). However, a detailed systematic understanding of air‐sea exchange processes remains to be developed. We analyze air and seawater as well as the exchange of greenhouse gases and other substances such as aerosols and soot (black carbon) between air and seawater at high resolution using modern materials and technologies. Scaled‐down, energy‐efficient, and automated probes developed over the past decade are being used to measure around 50 different characteristics of the marine environment. The work deck at the stern of the boat allows the use of custom‐made water samplers and plankton nets to study the ocean to below 1,000 m depth. In addition, the new data enables a better understanding of past ocean archives, such as the marine plankton accumulated in seafloor sediments, to reconstruct past climate changes. From 2019 to 2022, the S/Y ES sailed in the eastern North Atlantic and will operate in the tropical eastern Pacific until 2025. Key Points: New research platform for contamination‐free sampling of the water column and atmosphere of biological, chemical, and physical propertiesComprehensive marine geochemical analyzes including carbon (e.g., CO2) in air and sea surfaceProxy calibration of paleoclimate archives at high temporal and spatial resolution in relation to seawater and atmospheric parameters [ABSTRACT FROM AUTHOR]

The global demand for lithium is steadily increasing, driving an increased focus on exploration efforts worldwide. Lithium, a crucial metal for lithium-ion batteries (LIBs) used in renewable energy technologies, is vital in the global drive to reduce carbon emissions. India’s ambitions to become a manufacturing hub for LIBs and achieve 100% electric vehicle (EV) sales by 2030 require significant quantities of lithium. However, challenges due to limited domestic reserves within the country, prompting efforts to define new exploration targets and develop existing lithium occurrences. Recent discoveries in northern Jammu and Kashmir and southern Karnataka highlight promising lithium deposits. This study focuses on India’s lithium exploration within pegmatite belts across various cratonic blocks, identifying significant potential for lithium exploration and mining. Notably, spodumene-rich pegmatites are found in Karnataka’s Dharwar Craton, while lepidolite-rich pegmatites exist in Rajasthan’s Aravalli-Delhi Fold Belt and the Madhya Pradesh-Chhattisgarh region. Regions like Bihar-Jharkhand, Maharashtra, Odisha, and Assam-Meghalaya also exhibit promise for lithium exploration. These findings emphasize the diverse lithological settings where lithium exploration can be strategically pursued in India. This study recommends adopting modern exploration techniques and developing cost-effective extraction technologies to advance India’s lithium exploration efforts. These initiatives are crucial in meeting the escalating demand for lithium and advancing India’s clean energy objectives in the transition to renewable energy sources. [ABSTRACT FROM AUTHOR]

Abstract\nKEY POINTSStudies of lithogeochemical dispersion haloes of rare metal pegmatites, particularly those of economic interest, are known to display strong development of haloes of rare alkali elements (Li–Rb–Cs), in particular lithium, into country rocks. The use of these haloes in exploration for pegmatites has had apparently little application in an Australian context, where it has the potential to assist exploration undercover by expanding the known ‘footprint’ of these mineral systems. Dispersion haloes have two parts: proximal (typically of centimetres to metres thickness), characterised by visible changes to mineralogy relating to metasomatism, and distal, where there are typically cryptic geochemical changes, but no changes in host mineralogy. Collation of global data have shown that the lithogeochemical haloes of large rare metal pegmatites can extend laterally at least 200 m, with a few localities giving indications extending several kilometres along strike. Lithium displays the largest haloes, with Rb and Cs typically being less extensive; other elements are mostly localised close to the pegmatite wallrock interface. These haloes are more extensive in mafic host rocks than other host-rock types. Mafic host rocks also provide the best geochemical contrast for rare alkali elements. Of the 22 datasets reviewed here, many are simply ‘proof of concept’ studies based on single sample lines and may not have had their outer limits defined. The actual distribution of these haloes is likely to be controlled by anisotropies that control host-rock permeability in the host units, with fluids emanating from the rare metal pegmatites being commonly channelled into structures or exploiting foliation or bedding. Regional-scale structures are likely to control kilometre-scale haloes. Sheet silicates and amphiboles are the most important hosts for these elements, which consequently accumulate in units or structures rich in these minerals. The actual distributions of these elements are, in most cases, likely to be irregular and complex anomalies of varying three-dimensional shapes, and thus ‘vectoring’ based on systematic changes in concentration away from a source should be treated with caution. It is important to note that given anomaly types do not indicate the presence of particular minerals, such as spodumene. The presence of these haloes in Australian Archean cratons is supported by dispersion haloes in saprolite and saprock units in deep weathering profiles and is potentially applicable to lag sampling over near fresh or unweathered host-rock units in exposed terranes.Lithogeochemical haloes of Li–Rb–Cs represent a simple exploration tool that can be readily integrated into exploration workflows by assay of host rock units in proximity to LCT granitic pegmatites.Haloes extend laterally at least 200 m and show indications of kilometre-scale anomalies relating to structurally controlled fluid flow.Haloes are spatially more extensive and show greater geochemical contrast with backgrounds, in mafic host units.These rare alkali haloes may persist into weathered host-rock units such as saprolite in regolith profiles. [ABSTRACT FROM AUTHOR]

The Central lapetus Magmatic Province (CIMP) is a large igneous province (LIP) emplaced in the Baltican and Laurentian paleocontinents that marks the onset of the Caledonian Wilson Cycle. Paleozoic magmatism of the CIMP is preserved in both northeastern America and northern Europe. This study investigates rocks belonging to the hyper-extended margin of Baltica currently found in the Seve Nappe Complex of the Scandinavian Caledonides. Specifically, U-Pb zircon geochronology and whole-rock geochemistry are applied to a migmatitic variety of the Vierrucohkka amphibolite of the Marma Terrane, to the Aurek gabbro, and amphibolite of the Aurek Assemblage exposed in the Seve Nappe Complex in the Kebnekaise region, northern Swedish Caledonides. U-Pb zircon geochronology yields crystallization ages of 626 ±7 Ma for the protolith of the Vierrucohkka amphibolite, and 614 ±2 Ma and 609 ±1 Ma for the emplacement of the Aurek gabbro and amphibolite protolith, respectively. A younger age of 599 ±3 Ma is recorded in the Vierrucohkka amphibolite and is interpreted as the age of partial melting and migmatization. The geochemical signatures of the rocks demonstrate crustal assimilation during the emplacement of their protoliths and modification due to prograde metamorphic processes during Caledonian subduction. The Vierrucohkka amphibolite and the Aurek Assemblage samples display upper and lower crustal assimilation, respectively. Trace elements (Dy, Sm, Lu, and Y) record the growth of metamorphic garnet, while elevated TiO2contents record the crystallization of metamorphic rutile. Nevertheless, high field strength elements (HSFE) and ANb suggesta depleted mantle source forthe magmas of the protoliths of the investigated rocks. Altogether, geochemical data indicate that the igneous activity recorded in the Vierrucohkka amphibolite and the Aurek Assemblage between c. 626-609 Ma is related to continental rifting processes associated with the opening of the lapetus Ocean. [ABSTRACT FROM AUTHOR]

The MOS model (acronym coming from the French MOdèle Simplifié) was born from the desire to have a simple tool that can quantify the contribution of the diffusive reactive environment to the alteration of a vitrified nuclear waste package in deep geological disposal conditions. In the model, this environmental contribution consists partly of the ability of iron, metallic casing corrosion products, and argillite to consume silicon, and partly of the brake on diffusive transport provided by silicon through the successive layers of environmental material. It is a modeling tool serving as an intermediary between operational modeling for the calculation of the source term from the glass, mathematically more simple and giving higher upper margins, and models that use geochemistry and transport, giving greater accuracy for the interactions between glass and its environment. The goal of the MOS model is to calculate the possible impact of silicon reactive diffusion on the alteration rate within the different layers of material surrounding nuclear glass. This article lists the simplifying hypotheses on which the MOS is based, presents the digital resolution method for an environment consisting of several successive layers with different reactivity and transport properties, and explains the model's implementation. [ABSTRACT FROM AUTHOR]

In this study, laser ablation–multicollector–inductively coupled plasma–mass spectrometry (LA–MC–ICP–MS) of apatites and LA–ICP–MS of zircons are used to collect U–Pb geochronological data, Rb–Sr isotope chronology is used to analyze alkaline feldspar and plagioclase, and archival apatite geochemistry data for the exposed Naitoushan basalt and Heishigou dike in the Changbaishan Tianchi volcano (CTV) are accessed to examine the petrogenesis and determine the origin of basaltic magmatism in the CTV. The Naitoushan basalt and Heishigou dike formed at 22.2–18.7 and 0.230–0.218 Ma, respectively. In situ oxides, volatiles, trace element geochemistry and Sr–Nd isotopes of apatite are reported for two samples. Most apatites are in the early crystallization phase and form inclusions in plagioclase that are euhedral or subhedral. They have higher MgO and K2O/Na2O concentrations; lower F and Cl concentrations; Ba, Sr, Nb, Ta, Zr, Hf, K, and Ti depletion; and Th, U, Ce, Pb, P, and Nd enrichment. All apatite samples are enriched in light rare earth elements (REEs) relative to heavy REEs and have relatively homogeneous Th/U, Zr/Hf, La/Sm, and Nd/Tb ratios and Sr–Nd isotopic compositions; thus, their host magmas potentially have the same magmatic origin as oceanic island basalt. The apatite La, Yb, and U contents, Eu/Eu* and La/Yb values, and high REE contents show a weak crystallization sequence in the mafic magma. This study demonstrates that the pre-shield and post-shield mafic magmas in the CTV were likely derived from an enriched mantle source with an I-type signature related to the rollback of the Pacific plate. [ABSTRACT FROM AUTHOR]

Archaeological studies carried out in recent decades have demonstrated that the Pre‐Pyrenees, a mountain range in north‐east Iberia, were regularly frequented by several human groups during the Late Pleistocene. The Cova del Parco archaeological site is an example of this large‐scale and regular human presence. The site was discovered and first excavated in the 1970s, and since the 1980s, a team from the University of Barcelona has been conducting archaeological work. So far, we have found that the site was at least frequented from the Middle Magdalenian upon historical times. In this paper, we present the results of the archaeopetrological, geochemical and geographic information system (GIS) analyses of chert tools ascribed to the Middle Magdalenian sequence. The textural, micropalaeontological and geochemical analysis of the lithic artefacts has allowed us to identify several chert types from local, regional and long‐distance sources. Some of these cherts had their origin in the northern slopes of the Pyrenean chain, suggesting that this mountain chain was regularly crossed by Magdalenian groups. Next, we performed GIS analyses to determine the paths and connections that may have linked the archaeological site with the different chert outcrops, and to identify the best routes for crossing the Pyrenean Mountain range. Moreover, this study provides a larger vision of the mobility and the complex economic interactions between the different Magdalenian groups that settled Cova del Parco at the end of the Late Pleistocene. [ABSTRACT FROM AUTHOR]

This study discusses the potential of archaeological organic objects in anthropogenic sediments in terms of research into human impact on the medieval landscape and environment. In the Bohemian‐Moravian Highlands, at a mid‐altitudinal stream valley site (ca. 510 m asl), remains of a cut medieval forest stand with anthropogenic wooden structures and buried by technogenic sediments (e.g., ore, gangue and tailings) were archaeologically excavated. The site was analysed using an interdisciplinary approach, applying methods from archaeology, archaeobotany, sedimentology, pedology and geochemistry as well as dendrochronology and radiometric dating. The vegetation can be reconstructed as forest with a dominance of fir and an admixture of spruce and alder. The surrounding slopes were covered by broadleaf trees. Remains of wooden technical structures, stamped, ground and washed ores and gangue, together with fragments of grinding stones, allow the interpretation of the site as an ore and stamp mill linked to ore washing equipment. This record of a buried medieval fir forest can be likewise used as a historical testimony and analogue for present‐day issues on ecology and forestry, aiming at ecological revitalisation and adaptation of forests to ongoing climate change in Central Europe. [ABSTRACT FROM AUTHOR]

The content and distribution of precious metals in fine-grained bottom sediments, accumulated in the technogenic period (last decades) in the southwestern part of the Chukchi Sea, have been studied. The ubiquitous or local enrichment of the sediments with silver, gold, platinum, and palladium according to the average for the Earth's crust, as well as their enrichment with gold and palladium relative to pre-technogenic (Late Holocene) deposits, was shown. Differences in the conditions of the accumulation of precious metals in the Late Holocene and modern sediments were shown. Sources of input were determined, and the possibility of technogenic enrichment of the sources was proved by the methods of multicomponent statistical analysis of the total chemical composition of the sediments. [ABSTRACT FROM AUTHOR]

In recent years, a new Algoma-type banded iron formation (BIF) deposit has been discovered in the Lanling area of the North China Craton. However, its underlying formation origins remain elusive. To effectively address this issue, in this work, the major trace and rare earth elements were analysed to characterize their sources and formation environments. From their major geochemistry results, it was proven that the Lanling BIF is mainly composed of SiO2 + Fe2O3T with small amounts of Al2O3, MnO, K2O, CaO, MgO, Na2O, P2O5, and TiO2. After performing Post-Archean Australian Shale (PAAS) normalization, according to rare earth elements (REE) and yttrium (Y) (REE + Y = REY) analyses, it was demonstrated that light rare earths are depleted. On the contrary, heavy rare earths are enriched. In addition, La, Eu, and Y are positive anomalies, while Ce is a slightly negative anomaly. According to the REE geochemistry and REE-related parameters analyses, it was extracted that the ore-forming materials of Lanling BIF were mainly derived from the mixture of seawater and hydrothermal materials. Moreover, the formation of deposits is closely associated with seafloor hydrothermal fluids. Additionally, based on the negative Ce anomalies and REY characteristics, it was speculated that BIF formed in reducing conditions in Lanling. Our work provides valuable insights suggesting that the BIF in the study area is closely related to the volcanic sedimentary rock series, as well as to the possible existence of pyroclastic materials. [ABSTRACT FROM AUTHOR]

This study investigates the diagenetic history and timing of hydrocarbon migration in the lower Permian Ingleside Formation as revealed in the Ingleside roadcut at Owl Canyon area, Colorado. Fourteen beds were identified within the studied exposure and are composed of quartz arenite sandstone, limestone, dolomite, or siltstone. Observations from outcrop and thin sections, including calcite veins, carbonate-hosted vugs, and carbonate cement, indicate carbonate mobility throughout the outcrop. Stylolites parallel to bedding were probably formed by pressure solution related to compaction, and pressure solution of carbonates is one possible source of carbonate that could have precipitated in veins or as a cement. The Ingleside Formation was affected by other diagenetic processes, including feldspar dissolution and alteration and several stages of cementation. Hematite, calcite, dolomite, kaolinite, and quartz overgrowth cements are the major types of cements identified within the studied exposure. Hematite cement was determined to have precipitated very early, followed immediately by the precipitation of poikilotopic carbonate cement. Blocky calcite and blocky dolomite cements, the most common cements within the formation, formed after the hematite and poikilotopic cements. Kaolinite cement may have precipitated in association with feldspar dissolution and alteration or occurred with feldspar dissolution during modern weathering. Hydrocarbon migration may have taken place before the of the blocky carbonate cement. The CaO in sandstone samples is due to the occurrence of calcite and dolomite cement. The MgO in sandstone samples is related to dolomite content. Furthermore, the low concentration of K2O in sandstone samples could be attributed to the low proportion of K-feldspar, and other K-rich minerals and possibly reflects loss of K during diagenesis. The relationship fact that S and MgO are both more abundant in samples from the middle and upper parts of the outcrop than in deeper samples suggests that they were added by diagenetic fluids. This study of the Ingleside outcrop provides insights on the diagenesis, possible timing of possible hydrocarbon migration through the Ingleside Formation, and geochemical and mineralogical composition of the exposure, which was used to interpret the diagenetic history throughout the outcrop. Therefore, it adds to the understanding of hydrocarbon migration and hydrocarbon pathways in this part of the Denver Basin. [ABSTRACT FROM AUTHOR]

The carbonate rocks in the eastern part of NE Turkey are situated within the Pontide paleo-magmatic arc and are frequently in contact with granitoid formations, often hosting skarn mineralization in the region. These carbonate rocks, typically found on ridges and hillsides exhibit predominant orientations along east–west, northeast-southwest, and northwest-southeast directions. A part of limestone, named as biomicrite, metamorphosed and display a saccharoidal texture. Comprised mainly of calcite, with less secondary quartz and iron oxide minerals, these carbonate rocks are classified as Fe-poor calcio-carbonate and magnesio-carbonate, having higher CaO and LOI contents. Marble and recrystallized limestone with granoblastic texture mainly comprise of calcite, less quartz, magnetite, and hematite. Marble classification diagrams suggest calcic skarn mineralization, indicated by decreasing CaO (or CO2) and increasing MgO from limestone to marble (or skarn). Strontium contents deviate slightly from the lithosphere carbonate average, while low Rb contents, attributed to skarn metamorphism, indicate the absence of K-bearing minerals. The high Al2O3/SiO2 in the carbonate rocks can points out hydrothermal activity and carbonate disengagement can indicate to actualize at temperatures that can affect Ce and Al mobilities. The low authigenic U value, low U/Th and Ni/Co ratios in carbonate rocks have been implied that protolith constituents deposited under oxic conditions. Positive Eu anomalies in limestone and marble suggest the influence of hydrothermal fluids. Carbon and oxygen isotope values in marble are similar with those of metamorphic and skarn marbles, indicating a magmatic origin. Overall, mineralogical and geochemical analyses propose a uniform source and/or geological process for all studied marbles. [ABSTRACT FROM AUTHOR]

The Neoarchean Qingyuan greenstone belt (QGB) is located at the northeastern margin of the North China Craton (NCC) and has experienced amphibolite- to granulite-facies metamorphism. The supracrustal rock assemblage is composed of biotite-hornblende (Bt-Hb) monzonitic gneiss, garnet-biotite-hornblende (Grt-Bt-Hb) monzonitic gneiss, Grt-Bt-Hb plagioclase gneiss, amphibolite and orthopyroxene-biotite-hornblende (Opx-Bt-Hb) plagioclase gneiss. This study involves thorough field and petrographic observations, whole-rock geochemistry and LA-ICP-MS zircon U‒Pb ages of these rocks to constrain the Neoarchean geodynamic setting of the QGB. Zircon U‒Pb dating indicates that these metavolcanic rocks formed during 2.57‒2.52 Ga and experienced subsequent regional metamorphism at 2.52‒2.47 Ga. Lithological and geochemical characteristics show that the QGB protoliths were tholeiitic to calc-alkaline basalts, andesites, dacites and rhyolites. The andesite-dacite-rhyolite assemblage exhibits high SiO2 and Mg# values, low Yb and Y contents, strongly fractionated chondrite-normalized REE patterns and depletion in Nb, Ta, Ti and P, resembling Phanerozoic adakites. These geochemical characteristics suggest an origin from the partial melting of a subducted slab interacting with mantle wedge material. The tholeiitic to calc-alkaline basalts exhibit slightly LREE-enriched chondrite-normalized REE patterns and negative Nb and Ti anomalies, like island arc basalts. These basalts might have originated by partial melting of a mantle source affected by metasomatism from subduction-derived fluids and melts. The lithological associations and geochemical characteristics imply that the Qingyuan greenstone belt developed in a continental margin arc setting. [ABSTRACT FROM AUTHOR]

Reliable reconstructions of tephrostratigraphy and emplacement mechanisms of Early to Middle Miocene volcaniclastic deposits across the Alpine-Mediterranean region may yield important clues as to the nature, spread, volume, magnitude and frequency of large silicic eruptions of the Carpathian-Pannonian Region. Here we report on a sequence of Middle Miocene volcaniclastic deposits intercalated with lacustrine strata from the Livno-Tomislavgrad Basin, part of the Dinaride Lake System. We applied a multi-proxy approach to elucidate their source, decipher their emplacement mechanism, and evaluate their basin-scale and regional correlativity. New high-precision zircon geochronology (~ 14.32 Ma) reveals their simultaneity with numerous volcaniclastic deposits (and their alteration products) widely spread across the Alpine-Mediterranean region. Additionally, their correlativity is confirmed at the scale of the Livno-Tomislavgrad Basin, based on similar lithostratigraphy, mineralogy and volcanic glass geochemistry. Newly obtained zircon Hf isotope data imply that Livno-Tomislavgrad Basin distal volcaniclastic deposits and ~ 14.36 Ma Harsány ignimbrite of the Carpathian-Pannonian Region had shared a parental eruptive center. However, different volcanic glass geochemistry, bolstered by the high-precision geochronology, suggests distinct eruption events, implying more frequent explosive volcanism of the Carpathian-Pannonian Region during Middle Miocene than previously recognized. We suggest that the ~ 14.32 Ma fine fallout tephra, deposited in the distal basin in the Dinarides (> 400 km from the source), was likely re-mobilized by water-driven hillside erosion from the extensive paleo-relief, and further transported via land-derived gravity flows. Upon entering the lake, the gravity flows likely transformed into subaqueous sediment density flows. These deposited ~ 1 to 7-m-thick overall graded volcaniclastic turbidites, thinning away from the presumed source of tephra re-mobilization. Although over-thickened, the ~ 14.32 Ma Livno-Tomislavgrad Basin volcaniclastic deposits can still serve as a reliable tephro- and tectono-stratigraphic markers due to their rapid mode of accumulation. Schematic illustration of the formation of studied ~14.32 Ma volcaniclastic successions of the SE Livno-Tomislavgrad Basin, Dinaride Lake System [ABSTRACT FROM AUTHOR]

The Sierra de Famatina of northwestern Argentina contains one of the best Cambro-Ordovician stratigraphic records of the SW Gondwana margin. Two lithotectonic belts (Calalaste–Narváez and Famatina–Valle Fértil), separated by master faults, preserve evidence of two former volcano-sedimentary basins (Eastern and Western, respectively). The Calalaste–Narváez Lithotectonic Belt consists of an Ediacaran to early Cambrian basement unconformably overlain by a 490–480 Ma cover of very low-grade volcano-sedimentary and volcanic succession that presumably formed in an extensional tectonic regime. In contrast, the Famatina–Valle Fértil Lithotectonic Belt comprises a basement consisting of the late-lower-to-middle Cambrian metasedimentary Achavil and Negro Peinado formations unconformably overlain by meta/sedimentary and metavolcanic rocks ranging in age from the late Cambrian to the Middle Ordovician (ca. 490–460 Ma). This belt includes the Famatinian Cordilleran-type magmatic arc active mainly at ca. 473–468 Ma, coeval with andesite to rhyolitic volcanism (Suri and Las Planchadas formations). Rhyolitic tuffs of ca. 473 Ma (εNdi = − 4.1) were found in the La Aguadita Formation, allowing this unit to be re-assigned to the late Floian. The oldest magmatism of the Sierra de Famatina is characterized by isotopically evolved (εNdi = − 5.1) rhyolitic tuffs of ca. 490 Ma in the Bordo Atravesado Formation, which was coeval with deposition of Mn-enriched hydrothermal cherts. This early Famatinan volcanism contrast with that of similar age and isotopically less evolved occurred in the Calalaste–Narváez Lithotectonic Belt suggesting variations of the source of magmas across the space and time within the Famatinan Orogenic Cycle. We propose that both described lithotectonic belts likely diverge northwards into Chile and Peru, wrapping around the Arequipa–Antofalla Proterozoic block. [ABSTRACT FROM AUTHOR]

Deep biospheric anaerobic microbial sulfate reduction and oxidative sulfur cycling have been studied in long sediment cores mainly acquired as part of IODP explorations. The most remarkable observation in many of these studies is the existence of an active sulfur cycle in the deep subsurface sediments that have very low organic carbon content and are presumably refractory. Here, we investigate the interstitial sulfate concentrations and sulfur isotope ratios in a 290 m-long sediment core collected from the eastern Arabian Sea at a water depth of 2663 m. Continuous decrease in porewater-sulfate concentrations with depth (up to 75 mbsf) coupled with enrichment in δ34SSO4 values suggests organoclastic sulfate reduction (OSR) processes attributed to the activity of sulfate-reducing bacteria (SRB) and retention of labile organic substrates amenable to the SRBs. Below a depth of 75 mbsf, the absence of further reduction in sulfate concentration indicates insufficient labile substrate to drive sulfate-reduction activity. An increase in sulfate concentrations at the deeper subsurface (below 128.5 mbsf) coupled with decreasing δ34SSO4 values may be attributed to the oxidation of Fe-sulfide to sulfate. The increase in porewater alkalinity in the lower part of the core has been linked to the silicate degradation process by CO2 produced via the dissolution of CaCO3. Compilation of previous studies from this core, along with our investigation, intrigues future research on organic matter reactivity and microbiological activity in deeper subsurface under oligotrophic depositional regimes. [ABSTRACT FROM AUTHOR]

The Pannonian Basin is one of the best natural laboratories in the world to study the lithospheric response to continental extension and subsequent tectonic inversion. Here we address the topic of lithospheric structure by a combined geochemical and magnetotelluric analysis, which has been carried out in the framework of the Pannon LitH2Oscope project. The main objective was to detect the resistivity distribution over the entire lithosphere by magnetotelluric measurements, considering the lithological resistivity properties and relate the results to the structure and evolution of the Pannonian Basin. The Pannon LitH2Oscope MT array was used to estimate the depth of the Lithosphere-Asthenosphere Boundary (LAB), considering the legacy MT data and compared to previous estimates for the region. Using the MT and geomagnetic response functions, major structural zones of the Pannonian basin, such as the Mid-Hungarian Shear Zone or fault systems like the Makó Trough and the Békés Basin, were also imaged. In addition, we used the apparent resistivity soundings to compare 1D resistivity models computed from geochemistry and obtained from field MT measurements. This comparison provided new constrains for the composition, fluid and melt content variations at the local lithosphere-asthenosphere boundary. The Pannon LitH2Oscope MT dataset and the results presented in this paper provide input for more complex 3D inversions and further investigations of the lithospheric structure in the Carpathian-Pannonian region. [ABSTRACT FROM AUTHOR]