5,217 Search Results

In surface and near-surface weathering environments, the mobilization and partial loss of palladium (Pd) under oxidizing and weakly acidic conditions has been attributed to aqueous chloride complexation. However, prior work has also observed that a portion of Pd is retained by iron (oxyhydr)oxides in the weathering zone. The effect chloride has on the relative amount of Pd mobilization versus retention by iron (oxyhydr)oxides is currently unclear. We studied the effect of chloride complexation on Pd(II) adsorption to two iron (oxyhydr)oxides, hematite and 2-line ferrihydrite, at pH 4. Increasing chloride concentration suppresses Pd adsorption for both hematite and ferrihydrite, which displaymore » similar binding affinities under the conditions studied. Thermodynamic modeling of aqueous Pd speciation indicates that greater suppression of binding to iron (oxyhydr)oxides should occur than is observed because of the strength of Pd-Cl complexation, implying that additional interactions at the mineral surface are counteracting this effect. While increasing dissolved chloride concentration does not measurably impact mineral surface charging, extended X-ray absorption fine structure (EXAFS) spectra indicate that ternary Pd-Cl surface complexes form on both hematite and ferrihydrite. The number of Cl ligands in the surface species increase at greater chloride concentration. A mixture of bidentate and monodentate surface species are indicated by the EXAFS spectra, although the fitting uncertainties precludes determining whether these vary in relative abundance with chloride concentration. In order to offset the effect of strong aqueous Pd-Cl complexation and align with our EXAFS results, a surface complexation model developed for Pd adsorption to hematite involves a mixture of three ternary surface complexes containing 1, 2, and 3 chloride ligands. Our results show that Pd is mobilized as a chloride complex in platinum group element-rich weathering zones. As a result, porewater chloride concentrations are thus a dominant control on Pd retention by iron (oxyhydr)oxides in these weakly acidic environments.« less

In the past three decades, Puerto Rico (PR) experienced five hurricanes that met or exceeded category three, and they caused severe forest structural damage and elevated tree mortality. To improve our mechanistic understanding of hurricane impacts on tropical forests and assess hurricane-affected forest dynamics in Earth system models, we use in situ forest measurements at the Bisley Experimental Watersheds in Northeast PR to evaluate the Functionally Assembled Terrestrial Ecosystem Simulator coupled with the Energy Exascale Earth System Model Land Model (ELM-FATES). The observations show that before Hurricane Hugo, 77.3% of the aboveground biomass (AGB) is from the shade-tolerant plant functionmore » type (PFT). The Hugo-induced mortality rates are over ~50%, and they induce a ~39% AGB reduction, which recovers to a level like the pre-Hugo condition in 2014, following a second, lower intensity hurricane, Georges. We perform numerical experiments that simulate damage from Hugo and Georges on the forests, including defoliation, sapwood and structural biomass damage, and hurricane-induced mortality. ELM-FATES can reasonably represent coexistence between the two PFTs–light-demanding and shade-tolerant–for both the pre-Hugo and post-Hugo conditions. The model represents a reasonable size distribution of mid-and large-sized trees although it underestimates AGB, likely due to the overestimated nonhurricane mortality. ELM-FATES temporarily stimulated leaf biomass and diameter increment after Georges, an effect that should be tested with observations of future hurricane defoliation events. This research indicates that addressing model-data mismatches in tree mortality and understory dynamics are essential to simulation of more extreme hurricane effects under climate change.« less

A key aspect in the formation of rare earth elements (REE) deposits is the role of REE transport as aqueous REE complexes in supercritical hydrothermal solutions, where the nature of the aqueous complex is controlled by solution composition, temperature and pressure. Despite chloride being considered as one of the most abundant transporting ligands in magmatic-hydrothermal fluids, experimental investigations on the stability of aqueous REE chloride complexes are scarce above 300 °C. In this study, synthetic NdPO₄ crystals were reacted with non-saline and saline (0, 0.05 and 0.5 mNaCl), acidic (0.01 mHCl) aqueous solutions in a series of solubility experiments conductedmore » at 500–700 °C and 1.7 kbar, where the solubilities were determined using a stable Nd isotope (¹⁴⁵Nd isotope spike) dilution technique. NdPO₄ solubility ranges between 28 ppm and 10,858 ppm, where solubility increases with both temperature and salinity. At 500 °C, log mNdPO₄ increases from –3.93 to –1.60 and there is a strong correlation between NdPO₄ solubility and NaCl concentrations (slope of 1.2 ± 0.3), indicating stabilization of the Nd chloride aqueous complexes with a stoichiometry corresponding to NdCl²⁺. At 600 °C, this correlation is weaker (slope of 0.4, log mNdPO₄ increases from –2.63 to –1.88) indicating the stabilization of both Nd chloride and hydroxyl species controlling solubility. At 700 °C, NdPO₄ solubility is largely independent of NaCl concentration indicating that solubility is controlled by Nd hydroxyl complexes, where stoichiometry suggests the neutral Nd(OH)₃⁰ species is dominant. The solubility product (Ksp) of NdPO4 is derived from experimental data with the relation: log K_sp = -41.81 – 0.057T – 20987/T, with T temperature in Kelvin. Comparison of the measured Nd phosphate solubility to thermodynamic predictions using the available Helgeson-Kirkham-Flowers equation of state parameters for aqueous Nd complexes indicate that predictions are up to three orders of magnitude lower compared to experimental observations. This discrepancy is most pronounced in saline solutions, suggesting that thermodynamic properties of the REE chloride species in supercritical fluids require revision. Numerical simulations of fluid-rock interaction between acidic, saline fluids and a Strange Lake felsic mineral assemblage demonstrates that NdPO₄ solubility predictions from models are four to six orders of magnitude lower than those calculated based on empirical fits from experiments, which suggests that acidic, saline fluids may play an important role in mobilizing large amounts of light REE from 450 to 700 °C.« less

Enhanced Geothermal Systems (EGS) are a promising concept for unlocking the great potential of Hot Dry Rock (HDR) for sustainable clean-energy production. However, EGS has remained an elusive goal due to the unsolved challenges of induced seismicity, uneconomically low flow rates, and premature cooling of the produced fluid. We propose that fracture caging offers a path to solving these three challenges. Fracture caging is the placement of a cage of boundary wells around injection wells before injection begins. This cage captures injected fluid to halt fracture growth, even if injection continues at the high-pressures that are conventionally used only formore » hydraulic fracture stimulation. This pressure will hydroprop fractures to achieve the flowrates that are required for EGS, instead of relying on proppant or shear stimulation. In this study, we present laboratory experiments and a conceptual model to explore the physical limits of hydraulic fracture caging. More specifically we investigate the required number of wells, maximum flow rates, and boundary conditions needed to unlock caging and hydropropping as tools to achieve viable geothermal systems.« less

Naturally occurring bedded salt deposits are considered robust for the permanent disposal of heat-generating nuclear waste due to their unique physical and geological properties. The Brine Availability Test in Salt (BATS) is a US-DOE Office of Nuclear Energy funded project that uses heated borehole experiments underground (~655 meters depth) at the Waste Isolation Pilot Plant (WIPP) in the bedded salt deposits of the Salado Formation to investigate the capacity for safe disposal of high-level, heat generating nuclear waste in salt. Uncertainties associated with brine mobility near heat-generating waste motivates the need to characterize the processes and sources of brine inmore » salt deposits. Intragranular halite fluid inclusions are a potential source of brine that can migrate under temperature gradients toward heat sources. We developed a methodology to measure the stable isotopic compositions of water (δD_VSMOW, δ¹⁸O_VSMOW) in brine from halite fluid inclusions using Cavity Ring-Down Spectroscopy that accounts for memory effects using a unique reference-sample-reference bracketing approach and that minimizes sample size requirements. We applied this approach to halite samples obtained from WIPP and compare these data to seeped brines collected from horizontal boreholes at WIPP after drilling at ambient conditions. Here, the stable isotope compositions that we obtain for halite fluid inclusions (δ¹⁸O_VSMOW = +3.24 ± 0.53‰, δD_VSMOW = -25.3 ± 5.1‰, ±1σ, n = 5) generally agree with previous measurements and likely reflect a combination of syn-depositional and/or postdepositional processes. The seep brines are isotopically distinct (δ18OVSMOW = +3.46 ± 0.84‰, δD_VSMOW = +7.3 ± 3.5‰, ±1σ, n = 35) and instead resemble evaporated seawater. We discuss our results in the context of prior WIPP-proximal waters and lay the groundwork for using stable isotopes of water in brine as a tool to assess the heat-induced mobilization of halite fluid inclusions in ongoing heating experiments that comprise the Brine Availability Test in Salt.« less

The rare earth elements (REE) have important applications in green energy technologies. The formation of mineral deposits in geologic systems commonly involves hydrothermal fluids which can mobilize the REE. However, the REE speciation is not well known as a function of pH. The thermodynamic properties of REE hydroxyl complexes used in geochemical models are based on the Helgeson-Kirkham-Flowers (HKF) equation of state parameters which were derived by extrapolation of low temperature experimental and estimated data. In this study, Dy hydroxide solubility experiments are combined with available literature data to improve these models from 25 to 250 °C and optimize themore » thermodynamic properties of Dy³⁺ and Dy hydroxyl complexes using GEMSFITS. Batch-type solubility experiments were conducted from 150 to 250 °C and at saturated water vapor pressure in perchloric acid solutions with initial pH values of 2 to 5 in 0.5 pH unit increments. The measured solubility of Dy hydroxide is retrograde with temperature and decreases with pH. The logarithm of total dissolved Dy molality ranges from –2.3 to –5.3 at 150 °C (pH 4.7–5.5), from –2.4 to –5.6 at 200 °C (pH 3.9–5.1), and from –3.7 to –6.9 at 250 °C (pH of 3.4 and 5.0). The optimized standard partial molal Gibbs energies of formation (Δ_fG°_T) derived for Dy³⁺ and DyOH²⁺ display a close to linear relationship with temperature, fitting with previous optimizations based on DyPO₄ solubility data in the literature. A comparison of the optimized ΔfG°T values for aqueous Dy species with predictions from available HKF parameters indicates significant differences ranging from +11 to –26 kJ/mol between 25 and 250 °C. The experimental fits are used to derive the Dy hydroxide solubility products (K_s0) and formation constants for the hydrolysis of Dy (β_n with n = 1 to 3; Dy³⁺ + nOH^– = DyOH_n^3-n) as a function of temperature. The optimization method presented yields accurate thermodynamic properties for the Dy³⁺ aqua ions and the DyOH²⁺ species at the acidic to mildly acidic pH studied whereas more experimental work is needed at near-neutral and alkaline conditions to better constrain the other hydroxyl complexes. Furthermore, the optimized thermodynamic data have a significant impact on geochemical modeling of the mobility and solubility of REE minerals in acidic hydrothermal fluids.« less

The mobility of rare earth elements (REE) in natural hydrothermal systems can be assessed using geochemical modeling, which requires reliable thermodynamic data of relevant aqueous species. In this study, we evaluate the controls of pH and temperature on La speciation and the role of hydroxyl complexes in REE transport at hydrothermal conditions. Batch-type hydrothermal solubility experiments were conducted using synthetic La hydroxide powders equilibrated in perchloric acid-based aqueous solutions at temperatures between 150 and 250 °C and starting pH of 2 to 5. The La hydroxide solubility is retrograde with temperature and displays a strong pH dependence with a decreasemore » in La concentrations from acidic to mildly acidic pH spanning between 3 and 5 orders of magnitude (e.g. log La molality of –2.5 to –7.2 at 250 °C). Thermodynamic optimizations using GEMSFITS allow to retrieve the standard partial molal Gibbs energies for the La³⁺ aqua ion and the formation constants for the La hydroxyl species (i.e., LaOH²⁺, La(OH)₂⁺, La(OH)₃⁰) between 25 and 250 °C. A comparison between the experimentally derived thermodynamic properties with the calculated values from the Helgeson-Kirkham-Flowers equation of state parameters indicates an increased divergence with temperature. Discrepancies in standard partial molal Gibbs energies range between ~ 1 – 12 kJ/mol and result in a predicted La hydroxide solubility differing by up to 3 orders of magnitude at 250 °C. Speciation calculations indicate a higher stability of La³⁺ and LaOH²⁺ over the other La hydroxyl species in the studied pH range of 3.4 to 6. Here, the optimized thermodynamic properties for La aqueous species have important implications for modeling the solubility of REE minerals such as monazite and the mobility of REE in hydrothermal systems.« less

There has been widespread adoption of downscaled products amongst practitioners and stakeholders to ascertain risk from climate hazards at the local scale (e.g., ~5 km resolution). Such products must nevertheless be consistent with physical laws to be credible and of value to users. Here we evaluate statistically and dynamically downscaled products by examining local co-evolution of downscaled temperature and precipitation during convective and frontal precipitation events (two mechanisms testable with just temperature and precipitation). We find that two widely used statistical downscaling techniques (Localized Constructed Analogs version 2, LOCA2, and Seasonal Trends and Analysis of Residuals Empirical Statistical Downscaling Model,more » STAR-ESDM) generally preserve expected co-variances during convective precipitation events over the historical and future projected intervals as compared to European Centre for Medium-Range Weather Forecasts Reanalysis v5 (ERA5) and two observation-based data products (Livneh and nClimGrid-Daily). However, both techniques dampen future intensification of frontal precipitation that is otherwise robustly captured in global climate models (i.e., prior to downscaling) and with process-based dynamical downscaling across five different regional climate models. In the case of LOCA2, this leads to appreciable underestimation of future frontal precipitation event intensity. This study is one of the first to quantify a likely ramification of the stationarity assumption underlying statistical downscaling methods and identify a phenomenon where projections of future change diverge depending on data production method employed. Finally, our work proposes expected co-variances during convective and frontal precipitation as useful evaluation diagnostics that can be universally applied to a wide range of statistically downscaled products.« less

Geological interpretations, earthquake source inversions and ground motion modeling, among other applications, require models that jointly resolve crustal and mantle structure. With the second generation of the Collaborative Seismic Earth Model (CSEM2), we present a global multi-resolution tomographic Earth model that serves this purpose. The model evolves through successive regional- and global-scale refinements. While the first generation aggregated regional models, with this study, we ensure consistency between all individual submodels, resulting in a model that accurately explains wave propagation across scales. Recent regional tomographic models were incorporated, comprising continental-scale inversions for Asia and Africa, as well as regional inversions formore » the Western US, Central Andes, Iran, and Southeast Asia. Across all regional refinements, over 793,000 source-receiver pairs contributed. Moreover, the long-wavelength Earth model (LOWE) introduces large-scale structures outside of pre-existing local refinements. A full-waveform inversion for global anisotropic P-and S-wave speed structure over a total of 194 iterations with a minimum period of 50 s on a large data set of 1 hr of waveform data from 2,423 earthquakes and over 6 million source-receiver pairs ensures that regional updates in the crust and uppermost mantle translate into updates of deeper, global-scale structure. To test the performance of CSEM2, we evaluate waveform fits between observed and synthetic seismograms at 50 s for an independent data set on the global scale, and on the regional scale for lower periods. We accurately simulate waveforms within and across regional refinements, maintaining the original resolution of the submodels embedded in the global framework.« less

Land surface models (LSMs) play a crucial role in elucidating water and carbon cycles by simulating processes such as plant transpiration and evaporation from bare soil, yet calibration often relies on comparing LSM outputs of landscape total evapotranspiration (ET) and discharge with measured bulk fluxes. Discrepancies in partitioning into component fluxes predicted by various LSMs have been noted, prompting the need for improved evaluation methods. Stable water isotopes serve as effective tracers of component hydrologic fluxes, but data and model integration challenges have hindered their widespread application. Leveraging National Ecological Observation Network measurements of water isotope ratios at 16 USmore » sites over 3 years combined with LSM-modeled fluxes, we employed an isotope-enabled mass balance framework to simulate ET isotope values (δET) within three operational LSMs (Mosaic, Noah, and VIC) to evaluate their partitioning. Models simulating δET values consistent with observations were deemed more reflective of water cycling in these ecosystems. Mosaic exhibited the best overall performance (Kling-Gupta Efficiency of 0.28). For both Mosaic and Noah there were robust correlations between bare soil evaporation fraction and error (negative) as well as transpiration fraction and error (positive). We found the point at which errors are smallest (x-intercept of the multi-site regression) is at a higher transpiration fraction than is currently specified in the models. Which means that transpiration fraction is underestimated on average. Stable isotope tracers offer an additional tool for model evaluation and identifying areas for improvement, potentially enhancing LSM simulations and our understanding of land-surface hydrologic processes.« less