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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Hydrological control of chemical weathering and rock-carbon fluxes: East River, Colorado

This data package is used in the manuscript entitled “Hydrological control of chemical weathering and rock-carbon fluxes”. The field study was conducted in a lower montane hillslope of the East River watershed, underlain by Mancos Shale, within the lower 140 m section of a transect that extends nearly 1 km to its local peak. The data in this package, in CSV file format, were collected from Fall 2016 to fall 2021, including depth-resolved dynamic water table depths, subsurface water fluxes, solid phase (soil to bedrock) chemical compositions, geochemical properties of porewater and pore-gas, including radio carbon concentrations. The detailed methods of field studies, laboratory chemical analyses, and calculations are described in the Methods section and in the dataset file: Wan_et_al_Methods.pdf. The dataset additionally includes a file-level metadata (flmd.csv) file that lists each file contained in the dataset with associated metadata; and a data dictionary (dd.csv) file that contains column/row headers used throughout the files along with a definition, units, and data type.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

2D reactive transport model of shale chemical weathering and biogeochemical fluxes along a mountainous hillslope, East River Watershed, Colorado: Input files and simulation results

This data package contains input files and simulation results for a two-dimensional (2D) reactive transport model used to quantitatively analyze the coupled hydrological and biogeochemical processes governing shale weathering and associated biogeochemical fluxes under realistic environmental conditions in the high-elevation East River Watershed. These data support the conclusions presented in Stolze et al. (Water Resources Research, under review), "Model-based interpretation of solute exports and carbon partitioning during shale weathering in a mountainous hillslope". The model simulates atmospheric-subsurface gas exchange, subsurface water flow, and shale weathering processes under dynamic, year-scale conditions along a shale-underlain hillslope located in the East River watershed. The simulations were performed using the PFLOTRAN flow and reactive transport code and executed on the Perlmutter supercomputer to leverage its large-scale parallel computing capabilities. The data package contains two zipped folders, "model_input_files" and "simulation_results", and one readme.txt file. "model_input_files" contains the necessary input files to run the calibrated base-base model presented in Stolze et al. (Water Resources Research, under review). "simulation_results" contains a single hdf5 file ("Output_2D_hillslope_model.h5") which includes the results of simulation performed using the base-case model. This file can be opened with HDFView 3.1.4, Python, or MATLAB. "readme.txt" contains relevant information about the base-case model and provides guidelines on how to run the associated input files provided in the folder "model_input_files". Furthermore, readme.txt provides information regarding the model results provided in "Output_2D_hillslope_model.h5" such as matrix dimensionality and output units. Field datasets used to evaluate model performance were collected at three monitoring wells located along a hillslope transect (PLM1, PLM2, and PLM3). Dissolved ion concentration data were collected from November 2016 to October 2021 for Ca, Mg, DIC, Na, K, SO4 (Dong et al., 2025 - dic_npoc_data_2014_2024.zip - DOI:10.15485/1660459; Williams et al., 2025 - anion_data_2014_2024.zip - DOI:10.15485/1668054; Dong et al., 2025 - cation_data_2014_2024.zip - DOI:10.15485/1668055). Note that we used the files named er_PLM1_xx_yy, er_PLM2_xx_yy, and er_PLM3_xx_yy where xx stands for the name of the aqueous species and yy stands for the depth where the measurements were performed. Soil water content ([0 - 1] m) and water table depth were collected from November 2016 to October 2021 (Wan et al., 2024 - Dynamic_water_table__depthsFig2b.csv and Soil_water_content_Fig4e.csv - DOI:10.15485/2322567). Gaseous CO2 concentration were collected from October 2020 to December 2021(Wan et al., 2024 - Soil_CO2_concentrations_Fig4h.csv - DOI:10.15485/2322567) Gaseous CO2 flux from the subsurface to the atmosphere were collected in the vicinity of PLM2 from October 2019 to May 2022 (Wu et al., 2025). Soil microbial biomass concentration was measured from August 2016 to June 2017 (Sorensen et al., 2019 - 2017_East_River_Pumphouse_Microbial_Biomass__1_.csv - DOI:10.15485/1577267) All field data are published as CSV files compatible with Microsoft Excel, MATLAB, and Python, or as text files. The coordinates of the monitoring wells and the CO2(g) flux sensor in the coordinate system WGS84 are: -PLM1: [38.9197710 ; -106.9492750] -PLM2: [38.9201580 ; -106.9487170] -PLM3: [38.9207843 ; -106.9483668] -PLM4: 38.9210060 ; -106.9479528] -CO2(g) flux sensor: [38.9199180 ; -106.9489906] ------------------------------------------------------------------------------------------- This work was supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a Department of Energy User Facility using NERSC award BER-ERCAP 23980, BER-ERCAP 28550, and BER-ERCAP 33789.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Validating the rhenium proxy for rock organic carbon oxidation using weathering profiles

Chemical weathering over geological timescales acts as a source or sink of atmospheric carbon dioxide (CO 2 ), while influencing long-term redox cycling and atmospheric oxygen (O 2 ) at Earth's surface. There is a growing recognition that the oxidative weathering of rock organic carbon (OC petro ) can release more CO 2 than is locally drawn down by silicate weathering, and may vary due to changes in erosion and climate. The element rhenium (Re) has emerged as a proxy to track the oxidative weathering of OC petro , yet uncertainties in its application remain namely that we lack a systematic assessment of the comparative mobility of Re and OC petro during sedimentary rock weathering. Here we measure Re and OC petro loss across gradients in rock weathering at 9 global sites, spanning a range of initial OC petro values from ~0.2 % to >10 %. We use titanium to account for volume changes during weathering and assess Re and OC petro loss alongside major elements that reflect silicate (Na, Mg), carbonate (Ca, Mg) and sulfide (S) weathering. Across the dataset, Re loss is correlated with OC petro loss but not with loss of any other major element. Further, across the weathering profiles, the average molar ratio of OC petro to Re loss was 0.84 ± 0.15, with 8 out of 9 sites having a ratio >0.74. At one site (Marcellus Shale), the average ratio was lower at 0.58 ± 0.11. The excess loss of Re matches expectations that, typically, between ~0 and 20 % of the Re liberated by sedimentary rock weathering derives from silicate or sulfide phases, while some OC petro may be physically or chemically protected from weathering. Overall, our measurements provide validation for the Re proxy of OC petro oxidation and allow future work to further improve our knowledge of regional and global-scale rates of this important source of CO 2 in the geochemical carbon cycle.

58 GEOSCIENCES↗
DOE OSTI2023

The circular nutrient economy of terrestrial ecosystems and the consequences for rock weathering

Earth’s biosphere is thought to exert a substantial influence on regolith evolution and chemical weathering rates. However, ecosystems are also highly efficient at retaining and recycling nutrients. Thus, when the ecological demand for rock-derived nutrients (e.g., P, Ca, K) exceeds the rates of regolith supply, ecological retention and recycling strategies can minimize nutrient limitations. To evaluate the balance between nutrient recycling and new nutrient input, we combined a plant model that drives growth according to foliar P levels with a weathering model that includes regolith rejuvenation via erosion and export via chemical weathering according to water flow, regolith thickness, mineral dissolution rates, secondary minerals, and nutrient storage in organic and mineral phases. We find that plant growth is strongly dependent on the total regolith nutrient inventory, resulting in a strong correlation between plant productivity and erosion. Increased water export or decreased regolith thickness diminish the total inventory of nutrient corresponding to lower rates of recycling and lower plant growth. In contrast, purported biogenic drivers of weathering, such as enhanced mineral dissolution, only support higher growth rates at high erosion rates. At erosion rates typical of the global land surface, more rapid mineral dissolution combined with enhanced formation of secondary minerals, depletes the inventory of mineral P, resulting in no benefit for plant growth. We also find that the increased chemical weathering export does not scale directly with plant growth. For example, accelerated mineral weathering does increase chemical weathering export but not potential plant growth. Conversely, thicker regolith is associated with a small increase in weathering export, but a large increase in potential plant growth. Collectively, when plant growth is coupled to regolith weathering our calculations suggest that plant productivity is not directly correlated with silicate weathering fluxes, and that biotic drivers of silicate weathering may only be effective at high erosion rates not typical at the Earth’s surface.

58 GEOSCIENCES↗
DOE OSTI2020

Predicting Water Cycle Characteristics from Percolation Theory and Observational Data

The fate of water and water-soluble toxic wastes in the subsurface is of high importance for many scientific and practical applications. Although solute transport is proportional to water flow rates, theoretical and experimental studies show that heavy-tailed (power-law) solute transport distribution can cause chemical transport retardation, prolonging clean-up time-scales greatly. However, no consensus exists as to the physical basis of such transport laws. In percolation theory, the scaling behavior of such transport rarely relates to specific medium characteristics, but strongly to the dimensionality of the connectivity of the flow paths (for example, two- or three-dimensional, as in fractured-porous media or heterogeneous sediments), as well as to the saturation characteristics (i.e., wetting, drying, and entrapped air). In accordance with the proposed relevance of percolation models of solute transport to environmental clean-up, these predictions also prove relevant to transport-limited chemical weathering and soil formation, where the heavy-tailed distributions slow chemical weathering over time. The predictions of percolation theory have been tested in laboratory and field experiments on reactive solute transport, chemical weathering, and soil formation and found accurate. Recently, this theoretical framework has also been applied to the water partitioning at the Earth’s surface between evapotranspiration, ET, and run-off, Q, known as the water balance. A well-known phenomenological model by Budyko addressed the relationship between the ratio of the actual evapotranspiration (ET) and precipitation, ET/P, versus the aridity index, ET 0 /P, with P being the precipitation and ET 0 being the potential evapotranspiration. Existing work was able to predict the global fractions of P represented by Q and ET through an optimization of plant productivity, in which downward water fluxes affect soil depth, and upward fluxes plant growth. In the present work, based likewise on the concepts of percolation theory, we extend Budyko’s model, and address the partitioning of run-off Q into its surface and subsurface components, as well as the contribution of interception to ET. Using various published data sources on the magnitudes of interception and information regarding the partitioning of Q, we address the variability in ET resulting from these processes. The global success of this prediction demonstrated here provides additional support for the universal applicability of percolation theory for solute transport as well as guidance in predicting the component of subsurface run-off, important for predicting natural flow rates through contaminated aquifers.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Lithological controls on soil geochemistry and clay mineralogy across Spodosols in the coastal temperate rainforest of southeast Alaska

The interaction of similar soil forming factors with different parent materials determines soil chemical weathering, influencing soil processes and properties. In the coastal temperate rainforests of southeast Alaska, Spodosols is the dominant soil order in well-drained parent materials regardless of the lithology. Yet, the role of lithology on chemical weathering, base cation depletion, and mineral transformation during pedogenesis remains elusive. Here, we established a lithosequence comprised of soils derived from tonalite, phyllite, slate, and metavolcanic rocks to test the hypothesis that despite the soils in southeast Alaska presenting similar taxonomy and morphology, the influence of lithology in chemical weathering intensity and mineralogy can be detected. We evaluated physicochemical properties, clay mineralogy, Fe-Al oxides, chemical weathering, and elemental mass balance on eleven Spodosols sampled along the lithosequence. We also propose a new weathering index, the Weathering Index for Spodosols (WISP), suitable to evaluate the weathering degree of soils with Al mobility and base-rich parent materials. This index fills a gap in traditional weathering indices that uses Al as an immobile element and/or does not evaluate the leaching of main base cations. We found the pedons across the lithosequence expressed similar physicochemical properties, with predominantly thick profiles, presenting andic properties, relatively thick spodic horizons, and thin E horizons. Podzolization imposed similar mineral transformation trends, mainly dissolution of chlorite, mica alteration to interstratified mica-vermiculite, and formation of smectite in E horizons. Kaolinite was detected in the soils from all lithologies, but only in trace amounts in phyllite soils. Fe oxides depth distribution was similar but with a higher concentration in the slate (44.5 ± 4.2 g/kg), followed by metavolcanic (31.6 ± 4.0 g/kg), phyllite (27.9 ± 3.8 g/kg), and tonalite soils (19.9 ± 5.7 g/kg) and predominantly as organometallic complexes (extracted by Na-pyrophosphate). The stronger weathering of chlorite and mica in the E horizons was reflected in larger losses of Mg and K, while Ca and Na were more depleted in the spodic horizons, suggesting plagioclase weathering. Slate soils were the most depleted in base cations, followed by phyllite, tonalite, and metavolcanic soils. The more depleted status of slate soils was supported by the higher WISP values (WISP = 62), followed by phyllite (WISP = 55), tonalite (WISP = 53), and metavolcanic soils (WISP = 45). Our results demonstrated that lithology controlled elemental depletion intensities, Fe oxide concentrations, and partially the clay fraction mineralogy in addition to podzolization acting as a dominant pedogenic process across all sites. These findings advance our understanding of the role of lithology on soil mineralogy/geochemistry that impacts critical soil functions, such as the soil carbon cycle, elemental fluxes, organo-mineral interactions, and solid-solution reactions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Deep Roots Supply Reactivity and Enhance Silicate Weathering in the Bedrock Vadose Zone

In upland environments, roots commonly extend deep below soil into partially saturated bedrock. This Bedrock Vadose Zone (BVZ) has been shown to store and circulate water, host organic carbon respiration and serve as a critical source of rock-derived nutrients. However, the extent to which deep roots influence chemical weathering rates remains poorly understood. Here, we report 4 years of depth-resolved major ion chemistry over a 16-m thick BVZ hosting a deep rhizosphere in a catchment subject to a Mediterranean climate. These data allow development and validation of a reactive transport model (RTM), revealing that the timescales of water storage and drainage in the BVZ are sufficient to facilitate substantial chemical weathering of the shale bedrock. However, observed solute concentrations are only reproduced by the RTM when we explicitly include measured rates of CO 2(g) production meters below soil driven by the deeply rooted forest. By combining direct observations and a process-based RTM we conclude that the carbon respiration promoted by deep roots significantly enhances chemical weathering rates in the BVZ, constituting 43% ± 3% of total solute flux from the base of the BVZ to the water table.

Osorio‐Leon, Ivan D. [University of Illinois Urban↗
DOE OSTI2024

Advancing a Watershed Hydro-Biogeochemical Theory: Linking Water Travel Time and Reaction Rates Under Changing Climate

The major goal of the project is to answer the question how and to what degree does a warming climate alter hydrological functioning and (biogeochemical and chemical weathering) reaction rates at the watershed scale? In particular, how does hydrological functioning (water storage, flow paths, and travel time) change responding to a warming climate? What are the corresponding alterations in biogeochemical and chemical weathering rates at the watershed scale? What is the general watershed-scale reaction rate law that causally links reaction rates to metrics of hydrological functioning that are determined by external hydroclimatic conditions and internal watershed structure characteristics? To answer these questions, we have used field measurements and reactive transport modeling. We have found that: 1) stream chemistry has altered tremendously in warmer years; 2) In this water-limited environment, hydrology is the dominant driver for soil respiration and carbon lateral export at the watershed scale; 3) deeper carbon respiration plays an essential role in regulating the patterns of stream carbon in low and high flow conditions, and deeper groundwater will become increasingly important as warming intensifies. This indicates in mountain streams, a warming climate will modify not only the timing and magnitude of streamflow as expected, but also the chemistry and quality of stream water.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Permafrost Landscape History Shapes Fluvial Chemistry, Ecosystem Carbon Balance, and Potential Trajectories of Future Change

Intensifying permafrost thaw alters carbon cycling by mobilizing large amounts of terrestrial substrate into aquatic ecosystems. Yet, few studies have measured aquatic carbon fluxes and constrained drivers of ecosystem carbon balance across heterogeneous Arctic landscapes. Here, we characterized hydrochemical and landscape controls on fluvial carbon cycling, quantified fluvial carbon fluxes, and estimated fluvial contributions to ecosystem carbon balance across 33 watersheds in four ecoregions in the continuous permafrost zone of the western Canadian Arctic: unglaciated uplands, ice-rich moraine, and organic-rich lowlands and till plains. Major ions, stable isotopes, and carbon speciation and fluxes revealed patterns in carbon cycling across ecoregions defined by terrain relief and accumulation of organics. In previously unglaciated mountainous watersheds, bicarbonate dominated carbon export (70% of total) due to chemical weathering of bedrock. In lowland watersheds, where soil organic carbon stores were largest, lateral transport of dissolved organic carbon (50%) and efflux of biotic CO 2 (25%) dominated. In watersheds affected by thaw-induced mass wasting, erosion of ice-rich tills enhanced chemical weathering and increased particulate carbon fluxes by two orders of magnitude. From an ecosystem carbon balance perspective, fluvial carbon export in watersheds not affected by thaw-induced wasting was, on average, equivalent to 6–16% of estimated net ecosystem exchange (NEE). Finally, in watersheds affected by thaw-induced wasting, fluvial carbon export approached 60% of NEE. Because future intensification of thermokarst activity will amplify fluvial carbon export, determining the fate of carbon across diverse northern landscapes is a priority for constraining trajectories of permafrost region ecosystem carbon balance.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Ultraviolet Photooxidation of Smectite-Bound Fe(II) and Implications for the Origin of Martian Nontronites

Clay minerals detected with orbital and in situ instruments in ancient Martian terrains constrain Mars' climate and aqueous alteration history. Early in its history, Mars experienced an atmospheric redox change and iron-bearing clay minerals may preserve the effects of that transition. Ferrous smectites, the thermodynamically predicted product of chemical weathering of basalts under anoxic conditions, may have undergone oxidation by exposure to chemical oxidants in the atmosphere or regolith, or by direct photooxidation at the surface. To assess these potential oxidation pathways, ferrous trioctahedral smectites of varying initial iron content were synthesized and subjected to oxidation by ultraviolet (UV) irradiation. Experimental UV irradiation under an anoxic atmosphere equivalent to approximately 7 years of flux on the Martian surface caused partial oxidation of smectite-bound Fe (Fe 3+ /ΣFe = 16–18%) and octahedral sheet contraction. Metal-OH vibrational bands in visible/near infrared (VNIR) reflectance spectra of oxidized smectites changed in band depth and asymmetry with higher iron content. X-ray diffraction patterns of UV irradiated samples indicate the formation of a mixed di- and trioctahedral smectite or a secondary nontronite phase, possibly on the surfaces of higher iron content smectites. Furthermore, these experiments suggest that UV irradiation is able to oxidize structurally bound iron in smectites without the presence of other chemical oxidants. Photooxidation may have influenced the mineralogy, both syndepositionally and postdepositionally, of Martian alteration assemblages formed near the surface and this process needs not be limited to one part of their formation history.

58 GEOSCIENCES↗
DOE OSTI2021

Rock-Sourced Nitrogen in Semi-Arid, Shale-Derived California Soils

Models suggest that rock-derived nitrogen (N) inputs are of global importance to ecosystem N budgets; however, field studies demonstrating the significance of rock N inputs are rare. We examined rock-derived N fluxes in soils derived from sedimentary rocks along a catena formed under a semi-arid climate. Our measurements demonstrate that there are distinct and traceable pools of N in the soil and bedrock and that the fraction of rock-derived N declines downslope along the catena. We used geochemical mass balance weathering flux measurements to estimate a rock-derived N flux of 0.145 to 0.896 kg ha -1 yr -1 at the ridgecrest. We also developed independent N flux estimates using a 15 N-based isotope mixing model. While geochemical mass-balance-based estimates fell within the 95% confidence range derived from the isotope mixing model (-1.1 to 44.3 kg ha -1 yr -1 ), this range was large due to uncertainty in values for atmospheric 15 N deposition. Along the catena, N isotopes suggest a diminishing effect of rock-derived N downslope. Overall, we found that despite relatively large N pools within the saprolite and bedrock, slow chemical weathering and landscape denudation limit the influence of rock-derived N, letting atmospheric N deposition (7.1 kg ha -1 yr -1 ) and N fixation (0.9-3.1 kg ha -1 yr -1 ) dominate N inputs to this grassland ecosystem.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Speciation and diffusive dynamics in hydrated grain boundaries of complex oxide Gd2Ti2O7

Abstract Grain boundaries in polycrystalline materials significantly affect their properties, such as ionic transport, corrosion, and chemical durability. The pyrochlore compound (Gd 2 Ti 2 O 7 ) is employed as a model for complex oxides and is known for its diverse applications, including nuclear waste immobilization. Density functional theory-based first-principles molecular dynamics simulations were performed at different temperatures on the hydrated grain boundary system. The results show extensive transformations within the grain boundaries among hydrous water species (OH − , H 2 O, and H 3 O + ). The temperature dependence of self-diffusion coefficients follows Arrhenius behavior, with an activation energy of 35.9 kJ/mol for hydrogen and 46.3 kJ/mol for oxygen. The lifetime of OH − is about three to four times longer than that of H 2 O at temperatures from 800 to 2100 K, suggesting the greater stability of OH − over H 2 O, a unique characteristic of the grain boundaries. The estimated lifetime of the hydrous species decreases as the temperature increases, with an activation energy of 9.9 kJ/mol for OH − and 13.4 kJ/mol for H 2 O. While Gd 3 + is more mobile than Ti 4+ , both the Gd 3 + and Ti 4+ cations are orders of magnitude less mobile than the water species. The results suggest that water species are much more mobile within grain boundaries than in the bulk crystal and have the potential to penetrate deep into polycrystalline materials through grain boundaries, leading to grain boundary degradation and dissolution. The different mobilities of cations in complex oxides can lead to leaching of certain cations and incongruent dissolution during the chemical weathering of Earth and industrial materials.

B. Ghosh, Dipta↗
DOE OSTI2021

Colloidal metal transport in soils developing on historic coal mine spoil

Chemical weathering of pyrite via oxidative dissolution is well-known for generating Fe(III)-bearing colloids at acid mine drainage (AMD) sites; however, the potential for physical weathering of pyrite-bearing materials and subsequent release and transport of colloidal pyrite and associated trace metals has not been studied. Here, we monitored the colloidal metal transport in soil developing on abandoned coal mine spoil with a history of AMD generation to systematically study the contribution of colloids to base and trace metal transport and determine the elemental and mineralogical composition of colloids. Additionally, we collected soil pore water using lysimeters with a pore size of approximately 1.3 μm and centrifugation was used to separate the colloids from aqueous fractions. Metal concentrations of Na, Ca, Mg, K, Si, Al, Mn, Fe, Cu, and Zn were analyzed. Our results show only 14% of the total Al and Cu were present in colloidal fractions whereas 23%, 43%, and 54% of Fe, Mn, and Zn were transported in the colloidal phase, respectively. In contrast, all base metals were primarily present in the aqueous concentration with a small fraction (<10%) present in the colloidal phase. The colloidal fractions of the base metals were inferred to be associated with the concentration of clay colloids. The release of colloids exhibited possible sensitivity toward weather conditions such as alternating high temperatures and rainfall during summer (May–July) compared to fall (August–November). The morphology, elemental, and mineral composition of colloids were determined by a scanning electron microscopy equipped with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Colloids were dominated by phyllosilicates (biotite, muscovite, and kaolinite) with minor quartz and feldspars. Other minerals phases identified in colloidal fractions were hematite, goethite, arsenopyrite, and chalcopyrite. Colloids consisting of Fe, S, and O with structures resembling framboidal pyrite were identified, which is consistent with the non-silicates minerals identified by XRD. Our study suggests that the physical weathering of pyrite in the mine spoil can generate colloidal pyrite, which is mobilized and transported by soil pore water. Our results also indicate that these pyritic colloids are associated with toxic trace metals including Cu, Mn, and Zn. Colloid mobilization is also impacted by changes in temperature and precipitation, where clay mobilization afer rain events is favored. Further, sudden spikes in aqueous and/or colloidal concentrations may be the result of local heterogeneity within soils developing on mine spoil, indicating that further field-based work is necessary to better characterize pore-scale processes that control aqueous and colloid transport at similar sites to have a better understanding of potential contaminant transport from mine spoil systems.

58 GEOSCIENCES↗
DOE OSTI2024

Characterizing the combined impact of nucleation-driven precipitation and secondary passivation on carbon mineralization

The evolution of mineral reactive surface area is one of the primary phenomena controlling the progression and extent of mineral carbonation. The CO 2 mineralization begins with nucleation of crystals that provide initial surface area for subsequent growth of the mineral. However, many reactive transport models (RTMs) for CO 2 mineralization do not include the nucleation process. The few RTMs that do include it are yet to be validated against experimental data. Similarly, many RTMs ignore passivating effects of the secondary mineral, which coats the surface of the dissolving mineral, slow down the reaction process, and reduce the total extent of carbonation. Furthermore, the combined impact of nucleation and passivation on carbon mineralization is yet to be properly characterized. In this study, we consider the coupled effects of passivation and nucleation on the mineralization extent. The nucleation-driven precipitation model relies on the formation of nuclei to provide a surface area for crystal growth, while a new model is proposed to account for passivation effects. Our analysis shows that (i) omission of nucleation leads to overestimation of extent of mineralization, and (ii) omission of passivation leads to overestimation of host rock reactivity. The model was evaluated via comparison with CO 2 mineralization data from the literature and models that ignore these processes. We observed that including nucleation and passivation lead to closer predictions of the CO 2 mineralization extent. Therefore, this study highlights the importance of including the coupled nucleation-driven precipitation and secondary passivation in RTMs. Here, the findings from the study can be applied in various scientific and engineering applications such as petroleum production, cement carbonation, CO 2 sequestration, chemical weathering, and concrete degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Wildfire Produces Transient Minerals: Speciation, Reactivity, and Fate of Iron and Manganese in Surface Soils Post Wildfire

Wildfire leads to the deposition of an ash layer at the land surface. This material typically has alkaline properties, abundant pyrogenic carbon, and elevated metal concentrations compared to surface soils. Here, we compare ash and surface soils collected three weeks and two years after the Glass Fire (St. Helena, California, USA) to determine how wildfire affects the speciation and reactivity of iron (Fe) and manganese (Mn), two micronutrients that influence many soil processes. Synchrotron-based analyses revealed that wildfire generated stable Fe oxides like maghemite (γ-Fe 2 O 3 ) and hematite (α-Fe 2 O 3 ) that likely derived from surface soil or mineral dust rather than the vegetation, and Mn oxides such as hausmannite (Mn 3 O 4 ) and bixbyite (Mn 2 O 3 ) that derived primarily from aboveground biomass. However, these pyrogenic minerals were absent in soils collected two years after the fire. Their loss from the soil surface may result from a combination of erosion, translocation to deeper soil layers, and chemical weathering. The latter hypothesis is supported by the enhanced mobilization of Fe and Mn from ash upon the addition of pyoverdine, a model biogenic ligand. The increased mobility of micronutrients from fire-derived minerals in ash in response to microbial and root exudation may facilitate postfire soil and vegetation recovery.

bixbyite↗
DOE OSTI2023

Long-Term Changes in Concentration and Yield of Riverine Dissolved Silicon From the Poles to the Tropics

Riverine exports of silicon (Si) influence global carbon cycling through the growth of marine diatoms, which account for ~25% of global primary production. Climate change will likely alter river Si exports in biome-specific ways due to interacting shifts in chemical weathering rates, hydrologic connectivity, and metabolic processes in aquatic and terrestrial systems. Nonetheless, factors driving long-term changes in Si exports remain unexplored at local, regional, and global scales. We evaluated how concentrations and yields of dissolved Si (DSi) changed over the last several decades of rapid climate warming using long-term data sets from 60 rivers and streams spanning the globe (e.g., Antarctic, tropical, temperate, boreal, alpine, Arctic systems). We show that widespread changes in river DSi concentration and yield have occurred, with the most substantial shifts occurring in alpine and polar regions. The magnitude and direction of trends varied within and among biomes, were most strongly associated with differences in land cover, and were often independent of changes in river discharge. These findings indicate that there are likely diverse mechanisms driving change in river Si biogeochemistry that span the land-water interface, which may include glacial melt, changes in terrestrial vegetation, and river productivity. Finally, trends were often stronger in months outside of the growing season, particularly in temperate and boreal systems, demonstrating a potentially important role of shifting seasonality for the flux of Si from rivers. Our results have implications for the timing and magnitude of silica processing in rivers and its delivery to global oceans.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

The Global Biogeochemical Cycle of Rhenium

Here, this paper is the first comprehensive synthesis of what is currently known about the different natural and anthropogenic fluxes of rhenium (Re) on Earth's surface. We highlight the significant role of anthropogenic mobilization of Re, which is an important consideration in utilizing Re in the context of a biogeochemical tracer or proxy. The largest natural flux of Re derives from chemical weathering and riverine transport to the ocean (dissolved = 62 × 10 6 g yr -1 and particulate = 5 × 10 6 g yr -1 ). This review reports a new global average [Re] of 16 ± 2 pmol L -1 , or 10 ± 1 pmol L -1 for the inferred pre-anthropogenic concentration without human impact, for rivers draining to the ocean. Human activity via mining (including secondary mobilization), coal combustion, and petroleum combustion mobilize approximately 560 × 10 6 g yr -1 Re, which is more than any natural flux of Re. There are several poorly constrained fluxes of Re that merit further research, including: submarine groundwater discharge, precipitation (terrestrial and oceanic), magma degassing, and hydrothermal activity. The mechanisms and the main host phases responsible for releasing (sources) or sequestrating (sinks) these fluxes remain poorly understood. This study also highlights the use of dissolved [Re] concentrations as a tracer of oxidation of petrogenic organic carbon, and stable Re isotopes as proxies for changes in global redox conditions.

58 GEOSCIENCES↗
DOE OSTI2024

BioRT‐HBV 1.0: A Biogeochemical Reactive Transport Model at the Watershed Scale

Abstract Reactive Transport Models (RTMs) are essential tools for understanding and predicting intertwined ecohydrological and biogeochemical processes on land and in rivers. While traditional RTMs have focused primarily on subsurface processes, recent watershed‐scale RTMs have integrated ecohydrological and biogeochemical interactions between surface and subsurface. These emergent, watershed‐scale RTMs are often spatially explicit and require extensive data, computational power, and computational expertise. There is however a pressing need to create parsimonious models that require minimal data and are accessible to scientists with limited computational background. To that end, we have developed BioRT‐HBV 1.0, a watershed‐scale, hydro‐biogeochemical RTM that builds upon the widely used, bucket‐type HBV model known for its simplicity and minimal data requirements. BioRT‐HBV uses the conceptual structure and hydrology output of HBV to simulate processes including advective solute transport and biogeochemical reactions that depend on reaction thermodynamics and kinetics. These reactions include, for example, chemical weathering, soil respiration, and nutrient transformation. The model uses time series of weather (air temperature, precipitation, and potential evapotranspiration) and initial biogeochemical conditions of subsurface water, soils, and rocks as input, and output times series of reaction rates and solute concentrations in subsurface waters and rivers. This paper presents the model structure and governing equations and demonstrates its utility with examples simulating carbon and nitrogen processes in a headwater catchment. As shown in the examples, BioRT‐HBV can be used to illuminate the dynamics of biogeochemical reactions in the invisible, arduous‐to‐measure subsurface, and their influence on the observed stream or river chemistry and solute export. With its parsimonious structure and easy‐to‐use graphical user interface, BioRT‐HBV can be a useful research tool for users without in‐depth computational training. It can additionally serve as an educational tool that promotes pollination of ideas across disciplines and foster a diverse, equal, and inclusive user community.

Sadayappan, Kayalvizhi↗