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585 records · Page 33

Watershed zonation through hillslope clustering for tractably quantifying above- and below-ground watershed heterogeneity and functions

Abstract. In this study, we develop a watershed zonation approach for characterizing watershed organization and functions in a tractable manner by integrating multiple spatial data layers. We hypothesize that (1) a hillslope is an appropriate unit for capturing the watershed-scale heterogeneity of key bedrock-through-canopy properties and for quantifying the co-variability of these properties representing coupled ecohydrological and biogeochemical interactions, (2) remote sensing data layers and clustering methods can be used to identify watershed hillslope zones having the unique distributions of these properties relative to neighboring parcels, and (3) property suites associated with the identified zones can be used to understand zone-based functions, such as response to early snowmelt or drought and solute exports to the river. We demonstrate this concept using unsupervised clustering methods that synthesize airborne remote sensing data (lidar, hyperspectral, and electromagnetic surveys) along with satellite and streamflow data collected in the East River Watershed, Crested Butte, Colorado, USA. Results show that (1) we can define the scale of hillslopes at which the hillslope-averaged metrics can capture the majority of the overall variability in key properties (such as elevation, net potential annual radiation, and peak snow-water equivalent – SWE), (2) elevation and aspect are independent controls on plant and snow signatures, (3) near-surface bedrock electrical resistivity (top 20 m) and geological structures are significantly correlated with surface topography and plan species distribution, and (4) K-means, hierarchical clustering, and Gaussian mixture clustering methods generate similar zonation patterns across the watershed. Using independently collected data, we show that the identified zones provide information about zone-based watershed functions, including foresummer drought sensitivity and river nitrogen exports. The approach is expected to be applicable to other sites and generally useful for guiding the selection of hillslope-experiment locations and informing model parameterization.

58 GEOSCIENCES↗

Multi-omic characterization of a soil microbial consortium reveals critical role of succinate and glutamate metabolism during calcium carbonate precipitation

Microbially induced calcium carbonate precipitation (MICP) holds potential for use in soil stabilization and carbon sequestration, with the overall efficiency of the process being a major determinant for use in many environmental and civil engineering applications. While the biogeochemical pathways and enzymes driving MICP are known, the microbial metabolic networks and community dynamics underlying such precipitation remain poorly characterized. To address this gap, we developed a four-member consortium of soil bacteria (Curtobacterium flaccumfaciens, Rhodococcus qingshengii, Microbacterium sp., and Bacillus toyonensis), termed carbon storing consortium - A (CSC-A), that is capable of MICP. Prior work shows that MICP production is higher in CSC-A compared to the sum of carbonate produced by each member, suggesting carbonate production is driven by consortium dynamics. To that end we used a multi-omic integration approach of genomics, transcriptomics, and metabolomics to investigate potential inter-species interactions that may influence the MICP phenotype. Genomic life history characterizations identified evidence of niche specialization by B. toyonensis and Microbacterium, while metatranscriptomic analysis suggests R. qingshengii is a keystone species during growth in urea. By comparing individual species’ metabolomes to the metabolic profile of a shared well of precipitated metabolites, we identified over 200 metabolites predicted to be produced or consumed by CSC-A members. Integrating both data types to search the KEGG reactome highlighted a network centered around glutamine metabolism and branched chain amino acid biosynthesis under regulation during CSC-A growth in urea. Succinate metabolism was also a major node in this network and laboratory assays confirmed that increasing the amount of succinate in the growth medium leads to increased carbonate precipitation by CSC-A, a critical confirmation of our modeling approach. By isolating and identifying the interconnected metabolic components underlying MICP in CSC-A, we identified keystone taxa, metabolites, and pathways important for future optimization of the application of this consortia to carbonate precipitation.

carbon storing consortium - A (CSC-A)↗

Mapping Nitrogen Pathways in Organic Manure through GCAM

As the world has become more and more globalized, a need for a comprehensive and extensive modelling system that maps out the vast majority of processes and items around the world and can display how interdependent they are. Furthermore, such a model should be able to predict future processes and values such that it can guide scientific thinking and policy. This is where the importance of GCAM becomes so apparent. GCAM, the Global Change Analysis Model, that incorporates many different fields and can predict such a wide variety of processes. As the model expands and encompasses more fields and goes into greater detail, there is a need for previously incorporated processes to be further fleshed out. My project is dedicated to creating the organic nitrogen fertilizer pathway, such that there are two nitrogen fertilizer pathways, synthetic and organic (manure). Previously, only synthetic fertilizer was included, with all organic fertilizer (manure) being omitted from the model. Developing the synthetic path is relatively easy, as the process for creating synthetic fertilizer is an industrial process that has been perfected over decades, and thus has a very precise input/output coefficient of nitrogen, but determining that same coefficient for organic manure is much harder, because, well, digestion is not an industrial process, especially considering the many different types of animals have different processes, and a good amount of the manure they produce won’t be applied to the soil. I obtained data from the UN’s FAO on manure nitrogen applied to soil, and filled in the gaps and created many different visualizations to help comprehend the data. These findings will foster a greater understanding of nitrogen flows, which is crucial to fields like industrial agriculture, polluting runoff, and nitrifying bacteria and archaea in the soil.

54 ENVIRONMENTAL SCIENCES↗

WHONDRS River Corridor Sediment and Water Geochemistry and In Situ Sensor Data from Machine-Learning-Informed Sites across the Contiguous United States (v6)

This dataset supports a broader study examining hyporheic zone respiration rates to improve predictive models at a contiguous United States (CONUS) scale. The CONUS-Scale Model-Sample Study (CM) was designed following ICON (integrated, coordinated, open, and networked) principles to facilitate a model-experiment (ModEx) iteration approach, leveraging crowdsourced sampling across the CONUS. New machine learning models were created every month to guide sampling locations. Data from the resulting samples were used to test and rebuild the machine learning models for the next round of sampling guidance. Sampling began in April 2022 and ended in October 2023. In addition to the widely distributed CONUS sites, a more spatially focused sampling occurred in the Yakima River Basin, WA in summer 2022. Data from this more spatially intensive sampling occurred under the label “Second Spatial Study (SSS)” and were also included in the machine learning models. Other data types collected from SSS that were not part of CM were published in a separate data package (https://data.ess-dive.lbl.gov/view/doi:10.15485/1969566). This data package was originally published in February 2023. It was updated in June 2023 (v2; new and modified files); December 2023 (v3; new and modified files); June 2024 (v4; new and modified files); April 2024 (v5; new and modified files); and September 2025 (v6; modified files). See the change history section in the readme for more details. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. This dataset is comprised of two folders of field photos and videos, one folder of raw Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) data and one main data folder containing (1) file-level metadata; (2) data dictionary; (3) field metadata; (4) readme; (5) international generic sample number (IGSN) mapping file; (6) field protocols; (7) a subfolder with sample data; and (8) a subfolder with sensor data. The sample data subfolder contains (1) surface water and sediment dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) data and averages; (2) surface water and sediment total nitrogen data and averages; (3) surface water major cations and anions and averages; (4) sediment grain size data; (5) sediment iron (II) data and averages; (6) wet sediment mass, dry sediment mass, water mass, and wet sediment volume in incubation and sediment ICR vials; (7) sediment incubation respiration rate data and averages; (8) normalized respiration rate data and averages; (9) methods codes; (10) sediment specific surface area; (11) sediment percent carbon and nitrogen; (12) sediment gravimetric moisture and averages; (15) sediment X-ray diffraction (XRD) data; (16) sediment adenosine triphosphate (ATP) and averages; (17) a subfolder with sediment incubation respiration data, scripts, and plots; (18) surface water and sediment FTICR methods; and (19) a subfolder of 9.4 Tesla (9.4T) FTICR-MS data. This folder contains five subfolders, one containing the sediment .xml data files, one containing the water .xml files, one containing the sediment CoreMS output files, one containing the water CoreMS output files, and the other containing instructions and scripts for processing the files in CoreMS (https://github.com/EMSL-Computing/CoreMS).The sensor data subfolder contains (1) a subfolder with miniDOT dissolved oxygen and temperature data and plots; (2) miniDOT dissolved oxygen and temperature summary data; and (3) miniDOT installation methods. All files are .csv, .pdf, .R, .xml, .d, .html, .Rmd, .py, .cal, .json, .jpg, .jpeg, .png, .mov, or .mp4. CORRECTION: Carbon and nitrogen content are reported as percentages. The current column headers "01395_C_percent_per_mg" and "01397_N_percent_per_mg" are incorrect. These should read "01395_C_percent" and "01397_N_percent" and will be corrected in the next version of this data package. We thank the United States Forest Service, Washington Department of Fish and Wildlife, Washington Department of Natural Resources, Cowiche Canyon Conservatory, Washington State Parks and Recreation Commission (Scientific Research Permit #210901), and the Confederated Tribes and Bands of the Yakama Nation for access to field locations where the samples labeled “SSS” were collected. We also thank the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate sample collection and optimization of data usage according to their values and worldview. WHONDRS consortium members were asked to provide any acknowledgments for the collection of samples labeled “CM” and the following is a list of acknowledgments that were submitted with their corresponding Site IDs: (MART) Research activities were conducted in part on the Wind River Experimental Forest within the Gifford Pinchot National Forest; (MP- 100379) Philadelphia is part of Lenapehoking, the ancestral homelands of the Lenape peoples; (MP-102398) Land surveyed is the ancestral homelands of the Nookhose'iinenno (Arapaho), Tsis tsis'tas (Cheyenne), and Nuuchu (Ute); (MP-100749 and MP- 100747) Georgia Coastal Ecosystem LTER, OCE-1832178; (SP-70 and SP-72) Eastern Shoshone, Shoshone-Bannock; (MP- 102944) Funded by Oregon Watershed Enhancement Board. On the traditional lands of the Confederated Tribes of the Siletz, Confederated Tribes of the Grand Rhonde, and the Clatsop-Nehalem Confederated Tribe; (MP- 100607) Holiday Creek is located on the traditional territory of the Monacan Indian Nation; (SP-45) Lafayette Blue Springs State Park; (MP-102420) NSF DEB-2016749; (MP-100019) New Hampshire Agriculture Experiment Station; (SP-35) Rayonier (land owner; https://www.rayonier.com/); (MP- 101276) US Department of Energy, Office of Science, Biological and Environmental Research, Subsurface Biogeochemical Research, Watershed Dynamics and Evolution SFA at ORNL; (MP- 103224) Watershed Dynamics and Evolution SFA at ORNL; (MP- 101584) Traditional lands of the Oceti Sakowin (Dakota, Lakota, Nakoda) and Anishinaabe Peoples.

54 ENVIRONMENTAL SCIENCES↗

Brachiopod δ 34 S CAS microanalyses indicate a dynamic, climate-influenced Permo-Carboniferous sulfur cycle

Early isotopic studies of sulfate in carbonate minerals (carbonate associated sulfate; CAS) suggested that carbonates can provide a reliable, well-dated archive of the marine sulfur cycle through time. However, subsequent research has shown that diagenetic alteration can impose highly heterogeneous CAS sulfur isotopic compositions (δ 34 S CAS ) among different carbonate phases within sediments. Such alteration necessitates targeted sampling of well-preserved, primary carbonate phases. Here, we present a new record of Carboniferous and Early Permian brachiopod δ 34 S CAS generated from over 130 measurements of microsampled brachiopod shells. Our record refines existing brachiopod δ 34 S CAS records and confirms a large, ~6.5‰ δ 34 S CAS decrease in the Early Carboniferous. Importantly, the record also features a novel 3–5‰ increase in δ 34 S CAS near the Serpukhovian-Bashkirian boundary (323.4 Ma) that coincides with carbonate δ 13 C and δ 18 O increases. Variability in δ 34 S CAS is minor both within (≤0.3‰) and among (≤2‰) individual co-depositional brachiopod specimens. A taxon-specific δ 34 S CAS offset is present one species (Composita subtilita) that also exhibits a δ 13 C offset, supporting the existence of biological “vital effects” on δ 34 S CAS . Geologic evidence and mathematical modeling of the Permo-Carboniferous carbon and sulfur cycles suggest that changes in the burial ratio of organic carbon to pyrite sulfur (R C:S ) are insufficient to explain the observed mid-Carboniferous δ 34 S CAS record. We find that changes in the 34 S depletion of pyrite relative to seawater sulfate ( 34 ε) or in the δ 34 S of the input to the ocean (δ 34 S in ) are also needed. Large additions of O 2 from organic carbon burial during the Permo-Carboniferous cannot be entirely compensated for with sulfur cycle changes; lower than modern late Visean pO 2 and/or additional O 2 sinks are needed to keep pO 2 at plausible levels. Based on the geologic context surrounding our record's mid-Carboniferous δ 34 S CAS increase, we advocate for simultaneous changes in pyrite burial, 34 ε, and δ 34 S in , driven by sea level or tectonically induced changes in environments of sulfur burial, as a viable mechanism to produce rapid seawater δ 34 S changes.

54 ENVIRONMENTAL SCIENCES↗

Effects of spatial variability in vegetation phenology, climate, landcover, biodiversity, topography, and soil property on soil respiration across a coastal ecosystem

Coastal terrestrial-aquatic interfaces (TAIs) are crucial contributors to global biogeochemical cycles and carbon exchange. A systematic evaluation of the interaction between coastal catchment properties and carbon dioxide (CO2) emission by soil respiration is significant for assessing carbon dynamics and predicting the future trajectory of atmospheric CO2 concentrations in coastal TAIs. The soil CO2 efflux in these transition zones is however poorly understood due to the high spatiotemporal dynamics of TAIs, as various sub-ecosystems in this region are compressed and expanded by complex influences of tides, changes in river levels, climate, and land use. We focus on the Chesapeake Bay region to (i) investigate the spatial heterogeneity of the coastal ecosystem and identify spatial zones with similar environmental characteristics based on the spatial data layers, including vegetation index (kNDVI), climate, landcover, diversity, topography, soil property, and relative tidal elevation; (ii) understand the primary driving factors affecting soil respiration within sub-ecosystems of the coastal ecosystem. Specifically, we employed hierarchical clustering analysis to identify spatial regions with distinct environmental characteristics, followed by the determination of main driving factors using Random Forest regression and SHapley Additive exPlanations. Maximum and minimum temperature are the main drivers common to all sub-ecosystems, while each region also has additional unique major drivers that differentiate them from one another. Precipitation exerts an influence on vegetated lands, while soil pH value holds importance specifically in forested lands. In croplands characterized by high clay content and low sand content, the significant role is attributed to bulk density. Wetlands demonstrate the importance of both elevation and sand content, with clay content being more relevant in non-inundated wetlands than in inundated wetlands. The topographic wetness index significantly contributes to the mixed vegetation areas, including shrub, grass, pasture, and forest. Additionally, our research reveals that dense vegetation land covers and urban/developed areas exhibit distinct soil property drivers. Overall, there is no one-size-fits-all approach to modeling carbon fluxes in coastal TAIs, and our study highlights the importance of further research and monitoring practices to improve our understanding of carbon dynamics and promote the sustainable management of coastal TAIs.

54 ENVIRONMENTAL SCIENCES↗

Pore2Chip: All-in-one python tool for soil microstructure analysis and micromodel design

The Pore2Chip Python package is designed to create 2D micromodels using extracted data from 3D X-ray computed tomography (XCT) images. This package helps analyze soil structure and function, allowing for the investigation of hydro-biogeochemical processes that impact mineral extraction and reactivity, oxygen concentrations, and nutrient availability in disturbed or managed soils. Key metrics encompass pore size distributions, pore throat size distributions, and connectivity (pore coordination numbers). The final output is a 2D scalable SVG design representing a core or aggregate. Designs can be fabricated with methods such as laser etching, 3D printing, and photolithography.

lab-on-chip↗

Role of the Terrestrial Biosphere in Atmospheric Chemistry and Climate

The terrestrial biosphere–atmosphere interface provides a key chemical, biological, and physical lower boundary for the atmosphere. The presence of vegetation itself modifies the physical boundary, or the biogeophysical aspects of the system, by controlling important climate drivers such as soil moisture, light environment, and temperature. The leaf surface area of the terrestrial biosphere provides additional surface area for emissions, and it can be up to 55% of the total Earth’s surface area during the boreal summer. Vegetation also influences the biogeochemical aspects of the system by emitting a broad suite of reactive trace gases such as biogenic volatile organic compound (BVOC) emissions and climate-relevant primary biological aerosol particles (PBAP). Many of these emissions are a function of meteorological and climatological conditions at the surface, including temperature, light environment, soil moisture, and winds. Once emitted, they can be processed in the troposphere through a suite of chemical reactions. BVOC can contribute to the formation of ozone and secondary organic aerosols (SOA), and PBAP can rupture to form smaller particles with climatic relevance. These emissions and subsequent aerosol products can influence atmospheric processes that affect the surface climate, such as the attenuation of radiation, the formation of greenhouse gases such as ozone that can feedback to surface air temperature, and the alteration of clouds and subsequent precipitation. These atmospheric changes can then feedback to the land surface and emissions themselves, creating positive or negative feedback loops that can dampen or amplify the emission response. For the dominant BVOC isoprene, the feedback response to temperature can be positive or negative depending on ambient temperatures that drive isoprene emissions. The feedback response to soil moisture and precipitation can be positive, negative, or uncoupled depending on the moisture content of the soil and the total atmospheric aerosol loading. For light, the isoprene response can be positive or negative depending on the role of diffuse light. Overall, these feedbacks highlight the dynamical response of the biosphere to changing atmospheric conditions across a range of time scales, from minutes for trace gases and aerosols, to months for phenological changes, to years for land cover and land use change. Here, the dynamic aspect of this system requires us to understand, simulate, and predict the complex feedbacks between the biosphere and atmosphere and understand their role in the simulation and understanding of climate and global change. From the observational perspective, these feedbacks are challenging to identify in observations, and predictive modeling tools provide a crucial link for understanding how these feedbacks will change under warming climate scenarios.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Mineralogy–Based Anthropogenic Combustion–Iron Emission Inventory

Atmospheric supply of iron can modulate ocean biogeochemistry, due to its key role in global nitrogen and carbon cycles. Current estimates predict up to 20% of global ocean net primary productivity depends on an atmospheric iron source. Using a technology–based methodology, we revise total and soluble anthropogenic iron emissions and resolve iron into its mineral components, which allows modeling mineral–specific atmospheric reactions. We compare different methodologies for representing anthropogenic iron solubility: measured in mild and strong leaches and estimated using a mineralogy basis and identify the emissions that are most affected by such assumptions. The inclusion of metal smelting as an iron source increases iron emissions by up to 10 times higher in the fine aerosol fraction (smaller than 1 μm) than most previous inventories. Different solubility assumptions alter anthropogenic soluble iron emissions and deposition by a factor of 20 and 10, respectively. Using solubilities measured in mild leaches and calculated by mineralogy give 20–30 Gg/yr anthropogenic emissions and 40–50 Gg/yr deposition, while those measured in strong leaches give 80–440 Gg/yr emissions and 200–450 Gg/yr deposition. Here, this range of anthropogenic soluble iron deposition leads to global soluble iron deposition of 1,900–2,300 Gg/yr when dust, wildfires, and atmospheric processing are included, indicating such assumptions can affect global soluble iron supply by about 30%. In regions where marine primary productivity is iron limited, anthropogenic combustion–iron contributes up to half of the atmospheric soluble iron flux to the North Pacific Ocean but supplies less than 5% to the Southern Ocean.

54 ENVIRONMENTAL SCIENCES↗