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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Large emissions of CO2 and CH4 due to active-layer warming in Arctic tundra: Supporting Data

Climate warming may accelerate decomposition of Arctic soil carbon, but few controlled experiments have manipulated the entire active layer. To determine surface-atmosphere fluxes of carbon dioxide and methane under anticipated end-of-century warming, we used heating rods to warm soil (by 3.8 °C) to the depth of permafrost in polygonal tundra over two growing seasons at the Barrow Environmental Observatory in Utqiaġvik (formerly Barrow), Alaska. This data product includes supporting data for the companion paper entitled "Large emissions of CO2 and CH4 due to active-layer warming in Arctic tundra", published in Nature Communications by Torn et al. This data package contains seven data files in csv format with corresponding data dictionaries and file-level metadata, describing vegetation biomass dry weight ("Utqiagvik_Vegetation_Biomass_2014.csv"), radiocarbon measurements of respired carbon dioxide ("Utqiagvik_Radiocarbon_2015_2016.csv"), surface-atmosphere fluxes of carbon dioxide and methane and associated soil temperature ("Utqiagvik_Fluxes_Temperature_2015_2016.csv"), and soil temperature measurements averaged every 15-min and 1-hr for 2015 and 2016 ("Utqiagvik_Temperature_15min_2015.csv", "Utqiagvik_Temperature_15min_2016.csv", "Utqiagvik_Temperature_1hr_2015.csv", "Utqiagvik_Temperature_1hr_2016.csv"). There are no specific software requirements to use these data. UIC Science Native Corporation facilitated our scientific research on the Barrow Environmental Observatory, which is Iñupiat land.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Self-similar mesocrystals form via interface-driven nucleation and assembly

Crystallization by particle attachment (CPA) is a frequently occurring mechanism of colloidal crystallization that results in hierarchical morphologies. CPA has been exploited to create nanomaterials with unusual properties and is implicated in the development of complex mineral textures. Oriented attachment–a form of CPA in which particles align along specific crystallographic directions–produces mesocrystals that diffract as single crystals do, although the constituent particles are still discernible. The conventional view of CPA is that nucleation provides a supply of particles that aggregate via Brownian motion biased by attractive interparticle potentials. However, mesocrystals often exhibit regular morphologies and uniform sizes. Although many crystal systems form mesocrystals and individual attachment events have been directly visualized10, how random attachment events lead to well defined, self-similar morphologies remains unknown, as does the role of surface-bound ligands, which are ubiquitous in nanoparticle systems. Attempts to understand mesocrystal formation are further complicated in many systems by the presence of precursor nanoparticles with a phase distinct from that of the bulk. Some studies propose that such particles convert before attachment, whereas others attribute conversion to the attachment process itself and yet others conclude that transformation occurs after the mesocrystals exceed a characteristic size. Here we investigate mesocrystal formation by iron oxides, which are important colloidal phases in natural environments and classic examples of systems forming ubiquitous precursor phases and undergoing CPA accompanied by phase transformations. Combining in situ transmission electron microscopy (TEM) at 80 degrees Celsius with ‘freeze-and-look’ TEM, we tracked the formation of haematite (Hm) mesocrystals in the presence of oxalate (Ox), which is abundant in soils, where iron oxides are common. In this work, we find that isolated Hm particles rarely appear, but once formed, interfacial gradients at the Ox-covered surfaces drive Hm particles to nucleate repeatedly about two nanometres from the surfaces, to which they then attach, thereby generating mesocrystals. Comparison to natural and synthetic systems suggests that interface-driven pathways are widespread.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Radon kinetics in a natural indoor radon chamber

An unusual 180 m 3 storage room in the basement of a two-story laboratory building is unventilated, and separated from occupiable rooms by double steel doors. The space completely borders on soil through the concrete floor and two of its concrete walls. The room also contains a separate inner chamber with 1 m thick concrete walls designed to damp vibrations in the room above it. The space boasts a relatively high radon level, 1083 Bq m –3 , which varies with local outdoor environmental conditions. Measurements were made of radon concentrations at various locations and heights within the facility. More than a year of continuous radon concentration data corresponding to a single location are also available, along with measurements of indoor and outdoor pressure, temperature, and humidity. Data were also collected with as many as five fans placed in different locations and cycled on for variable time periods. First order linear kinetic models were created to explain the observed approaches to steady state due to changing conditions and wash-out resulting from intentional ventilation. Results demonstrate a good fit between changes in the radon concentration level and the developed compartmental models. Furthermore, no significant differences were observed between radon concentration at different locations or heights in the chamber.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Temporal changes in global soil respiration since 1987

As the second-largest terrestrial carbon (C) flux, soil respiration (R S ) has been stimulated by climate warming. However, the magnitude and dynamics of such stimulations of soil respiration are highly uncertain at the global scale, undermining our confidence in future climate projections. Here, we present an analysis of global R S observations from 1987–2016. R S increased (P < 0.001) at a rate of 27.66 g C m -2 yr -2 (equivalent to 0.161 Pg C yr -2 ) in 1987–1999 globally but became unchanged in 2000–2016, which were related to complex temporal variations of temperature anomalies and soil C stocks. However, global heterotrophic respiration (R h ) derived from microbial decomposition of soil C increased in 1987–2016 (P < 0.001), suggesting accumulated soil C losses. Given the warmest years on records after 2015, our modeling analysis shows a possible resuscitation of global R S rise. This study of naturally occurring shifts in R S over recent decades has provided invaluable insights for designing more effective policies addressing future climate challenges.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Microbial carbon limitation: The need for integrating microorganisms into our understanding of ecosystem carbon cycling

Abstract Numerous studies have demonstrated that fertilization with nutrients such as nitrogen, phosphorus, and potassium increases plant productivity in both natural and managed ecosystems, demonstrating that primary productivity is nutrient limited in most terrestrial ecosystems. In contrast, it has been demonstrated that heterotrophic microbial communities in soil are primarily limited by organic carbon or energy. While this concept of contrasting limitations, that is, microbial carbon and plant nutrient limitation, is based on strong evidence that we review in this paper, it is often ignored in discussions of ecosystem response to global environment changes. The plant‐centric perspective has equated plant nutrient limitations with those of whole ecosystems, thereby ignoring the important role of the heterotrophs responsible for soil decomposition in driving ecosystem carbon storage. To truly integrate carbon and nutrient cycles in ecosystem science, we must account for the fact that while plant productivity may be nutrient limited, the secondary productivity by heterotrophic communities is inherently carbon limited. Ecosystem carbon cycling integrates the independent physiological responses of its individual components, as well as tightly coupled exchanges between autotrophs and heterotrophs. To the extent that the interacting autotrophic and heterotrophic processes are controlled by organisms that are limited by nutrient versus carbon accessibility, respectively, we propose that ecosystems by definition cannot be ‘limited’ by nutrients or carbon alone. Here, we outline how models aimed at predicting non‐steady state ecosystem responses over time can benefit from dissecting ecosystems into the organismal components and their inherent limitations to better represent plant–microbe interactions in coupled carbon and nutrient models.

Soong, Jennifer L.↗
DOE OSTI2022

Minimizing Fraud in the Carbon Offset Market Using Blockchain Technologies

Fraud in the Environmental Benefit Credit (EBC) markets is pervasive. To make matters worse, the cost of creating EBCs is often higher than the market price. Consequently, a method to create, validate, and verify EBCs and their relevance is needed to mitigate fraud. The EBC market has focused on geologic (fossil fuel) CO 2 sequestration projects that are often over budget and behind schedule and has failed to capture the "lowest hanging fruit" EBCs - terrestrial sequestration via the agricultural industry. This project reviews a methodology to attain possibly the least costly EBCs by tracking the reduction of inputs required to grow crops. The use of bio- stimulant products, such as humate, allows a farmer to use less nitrogen without adversely affecting crop yield. Using less nitrogen qualifies for EBCs by reducing nitrous oxide emissions and nitrate runoff from a farmer's field. A blockchain that tracks the bio-stimulant material from source to application provides a link between a tangible (bio-stimulant commodity) and the associated intangible (EBCs) assets. Covert insertion of taggants in the bio-stimulant products creates a unique barcode that allows a product to be digitally tracked from beginning to end. This process (blockchain technology) is so robust, logical, and transparent that it will enhance the value of the associated EBCs by mitigating fraud. It provides a real time method for monetizing the benefits of the material. Substantial amounts of energy are required to produce, transport, and distribute agricultural inputs including fertilizer and water. Intelligent optimization of the use of agricultural inputs can drive meaningful cost savings. Tagging and verification of product application provides a valuable understanding of the dynamics in the water/food energy nexus, a major food security and sustainability issue. As technology in agriculture evolves so to must methods to verify the Enterprise Resource Planning (ERP) potential of innovative solutions. The technology reviewed provides the ability to combine blockchain and taggants ("taggant blockchains") as the engine by which to (1) mitigate fraudulent carbon credits; (2) improve food chain security, and (3) monitor and manage sustainability. The verification of product quality and application is a requirement to validate benefits. Recent upgrades to humic and fulvic quality protocols known as ISO CD 19822 TC134 offers an analytical procedure. This work has been assisted by the Humic Products Trade Association and International Humic Substance Society. In addition, providing proof of application of these products and verification of the correct application of prescriptive humic and bio-stimulant products is required. Individual sources of humate have unique and verifiable characteristics. Additionally, methods for prescription of site- specific agricultural inputs in agricultural fields are available. (See US Patents 734867B2, US 90658633B2.) Finally, a method to assure application rate is required through the use of taggants. Sensors using organic solid to liquid phase change nanoparticles of various types and melting temperatures added to the naturally occurring materials provide a barcode. Over 100 types of nanoparticles exist ensuring numerous possible barcodes to reduce industry fraud. Taggant materials can be collected from soil samples of plant material to validate a blockchain of humic, fulvic and other soil amendment products. Other non-organic materials are also available as taggants; however, the organic tags are biodegradable and safe in the environment allowing for use during differing application timeliness.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Roads to Removal: Options for Carbon Dioxide Removal in the United States

Our analysis shows it is feasible for the United States to remove a staggering amount of CO 2 from the air—this will be critical to becoming carbon neutral by 2050. Our comprehensive, first-of-its-kind, county-resolution analysis indicates that our country can accomplish this goal by relying on demonstrated technology, natural resources, and workforces we already have. Additionally, ongoing technology development can lower costs, shorten timelines, and deliver new solutions. Our analysis evaluated how we can use forests, cropland soils, and waste biomass, along with purpose-built machines, to get us to net-zero. Further, we considered community impacts and identified locations where certain solutions could be uniquely beneficial or potentially counterproductive. Our findings enable decisionmakers to weigh both opportunities and constraints and to decide what roads to use to meet our national climate goal for net-zero CO 2 emissions.

03 NATURAL GAS↗
DOE OSTI2025

Temporal Patterns in Soil Redox Potential Vary Across a Freshwater Coastal Delta

Widespread and persistent flooding is submerging coastal ecosystems, particularly along the Louisiana Gulf coast, where flooding results from the compounding effects of ground subsidence and rising sea level. Restoration projects aim to mitigate land loss by diverting sediment loads from rivers into degraded areas to increase ground elevation. To predict how coastal ecosystems will change over time in response to projected changes in relative sea level and restoration, it is necessary to understand how subsurface biogeochemical processes respond to dynamic hydrologic forcings. Here, this study evaluates how environmental parameters that integrate biogeochemical processes vary with water table fluctuations in the freshwater Wax Lake Delta (WLD) in Louisiana, USA, where water diversions have formed one of the only active deltas along the coast. High‐frequency observations of water level, soil redox potential, specific conductance and pH were made for 1 year along elevation transects located on the older, proximal and younger, distal ends of a deltaic island. Redox responded rapidly to changing water tables, with fluctuations occurring primarily in shallow soils (< 20 cm) and at higher elevations. Deeper soils and those at lower elevation remained inundated and reduced. Semi‐diurnal tidal fluctuations were pronounced in younger, distal soils, presumably due to rapid groundwater exchange with the river channel. Tidal signals were muted in older soils that instead exhibited seasonal variability associated with river discharge and evapotranspiration. Although much of the delta sediments are persistently reducing and anoxic, redox fluctuations in the natural levees that border the deltaic islands likely drive high rates of biogeochemical activity. Evaluating how hydrology drives the frequency and duration of redox fluctuations provides a basis for understanding how biogeochemical processes might vary with complex hydrological interactions in coastal systems.

Herndon, Elizabeth [Oak Ridge National Laboratory ↗
DOE OSTI2020

Quantitative Analysis of the Effects of Natural and Human Factors on a Hydrological System in Zhangweinan Canal Basin

Drought is a water deficit state caused by large-scale climate change that cannot be avoided by a water resource management system. Water scarcity refers to the unsustainable utilization of water resources over a long time, which is the result of water management policies. However, water deficits caused by drought and water scarcity often occur simultaneously and are indistinguishable. This study proposes a model-based simulation framework that can quantitatively distinguish natural factors (drought) from human factors (water scarcity) in a hydrological system. The simulation was applied to the Zhangweinan Canal Basin, based on the runoff sequences from 1950 to 2004. The results show that the runoff curve number, soil depth, soil available water, soil evaporation compensation coefficient, base runoff α coefficient and the maximum canopy interception have the highest sensitivity to runoff, and that the calibrated and validated SWAT model can effectively simulate the runoff process in the Zhangweinan Canal Basin and similar areas. Abrupt changes in human activities in 1975 and water scarcity led to the disappearance of the summer peak runoff period in both wet and dry years. Human factors are the main reason for the change in the hydrological system in the study area; the runoff loss caused by human factors is four times that caused by natural factors according to the proposed variable threshold. This study proposes a model-based simulation framework that can help water resource managers to distinguish the effects of drought and water scarcity in water-stressed areas and adjust management accordingly.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

MIBiG 4.0: advancing biosynthetic gene cluster curation through global collaboration

Specialized or secondary metabolites are small molecules of biological origin, often showing potent biological activities with applications in agriculture, engineering and medicine. Usually, the biosynthesis of these natural products is governed by sets of co-regulated and physically clustered genes known as biosynthetic gene clusters (BGCs). To share information about BGCs in a standardized and machine-readable way, the Minimum Information about a Biosynthetic Gene cluster (MIBiG) data standard and repository was initiated in 2015. Since its conception, MIBiG has been regularly updated to expand data coverage and remain up to date with innovations in natural product research. Here, we describe MIBiG version 4.0, an extensive update to the data repository and the underlying data standard. In a massive community annotation effort, 267 contributors performed 8304 edits, creating 557 new entries and modifying 590 existing entries, resulting in a new total of 3059 curated entries in MIBiG. Particular attention was paid to ensuring high data quality, with automated data validation using a newly developed custom submission portal prototype, paired with a novel peer-reviewing model. MIBiG 4.0 also takes steps towards a rolling release model and a broader involvement of the scientific community. MIBiG 4.0 is accessible online at https://mibig.secondarymetabolites.org/.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Consistent Controls on Trace Metal Micronutrient Speciation in Wetland Soils and Stream Sediments

Trace metal are essential for microbially-mediated biogeochemical processes occurring in anoxic wetland soils and stream bed sediments, but low availability of these elements may inhibit anaerobic element cycling and transformations. Solid-phase speciation is likely a critical control on trace metal availability but has seen limited study in anoxic systems having concentrations similar to geological background levels, where metal limitations may be most prevalent. We have investigated trace metal concentrations and solid-phase speciation in three freshwater subsurface aquatic systems: marsh wetland soils, riparian wetland soils, and the sediments of a streambed. These systems displayed low solid-phase trace metal concentrations, generally at or below geological background levels, which generally followed the trend Zn > Cu ≈ Ni > Co and showed no correlation with major element compositions. All soils and sediments were dominated by quartz but varied in clay mineralogy as well as the organic matter, total sulfur, and total iron contents. X-ray absorption near-edge structure (XANES) spectroscopy shows that sulfur speciation in both wetlands is dominated by organic sulfur. Elemental sulfur and iron sulfides together made up <25% of the sulfur in the wetland soils, but the distribution between inorganic and organic forms was reversed in the stream sediments. Ferrous and ferric iron in clay minerals were common species identified by both XANES and extended X-ray absorption fine structure (EXAFS) spectroscopies at all sites. Iron(III) oxides were substantial components in all but the marsh wetland soils. Quantitative analysis of copper, nickel, and zinc XANES spectra revealed similar metal speciation across all sites. Copper speciation was dominated by sulfides, adsorbed species, and minor amounts of copper bound to organic matter; no metallic copper was detected. Nickel speciation also varied little and was dominated by nickel in clay mineral octahedral sheets and nickel sulfide, with adsorbed species also present. Zinc speciation was slightly more varied, with the marsh wetland soils and stream bed sediments containing adsorbed species, zinc associated with clay mineral structures, and zinc bound to reduced sulfur groups on organic matter, whereas the riparian wetland soils lacked clay-associated zinc but contained zinc sulfide. Trace metals bound to reduced sulfur occurred at every site, with a greater sulfur-bound fraction for copper. The fractional abundance of sulfur-bound species showed no relationship with soil or sediment total sulfur content, which varied by two orders of magnitude. More broadly, the observations in this study suggest that trace metal speciation in freshwater wetland soils and stream sediments is consistently dominated by a small set of recurring components which are distinct for each metal. Furthermore, this may represent a general geochemical phenomenon in anoxic soils and sediments containing trace metals at background concentrations (as low as 3 µg g -1 ) that was not predicted from systems that are contaminated with or naturally-enriched in copper, nickel, or zinc.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Tracking fungal species-level responses in soil environments exposed to long-term warming and associated drying

Climate change is affecting fungal communities and their function in terrestrial ecosystems. Despite making progress in the understanding of how the fungal community responds to global change drivers in natural ecosystems, little is known on how fungi respond at the species level. Understanding how fungal species respond to global change drivers, such as warming, is critical, as it could reveal adaptation pathways to help us to better understand ecosystem functioning in response to global change. Here, we present a model study to track species-level responses of fungi to warming—and associated drying—in a decade-long global change field experiment; we focused on two free-living saprotrophic fungi which were found in high abundance in our site, Mortierella and Penicillium. Using microbiological isolation techniques, combined with whole genome sequencing of fungal isolates, and community level metatranscriptomics, we investigated transcription-level differences of functional categories and specific genes involved in catabolic processes, cell homeostasis, cell morphogenesis, DNA regulation and organization, and protein biosynthesis. We found that transcription-level responses were mostly species-specific but that under warming, both fungi consistently invested in the transcription of critical genes involved in catabolic processes, cell morphogenesis, and protein biosynthesis, likely allowing them to withstand a decade of chronic stress. Overall, our work supports the idea that fungi that invest in maintaining their catabolic rates and processes while growing and protecting their cells may survive under global climate change.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

High-affinity amide-lanthanide adsorption to gram-positive soil bacteria

The gram-positive soil bacterium, Arthrobacter nicotianae, uses multiple organic acid functional groups to adsorb lanthanides onto its cell surface. At relevant soil pH conditions of 4.0–6.0, many of these functional groups are de-protonated and available for cation sorption and metal immobilization. However, among the plethora of naturally occurring site types, A. nicotianae is shown to possess high-affinity amide and phosphate sites that disproportionately affect lanthanide adsorption to the cell wall. We quantify neodymium (Nd)-selective site types, reporting an amide-Nd stability constant of log 10 K = 6.41 ± 0.23 that is comparable to sorption via phosphate-based moieties. These sites are two to three orders of magnitude more selective for Nd than the adsorption of divalent metals to ubiquitous carboxyl-based moieties. This implies the importance of lanthanide biosorption in the context of metal transport in subsurface systems despite trace concentrations of lanthanides found in the natural environment.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Evaluation of H-Canyon Ventilation Exhaust Tunnel Inspection at the Savannah River Site - 20052

The Department of Energy (DOE) H-Canyon Facility at the Savannah River Site (SRS) is operated by Savannah River Nuclear Solutions (SRNS). The Facility Structural Integrity Program [1] provides a process to inspect, evaluate, and document the conditions of passive safety related structural systems and components, their degradation mechanisms and their impact on the safety envelope. The Structural Integrity Program performs periodic visual inspections to confirm the systems and components can perform their safety function and recommend corrective actions before the function is compromised. The H-Canyon Exhaust Tunnel is part of the H-Canyon Ventilation System and is periodically inspected under the Structural Integrity Program. The Tunnel performs a Safety Class passive design feature function that is available 100% of the time. The underground reinforced concrete Tunnel directs Canyon process air from the Canyon to the Sand Filter System. The radiological and chemical airborne activity coupled with the physical configuration of the tunnel precludes a manned entry into the tunnel to perform the inspection. Unlike active systems that can be subjected to physical testing to confirm capability, qualification calculations, including modeling, is performed to assess passive design feature capabilities relative to operational, accident and natural phenomena hazards events. Input for these calculations come from knowledge of field conditions, design drawings and conservative assumptions. The knowledge of field conditions comes from concrete and soil testing activities as well as inspection data. The use of cameras on crawlers to obtain inspection data and how that data is used in qualification calculations is the focus of this discussion. Remote Tunnel inspections have been performed using cameras on a stick, referred to as pole cameras, prior to Calendar Year 2003 (CY2003). Since CY2003, six camera equipped crawlers have been used. Crawlers have evolved and improved by incorporating lessons learned from the previous inspections. The latest 2019 crawler successfully traveled the entire length of the tunnel between the Canyon and Sand Filter System and captured images that were previously unseen, thus providing key visual data for the Structural Integrity Program report [2]. The inspection data serves as 1) input to qualification calculations, 2) validates current conditions remain bounded by qualification calculations, and 3) documents a record of change over time. This data is vital for the effective evaluation of the tunnel structure and aids with predicting the life cycle service life safety envelope to protect the public, environment, and facility worker. The goal of the 2019 deployment was to use a more robust vehicle to ensure travel over obstacles, perform the inspection with higher resolution cameras, and have the ability to elevate the cameras to view surfaces previously obscured by abandon-in-place ducts in the tunnel. The inspection information will serve to strengthen the input basis for qualification calculations, versus using excessive conservative calculation assumptions. This 2019 inspection was compared with previous crawler visual evidence to identify change over time to project remaining service life and confirm field conditions remain bounded by qualification calculations. The results of the 2019 Exhaust Tunnel inspection continue to improve and provide a firm basis to make sound engineering judgements regarding tunnel capability and approaches in projecting remaining service life with an aging system and component. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Soil Water Retention and Hydraulic Conductivity Data and Model at Trail Creek in Taylor River Watershed, Colorado 2024-2025

This data package includes soil water retention and hydraulic conductivity data and model fitting results from measurements of ex-situ soil samples and in-situ soil sensors near Trail Creek. Soil water retention curves (SWRC) characterize soil water content as a function of soil water potential. SWRC depends on soil texture and pore structure and can be used to describe the constraints on biogeochemical processes in terms of soil water availability. In this data package, the sample identification follows the format TR-X-Y, where TR refers to Trail Creek, X is the treatment block identifier, and Y is the location identifier. Specifically, TR-ASCC1 is the control treatment block under the Adaptive Silviculture for Climate Change (ASCC) project, and TR-ASCC2 is the clear-cut treatment block. TR-ASCC-EHSn is associated with ecohydrology sites under the East-Taylor Watershed Community Observatory Sites directory, and TR-ASCC-ERTn (upslope n=1) are ecohydrology sites along the electrical resistivity tomography transects. The sample and location information can be found in metadata.csv, and the data from the soil sensors will be included in a future data version when the observation period becomes sufficiently long for data analysis. Sampling and Measurements Each sample falls into one of the two sampling methods – (1) intact cores or (2) soil sensors – and one of the two measurement methods – (a) laboratory or (b) in-situ. The intact cores were measured using the laboratory methods, which include measurements of soil water potential (HYPROP & WP4C, METER), saturated (KSAT, METER) and unsaturated hydraulic conductivity (HYPROP). The in-situ method uses a pair of co-located soil sensors to measure volumetric water content (TEROS12, METER) and soil water potential (TEROS21, METER), and the hydraulic conductivity was not measured. In comparison, the laboratory methods progress from full saturation to dry conditions, and the in-situ method includes both dry-to-wet and wet-to-dry cycles. The sampling and measurement methods for each sample can be found in metadata.csv, and more information about the measurements is detailed in the Methods section below. Models Retention and hydraulic conductivity data were fitted with four van-Genuchten-type models (specified by “model_name” column in the files): (1) traditional constrained van Genuchten model (“vG_constrained”), (2) traditional unconstrained van Genuchten model (“vG_unconstrained”), (3) PDI-variant of the constrained van Genuchten model (“vG_constrained_PDI”), and (4) PDI-variant of the unconstrained van Genuchten model (“vG_unconstrained_PDI”). The difference between the constrained (1: n) and the unconstrained (2: n, m) van Genuchten models is the number of pore-size distribution parameters in the model equations, giving the unconstrained model more degrees of freedom when fitting the data. Between the traditional and the PDI-variant models, model fitting differs the most at the dry end of the measurements. The traditional models allow infinite suction at the residual water content (water content does not drop below residual water content), and the PDI-variant models enforce a soil water potential value of pF=6.8 (~ -630 MPa) at oven-dryness (water content reaches 0). The inclusion of the van-Genuchten-type models is due to their common application. If other retention models are required, users can access the data in data.csv for further data fitting. More information about the models can be found in the Methods section below. Fitting Tasks The model fitting can be categorized into three levels of tasks (specified by “fitting_task” column in the files). Level 1 (“fit_retention”) only includes retention data fitting (the only level available for the in-situ method). Level 2 (“fit_retention_conductivity”) includes both retention and hydraulic conductivity data fitting, and the saturated hydraulic conductivity (Ks, a parameter of the hydraulic conductivity functions) is fixed by the measurements from KSAT. Level 3 (“fit_retention_conductivity_Ks”) also includes both retention and hydraulic conductivity data fitting, but Ks is a fitted parameter without the constraints from KSAT measurements. Among the same retention models (e.g. vG_constrained models of the same sample), level 1 should produce the best retention data fitting. Level 2 should have the highest misfit of the retention and hydraulic conductivity data, because the retention and hydraulic conductivity functions share common model parameters, and the unsaturated hydraulic conductivity (HYPROP) data fitting is subject to Ks measured independently by KSAT. Level 3 should have mid-level misfits of the retention and hydraulic conductivity data. While level 3 fits the hydraulic conductivity data better than level 2, the fitted Ks value might be unreasonable due to the lack of constraints at the wet end of the measurements. General recommendation when using this data package: (1) Choice of sampling methods: Intact cores might suffer from sample gaps that would lead to overestimation of Ks (sample gaps can be inferred from the “soil_sample_volume” column in metadata.csv when the value is < 249). In-situ method has higher uncertainty in characterizing the wet end of the SWRC because of sensor limitations and the difficulty in reaching full saturation under natural conditions. (2) Choice of fitting tasks: When only retention data is needed, level 1 (“fit_retention”) should be prioritized. When both retention and hydraulic conductivity data are needed, level 2 (“fit_retention_conductivity”) could be prioritized. (3) Choice of models: This could depend on what the downstream models call for. If no specific model is required, model misfit could be used as a ranking criterion. Model misfit values in terms of RMSE can be found in model_parameters.csv. The following files are included in this data package: (1) metadata.csv – This file includes the general information of each sample, including location (description, geocoordinates, elevation), sampling and measurements details (method, depth, time or period, volume, instruments), and soil physical properties (bulk density, saturated hydraulic conductivity, only applicable to physical soil samples). (2) data.csv – This file includes soil water potential, volumetric water content, and unsaturated hydraulic conductivity data of each sample. Column “instrument” specifies the instrument (HYPROP, WP4C, or TEROS) used to perform the measurements. (3) model_fit.csv – This file includes soil water potential, volumetric water content, and unsaturated hydraulic conductivity fitted from the four models and three fitting tasks. Column “model_name” specifies the retention model used, and “fitting_task” specifies the level of data fitting. Missing values indicate that the variable does not apply to that fitting task. (4) model_parameters.csv – This file includes the fitted model parameters, model misfits, and conventional water content thresholds (field capacity and wilting point) from the four models and three fitting tasks. Column “model_name” specifies the retention model used, and “fitting_task” specifies the level of data fitting. Missing values indicate that the parameter does not apply to that model and/or that fitting task. (5) data_Ks.csv – This file includes the saturated hydraulic conductivity measurements from KSAT. (6) /figure/*.png – This folder includes three quick visualizations of the data, retention model fitting results and misfits, and hydraulic conductivity model fitting results, misfits, and parameters. The model fitting results are separated by samples and fitting tasks and colored by models. Zoom-in required. (7) /hyprop/*.bdhx – This folder includes proprietary hyprop files that require the free Labros SoilView-Analysis (METER) to open. Users can explore data fitting using other retention models (i.e. Brooks-Corey, Fredlund-Xing, Kosugi, bimodal models). Be aware that Ks value is pre-entered under “Fitting tab, Conductivity functions parameters” for level 2 fitting. If the value is lost, please refer to metadata.csv under “Ks” column. (8) Six file-level metadata that summarize file, header, column, and variable information of all files. 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.

EARTH SCIENCE > LAND SURFACE > SOILS↗
DOE OSTI2022

Uranium sorption to organic matter and long-term accumulation in a pristine alpine wetland

Understanding the controls on uranium (U) mobility in the environment is key to improve the management of sites contaminated by U mining activities. Previous research has shown that natural or engineered wetlands are particularly able to scavenge high amounts of U(VI) and U(IV) under noncrystalline forms. However, questions remain on the respective roles of sorption and reduction processes in the removal of U from running waters in wetlands, as well as on the long-term stability of U storage. Here, we performed a series of geochemical, isotopic ($δ$ 238 U, ( 234 U/ 238 U)), microscopic (SEM-EDXS, EPMA) and spectroscopic (µ-XRF, µ-XAS, XANES and EXAFS at the U L 3 and M 4 -edges and Fe K-edge) investigations to determine the modes of U accumulation and assess U mobility in a natural exceptionally U-enriched (up to 5000 µg/g) wetland on the shore of Lake Nègre (Mediterranean Alps, France). Uranium (VI) was largely dominant in the two studied soil cores, except a few samples containing as much as ~50 % U(IV). At the particle scale, U is associated to a variety of organic constituents of the soil matrix with a homogenous oxidation state. Bulk EXAFS spectroscopy at the U L 3 -edge shows that U is mostly mononuclear, with dominant monodentate binding to organic moieties (C neighbors at ~3.45 Å). An additional minor fraction of U under polymeric forms is inferred from wavelet (CCWT) analysis of the EXAFS data. These observations are reinforced by 1 M bicarbonate extractions that result in the dissolution of 82–96 % of total U, including putative polymeric species. At the wetland scale, similar or slightly fractionated isotopic ratios ($δ$ 238 U) between the wetland-feeding creek waters and the wetland soils are observed, supporting the idea that U(VI) sorption on organic matter is the primary U scavenging mechanism. Furthermore, it indicates that partial U(VI) reduction to U(IV) occurs as a second step, after sorption. Analysis of U decay chain disequilibria in the cores as a function of depth suggests that U accumulation in this wetland has lasted for several thousand years. In conclusion, we propose that the wetland acts as an active reactor where U has been massively accumulating for ~14500 years, especially as U(VI) forms associated to organic matter and is further partly exported to the lake through soil erosion.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
DOE OSTI2024

A hidden demethylation pathway removes mercury from rice plants and mitigates mercury flux to food chains

Dietary exposure to methylmercury (MeHg) causes irreversible damage to human cognition and is mitigated by photolysis and microbial demethylation of MeHg. Rice (Oryza sativa L.) has been identified as a major dietary source of MeHg. However, it remains unknown what drives the process within plants for MeHg to make its way from soils to rice and the subsequent human dietary exposure to Hg. Here we report a hidden pathway of MeHg demethylation independent of light and microorganisms in rice plants. This natural pathway is driven by reactive oxygen species generated in vivo, rapidly transforming MeHg to inorganic Hg and then eliminating Hg from plants as gaseous Hg°. MeHg concentrations in rice grains would increase by 2.4- to 4.7-fold without this pathway, which equates to intelligence quotient losses of 0.01–0.51 points per newborn in major rice-consuming countries, corresponding to annual economic losses of US$30.7–84.2 billion globally. Importantly, this discovered pathway effectively removes Hg from human food webs, playing an important role in exposure mitigation and global Hg cycling.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Alpha Spectrometry Results for Groundwater Samples Collected in Northern Iraq and a Summary of the Environmental Setting of the Adaya Burial Site

The Radiation Protection Center (RPC) of the Iraqi Ministry of Environment continues to evaluate the potential health impacts associated with the Adaya Burial Site, which is located 33 kilometers (20.5 miles) southwest of Mosul. This report documents the radiological analyses of 16 groundwater samples collected from wells located in the vicinity of the Adaya Burial Site and at other sites in northern Iraq. The Adaya Burial Site is a high-risk dump site because a large volume of radioactive material and contaminated soil is located on an unsecure hillside above the village of Tall ar Ragrag. The uranium activities for the 16 water samples in northern Iraq are considered to be naturally occurring and do not indicate artificial (man-made) contamination. With one exception, the alpha spectrometry results for the 16 wells that were sampled in 2019 indicate that the water quality concerning the three uranium isotopes (Uranium-233/234, Uranium-235/236, and Uranium-238) was acceptable for potable purposes (drinking and cooking). However, Well 7 in Mosul had a Uranium-233/234 activity concentration that slightly exceeded the World Health Organization guidance level. Eight of the 16 wells are located in the villages of Tall ar Ragrag and Adaya and had naturally occurring uranium concentrations. Wells in the villages of Tall ar Ragrag and Adaya are located near the Adaya Burial Site and should be sampled on an annual schedule. The list of groundwater analytes should include metals, total uranium, isotopic uranium, gross alpha/beta, gamma spectroscopy, organic compounds, and standard water quality parameters. Our current understanding of the hydrogeologic setting in the vicinity of the Adaya Burial Site is solely based on villager's domestic wells, topographic maps, and satellite imagery. To better understand the hydrogeologic setting, a Groundwater Monitoring Program needs to be developed and should include the installation of twelve groundwater monitoring wells in the vicinity of Tall ar Ragrag and the Adaya Burial Site. Characterization of the limestone aquifer and overlying alluvium is needed. RPC should continue to support health assessments for the villagers in Tall ar Ragrag and Adaya. Collecting samples for surface water (storm water), airborne dust, vegetation, and washway sediment should be conducted on a routine basis. Human access to the Adaya Burial Site needs to be strictly limited. Livestock access on or near the burial site needs to be eliminated. The surface-water exposure pathway is likely a greater threat than the groundwater exposure pathway. Installation of a surface-water diversion or collection system is recommended in order to reduce the potential for humans and livestock to come in contact with contaminated water and sediment. To reduce exposure to villagers, groundwater treatment should be considered if elevated uranium or other contaminants are detected in drinking water. Installing water-treatment systems would likely be quicker to accomplish than remediation and excavation of the Adaya Burial Site. The known potential for human exposure to uranium and metals (such as arsenic, chromium, selenium, and strontium) at the Adaya Burial Site is serious. Additional characterization , mitigation, and remediation efforts should be given a high priority.

54 ENVIRONMENTAL SCIENCES↗