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All sourcesNASA NTRSDOE OSTI
NASA NTRS2010

Experimental Investigation of Space Radiation Processing in Lunar Soil Ilmenite: Combining Perspectives from Surface Science and Transmission Electron Microscopy

Energetic ions mostly from the solar wind play a major role in lunar space weathering because they contribute structural and chemical changes to the space-exposed surfaces of lunar regolith grains. In mature mare soils, ilmenite (FeTiO3) grains in the finest size fraction have been shown in transmission electron microscope (TEM) studies to exhibit key differences in their response to space radiation processing relative to silicates [1,2,3]. In ilmenite, solar ion radiation alters host grain outer margins to produce 10-100 nm thick layers that are microstructurally complex, but dominantly crystalline compared to the amorphous radiation-processed rims on silicates [1,2,3]. Spatially well-resolved analytical TEM measurements also show nm-scale compositional and chemical state changes in these layers [1,3]. These include shifts in Fe/Ti ratio from strong surface Fe-enrichment (Fe/Ti >> 1), to Fe depletion (Fe/Ti < 1) at 40-50 nm below the grain surface [1,3]. These compositional changes are not observed in the radiation-processed rims on silicates [4]. Several mechanism(s) to explain the overall relations in the ilmenite grain rims by radiation processing and/or additional space weathering processes were proposed by [1], and remain under current consideration [3]. A key issue has concerned the ability of ion radiation processing alone to produce some of the deeper- penetrating compositional changes. In order to provide some experimental constraints on these questions, we have performed a combined X-ray photoelectron spectroscopy (XPS) and field-emission scanning transmission electron (FE-STEM) study of experimentally ion-irradiated ilmenite. A key feature of this work is the combination of analytical techniques sensitive to changes in the irradiated samples at depth scales going from the immediate surface (approx.5 nm; XPS), to deeper in the grain interior (5-100 nm; FE-STEM).

Christoffersen, R.↗
NASA NTRS1993

Application of MAC-Europe AVIRIS data to the analysis of various alteration stages in the Landdmannalauger Hydrothermal Area (South Iceland)

In June 1991 extensive airborne remote sensing data-sets have been acquired over Iceland in the framework of the joint NASA/ESA Multisensor Airborne Campaign Europe (MAC-Europe). The study area is located within the Torfajokull central volcanic complex in South Iceland. This complex is composed by anomalously abundant rhyolitic acid volcanics, which underwent intensive hydrothermal alteration. Detailed studies of surface alteration of rhyolitic rocks in the area showed that all the major elements are leached as the rock is affected by complex mineralogical changes. Montmorillonite appears during the earliest stages of alteration. In the ultimate alteration product montmorillonite is absent and the rock consists mostly of amorphous silica, anatase, up to a volume of 50% kaolinite and variable amounts of native sulphur and pyrite. The case study presented shall endeavor to assess the potential of MAC-Europe AVIRIS and TMS data in determining a possible zonation of hydrothermal alteration in relationship to the active geo-thermal fields and structural features. To this end, the airborne data is analysed in comparison with laboratory spectral measurements of characteristics rock, soil, and vegetation samples collected in the study areaduring the summer of 1992. Various spectral mapping algorithms as well as unmixing approaches are tested and evaluated. Detailed geological and structural mapping as well as geochemical analysis of the main rock and soil types were performed to underpin the analysis of the airborne data.

Sommer, S.↗
DOE OSTI2020

Pathways for methane emissions and oxidation that influence the net carbon balance of a subtropical cypress swamp

We evaluated the major pathways for methane emissions from wetlands to the atmosphere at four wetland sites in the Big Cypress National Preserve in southwest Florida. Methane oxidation was estimated based on the d13C-CH4 of surface water, porewater, and bubbles to evaluate mechanisms that limit surface water emissions. Spatially-scaled methane fluxes were then compared to organic carbon burial rates. The pathway with the lowest methane flux rate was diffusion from surface waters (3.50 ± 0.22 mmol m-2 d-1). Microbial activity in the surface water environment and/or shallow oxic sediment layer oxidized 26 ± 3% of the methane delivered from anerobic sediments to the surface waters. The highest rates of diffusion were observed at the site with the lowest extent of oxidation. Ebullition flux rates were 2.2 times greater than diffusion and more variable (7.79 ± 1.37 mmol m-2 d-1). Methane fluxes from non-inundated soils were 1.6 times greater (18.4 ± 5.14 mmol m-2 d-1) than combined surface water fluxes. Methane flux rates from cypress knees (emergent cypress tree root structures) were 3.7 and 2.3 times higher (42.0 ± 6.33 mmol m-2 d-1) than from surface water and soils, respectively. Cypress knee flux rates were highest at the wetland site with the highest porewater methane partial pressure, suggesting that the emergent root structures allow methane produced in anaerobic sediment layers to bypass oxidation in aerobic surface waters or shallow sediments. Scaled across the four wetlands, emissions from surface water diffusion, ebullition, non-inundated soils, and knees contributed to 14 ± 2%, 25 ± 6%, 34 ± 10%, and 26 ± 5% of total methane emissions, respectively. When considering only the three wetlands with cypress knees present, knee emissions contributed to 39 ± 5% of the total scaled methane emissions. Finally, the molar ratio of CH4 emissions to OC burial ranged from 0.03 to 0.14 in the wetland centers indicating that all four wetland sites are net sources of atmospheric warming potential on 20-100 yr timescales, but net sinks over longer time scales (500 yr) with the exception of one wetland site that was a net source even over 500 yr time scales.

Ward, Nicholas D.↗
DOE OSTI2025

Soil biogeochemical properties and metrics of tree-mycorrhizal dominance for a 25-Ha forest in South Central Indiana, USA.

This data package contains a dataset used in the papers “Seeing the forest for all the trees: Mycorrhizal-associated nutrient economies are modulated by stem density and the synchrony between overstory and understory communities” and “Mycorrhizal associations of tree species influence soil nitrogen dynamics via effects on soil acid–base chemistry”. Four csv files are included along with a dataset. The dataset features chemical soil properties for a single sampling campaign within the 25 Ha Lilly-Dickey Woods Smithsonian Forest Global Earth Observatory (ForestGEO) plot in South Central Indiana, USA (ldw_dat_raw.csv). Also included are separate files focused on pH (pH_data.csv), carbon and nitrogen (CN_data.csv), and nitrification rates (Nitrification_data.csv). These variables are commonly associated with the tree-mycorrhizal dominance of forest stands. In these data subsets, each soil variable was matched to a 10 meter radius neighborhood wherein metrics of tree-mycorrhizal dominance (basal area, stem count, importance value, etc.) were calculated. Models between these soil variables and dominance metrics were used to investigate how different assessments of mycorrhizal associated nutrient economies (MANE) capture these relationships. This research was performed as a part of the Smithsonian ForestGEO project. This data package can be used to explore spatial variability in soil chemistry within a mature hardwood forest, or it can be combined with the included tree data, other fine-scale spatial information, or other tree inventory data for the site to evaluate how soil chemistry varies with tree community composition or edaphic or topographic properties.

Craig, Matthew [ORNL] (ORCID:0000000288907920)↗
DOE OSTI2023

Microbial Drivers of Plant Performance during Drought Depend upon Community Composition and the Greater Soil Environment

The increasing occurrence of drought is a global challenge that threatens food security through direct impacts to both plants and their interacting soil microorganisms. Plant growth promoting microbes are increasingly being harnessed to improve plant performance under stress. However, the magnitude of microbiome impacts on both structural and physiological plant traits under water limited and water replete conditions are not well-characterized. Using two microbiomes sourced from a ponderosa pine forest and an agricultural field, we performed a greenhouse experiment that used a crossed design to test the individual and combined effects of the water availability and the soil microbiome composition on plant performance. Specifically, we studied the structural and leaf functional traits of maize that are relevant to drought tolerance. We further examined how microbial relationships with plant phenotypes varied under different combinations of microbial composition and water availability. We found that water availability and microbial composition affected plant structural traits. Surprisingly, they did not alter leaf function. Maize grown in the forest-soil microbiome produced larger plants under well-watered and water-limited conditions, compared to an agricultural soil community. Although leaf functional traits were not significantly different between the watering and microbiome treatments, the bacterial composition and abundance explained significant variability in both plant structure and leaf function within individual treatments, especially water-limited plants. Our results suggest that bacteria-plant interactions that promote plant performance under stress depend upon the greater community composition and the abiotic environment.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1973

Fracture trends identified by ERTS-1 imagery in Utah and Nevada

The author has identified the following significant results. Structures clearly traceable through bed rock are considered most reliable. Continuity, however, is frequently traceable through ranges and across adjoining sedimentary basins where changes in drainage, erosion pattern, soil color, or vegetation suggest that the basin sediments are extremely sensitive to underlying structures. Many large and continuous trends, too smeared by erosion to be visible on the ground or from aircraft photos, become quite evident at the scale of the ERTS-1 images. The study was made with little regard for surface geology. The trends have been retraced to separate and unidirectional sets. These are now being related to surface geology, geophysical studies, volcanic and intrusive centers, and areas of mineralization.

Jensen, M. L.↗
DOE OSTI2023

Microbiome differences in sugarcane and metabolically engineered oilcane accessions and their implications for bioenergy production

Abstract Oilcane is a metabolically engineered sugarcane ( Saccharum spp. hybrid) that hyper-accumulates lipids in its vegetable biomass to provide an advanced feedstock for biodiesel production. The potential impact of hyper-accumulation of lipids in vegetable biomass on microbiomes and the consequences of altered microbiomes on plant growth and lipid accumulation have not been explored so far. Here, we explore differences in the microbiome structure of different oilcane accessions and non-modified sugarcane. 16S SSU rRNA and ITS rRNA amplicon sequencing were performed to compare the characteristics of the microbiome structure from different plant compartments (leaf, stem, root, rhizosphere, and bulk soil) of four greenhouse-grown oilcane accessions and non-modified sugarcane. Significant differences were only observed in the bacterial microbiomes. In leaf and stem microbiomes, more than 90% of the entire microbiome of non-modified sugarcane and oilcane was dominated by similar core taxa. Taxa associated with Proteobacteria led to differences in the non-modified sugarcane and oilcane microbiome structure. While differences were observed between multiple accessions, accession 1566 was notable in that it was consistently observed to differ in its microbial membership than other accessions and had the lowest abundance of taxa associated with plant-growth-promoting bacteria. Accession 1566 is also unique among oilcane accessions in that it has the highest constitutive expression of the WRI 1 transgene. The WRI 1 transcription factor is known to contribute to significant changes in the global gene expression profile, impacting plant fatty acid biosynthesis and photomorphogenesis. This study reveals for the first time that genetically modified oilcanes associate with distinct microbiomes. Our findings suggest potential relationships between core taxa, biomass yield, and TAG in oilcane accessions and support further research on the relationship between plant genotypes and their microbiomes.

09 BIOMASS FUELS↗
DOE OSTI2024

Coupled aero-hydro-geotech real-time hybrid simulation of offshore wind turbine monopile structures

Real-time hybrid simulation (RTHS) divides a structural system into an analytical and experimental substructure. The former is based on a well-established analytical model while the latter consists of a physical model in the laboratory, for which there is not a well-established analytical model. This paper extends real-time hybrid simulation to monopile-type Offshore Wind Turbines (OWTs) to enable the investigation of their behavior considering the response of pile foundations under operational and more severe conditions. The embedded foundation and surrounding soil of the OWT are modeled physically in a soil box in the laboratory while the remaining parts of the system and loading are modeled analytically. The program OpenFAST, developed by the National Renewable Energy Laboratory (NREL), is linked to the RTHS coordinator to determine the hydrodynamic and aerodynamic loads acting on the OWT, along with modeling the dynamics of the electric power generation equipment and associated controller for the OWT. The RTHS framework along with its initial implementation and validation are described in this paper. RTHSs of a 5 MW OWT subjected to operational and more severe conditions are performed to experimentally validate the framework. The framework offers a realistic approach to investigate the behavior of OWT structures supported on monopiles. Furthermore, this approach accounts for the coupled response of the OWT structure with its foundation, while experimentally capturing the nonlinearities of the soil-foundation interaction in real-time.

17 WIND ENERGY↗
DOE OSTI2023

Using root and soil traits to forecast woody encroachment dynamics in mesic grassland

Grasslands are a widespread and globally important biome providing key ecosystem services including C storage and regulation of the water cycle. Grasslands face multiple threats, including changes in drought intensity and woody encroachment - a process that results in increased woody plant abundance corresponding with decreased herbaceous plant abundance. The combination of reduced soil moisture and shifts in plant dominance from herbaceous to woody are likely to alter C pools in the soil profile. We currently do not have the capacity to predict either the magnitude or rates of change in these C pools. In order to predict changes in grassland vegetation structure and the associated impacts on C cycling requires greater understanding of changes in soil C pools at multiple soil depths, and the responses of these pools to changes in precipitation. To support and perform this parameterization of Land Surface Models, we performed detailed investigations of root (anatomical and physiological) and soil traits (microbial function) at varying soil depths, to capture the belowground impacts of changing dominant plant growth forms (grasses to shrubs) and the impacts of frequent drought.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Partitioning of Fe(II) in reduced nontronite (NAu-2) to reactive sites: Reactivity in terms of Tc(VII) reduction

Abstract Clay minerals impart important chemical properties to soils, in part, by virtue of changes in the redox state of Fe in their crystal structures. Therefore, measurement of Fe(III)/Fe(II) and partitioning of Fe(II) in different reactive sites in clay minerals (during biological and chemical Fe(III) reduction) is essential to understand their role and their relative reactivity in terms of reduction and immobilization of heavy metal contaminants such as technetium. This study had three objectives: (1) to understand the degree of dissolution of nontronite (Fe-rich smectite) as a result of chemical and biological reduction of Fe(III) in the structure; (2) to quantify partitioning of chemically and biologically produced Fe(II) into different reactive sites in reduced nontronite, including aqueous Fe 2+ , ammonium chloride-extractable Fe(II) (mainly from the ion-exchangeable sites, denoted as Fe ( II ) NH 4 Cl ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ ), sodium acetate-extractable Fe(II) (mainly from the surface complexation sites, denoted as Fe(II) acetate ), and structural Fe(II) (denoted as Fe(II) str ); and (3) to evaluate the reactivity of these Fe(II) species in terms of Tc(VII) reduction. Chemical and biological reduction of Fe(III) in nontronite (NAu-2) was performed, and reduced nontronite samples with different extents of Fe(III) reduction (1.2–71%) were prepared. The extent of reductive dissolution was measured as a function of the extent of Fe(III) reduction. Our results demonstrated that chemically and biologically produced Fe(II) in NAu-2 may be accommodated in the NAu-2 structure if the extent of Fe(III) reduction is small (< ∼30%). When the extent of reduction was >∼30%, dissolution of nontronite occurred with a corresponding decrease in crystallinity of residual nontronite. The Fe(II) produced was available for partitioning into four species: Fe ( ab ) 2 + ${\rm{Fe}}_{\left( {{\rm{ab}}} \right)}^{2 + }$ , Fe(II) acetate , Fe ( II ) NH 4 Cl ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ , and Fe(II) str . The increase in Fe(II) acetate during the early stages of Fe(III) reduction indicated that the Fe(II) released had the greatest affinity for the surface-complexation sites, but this site had a limited capacity (∼60 µmol of Fe(II)/g of NAu-2). The subsequent increase in Fe ( II ) NH 4 Cl ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ indicated that the released Fe(II) partitioned into the exchangeable sites once the amount of Fe at the surface-complexation sites reached half of its maximum site capacity. The fraction of Fe(II) str decreased concomitantly, as a result of Fe(II) release from the NAu-2 structure, from 100% when the extent of Fe(III) reduction was <30% to nearly 65% when the extent of Fe(III) reduction reached 71%. The Fe(II) acetate and Fe(II) str exhibited greater reactivity in terms of Tc(VII) reduction than the Fe ( II ) NH 4 Cl ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ . Clearly, the surface-complexed and structural Fe(II) are the desirable species when reduced clay minerals are used to reduce and immobilize soluble heavy metals in contaminated groundwater and soils. These results have important implications for understanding microbe—clay mineral interactions and heavy metal immobilization in clay-rich natural environments.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1994

Lunar vertical-shaft mining system

This report proposes a method that will allow lunar vertical-shaft mining. Lunar mining allows the exploitation of mineral resources imbedded within the surface. The proposed lunar vertical-shaft mining system is comprised of five subsystems: structure, materials handling, drilling, mining, and planning. The structure provides support for the exploration and mining equipment in the lunar environment. The materials handling subsystem moves mined material outside the structure and mining and drilling equipment inside the structure. The drilling process bores into the surface for the purpose of collecting soil samples, inserting transducer probes, or locating ore deposits. Once the ore deposits are discovered and pinpointed, mining operations bring the ore to the surface. The final subsystem is planning, which involves the construction of the mining structure.

Introne, Steven D.↗
NASA NTRS1998

GCM Studies on the Interactions Between Photosynthesis and Climate at Diurnal to Decadal Time Scales

Transpiration, a major component of total evaporation from vegetated surfaces, is an unavoidable consequence of photosynthetic carbon fixation. Because of limiting soil moisture and competition for solar radiation plants invest most of their fixed carbon into structural and hydraulic functions (roots and stems) and solar radiation absorption (leaves). These investments permit individuals to overshadow competitors and provide for transport of water from the soil to the leaves where photosynthesis and transpiration occur. Often low soil moisture or high evaporative demand limit the supply of water to leaves reducing photosynthesis and thus transpiration. The absorption of solar radiation for photosynthesis and dissipation of this energy via radiation, heat, mass and momentum fluxes represents the link between photosynthesis and climate. Recognition of these relationships has led to the development of hydro/energy balance models that are based on the physiological ecology of photosynthesis. We discuss an approach to study vegetation-climate interactions using photosynthesis-centric models embedded in a GCM. The rate at which a vegetated area transpires and photosynthesizes is determined by the physiological state of the vegetation, its amount and its type. The latter two are specified from global satellite data collected since 1982. Climate simulations have been carried out to study how this simulated climate system responds to changes in radiative forcing, physiological capacity, atmospheric CO2, vegetation type and variable vegetation cover observed from satellites during the 1980's. Results from these studies reveal significant feedbacks between the vegetation activity and climate. For example, vegetation cover and physiological activity increases cause the total latent heat flux and precipitation to increase while mean and maximum air temperatures decrease. The reverse occurs if cover or activity'decreases. In general climate response of a particular region was dominated by local processes but we also find evidence that plausible climate-vegetation scenarios lead to changes in global atmospheric circulation and strong non-local influences in some cases.

Collatz, G. James↗
NASA NTRS1998

Monitoring Direct Effects of Delta, Atlas, and Titan Launches from Cape Canaveral Air Station

Launches of Delta, Atlas, and Titan rockets from Cape Canaveral Air Station (CCAS) have potential environmental effects that could arise from direct impacts of the launch exhaust (e.g., blast, heat), deposition of exhaust products of the solid rocket motors (hydrogen chloride, aluminum oxide), or other effects such as noise. Here we: 1) review previous reports, environmental assessments, and environmental impact statements for Delta, Atlas, and Titan vehicles and pad areas to clarity the magnitude of potential impacts; 2) summarize observed effects of 15 Delta, 22 Atlas, and 8 Titan launches; and 3) develop a spatial database of the distribution of effects from individual launches and cumulative effects of launches. The review of previous studies indicated that impacts from these launches can occur from the launch exhaust heat, deposition of exhaust products from the solid rocket motors, and noise. The principal effluents from solid rocket motors are hydrogen chloride (HCl), aluminum oxide (Al2O3), water (H2O), hydrogen (H2), carbon monoxide (CO), and carbon dioxide (CO2). The exhaust plume interacts with the launch complex structure and water deluge system to generate a launch cloud. Fall out or rain out of material from this cloud can produce localized effects from acid or particulate deposition. Delta, Atlas, and Titan launch vehicles differ in the number and size of solid rocket boosters and in the amount of deluge water used. All are smaller and use less water than the Space Shuttle. Acid deposition can cause damage to plants and animals exposed to it, acidify surface water and soil, and cause long-term changes to community composition and structure from repeated exposure. The magnitude of these effects depends on the intensity and frequency of acid deposition.

Schmalzer, Paul A.↗
NASA NTRS1995

Raman Spectroscopy as a Method for Mineral Identification on Lunar Robotic Exploration Missions

The sharp, nonoverlapping Raman bands for plagioclase, pyroxene, and olivine would be advantageous for on-surface, active mineralogical analysis of lunar materials. A robust, light-weight, low-power, rover-based Raman spectrometer with a laser exciting source, entirely transmission-mode holographic optics, and a charge-coupled device (CCD) detector could fit within a less than 20 cm cube. A sensor head on the end of an optical fiber bundle that carried the laser beam and returned the scattered radiation could be placed against surfaces at any desired angle by a deployment mechanism; otherwise, the instrument would need no moving parts. A modem micro-Raman spectrometer with its beam broadened (to expand the spot to 50-micrometer diameter) and set for low resolution (7/cm in the 100-1400/cm region relative to 514.5-nm excitation), was used to simulate the spectra anticipated from a rover instrument. We present spectra for lunar mineral grains, less than 1 mm soil fines, breccia fragments, and glasses. From frequencies of olivine peaks, we derived sufficiently precise forsterite contents to correlate the analyzed grains to known rock types and we obtained appropriate forsterite contents from weak signals above background in soil fines and breccias. Peak positions of pyroxenes were sufficiently well determined to distinguish among orthorhombic, monoclinic, and triclinic (pyroxenoid) structures; additional information can be obtained from pyroxene spectra, but requires further laboratory calibration. Plagioclase provided sharp peaks in soil fines and most breccias even when the glass content was high.

Wang, Alian↗
NASA NTRS1984

Geology

Three objectives were outlined: (1) global distribution, geometry and composition of continental rock units; (2) morphology and structure of the continental crust; and (3) monitoring selected surface processes. Mapping soil, sediment and rock characteristics for land surfaces requires the use of visible, reflected, thermal and radio parts of the spectrum. Digital topographic data (elevation, slope angle, slope magnitude) are needed to correct reflectance, emission, and radar data. In addition, images of the topographic data provide fundamental information on the morphology and structure of the land.

Arvidson, R.↗
DOE OSTI2025

Post-Wildfire Mobilization of Organic Carbon

Wildfires significantly alter watershed functions, particularly the mobilization of organic carbon (OC). This study investigated OC mobility and the physicochemical characteristics of wildfire-impacted soils and ashes from the northern California and Nevada fires (Dixie, Beckworth, Caldor). Organic carbon in wildfire-derived ashes (9.2–57.3 mg/g) generally exceeded levels in the background soils (4.3–24.4 mg/g), except at the Dixie fire sites. The mobile OC fraction varied from 0.0093 to 0.029 in ashes and 0.010 to 0.065 in soils, though no consistent trend was observed between the ashes and soils. Notably, the ash samples displayed lower OC mobility compared with the soils beneath them. A negative correlation was found between the mobile OC fraction and bulk OC content. Wildfire increased the total amount of mobile OC substantially by 5.2–574% compared to the background soils. Electron paramagnetic resonance (EPR) spectra confirmed the presence of environmentally persistent free radicals (EPFRs), which correlated with observed redox reactivity. Additionally, X-ray absorption near edge structure (XANES) and X-ray fluorescence (XRF) imaging revealed that Fe(II) oxidation in soils beneath the ashes may have enhanced the OC mobility, likely driven by pyrogenic carbon and free radicals. These findings enhance our understanding of post-wildfire OC mobilization and the impact of ash–soil physicochemical properties on watershed health.

organic carbon↗
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 OSTI2020

Three Decades of Divergent Land Use and Plant Community Change Alters Soil C and N Content in Tallgrass Prairie

Frequent fire and grazing by megafauna are important determinants of tallgrass prairie plant community structure. However, fire suppression and removal of native grazers have altered these natural disturbance regimes and changed grassland plant communities with potential long-term consequences for soil carbon (C) and nitrogen (N) storage. We investigated multidecade changes in soil C and N pools in response to contrasting long-term burning and grazing treatments. Fire suppression with or without grazers and exclusion of grazers in annually burned prairie increased soil C content and shifted the δ 13 C signature of soil C over time, concomitant with changes in plant community composition. Soil δ 13 C values indicated that increased soil C content was associated with an increased contribution from plants using a C 3 photosynthetic pathway (i.e., woody shrubs) under fire suppression. Soil N content also increased when fire was suppressed, relative to frequently burned grassland, but the rate of increase was slower when grazers were present. Additionally, changes in δ 15 N values suggested that grazing increased the openness of the N cycle, presumably due to greater N losses. By coupling long-term fire and grazing treatments with plant community data and soil samples archived over three decades, we demonstrate that human-caused changes to natural disturbance regimes in a tallgrass prairie significantly alter soil C and N cycles through belowground changes associated with shifts in the plant community. Since natural disturbance regimes have been altered in grasslands across the world, our results are relevant for understanding the long-term biogeochemical consequences of these ongoing land use changes.

54 ENVIRONMENTAL SCIENCES↗