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DOE OSTI2022

Microtopographic and Depth Controls on Active Layer Chemistry in Arctic Polygonal Ground: Supporting Data

Polygonal ground is a signature characteristic of the Arctic, and permafrost thaw can potentially generate substantial feedbacks to Arctic ecosystems and climate. This study describes the first comprehensive spatial examination of active layer biogeochemistry that extends across high- and low-centered polygons and their features, including depth. Water chemistry measurements were made on active layer water samples collected near Barrow, Alaska during summer, 2012. Several significant differences in chemistry were observed between high- and low-centered polygons suggesting polygon types may be useful for landscape-scale geochemical classification. However, differences were found for polygon features (centers and troughs) for analytes that were not significant for type, suggesting that finer scale features control biogeochemistry in a different way than polygon type. Depth variations were also significant, demonstrating important multi-dimensional aspects of polygonal ground biogeochemistry. These results have major implications for understanding how polygonal ground ecosystems function, and how they may respond to future change. This data package includes one *.csv data file and one *.pdf user guide. 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 OSTI2024

Using Diel Solute Signals to Assess Ecohydrological Processing in Lotic Systems

Lotic systems are a prominent ecohydrological interface within which complex, coupled interactions occur between ecological, hydrological, and geochemical processes. This chapter reviews the ecological processes driving diel signals in oxygen as well as major nutrients and other trace elements. It discusses how diel signals can be used to evaluate functioning and interactions within stream ecosystems. The chapter considers potential future research directions and outstanding questions still to be addressed by or about diel solute signals and associated processes. High-resolution sensor-based time series and associated tools and conceptual advances are being integrated into environmental management. Quantitative tools to disentangle diel biogeochemically-driven signals from other sources of variability in continuous time series are growing. Theoretical models of diel process dynamics are helping to spur hypothesis generation and new ways of approaching diel signals in lotic systems.

Kurz, Marie↗

NASA NTRS1996

An Apollo 15 Mare Basalt Fragment and Lunar Mare Provinces

Lunar sample 15474,4 is a tiny fragment of olivine-augite vitrophyre that is a mare basalt. Although petroraphically distinct from all other Apollo 15 samples, it has been ignored since its first brief description. Our new petrographic and mineral chemical data show that the olivines and pyroxenes are distinct from those in other basalts. The basalt cooled and solidified extremely rapidly; some of the olivine might be cumulate or crystallized prior to extrusion. Bulk-chemical data show that the sample is probably similar to an evolved Apollo 15 olivine-normative basalt in major elements but is distinct in its rare earth element pattern. Its chemical composition and petrography both show that 15474,4 cannot be derived from other Apollo 15 mare basalts by shallow-level crystal fractionation. It represents a distinct extrusion of magma. Nonetheless, the chemical features that 15474,4 has in common with other Apollo 15 mare basalts, including the high FeO/Sc, the general similarity of the rare earth element pattern, and the common (and chondritic) TiO2/Sm ratio, emphasize the concept of a geochemical province at the Apollo 15 site that is distinct from basalts and provinces elsewhere. In making a consistent picture for the derivation of all of the Apollo 15 basalts, both the commonalities and the differences among the basalts must be explained. The Apollo 15 commonalities and differences suggest that the sources must have consisted of major silicate phases with the same composition but with varied amounts of a magma trapped from a contemporary magma ocean. They probably had a high olivine/pyroxene ratio and underwent small and reasonably consistent degrees of partial melting to produce the basalts. These inferences may be inconsistent with models that suggest greatly different depths of melting among basalts, primitive sources for the green glasses, or extensive olivine fractionation during ascent. An integrated approach to lunar mare provinces, of which the Apollo 15 mare basalts constitute only one, offers advances in our understanding of the physical and chemical processes of source formation and mare production but has so far not been utilized.

Ryder, Graham↗

NASA NTRS2012

Crystallization of Yamato 980459 at 0.5 GPA: Are Residual Liquids Like QUE 94201?

The Martian basaltic meteorites Y980459 and QUE94201 (henceforth referred to as Y98 and QUE respectively) are thought to represent magmatic liquid compositions, rather than being products of protracted crystallization and accumulation like the majority of other martian meteorites. Both meteorite compositions have been experimentally crystallized at 1 bar, and liquidus phases were found to match corresponding mineral core compositions in the meteorites, consistent with the notion that these meteorites represent bona fide melts. They also represent the most primitive and most evolved basaltic martian samples, respectively. Y98 has Mg# (molar Mg/Mg+Fe) approximates 65, and lacks plagioclase; whereas QUE has Mg# approximates 40, and lacks olivine. However they share important geochemical characteristics (e.g. superchondritic CaO/Al2O3, very high epsilon(sub Nd) and low Sr-87/Sr-87) that suggest they sample a similar highly depleted mantle reservoir. As such, they represent likely endmembers of martian magmatic liquid compositions, and it is natural to seek petrogenetic linkages between the two. We make no claim that the actual meteorites themselves share a genetic link (the respective ages rule that out); we are exploring only in general whether primitive martian liquids like Y98 could evolve to liquids resembling QUE. Both experimental and computational efforts have been made to determine if there is indeed such a link. Recent petrological models at 1 bar generated using MELTS suggest that a QUE-like melt can be derived from a parental melt with a Y98 composition. However, experimental studies at 1 bar have been less successful at replicating this progression. Previous experimental crystallization studies of Y98 by our group at 0.5 GPa have produced melt compositions approaching that of QUE, although these results were complicated by the presence of small, variable amounts of H2O in some of the runs owing to the use of talc/pyrex experimental assemblies. Therefore we have repeated the four experiments, augmented with additional runs, all using BaCO3 cell assemblies, which are devoid of water, and these new experiments supersede those reported earlier. Here we report results of experiments simulating equilibrium crystallization; fractional crystallization experiments are currently underway.

Rapp, J. F.↗

NASA NTRS2017

Chlorine in Lunar Basalts

In the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs, and P, collectively called KREEP, and in its primitive form - urKREEP, [1]), given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO (e.g., [2]). When compared to chondritic meteorites and terrestrial rocks (e.g., [3-4]), lunar samples often display heavy chlorine isotope compositions [5-9]. Boyce et al. [8] found a correlation between delta Cl-37 (sub Ap) and bulk-rock incompatible trace elements (ITEs) in lunar basalts, and used this to propose that early degassing of Cl (likely as metal chlorides) from the LMO led to progressive enrichment in remaining LMO melt in Cl-37over Cl-35- the early degassing model. Barnes et al. [9] suggested that relatively late degassing of chlorine from urKREEP (to yield delta Cl-37 (sub urKREEP greater than +25 per mille) followed by variable mixing between KREEPy melts and mantle cumulates (characterized by delta Cl-37~0 per mille) could explain the majority of Cl isotope data from igneous lunar samples. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed an in situ study of chlorine isotopes and abundances of volatiles in lunar apatite from a diverse suite of lunar basalts spanning a range of geochemical types.

Barnes, J. J.↗

DOE OSTI2022

Dynamic Earth Energy Storage: Terawatt-year, Grid-scale Energy Storage Using Planet Earth as a Thermal Battery (GeoTES): Phase I Project (Final Report)

Grid-scale energy storage has been identified by the U.S. Department of Energy’s (DOE) Energy Storage Grand Challenge as a necessary technology to support the continued build-out of intermittent renewable energy resources required to attain a carbon-free energy future. To meet this goal, the 2018 Department of Energy Research and Innovation Act mandated the creation of a comprehensive program to accelerate the development and commercialization of next-generation energy storage technologies. One of numerous energy storage technology options is the storage of excess energy as heated geothermal brine in suitable geologic formations. This concept, known as reservoir thermal energy storage (RTES), geologic thermal energy storage (GeoTES), aquifer thermal energy storage (ATES), etc., relies on the storage of thermal energy in geologic formations for recovery and use in large-scale direct use geothermal (e.g., district heating, industrial processes, etc.) and electrical power generation applications. This thermal energy is derived from excess or waste heat from any high-temperature heat source, such as concentrated solar or from conventional thermal/nuclear generation. As such, RTES can potentially play a significant role in meeting the energy storage shortfall in the coming decades. RTES can provide energy arbitrage through both the storage and production of thermal energy stored in geologic formations for direct use applications and can serve as a source of hot fluids that can be used to generate electricity to support peak demand ramping, thus easing stress on transmission and distribution. This energy storage option has geographic benefits in that energy can be stored locally or regionally depending on the various needs/loads. RTES can also be located across an enormous geographic area, without the need for a traditional hydrothermal resource but where thermal gradients and hydrogeology allow economic exploitation of subsurface heat. The work conducted for this project includes (1) a review of lessons learned from past high-temperature RTES international projects; (2) geochemical experimental investigation and numerical simulations of potential domestic sedimentary reservoirs and (3) development of a thermo-hydrological-mechanical (THM) numerical simulation tool for optimizing formation properties and design parameters to maximize thermal energy storage performance.

15 GEOTHERMAL ENERGY↗

NASA NTRS1974

The evolution of the moon

The thermal evolution of the moon as it can be defined by the available data and theoretical calculations is discussed. A wide assortment of geological, geochemical and geophysical data constrain both the present-day temperatures and the thermal history of the lunar interior. On the basis of these data, the moon is characterized as a differentiated body with a crust, a 1000-km-thick solid mantle (lithosphere) and an interior region (core) which may be partially molten. The presence of a crust indicates extensive melting and differentiation early in the lunar history. The ages of lunar samples define the chronology of igneous activity on the lunar surface. This covers a time span of about 1.5 billion years, from the origin to about 3.16 billion years ago. Most theoretical models require extensive melting early in the lunar history, and the outward differentiation of radioactive heat sources.

Toksoz, M. N.↗

NASA NTRS1986

Global geochemical cycles of carbon, sulfur and oxygen

Time resolved data on the carbon isotopic composition of carbonate minerals and the sulfur isotopic composition or sulfate minerals show a strong negative correlation during the Cretaceous. Carbonate minerals are isotopically heavy during this period while sulfate minerals are isotopically light. The implication is that carbon is being transferred from the oxidized, carbonate reservoir to the reservoir of isotopically light reduced organic carbon in sedimentary rocks while sulfur is being transferred from the reservoir of isotopically light sedimentary sulfide to the oxidized, sulfate reservoir. These apparently oppositely directed changes in the oxidation state of average sedimentary carbon and sulfur are surprising because of a well-established and easy to understand correlation between the concentrations of reduced organic carbon and sulfide minerals in sedimentary rocks. Rocks rich in reduced carbon are also rich in reduced sulfur. The isotopic and concentration data can be reconciled by a model which invokes a significant flux of hydrothermal sulfide to the deep sea, at least during the Cretaceous.

Non-NASA Center↗

NASA NTRS1979

Volatiles in Chainpur chondrules

A study of volatile element concentrations in individual chondrules in the Chainpur LL3 chondrite is presented. Volatile elements differing in geochemical behavior tended to vary randomly and correlated variations were observed only for those elements inferred to occupy similar mineral sites. Variations in Co and Ni in kamacite show that metal in chondrule interiors has not approached equilibrium, and that postformational element distribution has mainly altered siderophile concentrations in surface metal grains, and has probably left ionic species unaltered. Etching to remove 3 to 5% of the chondrule dissolved siderophiles, enhanced Zn and Na volatiles relative to nonvolatile Cr in the etch, and produced a large Cd enhancement. If metamorphic redistribution of nonsiderophile volatiles was neglible, their high concentrations are inconsistent with chondrule formation by direct condensation, and models involving sudden melting of preexisting solids can explain the observations but require rapid cooling to prevent volatile loss.

Grossman, J. N.↗

NASA NTRS1977

Geochemical and mineralogical interpretation of the Viking inorganic chemical results

The current status of geochemical, mineralogical, petrological interpretation of refined Viking Lander data is reviewed, and inferences that can be drawn from data on the composition of Martian surface materials are presented. The materials are dominantly fine silicate particles admixed with, or including, iron oxide particles. Both major element and trace element abundances in all samples are indicative of mafic source rocks (rather than more highly differentiated salic materials). The surface fines are nearly identical in composition at the two widely separated Lander sites, except for some lithologic diversity at the 100-m scale. This implies that some agency (presumably aeolian processes) has thoroughly homogenized them on a planetary scale. The most plausible model for the mineralogical constitution of the fine-grained surface materials at the two Lander sites is a fine-grained mixture dominated by iron-rich smectites, or their degradation products, with ferric oxides, probably including maghemite and carbonates (such as calcite), but not such less stable phases as magnesite or siderite.

Toulmin, P., III↗

NASA NTRSDate not supplied

Warm-Based Glacial Landforms and Past Climate Signals: Icelandic Eskers as Proxies for Small Sinuous Ridges on Mars

The surface of Mars exhibits plentiful geomorphic evidence for glacial processes, but the history of the cryosphere on Mars remains debated [e.g., 1, 2]. Recent hydrological modeling predicts that warm-based ice sheets on Mars may have resulted in subglacial incised channels (e.g., valley networks) and eskers [3]. Evidence on Mars for warm-based glaciation includes candidate moraines, bedrock channels, and candidate eskers [e.g., 4-6]. Eskers are sinuous ridges comprising glaciofluvial sediments deposited by meltwater flowing through tunnels at the bed of warm-based large glaciers [e.g., 7, 8]. They provide direct evidence of basal melting of ice and preserve glaciofluvial sediments. Warm-based glacial transport is primarily driven by meltwater and can chemically weather the underlying bedrock. An alternative signature of past climate on Mars may thus be the geochemical record, due to alteration by interactions with glacial meltwater, preserved in esker sediments and strata. At present, the sedimentology and stratigraphy of terrestrial eskers is poorly understood. This study will combine sedimentology, geochemistry, and geomorphology to better constrain the unique properties of eskers resulting from warm-based glaciation on Mars-like substrates by leveraging a natural laboratory in Iceland.

A. M. Rutledge↗

DOE OSTI2023

Organic sulfur from source to sink in low‐sulfate Lake Superior

Abstract Organic sulfur plays a crucial role in the biogeochemistry of aquatic sediments, especially in low sulfate (< 500 μ M) environments like freshwater lakes and the Earth's early oceans. To better understand organic sulfur cycling in these systems, we followed organic sulfur in the sulfate‐poor (< 40 μ M) iron‐rich (30–80 μ M) sediments of Lake Superior from source to sink. We identified microbial populations with shotgun metagenomic sequencing and characterized geochemical species in porewater and solid phases. In anoxic sediments, we found an active sulfur cycle fueled primarily by oxidized organic sulfur. Sediment incubations indicated a microbial capacity to hydrolyze sulfonates, sulfate esters, and sulfonic acids to sulfate. Gene abundances for dissimilatory sulfate reduction ( dsrAB ) increased with depth and coincided with sulfide maxima. Despite these indicators of sulfide formation, sulfide concentrations remain low (< 40 nM) due to both pyritization and organic matter sulfurization. Immediately below the oxycline, pyrite accounted for 13% of total sedimentary sulfur. Both free and intact lipids in this same interval accumulated disulfides, indicating rapid sulfurization even at low concentrations of sulfide. Our investigation revealed a new model of sulfur cycling in a low‐sulfate environment that likely extends to other modern lakes and possibly the ancient ocean, with organic sulfur both fueling sulfate reduction and consuming the resultant sulfide.

Phillips, Alexandra A.↗

DOE OSTI2023

Natural attenuation of uranium in a fluvial Wetland: Importance of hydrology and speciation

A nuclear fuel fabrication facility released 43,500 kg of uranium into a riparian wetland located on the Savannah River Site between 1955 and 1988. Studies were undertaken to evaluate hydrological and geochemical processes influencing uranium accumulation in the wetland. Gamma-radiation-mapping surveys were conducted by systematically walking over the contaminated wetland with backpacks equipped with global positioning systems and NaI gamma detectors. Based on maps compiled from >700,000 gamma spectra and eight sediment uranium depth profiles, it was determined that 94% of the released uranium remained in the wetland. The uranium in the wetland is concentrated in five multi-hectare areas along the stream, accounting for ~11% of the land area adjacent to the stream. While land type (upland or wetland) and topography provided a reasonable first approximation of where much of the uranium was deposited, hydrological watershed modeling revealed that the stream velocity was especially slow through many of the hot spots. Here, using autoradiography combined with SEM/EDX measurements of contaminated sediments, surprisingly few hot particles were detected. Instead, uranium was evenly distributed throughout the sampled sediment, suggesting that dissolved uranium had bound to sediment particles that became suspended and later deposited in low energy (low flow velocity) portions of the stream. EXAFS suggested that U atoms were present as individual ions in disordered complexes within the sediment. Furthermore, linear combination analyses suggested that the predominant component of the U(VI) was adsorbed to sediment minerals (~70%) and a minor component (~30%) was associated with organic matter phases. Furthermore, these studies show that wetlands can be extraordinarily effective at binding and retaining uranium, thereby providing a natural barrier to the transport of uranium out of a watershed. However, significant anthropogenic or climatic changes to wetlands, such as those associated with flooding, forest fires, or land use, may disrupt the complex hydrological and biogeochemical balance necessary to maintain long-term immobilization of uranium.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS2001

Unambiguous Spectral Evidence for High- (and Low-) Calcium Pyroxene in Asteroids and Meteorites

Spectroscopy remains a powerful tool for inferring the modal mineralogy and mafic mineral composition of asteroid surfaces. Since similar measurements can be made on meteorite samples, spectroscopy can help link the two populations and add spatial and geologic context to detailed geochemical knowledge derived from meteorite samples. For example, analysis of the recent NEAR-Shoemaker mission to Eros include detailed study of NIS spectra to assess the affinity of Eros to ordinary chondrites. As discussed in these studies, pyroxene (PYX) and olivine (OLV) absorption are readily detectable in the spectra. Furthermore, subtleties in band parameters (position vs. area) suggest the presence of both low- and high-calcium pyroxene (LCP and HCP), as expected from the petrology of ordinary chondrites. However unambiguous identification and detailed compositional inferences for both LCP and HCP (and OLV) are difficult from band parameters analysis. In this study, we examine spectra of S-asteroids and meteorites with the Modified Gaussian Model (MGM), an absorption band model, to explore the role of HCP in these silicate-rich spectra.

Sunshine, J. M.↗

NASA NTRS1978

Residual glasses and melt inclusions in basalts from DSDP Legs 45 and 46 - Evidence for magma mixing

Microprobe analyses of natural glasses in basalts recovered by Legs 45 and 46 of the Deep Sea Drilling Project are reported and interpreted in the context of other geochemical, petrographic and experimental data on the same rocks (Rhodes et al., 1978). Residual glass compositions in the moderately evolved aphyritic and abundantly phyric basalts within each site indicate that none of the units is related to any other or to a common parent by simple fractional crystallization. The compositional trends, extensive disequilibrium textures in the plagioclase phenocrysts and the presence in evolved lavas of refractory plagioclase and olivine phenocrysts bearing primitive melt inclusions provide evidence that magma mixing had a major role in the genesis of the Leg 45 and 46 basalts. The magma parental to these basalts was most likely characterized by high Mg/(Mg + Fe/+2/), CaO/Al2O3, CaO/Na2O and low lithophile concentrations. A mixing model involving incremental enrichment of magmaphile elements by repeated episodes of mixing of relatively primitive and moderately evolved magmas, followed by a small amount of fractionation is consistent with the characteristics of the basalts studied.

Dungan, M. A.↗

DOE OSTI2024

The application of synthetic antibacterial minerals to combat topical infections: exploring a mouse model of MRSA infection

Abstract The development of new antibiotics has stalled, and novel strategies are needed as we enter the age of antibiotic resistance. Certain naturally occurring clays have been shown to be effective in killing antibiotic resistant bacteria. However, these natural clays are too variable to be used in clinical settings. Our study shows that synthetic antibacterial minerals exhibit potent antibacterial activity against topical MRSA infections and increase the rate of wound closure relative to controls. The antibacterial minerals maintain a redox cycle between Fe 2+ /Fe 3+ and the surfaces of pyrite minerals, which act as a semiconductor and produce reactive oxygen species (ROS), while smectite minerals act as a cation exchange reservoir. Acidic conditions are maintained throughout the application of the hydrated minerals and can mitigate the alkaline pH conditions observed in chronic non-healing wounds. These results provide evidence for the strategy of ‘iron overload’ to combat antibiotic resistant infections through the maintained release of Fe 2+ and generation of ROS via distinct geochemical reactions that can break the chronic wound damage cycle.

58 GEOSCIENCES↗

DOE OSTI2025

Basin & Range Investigation for Developing Geothermal Energy

Hidden geothermal systems represent a potentially prolific energy resource that could support critical U.S. public and government energy priorities. Basin and Range Investigations for Developing Geothermal Energy (BRIDGE) addressed some the challenges associated with hidden system exploration by prioritizing cost-effective exploration early on through strategic workflow and informed decision-making that mitigates early risk and shifts resources to later exploration stages (e.g., drilling). Sandia National Laboratories partnered with U.S. Navy Geothermal Office, Geologic Geothermal Group, and independent consultants, with additional collaboration with U.S. Geological Survey and private industry. The primary tool of the BRIDGE project was to deploy a regional-scale airborne electromagnetic method to investigate the shallow resistivity structure in areas with high prospectivity. This was followed up at several prospects by a multidisciplinary exploration approach, including additional geologic, geophysical and geochemical studies. A central tenet to the BRIDGE methodology is that zones of low resistivity frequently occur over geothermal systems in the Basin and Range, and when paired with other data constraints, imaging these zones can enable discovery of these systems. In addition to exploring greenfield areas (i.e., Grover Point), the BRIDGE project also flew HTEM resistivity surveys over known geothermal systems including those with established power plants (Don A. Campbell and Salt Wells) and prospects that are known to the literature but remain undeveloped, at least in part, due to a lack of understanding on the location of their producible reservoirs. BRIDGE produced a comprehensive set of data from prospects identified in the Nevada Play Fairway Analysis along with conceptual models for top ranking prospects, wherein all of the observations are used to inform an interpreted model of the system. These models present a range of possible system parameters such as temperature and size, and they are further informed by system analogues in the Basin and Range province and elsewhere. The results of this work leave space for further exploration that may now occur at prospects ‘down the list’ rather than distribution exploration resources evenly across all prospects.

15 GEOTHERMAL ENERGY↗

NASA NTRS1986

Thematic mapper study of Alaskan ophiolites

The combinations of Thematic Mapper (TM) bands that best distinguish basalts of the Brooks Range ophiolites were determined. Geochemical analyses, including major, trace, and rare earth elements (REE), are being done in order to study the significance of TM spectral variations that were observed within some of the sampled rock units. An image of the topography of the western Brooks Range and Colville Basin was constructed. Elevation data for the rest of Northern Alaska are being acquired to expand the area covered by the topography image. Two balanced cross sections (one along the eastern margin, the other along the western margin of the Brooks Range) are being constructed, using the techniques of fault-bend and fault-propagation folding. These are being used to obtain regional shortening estimates for the Brooks Range in an attempt to constrain tectonic models for the evolution of Northern Alaska. The TM data are being used to confirm reconnaissance maps and to obtain structural data where no maps exist. Along with the TM data, digital topography, seismic reflection profiles, and magnetic and gravity surveys are examined to better understand the evolution of the Colville Basin, north of the Brooks Range.

Bird, J. M.↗