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At least 55 records · Page 3

Properties of the Hermean Regolith: New Optical Reflectance Spectra, Comparison with Lunar Anorthosites and Mineralogical Modelling - 5

We present new optical (0.4-0.65 micron) spectra of Mercury and lunar pure anorthosite locations, obtained quasi-simultaneously with the Nordic Optical Telescope (NOT) in 2002. A comparative study is performed with the model of Lucey et al. between iron-poor, mature, pure anorthosite (less than 90% plagioclase feldspar) Clementine spectra from the lunar farside and a combined 0.4-1.0 micron mercurian spectrum, obtained with the NOT, calculated for standard photometric geometry. Mercury is located at more extreme locations in the Lucey ratio-reflectance diagrams than any known lunar soil, specifically with respect to the extremely iron-poor mature anorthosites. Though quantitative prediction of FeO and TiO2 abundances cannot be made without a more generally applicable model, we find qualitatively that the abundances of both these oxides must be near zero for Mercury. We utilize the theory of Hapke, with realistic photometric parameters, to model laboratory spectra of matured mineral powders and lunar soils, and remotely sensed spectra of lunar anorthosites and Mercury. An important difference between fabricated and natural powders is the high value for the internal scattering parameter necessary to interpret the spectra for the former, and the requirement of rough and non-isotropically scattering surfaces in the modelling of the latter. The mature lunar anorthosite spectra were well modelled with binary mixtures of calcic feldspars and olivines, grain sizes of 25-30 micron and a concentration of submicroscopic metallic iron (SMFe) of 0.12-0.15% in grain coatings. The mercurian spectrum is not possible to interpret from terrestrial mineral powder spectra without introducing an average particle scattering function for the bulk soil that increases in backscattering efficiency with wavelength. The observed spectrum is somewhat better predicted with binary mixture models of feldspars and pyroxenes, that single-component regoliths consisting of either albite or diopside. Correct spectral reflectance values were predicted with a concentration of 0.1 wt% SMFe in coatings of 15-30 micron sized grains. Since reasonable cosmogonical formation scenarios for Mercury, or meteoritic infall, predict iron concentrations at least this high, we draw the conclusion that the average grain size of Mercury is about a factor of two smaller than for average returned lunar soil samples. The 0.6-2.5 micron spectrum of McCord and Clark is used to further limit the possible range of mineralogical composition of Mercury. It is found that an intimately mixed and matured 3 : 1 labradorite-to-enstatite regolith composition best matches both the optical and near-infrared spectra, yielding an abundance of approx. 1.2 wt% FeO and -approx. 0 wt% TiO2.

Warell, J.↗

Pathways for Energization of Ca in Mercury's Exosphere

We investigate the possible pathways to produce the extreme energy observed in the calcium exosphere of Mercury. Any mechanism must explain the facts that Ca in Mercury's exosphere is extremely hot, that it is seen almost exclusively on the dawnside of the planet, and that its content varies seasonally, not sporadically. Simple diatomic molecules or their clusters are considered, focusing on calcium oxides while acknowledging that Ca sulfides may also be the precursor molecules. We first discuss impact vaporization to justify the assumption that CaO and Ca-oxide clusters are expected from impacts on Mercury. Then we discuss processes by which the atomic Ca is energized to a 70,000 K gas. The processes considered are (1) electron-impact dissociation of CaO molecules, (2) spontaneous dissociation of Ca-bearing molecules following impact vaporization, (3) shock-induced dissociative ionization, (4) photodissociation and (5) sputtering. We conclude that electron-impact dissociation cannot produce the required abundance of Ca, and sputtering cannot reproduce the observed spatial and temporal variation that is measured. Spontaneous dissociation is unlikely to result in the high energy that is seen. Of the two remaining processes, shock induced dissociative ionization produces the required energy and comes close to producing the required abundance, but rates are highly dependent on the incoming velocity distribution of the impactors. Photodissociation probably can produce the required abundance of Ca, but simulations show that photodissociation cannot reproduce the observed spatial distribution.

Sulfides↗

Trace Metal Dynamics and Limitations on Biogeochemical Cycling in Wetland Soils and Hyporheic Zones

Biogeochemical cycling in subsurface aquatic systems is driven by anaerobic microbial processes that employ metalloenzymes. Pure culture studies reveal that low availability of trace metals may inhibit methanogenesis, mercury methylation, and reduction of N 2 O to N 2 during denitrification. However, whether such limitations occur in natural subsurface aquatic systems is currently unclear. This project sought to establish mechanistic links between trace metal availability and biogeochemical transformations in subsurface systems. Integrated field and laboratory studies of trace metal availability and biogeochemical processes were conducted in riparian wetlands in the Tims Branch watershed at the Savannah River Site, marsh wetlands at Argonne National Laboratory, and the streambed of East Fork Poplar Creek at Oak Ridge National Laboratory, with supplemental work with wetland soils from sites in Missouri and Florida.

54 ENVIRONMENTAL SCIENCES↗

High rate, high reliability Li/SO2 cells

The use of the lithium/sulfur dioxide system for aerospace applications is discussed. The high rate density in the system is compared to some primary systems: mercury zinc, silver zinc, and magnesium oxide. Estimates are provided of the storage life and shelf life of typical lithium sulfur batteries. The design of lithium cells is presented and criteria are given for improving the output of cells in order to achieve high rate and high reliability.

Chireau, R.↗

Experimental Investigation of Chromium Behavior During Mercury's Differentiation

Mercury is the most reduced terrestrial planet with the largest core/mantle size ratio and highest sulfur concentration on the surface. The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft data allowed mapping of Mercury's surface elemental composition. Recent chromium mapping suggests Mercury's surface has on average 800 parts per million Cr with the highest values in the High Magnesium Region. These new data can give clues about Mercury's internal structure and the redox conditions under which it differentiated. In the present study, we present experimental data on the distribution of Cr among metal, silicate and sulfide liquids. We then combine them with data from previous studies and a model of planetary differentiation to discuss Mercury's bulk composition and its oxidation state.

Boujibar, A.↗

Carbon Solubility in Silicon-Iron-Bearing Metals during Core Formation on Mercury

Recent results obtained from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft showed the surface of Mercury has high S abundances (approximately 4 wt%) and low Iron(II) Oxide abundances (less than 2 wt%). Based on these extreme values, the oxygen fugacity of Mercury's surface materials was estimated to be approximately 3 to 7 log(sub 10) units below the IW buffer (Delta IW-3 to Delta IW-7). This highly reducing nature of the planet has resulted in a large core and relatively thin mantle, extending to only approximately 420 km depth (corresponding to a core-mantle boundary pressure of approximately 4-7 GPa) within the planet. Furthermore, MESSENGER results have suggested the presence of carbon on the surface of the planet. Previous experimental results from have also suggested the possibility of a primary floatation crust on Mercury composed of graphite, produced after a global magma ocean event. With these exotic conditions of this compositional end-member planet, it begs the question, what is the core composition of Mercury? Although no definitive conclusion has been reached, previous studies have made advances towards answering this question. Riner et al. and Chen et al. looked at iron sulfide systems and implemented various crystallization and layered core scenarios to try and determine the composition and structure of Mercury's core. Malavergne et al. examined core crystallization scenarios in the presence of sulfur and silicon. Hauck et al. used the most recent geophysical constraints from the MESSENGER spacecraft to model the internal structure of Mercury, including the core, in a iron-sulfur-silicon system. More recently, Chabot et al. conducted a series of metal-silicate partitioning experiments in a iron-sulfur-silicon system. These results showed the core of Mercury has the potential to contain more than 15 wt% silicon. However, with the newest results from MESSENGER's low altitude campaign, carbon is another potential light element that could be incorporated into Mercury's core. The goal of this study is to determine the carbon concentration at graphite saturation in various silicon-iron bearing metals relevant to possible mercurian core compositions. Future experiments will include the addition of sulfur into these metals.

Vander Kaaden, Kathleen E.↗

Mercury: Evidence for anorthosite and basalt from mid-infrared (7.3-13.5 micrometers) spectroscopy

Spectroscopic observations (7.3-13.5 micrometers) of three locations on the surface of Mercury are reported. The observed spectral radiance emanated from equatorial and low altitude regions between 12 and 32 deg mercurian longitude on 8 December 1990, from the longitudinal region 22-44 deg on 10 December 1990, and from the longitudinal region 110-130 deg on 12 July 1992; all locations are primarily intercrater plains. Spectra indicate compositional differences among these three locations. The emissivity maximum, or Christiansen emission peak, occurs at 8.1 micrometers in the 8 December 1990 spectra, but at shorter wavelengths in the data of 10 December 1990 and 12 July 1992. Emission peaks near 8 micrometers indicate rocks of intermediate or mafic composition. Spectra from 22 to 44 deg longitude resemble spectra of terrestrial basalt and diorite with SiO2 content between 49 and 55%. The Christiansen feature in spectra from near 110-130 deg longitude strongly suggests the presence of plagioclase, in particular labradorite, while the overall spectrum resembles anorthosite. The spectra from all three locations on Mercury show distinct and recognizable features, the principal Christiansen emission peak being the most prominent, but they also contain features that we have not yet identified. The general indication from the spectra is that Mercury's surface consists of minerals more depleted in oxidized iron than those on the Moon. We also explore the theoretical and observational complexities of ground-based mid-infrared spectroscopy of airless bodies in general and Mercury in particular. A spectroscopic study of quartzite in both reflectance and emittance illustrates the practical, spectral validity of Kirchhoff's law.

Sprague, A. L.↗

Ascorbic Acid Stability and pH Testing to Support RWM-018 Pilot Scale Wellhead Treatment System Feasibility Determination

A multitude of groundwater remediation techniques for chlorinated volatile organic compounds (cVOCs) have been conducted at the A/M-Areas of the Savannah River Site (SRS). Historical in-situ chemical oxidation (ISCO) injections of potassium permanganate and sodium persulfate conducted in 2018 and 2020, have left residual oxidant concentrations in the A/M-Area groundwater system. ISCO events targeted dense non-aqueous phase liquids (DNAPLs) through the injection of strong oxidants within plume zones upgradient of current groundwater recovery wells RWM-008 and RWM-018. These residual oxidants could significantly impede the operation of the mercury removal system needed to meet National Pollutant Discharge Elimination System (NPDES) permit requirements for the ongoing pump-and-treat system that hydraulically controls potions of the A/M-Area plume. Effluent treated groundwater from this system is discharged to surface water at the receiving outfall of the M-1 Air Stripper. To prevent interference of the M-1 Air Stripper system by residual oxidants, groundwater recovery has been ceased at well RWM-018. Modeling of oxidant transport in A/M-Area from ISCO estimated that the potential oxidant load contributed by RWM-018 could be as high as 120 mg/L. It is also possible that oxidants may be contributed via pumping at well RWM-008 in the near future as residual oxidants within the aquifer migrate toward its zone of influence. Savannah River National Laboratory (SRNL) has conducted research to investigate potential pre-treatment chemicals to neutralize these residual oxidants, before reaching the M-1 Air Stripper, to allow for resumed groundwater recovery at RWM-018 and continued pumping at RWM-008. Deployment of ascorbic acid for neutralization of residual oxidants at RWM-018 (and possibly RWM-008) is recommended based on results from previous reductant testing (SRNL, 2021). For a maximum estimated oxidant load at RWM-0018, a well-head treatment system would need to dose about 400 gallons of ascorbic acid each month to ensure complete neutralization. A second system with additional reagent should also be considered for deployment at RWM-008.

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Review of Mercury Sequestration in Cementitious Waste Forms

Decontaminated salt solution from Tank 50 at the Savannah River Site (SRS) is known to contain dissolved mercury species which are present as hydroxides and oxides. These species are reported in analytical measurements as the organic cation [CH 3 Hg] + and the inorganic cation Hg 2+ . The salt solution is mixed with cementitious reagents, blast-furnace slag (BFS) and thermally beneficiated Class F fly ash in the Saltstone Processing Facility and pumped into engineered Saltstone Disposal Units, (SDUs), to produce a solidified waste form. The solidified waste form, saltstone, encapsulates and chemically stabilizes the mercury and other contaminants, sequestering them from release into the environment. With the discovery of methylmercury in the salt solution, testing was performed to determine the extent to which saltstone prepared with methylmercury (MeHg) retains mercury in the Toxicity Characteristic Leaching Procedure (TCLP). Results from this testing indicated that the amount of mercury extracted remained below the regulatory limit, and that the saltstone formulation with a greater proportion of BFS performed slightly better at retaining Hg in the solid.

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Complete Genome Sequence of Desulfobulbus oligotrophicus Prop6, an Anaerobic Deltabacterota Strain That Lacks Mercury Methylation Capability

Desulfobulbus oligotrophicus Prop6 is a sulfate-reducing, propionate-oxidizing Deltabacterota (formerly Deltaproteobacteria) strain from sewage sludge. Desulfobulbus species are found in anoxic environments, in animal microbiota, and some produce the neurotoxin methylmercury. The 3.1-Mbp D. oligotrophicus genome sequence enables studies of diverse environmental adaptations and the evolutionary genomics of mercury methylation mechanisms.

59 BASIC BIOLOGICAL SCIENCES↗

Year-round trace gas measurements in the central Arctic during the MOSAiC expedition

Despite the key role of the Arctic in the global Earth system, year-round in-situ atmospheric composition observations within the Arctic are sparse and mostly rely on measurements at ground-based coastal stations. Measurements of a suite of in-situ trace gases were performed in the central Arctic during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition. These observations give a comprehensive picture of year-round near-surface atmospheric abundances of key greenhouse and trace gases, i.e., carbon dioxide, methane, nitrous oxide, ozone, carbon monoxide, dimethylsulfide, sulfur dioxide, elemental mercury, and selected volatile organic compounds (VOCs). Redundancy in certain measurements supported continuity and permitted cross-evaluation and validation of the data. This paper gives an overview of the trace gas measurements conducted during MOSAiC and highlights the high quality of the monitoring activities. In addition, in the case of redundant measurements, merged datasets are provided and recommended for further use by the scientific community.

54 ENVIRONMENTAL SCIENCES↗

Materials Data on Nb6Hg(Br8O9)2 by Materials Project

Hg(NbO)6(O2)6(Br)16 crystallizes in the cubic Fd-3m space group. The structure is zero-dimensional and consists of sixteen hexaoxane molecules, one hundred and twenty-eight hydrobromic acid molecules, eight mercury molecules, and forty-eight niobium(ii) oxide molecules.

36 MATERIALS SCIENCE↗

A study of the deposition of carbide coatings on graphite fibers

The chemical vapor deposition of boron carbide and silicon carbide on graphite fibers to increase their electrical resistance was studied. Silicon carbide coatings were applied without degradation of the mechanical properties of the filaments. These coatings typically added 1000 ohms to the resistance of a filament as measured between two mercury pools. When SiC-coated filaments were oxidized by refluxing in boiling phosphoric acid, average resistance increased by an additional 1000 ohms; in addition resistance increases as high as 150 K ohms and breakdown voltages as high as 17 volts were noted. Data on boron carbide coatings indicated that such coatings would not be effective in increasing resistance, and would degrade the mechanical properties.

Suplinskas, R. J.↗

Panel Session 90: US DOE Mixed Waste: Proposals for Dealing with Problematic Waste Streams and Policy Changes

This panel focused on generation and management of low level and mixed low-level radioactive wastes, challenges for disposition, innovative solutions applied at DOE sites, and collaboration among sites to ensure that waste disposition pathways are understood. In addition, potential policy initiatives were discussed including depleted uranium, elemental mercury, and treatment of legacy mixed waste components. As part of the introduction, Theresa Kliczewski provided an overview of why this panel is relevant: problematic mixed waste streams still exist across the DOE cleanup complex. Theresa noted that the DOE EM Headquarters Office of Waste and Materials Management (EM-4.2), for which she is employed with, continues to work with the DOE cleanup sites on a path forward for these problematic mixed waste streams. As part of this effort, EM-4.2 requested that the Energy Facility Contractors Group (EFCOG) perform a review of all the DOE sites problematic mixed waste streams. Panelists with presentations: Challenging Waste Streams: Disposition of Depleted Uranium Oxide Conversion Product (Douglas Tonkay); EFCOG WMWG Challenging Waste Subgroup (Tammy Monday); Mercury Waste Challenges (John Wrapp); Legacy Large Mixed Waste Components (Kalli Shupe)

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