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Insights into the Martian Regolith from Martian Meteorite Northwest Africa 7034

Everything we know about sedimentary processes on Mars is gleaned from remote sensing observations. Here we report insights from meteorite Northwest Africa (NWA) 7034, which is a water-rich martian regolith breccia that hosts both igneous and sedimentary clasts. The sedimentary clasts in NWA 7034 are poorly-sorted clastic siltstones that we refer to as protobreccia clasts. These protobreccia clasts record aqueous alteration process that occurred prior to breccia formation. The aqueous alteration appears to have occurred at relatively low Eh, high pH conditions based on the co-precipitation of pyrite and magnetite, and the concomitant loss of SiO2 from the system. To determine the origin of the NWA 7034 breccia, we examined the textures and grain-shape characteristics of NWA 7034 clasts. The shapes of the clasts are consistent with rock fragmentation in the absence of transport. Coupled with the clast size distribution, we interpret the protolith of NWA 7034 to have been deposited by atmospheric rainout resulting from pyroclastic eruptions and/or asteroid impacts. Cross-cutting and inclusion relationships and U-Pb data from zircon, baddelleyite, and apatite indicate NWA 7034 lithification occurred at 1.4-1.5 Ga, during a short-lived hydrothermal event at 600-700 C that was texturally imprinted upon the submicron groundmass. The hydrothermal event caused Pb-loss from apatite and U-rich metamict zircons, and it caused partial transformation of pyrite to submicron mixtures of magnetite and maghemite, indicating the fluid had higher Eh than the fluid that caused pyrite-magnetite precipitation in the protobreccia clasts. NWA 7034 also hosts ancient 4.4 Ga crustal materials in the form of baddelleyites and zircons, providing up to a 2.9 Ga record of martian geologic history. This work demonstrates the incredible value of sedimentary basins as scientific targets for Mars sample return missions, but it also highlights the importance of targeting samples that have not been overprinted by metamorphic processes, which is the case for NWA 7034.

McCubbin, Francis M.↗

Acidic Fluids Across Mars: Detections of Magnesium-Nickel Sulfates

Calcium, magnesium and ferric iron sulfates have been detected by the instrument suites on the Mars rovers. A subset of the magnesium sulfates show clear associations with nickel. These associations indicate Ni(2+) co-precipitation with or substitution for Mg(2+) from sulfate-saturated solutions. Nickel is ex-tracted from primary rocks almost exclusively at pH values less than 6, constraining the formation of these Mg-Ni sulfates to mildly to strongly acidic conditions. There is clear evidence for aqueous alteration at the rim of Endeavour Crater (Meridiani Planum), in the Murray formation mudstone (Gale Crater), and near Home Plate (Gusev Crater). The discovery of Mg-Ni sulfates at these locations indicates a history of fluid-rock interactions at low pH.

Yen, A. S.↗

Effect of Ni2+, Zn2+, and Co2+ on green rust transformation to magnetite

In this study, we investigated Ni2+, Zn2+, and Co2+ mineralogical incorporation and its effect on green rust transformation to magnetite. Mineral transformation experiments were conducted by heating green rust suspensions at 85 °C in the presence of Ni2+, Zn2+, or Co2+ under strict anoxic conditions. Transmission electron microscopy and powder X-ray diffraction showed the conversion of hexagonal green rust platelets to fine grained cubic magnetite crystals. The addition of Ni2+, Zn2+, and Co2+ resulted in faster rates of mineral transformation. The conversion of green rust to magnetite was concurrent to significant increases in metal uptake, demonstrating a strong affinity for metal sorption/ co-precipitation by magnetite. Dissolution ratio curves showed that Ni2+, Zn2+, and Co2+ cations were incorporated into the mineral structure during magnetite crystal growth. The results indicate that the transformation of green rust to magnetite is accelerated by metal impurities, and that magnetite is a highly effective scavenger of trace metals during mineral transformation. The implications for using diagenetic magnetite from green rust precursors as paleoproxies of Precambrian ocean chemistry are discussed.

Hydrosulfate green rust↗

Cathode materials for lithium ion batteries

A process of forming a coated cathode active material include preparing a cathode material precursor by co-precipitation; coating the cathode material precursor with an electrochemically inert coating material precursor by precipitation to form a coated cathode material precursor; lithiating the coated cathode material precursor with a lithium source material to form a lithiated coated cathode material precursor; and sintering the lithiated coated cathode material precursor to form a cathode active material coated with an electrochemically inert material.

Wu, Huiming↗

Uranium Partitioning upon Ammonia Gas Treatment on Phyllosilicate Minerals

In the past, > 200,000 kg of U was released to the Hanford Site vadose zone from disposal and leakage of waste byproducts from plutonium production during World War II and the Cold War (Zachara et al., 2007). U is highly mobile due to the presence of carbonates and oxidizing conditions, with K{sub d} of 0.1 - 8 mL/g at the site (Zachara et al., 2007; Szecsody et al., 2013; Serne et al., 2008). NH{sub 3} (gas) injection is being investigated as a remediation technique as it is an in situ method that will not introduce additional liquid that could drive contaminants deeper into vadose zone towards groundwater. Objectives: To understand the impact of alkaline injection on geochemical processes in the Hanford Site vadose zone, including: 1)Long-term fate of uranium (U); 2)Dissolution and re-precipitation of secondary minerals. Apparent K{sub d}'s increase significantly with NH{sub 3} gas treatment, especially for six-month aging. - K{sub d} decreases after aeration, primarily due to U desorption at lower pH. U removal is still significantly greater than natural conditions (K{sub d} < 8 vs. > 100 mL/g). - Three-day aeration has higher loading than six-month after ammonia gas treatment and aeration. However, significantly greater desorption of U occurs with aeration in the six-month aged sample potentially due to transformation into different, more soluble solid phases with longer term aging. - U removal is primarily due to (1) co-precipitation of U with secondary minerals and (2) adsorption to minerals' surface, although further research is required to identify dominant mechanisms. Future experiments will focus on garnering a better understanding of the solid phase U speciation. Solids will be characterized using SEM-EDS, EMPA, XPS, XAFS, and TEM to better understand the effects of basic treatments on initial minerals and formation of secondary precipitates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Rapid Sequential Separation Method for Determination of Actinides and TENORM in Fracking Wastes - 20223

With recent advances in unconventional drilling technology in the US and around the world, the risks of environmental contamination and exposure due to technologically enhanced naturally occurring radioactive materials (TENORM) from fracking wastes have also surfaced. Although the Permian Basin (southeastern New Mexico, western Texas) has long been a modest producer of oil, the advent of fracking technology a decade ago turned it into hot property for producers. A 2018 assessment of undiscovered, technically recoverable continuous oil and gas resources by the U.S. Geological Survey estimates an average 46.3 billion barrels of oil and 281 trillion cubic feet of gas. This is likely to increase the use of unconventional drilling and TENORM generation. TENORM concentrations in oil and gas exploration and production waste can be several hundred to several thousand times higher than background TENORM concentrations. Both the thorium and uranium decay chains contribute to airborne radionuclides arising from the radon gas escaping the ground and subsequently decaying as airborne particulates. Additionally, radon decay products {sup 210}Pb and {sup 210}Po can build up in scale on the internal surfaces of oil and gas handling pipes and in sludge in refineries, becoming potential inhalation and ingestion hazards for workers. Furthermore, southeastern NM is also home to world's only licensed and operating transuranic nuclear waste repository, the DoE's Waste Isolation Pilot Plant (WIPP). Plutonium isotopes ({sup 239+240}Pu) and {sup 241}Am, are expected to account for more than 99% of the total radioactivity scheduled for disposal in the WIPP repository. Thus, an improved understanding of the environmental fate and transport of TENORM, liberated by unconventional drilling, is essential to assess how best to protect individuals and the environment. In this context, accurate measurement of TENORM and actinides in environmental and biological samples is essential. In this presentation, a new sequential method for the separation and pre-concentration of actinides (Pu, Am, Np) and TENORM (Po, U and Th) derived from oil and gas exploration is proposed. The TEVA method involves a rapid co-precipitation step to remove matrix interferences from the samples, followed by plutonium oxidation state adjustment to Pu (IV) and an incubation period of ∼ 1 hour at 50-60 deg. C to allow the resultant Po (II) to oxidize into Po(IV). The polonium, neptunium, thorium and plutonium are then separated on a TEVA column, while americium and uranium are separated on a TRU column. After separation, the alpha counting source was prepared by micro-precipitation with copper sulfide (CuS) for polonium and neodymium fluoride (NdF{sub 3}) for actinides. The efficiency and reliability of the procedures were tested by analyzing filter, drinking water and frack sand samples. The method is simple, robust and can be performed quickly with excellent removal of interferences, high chemical recovery and very good alpha peak resolution. (authors)

07 ISOTOPE AND RADIATION SOURCES↗

Precipitation-site competition in duplex stainless steels: Cu clusters vs spinodal decomposition interfaces as nucleation sites during thermal aging

Competing microstructural evolution mechanisms can exist simultaneously when duplex stainless steels are operating for several decades in a high temperature service environment. Such competition between different microstructural evolution pathways can be difficult to ascertain using simple model alloy systems necessitating detailed structural and compositional analysis of phase transformation mechanisms in complex alloys Thus, in this study duplex stainless steels with complex but well understood chemistries were used to investigate the relative importance of different heterogeneous nucleation sites – specifically spinodal decomposition and Cu clustering – on precipitation of Ni-Si-Mn particles during long term thermal aging. Precipitation of Ni-Si-Mn particles in duplex stainless steels and ferritic steels during thermal aging and irradiation is known to have profound effect on mechanical properties. Using duplex stainless steels with custom modified compositions along with atom probe tomography characterization and first-passage kinetic Monte Carlo (FPKMC) simulations it is revealed that while the interface between Cr and Fe formed during spinodal decomposition can be a pathway for diffusion of Ni, Si, Mn, and Cu, it is not a site that encourages precipitation of Ni-Si-Mn rich particles. Instead, the presence of a higher concentration of Cu in these steels leads to formation of small Cu clusters with high energy interfaces that act as nucleation sites for Ni-Si-Mn particles because of its strong interaction particularly with Ni increasing the chemical driving force for precipitation. These results will help inform predictive models for the use of duplex stainless steels and other precipitation-hardened alloys for extended operation at high temperatures.

Duplex stainless steel, Thermal aging, Precipitati↗