Thermal and Evolved Gas Analysis of Hydromagnesite and Nesquehonite: Implications for Remote Thermal Analysis on Mars
Here we present the thermal and evolved gas analyses for hydromagnesite and nesquehonite under reduced pressure.
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Here we present the thermal and evolved gas analyses for hydromagnesite and nesquehonite under reduced pressure.
Abuse testing is useful for informing the risks of different battery chemistries but has been limited to larger formats. This paper conducted thermal abuse tests at the smaller coin cell level to determine its relevance in specifying vent gas flammability and toxicity. A nitrogen purge carried the evolved gases into a parallel Fourier-transform infrared spectrometer (FTIR) and a mass spectrometer (MS) downstream of the tube furnace. The experimental system was validated by comparing evolved gas data for single components between the tube furnace system and a thermogravimetric analysis (TGA) instrument. Multiple samples were tested during validation, including CaCO3, electrolyte, delithiated NMC 811 cathode, and lithiated graphite anode. Temperature-resolved gas evolution of HF, CO2, CO, H2, and hydrocarbons from isolated components helped to characterize the emission sources. A previously unreported H2 generation mechanism was found. It was shown that the reduced NMC cathode acts as a catalyst to crack polypropylene-decomposed hydrocarbons into H2 at around 450 degrees C. It was also shown, while studying LiPF6 thermal decomposition, that using the tube furnace with a coin cell casing as the sample holder has some advantages for evolved-gas analysis of environmentally sensitive samples relative to testing in TGA instruments. After validation with single components, a fully charged NMC 811 coin cell was failed in the tube furnace. The measured evolved gases were found to be a combination of the species measured from the single component tests. H2 formation related to the reduced cathode was found to have greater abundance than H2 formed from the anode. Hydrogen fluoride emission factors and diethyl carbonate conversion emission factors assist in understanding the gaseous hazards for larger format cells.
The 2011 Arctic Mars Analog Svalbard Expedition (AMASE) investigated several geologic settings on Svalbard, using methodologies and techniques being developed or considered for future Mars missions, such as the Mars Science Laboratory (MSL). The Sample Analysis at Mars (SAM) instrument suite on MSL consists of a quadrupole mass spectrometer (QMS), a gas chromatograph (GC), and a tunable laser spectrometer (TLS), which analyze gases created by pyrolysis of samples. During AMASE, a Hiden Evolved Gas Analysis-Mass Spectrometer (EGA-MS) system represented the EGA-QMS capability of SAM. Another MSL instrument, CheMin, will use x-ray diffraction (XRD) and x-ray fluorescence (XRF) to perform quantitative mineralogical characterization of samples. Field-portable versions of CheMin were used during AMASE. AMASE 2011 sites spanned a range of environments relevant to understanding martian surface materials, processes and habitability. They included the basaltic Sverrefjell volcano, which hosts carbonate globules, cements and coatings, carbonate and sulfate units at Colletth0gda, Devonian sandstone redbeds in Bockfjorden, altered basaltic lava delta deposits at Mt. Scott Keltie, and altered dolerites and volcanics at Botniahalvoya. Here we focus on SAM-like EGA-MS of a subset of the samples, with mineralogy comparisons to CheMin team results. The results allow insight into sample organic content as well as some constraints on sample mineralogy.
The 2010 Arctic Mars Analog Svalbard Expedition (AMASE) investigated two geologic settings using methodologies and techniques being developed or considered for future Mars missions, such as the Mars Science Laboratory (MSL), ExoMars, and Mars Sample Return. The Sample Analysis at Mars (SAM) [1] instrument suite, which will be on MSL, consists of a quadrupole mass spectrometer (QMS), a gas chromatograph (GC), and a tunable laser mass spectrometer (TLS); all will be applied to analyze gases created by pyrolysis of samples. During AMASE, a Hiden Evolved Gas Analysis-Mass Spectrometer (EGA-MS) system represented the EGA-MS capability of SAM. Another MSL instrument, CheMin, will use x-ray diffraction (XRD) and x-ray fluorescence (XRF) to perform quantitative mineralogical characterization of samples [e.g., 2]. Field-portable versions of CheMin were used during AMASE. AMASE 2010 focused on two sites that represented biotic and abiotic analogs. The abiotic site was the basaltic Sigurdfjell vent complex, which contains Mars-analog carbonate cements including carbonate globules which are excellent analogs for the globules in the ALH84001 martian meteorite [e.g., 3, 4]. The biotic site was the Knorringfjell fossil methane seep, which featured carbonates precipitated in a methane-supported chemosynthetic community [5]. This contribution focuses on EGA-MS analyses of samples from each site, with mineralogy comparisons to CheMin team results. The results give insight into organic content and organic-mineral associations, as well as some constraints on the minerals present.
Volatile-bearing minerals (e.g., Fe-oxyhydroxides, phyllosilicates, carbonates and sulfates) may be important phases on the surface of Mars. In order to characterize these phases the Thermal and Evolved Gas Analyzer (TEGA) flying on the Mars'98 lander will perform analyses on surface samples from Mars. Hydromagnesite [Mg5(CO3)4(OH)2.4H2O] is considered a good standard mineral to examine as a Mars soil analog component because it evolves both H2O and CO2 at temperatures between 0 and 600 C. Our aim here is to interpret the DSC signature of hydromagnesite under ambient pressure and 20 sccm N2 flow in the range 25 to 600 C. The DSC curve for hydromagnesite under the above conditions consists of three endothermic peaks at temperatures 296, 426, and 548 and one sharp exotherm at 511 C. X-ray analysis of the sample at different stop temperatures suggested that the exotherm corresponded with the formation of crystalline magnesite. The first endotherm was due to dehydration of hydromagnesite, and then the second one was due to the decomposition of carbonate, immediately followed by the formation of magnesite (exotherm) and its decomposition to periclase (last endotherm). Evolution of water and CO2 were consistent with the observed enthalpy changes. A library of such DSC-evolved gas curves for putative Martian minerals are currently being acquired in order to facilitate the interpretation of results obtained by a robotic lander.
Perchlorate salts were discovered in the soils around the Phoenix landing site on the northern plains of Mars [1]. Perchlorate was detected by an ion selective electrode that is part of the MECA Wet Chemistry Laboratory (WCL). The discovery of a mass 32 fragment (likely 02) by the Thermal and Evolved-Gas Analyzer (TEGA) provided additional confirmation of a strong oxidizer in the soils around the landing site. The purpose of this paper is to evaluate the thermal and evolved gas behavior of perchlorate salts using TEGA-like laboratory testbed instruments. TEGA ovens were fabricated from high purity Ni. Hence, an additional objective of this paper is to determine the effects that Ni might have on the evolved gas behavior of perchlorate salts.
The Sample Analysis at Mars (SAM) instrument suite on board the Mars Science Laboratory (MSL) recently ran four samples from an aeolian bedform named Rocknest. Rocknest was selected as the source of the first samples analyzed because it is representative of both windblown material in Gale crater as well as the globally-distributed dust. The four samples analyzed by SAM were portioned from the fifth scoop at this location. The material delivered to SAM passed through a 150 m sieve and should have been well mixed during the sample acquisition/ preparation/handoff process. Rocknest samples were heated to ~835 C at a 35 C/minute ramp rate with a He carrier gas flow rate of ~1.5 standard cubic centimeters per minute and at an oven pressure of ~30 mbar. Evolved gases were detected by a quadrupole mass spectrometer (QMS).
The Sample Analysis at Mars (SAM) instrument suite on board the Mars Science Laboratory (MSL) recently ran four samples from an aeolian bedform named Rocknest. SAM detected the evolution of H2O, CO2, O2, and SO2, indicative of the presence of multiple volatile bearing species (Fig 1). The Rocknest bedform is a windblown deposit selected as representative of both the windblown material in Gale crater as well as the globally-distributed martian dust. Four samples of Rocknest material were analyzed by SAM, all from the fifth scoop taken at this location. The material delivered to SAM passed through a 150 m sieve and is assumed to have been well mixed during the sample acquisition/preparation/handoff process. SAM heated the Rocknest samples to approx.835 C at a ramp rate of 35 C/min with a He carrier gas flow rate of apprx.1.5 standard cubic centimeters per minute and at an oven pressure of ~30 mbar [1]. Evolved gases were detected by a quadrupole mass spectrometer (QMS). This abstract presents the molar abundances of H2O, CO2, O2, and SO2 as well as their concentration in rocknest samples using an estimated sample mass.
Decades of space exploration have shown that three to four billion-year old surface environments on Mars may have been habitable. Ancient surface environments which resemble paleosols (buried sedimentary deposits which formed from subaerial weathering) on Mars have recently been named a high-priority target for biosignature investigation and Mars Sample Return because paleosol mineralogy records valuable information about past climates, and because Archean (~2.6 Ga) paleosols from Earth preserve some of the oldest biosignatures of life on land. However, there has been little effort to characterize terrestrial paleosols with Mars-like mineralogy using instruments analogous to those on current and future missions to Mars, which is imperative for understanding if putative paleosols on Mars should be targeted for future exploration. The objectives of this study were to perform the first comprehensive analysis of Mars-analog paleosols with Mars flight-analog instrumentation and to determine if organic carbon in these paleosols is detectable in the presence of a perchlorate salt.
Reductants, such as sucrose, are added to nuclear waste melter feeds containing high fractions of nitrates and nitrites to reduce excessive foaming during feed-to-glass conversion and to decrease sulfate segregation and increase technetium retention. The sucrose effect on foaming and melting reactions during the conversion was examined using the feed volume expansion, thermogravimetric analysis, evolved gas analysis, X-ray diffraction, and scanning electron microscopy with energy dispersive X-ray spectrometry. Different sucrose additions were used to vary the carbon to nitrogen (C/N) ratio in the melter feed. As C/N ratio increased, the extent of foaming decreased and N2/NO ratio increased in the gas phase evolved. Significant foam suppression, rapid gas release at approximately 250°C, and reduction of transition metal oxides were observed at C/N > 1.1.
Ancient aquatic environments in Yellowknife Bay, Gale crater, Mars, could create favorable conditions for adsorption of chlorine compounds (perchlorate and chloride) on Fe (III) (hydr)oxides present in the Sheepbed mudstone, such as akaganeite and ferrihydrite. In this work, 5.2 mM ClO4− and 1.7 to 12 mM Cl− were adsorbed onto ferrihydrite and 5.2 mM ClO4− was adsorbed onto akaganeite at ultraacidic (pH 2–2.5), acidic (pH 3.8–4.5), and near‐neutral (pH 6.2–7.7) pH. Samples were characterized by evolved gas analysis and compared to the data collected for the Cumberland sample from the Sheepbed mudstone. Evolved gas analysis showed that ferrihydrite with 0.5–1 wt.% ClO4− adsorbed under ultraacidic and acidic conditions had a well‐resolved O2 peak at 306 °C due to the thermal decomposition of adsorbed ClO4−. All akaganeite samples with 0.5 wt.% adsorbed ClO4− had a weak peak at 312 °C tentatively assigned to decomposing perchlorate. Evolved gas analysis demonstrated that 0.5–2 wt.% Cl− adsorbed on ferrihydrite at ultraacidic and acidic pH was the main contributor to HCl evolved at >470 °C. Comparison with martian observations indicated that the temperature of the O2 peak originating from ClO4− adsorbed on ferrihydrite matched well with the thermal evolution of O2 from the Cumberland. Evolved HCl originating from Cl− adsorbed on ferrihydrite was within the temperature range of the high‐temperature HCl release from Cumberland (~770 °C). These observations suggest that ferrihydrite containing adsorbed ClO4− and Cl− could exist in the mudstone. Experimental results are consistent with adsorption at acidic pH < 4 environments through postdepositional water‐rock interactions of ferrihydrite with acid‐sulfate groundwater containing dissolved chloride and perchlorate.
Primitive carbonaceous asteroids are the target bodies for the JAXA Hayabusa2 mission to Ryugu and the NASA OSIRIS-REx mission to Bennu. Both asteroids share spectral characteristics of CI/CM type carbonaceous chondrites. Ryugu, in particular, appears to have undergone thermal processing that has modified its spectral properties. The nature and extent of space weathering processes on the surfaces of Bennu and Ryugu are under active investigation using remote sensing data from the missions [4] and through laboratory studies on analog materials. The analog studies are needed in order to understand the mineralogical and chemical changes that occur in space weathered samples that give rise to the observed optical effects measured by remote-sensing and to prepare for the analysis of returned samples. The space weathering effects of micrometeorite impact and solar wind irradiation on primitive carbonaceous chondrites have been simulated by analog studies on the Murchison CM2 chondrite. We performed a coordinated mineralogical, chemical and spectroscopic study to examine in detail the effects of thermal metamorphism on Murchison samples as an analog to processes that may have occurred on Ryugu. The bulk measurements including X-ray diffraction (XRD), Mössbauer spectroscopy, UV-VIS-NIR spectroscopy, thermogravimetric analysis, and evolved gas analysis are reported in a companion paper. Here we report on our preliminary nanoscale mineralogical and chemical analyses of pre- and post-heated Murchison samples using multiple electron beam techniques to understand how the mineralogical, chemical, and physical characteristics of carbonaceous chondrites change with increasing thermal effects.
A new simulant of the lunar highlands regolith, NUW-LHT-5M, was designed by NASA and manufactured by Washington Mills. The simulant was based on Apollo 16 data and is a member of the NU-LHT-series. NASA’s Marshall Space Flight Center and Johnson Space Center have already purchased 3 metric tons of the simulant for advanced engineering work. In support of engineering uses of the simulant, we provided measurements of the simulant including: mineral abundance and composition, liberation, X-ray fluorescence (XRF), ferrous iron, carbon, sulfur, 60 element inductively coupled plasma (ICP), loss on ignition, particle size, both 2D and 3D particle shape, specific surface area, shear, cohesion, internal friction, helium pycnometry, minimum index density, tap density, magnetic susceptibility, cryogenic and high temperature permittivity, visible and near-infrared (VNIR) and middle infra-red spectroscopy (MIR), differential scanning calorimetry (DSC), viscosity, thermal diffusivity, thermal conductivity, thermal gravimetric analysis (TGA), evolved gas analysis (EGA), and spark sintering. For the crystalline components the design of the simulant called for two rocks from the Stillwater Complex, Montana: 17.6 wt% norite, 37.7% anorthosite, and 4.7 wt% olivine from an unspecified commercial source. The other 40% of the simulant was a high calcium (An100), vesicular glass that Washington Mills made specifically for the simulant. Fabrication and quality control processes for both the glass and the simulant are described. Importantly, most of the graphs and tables presented herein provide values for both the new simulant and data for the older NASA mare simulant, JSC-1A. Finally, we discussed the current limitations of NUW-LT-5M and most other lunar regolith simulants to replicate the lunar material.
The search for reduced carbon has been a major focus of past and present missions to Mars. Thermal evolved gas analysis was used by the Viking and Phoenix landers and is currently in use by the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) to characterize volatiles evolved from solid samples, including those associated with reduced organic species. SAM has the additional capability to perform a combustion experiment, in which a sample of Mars regolith is heated in the presence of oxygen and the composition of the evolved gases is measured using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS) [1]. Organics detection on the Martian surface has been complicated by oxidation and destruction during heating by soil oxidants [2], including oxychlorine compounds, and terrestrial organics in the SAM background contributed by one of the SAM wet chemistry reagents MTBSTFA (N-Methyl-N-tertbutyldimethylsilyl- trifluoroacetamide) [3,4]. Thermal Evolved Gas Analysis (TEGA) results from Phoenix show a mid temperature CO2 release between 400 C - 680 C speculated to be carbonate, CO2 adsorbed to grains, or combustion of organics by soil oxidants [5]. Low temperature CO2 evolutions (approx. 200 C - 400 C) were also present at all three sites in Gale Crater where SAM Evolved Gas Analysis (EGA) was performed, and potential sources include combustion of terrestrial organics from SAM, as well as combustion and/or decarboxylation either indigenous martian or exogenous organic carbon [4,6]. By performing an experiment to intentionally combust all reduced materials in the sample, we hope to compare the bulk abundance of CO2 and other oxidized species evolved by combustion to that evolved during an EGA experiment to estimate how much CO2 could be contributed by reduced carbon sources. In addition, C, O, and H isotopic compositions of CO2 and H2O measured by TLS can contribute information regarding the potential sources of these volatiles.
Neptunium oxalate (Np(C 2 O 4 ) 2 ·6H 2 O) is a historically relevant solid phase used in nuclear processing as a precursor for neptunium dioxide (NpO 2 ). Although Np oxalate has been synthesized and used for NpO 2 production for decades, the thermal decomposition mechanism of this phase remains poorly understood and has not been evaluated in over 30 years. Conflicting reports in historical literature suggest either a direct conversion from anhydrous oxalate to NpO 2 or a decomposition that includes the formation of Np carbonate or oxidized Np intermediate phases. In this work, we reexamine the decomposition pathway of Np(C 2 O 4 ) 2 ·6H 2 O using thermal analysis coupled with evolved gas analysis and temperature-dependent Raman spectroscopy to elucidate decomposition mechanisms and intermediate phases using modern analytical techniques. Thermal analysis revealed a three-stage decomposition process, including dehydration below 200 °C, oxalate breakdown between 170 and 370 °C, and NpO 2 formation by 500 °C. However, an unidentified plateau in the thermal data was observed during measurements. Raman spectroscopy confirmed the stages of decomposition, and in the analysis of potential intermediate phases, no carbonate phases or Np 2 O 5 were identified. Raman data suggest that residual oxalate or nonstoichiometric oxide are present during decomposition before pure NpO 2 is formed. These findings clarify aspects of the Np oxalate decomposition mechanism and address longstanding discrepancies in the literature, with a specific focus on Np-specific materials chemistry.
The capabilities of the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) to detect trace amounts of organic carbon compounds are unprecedented, and MSL may be the first mission to reveal the presence of organic carbon on Mars. The search for reduced organic carbon on Mars is inextricably tied to: a) the preservation potential of the environment from which we take a solid sample, and b) the evolved gas analysis (EGA) techniques used by SAM to release volatiles from this solid sample. Several prospective targets have been identified for sample analysis at Gale Crater. Stratigraphic sequences of phyllosilicates and sulfates at Gale are thought to represent a period of global climate transition from a moderate pH lacustrine environment to an evaporitic environment, both of which could sequester organic carbon (Thomson et al. 2011). The sediment mound in Gale Crater contains a range of lithologies suggesting changes in redox conditions, and evidence of both lacustrine and fluvial depositional processes, which may have transported organic carbon from the layer in which it formed and resulted in its preservation elsewhere within the crater (Anderson and Bell, 2010). Inverted channel fills suggest erosion resistant material that could serve to preserve organics originally deposited in a low energy aqueous environment. The lithology sampled will affect not only the preservation of organics, but also our ability to detect organics during our evolved gas analysis, based on the sample matrix. For example, reduced organics may be trapped in the mineral structure, and thermal evolution of these organics will occur during thermal decomposition of the host mineral. If organics are occluded in minerals that have very high thermal decomposition temperatures, they may be, in effect, "too well preserved," and difficult to detect during EGA. Alternatively, the possible presence of perchlorate, or other strong oxidants in surface regolith, may result in destruction of structural information identifying organic molecules before reaching the QMS on SAM via oxidation to C02 during heating. If this is the case, the stable carbon isotopic composition (delta 13C) of the C02 evolved and measured by the Tunable Laser Spectrometer (TLS) on SAM may help identify the presence of organics. On Earth, biological activity can cause large fractionations of 13C/12C, which can preserved in sedimentary deposits and distinguish the organic products of biotic processes from inorganic atmospheric and geological reservoirs. It is plausible that similar fractionations could occur on Mars and be preserved in reduced organic matter in sediments. Bulk delta 13C measurements alone may not reveal a signature of trace organic carbon that may be present along with inorganic carbon. If both organic and inorganic carbon compounds are present, it may be possible to detect the organic carbon by comparing the 013C of pyrolysis and combustion experiments. The TLS on SAM is capable of obtaining high precision measurements of delta13C from C02 evolved during pyrolysis and combustion of solid regolith samples. Because carbonates are expected to be present at abundances of 0.1-1 % in Martian soil, and organics in the ppb range (Webster and Mahaffy, 2011), analog samples must represent this mix of reduced organic carbon and carbonate. The work presented here will examine the use of delta13C of C02 produced during combustion of bulk Mars analog samples as a proxy for detection of reduced organic carbon.
In this work, we experimentally investigated the batch-to-glass conversion kinetics of two low-activity and two high-level nuclear waste melter feeds that represent widely different behavior during melting; tests comprised thermogravimetric analysis, the feed expansion test, evolved gas analysis, and x-ray diffraction. Our study indicates that the conversion processes, which include gas-evolving reactions, dissolution of crystalline phases, and primary foam expansion and collapse, are interconnected and influenced by the feed’s thermal history. The fraction of dissolved silica was adopted as a measure of the extent of conversion inside the cold cap—the floating layer of feed material on the top surface of the melt in an electric melter. The interface between the cold cap and the free-flowing melt below was associated with a constant fraction of dissolved silica. The estimated viscosity of glass-forming melt at this interface lies within a narrow range for the feeds studied.
The rate of conversion of nuclear waste melter feed to glass is affected by the selection of melter feed materials and by melter design and operation. The melting rate correlation (MRC) is an equation that relates the glass production rate with two types of variables: (1) feed and melt properties: conversion heat, cold-cap bottom temperature, and glass melt viscosity; and (2) melter design and operation parameters: melter geometry, melter operating temperature, and gas bubbling rate. The MRC shows good agreement for an extended melting-rate data set of high-level waste (HLW) melter feeds and a data set generated for low-activity waste (LAW) melter feeds. Laboratory observation of heated melter feed samples is often used to assess the cold-cap bottom temperature of HLW melter feeds (moderately foaming feeds), but this technique appears inadequate for LAW melter feeds (vigorously foaming feeds). For LAW feeds, an adequate assessment of the cold-cap bottom temperature was achieved using evolved gas analysis, which allows identification of the collapse of primary foam for oxidized feeds. This assessment shows that the cold-cap bottom temperature for vigorously foaming LAW feeds is higher than that for moderately foaming HLW feeds. When the results of MRC are compared, LAW feeds are generally less sensitive to the bubbling rate and melt viscosity, and more sensitive to the cold-cap bottom temperature than HLW feeds. The MRC qualifies as a promising tool to support the selection of melter feed materials and melter operating conditions, which is determined from expensive independent scaled melter experiments, and sophisticated mathematical models.