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Record of fluid-rock interactions on Mars from the meteorite ALH84001

Allan Hills (ALH) 84001 is the most recently recognized member of a suite of meteorites--the SNCs--that almost certainly originated on Mars. Several factors distinguish ALH84001 from the other SNC meteorites. Preliminary studies suggest that it may be older than other martian meteorites. Moreover, it contains abundant, zoned domains of calcium-iron-magnesium carbonate that are indigenous to the sample and thus may hold important clues regarding near-surface processes on Mars and the evolution of the martian atmosphere. We report here analyses of the carbon and oxygen stable-isotope compositions of the carbonates that place constraints on their formation conditions. Our results imply the presence of at least two chemically distinct carbonates--one Ca,Fe-rich, the other Mg-rich--that are enriched in 13C relative to terrestrial carbonates (delta 13C approximately +41/1000), consistent with martian atmospheric CO2 as the carbon source. The oxygen isotope compositions of the carbonates indicate that they precipitated from a low-temperature fluid in the martian crust. Combined with textural and bulk geochemical considerations, the isotope data suggest that carbonate deposition took place in an open-system environment in which the ambient temperature fluctuated.

Carbonates/analysis↗

Abundance and Isotopic Composition of Gases in the Martian Atmosphere: First Results from the Mars Curiosity Rover

Repeated measurements of the composition of the Mars atmosphere from Curiosity Rover yield a (40)Ar/N2 ratio 1.7 times greater and the (40)Ar/(36)Ar ratio 1.6 times smaller than the Viking Lander values in 1976. The unexpected change in (40)Ar/N2 ratio probably results from different instrument characteristics although we cannot yet rule out some unknown atmospheric process. The new (40)Ar/(36)Ar ratio is more aligned with Martian meteoritic values. Besides Ar and N2 the Sample Analysis at Mars instrument suite on the Curiosity Rover has measured the other principal components of the atmosphere and the isotopes. The resulting volume mixing ratios are: CO2 0.960(+/- 0.007); (40)Ar 0.0193(+/- 0.0001); N2 0.0189(+/- 0.0003); O2 1.45(+/- 0.09) x 10(exp -3); and CO 5.45(+/- 3.62) x 10(exp 4); and the isotopes (40)Ar/(36)Ar 1.9(+/- 0.3) x 10(exp 3), and delta (13)C and delta (18)O from CO2 that are both several tens of per mil more positive than the terrestrial averages. Heavy isotope enrichments support the hypothesis of large atmospheric loss. Moreover, the data are consistent with values measured in Martian meteorites, providing additional strong support for a Martian origin for these rocks.

Results from Curiosity↗

The carbon isotope biogeochemistry of acetate from a methanogenic marine sediment

The delta C-13 value of porewater acetate isolated from the anoxic sediments of Cape Lookout Bight (North Carolina) ranged from -17.6 percent in the sulfate reduction zone to -2.8 percent in the underlying methanogenic zone. The large C-13 enrichment in the sulfate-depleted sediments appears to be associated with the dissimilation of acetate to CH4 and CO2. Fractionation factors for that process were estimated to be 1.032 +/- 0.014 and 1.036 +/- 0.019 for the methyl and carboxyl groups. A subsurface maximum in delta C-13 of the total acetate molecule, as well as the methyl and carboxyl carbons at 10-15 cm depth within the sediment column, indicate that changes in the relative rates of acetate cycling pathways occur in the methanogenic zone. The methyl group of the acetate was depleted in C-13 by 7-14 percent relative to the carboxyl moiety. The intramolecular heterogeneity may be the result of both synthetic and catabolic isotope effects.

Blair, N. E.↗

Soil enzymes as indicators of soil function: A step toward greater realism in microbial ecological modeling

Soil carbon (C) and nitrogen (N) cycles and their complex responses to environmental changes have received increasing attention. However, large uncertainties in model predictions remain, partially due to the lack of explicit representation and parameterization of microbial processes. One great challenge is to effectively integrate rich microbial functional traits into ecosystem modeling for better predictions. Here, using soil enzymes as indicators of soil function, we developed a competitive dynamic enzyme allocation scheme and detailed enzyme-mediated soil inorganic N processes in the Microbial-ENzyme Decomposition (MEND) model. We conducted a rigorous calibration and validation of MEND with diverse soil C-N fluxes, microbial C:N ratios, and functional gene abundances from a 12-year CO 2 × N grassland experiment (BioCON) in Minnesota, USA. In addition to accurately simulating soil CO 2 fluxes and multiple N variables, the model correctly predicted microbial C:N ratios and their negative response to enriched N supply. Model validation further showed that, compared to the changes in simulated enzyme concentrations and decomposition rates, the changes in simulated activities of eight C-N-associated enzymes were better explained by the measured gene abundances in responses to elevated atmospheric CO 2 concentration. In conclusion, our results demonstrated that using enzymes as indicators of soil function and validating model predictions with functional gene abundances in ecosystem modeling can provide a basis for testing hypotheses about microbially mediated biogeochemical processes in response to environmental changes. Further development and applications of the modeling framework presented here will enable microbial ecologists to address ecosystem-level questions beyond empirical observations, toward more predictive understanding, an ultimate goal of microbial ecology.

59 BASIC BIOLOGICAL SCIENCES↗

Sooting Limits Of Diffusion Flames With Oxygen-Enriched Air And Diluted Fuel

Oxygen-enhanced combustion permits certain benefits and flexibility that are not otherwise available in the design of practical combustors, as discussed by Baukal. The cost of pure and enriched oxygen has declined to the point that oxygen-enhanced combustion is preferable to combustion in air for many applications. Carbon sequestration is greatly facilitated by oxygen enrichment because nitrogen can be eliminated from the product stream. For example, when natural gas (or natural gas diluted with CO2) is burned in pure oxygen, the only significant products are water and CO2. Oxygen-enhanced combustion also has important implications for soot formation, as explored in this work. We propose that soot inception in nonpremixed flames requires a region where C/O ratio, temperature, and residence time are above certain critical values. Soot does not form at low temperatures, with the threshold in nonpremixed flames ranging from about 1250-1650 K, a temperature referred to here as the critical temperature for soot inception, Tc. Soot inception also can be suppressed when residence time is short (equivalently, when the strain rate in counterflow flames is high). Soot induction times of 0.8-15 ms were reported by Tesner and Shurupov for acetylene/nitrogen mixtures at 1473 K. Burner stabilized spherical microgravity flames are employed in this work for two main reasons. First, this configuration offers unrestricted control over convection direction. Second, in steady state these flames are strain-free and thus can yield intrinsic sooting limits in diffusion flames, similar to the way past work in premixed flames has provided intrinsic values of C/O ratio associated with soot inception limits.

Sunderland, P. B.↗

The effects of rising CO 2 concentrations on terrestrial systems: scaling it up

Since the Industrial Revolution, atmospheric CO 2 concentrations have increased by c. 50%, from 280 ppm to a current level of 415 ppm and rising (Ciais et al., 2013). But CO 2 concentrations would be even higher if the terrestrial biosphere was not acting as a carbon sink, absorbing c. 30% of the CO 2 we emit every year (Le Quéré et al., 2016). Understanding how increasing CO 2 concentrations will alter the ability of vegetation and soils to sequester carbon is therefore critical for predicting the trajectory of future climate change, since a reduction in this carbon sink would cause a more rapid accumulation of CO2 in the atmosphere (Dusenge et al., 2019). In this issue of New Phytologist, Walker et al. (2021; pp. 2413–2445) synthesize data from an incredibly broad range of sources, including herbaria, free air CO 2 enrichment (FACE) studies, ice cores, eddy covariance sites, and remote sensing, and examine an enormous diversity of measurements (such as soil respiration rates, glucose isotopomers from leaves, tree ring width data, stream-gauges for runoff, and direct atmospheric CO 2 measurements) to address the question of how increasing CO2 concentrations are affecting the carbon uptake capacity of our planet.

54 ENVIRONMENTAL SCIENCES↗

Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variation Seen in Cryogenic Laboratory Studies of Carbonate Salts

The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average delta13C(DIC-CARB) values of ~20.5%0 which exceed the expected equilibrium fractionation factor of [10(sup 3) ln alpha = ~13%0] at 0 degC. Oxygen isotopes showed a smaller enrichment with delta18O(H2O-CARB) values of ~35.5%0, slightly exceeding the equilibrium fractionation factor of [10(sup 3) ln alpha = ~34%0 ] at 0degC. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the relative paucity of carbonate minerals in the martian crust.

Socki, Richard↗

Light-Dependence of Formate (C1) and Acetate (C2) Transport and Oxidation in Poplar Trees

Although apparent light inhibition of leaf day respiration is a widespread reported phenomenon, the mechanisms involved, including utilization of alternate respiratory pathways and substrates and light inhibition of TCA cycle enzymes are under active investigation. Recently, acetate fermentation was highlighted as a key drought survival strategy mediated through protein acetylation and jasmonate signaling. Here, we evaluate the light-dependence of acetate transport and assimilation in Populus trichocarpa trees using the dynamic xylem solution injection (DXSI) method developed here for continuous studies of C1 and C2 organic acid transport and light-dependent metabolism. Over 7 days, 1.0 L of [13C]formate and [13C2]acetate solutions were delivered to the stem base of 2-year old potted poplar trees, while continuous diurnal observations were made in the canopy of CO2, H2O, and isoprene gas exchange together with δ13CO2. Stem base injection of 10 mM [13C2]acetate induced an overall pattern of canopy branch headspace 13CO2 enrichment (δ13CO2 +27‰) with a diurnal structure in δ13CO2 reaching a mid-day minimum followed by a maximum shortly after darkening where δ13CO2 values rapidly increased up to +12‰. In contrast, 50 mM injections of [13C]formate were required to reach similar δ13CO2 enrichment levels in the canopy with δ13CO2 following diurnal patterns of transpiration. Illuminated leaves of detached poplar branches pretreated with 10 mM [13C2]acetate showed lower δ13CO2 (+20‰) compared to leaves treated with 10 mM [13C]formate (+320‰), the opposite pattern observed at the whole plant scale. Following dark/light cycles at the leaf-scale, rapid, strong, and reversible enhancements in headspace δ13CO2 by up to +60‰ were observed in [13C2]acetate-treated leaves which showed enhanced dihydrojasmonic acid and TCA cycle intermediate concentrations. The results are consistent with acetate in the transpiration stream as an effective activator of the jasmonate signaling pathway and respiratory substrate. The shorter lifetime of formate relative to acetate in the transpiration stream suggests rapid formate oxidation to CO2 during transport to the canopy. In contrast, acetate is efficiently transported to the canopy where an increased allocation towards mitochondrial dark respiration occurs at night. The results highlight the potential for an effective integration of acetate into glyoxylate and TCA cycles and the light-inhibition of citrate synthase as a potential regulatory mechanism controlling the diurnal allocation of acetate between anabolic and catabolic processes.

59 BASIC BIOLOGICAL SCIENCES↗

Quantifying the Hypervolatile Abundances in Jupiter-family Comet 46P/Wirtanen

We present analysis of IR and optical spectroscopy of Jupiter-family comet (JFC) 46P/Wirtanen obtained in 2019 January, when the comet had sufficient geocentric velocity to enable studies of the hypervolatiles CO and CH4, as well as [OI] emission. These species could not be studied near closest approach in mid-December because there was insufficient Doppler shift to separate the cometary emission from their corresponding telluric absorption lines. We employed the [OI] observations as a proxy for the CO2/H2O ratio, as CO2 cannot be observed directly from the ground, and space-based assets sensitive to CO2 were not able to observe 46P during this apparition. We focused our analysis on H2O, CO, CH4, C2H6, CH3OH, and CO2 (via [OI] emission). We detected strong emissions from H2O, C2H6, and CH3OH. Over the 3 nights, we found evidence for changing mixing ratios, mostly due to a variable H2O production rate. In 46P, C2H6 and CH3OH are enriched compared to cometary averages, with mixing ratios relative to H2O of ∼1% and ∼3%, respectively. Measurements of CH4 and CO have been especially rare in JFCs. We report significant 3σ upper limits on CH4/H2O<0.97% and CO/H2O<0.54%. They place CH4 being near-average or depleted, and CO being strongly depleted in 46P compared with Oort cloud comets. 46P has comparable CO/H2O to the few other measurements in JFCs, but enriched in C2H6 and CH3OH. Our inferred CO2/H2O mixing ratio is∼15%, though accounting for systematic uncertainties from the lack of knowledge of [OI] photochemistry means a value between 10% and 20% is likely. The compositional profile of46P is similar to another small, hyperactive comet: 103P/Hartley 2. The mechanism of CO2-driven water-rich ice grain production proposed for 103P/Hartley 2 may be operating on 46P as well.

Comets↗

Carbonaceous chondrites. II - Carbonaceous chondrite phyllosilicates and light element geochemistry as indicators of parent body processes and surface conditions

Petrographic analyses of CM matrices characterized four phyllosilicates in Murray and Murchison meteorites and Fe- and Mg-serpentines in Nogoya. All phyllosilicates and bulk matrices show enrichment of K relative to Na when compared with bulk meteorites; the loss of Na and some Cl, and the addition of H2O, CO2, and water-soluble organics during alteration indicates a partially open system. Synthesis of soluble organic materials may have occurred in CM matrices before aqueous alteration of the precursive phases. Nogoya was 95% altered and has a bulk C content of 5.2%, higher than any meteorite; also, it has the lowest measured C-13/C-12 ratio of any carbonaceous chondrite except for Karoonda.

Bunch, T. E.↗

Carbon isotopic fractionation in heterotrophic microbial metabolism

Differences in the natural-abundance carbon stable isotopic compositions between products from aerobic cultures of Escherichia coli K-12 were measured. Respired CO2 was 3.4 percent depleted in C-13 relative to the glucose used as the carbon source, whereas the acetate was 12.3 percent enriched in C-13. The acetate C-13 enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6 percent depleted in C-13, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7 percent, respectively. Aspartic and glutamic acids were -1.6 and +2.7 percent, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle.

Blair, N.↗

Data from the Mars Science Laboratory CheMin XRD/XRF Instrument

The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity uses a Co tube source and a CCD detector to acquire mineralogy from diffracted primary X-rays and chemical information from fluoresced X-rays. CheMin has been operating at the MSL Gale Crater field site since August 5, 2012 and has provided the first X-ray diffraction (XRD) analyses in situ on a body beyond Earth. Data from the first sample collected, the Rocknest eolian soil, identify a basaltic mineral suite, predominantly plagioclase (approx.An50), forsteritic olivine (approx.Fo58), augite and pigeonite, consistent with expectation that detrital grains on Mars would reflect widespread basaltic sources. Minor phases (each <2 wt% of the crystalline component) include sanidine, magnetite, quartz, anhydrite, hematite and ilmenite. Significantly, about a third of the sample is amorphous or poorly ordered in XRD. This amorphous component is attested to by a broad rise in background centered at approx.27deg 2(theta) (Co K(alpha)) and may include volcanic glass, impact glass, and poorly crystalline phases including iron oxyhydroxides; a rise at lower 2(theta) may indicate allophane or hisingerite. Constraints from phase chemistry of the crystalline components, compared with a Rocknest bulk composition from the APXS instrument on Curiosity, indicate that in sum the amorphous or poorly crystalline components are relatively Si, Al, Mg-poor and enriched in Ti, Cr, Fe, K, P, S, and Cl. All of the identified crystalline phases are volatile-free; H2O, SO2 and CO2 volatile releases from a split of this sample analyzed by the SAM instrument on Curiosity are associated with the amorphous or poorly ordered materials. The Rocknest eolian soil may be a mixture of local detritus, mostly crystalline, with a regional or global set of dominantly amorphous or poorly ordered components. The Rocknest sample was targeted by MSL for "first time analysis" to demonstrate that a loose deposit could be scooped, sieved to <150 microns, and delivered to instruments in the body of the rover. A drilled sample of sediment in outcrop is anticipated. At the time of writing this abstract, promising outcrops are in range and this talk will provide an update on data collected with the CheMin instrument.

Vaniman, David↗

Application of Analytical Hierarchy Process for Narrowing Down Nep Candidate Reactor Designs

Nuclear electric propulsion (NEP)-powered vehicles have been contemplated for human Mars missions. The nuclear power system contemplates using a high temperature light-weight nuclear reactor for the production of electrical power in the range of 2-5 MWe with a 3-10 year service life. A myriad of technology options exist for achieving these mission objectives. The analytic hierarchy process (AHP), a multi-attribute decision method, is being used to narrow down the candidate designs. The AHP is a structured decision process that fuses model-supplied quantitative data with subjective assessments to facilitate decisions that involve multiple competing criteria. Proven end-to-end nuclear design and systems analysis tools will be used to provide quantitative performance data such as end-to-end system reliability, system robustness to recover from off-normal conditions, system specific weight (α in kg/kWe), and the ability to meet the service life-time and power level requirements. Three high assay low enriched uranium (HALEU) reactor concepts, namely, gas-, heat pipe- and pumped liquid-cooled nuclear cores coupled to a He/Xe gas or supercritical CO2- Brayton power conversion system are being modeled using the AHP to understand the trade-offs associated with these design combinations. In addition to the reactor and power conversion options, there are a myriad of additional components and subsystems – e.g., radiators, heat exchangers, and recuperators – that also figure into the evaluation process. The choice of the right overall system is a multidimensional problem that has to include not only quantitative data, but also the so called “external factors”, examples of which include the component and subsystem Technology Readiness Levels (TRLs), the associated Advancement Degrees of Difficulty (AD2), the cost and schedule required to achieve a technical maturity consistent with mission infusion, alignment with the priorities of NASA’s Space Nuclear Propulsion program, and alignment with other ongoing government and commercial investments in micro reactors. Focused expert elicitations form the basis for qualitative data set. As a final step, decision-makers individually express their opinions regarding the relative importance of the criteria and preferences among the alternatives through pairwise comparisons. The paper will describe the AHP approach, progress to-date applying it to the NEP human Mars mission problem, and preliminary results. Use of AHP provides sufficient flexibility for incorporating industry input at different stages as the technologies evolve through additional research and development. It is expected that the decision process will be ongoing and expanded to examine additional options and technology choices, culminating in a defensible set of candidate reactor concepts that will form the basis for developing a multi-year NEP technology maturation strategy. .

Dasari V Rao↗

Solar helium and neon in the Earth

Neon isotopic compositions in mantle-derived samples commonly are enriched in (20)Ne and (21)Ne relative to (22)Ne compared with atmospheric neon ((20)Ne/(22)Ne and (21)Ne/(22)Ne ratios in atmospheric neon are 9.8 and 0.029, respectively), together with significant primordial (3)He. Such results have been obtained on MORB's, intraplate plume-related oceanic island basalts, backarc basin basalts, mantle xenoliths, ancient diamonds and CO2 well gases (e.g., 1 - 8). The highest (20)Ne/(22)Ne ratio observed in MORB glasses (= 13.6 plus or minus 1.3 is close to the solar value (= 13.6, as observed in solar wind). In order to explain the enrichment of (20)Ne and (21)Ne relative to atmospheric neon for samples derived from the mantle, it is necessary to postulate the presence of at least two distinct non-atmospheric components. The two most likely candidates are solar and nucleogenic ((20)Ne/(22)Ne solar = 13.6 (21)Ne/(22)Ne solar = 0.032, (20)Ne/(22)Ne nucleogenic = 2.5 and (21)Ne/(22)Ne nucleogenic = 32). This is because solar neon is the only known component with a (20)Ne/(22)Ne ratio greater than both the atmospheric value and that observed in samples derived from the mantle. Nucleogenic neon is well known to elevate (21)Ne/(22)Ne ratios. Neon isotopic signatures observed in mantle-derived samples can be accounted for by mixing of the three neon end members: solar, nucleogenic and atmospheric.

Honda, M.↗

Implications of isotopic compositions of N and Ne in the Martian atmosphere to temporal evolution of its atmosphere and regolith

The isotopic compositions of N and Ne in the Martian atmosphere are governed by several factors, principal among which are the temporal evolution in (1) the absolute surface pressure of oxygen, (2) the physicochemical characteristics of the regolith, and finally (3) the N-15 enrichment expected due to preferential hydrodynamical escape of N-14 (due to solar wind bombardment). Each of these factors is unique to Mars. In fact, no other planet offers the uniquely favorable situations for N-15 and Ne-21 enrichments. The cosmogenic production of N-15 is, in particular, unique. It promises to provide very valuable constraints on the temporal evolution of the martian CO2 and H2O, both in the atmosphere and regolith. The rate of production of cosmogenic (spallation) N-15 is dependent on the surface pressure of oxygen, the principal target element for formation of N-15. In view of the relatively high O/N ratio in the martian atmosphere, relatively high N-15/N ratio are expected to arise from cosmogenic reactions. The added bonus comes from the fact that an appreciable production of N-15 is expected in the martian regolith because of its thin atmosphere. From model calculations it is shown that if accurate isotopic composition data become available for N and Ne, it should be possible to put robust constraints on the time averages martian oxygen surface pressure and subsurface water in the upper layers.

Lal, D.↗

Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from 'noncompetitive' substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94 per thousand. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in C-13, reaching a maximum delta(C-13) value of -42 per thousand. Third, the acetate pool experienced a precipitous decline from greater than 5 mM to less than 20 micro-M and methane production was again dominated by CO2 reduction. The delta(C-13) of methane produced during this final phase ranged from -46 to -58 per thousand. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8 percent of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane emitted from undisturbed Cape Lookout Bight sediment.

Alperin, M. J.↗

Shifting Valencies and Magnetic Responses in La-Based High-Entropy Oxide Perovskite Thin Films with Variable Mn Presence

Chemical disorder in compositionally complex perovskite oxides generates a broad distribution of exchange pathways and spin states, but the microscopic origin and spatial homogeneity of the resulting magnetic phases remain debated. Here, we tune the Mn fraction (x = 0.2–0.6) in epitaxial La(Cr, Mn, Fe, Co, Ni)O3 thin films and resolve the coupled evolution of valence, spin state, and magnetism using element-specific x-ray absorption spectroscopy and x-ray magnetic circular dichroism (XMCD). Mn enrichment drives an internal redistribution of charge, in which Mn evolves toward a Mn3+-rich mixed valence, while Co converts from predominantly Co3+ to high-spin Co2+. This valence/spin-state coupling amplifies the Mn- and Co-derived ferromagnetic response by nearly an order of magnitude while increasing the magnetic onset temperature to at least 250 K, whereas Fe and Cr remain essentially trivalent with weak dichroism. Depth-resolved low-energy muon spin spectroscopy (LE-μSR) shows magnetic homogeneity through the film thickness, with a secondary relaxation maximum near 25 K indicating a low-temperature dynamical crossover consistent with frustrated magnetism in a strongly disordered spin lattice.

Miertschin, Duncan [Baylor University]↗

Mars Atmospheric Composition, Isotope Ratios and Seasonal Variations: Overview and Updates of the SAM Measurements at Gale Crater

We will summarize the in situ measurements of atmospheric composition and the isotopic ratios of D/H in water, C-13/C-12, O-18/O-16, O-17 / O-16, and C-13 O-18 / C-12 O-16 in carbon dioxide, and Ar-38 / Ar-36, Kr-x / Kr-84, and N-15 / N-14 made in the martian atmosphere at Gale Crater from the Curiosity Rover using the Sample Analysis at Mars (SAM)'s Quadrupole Mass Spectrometer (QMS) and Tunable Laser Spectrometer (TLS). With data over 700 sols since the Curiosity landing, we will discuss evidence and implications for changes on seasonal and other timescales. We will also present results for continued methane and methane enrichment experiments over this time period. Comparison between our measurements in the modern atmosphere and those of martian meteorites like ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established approximately 4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing.

Niles, Paul↗