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Plants and mycorrhizal symbionts acquire substantial soil nitrogen from gaseous ammonia transport

Nitrogen (N) is an essential nutrient that limits plant growth in many ecosystems. Here we investigate an overlooked component of the terrestrial N cycle – subsurface ammonia (NH 3 ) gas transport and its contribution to plant and mycorrhizal N acquisition. In this work, we used controlled mesocosms, soil incubations, stable isotopes, and imaging to investigate edaphic drivers of NH 3 gas efflux, track lateral subsurface N transport originating from 15 NH 3 gas or 15 N-enriched organic matter, and assess plant and mycorrhizal N assimilation from this gaseous transport pathway. NH3 is released from soil organic matter, travels belowground, and contributes to root and fungal N content. Abiotic soil properties (pH and texture) influence the quantity of NH 3 available for subsurface transport. Mutualisms with arbuscular mycorrhizal (AM) fungi can substantially increase plant NH 3 -N uptake. The grass Brachypodium distachyon acquired 6–9% of total plant N from organic matter-N that traveled as a gas belowground. Colonization by the AM fungus Rhizophagus irregularis was associated with a two-fold increase in total plant N acquisition from subsurface NH 3 gas. NH 3 gas transport and uptake pathways may be fundamentally different from those of more commonly studied soil N species and warrant further research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Porewater and Surface Water Chemistry of Wetland, Old Woman Creek National Estuarine Research Reserve, Huron, OH, 2022-07-06 to 2023-12-15

This dataset contains the chemistry data of surface water and porewater samples collected from a wetland, referred to as The Cove, at Old Woman Creek Estuarine Research Reserve in Huron, OH. Surface and pore water samples were taken to analyze what nutrient and/or metal constituents were present at different depths in the wetland at different times and to compare to redox potential values. Porewater was collected by constructed sippers and deployed into the underlying soil of the wetland, and they were samples approximately every 2 weeks (when groundwater was present) in 2023. Surface water was collected approximately 1 inch below the surface of the water column (if available) via a syringe. Unfiltered and 0.45 micron filtered samples were collected. Samples were analyzed for various chemistry and is reported in the SWChem (surface water chemistry) and PWChem (porewater chemistry) .csv datafiles. Collection information about the samples can be found within the PWChem_SWChem_SampleMetdata.csv file. All files associated with this dataset are listed in the PWChem_SWChem_FLMD.csv file.

54 ENVIRONMENTAL SCIENCES↗

X-ray Amorphous Components of Antarctica Dry Valley Soils: Weathering Implications for Mars

The Antarctic Dry Valleys (ADV) comprise the largest ice-free region of Antarctica. Precipitation usually occurs as snow, relative humidity is frequently low, and mean annual temperatures are about -20°C [1]. Substantial work has focused on soil formation in the ADVs [2], however, little work has focused on the mineralogy of secondary alteration phases. The dominant weathering process in the ADV region is physical weathering, however, chemical weathering has been well documented [3]. The occurrence of chemical weathering processes are suggested by the presence of clay minerals and iron and titanium oxides in soil. Previously we have investigated soils from two sites in the ADV’s and have shown evidence of chemical weathering by the presence of clay minerals (vermiculite, smectite), short-range ordered (SRO) and/or X-ray amorphous materials, and Fe- and Tioxides as well as the presence of discrete calcite crystals [4, 5]. The Chemistry and Mineralogy (CheMin) instrument onboard the Mars Curiosity rover has detected abundant amounts (approx. 25-30 wt. %) of X-ray amorphous materials in a windblown deposit or “soil” (Rocknest) and in a sedimentary rocks [6,7,8]. The occurrence of large amounts of X-ray amorphous materials in Mars sediments is surprising because these materials are usually present in small quantities in terrestrial environments. The objective of this study is to further characterize the chemistry and mineralogy, specifically the secondary alteration mineralogy and the presence of X-ray amorphous material, of soils from two sites we have previously studied, a subxerous soil in Taylor Valley, and an ultraxerous soil in University Valley. While the chemical alteration processes and mineralogy of the ADV has been documented previously, there has been limited discussion on the occurrence and formation of X-ray amorphous and SRO materials in Antarctica soils. The process of aqueous alteration in the ADVs may have implications for pedogenic processes on Mars, and may lead to a better understanding to the abundance of amorphous material found in sediments in Gale crater.

Quinn, J. E.↗

Lunar and Planetary Science Conference, 18th, Houston, TX, Mar. 16-20, 1987, Proceedings

Papers on lunar and planetary science are presented, including petrogenesis and chemistry of lunar samples, geology and petrogenesis of the Apollo 15 landing site, lunar geology and applications, cratering records and cratering effects, differentiated meteorites, chondritic meteorites and asteroids, extraterrestrial grains, Venus, Mars, and icy satellites. The importance of lunar granite and KREEP in very high potassium basalt petrogenesis, indentifying parent plutonic rocks from lunar breccia and soil fragments, glasses in ancient and young Apollo 16 regolith breccias, the formation of the Imbrium basin, the chemistry and petrology of the Apennine Front, lunar mare ridges, studies of Rima Mozart, electromagnetic energy applications in lunar resource mining and construction, detecting a periodic signal in the terrestrial cratering record, and a search for water on the moon, are among the topics discussed. Other topics include the bidirectional reflectance properties of Fe-Ni meteorites, the nature and origin of C-rich ordinary chondrites and chondritic clasts, the dehydration kinetics of shocked serpentine, characteristics of Greenland Fe/Ni cosmic grains, electron microscopy of a hydrated interplanetary dust particle, trapping Ne, Ar, Kr, and Xe in Si2O3 smokes, gossans on Mars, and a model of the porous structure of icy satellites.

Ryder, Graham↗

Searching for Reduced Carbon on the Surface of Mars: The SAM Combustion Experiment

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.

Stern, J. C.↗

Bedrock weathering rates, reactive nitrogen influxes and effluxes, and nitrous oxide emissions rates from the Pumphouse Hillslope, East River Watershed, Colorado

Atmospheric nitrous oxide contributes directly to global warming, yet models of the nitrogen cycle do not account for bedrock, the largest pool of terrestrial nitrogen, as a source of nitrous oxide. Although it is known that release rates of nitrogen from bedrock are large, there is an incomplete understanding of the connection between bedrock-hosted nitrogen and atmospheric nitrous oxide. Here, we quantify nitrogen fluxes and mass balances at a hillslope underlain by marine shale. We found that at this site bedrock weathering contributes 78% of the subsurface reactive nitrogen, while atmospheric sources (commonly regarded as the sole sources of reactive nitrogen in pristine environments) account for only the remaining 22%. About 56% of the total subsurface reactive nitrogen denitrifies, including 14% emitted as nitrous oxide. The remaining reactive nitrogen discharges in porewaters to a floodplain where additional denitrification likely occurs. We also found that the release of bedrock nitrogen occurs primarily within the zone of the seasonally fluctuating water table and suggest that the accumulation of nitrate in the vadoes zone, often attributed to fertilization and soil leaching, may also include contributions from weathered nitrogen-rich bedrock. Our hillslope study suggests that under oxygenated and moisture-rich conditions, weathering of deep, nitrogen-rich bedrock makes an important contribution to the nitrogen cycle. The data files are in Excel, which can be accessed using Microsoft Office, and consist of many data sets from the Pumphouse Hillslope PLM (Pumphouse Lower Montane) 1, 2, 3, and 4. They include soil to rock (0-10 meters) solid phase minerals and elements compositions; time- and depth-resolved pore-water chemistry and pore-gas compositions; time- and depth-resolved water table depths and water fluxes; subsurface weathering rates; nitrogen influxes and effluxes and mass balance. The attached paper is in a Word document, which can be accessed using Microsoft Office, and in pdf format.

54 ENVIRONMENTAL SCIENCES↗

Characterizing Natural Organic Matter Transformations by Microbial Communities in Terrestrial Subsurface Ecosystems: A Critical Review of Analytical Techniques and Challenges

Determining the mechanisms, traits, and pathways that regulate microbial transformation of natural organic matter (NOM) is critical to informing our understanding of the microbial impacts on the global carbon cycle. The capillary fringe of subsurface soils is a highly dynamic environment that remains poorly understood. Characterization of organo-mineral chemistry combined with a nuanced understanding of microbial community composition and function is necessary to understand microbial impacts on NOM speciation in the capillary fringe. We present a critical review of the popular analytical and omics techniques used for characterizing complex carbon transformation by microbial communities and focus on how complementary information obtained from the different techniques enable us to connect chemical signatures with microbial genes and pathways. This holistic approach offers a way forward for the comprehensive characterization of the formation, transformation, and mineralization of terrestrial NOM as influenced by microbial communities.

59 BASIC BIOLOGICAL SCIENCES↗

The Mars Environmental Compatibility Assessment (MECA) Wet Chemistry Experiment on the Mars 2001 Lander

The Mars Environmental Compatibility Assessment (MECA) is an instrument suite that will fly on the Mars Surveyor 2001 Lander Spacecraft. MECA is sponsored by the Human Exploration and Development of Space (HEDS) program and will evaluate potential hazards that the dust and soil of Mars might present to astronauts and their equipment on a future human mission to Mars. Four elements constitute the integrated MECA payload: a microscopy station, patch plates, an electrometer, and the wet chemistry laboratory (WCL). The WCL consists of four identical cells, each of which will evaluate a sample of Martian soil in water to determine conductivity, pH, redox potential, dissolved C02 and 02 levels, and concentrations of many soluble ions including sodium, potassium, magnesium, calcium and the halides. In addition, cyclic voltammetry will be used to evaluate reversible and irreversible oxidants present in the water/soil solution. Anodic stripping voltammetry will be used to measure concentrations of trace metals including lead, copper, and cadmium at ppb levels. Voltammetry is a general electrochemical technique that involves controlling the potential of an electrode while simultaneously measuring the current flowing at that electrode. The WCL experiments will provide information on the corrosivity and reactivity of the Martian soil, as well as on soluble components of the soil which might be toxic to human explorers. They will also guide HEDS scientists in the development of high fidelity Martian soil simulants. In the process of acquiring information relevant to HEDS, the WCL will assess the chemical composition and properties of the salts present in the Martian soil.

Grannan, S. M.↗

Dynamic Responses of Trace Metal Bioaccessibility to Fluctuating Redox Conditions in Wetland Soils and Stream Sediments

Natural aquatic systems undergo fluctuating redox conditions due to microbial activity, varying water saturation levels, and nutrients dynamics. With fluctuating redox conditions, trace metals can mobilize or sequester in response to changes in iron and sulfur speciation and the concentrations and lability of organic carbon. This study examined the effect of redox fluctuations on trace metal mobility in samples collected from two different natural aquatic systems: riparian wetlands and a stream. The wetland soils contained low sulfur and total Fe contents as compared to stream sediments. The mineral composition at both sites was dominated by quartz. We incubated water-saturated soils under three cycles of anoxic-oxic conditions (τanoxic:τoxic = 3) spanning 24 days and monitored the change in dissolved and bioavailable metal concentrations. For both natural systems, reduction of iron oxides under anoxic conditions caused Co and Zn release. In contrast, oxidation of sulfides mobilized Cu under oxic conditions in both sites. In wetland soils, dissolution of Fe (hydr)oxides increased Ni solubility; however, in stream sediments, Ni release occurred when sulfides or organic matter were oxidized. For stream sediments, each subsequent redox cycle increased the bioavailability of trace metals. Redox fluctuations in wetland soils increased bioavailable Zn and Cu and decreased bioavailable Ni and Co. This study illustrates that different trace metals display distinct bioavailability patterns during redox fluctuations in natural environments. The biogeochemical cycling of nutrients in systems with redox fluctuations may be influenced by these trace metal availability patterns in addition to the availability of electron donors and acceptors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analytical Determination of Radioactive Strontium and Cesium by Thermal Ionization Mass Spectrometry

Thermal ionization mass spectrometry (TIMS) has been evaluated for the detection of the radioactive isotopes of strontium and cesium. The instrument was investigated for the analysis of isotopic ratios of 89Sr to 90Sr and 135Cs to 137Cs in the presence of atomic isobars (Y and Zr for Sr analysis and Ba for Cs analysis). Signicant discrimination using TIMS was found for both Sr and Cs through evaluation using stable isotopes. Fusion procedures with different flux were evaluated for preparation of sample matrices. Chemical separations were developed and used after fusion to isolate the Sr and Cs from a prepared background matrix (i.e., Montana Soil). A graded approach, increasing in stable background isotopes, was performed to monitor the chemistry and instrument response. A thermal neutron irradiation was performed to produce a sample that contained the radioisotopes of Sr and Cs. Even though the irradiated sample was not a certified standard it does provide accurate expectation values via published, well understood cumulative fission yield data. The results presented in this work correlate extremely well with the published data. Furthermore, a significant decrease in uncertainty (by a factor of 5 { 10) was found for the isotopic ratios measured with TIMS compared to the published values.

TIMS, environmental contamination, radiostrontium,↗

pH-Mediated Colorimetric and Luminescent Sensing of Aqueous Nitrate Anions by a Platinum(II) Luminophore@Mesoporous Silica Composite

Increased levels of nitrate (NO 3 – ) in the environment can be detrimental to human health. Herein, we report a robust, cost-effective, and scalable, hybrid material-based colorimetric/luminescent sensor technology for rapid, selective, sensitive, and interference-free in situ NO 3 – detection. These hybrid materials are based on a square-planar platinum(II) salt [Pt(tpy)Cl]PF6 (tpy = 2,2';6',2''-terpyridine) supported on mesoporous silica. The platinum salt undergoes a vivid change in color and luminescence upon exposure to aqueous NO 3 – anions at pH ≤ 0 caused by substitution of the PF6– anions by aqueous NO 3 – . This change in photophysics of the platinum salt is induced by a rearrangement of its crystal lattice that leads to an extended Pt···Pt···Pt interaction, along with a concomitant change in its electronic structure. Furthermore, incorporating the material into mesoporous silica enhances the surface area and increases the detection sensitivity. A NO 3 – detection limit of 0.05 mM (3.1 ppm) is achieved, which is sufficiently lower than the ambient water quality limit of 0.16 mM (10 ppm) set by the United States Environmental Protection Agency. The colorimetric/luminescence of the hybrid material is highly selective to aqueous NO 3 – anions in the presence of other interfering anions, suggesting that this material is a promising candidate for the rapid NO 3 – detection and quantification in practical samples without separation, concentration, or other pretreatment steps.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nutrient Inputs Stimulate Mercury Methylation by Syntrophs in a Subarctic Peatland

Climate change dramatically impacts Arctic and subarctic regions, inducing shifts in wetland nutrient regimes as a consequence of thawing permafrost. Altered hydrological regimes may drive changes in the dynamics of microbial mercury (Hg) methylation and bioavailability. Important knowledge gaps remain on the contribution of specific microbial groups to methylmercury (MeHg) production in wetlands of various trophic status. Here, we measured aqueous chemistry, potential methylation rates (k meth ), volatile fatty acid (VFA) dynamics in peat-soil incubations, and genetic potential for Hg methylation across a groundwater-driven nutrient gradient in an interior Alaskan fen. We tested the hypotheses that (1) nutrient inputs will result in increased methylation potentials, and (2) syntrophic interactions contribute to methylation in subarctic wetlands. We observed that concentrations of nutrients, total Hg, and MeHg, abundance of hgcA genes, and rates of methylation in peat incubations (k meth ) were highest near the groundwater input and declined downgradient. hgcA sequences near the input were closely related to those from sulfate-reducing bacteria (SRB), methanogens, and syntrophs. Hg methylation in peat incubations collected near the input source (FPF2) were impacted by the addition of sulfate and some metabolic inhibitors while those down-gradient (FPF5) were not. Sulfate amendment to FPF2 incubations had higher k meth relative to unamended controls despite no effect on k meth from addition of the sulfate reduction inhibitor molybdate. The addition of the methanogenic inhibitor BES (25 mM) led to the accumulation of VFAs, but unlike molybdate, it did not affect Hg methylation rates. Rather, the concurrent additions of BES and molybdate significantly decreased k meth , suggesting a role for interactions between SRB and methanogens in Hg methylation. The reduction in k meth with combined addition of BES and molybdate, and accumulation of VFA in peat incubations containing BES, and a high abundance of syntroph-related hgcAsequences in peat metagenomes provide evidence for MeHg production by microorganisms growing in syntrophy. Collectively the results suggest that wetland nutrient regimes influence the activity of Hg methylating microorganisms and, consequently, Hg methylation rates. Our results provide key information about microbial Hg methylation and methylating communities under nutrient conditions that are expected to become more common as permafrost soils thaw.

59 BASIC BIOLOGICAL SCIENCES↗

A reexamination of amino acids in lunar soil

Amino acids in lunar soils provide an important indicator of the level of prebiotic organic compounds on the moon. The results provide insight into the chemistry of amino acid precursors, and furthermore, given the flux of carbonaceous material to the moon, we can evaluate the survival of organics upon impact. The amino acid contents of both hydrolyzed and unhydrolyzed hot-water extracts of Apollo 17 lunar soil were determined using ophthaldialdehyde/N-acetyl cysteine (OPA/NAC) derivatization followed by HPLC analysis. Previous studies of lunar amino acids were inconclusive, as the technique used (derivatization with ninhydrin followed by HPLC analysis) was unable to discriminate between cosmogenic amino acids and terrestrial contaminants. Cosmogenic amino acids are racemic, and many of the amino acids found in carbonaceous meteorites such as Murchison, i.e., alpha-amino-i-butyric acid (aib), are extremely rare on Earth. The ninhydrin method does not distinguish amino acid enantiomers, nor does it detect alpha-alkyl amino acids such as aib, whereas the OPA/NAC technique does both.

Brinton, K. L. F.↗

Global Partitioning of NOx Sources Using Satellite Observations: Relative Roles of Fossil Fuel Combustion, Biomass Burning and Soil Emissions

This document contains the following abstract for the paper "Global partitioning of NOx sources using satellite observations: Relative roles of fossil fuel combustion, biomass burning and soil emissions." Satellite observations have been used to provide important new information about emissions of nitrogen oxides. Nitrogen oxides (NOx) are significant in atmospheric chemistry, having a role in ozone air pollution, acid deposition and climate change. We know that human activities have led to a three- to six-fold increase in NOx emissions since pre-industrial times, and that there are three main surface sources of NOx: fuel combustion, large-scale fires, and microbial soil processes. How each of these sources contributes to the total NOx emissions is subject to some doubt, however. The problem is that current NOx emission inventories rely on bottom-up approaches, compiling large quantities of statistical information from diverse sources such as fuel and land use, agricultural data, and estimates of burned areas. This results in inherently large uncertainties. To overcome this, Lyatt Jaegle and colleagues from the University of Washington, USA, used new satellite observations from the Global Ozone Monitoring Experiment (GOME) instrument. As the spatial and seasonal distribution of each of the sources of NOx can be clearly mapped from space, the team could provide independent topdown constraints on the individual strengths of NOx sources, and thus help resolve discrepancies in existing inventories. Jaegle's analysis of the satellite observations, presented at the recent Faraday Discussion on "Atmospheric Chemistry", shows that fuel combustion dominates emissions at northern mid-latitudes, while fires are a significant source in the Tropics. Additionally, she discovered a larger than expected role for soil emissions, especially over agricultural regions with heavy fertilizer use. Additional information is included in the original extended abstract.

Jaegle, Lyatt↗

Molecular Nature of Mineral-Organic Associations within Redox-Active Mountainous Floodplain Sediments

Floodplains are critical terrestrial-aquatic interfaces that act as hotspots of organic carbon (OC) cycling, regulating ecosystem carbon storage as well as export to riverine systems. Within floodplain sediments, regular flooding and textural gradients interact to create dynamic redox conditions. While anaerobic protection of OC upon burial is a well-recognized carbon storage mechanism in redox-active floodplain sediments, the impact of protective mineral-organic associations is relatively unknown. Here we determined the quantitative importance and chemical composition of mineral-organic associations along well-defined redox gradients emerging from textural variations and depth within meander sediments of the subalpine East River watershed (Gothic, CO). Here we characterized mineral-organic associations using a combination of sequential extractions, physical fractionation, and high-resolution mass spectrometry. Across the meander, we found that mineral-associated OC constitutes a significant fraction of total OC, and that extractable iron (Fe) and aluminum (Al) phases as well as high-density isolates were strongly correlated with total OC content, suggesting that mineral-organic associations are quantitatively important for floodplain sediment OC protection. Our mass spectrometry results showed OC associated with increasingly ordered Fe and Al phases are relatively enriched in low-molecular weight, oxidized, aromatic compounds. Surprisingly, however, total OC content showed weak or no correlation with indicators of anaerobic protection, such as relatively bioavailable OC pools (water-extractable and particulate OC) or the molecular weight and oxidation state of OC. Overall, this work highlights that protection of OC bound to reactive mineral phases-in addition to anaerobic protection-can play a quantitatively important role in controlling soil carbon storage in redox-active floodplain sediments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Satellite Mapping of Rain-Induced Nitric Oxide Emissions from Soils

We use space-based observations of NO2 columns from the Global Ozone Monitoring Experiment (GOME) to map the spatial and seasonal variations of NOx emissions over Africa during 2000. The GOME observations show not only enhanced tropospheric NO2 columns from biomass burning during the dry season but also comparable enhancements from soil emissions during the rainy season over the Sahel. These soil emissions occur in strong pulses lasting 1-3 weeks following the onset of rain, and affect 3 million sq km of semiarid sub-Saharan savanna. Surface observations of NO2 from the International Global Atmospheric Chemistry (IGAC)/Deposition of Biochemically Important Trace Species (DEBITS)/Africa (IDAF) network over West Africa provide further evidence for a strong role for microbial soil sources. By combining inverse modeling of GOME NO2 columns with space-based observations of fires, we estimate that soils contribute 3.3+/-1.8 TgN/year, similar to the biomass burning source (3.8+/-2.1 TgN/year), and thus account for 40% of surface NO(x) emissions over Africa. Extrapolating to all the tropics, we estimate a 7.3 TgN/year biogenic soil source, which is a factor of 2 larger compared to model-based inventories but agrees with observation-based inventories. These large soil NO(x) emissions are likely to significantly contribute to the ozone enhancement originating from tropical Africa.

Jaegle, L.↗

The role of Ca-bridged organic matter in an alkaline soil, as revealed by multimodal chemical imaging

Mineral–organic matter (OM) studies have predominantly focused on acidic soils that are abundant in iron (Fe) oxides and aluminum (Al) oxides. We have probed mineral–OM interactions in an alkaline or calcareous soil of the Aridisols class. Unlike the role of Fe and Al, the role of Ca-minerals (particularly calcite), which are ubiquitous in alkaline soils, in OM sequestration is not well understood. Multiple recent model studies with aqueous Ca2+ or synthetic calcite and a suite of OM compounds have shown Ca-OM assemblages to be spatially correlated with calcite at the microscale. To study the chemical state of both Ca and Fe and their competing role in soil organic matter (SOM) stabilization, we performed laboratory characterization using x-ray diffraction, Mössbauer spectroscopy, x-ray photoelectron spectroscopy, scanning electron microscopy, and scanning transmission electron microscopy, alongside synchrotron-based microscale chemical imaging using scanning transmission x-ray microscopy combined with near-edge x-ray absorption fine structure. Ca mineral–organic associations were found to be ubiquitous in this system and are likely critical for understanding SOM stabilization/degradation in alkaline soils. From our findings on mineralogy, speciation, and the nature of Ca-OM bridging, we identified differences in C and Ca chemistry based on the relative location of OM to Ca minerals. The OM near the calcite crystal was enriched in lipid and protein moieties, Ca-OM next to Fe minerals displayed a strong contribution from aromatic compounds, while on the surface of microbes, the carbonate was believed to be of microbial in origin, as also suggested by preliminary works reporting on the formation of amorphous calcite or nano-calcite. In Ca-OM admixed with carbonate, it was difficult to distinguish Ca-associated OM from amorphous calcite or nano-calcite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermal and Evolved Gas Analysis of Magnesium Perchlorate: Implications for Perchlorates in Soils at the Mars Phoenix Landing Site

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.

Ming, Douglas W.↗