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At least 235 records · Page 13

Mapping microhabitats of lignocellulose decomposition by a microbial consortium

The leaf-cutter ant fungal garden ecosystem is a naturally evolved model system for efficient plant biomass degradation. Degradation processes mediated by the symbiotic fungus Leucoagaricus gongylophorus are difficult to characterize due to dynamic metabolisms and spatial complexity of the system. Herein, we performed microscale imaging across 12-µm-thick adjacent sections of Atta cephalotes fungal gardens and applied a metabolome-informed proteome imaging approach to map lignin degradation. This approach combines two spatial multiomics mass spectrometry modalities that enabled us to visualize colocalized metabolites and proteins across and through the fungal garden. Spatially profiled metabolites revealed an accumulation of lignin-related products, outlining morphologically unique lignin microhabitats. Metaproteomic analyses of these microhabitats revealed carbohydrate-degrading enzymes, indicating a prominent fungal role in lignocellulose decomposition. Integration of metabolome-informed proteome imaging data provides a comprehensive view of underlying biological pathways to inform our understanding of metabolic fungal pathways in plant matter degradation within the micrometer-scale environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Minerals limit the deep soil respiration response to warming in a tropical Andisol

Tropical regions hold one third of the world’s soil organic carbon, but few experiments have warmed tropical soils in situ. The vulnerability of these soils to climate change-induced losses is uncertain with many hypothesizing these soils would be less sensitive to climate change because already-high temperatures in tropical systems might limit microbial sensitivity or due to increased mineral protection of organic carbon in highly weathered tropical soils. Here we present the results of a deep soil (0–100 cm) warming experiment in a tropical Andisol. Andisols can store large, persistent pools of soil carbon that are protected from decomposition by poorly and non-crystalline minerals (PNCM). In 20 cm depth intervals, we measured key soil properties including carbon, nitrogen, pH, PNCM, bacterial and fungal richness along with temperature, moisture, and CO 2 production. Over a year of soil warming, CO 2 production significantly increased by 50–300% per degree of warming, but only in the top 40 cm of the soil profile in contrast to the results of other deep soil warming experiments. Multimodal analysis supported our hypothesis that high concentrations of PNCM was the primary driver of the lack of CO 2 response, followed by high relative soil moisture and low bacterial richness, which may be a proxy for organic carbon availability. The lack of elevated CO 2 production in response to warming suggests a limited positive feedback to climate change in Andisols driven by their strong mineral protection of organic matter. Therefore, Andisols should be considered high priority restoration or protection areas when considering the management of soil carbon stocks as part of climate action.

54 ENVIRONMENTAL SCIENCES↗

Incorporating Microtopography in a Land Surface Model and Quantifying the Effect on the Carbon Cycle

Abstract Northern peatlands are a terrestrial carbon store, with an annual sink of 0.1 Pg C yr −1 and a total storage estimate of 547 Pg C. Northern peatlands are also major contributors of atmospheric methane. Most land surface models do not accurately represent peatland carbon emissions, partly because they do not represent the hydrologic cycle and/or microtopography adequately. Interactions between water table depth and microtopography in peatlands influence decomposition and modulate CO 2 and CH 4 fluxes. A modified version of the land surface component of the Energy Exascale Earth System Model, was recently created to represent the microtopography and hydrology of a raised dome bog in northern Minnesota, USA. In this study, three microtopographic parameters are analyzed in the modified version: hummock height, hummock‐hollow spacing, and percent hollow. Terrestrial laser scanning observations are used to set uncertainty bounds for these parameters. Our model experiment results suggest that carbon‐related quantities of interest (QOI) were typically the most sensitive to hummock height, and those QOI (especially net ecosystem exchange, NEE) were sensitive to interactions between parameters. Furthermore, NEE was most relatively influenced by microtopographic parameters in the model, varying by 35%. We found that increasing hummock height resulted in more C being stored in plant tissue and less in soil organic matter. This coincided with decreases in Sphagnum and increases in Picea and shrub net primary production. These results suggest that future studies may consider extending prognostic capabilities of carbon cycling by incorporating hummock hollow microtopography into earth system models.

58 GEOSCIENCES↗

Diversifying and perennializing plants in agroecosystems alters retention of new C and N from crop residues

Abstract Managing soils to retain new plant inputs is key to moving toward a sustainable and regenerative agriculture. Management practices, like diversifying and perennializing agroecosystems, may affect the decomposer organisms that regulate how new residue is converted to persistent soil organic matter. Here we tested whether 12 years of diversifying/perennializing plants in agroecosystems through extended rotations or grassland restoration would decrease losses of new plant residue inputs and, thus, increase retention of carbon (C) and nitrogen (N) in soil. We tracked dual‐labeled ( 13 C and 15 N), isotopically enriched wheat ( Triticum aestivum ) residue in situ for 2 years as it decomposed in three agroecosystems: maize–soybean (CS) rotation, maize–soybean–wheat plus red clover and cereal rye cover crops (CSW2), and spring fallow management with regeneration of natural grassland species (seven to 10 species; SF). We measured losses of wheat residue (C wheat and N wheat ) in leached soil solution and greenhouse gas fluxes, as well as how much was recovered in microbial biomass and bulk soil at 5‐cm increments down to 20 cm. CSW2 and SF both had unique, significant effects on residue decomposition and retention dynamics that were clear only when using nuanced metrics that able to tease apart subtle differences. For example, SF retained a greater portion of C wheat in 0–5 cm surface soils (155%, p = 0.035) and narrowed the C wheat to N wheat ratio ( p < 0.030) compared to CS. CSW2 increased an index of carbon‐retention efficiency, C wheat retained in the mesocosm divided by total measured, from 0.18 to 0.27 (49%, p = 0.001), compared to CS. Overall, we found that diversifying and extending the duration of living plants in agroecosystems can lead to greater retention of new residue inputs in subtle ways that require further investigation to fully understand.

McDaniel, Marshall D.↗

Lipid–enhanced Oilcane does not impact soil carbon dynamics compared with wild–type Sugarcane

The carbon neutral potential of bioenergy relies in part on the ability of feedstocks to sequester carbon (C) in the soil. Sugarcane is one of the most widely used bioenergy crops, yet there remain unknowns about how it impacts soil C dynamics. In addition, Oilcane, a genetically modified version of Sugarcane has been produced to accumulate more energy-dense oils and less soluble lignin, which enhances conversion efficiency but may also impact soil C cycling. Thus, our objectives were to examine the impact of Sugarcane litter decomposition on soil C formation and losses and determine if the genetic modifications to produce Oilcane alter these dynamics. To do this, we incubated bagasse (processed stem litter) and leaf litter from Sugarcane and Oilcane in microcosms with forest soil for 11 weeks. We used differences in natural abundance δ 13 C between C 3 forest soil and C 4 litter to trace the fate of the litter into respiratory losses as well as stable and unstable soil C pools. Our results show that genetic modifications to Oilcane did not substantially alter soil C dynamics. Sugarcane and Oilcane litter both led to net soil C gains dominated by an accumulation of the added litter as unstable, particulate organic C (POC). Oilcane litter led to small but significantly greater net soil C gains than Sugarcane litter due to greater POC formation, but the formation of stable, mineral associated organic matter (MAOC) did not differ between crop types. Sugarcane and Oilcane had opposing effects on tissue type where Sugarcane bagasse formed more MAOC, while Oilcane leaves preferentially remained as POC which may have important management implications. These results suggest that genetic modifications to Sugarcane will not significantly impact soil C dynamics; however, this may not be universal to other crops particularly if modifications lead to greater differences in litter chemistry.

09 BIOMASS FUELS↗

Out-of-equilibrium processes in crystallization of organic-inorganic perovskites during spin coating

Complex phenomena are prevalent during the formation of materials, which affect their processing-structure-function relationships. Thin films of methylammonium lead iodide (CH 3 NH 3 PbI 3 , MAPI) are processed by spin coating, antisolvent drop, and annealing of colloidal precursors. The structure and properties of transient and stable phases formed during the process are reported, and the mechanistic insights of the underlying transitions are revealed by combining in situ data from grazing-incidence wide-angle X-ray scattering and photoluminescence spectroscopy. Here, we report the detailed insights on the embryonic stages of organic-inorganic perovskite formation. The physicochemical evolution during the conversion proceeds in four steps: i) An instant nucleation of polydisperse MAPI nanocrystals on antisolvent drop, ii) the instantaneous partial conversion of metastable nanocrystals into orthorhombic solvent-complex by cluster coalescence, iii) the thermal decomposition (dissolution) of the stable solvent-complex into plumboiodide fragments upon evaporation of solvent from the complex and iv) the formation (recrystallization) of cubic MAPI crystals in thin film.

36 MATERIALS SCIENCE↗

Multi-modelling predictions show high uncertainty of required carbon input changes to reach a 4‰ target

Soils store vast amounts of carbon (C) on land, and increasing soil organic carbon (SOC) stocks in already managed soils such as croplands may be one way to remove C from the atmosphere, thereby limiting subsequent warming. The main objective of this study was to estimate the amount of additional C input needed to annually increase SOC stocks by 4‰ at 16 long-term agricultural experiments in Europe, including exogenous organic matter (EOM) additions. We used an ensemble of six SOC models and ran them under two configurations: (1) with default parametrization and (2) with parameters calibrated site-by-site to fit the evolution of SOC stocks in the control treatments (without EOM). We compared model simulations and analysed the factors generating variability across models. The calibrated ensemble was able to reproduce the SOC stock evolution in the unfertilised control treatments. We found that, on average, the experimental sites needed an additional 1.5 ± 1.2 Mg C ha -1 year -1 to increase SOC stocks by 4‰ per year over 30 years, compared to the C input in the control treatments (multi-model median ± median standard deviation across sites). That is, a 119% increase compared to the control. While mean annual temperature, initial SOC stocks and initial C input had a significant effect on the variability of the predicted C input in the default configuration (i.e., the relative standard deviation of the predicted C input from the mean), only water-related variables (i.e., mean annual precipitation and potential evapotranspiration) explained the divergence between models when calibrated. Here, our work highlights the challenge of increasing SOC stocks in agriculture and accentuates the need to increasingly lean on multi-model ensembles when predicting SOC stock trends and related processes. To increase the reliability of SOC models under future climate change, we suggest model developers to better constrain the effect of water-related variables on SOC decomposition.

4 per 1000 initiative↗

Soil organic matter, tree communities, and fungal communities across mycorrhizal gradients in the Eastern United States

We collected these data to investigate how mycorrhizal associations are related to soil C and N across four sites in the eastern U.S. broadleaf forest biome, which capture broad variability in climate and tree species. Our sites represented each of the four ecoregions in the eastern United States temperate forest—warm continental (New Hampshire), hot continental (Wisconsin), Prairie (Illinios), and subtropical (Georgia). This breadth naturally provided tree species diversity and allowed us to also investigate how soil C and N are related to canopy tree and EcM fungal community composition. Specifically, we analyzed the effects of mycorrhizal association, canopy tree family, and EcM fungal taxa on the proportion of C and N associated with soil minerals (MAOM) and bulk soil C:N. These are plot level data from forests in New Hampshire, Georgia, Wisconsin, and Illinois. The plots are 10 m in radius and vary across gradients of ectomycorrhizal tree basal area. Within each plot, data include the basal area of all trees >2 cm in diameter identified to species, the abundance of different fungal taxa based on ITS sequences, and the %C, %N, C:N of bulk soil and of soil density fractions (free light, occluded light, and particulate) as well as the proportion of soil C and N within each fraction. The soil data (both organic matter and fungal communities) are from the top 10 cm of the mineral soil. This also includes a meta-analysis of leaf litter k and C:N values for the tree species present in the forests.The "Tree_BA_ALL.csv" files include the basal area of all trees >2 cm in diameter at breast height within our 10 cm radii plots. The "Soil_Data_Final.csv" file contains the soil carbon and nitrogen in bulk and density fractions (concentrations as well as proportion for free light fraction (fLF), occluded light fraction (oLF), and heavy or dense fraction (HF), oxalate extractable iron and aluminum concentrations, as well as the geographic coordinates of each plot's location. The "FungiNonRelative.csv" file contains the abundances of fungal taxa identified via ITS sequencing for each plot (with the exception of 4 plots from GA where there was not enough quality DNA to extract).The "R_ReadyK.csv" and "R_Ready_CN.csv" files contain leaf litter decomposition constant (k) and C:N values from the literature for the tree species found at our sites.

54 ENVIRONMENTAL SCIENCES↗

Age and chemistry of dissolved organic carbon reveal enhanced leaching of ancient labile carbon at the permafrost thaw zone

Abstract. Climate change will alter the balance between frozen and thawed conditions in Arctic systems. Increased temperatures will make the extensive northern permafrost carbon stock vulnerable to decomposition and translocation. Production, cycling, and transport of dissolved organic carbon (DOC) are crucial processes for high-latitude ecosystem carbon loss that result in considerable export off the Arctic landscape. To identify where and under what conditions permafrost DOC is mobilized in an Arctic headwater catchment, we measured radiocarbon (14C) of DOC and assessed DOC composition with ultraviolet–visible spectroscopy (UV–Vis) of surface waters and shallow and deep subsurface porewaters from 17 drainages in the Barrow Environmental Observatory in Alaska. Samples were collected in July and September 2013 to assess changes in age and chemistry of DOC over time. DOC age was highly variable ranging from modern (19 ‰ Δ14C) to approximately 7000 BP (−583 ‰ Δ14C). DOC age increased with depth, over the summer as the active layer deepened, and with increasing drainage size. DOC quality indicators reflected a DOC source rich in high molecular-weight and aromatic compounds, characteristics consistent with vegetation-derived organic matter that had undergone little microbial processing, throughout the summer and a weak relationship with DOC age. In deep porewaters, DOC age was also correlated with several biogeochemical indicators (including dissolved methane concentration, δ13C, and the apparent fractionation factor), suggesting a coupling between carbon and redox biogeochemistry influencing methane production. In the drained thawed lake basins included in this study, DOC concentrations and contributions of vegetation-derived organic matter declined with increasing basin age. The weak relationship between DOC age and chemistry and consistency in DOC chemical indicators over the summer suggest a high lability of old DOC released by thawing permafrost.

54 ENVIRONMENTAL SCIENCES↗

The transformation of diamond to graphite: Experiments reveal the presence of an intermediate linear carbon phase

Natural diamonds that have been partially replaced by graphite have been observed to occur in natural rocks. While the graphite-to-diamond phase transition has been extensively studied the opposite of this (diamond to graphite) remains poorly understood. We performed high-pressure and temperature hydrous and anhydrous experiments up to 1.0 GPa and 1300 °C using Amplex premium virgin synthetic diamonds (20–40 μm size) as the starting material mixed with Mg(OH) 2 as a source of H 2 O for the hydrous experiments. The experiments revealed that the diamond-to-graphite transformation at P = 1.0 GPa and T = 1300 °C was triggered by the presence of H 2 O and was accomplished through a three-stage process. Stage 1: diamond reacts with a supercritical H 2 O producing an intermediate 200–500 nm size “globular carbon” phase. This phase is a linear carbon chain; i.e. a polyyne or carbyne. Stage 2: the linear carbon chains are unstable and highly reactive, and they decompose by zigzagging and cross-linking to form sp 2 -hybridized structures. Stage 3: normal, disordered, and onion-like graphite is produced by the decomposition of the sp-hybridized carbon chains which are re-organized into sp 2 bonds. Our experiments show that there is no direct transformation from sp 3 C-bonds into sp 2 C-bonds. Our hydrous high-pressure and high-temperature experiments show that the diamond-to-graphite transformation requires an intermediate metastable phase of a linear hydrocarbon. This process also provides a simple mechanism for the substitution of other elements into the graphite structure (e.g. H, S, O).

36 MATERIALS SCIENCE↗

Effects of 9.5 Years of Whole-Soil Warming on the Fatty Acid and n-Alkanes Composition in Bulk Soil and Density Fractions at Blodgett Experimental Forest, California, USA

Original data of molecular data (fatty acids and n-alkanes) including concentrations and calculated molecular proxies in a whole-soil warming experiment at the Blodgett Forest Research Station after 9.5 years of warming. The study site has a Mediterranean climate with annual average temperature of 12.5 ℃ and annual average precipitation of 1774 mm. The study site is characterized by a mesic Ultic Alfisol formed from granitic parent material, corresponding to a Dystric Cambisol under the World Reference Base for Soil Resources (WRB) classification system. Experimental warming is applied throughout the soil profile to a depth of 1 m using vertically embedded heating cables that raise soil temperature by 4 °C relative to ambient conditions. Soil samples were collected on 1 May 2023, after the experiment had been operating continuously for about 9.5 years since its initiation in January 2014.The data has been processed from raw data and cross-validated by other peers. The dataset includes: - Bulk_Fattyacid_9.5-year_Soil_Warming_Blodgett, California, USA: fatty acid concentrations and proxies including Carbon Preference Index (CPI) and Average Chain Length (ACL) of bulk soil organic carbon; - Fractions_Fattyacid_9.5-year_Soil_Warming_Blodgett, California, USA: fatty acid concentrations and proxies including CPI and ACL of free particulate organic matter (fPOM) and mineral-associated organic matter (MAOM); - Bulk_Alkanes_9.5-year_Soil_Warming_Blodgett, California, USA: n-alkanes concentrations and proxies including CPI and ACL of bulk soil organic carbon; - Fractions_Alkanes_9.5-year_Soil_Warming_Blodgett, California, USA: n-alkanes concentrations and proxies including CPI and ACL of fPOM and MAOM; - n-Alkanes_All_Monomer_Concentration_9.5-year_Soil_Warming_Blodgett, California, USA: concentration of all the n-alkane monomers identified and integrated for bulk soil, fPOM and MAOM; - Fattyacid_All_Monomer_Concentration_9.5-year_Soil_Warming_Blodgett, California, USA: concentration of all the fatty acid monomers including diacids identified and integrated for bulk soil, fPOM, and MAOM. All data are provided in CSV format and can be viewed using Microsoft Excel. We specifically look at fatty acids (FA) and n-alkanes in bulk soil, fPOM and MAOM and calculated molecular proxies such as CPI and ACL to understand the source of oragnic carbon (with ACL) and degree of decomposition (CPI) of each soil fraction. Due to lack of long-chain fatty acids (carbon number ⩾ 20), microorganism-derived organic carbon is characterized by shorter ACL in comparison to plant-derived organic carbon. Fresh SOC is characterized by even-over-odd dominance for fatty acids and odd-over-even dominance for n-alkanes. Therefore, CPI indicates whether soil organic carbon (SOC) represents fresh input (CPI > 10) or is strongly decomposed (close to 1). The research questions should be then, after 9.5-year warming: 1. whether the relative contribution between microorganism-derived and plant-derived SOC in each soil fraction? 2. whether fPOM became more decomposed whereas MAOM remained relatively persistent in each soil fraction across the soil depth?

Carbon↗

An In Situ , Automated High-Explosives Aging Method Utilizing Two-Dimensional Gas Chromatography–Mass Spectrometry

Understanding chemical changes that occur in high explosives as they age is of great importance to the safe employment and storage of these compounds. Traditional methods of aging high explosives even under accelerated aging conditions are time intensive with durations on the order of months to years. The nature of traditional aging analyses reduces each sample to a snapshot data point often separated widely in time, requiring many assumptions as to how the degradation products develop. Further complicating matters, several analytical techniques are typically employed for each sample analysis in order to ascertain an entire picture of the decomposition pathways. To address these shortcomings with existing methods, a new method of accelerated aging of high explosives utilizing comprehensive two-dimensional gas chromatography coupled to high-resolution mass spectrometry (GC × GC-HRMS) was developed using 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) as a model compound for method development. This in situ automated method reduces the time scale of aging to a matter of hours using the inlet of the GC × GC as the aging vessel. GC × GC in combination with HRMS allowed for the collection of both evolved gases and other decomposition products produced during the entire aging process in real time with HRMS providing far greater certainty in identification of explosives aging products. Additionally, this method allowed for a higher throughput of samples with greatly simplified sample preparation. Chemometric analysis of the GC × GC-HRMS data set via the alteration analysis (ALA) enabled discovery of statistically significant chemical changes providing insight into the variation of decomposition pathways with varying aging temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen Dynamics in Supercritical Water Probed by Neutron Scattering and Computer Simulations

In this work, an investigation of supercritical water is presented combining inelastic and deep inelastic neutron scattering experiments and molecular dynamics simulations based on a machine-learned potential of ab initio quality. The local hydrogen dynamics is investigated at 250 bar and in the temperature range of 553–823 K, covering the evolution from subcritical liquid to supercritical gas-like water. The evolution of libration, bending, and stretching motions in the vibrational density of states is studied, analyzing the spectral features by a mode decomposition. Moreover, the hydrogen nuclear momentum distribution is measured, and its anisotropy is probed experimentally. It is shown that hydrogen bonds survive up to the higher temperatures investigated, and we discuss our results in the framework of the coupling between intramolecular modes and intermolecular librations. Results show that the local potential affecting hydrogen becomes less anisotropic within the molecular plane in the supercritical phase, and we attribute this result to the presence of more distorted hydrogen bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling Photolytic Decomposition of Energetically Functionalized Dodecanes

The photolytic stability of explosives and energetic functional groups is of importance for those who regularly handle or are exposed to explosives in typical environmental conditions. This study models the photolytic degradation of dodecane substituted with various energetic functional groups: azide, nitro, nitrate ester, and nitramine. For the studied molecules, it was found that excitons localize on the energetic functional group, no matter where they were initially formed, and thus, the predominant degradation pathway involves the degradation of the energetic functional group. The relative trends for both 4 and 8 eV excitation energies followed with what is expected from the relative stability of the energetic functional groups to thermal and sub-shock degradation. The one notable exception was the azide functional group; more work should be done to further understand the photolytic effects on the azide functional group.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Substrate quality drives fungal necromass decay and decomposer community structure under contrasting vegetation types

Fungal mycelium is increasingly recognized as a central component of soil biogeochemical cycling, yet our current understanding of the ecological controls on fungal necromass decomposition is limited to single sites and vegetation types. By deploying common fungal necromass substrates in a temperate oak savanna and hardwood forest in the midwestern USA, we assessed the generality of the rate at which high- and low-quality fungal necromass decomposes; further, we investigated how the decomposer ‘necrobiome’ varies both across and within sites under vegetation types dominated by either arbuscular or ectomycorrhizal plants. In this work, the effects of necromass quality on decay rate were robust to site and vegetation type differences, with high-quality fungal necromass decomposing, on average, 2.5 times faster during the initial stages of decay. Across vegetation types, bacterial and fungal communities present on decaying necromass differed from bulk soil microbial communities and were influenced by necromass quality. Moulds, yeasts and copiotrophic bacteria consistently dominated the necrobiome of high-quality fungal substrates. Synthesis. We show that regardless of differences in decay environments, high-quality fungal substrates decompose faster and support different types of decomposer micro-organisms when compared with low-quality fungal tissues. These findings help to refine our theoretical understanding of the dominant factors affecting fast cycling components of soil organic matter and the microbial communities associated with rapid decay.

59 BASIC BIOLOGICAL SCIENCES↗

Carbon Storage in Wetlands and Lakes of the Eastern US

Carbon stored underground may participate in a positive feedback with climate warming, as higher temperatures accelerate decomposition reactions and hence CO2 release. Assessing how below-ground carbon storage varies with modern climate and paleoclimate will advance understanding of this feedback in two ways. First, it will estimate the sensitivity of carbon storage to temperature and precipitation changes. Second, it will help quantify the size of carbon stocks available for the feedback, by indicating how current regional climate differences affect carbon storage. Whereas many studies of below-ground carbon storage concentrate on soils, this investigation focuses on the saturated and primarily organic material stored in wetlands and lake sediments. This study surveys research done on organic sediment depth and organic content at 50-100 sites in the eastern U.S., integrating our own research with the work of others. Storage depth is evaluated for sediments from the past 10,000 years, a date reflected in pollen profiles. Organic content is measured chiefly by loss-on-ignition (101). These variables are compared to characteristics of the sites such as latitude, altitude, and vegetation as well as local climate. Preliminary results suggest a strong relationship between latitude and depth of organic material stored over the last 10,000 years, with more accumulation in the northeastern US than the southeastern US. Linking the percent organic matter to actual carbon content is in progress with wetlands from Black Rock Forest and Alpine Swamp.

Renik, Byrdie↗

Liquid and Glass Phases of an Alkylguanidinium Sulfonate Hydrogen-Bonded Organic Framework

Glassy phases of framework materials feature unique and tunable properties that are advantageous for gas separation membranes, solid electrolytes, and phase-change memory applications. However, the structural and chemical diversity of porous frameworks that can be liquified and quenched into a glass has been limited by thermal decomposition at-or below-the high temperatures required to induce a melting transition. Utilizing a desymmetrization strategy, in this work we report a new guanidinium organosulfonate hydrogen-bonded organic framework (HOF) that melts and vitrifies below 100 °C. In this low-temperature regime, non-covalent interactions between guest molecules and the porous framework become a dominant contributor to the overall stability of the structure, resulting in unusual phase behavior such as guest dependent melting, glass, and recrystallization transitions. Through molecular dynamics simulations and pair distribution function analysis, we show that the local structure of the amorphous liquid and glass phase resembles that of the parent crystalline framework. Access to molten phases of framework materials at moderate temperatures should permit the use of more thermally sensitive functional groups and enhance the structural control and tunability that can be realized in network-forming glasses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Getting to the root of the problem: Soil carbon and microbial responses to root inputs within a buried paleosol along an eroding hillslope in southwestern Nebraska, USA

Large quantities of soil carbon (C) can persist within paleosols for millennia due to burial and subsequent isolation from plant-derived inputs, atmospheric conditions, and microbial activity at the modern surface. Erosion exposes buried soils to modern root-derived C influx via root exudation and root turnover, thus stimulating microbial activity leading to SOC decomposition and accumulation through organo-mineral stabilization of modern C. With this study we aim to quantify how modern root-derived C inputs impact paleosol C decomposition and stabilization across varying degrees of isolation from modern surface conditions in southwestern Nebraska, USA, where hillslope erosion is bringing a buried Late-Pleistocene-early Holocene paleosol (the “Brady Soil”) closer to the modern surface. We collected Brady Soil samples from 0.2m, 0.4m, and 1.2m below the modern surface and conducted two lab-based incubations. Soils were amended with either (1) a lab-synthesized mixture of low molecular weight compounds (12 atom% 13 C), or (2) 13 C enriched root residues (92 atom% 13 C), in 30-day and 240-day incubation experiments, respectively. Here we determined microbial responses to synthetic root exudates and residues by partitioning the 13 C label from Brady Soil C, including measurements of total, root, and primed C respiration, microbial biomass C (MBC), microbial C use efficiency (CUE). To assess the capacity of isolated paleosols to accrue modern plant C, we used Nano-scale Secondary Ion Mass Spectrometry imaging. We found that: (1) adding root-derived C inputs primed Brady Soil C across all depths, and was mediated by depth and composition of root additions; (2) root-derived C inputs stimulated microbial biomass C (MBC) growth similarly across depths, but the magnitude of CUE and MBC varied by chemistry of root-derived additions; (3) new particulate organic matter was incorporated into mineral-associated pools over time; (4) material from the added root residues was found in association with bacterial cells and fungal hyphae as well as with soil aggregate and mineral surfaces. Our study shows that paleosols defy expectations of C content and reactivity with depth, and changes in land cover and climate will expose buried paleosols to modern surface conditions, increasing respired C. This work highlights the importance of evaluating the role resurfacing buried soils through landscape change plays in C cycle feedbacks to the climate system.

54 ENVIRONMENTAL SCIENCES↗