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At least 109 records · Page 6

Aircraft Measurements from a U.S. Western Wildfire Demonstrating Day and Night Differences in the Chemical Composition and Optical Properties of Biomass Burning Aerosols and Their Atmospheric Evolution

The composition and transformations of biomass burning aerosols (BBA) have been measured onboard the NOAA Twin Otter research aircraft during the Fire Influence on Regional to Global Environments and Air Quality field study. Here, we analyze real-time aerosol mass spectrometry measurements across three flights during the afternoon, late afternoon, and night of August 28, 2019, for one midsized wildfire. Analysis of several metrics showed that the aerosol composition and optical properties varied depending on the burning conditions at the fire zone and the time of day the BBA was emitted, with substantial variations in the available sunlight. The total aerosol mass loadings were dominated by organic components with a much smaller contribution from inorganic species. A gradual buildup of organic material was observed during the afternoon as the plume aged, indicating the condensation of photochemically formed low-volatility oxidized organic compounds. Highly hygroscopic ammonium nitrate was the main inorganic component, suggesting potential water content in BBA particles and the likelihood of their aqueous-phase reactivity. Depletions of particle-phase NO 3 – and Cl – relative to carbon monoxide were observed in the late afternoon and nighttime plumes, respectively, aligning with known gas-particle partitioning thermodynamics and the heterogeneous chemistry of dissolved nitrate and chloride. The wavelength-dependent light absorption by aerosol species was higher for the plume sampled at night and showed no significant changes with plume age, despite observed trends in composition and mass downwind. These differences in particle composition and optical properties demonstrate that the processes involved in BBA aging are not uniform for the same wildfire over the course of the day and depend highly on when the BBA was emitted, as well as the burning phase at the emissions source.

54 ENVIRONMENTAL SCIENCES↗

Chemostatic concentration–discharge behaviour observed in a headwater catchment underlain with discontinuous permafrost

Concentration–discharge dynamics were evaluated in a small (~ 2.25 km2) headwater catchment underlain with discontinuous permafrost on the Seward Peninsula of western Alaska. A large storm, during which 48 mm of rain fell over a 24-h period, enabled the evaluation of solute concentration–discharge response to a sizeable hydrological event, while water stable isotopes enabled an appraisal of the contributions of event water. Under normal catchment conditions, chemostatic behaviour was observed for solutes typically derived from mineral weathering (e.g. calcium, magnesium, sodium and silica). The chemostatic behaviour observed for most solutes under normal catchment conditions indicated that catchment storage and residence times are sufficiently long for many solute generating reactions to approach equilibrium. Following the storm however, most solutes exhibited dilutive and highly variable behaviour. This likely indicated the exceedance of a discharge threshold where chemostatic behaviour could no longer be maintained for most solutes. Dissolved organic carbon and silica were the only solutes monitored to exhibit chemostatic behaviour during all time periods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Replacement of Calcium Carbonate Polymorphs by Cerussite

Calcium carbonate (CaCO 3 ) polymorphs, calcite, aragonite, and vaterite, serve as a major sink to retain various metal ions in natural and engineered systems. Here, we visualize the systematic trends in reactivities of calcite, vaterite, and aragonite to Pb 2+ dissolved in acidic aqueous solutions using in situ optical microscopy combined with ex situ scanning electron and transmission X-ray microscopies. All three polymorphs undergo pseudomorphic replacement by cerussite (PbCO 3 ) but with distinct differences in the evolution of their morphologies. The replacement of calcite and aragonite occurs through the formation of a pseudomorphic cerussite shell (typically 5–10 μm thick) followed by a slower inward propagation of reaction fronts through a thin solution gap (~0.1 μm wide) between the shell and the CaCO 3 substrate. The replacement of vaterite is characterized by the formation of a thinner cerussite shell (≤1 μm thick) and a larger cavity between the shell and the host mineral. These systematic differences in cerussite morphology for different CaCO 3 polymorphs are explained by the relative dissolution and precipitation rates of the reactant and product minerals, coupled with the role of ion transport through the cerussite shells. We also find that the replacement of calcite by cerussite is the slowest when all three polymorphs coexisted. Furthermore, our results provide mechanistic insights into the growth mode of cerussite on dissolving calcium carbonate and demonstrate these CaCO 3 polymorphs as promising substrate materials for removal and recycling of Pb from acidic polluted water and industrial effluents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterizing the localization of organic C on mineral surfaces: a correlative microscopy/spectroscopy approach

It is estimated that organic carbon (OC) in soils exceeds the amount of OC in atmosphere and in vegetation pools combined.1 Given the current changes in climate and increasing temperatures in the environment, the fraction of OC sequestered in soils and sediments is more sensitive to decomposition and release as CO 2 in the atmosphere. Evidence implies that sorption and association of dissolved OC with inorganic soil components, i.e., soil minerals, is a key mechanism that contributes to stabilization and retention of OC in soil environment. Studies have shown a direct correlation between sorption of dissolved OC and soil mineral surface properties and their surface area. In addition, properties of organic compounds such as chemical structure and functional groups play a significant role in interaction of dissolved organic species with mineral surfaces. Association of OC with minerals via ligand exchange reactions, polyvalent tertiary bonding, or complexation with metal ions, is found to be preferential and dependent on the organic compounds’ functional groups.

54 ENVIRONMENTAL SCIENCES↗

Investigation of the structure, filler interaction and degradation of disulfide elastomers made by Reversible Radical Recombination Polymerization (R3P)

In this paper we report the synthesis and analysis of cyclic polydisulfides, their redox depolymerization as well as their interaction with carbon black. Cyclic poly(3,6-dioxa-1,8-octanedithiol)s (pDODT) were synthesized by Reversible Radical Recombination Polymerization (R3P). R3P is a scalable “green” polymerization process using triethylamine (TEA), H 2 O 2 and air for the polymerization of dithiol monomers. pDODTs were synthesized in 5 and 20 g batches. The effect of peroxide concentration (3, 5, 10, 20, 30%) was investigated. It was found that the molecular weights increased exponentially with increasing peroxide concentrations. At 30% peroxide concentration pDODTs with M n up to 400,000 g/mol and polydispersity of 2 were obtained. 700 and 800 MHz NMR were used for investigating the chemical structure of the polymers. The absence of thiol end group signals in polymers made with > 10wt % H 2 O 2 and M n < 100,000 g/mol, including a sample of a fractionated polymer with starting Mn = 600,000 g/mol, verified cyclic structures. Dithiothreitol reduced the polymers to monomer and a small percentage of oligomers. Carbon black was shown to increase the moduli of high molecular weight pDODTs. Swelling tests in chloroform showed that polymers made with 20 and 30w% peroxide swelled 14 and 10 times of their starting weight without dissolving, indicating chemical interaction between the polymers and carbon black. In conclusion, further analysis of these interesting elastomers, available at the 20 g scale, is in progress.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Physics-informed machine learning to predict solvatochromic parameters of designer solvents with case studies in CO 2 and lignin dissolution

The polarity of solvents plays a critical role in various research applications, particularly in their solubilities. Polarity is conveniently characterized by the Kamlet-Taft parameters that is, the hydrogen bonding acidity (α), the basicity (β), and the polarizability (π*). Obtaining Kamlet-Taft parameters is very important for designer solvents, namely ionic liquids (ILs) and deep eutectic solvents (DESs). However, given the unlimited theoretical number of combinations of ionic pairs in ILs and hydrogen-bond donor/acceptor pairs in DESs, experimental determination of their Kamlet-Taft parameters is impractical. To address this, the present study developed two different machine learning (ML) algorithms to predict Kamlet-Taft parameters for designer solvents using quantum chemically derived input features. The ML models developed in the present study showed accurate predictions with high R 2 and low RMSE values. Further, in the context of present interest in the circular bioeconomy, the relationship between the basicities and acidities of designer solvents and their ability to dissolve lignin and carbon dioxide (CO 2 ) is discussed. Our method thus guides the design of effective solvents with optimal Kamlet-Taft parameter values dissolving and converting biomass and CO 2 into valuable chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impacts of Forest Fire Ash on Aquatic Mercury Cycling

Mercury (Hg) is a ubiquitous contaminant in the environment and its methylated form, methylmercury (MeHg), poses a worldwide health concern for humans and wildlife, primarily through fish consumption. Global production of forest fire ash, derived from wildfires and prescribed burns, is rapidly increasing due to a warming climate, but their interactions with aqueous and sedimentary Hg are poorly understood. In this study, we compared the differences of wildfire ash with activated carbon and biochar on the sorption of aqueous inorganic Hg and sedimentary Hg methylation. Sorption of aqueous inorganic Hg was greatest for wildfire ash materials (up to 0.21 μg g ₋1 or 2.2 μg g ₋1 C) among all of the solid sorbents evaluated. A similar Hg adsorption mechanism for activated carbon, biochar made of walnut, and wildfire ash was found that involves the formation of complexes between Hg and oxygen-containing functional groups, especially the ₋COO group. Notably, increasing dissolved organic matter from 2.4 to 70 mg C L ₋1 remarkably reduced Hg sorption (up to 40% reduction) and increased the time required to reach Hg–sorbent pseudo-equilibrium. Surprisingly, biochar and wildfire ash, but not activated carbon, stimulated MeHg production during anoxic sediment incubation, possibly due to the release of labile organic matter. Overall, our study indicates that while wildfire ash can sequester aqueous Hg, the leaching of its labile organic matter may promote production of toxic MeHg in anoxic sediments, which has an important implication for potential MeHg contamination in downstream aquatic ecosystems after wildfires.

54 ENVIRONMENTAL SCIENCES↗

Predicting chemical reaction equilibria in molten carbonate fuel cells via molecular simulations

It has been recently suggested that hydroxide ions can be formed in the electrolyte of molten carbonate fuel cells when water vapor is present. The hydroxide can replace carbonate in transporting electrons across the electrolyte, thereby reducing the CO 2 separation efficiency of the fuel cell although still producing electricity. In this work, we obtain the equilibrium concentration of hydroxide in five molten alkali carbonate salts from molecular simulations. The results reveal that there can be a substantial amount of hydroxide in the electrolyte at low partial pressures of CO 2 . In addition, we find that the equilibrium concentration of molecular water dissolved in the electrolyte is over two orders of magnitude higher than that of CO 2 . Increasing the size and polarizability (or in other words reducing the “hardness”) of the cations present in the electrolyte can reduce the hydroxide fraction, but at the cost of lowering ionic conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Real-Time Atomic-Scale Structural Analysis Resolves the Amorphous to Crystalline CaCO 3 Mechanism Controversy

Amorphous calcium carbonate (ACC) occurs as a precursor to geological and biogenic calcium carbonate (CaCO 3 ), yet its transformation pathways and reaction mechanisms remain inconsistent and controversial. In this study, we investigated the transformation of ACC to calcite under both solution and dry conditions, in the presence and absence of impurity ions, utilizing operando time-resolved synchrotron X-ray diffraction (TRXRD) and reactive transport modeling. Results demonstrate that TRXRD techniques allow us to differentiate dissolution-reprecipitation versus solid-state transformation mechanisms for amorphous to crystalline phase transitions. Specifically, we observe that in environments with abundant water, ACC transforms to calcite through a dissolution-reprecipitation mechanism. This features an activation energy of 63 ± 2 kJ/mol and unit cell volume contraction during calcite crystal growth. Conversely, under water-limited conditions, ACC to calcite transformation proceeds via a solid-state transformation mechanism, with an activation energy of 210 ± 2 kJ/mol, three times greater than the dissolution-reprecipitation route, and a unit cell expansion during crystalline calcite growth. Further, to illustrate the magnitude of these effects, the rates of calcite growth were similar during dissolution-reprecipitation at 3 °C [0.00207(35) s –1 ] and solid-state transformation at 280 °C [0.00134(11) s –1 ]. Moreover, the incorporation of an impurity, strontium, significantly retards the rate of calcite growth while expanding its unit cell but whose incorporation is history dependent. Reactive transport modeling of the dissolution–precipitation kinetics suggests that ACC must be dissolving as compact aggregates. These various transformation mechanisms drive diverse geological and biological carbonate formations, impacting their use as paleoenvironmental markers and functional materials synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of carbon treating in piperazine oxidation

Bench-scale experiments were performed to test the effects of carbon treating (8 × 30 mesh, lignite-based granular activated carbon from Nowata Filtration) on the oxidation of aqueous piperazine (PZ) at conditions of CO 2 capture. The combined mitigation with carbon treating and N 2 sparging was also tested. When carbon treating is applied, the UV–Vis absorbance at 320 nm, the NH 3 production rate, and the accumulation rate of dissolved Fe concentration and total formate concentration decrease. The effects of carbon treating last even when the carbon is bypassed, which is possibly due to the removal of catalytic degradation products. Therefore, it is better to apply carbon treating in the early stages of oxidation. Combining carbon treating and nitrogen sparging is more effective in oxidation mitigation than applying the methods separately. The amount of Fe removed by the carbon bed is greater than the result calculated from the solvent inventory and concentration difference of Fe in solvent, indicating that Fe colloids or other “soluble” Fe will dissolve into the solvent and replace the dissolved Fe that is adsorbed and removed. Furthermore, the carbon removes the degradation products that can complex with Fe 3+ , even if they are not complexed. Since the source of Fe includes fly ash and corrosion, removing the complexing agents instead of all the available Fe is a more feasible target.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A New Coupled Biogeochemical Modeling Approach Provides Accurate Predictions of Methane and Carbon Dioxide Fluxes Across Diverse Tidal Wetlands

Abstract Tidal wetlands provide valuable ecosystem services, including storing large amounts of carbon. However, the net exchanges of carbon dioxide (CO 2 ) and methane (CH 4 ) in tidal wetlands are highly uncertain. While several biogeochemical models can operate in tidal wetlands, they have yet to be parameterized and validated against high‐frequency, ecosystem‐scale CO 2 and CH 4 flux measurements across diverse sites. We paired the Cohort Marsh Equilibrium Model (CMEM) with a version of the PEPRMT model called PEPRMT‐Tidal, which considers the effects of water table height, sulfate, and nitrate availability on CO 2 and CH 4 emissions. Using a model‐data fusion approach, we parameterized the model with three sites and validated it with two independent sites, with representation from the three marine coasts of North America. Gross primary productivity (GPP) and ecosystem respiration (R eco ) modules explained, on average, 73% of the variation in CO 2 exchange with low model error (normalized root mean square error (nRMSE) <1). The CH 4 module also explained the majority of variance in CH 4 emissions in validation sites ( R 2 = 0.54; nRMSE = 1.15). The PEPRMT‐Tidal‐CMEM model coupling is a key advance toward constraining estimates of greenhouse gas emissions across diverse North American tidal wetlands. Further analyses of model error and case studies during changing salinity conditions guide future modeling efforts regarding four main processes: (a) the influence of salinity and nitrate on GPP, (b) the influence of laterally transported dissolved inorganic C on R eco , (c) heterogeneous sulfate availability and methylotrophic methanogenesis impacts on surface CH 4 emissions, and (d) CH 4 responses to non‐periodic changes in salinity.

54 ENVIRONMENTAL SCIENCES↗

Isotopically labelled inorganic carbon delivered to algalcultures via bubbler bottle

This protocol describes a method for delivering labelled inorganic carbon as 13 CO 2 to algal cultures by bubbling air through a solution of H 13 CO 3 - , and then into the culture. We developed this method to deliver label to cultures grown under continuous bubbling with air, without the use of 13 CO 2 labelled gas and the necessary equipment to mix labelled gas with air at near-atmospheric levels. Bubbling precludes the more common approach of adding H 13 CO 3 - label directly to the media, because dissolved HCO 3 - is in equilibrium with atmospheric CO 2 . Thus, excess HCO 3 - added to a solution will leave the solution as CO 2 gas as it equilibrates. Bubbling rapidly accelerates this equilibration which is typically diffusion limited. The method described here takes advantage of this aspect of carbonate chemistry, and uses a solution of H 13 CO 3 - —which is less expensive and more convenient than 13 CO 2 gas—to generate a flux of 13 CO 2 that can be bubbled into a culture.

59 BASIC BIOLOGICAL SCIENCES↗

Hybrid biophysical systems for atmospheric CO 2 capture

Negative emissions technologies will be essential for limiting anthropogenic global temperature increases to 2 °C in the later years of the 21st century. Carbonic anhydrase (CA) metalloenzymes catalyze the otherwise slow conversion of CO 2 into carbonic acid (H 2 CO 3 ), suggesting their utility in the rapid hydration and downstream capture of dissolved CO 2 in aqueous media for a variety of CO 2 capture methods, such as thermal and pH swings and mineralization. The possibility of driving the rapid capture of CO 2 by catalyzing the CO 2 hydration bottleneck carries real potential for realizing efficient direct air capture (DAC) and direct ocean capture (DOC) systems. However, scaled application of CAs will be dependent on some way of economically sourcing the enzymes at volumes relevant to scaled DAC/DOC operations. In this perspective, we consider the prospect of catalyzing CO 2 hydration using a CA that is bound to the outer membrane of a cyanobacterial host, engineered constructs we call CyCAMs. Coupling extracellular CA expression to a marine, photosynthetic cyanobacterial host results in a CO 2 hydration catalyst that is continuously refreshed during the bacterial growth cycle, without the need for enzyme purification or harvesting steps. In the case of marine cyanobacteria, sunlight and the solutes native to seawater provide the respective energy, nutrients and sources of inorganic carbon essential to maintaining the bacterial population. We consider the potential impact of CA-mediated CO 2 hydration on a variety of DAC processes, with CO 2 mineralization explored as a primary use case.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystallographic Study of Product Phases of Carbothermic Reduction and Nitridation of Hafnium Dioxide

Details of the carbothermic reduction/nitridation to synthesize hafnium nitride (HfN) and hafnium carbide (HfC) are scarce in the literature. Therefore, this current study was carried out to evaluate two pathways for synthesizing these two refractory materials: direct nitridation and carbothermic reduction/nitridation. Two mixtures of hafnium dioxide and carbon with C/HfO 2 molar ratios of 2.15 and 3.1 were nitridized directly using flowing nitrogen gas at elevated temperatures (1300–1700 °C). The 3.1 C/HfO 2 molar ratio mixture was also carbothermically reduced under flowing argon gas to synthesize HfC, which was converted into HfN by introducing a nitridation step under both N 2(g ) and N 2(g) -10% H 2(g) . X-ray diffraction results showed the formation of HfN at 1300 and 1400 °C and HfC 1–y N y at ≥1400 °C under direct nitridation of samples using a C/HfO 2 molar ratio of 2.15. These phase analysis data together with lower lattice strain and greater crystallite sizes of HfC 1–y N y that formed at higher temperatures suggested that the HfC 1–y N y phase is preferred over HfN at those temperatures. Carbothermic reduction of 3.1 C/HfO 2 molar ratio samples under an inert atmosphere produced single-phased HfC with no significant levels of dissolved oxygen. In conclusion, carbothermic reduction nitridation made two phases of different carbon levels (HfC 1–y N y and HfC 1–y 'N y ', where y' < y), while direct nitridation produced a single HfC 1–y N y phase under both N 2 and N 2 -10% H 2 cover gas environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lithium-sulfur battery with polyanthraquinone binder

A cathode for a lithium-sulfur (Li—S) battery is described herein, which comprises elemental sulfur (e.g., S8) and an electroactive polyanthraquinone-containing binder. In some embodiments, the cathode also includes a conductive carbon material in addition to the sulfur and binder. Also described herein is a Li—S battery comprising the cathode, in combination with a metallic lithium-containing anode, a lithium conductive separator membrane between the anode and the cathode, and a liquid electrolyte comprising a lithium salt dissolved in a non-aqueous organic solvent.

25 ENERGY STORAGE↗

Root exudates induced coupled carbon and phosphorus cycling in a soil with low phosphorus availability

The amount and type of root exudates can influence P availability in the rhizosphere directly by desorption or dissolution of soil minerals, or indirectly by decomposition of soil organic matter (SOM). Here this study aimed to determine the mechanisms by which specific root exudates influence the distribution and availability of P in soils with low P availability. Water, glucose, alanine, and oxalate were delivered through a simulated root into soils for 15 days. Zymography and planar optodes were used to image potential phosphatase activity, and O2 and pH distribution, respectively. Soils were analyzed for resin extractable inorganic P (Pi), dissolved organic C (DOC), water soluble Fe, and Al, and microbial community structure. Characterization of SOM and P were conducted using ultra-high resolution mass spectrometry and 31P solution nuclear magnetic resonance (NMR), respectively. The addition of oxalate resulted in the greatest resin extractable Pi, DOC, and water-soluble Fe, and Al compared to the other exudates suggesting destabilization of mineral associated organic matter (MAOM) and release of organic P (Po). Both 31P solution NMR and ultra-high resolution mass spectrometry analysis provided evidence of mineralization of Po released from the destabilization of MAOM. The study demonstrates the important role microbial and plant-derived metal chelating ligands play in destabilizing MAOM, releasing SOM and importantly Po, that when mineralized may contribute to increasing Pi availability in soils with low P availability.

59 BASIC BIOLOGICAL SCIENCES↗

Leptothrix ochracea genomes reveal potential for mixotrophic growth on Fe(II) and organic carbon

ABSTRACT Leptothrix ochracea creates distinctive iron-mineralized mats that carpet streams and wetlands. Easily recognized by its iron-mineralized sheaths, L. ochracea was one of the first microorganisms described in the 1800s. Yet it has never been isolated and does not have a complete genome sequence available, so key questions about its physiology remain unresolved. It is debated whether iron oxidation can be used for energy or growth and if L. ochracea is an autotroph, heterotroph, or mixotroph. To address these issues, we sampled L. ochracea -rich mats from three of its typical environments (a stream, wetlands, and a drainage channel) and reconstructed nine high-quality genomes of L. ochracea from metagenomes. These genomes contain iron oxidase genes cyc2 and mtoA, showing that L. ochracea has the potential to conserve energy from iron oxidation. Sox genes confer potential to oxidize sulfur for energy. There are genes for both carbon fixation (RuBisCO) and utilization of sugars and organic acids (acetate, lactate, and formate). In silico stoichiometric metabolic models further demonstrated the potential for growth using sugars and organic acids. Metatranscriptomes showed a high expression of genes for iron oxidation; aerobic respiration; and utilization of lactate, acetate, and sugars, as well as RuBisCO, supporting mixotrophic growth in the environment. In summary, our results suggest that L. ochracea has substantial metabolic flexibility. It is adapted to iron-rich, organic carbon-containing wetland niches, where it can thrive as a mixotrophic iron oxidizer by utilizing both iron oxidation and organics for energy generation and both inorganic and organic carbon for cell and sheath production. IMPORTANCE Winogradsky's observations of L. ochracea led him to propose autotrophic iron oxidation as a new microbial metabolism, following his work on autotrophic sulfur-oxidizers. While much culture-based research has ensued, isolation proved elusive, so most work on L. ochracea has been based in the environment and in microcosms. Meanwhile, the autotrophic Gallionella became the model for freshwater microbial iron oxidation, while heterotrophic and mixotrophic iron oxidation is not well-studied. Ecological studies have shown that Leptothrix overtakes Gallionella when dissolved organic carbon content increases, demonstrating distinct niches. This study presents the first near-complete genomes of L. ochracea , which share some features with autotrophic iron oxidizers, while also incorporating heterotrophic metabolisms. These genome, metabolic modeling, and transcriptome results give us a detailed metabolic picture of how the organism may combine lithoautotrophy with organoheterotrophy to promote Fe oxidation and C cycling and drive many biogeochemical processes resulting from microbial growth and iron oxyhydroxide formation in wetlands.

59 BASIC BIOLOGICAL SCIENCES↗