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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Water effects on NH 3 -SCR over Cu-based small-pore zeolite catalysts: A review

The selective catalytic reduction (SCR) of NO x with NH 3 as the reductant over small-pore Cu-zeolite catalysts is a leading strategy for controlling emissions from diesel engines and mobile sources. While the hydrothermal stability of Cu-zeolites such as Cu-SSZ-13, Cu-SAPO-34, and Cu-SSZ-39 has been extensively studied, the multifaceted role of water vapor under operating conditions has only recently received systematic attention. Water impacts multiple aspects of SCR catalysis, including NO x conversion, N 2 O formation, Cu ion speciation, redox kinetics, and surface reactions. This review comprehensively summarizes recent advances in understanding the effect of water on NH 3 -SCR over Cu-based catalysts. For Cu-SSZ-13, water vapor induces both inhibitory and promotive effects depending on temperature, Cu loading, and Si/Al ratio by altering NH 3 adsorption, Cu mobility, and redox half-cycle kinetics. Studies have revealed that water can suppress ammonium nitrate formation at low temperatures and enhance nitrate pathways at higher temperatures. Over Cu-SAPO-34, water promotes NO conversion by improving Cu(II) reducibility and strengthening Brønsted acidity. First-principles calculations confirm that water-coordinated Cu species lower O 2 activation barriers. In Cu-SSZ-39, water was found to facilitate Cu reduction, migration, and O 2 activation, resulting in superior water tolerance and unexpected catalytic promotion. Both experimental and computational studies highlight that water vapor exerts complex, catalyst-dependent effects on NH 3 -SCR performance, underscoring the need for tailored catalyst designs that leverage beneficial water interactions while minimizing inhibitory impacts.

Ammonia selective catalytic reduction↗
DOE OSTI2025

Reduced soil diazotroph diversity decreases nitrogen fixation rates, but depends on land management

Soil diazotrophs convert atmospheric nitrogen into plant-available ammonium through free-living nitrogen fixation (FLNF). This sustainable nitrogen source can reduce our dependence on synthetic fertilizer inputs in conventional agricultural systems. However, we know little about the effect of diazotroph diversity on FLNF, especially given that FLNF is intermediate within the broad-narrow functional spectrum. Here, we determined how management-mediated shifts in diazotroph diversity would impact their ecosystem function (FLNF) by quantifying diazotroph diversity across a long-term management gradient during and after the growing season. In addition to field observations, we leveraged the same management gradient to manipulate diversity in soil microcosms via chloroform fumigation exposure. In the field, diazotroph diversity was significantly higher after the growing season, and the biologically-based annual cropping system harbored the highest diazotroph diversity. However, perennial cropping systems maintained the highest FLNF despite lower diazotroph diversity, and both soil moisture and temperature were stronger predictors of FLNF. Based on these results, integrating diverse perennial crops into agricultural landscape could result in greater N from FLNF, particularly at the end of the growing season. When we reduced biodiversity in a manipulation experiment, the diversity-FLNF association was stronger than in the field experiment, suggesting that FLNF communities are not as functionally redundant as taxonomically ‘broad’ ecosystem functions. Here, the strength of diversity-FLNF correlation varied by previous land management. Diazotroph diversity better predicted FLNF in annual and forest soil microcosms, and microbial biomass carbon better predicted FLNF in perennial soil microcosms. Taken together, our results show that while diazotroph diversity influences FLNF, especially under extreme environmental disturbances, abiotic factors like soil moisture and temperature are stronger constraints on FLNF in the field.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Manganese concentration influences nitrogen cycling in agricultural soil

Manganese (Mn) can modulate nitrogen (N) transformations in soil, yet its role in agroecosystems remains understudied. We conducted a 51-day microcosm incubation with agricultural soils differing in long-term N history (N 0 , no added N; N 1 , added 225 kg N ha −1 for a duration of 27 years) and amended with soluble Mn at 0 (M 0 ), 50 (M 1 ), or 250 (M 2 ) mg kg −1 and Glyceria striata (Lam.) residue. In N 1 soils, Mn additions (both M 1 and M 2 ) lowered total mineral N by 25 % relative to N 1 M 0 at day 51 and reduced 51-day cumulative N₂O by 32 % (N 1 M 1 ) and 42 % (N 1 M 2 ) vs. N 1 M 0 , whereas effects in N 0 were negligible. Mn also depressed ammonia-oxidizing bacterial amoA gene transcripts at day 15 in N 1 M 2 vs. N 1 M 0 (2.5 fold change). This reduction was likely due to increased N loss via complete denitrification to N₂ through microbial pathways such as nitrate/nitrite-dependent manganese oxidation (NDMO), where bacteria directly used the added Mn 2+ to reduce nitrate (NO 3 − ) and nitrite (NO 2 − ) to N 2 or as Mn dependent-ammonia oxidation (Mnammox) where bacteria oxidized ammonium (NH 4 + ) to N 2 , using Mn oxides as electron acceptors that formed from the oxidation of the added Mn. Other contributing mechanisms may include Mn-induced N immobilization, toxicity, and changes in the microbial community. These mechanistic results indicate that background Mn availability and redox dynamics can shape nitrification–denitrification pathways under N-rich conditions. In conclusion, we highlight how native Mn pools and redox state may help explain observed variability in N losses and greenhouse gas production across agricultural soils.

Decomposition↗
DOE OSTI2021

Vapor-phase grafting of a model aminosilane compound to Al 2 O 3 , ZnO, and TiO 2 surfaces prepared by atomic layer deposition

Atomic layer deposition (ALD) is a highly versatile surface functionalization technique that can conformally coat both planar and porous substrates. Here we use ALD metal oxide layers to establish a well-defined starting surface for vapor-phase surface organic modification. Vapor-phase (3-aminopropyl)triethoxysilane (APTES) surface silanization of ALD Al 2 O 3 , ZnO and TiO 2 surfaces were studied at 100 °C, 150 °C and 200 °C. In situ quartz crystal microbalance (QCM) and Fourier-transform infrared (FTIR) spectroscopy measurements, and ex situ atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) measurements showed uniform monolayer silane formation through self-limiting APTES reaction. We observed a higher surface density of grafted APTES species following silanization at 100 °C compared to 200 °C, and we attribute this to the temperature-dependent reactivity of the surface hydroxyls and changes in the mode of APTES reaction. The FTIR and XPS measurements revealed that APTES reacts with Al 2 O 3 and ZnO exclusively through metal siloxy bond formation. However, APTES reacts with TiO 2 through both siloxy bond formation and ammonium salt formation via the amine group.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Atmospheric ice nuclei concentration measurements over a high altitude-station in the Western Ghats, India

Mixed-phase and ice clouds play a significant role in modulating the Indian summer monsoon rainfall, and modeling studies suggest that inaccurate representation of ice nucleating particles (INP) is one of the factors, which have resulted in a deficiency in the prediction of cloud properties and hydrological cycle. We do not understand the ice nucleation mechanisms to represent the ice formation in the model, and therefore more INP measurements at various supercooled temperatures are needed. This study reports for the first time real-time INP concentration at a high altitude station in the Western Ghats region of India, and these results will be used to constrain the ice nucleation parameterizations in the model. The variation of INP for any particular cloud condition can have strong microphysical responses of mixed-phase precipitation formation processes. Also, to improve the representation of heterogeneous ice nucleation, INP measurements of various types of aerosols commonly observed over the Indian region are needed. This study presents, the INP concentrations and daily concentration of non-refractory chemical composition (organics, sulfate, nitrate, ammonium, and chloride), cloud condensation nuclei (CCN), and aerosol size distribution. Spectrometer for Ice Nuclei (SPIN) was operated to measure INP concentration at the mountain site from August to December 2018. INP measurements were performed at three different temperatures (-25, -30, and - 34 °C) in the immersion freezing mode relevant for mixed-phase cloud conditions. The average INP concentrations approximately varied from 0.18 to 12.4 L-1, 0.39 to 24 L-1, 1.1 to 40.2 L-1 at -25, -30, and - 34 °C, respectively. These concentrations are within the concentrations reported in the literature from different regions across the globe. The air mass back trajectory analysis showed that continental air mass contains more INP compared to maritime air mass. The information on INP concentration and chemical characteristics of aerosol will help to improve heterogeneous ice nucleation parameterization in numerical models.

Kumar, Anil V.↗
DOE OSTI2020

Synergistic effect of dual Brønsted acidic deep eutectic solvents for oxidative desulfurization of diesel fuel

Deep eutectic solvents (DESs) are generally used as attractive solvents or extractants rather than catalysts in the field of synthesis and separation. Herein, dual Brønsted acidic DESs were prepared by mixing sulfonated quaternary ammonium and oxalic acid as extractants and catalysts for deep oxidative desulfurization. Compared to the DESs with single acidic group, the dual acidic DESs exhibited much higher catalytic activity likely due to the synergistic effect. The 1 H NMR study indicated that the weak interaction between DES and sulfur compounds led to a low extraction capacity. However, the sulfur removal could reach 97.7% under optimized reaction conditions. Density functional theory (DFT) calculations demonstrated that sulfonic group and carboxylic group are of equal importance to desulfurization performance. Further, the desulfurization efficiency was also strongly affected by the viscosity of DESs. Here, we put forward a new strategy that the reaction time could be sharply shortened to 40 min and 100 min by adding low viscous acetonitrile and polyethylene glycol into DES to form mixing reaction system, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A de novo sacrificial-MOF strategy to construct enhanced-flux nanofiltration membranes for efficient dye removal

Nanofiltration membanes play a critical role in alleviating global water scarcity, affecting more than 4 billion people. Here, a new metal organic framework (MOF) sacrificicial strategy is designed to synthesize flux-enhancing nanofiltration membrane for efficient dye removal. With the aid of polyphenol chemistry, ZIF-67 MOF was first coated onto a porous support and in situ transformed into a selective layer by virtue of pyrrole polymerization. Trigerred by ammonium persulfate, polypyrrole selective layer functioalized nanofiltration membrane was fabricated when accompanying pore regulation by MOF self-sacrifice. The membrane demonstrated a flux enhancement of 745% than pristine polypyrrole (PPy) one with maintained rejection. Furthermore, the synergistic interactions among polypyrrole, polyphenol, and porous support endowed membrane with excellent stability during long term test. The designed MOF sacrificed route may open a new avenue for fabricating advanced energetic-efficient membranes with the reconstructed architecture towards diverse separation applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Film formation mechanisms in mixed-dimensional 2D/3D halide perovskite films revealed by in situ grazing-incidence wide-angle X-ray scattering

We report mixed dimensionality 2D/3D hybrid halide perovskites retain the stability of 2D perovskites (formula (A')2(A)n-1PbnI3n+1) and long diffusion lengths of the 3D materials (formula AMX3), thereby affording solar cells with extended stability as well as state of the art efficiencies approaching that of the 3D materials. These films are made by spin coating precursor solutions with arbitrarily large average layer thickness n ($\langle$n$\rangle$ > 7) to give films with both 2D and 3D phases present. While the 2D and 3D perovskite film formation mechanisms have been studied previously, little is understood about composite 2D/3D film formation. We used in situ grazing-incidence wide-angle scattering (GIWAXS) with synchrotron radiation to fully characterize films fabricated from precursor solutions with stoichiometries of (BA) 2 (MA) n-1 Pb n I 3n+1 ($\langle$n$\rangle$ = 3, 4, 5, 7, “12,” “50,” and ∞ (MAPbI 3 )). Four different mechanisms are seen depending on the stoichiometry in the precursor solution. When $\langle$n$\rangle$ = 3, oriented perovskite grows directly. For $\langle$n$\rangle$ = 4-5, the needle-shaped solvate (MA) 2 Pb 3 I 8 ·2DMF forms concomitantly with the oriented perovskite which leads to 2D/3D composite films. For $\langle$n$\rangle$ ≥ 7, this solvate dominates and unoriented perovskite grows in secondarily. For 3D perovskite, the solvate is the only phase formed. Kinetic analysis shows faster and earlier growth of the solvate with increasing $\langle$n$\rangle$. Using this knowledge, we show that the undesirable solvate mechanism can be reduced by addition of excess ammonium iodide in the precursor solution to give highly oriented films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A study of rare earth ion-adsorption clays: The speciation of rare earth elements on kaolinite at basic pH

Synthesized rare earth ion-adsorption clays (La, Ce, Nd, Dy and Y, ~ 400 ppm each) were prepared from kaolinite at various basic pH in open-air conditions. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma mass spectrometry (ICP-MS) were used to characterize the effect of pH on the adsorption mechanism of rare earth elements (REEs) on kaolinite. The crystal structure of kaolinite by XRD analysis is not altered after REE adsorption, suggesting that REEs are bound to the surface of kaolinite. Elemental analysis by XPS and ICP-MS show that the surface concentration of REEs on kaolinite is pH dependent, and a local maximum of the surface concentration is achieved at pH 10. Three characteristics of the La 3d 5/2 XPS photoemission feature were measured and compared to those of standard La compounds to probe the speciation of REEs, and electrostatically bound hydroxides such as REE(OH) 2 + are identified as the primary species on the surface of kaolinite. Finally, compared to the typical ion-adsorption clays with intrinsic acidic pH, clays synthesized at basic pH exhibit similarly high rare earth ion-exchange efficiency with ammonium sulfate (AS), suggesting that rare earth ion-adsorption clays can exist in both acidic and basic environments.

36 MATERIALS SCIENCE↗
DOE OSTI2020

An Eulerian multimaterial framework for simulating high-explosive aquarium tests

Aquarium tests of cylindrical high-explosive charges provide optical data of the detonation front velocity and shape, propagation of the shock wave in the surrounding water, and expansion rates of the detonation products behind the front. Data from aquarium experiments is often used for calibration of reactive burn models based on phenomenological equations of state (EOS) and reaction rate laws. This paper presents a multimaterial numerical modeling framework to solve the 2D axisymmetric reactive Euler equations for high-explosive aquarium tests, in particular for ammonium nitrate - fuel oil (ANFO) explosives. An extension of the Ghost Fluid Method (GFM) is used to handle the dynamic material interfaces for the ANFO explosion products, the charge-confining material (polymethyl methacrylate PMMA), and the surrounding water. This study analyzes the sensitivity of calculations (both computational efficiency and numerical accuracy) to different algorithms for the material interface models including the original GFM versus Riemann solver-based strategies. A novel method for defining the left and right states in the interfacial Riemann problem eliminates the need for sorting or nodal interpolation during the projection along the material interface. Numerical tests indicate that populating the interface node values using the Riemann solution mitigate the overheating error observed in steady-state calculations. Solution convergence and computational efficiency are explored as a function of the spatial and temporal order of the schemes. Results from the computational model with analytical equations of state and fitted reaction rate parameters show very good quantitative agreement with experimentally observed detonation front velocity, reaction products expansion, and shock wave propagation in the surrounding water for a cylindrical ANFO charge encased in PMMA. Finally, the proposed modeling framework, in conjunction with experimental tests, provides a reliable tool to assess equations of state and reaction rate expressions for reactive burn models of confined high explosives.

42 ENGINEERING↗
DOE OSTI2020

Polycation ionic liquid tailored PEO-based solid polymer electrolytes for high temperature lithium metal batteries

Poly(ethylene oxide) (PEO)-based polymer electrolytes are promising candidates for solid-state electrolytes in safer, next generation lithium metal batteries. Despite their benefits however, PEO-based electrolyte exhibits highly crystalline ethylene oxide chains that provide poor ionic conductivity and, thus severely limit its practical application. Here, we report the use of hydroxypropyl trimethylammonium bis(trifluoromethane) sulfonimide chitosan salt (HACC-TFSI), which is an amorphous poly(ionic liquid) based biomass chitosan derivative, as a modifier for PEO-based solid polymer electrolytes (SPEs) to address these deficiencies. Hybrid SPEs with HACC-TFSI display enlarged amorphous regions with enhanced ionic conductivity. Interactions between quaternary ammonium cations and TFSI-anions in hybrid SPEs are also found to promote dissociation between Li + and TFSI - , which further increases ionic mobility. Moreover, the electrochemical stability, mechanical strength, and thermal stability of hybrid SPEs are collectively superior to blank SPEs without HACC-TFSI. LiFePO 4 /SPEs/Li full-cells assembled using 10wt% HACC-TFSI in PEO (10%HACC-TFSI/SPEs) electrolyte provide a capacity of 161.3 mAh g -1 and operate with excellent cycle performances at 0.2 C and 60 C. Finally, even when the temperature is increased to 150 C, LiFePO 4 /SPEs/Li cells with 10%HACC-TFSI/SPEs still display remarkable cycle performance with 73% capacity retention after 100 cycles at 1 C rate.

25 ENERGY STORAGE↗
DOE OSTI2024

Stabilizing a low temperature phase change material based on Glaubers salt

The aim of this research is to enhance the performance of Glauber's salt (sodium sulfate decahydrate, SSD) as a phase change material (PCM) for thermal energy storage applications, as well as for shipping of temperature-sensitive materials. The study investigates the effects of modifying SSD with potassium chloride (KCl) and ammonium chloride (NH 4 Cl) to achieve lower phase transition temperatures of between +6 °C and + 13 °C. Sodium polyacrylate (PAAS) is employed as a thickening agent to prevent phase separation, and borax is used as a nucleating agent to suppress supercooling. Various ratios of KCl:NH 4 Cl are tested, and the impact of PAAS concentration on phase segregation is explored. The results show that a 2 wt% concentration of PAAS effectively prevents phase separation. Samples with a KCl:NH 4 Cl ratio of 1:1.83 exhibit stable phase transition behavior and maintain latent heat values within the range of 130–140 J/g after 30 thermal cycles. Maintaining a total KCl and NH 4 Cl proportion of 10 wt% is crucial to achieve the desired lower melting temperature. As a result, the study highlights the significance of thermal cycling in improving the stability of the PCM. The optimized SSD-based eutectic PCM formulations hold promise for applications in the cold chain industry.

25 ENERGY STORAGE↗
DOE OSTI2022

Quaternized chitosan as a biopolymer sanitizer for leafy vegetables: synthesis, characteristics, and traditional vs. dry nano-aerosol applications

A series of quaternary dimethyl-(alkyl)-ammonium chitosan derivatives (QACs) was synthesized and studied for physicochemical properties and bioactivity. The QACs tended to spontaneously self-assembly into nanoaggregates. Antimicrobial activity was examined in vitro on Gram-negative Escherichia coli (E. coli) and Gram-positive Listeria innocua (L. innocua) bacteria as well as phytopathogenic fungus Botrytis cinerea. The hexyl chain-substituted QAC-6 demonstrated the highest potency causing 3.0- and 4.5-log CFU mL-1 reduction of E. coli and L. innocua, respectively. QAC-6 was tested for antimicrobial activity on stainless steel coupons and fresh spinach leaves. A traditional ‘wet’ application (spray) and dry Engineered Water Nanostructure (EWNS) approach were used for spinach decontamination. With both approaches, significant reduction of microbial load on the treated produce was achieved. Finally, the wet application showed a greater reduction of microbial load, while the advantages of EWNS were reaching the antimicrobial effect with miniscule dose of active agent leaving treated surface visibly dry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Effect of oxidative breakers on organic matter degradation, contaminant mobility and critical mineral release during shale-fracturing fluid interactions in the Marcellus Shale

Oil and gas production from organic-rich shale formations has become viable through advancements in multistage hydraulic fracturing. However, fluctuations in oil and gas prices, coupled with the sharp decline in gas production after the initial days of fracturing operations, drive operators to devise strategies for enhancing hydrocarbon production. The use of highly reactive fracturing fluids that include strong oxidizing agents, also known as breakers, can potentially increase well productivity. The oxidative breakers are used to reduce the viscosity of gel-based fluids after the proppant is transported into fracture zones of the target formation. These breakers can also degrade the organic matter, enhancing the release of hydrocarbons. However, chemical byproducts generated by the interaction of oxidative breakers with the shale matrix have not been extensively studied. Here, this study investigated the fluid-rock interactions between Marcellus Shale and synthetic hydraulic fracturing fluid (HFF) solutions comprising three different oxidative breakers, i.e., ammonium persulfate, sodium bromate, and sodium hypochlorite, commonly used in the Appalachian Basin, USA. Our results demonstrate that the type of oxidizing breakers used in the HFF controlled the type and amount of volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) produced. In all HFF reacted effluents, we observed the transformation of VOCs and the presence of organic acids in variable amounts. However, effluents from HFF containing sodium bromate and sodium hypochlorite breakers showed the presence of several halogenated organic compounds. Changes in major ions and mineralogy indicate that carbonate dissolution and barite precipitation were ubiquitous in all shale reacted effluents. Our results also demonstrate that the addition of oxidative breakers increased the concentration of several major and trace elements in the effluents. These elements fall under the critical mineral (CM) or critical element category due to their high demand in emerging technologies and susceptibility to supply chain disruption due to variety of factors. However, before oxidative breakers can be used at a larger field scale to enhance the release and recovery of CM and hydrocarbons, a better understanding is required of the potential environmental impacts associated with the generation and transformation of contaminants during breaker-fluid-rock interaction.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

High manganese redox variability and manganate predominance in temperate soil profiles as determined by X-ray absorption spectroscopy

Manganese speciation is a key to understanding the fate of contaminants, nutrients, and organic matter in soils. To date, quantification of Mn species in bulk soils has been performed mainly by sequential extraction methods and rarely supported by spectroscopic analysis. In order to obtain quantitative information on the Mn species inventory of soils, we investigated 46 soil horizons (<2-mm fraction, 45.1–2,280 mg/kg Mn) of nine typical Central European soils (Cambisols, Chernozems, Luvisols, Podzol, Stagnosol) by chemical Mn analyses and Mn K-edge X-ray absorption spectroscopy, and related speciation results to major soil properties. Amounts of Mn 2+ , Mn 3+ , and Mn 4+ and the average oxidation state of Mn were evaluated by linear combination fitting (LCF) of X-ray absorption near edge structure (XANES) spectra. Additionally, we used extended X-ray absorption fine structure (EXAFS) spectroscopy to identify and quantify major Mn species. For this, EXAFS spectra of 20 organic and mineral soil samples from five soils (Cambisols, Chernozem, Luvisol) were analyzed by LCF and shell fitting. XANES analyses revealed a high Mn redox variability in organic surface layers, with Mn 2+ being most abundant (≤100%, $\overline{x}$ = 54%), followed by Mn 3+ (≤80%, $\overline{x}$ = 32%) and Mn 4+ (≤55%, $\overline{x}$ = 14%). Mineral soil horizons contained significantly less Mn 2+ (≤56%, $\overline{x}$ = 23%), about equal quantities of Mn 3+ (≤68%, $\overline{x}$ = 31%), and were enriched in Mn 4+ (≤89%, $\overline{x}$ = 46%). EXAFS analyses implied the presence of six major Mn species groups: manganates, organically complexed Mn, Mn(III) oxyhydroxides, silicate-bound Mn, Mn oxides without tunnel- or layer structure, and physisorbed Mn. In litter horizons, Mn was mainly present in organic complexes (58–91%, $\overline{x}$ = 78%) and as physisorbed Mn (≤15%), but individual horizons also comprised manganates, Mn(III) oxyhydroxides, and silicate-bound Mn. Manganates, likely mixtures of phyllomanganates with hexagonal layer symmetry and tectomanganates, dominated in all mineral soil horizons (37–94%, $\overline{x}$ = 67%). Correlation analysis showed that manganates dissolve completely during dithionite-citrate and acid ammonium oxalate extractions, and suggested that Mn 4+ -rich manganates preferentially form under less acidic soil conditions, partly by oxidation of organically complexed Mn(II), and that they are enriched in the soil clay fraction. Mineral soil horizons also contained minor quantities of organically complexed Mn (≤39%, $\overline{x}$ = 11%), silicate-bound Mn (≤30%, $\overline{x}$ = 8%), Mn(III) oxyhydroxides (≤37%, $\overline{x}$ = 7%), Mn oxides without tunnel- or layer structure (≤18%, $\overline{x}$ = 5%), and physisorbed Mn (≤14%, $\overline{x}$ <1%). The detection of Mn(III) oxyhydroxides such as feitknechtite (β-MnOOH) or groutite (α-MnOOH) as well as the spinel hausmannite (Mn 3 O 4 ) in acidic soils is remarkable, since their formation is normally linked to neutral or alkaline pH conditions. Minor contributions of silicate-bound Mn indicate the release of Mn from primary minerals already at early stages of soil formation, and low concentrations of physisorbed Mn suggest that exchangeable Mn is rapidly converted into manganates in oxic soils. In conclusion, the predominance of manganates in mineral soils has far-reaching implications for the functioning of soils and biogeochemical element cycles, as these minerals play an important role in metal binding, plant nutrition, and redox-related processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Repeated freeze-thaw cycles increase extractable, but not total, carbon and nitrogen in a Maine coniferous soil

Northeastern North America has been experiencing warmer winters with reduced snow accumulation, with more frequent winter freeze-thaw cycles. We conducted a laboratory experiment to investigate how increased frequency of freeze-thaw cycles (FTC) would alter soil C and N availability. Organic (O) and mineral (B) horizon soils were collected from a coniferous forest in Maine, processed to exclude roots, and then frozen in the laboratory (-10 °C) with one (FTC-1), two (FTC-2), or six (FTC-6) thaw periods. Soils were analyzed for extractable inorganic ammonium (NH4-N), water extractable organic carbon (WEOC), carbon dioxide flux (respiration), and total C and N. Extractable NH4-N increased following FTC, for both horizons. WEOC in O horizons had a lower SUVA254, indicating a stronger microbial influence (i.e., microbial cell lysis) in these soils after FTC. Respiration in O horizon soils decreased post-incubation and did not differ between FTC and Control soils. In the B horizon, however, FTC soils showed greater respiration than Control soils, suggesting that the newly available nutrients may have stimulated microbial activity. In contrast to these results, total C and N remained unaltered by FTC, presumably because the FTC disturbances represented mostly a translocation of C and N from one pool into another, and losses due to respiration were too small to significantly influence the large TC and TN pools. The effect of FTC on NH4-N did not change with FTC frequency, suggesting that a single FTC is sufficient to alter both C and N availability and quality, and that additional FTC may not have a significant further effect. This study provides fresh insights on how organic and mineral soils might respond to increased freeze-thaw frequency in winter.

Patel, Kaizad F.↗
DOE OSTI2023

Carbon sequestration and nitrogen and phosphorus accumulation in a freshwater, estuarine marsh: Effects of microtopography and nutrient loads

Wetlands are widely recognized as nutrient sinks for their ability to remove nutrients in runoff and retain them in soils. This is a valuable service, especially in agricultural watersheds, making nutrient removal one of the main goals in many wetland creation and restoration projects. However, incorporating nutrient management considerations requires site-level assessments, the scale at which wetland creation and restoration occur. Here we studied how carbon (C) sequestration, and nitrogen (N) and phosphorus (P) accumulation vary at different microtopographic levels and locations within a freshwater, estuarine marsh on the coast of Lake Erie. We further explored links between C sequestration, and N and P accumulation in recent years, and orthophosphate ($PO_{4}^{3-}$), ammonium ($NH_{4}^{+}$), and nitrate ($NO_{3}^{-}$) concentrations and loads. The rates of C sequestration and N accumulation were relatively lower at spots of intermediate depth and locations closer to the wetland’s main channel. P accumulation was highest at deep spots but did not differ among locations based on distance from the channel. Empirical models showed that nitrate load is the most important variable explaining the variability in C, N, and P sequestration/accumulation (r2 = 0.57, 0.61, and 0.32, respectively) and that the relationship between inorganic nutrient loads and accumulation was negative. Our findings suggest that including microtopographic relief features in wetland creation and design, especially deeper spots, is critical to enhancing wetland ecosystems’ C, N, and P sinking capacity. Also, that upstream nitrate management should be a priority to increase benefits from C sequestration and long-term N and P accumulation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Evaluation of assumptions made by Hygroscopic Tandem Differential Mobility Analyzer inversion routines

The Hygroscopic Tandem Differential Mobility Analyzer (H-TDMA) measures the hygroscopicity of atmospheric particles, and many atmospheric processes that change this hygroscopicity also change the atmospheric size distribution. Two assumptions made during H-TDMA inversion create spurious hygroscopic trends as a function of the changing inlet size distribution. These two assumptions—that the particles exiting the first Differential Mobility Analyzer (DMA1) are singly charged and that the inlet size distribution has a slope of zero (flat)— generate Multi-Charge Dispersion (MCD) bias and Slope bias, respectively. First, we use a model, named TAO, to show that the inlet size distribution could theoretically change the measured ammonium sulfate hygroscopicity by 10%–20% as a function of diameter or experimental time with no change in relative humidity. Secondly, we show experimentally that aerosol emitted from the flaming combustion of grass creates MCD bias. Here, in this experiment, we measure the CPC response of the first three charges and invert these responses using a new routine named Junior. Junior's inversion of each charge shows that one growth factor distribution describes all measured diameters (no growth dependence on diameter). As in the modeling study above, previous publications of this aerosol system, using traditional inversion assumptions, report a decrease in hygroscopicity as DMA1 diameter increases. Unlike traditional inversions, Junior's inversion does not assume the particles are singly charged nor does it make the flat inlet size distribution assumption. Instead, both the inlet size distribution and each charge's CPC response are measured quantities. Thus, the discrepancy between our inversion results and previous publications is likely due to the traditional inversion routine assumptions. This underscores the importance for accounting for Slope and MCD bias during inversions. Experimental results should be carefully analyzed when reporting hygroscopic trends with respect to diameter or experimental time when using the traditional inversion assumptions.

42 ENGINEERING↗