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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3

Effects of Plasma on Physical Properties of Water: Nanocrystalline-to-Amorphous Phase Transition and Improving Produce Washing

Washing fresh produce using Plasma-activated water recently became a promising eco-friendly alternative to using chemical additives such as Chlorine. We discuss the produce-washing experiments that illustrate that addition of plasma to washing water is a multi-faced phenomena. Not only it increases the sterilization ability of water by killing pathogens, but it also has improved washibility: the ability to remove pathogens from the cleaning surface. We propose an explanation of these features based on the recently discoveries that many physical and chemical properties of water change their temperature dependence between about 35 and 60 degrees Celsius. In particular, heat conductance, light absorption, and surface tension all change their temperature dependence. These drastic changes were associated with water gradually changing its mesoscopic structure: while at the higher temperatures water is a uniform media (amorphous state), at the temperatures below transition it consists of many nano-to-micro-scale clusters (crystalline state). This transition is similar to the second order phase transition. In the present paper we propose that treating water with non-thermal plasma (adding plasma-created active compounds) can lower the temperature of the transition and thus cause a significant change in such physical quantities as surface tension, viscosity, freezing rate, and wettability and washability.

He, Jinjie↗

The water-soluble fraction of extracellular polymeric substances from a resource recovery demonstration plant: characterization and potential application as an adhesive

Currently, there is a growing interest in transforming wastewater treatment plants (WWTPs) into resource recovery plants. Microorganisms in aerobic granular sludge produce extracellular polymeric substances (EPS), which are considered sustainable resources to be extracted and can be used in diverse applications. Exploring applications in other high-value materials, such as adhesives, will not only enhance the valorization potential of the EPS but also promote resource recovery. This study aimed to characterize a water-soluble fraction extracted from the EPS collected at the demonstration plant in the Netherlands based on its chemical composition (amino acids, sugar, and fatty acids) and propose a proof-of-concept for its use as an adhesive. This fraction comprises a mixture of biomolecules, such as proteins (26.6 ± 0.3%), sugars (21.8 ± 0.2%), and fatty acids (0.9%). The water-soluble fraction exhibited shear strength reaching 36–51 kPa across a pH range of 2–10 without additional chemical treatment, suggesting a potential application as an adhesive. The findings from this study provide insights into the concept of resource recovery and the valorization of excess sludge at WWTPs.

59 BASIC BIOLOGICAL SCIENCES↗

Evaluating Mineral Lattices as Evolutionary Proxies for Metalloprotein Evolution

Protein coordinated iron-sulfur clusters drive electron flow within metabolic pathways for organisms throughout the tree of life. It is not known how iron-sulfur clusters were first incorporated into proteins. Structural analogies to iron-sulfde minerals present on early Earth, suggest a connection in the evolution of both proteins and minerals. The availability of large protein and mineral crystallographic structure data sets, provides an opportunity to explore co-evolution of proteins and minerals on a large-scale using informatics approaches. However, quantitative comparisons are confounded by the infnite, repeating nature of the mineral lattice, in contrast to metal clusters in proteins, which are fnite in size. We address this problem using the Niggli reduction to transform a mineral lattice to a fnite, unique structure that when translated reproduces the crystal lattice. Protein and reduced mineral structures were represented as quotient graphs with the edges and nodes corresponding to bonds and atoms, respectively. We developed a graph theory-based method to calculate the maximum common connected edge subgraph (MCCES) between mineral and protein quotient graphs. MCCES can accommodate differences in structural volumes and easily allows additional chemical criteria to be considered when calculating similarity. To account for graph size differences, we use the Tversky similarity index. Using consistent criteria, we found little similarity between putative ancient iron-sulfur protein clusters and iron-sulfur mineral lattices, suggesting these metal sites are not as evolutionarily connected as once thought. We discuss possible evolutionary implications of these findings in addition to suggesting an alternative proxy, mineral surfaces, for better understanding the coevolution of the geosphere and biosphere

Kenneth N. McGuinness↗

Advanced Brine Processing to Enable U.S. Lithium Independence (CRADA Report)

Current production of LiOH, which is needed to make Li-ion battery cathode active materials, utilizes a multistep process including solar evaporation, precipitation with Na 2 CO 3 and then conversion to LiOH using Ca(OH) 2 . This process requires a large amount of land area for solar evaporation, the right weather conditions, and chemicals for the conversion process that result in NaCl and CaCO 3 waste products. The production of Ca(OH) 2 is very energy intensive and evolves significant quantities of CO 2 . An alternative process flow utilizing direct lithium extraction techniques, followed by a chemical free conversion process can have benefits in reducing the needed land requirements and chemicals for traditional brine processing. There are many potential direct lithium extraction technologies that are currently being developed. The direct lithium extraction process from typical brine sources will produce a LiCl solution with some impurities including typically high concentrations of Na. This brine then needs to be converted to LiOH for use in battery cathode production. Ideally this conversion could occur without the use of additional chemicals. Electrochemistry can do this conversion either via electrolysis or bipolar membrane electrodialysis (BPED) to produce LiOH and HCl in solution. BPED utilized bipolar membranes to split water, which has a reduced potential as compared to splitting water at electrodes into hydrogen and oxygen gas. This reduced potential required results in a significant energy savings for BPED over electrolysis methods. This CRADA project aimed to develop such an integrated process using direct lithium extraction followed by BPED to produce a LiOH solution. That solution can then be crystallized into battery grade LiOH. In particular, Albemarle utilized a direct lithium extraction process to produce a concentrated LiCl solution that could be used for the BPED process. The BPED process was first tested using various LiCl solutions with impurity ions added at bench scale to understand the effects of impurities and determine processing parameters. Then testing was performed using the direct lithium extracted brine at the bench scale before scaling the process up. After the process was scaled up a long duration test was carried out to estimate the lifetime of the membranes, which is key to the economics of the BPED process.

25 ENERGY STORAGE↗

Additive‐Free, Low‐Temperature Crystallization of Stable α‐FAPbI 3 Perovskite

Abstract Formamidinium lead triiodide (FAPbI 3 ) is attractive for photovoltaic devices due to its optimal bandgap at around 1.45 eV and improved thermal stability compared with methylammonium‐based perovskites. Crystallization of phase‐pure α‐FAPbI 3 conventionally requires high‐temperature thermal annealing at 150 °C whilst the obtained α‐FAPbI 3 is metastable at room temperature. Here, aerosol‐assisted crystallization (AAC) is reported, which converts yellow δ‐FAPbI 3 into black α‐FAPbI 3 at only 100 °C using precursor solutions containing only lead iodide and formamidinium iodide with no chemical additives. The obtained α‐FAPbI 3 exhibits remarkably enhanced stability compared to the 150 °C annealed counterparts, in combination with improvements in film crystallinity and photoluminescence yield. Using X‐ray diffraction, X‐ray scattering, and density functional theory simulation, it is identified that relaxation of residual tensile strains, achieved through the lower annealing temperature and post‐crystallization crystal growth during AAC, is the key factor that facilitates the formation of phase‐stable α‐FAPbI 3 . This overcomes the strain‐induced lattice expansion that is known to cause the metastability of α‐FAPbI 3 . Accordingly, pure FAPbI 3 p–i–n solar cells are reported, facilitated by the low‐temperature (≤100 °C) AAC processing, which demonstrates increases of both power conversion efficiency and operational stability compared to devices fabricated using 150 °C annealed films.

36 MATERIALS SCIENCE↗

Extremely Bright, Near-IR Emitting Spontaneously Blinking Fluorophores Enable Ratiometric Multicolor Nanoscopy in Live Cells

New bright, photostable, emission-orthogonal fluorophores that blink without toxic additives are needed to enable multicolor, live-cell, single-molecule localization microscopy (SMLM). Here we report the design, synthesis, and biological evaluation of Yale676sb, a photostable, near-IR-emitting fluorophore that achieves these goals in the context of an exceptional quantum yield (0.59). When used alongside HMSiR, Yale676sb enables simultaneous, live-cell, two-color SMLM of two intracellular organelles (ER + mitochondria) with only a single laser and no chemical additives.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advancing Post-Combustion CO 2 Capture through Increased Mass Transfer and Lower Degradation

The over-arching goal of the proposed project is to develop three techniques to enable aqueous post-combustion CO 2 capture technologies to meet the DOE performance and cost targets of 90% CO 2 capture, 95% purity, at a cost of less than $30/tonne CO 2 captured. This will be accomplished by the development of materials and processes to increase mass transfer in the absorber and reduce the environmental impacts. While constantly working to reduce the cost of CO 2 capture via solvent development and process & heat integration, increasing CO 2 mass transfer through development of custom dynamic packing materials and tuning solvent physical properties may offer a route to increased solvent capacity, lower energy consumption and reduced aerosol formation. The environmental concerns that have been identified in amine-based CO 2 capture systems, nitrosamines specifically, are another critical element that will be addressed in this project. The specific objectives of the project were to: 1) conduct detailed studies to understand how solvent physical properties and aerosol formation are impacted by additives; 2) quantify the CO 2 mass transfer improvement from the dynamic polarity packing in the absorber and the additive-modified solvent using the existing UK bench-scale CO 2 capture unit; 3) quantify the energy consumption savings associated with enhanced mass transfer; 4) quantify the benefits of the UK’s electrochemical cell to decompose nitrosamines; and 5) collect the necessary information/data to conduct a high-level TEA assessment of the proposed technologies. The project involved the fabrication and installation of customized dynamic polarity packing and an investigation into the understanding of the impact of chemical additives on solvent properties to increase CO 2 mass transfer in the absorber column, and lastly the design of an electrochemical cell to decompose nitrosamines in a water wash. After both systems were fabricated, they were tested at UK facilities, including on the bench-scale CO 2 capture unit under parametric and long-term operation.

20 FOSSIL-FUELED POWER PLANTS↗

Full Moment Tensor Solutions of U.S. Underground Nuclear Tests for Event Screening and Yield Estimation

Moment tensor (MT) solutions are proving increasingly valuable in explosion monitoring, especially now that they are more routinely calculated for the unconstrained, full (six component) MT. In this study, we have calculated MTs for U.S. underground nuclear tests conducted at the Nevada National Security Site using seismic recordings primarily from the Livermore Nevada Network. We are able to determine them for 130 nuclear explosions from 1970 to 1996 for a range of yields and under a variety of material conditions, which we have supplemented with 10 additional chemical explosions at the test site. The result is an extensive database of MTs that can be used to assess the performance of important monitoring tasks such as event identification and yield determination. We test the explosion event screening on the fundamental lune of the MT eigensphere and find MT screening to be a robust discriminant between earthquakes and explosions. We then explore the estimation of moment-derived yield, in which we find that material properties are the largest contributor to differences in the estimated moment-to-yield ratio. Additionally, further research conducted on this dataset can be used to develop, test, and improve various explosion monitoring methodologies.

58 GEOSCIENCES↗

Corrosion Behavior of Laser-Interference Structured AA2024 Coated with a Chromate-Containing Epoxy Primer

In this study, the corrosion behavior of laser-interference treated AA2024-T3 specimens, which are coated with a primer, is presented. The surface of as-received AA2024-T3 specimens were laser-interference structured by splitting the primary beam of a Q-switched Nd:YAG pulsed nanosecond laser into two beams and focusing them to the same spot on the specimen surface. After being stored in plastic cases for up to 70 d, without any additional cleaning, the specimens were spray painted with a chromate-containing epoxy primer, CA7233, compliant to MIL-PRF-23377 Type I Class C2 specification. The corrosion behavior of laser-interference specimens was assessed against that of specimens prepared by chromated conversion coating and sulfuric acid anodizing treatments. After the ASTM B117 corrosion exposure, it was found that the laser processed specimens exhibited only few blisters. On one hand, most specimens prepared at a laser fluence of 1.78 J/cm 2 , without any additional chemical cleaning, were found to develop one very small blister after only 96 h of exposure. However, the growth of these blisters was not significant even after 1,000 h of salt spray exposure. On the other hand, only a fraction of the specimens prepared at a laser fluence of 1.24 J/cm 2 and acetone wiped right after the laser structuring were found to develop several tiny blisters after 790 h and longer exposure. Overall, it was found that the corrosion damage was minimized at a laser rastering speed of 4 mm/s, a condition for which only 33% of specimens developed very minor corrosion damage. Furthermore, the ASTM D1654 creepage ratings, which was used to evaluate the corrosion damage along the scribe lines, were found to be at least nine for all coated panels. These results indicate that the laser-interference technique with the additional acetone wiping has the potential to be further developed as a nonchemical surface preparation technique for chromate-containing epoxy primers coating systems.

36 MATERIALS SCIENCE↗

A Scalable & Non-Destructive Characterization Strategy to Study Semiconductor/Dielectric Interfaces and Predict Wafer-Level Device Performance

The defect density present at the dielectric-semiconductor interface in an MOS structure directly influences the channel carrier characteristics in semiconductor devices, especially in wide bandgap material systems used in power devices. While these trap defects are typically quantified through electrical characterization of MOS-capacitor test structures, this treatment offers very little insight into the physical nature of interface defects. Such shortcomings demand a physical characterization strategy to guide fabrication optimization. X-ray photoelectron spectroscopy (XPS) is suggested as a viable technique to determine chemical data for dielectric interfaces formed using atomic layer deposition (ALD) on GaN substrates. Previously, 1-D XPS characterization has confirmed the presence of a Ga x O y interlayer between ALD dielectrics and the GaN substrate. In this work, XPS data is serially collected to form 2-D images of an ALD-Al 2 O 3 /GaN interface as a proof-of-concept experiment for in-situ XPS quality monitoring during ALD processing. The information provided by this work reveals some of the challenges for incorporating XPS characterization as an in-situ strategy during fabrication of GaN-based devices. Separately, electrical mapping of a 2-D array of ALD-Al 2 O 3 /GaN MOS-capacitor devices provide a means to quantify the spatial variations in interface quality across a single wafer. Physical characterization techniques, such as time-of-flight secondary ion mass spectroscopy, provide additional chemical information about the Al 2 O 3 /Ga x O y /GaN structure that complement the electrical mapping results. This analysis shows that a higher Ga x O y content correlates with higher interface state defects for trap energies deep in the band gap.

42 ENGINEERING↗

Detection and confirmation of fentanyls in high clay‐content soil by electron ionization gas chromatography‐mass spectrometry

Abstract Detection of illicit drugs in the environment, particularly in soils, often suggests the present or past location of a clandestine production center for these substances. Thus, development of efficient methods for the analysis and detection of these chemicals is of paramount importance in the field of chemical forensics. In this work, a method involving the extraction and retrospective confirmation of fentanyl, acetylfentanyl, thiofentanyl, and acetylthiofentanyl using trichloroethoxycarbonylation chemistry in a high clay‐content soil is presented. The soil was spiked separately with each fentanyl at two concentrations (1 and 10 μg/g) and their extraction accomplished using ethyl acetate and aqueous NH 4 OH (pH ~ 11.4) with extraction recoveries ranging from ~56% to 82% for the high‐concentration (10 μg/g) samples while ranging from ~68% to 83% for the low‐concentration (1 μg/g) samples. After their extraction, residues containing each fentanyl were reacted with 2,2,2‐trichloroethoxycarbonyl chloride (Troc‐Cl) to generate two unique and predictable products from each opioid that can be used to retrospectively confirm their presence and identity using EI‐GC‐MS. The method's limit of detection (MDL/LOD) for Troc‐norfentanyl and Troc‐noracetylfentanyl were estimated to be 29.4 and 31.8 ng/mL in the organic extracts. In addition, the method's limit of quantitation for Troc‐norfentanyl and Troc‐noracetylfentanyl were determined to be 88.2 and 95.5 ng/mL, respectively. Collectively, the results presented herein strengthen the use of chloroformate chemistry as an additional chemical tool to confirm the presence of these highly toxic and lethal substances in the environment.

Valdez, Carlos A.↗

CASM — A software package for first-principles based study of multicomponent crystalline solids

CASM is a software package that enables first-principles based studies of crystalline materials. It has been designed to treat coupled chemical, mechanical, vibrational, and magnetic degrees of freedom to determine ground state and finite temperature properties of crystals. The symmetry of the underlying parent crystal structure is used to enumerate perturbations of the parent crystal structure and generate derivative structures which can be input to first-principles calculations in order to explore the ground state energy landscape. CASM algorithmically constructs cluster expansions that fully couple discrete and continuous degrees of freedom, and generates highly efficient code to evaluate the cluster expansion basis functions. Widely used machine learning methods are integrated for fitting expansion coefficients to first-principle calculations. The fully parameterized cluster expansions can be combined with (kinetic) Monte Carlo methods to calculate finite temperature thermodynamic and kinetic properties. CASM Alloy Manager identifies distinct parent crystal structures in an alloy system, creating individual projects for each, and integrating the results. The integrated infrastructure facilitates the linkage between first-principles statistical mechanics predictions with higher length scale computational methods, such as phase field simulations. In conclusion, CASM projects are designed to be easy to share in repositories, to re-use, and to extend to include additional chemical species or types of degrees of freedom.

36 MATERIALS SCIENCE↗

Higher Order Chemistry Models in the CFD Simulation of Laser-Ablated Carbon Plumes

Production of single-walled carbon nanotubes (SWNT) has taken place for a number of years and by a variety of methods such-as laser ablation, chemical vapor deposition, and arc-jet ablation. Yet, little is actually understood about the exact chemical kinetics and processes that occur in SWNT formation. In recent time, NASA Johnson Space Center has devoted a considerable effort to the experimental evaluation of the laser ablation production process for SWNT originally developed at Rice University. To fully understand the nature of the laser ablation process it is necessary to understand the development of the carbon plume dynamics within the laser ablation oven. The present work is a continuation of previous studies into the efforts to model plume dynamics using computational fluid dynamics (CFD). The ultimate goal of the work is to improve understanding of the laser ablation process, and through that improved understanding, refine the laser ablation production of SWNT. Fig. 1 shows a basic schematic of the laser-ablation oven at NASA-JSC. Construction of the facility is simple in concept. Two concentric quartz tubes of 1.5 mm thickness form the inner and outer tubes with inside diameters of 2.2 and 5.08 cm respectively. At one end of the inner tube are located two 60 Hz pulsed lasers operating at 1064 nm and 532 nm wavelength with beam diameters of 5 mm aligned coaxially with the longitudinal axis of the inner quartz tube. For standard nanotube production runs, a 10 ns 532 nm pulse is followed 50 ns later by a 10 ns 1064 nm pulse. Each pulse is of 300 mJ energy. A target of carbon graphite with approximately 1% nickel and cobalt catalysts is located at the other end of the inner quartz tube. In the ordinary processing of SWNT, a base flow of 100 sccm of argon is maintained from the laser location and exits past the carbon target at a pressure of 66.7 kPa. These conditions yield a baseline mass flow through the chamber of 2.723x10(exp -6)kg/s of argon. The whole oven facility is heated to a temperature of 1473 K prior to nanotube production runs. Upon laser irradiation, part of the carbon target ablates immediately and forms a carbon vapor plume that penetrates into the argon base flow towards the laser initially at supersonic velocities. In the previous studies either a single carbon species, C3, was used to model the plume development, or a simplified 11 species carbon model reduced down from the Krestinin and Moravsky model for full fullerene chemistry was used. While both of these options yielded significant results, it was felt that the actual chemistry occ&g in the carbon plume might have a greater affect on the plume than assumed. Indeed, in the earlier attempts at modeling the carbon plume, several thermophysical characteristics could never be matched to experimental observations of plume development - mainly the propagation distance of the plume itself. In the present study, two additional chemistry models will be used to duplicate the previous studies simulations of the carbon plume. The first chemistry model used in this study is again a reduced form of the Krestinin and Moravsky rates. However the highest order carbon species allowed has been increased from C6 to C30 - therefore allowing the simulation of up to a half of the standard C60 fullerene. The second chemistry model investigated is a reduced form of a full carbon nanotube model developed at NASA-JSC. The C30 studies have already been accomplished at the present time, and the reduced SWNT model studies are currently underway. To pursue the current study, one sacrifice had to be made in that the simulation grid spacing had to be increased from 0.5 mm spacing to 1 mm spacing for the sake of computational efficiency since computational effort is proportional to the square of the number of grid points multiplied by the number of species considered. propagation that is far more in line with the experimental results observed by Puretzky et al as shown in Fig. 2. e C6 studies had yielded a far greater propagation in previous studies. In addition, chemical species development with the C30 model indicates that many higher order carbon species are produced outside of the plume proper (indicated by plotting contours of the background argon concentrations in Fig. 3) - this result was not observed in previous studies. In fact, some species primarily occurred outside of the plume itself - as shown for C27 in Fig. 4 when it is compared to Fig. 3. It could be asserted that this has occurred because all of the C27 in the plume had already been consumed in the formation of C30, but this does not seem to be indicated over time. Several other factors that arose in the previous studies have also been made more clear by the use of the higher order chemical models - one being that the use of c6 as an indicator species was mistaken. C6 is the only carbon species in the previous studies that was not injected into the flowfield as a boundary condition; it was therefore hoped that this species would provide insight into the formation of higher order carbon species for comparison to full SWNT production. But, when the plot of total mass in the plume is examined on a species by species basis in Fig. 5, it is seen that Cg was a fairly insignificant contributor to the total carbon mass in the plume and would not provide information on higher order carbon formation. the thermophysical characteristics of the carbon plume as well as simulate the carbon plume using the reduced SWNT model to provide an even better simulation of full chemistry effects upon plume propagation.

Scott, C. D.↗

Unlocking Electrostrain in Plastically Deformed Barium Titanate

Achieving substantial electrostrain alongside a large effective piezoelectric strain coefficient (d 33 *) in piezoelectric materials remains a formidable challenge for advanced actuator applications. Here, in this work, a straightforward approach to enhance these properties by strategically designing the domain structure and controlling the domain switching through the introduction of arrays of ordered {100}<100> dislocations is proposed. This dislocation engineering yields an intrinsic lock-in steady–state electrostrain of 0.69% at a low field of 10 kV cm -1 without external stress and an output strain energy density of 5.24 J cm -3 in single-crystal BaTiO 3 , outperforming the benchmark piezoceramics and relaxor ferroelectric single-crystals. Additionally, applying a compression stress of 6 MPa fully unlocks electrostrains exceeding 1%, yielding a remarkable d 33 * value over 10 000 pm V -1 and achieving a record-high strain energy density of 11.67 J cm -3 . Optical and transmission electron microscopy, paired with laboratory and synchrotron X-ray diffraction, is employed to rationalize the observed electrostrain. Phase-field simulations further elucidate the impact of charged dislocations on domain nucleation and domain switching. These findings present an effective and sustainable strategy for developing high-performance, lead-free piezoelectric materials without the need for additional chemical elements, offering immense potential for actuator technologies.

36 MATERIALS SCIENCE↗

Cathode Upcycling for Direct Recycling of Lithium‐Ion Batteries Using a Precipitation Approach

With the increased production of electric vehicles to reduce carbon emissions, the lithium-ion battery market to supply those vehicles has grown dramatically. To enhance battery sustainability and circularity, direct recycling methods aim to recover intact cathode materials. However, end-of-life cathode materials are typically 15–20 years old and often have lower energy density compared to current cathode materials. To address this challenge, a rapid precipitation process is developed to boost energy density by converting low Ni-compositions, LiNi 0.33 Co 0.33 Mn 0.33 O 2 (NMC111), into higher Ni-compositions (NMC622). This process forms a Ni-rich coating on cathode particles that diffuses into the core upon high-temperature relithiation, increasing compositional homogeneity. The upcycling process leverages existing infrastructure, offering low capital cost and minimal additional chemical input. Through ex situ tomographic transmission X-ray microscopy (TXM), 3D Ni:Co elemental mixing is quantified, confirming that elemental content evens at the secondary particle level with a mean NMC622 composition upon relithiation. However, elemental gradients remain in the single crystalline primary particles. Ex situ high-resolution and in situ wide-angle X-ray diffraction reveals concurrent structural changes during the relithiation process. These findings provide key insights into the structural and chemical mechanisms of elemental diffusion to obtain further improvements of increased capacity and retention through compositional conversion of cathode materials.

Cathode Upcycling↗

Drought shifts dissolved organic matter sources from above- to belowground and stress-induced processes in Amazon white-sand forests

White-sand forests contribute significantly to dissolved organic matter (DOM) production in the central Amazon, forming blackwater rivers that dominate organic matter export from the Amazon basin to the ocean. Despite their importance in controlling DOM export, white-sand forests are understudied, and it remains unclear whether systematic changes in the formation of blackwater DOM occur and how seasonal variations and extremes like El Niño-associated droughts impact them. We collected soil porewater from two central Amazon white-sand forests for two years, spanning a wet La Niña year followed by an El Niño drought year. The molecular composition of DOM was analyzed using high-resolution mass spectrometry, and correlation network analysis was employed to identify ecologically meaningful DOM subsets. Using additional chemical characterization, database annotations, correlation with 14C-age of DOM and climatic variables, and ecological null modeling, we propose five distinct DOM sources: plant litter and throughfall, soil organic matter (SOM) decomposition, root exudation, and two drought response subsets of likely microbial and plant origin. During drought conditions, aboveground plant-derived compounds decreased, while SOM products, root exudates, and drought response compounds increased. These drought responses were qualitatively similar in both years but notably amplified in the drier El Niño year. Drought amplified deterministic control over DOM composition, indicating that DOM reflected directed biological responses and that future droughts are likely to generate similar shifts. Overall, drought substantially altered belowground carbon cycling by shifting DOM sources and inducing stress responses, effects expected to recur and potentially intensify under future climate scenarios.

Lange, Dan F.↗

Modification of conventional peak shapes to accurately represent spectral asymmetry: High-Resolution X-ray photoelectron spectra of [C 4 C 1 Pyrr][NTf 2 ] and [C 8 C 1 Im][NTf 2 ] ionic liquids

X-ray photoelectron spectroscopy (XPS) is one of the most widely used techniques for surface characterization. Analysis of XPS data is challenging and requires the analyst to fit the data with synthetic line shapes to reach physically meaningful interpretations. Experimental spectral envelopes, however, are complex and display asymmetric features that are often ignored or attributed to additional chemical components. The high-resolution XPS spectra of [C 4 C 1 Pyrr][NTf 2 ] and [C 8 C 1 Im][NTf 2 ] all exhibit a degree of asymmetry which is systematically observed at the higher binding energy side of photoemission envelopes. Here, we present the development of a refined fitting procedure for XPS spectra of these ionic liquid-based systems which include (a) Shirley background offset necessary to account for the insulator-like region and (b) spectral asymmetry in C 1s and N 1s regions. Further, Shirley and trapezoid components are applied to compensate for inelastic scattering taking place during electron transitions as high as 7.8 eV above the start of the fitting region in C 1s high-resolution spectrum. To demonstrate the fitness of this model, we present an analysis of a 2:1 mixture of [C 4 C 1 Pyrr][NTf 2 ]: [C 8 C 1 Im][NTf 2 ].

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗