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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Thermal Decomposition Kinetics of 4,6‐Diamino‐5,7‐dinitro‐benzo‐furazan

This experimental study investigated the thermal decomposition kinetics of 4,6-diamino-5,7-dinitro-benzo-furazan (referred to as F1 hereafter)—an important decomposition product of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB—a prototypical insensitive high explosive). Simultaneous differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and mass spectrometry (MS) measurements were employed to determine the decomposition kinetics of F1 and to track the evolution of product gases. The DSC profiles were measured at 10 different heating rates between 0.025°C/min and 10°C/min. The measured exotherms were influenced by F1 melting at heating rates above 0.25°C/min, and corresponding changes in decomposition enthalpy and TGA mass-loss-rate profiles indicated a transition from solid-to-gas decomposition to an increasing contribution from liquid-to-gas decomposition. Analysis of low-heating-rate DSC data between 0.025°C/min and 0.17°C/min with the extended Prout–Tompkins model yielded an activation energy of 305 kJ/mol for solid-to-gas F1 decomposition, higher than previous values inferred from TATB decomposition models involving F1. This study provides the first direct experimental determination of the energy barrier for F1 decomposition. MS measurements showed that the major gaseous products matched species previously reported for TATB decomposition (e.g., CO 2 , HCN, C 2 N 2 , etc.), with water identified as the dominant product. Furthermore, these results provide important experimental constraints for improving chemical kinetics models of TATB decomposition and for predicting the reactivity, stability, and safety of TATB-based high explosives under long-term aging conditions and abnormal thermal environments.

4,6-Diamino-5,7-dinitro-benzo-furazan↗
DOE OSTI2022

Nitrogen increases early‐stage and slows late‐stage decomposition across diverse grasslands

1. To evaluate how increased anthropogenic nutrient inputs alter carbon cycling in grasslands, we conducted a litter decomposition study across 20 temperate grasslands on three continents within the Nutrient Network, a globally distributed nutrient enrichment experiment 2. We determined the effects of addition of experimental nitrogen (N), phosphorus (P) and potassium plus micronutrient (K μ ) on decomposition of a common tree leaf litter in a long-term study (maximum of 7 years; exact deployment period varied across sites). The use of higher order decomposition models allowed us to distinguish between the effects of nutrients on early- versus late-stage decomposition. 3. Across continents, the addition of N (but not other nutrients) accelerated early-stage decomposition and slowed late-stage decomposition, increasing the slowly decomposing fraction by 28% and the overall litter mean residence time by 58%. 4. Synthesis. Using a novel, long-term cross-site experiment, we found widespread evidence that N enhances the early stages of above-ground plant litter decomposition across diverse and widespread temperate grassland sites but slows late-stage decomposition. These findings were corroborated by fitting the data to multiple decomposition models and have implications for N effects on soil organic matter formation. For example, following N enrichment, increased microbial processing of litter substrates early in decomposition could promote the production and transfer of low molecular weight compounds to soils and potentially enhance the stabilization of mineral-associated organic matter. By contrast, by slowing late-stage decomposition, N enrichment could promote particulate organic matter (POM) accumulation. Such hypotheses deserve further testing.

Nutrient Network (NutNet)↗
DOE OSTI2024

Decomposition characteristics of C4F7N-based SF6-alternative gas mixtures

C4F7N [2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanenitrile]/CO2 gas mixtures are being developed as an eco-friendly electrical insulator to replace SF6, the most potent greenhouse industrial gaseous dielectric. However, recent studies have reported complicated and often conflicting decomposition pathways for C4F7N/CO2 gas mixtures, which has raised concerns. In this work, the decomposition characteristics of C4F7N/CO2 gas mixtures were studied comprehensively by both designed computations and experiments. Computations were performed starting from fundamental propositions of C4F7N/CO2 decompositions, which were further experimentally verified by pyrolysis, long-term thermal aging with/without catalytic materials (industrial-grade molecular sieves 4A), and electrical decomposition by spark discharge. The results of both computations and experiments suggest that in an ideal thermal decomposition, C4F7N is likely to decompose into C2F6 and small fluoronitriles first at high temperatures. The generation of C3F6 and C2N2 from C4F7N thermal decomposition at lower temperatures appears because of the catalytic effect of incompatible materials, for example, the industrial-grade molecular sieves 4A that we tested. The electron impact dissociation of C4F7N plays an important role in C4F7N electrical decomposition, leading to additional formation of distinctive small molecules of CF4 and C2N2 of low concentrations. It was pointed out based on a real arcing test in a load disconnector that the decomposition of C4F7N gas mixtures in real applications will be at a much moderate and manageable rate than what was obtained from the highly accelerated laboratory tests presented in this work. The signatures of decomposition products extracted in this study provide invaluable guidance for developing decomposition-based diagnosis and fixation of decomposition byproducts toward SF6-free power grids.

Physics↗
DOE OSTI2026

Point-scale organic-matter decomposition in streambeds is weakly associated with reach-scale respiration

Stream and river ecosystems play a central role in the movement and decomposition of particulate organic matter, serving as a conduit between terrestrial hillslopes and coastal environments. Microbial-catalyzed decomposition generates simpler organic molecules that fuel respiration, often in the sediments of these ecosystems. However, the degree of connection between sediment-associated respiration (ER??d) and organic-matter decomposition remains poorly understood. How that relationship compares to decomposition’s relationship with whole ecosystem (ERtot) and water column (ERwc) respiration is also not clear. We examined the link between particulate organic matter decomposition—using cellulose-based cotton strips as a standardized substrate—and all three components of respiration across 48 sites in the environmentally diverse Yakima River Basin (Washington State, USA). We hypothesized that decomposition within sediments would be most strongly related to ERsed, but decomposition rates were more closely associated with ERtot, with little connection to ERsed or ERwc. This suggests that particulate organic matter decomposition within stream/river sediments reflects integrated system respiration rather than processes confined to sediments or the water column alone. Further, across the basin, decomposition rates nearly spanned the previously reported global range for streams and rivers and were best explained by total dissolved nitrogen (TDN), sediment grain size, and aridity of the upstream drainage area. These results highlight the strong influence of land cover and basin-scale biophysical variation on sediment-associated decomposition processes and indicate that mechanistic models of organic matter decomposition in streams/rivers should account for coupled sediment–water–land interactions.

Stegen, James C. (ORCID:0000000191357424)↗
DOE OSTI2025

Thermal decomposition pathways of bulk electrolytes on vanadium oxide nanocrystals

The thermal stability of electrolytes at an elevated temperature induced by battery charge-discharge cycling is critical for the long cycling performance of a rechargeable battery. For many multivalent systems, such as rechargeable magnesium batteries, which offer great potential for high energy density and utilize earth-abundant resources, electrolyte instability and electrode surface passivation, arising from electrolyte decomposition, remain as major roadblocks. Understanding the electrolyte decomposition pathways at the electrode-electrolyte interface is essential to provide guidance in overcoming this challenge. In this work, in situ 13 C magic angle spinning nuclear magnetic resonance (MAS NMR) and first-principles calculations were used to investigate the thermal decomposition of the electrolyte in a system consisting of MgV 2 O 4 , a novel cathode for magnesium batteries, mixed with a bulk electrolyte consisting of magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2 ) in diglyme (G2). We show that significant electrolyte decomposition is observed in bulk 1.0 M Mg(TFSI) 2 in G2 mixed with nanometer sized MgV 2 O 4 powder at elevated temperatures. This observation is to mimic the possible thermal decomposition that might happen during battery cycling. We demonstrate that the MgV 2 O 4 surface is covered by a layer of decomposed G2 products. We conclude that the dominant reaction pathway for electrolyte decomposition is the thermal decomposition of the pure electrolytes at elevated temperatures, followed by adsorption of G2 decomposition products to the MgV 2 O 4 surface. The activation energy for the major decomposition pathway is obtained. In conclusion, this work highlights the importance of studying thermal decomposition of electrolytes for overall system stability and explores electrolyte stability at significantly elevated temperatures.

25 ENERGY STORAGE↗
DOE OSTI2023

Contrasting geochemical and fungal controls on decomposition of lignin and soil carbon at continental scale

Lignin is an abundant and complex plant polymer that may limit litter decomposition, yet lignin is sometimes a minor constituent of soil organic carbon (SOC). Accounting for diversity in soil characteristics might reconcile this apparent contradiction. Tracking decomposition of a lignin/litter mixture and SOC across different North American mineral soils using lab and field incubations, here we show that cumulative lignin decomposition varies 18-fold among soils and is strongly correlated with bulk litter decomposition, but not SOC decomposition. Climate legacy predicts decomposition in the lab, and impacts of nitrogen availability are minor compared with geochemical and microbial properties. Lignin decomposition increases with some metals and fungal taxa, whereas SOC decomposition decreases with metals and is weakly related with fungi. Decoupling of lignin and SOC decomposition and their contrasting biogeochemical drivers indicate that lignin is not necessarily a bottleneck for SOC decomposition and can explain variable contributions of lignin to SOC among ecosystems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Plant roots stimulate the decomposition of complex, but not simple, soil carbon

Roots release carbon into soil and can alleviate energy limitation of microbial organic matter decomposition. We know little about the effects of roots on microbial decomposition of different organic matter substrates, despite the importance for soil carbon stocks and turnover. Through implementing root-microbe interactions, the Carbon, Organisms, Rhizosphere, and Protection in the Soil Environment (CORPSE) model was previously shown to represent dynamics of total soil carbon in temperate forest field experiments. However, the model permits alternative hypotheses concerning microbial-substrate affinity. We investigated how root inputs affect decomposition of soil organic carbon (SOC) with variable decomposability. We simulated SOC stocks in CORPSE and compared microbial degradation of two substrates types with varying root-microbe interactions under two alternative hypotheses that varied in microbial-substrate affinity. We compared our modeled hypotheses to a forest field experiment where we quantified decomposition of isotopically-labeled starch and leaf tissues in soils with manipulated root access to microbes. Here, we tested the hypothesis that decomposition of leaves would be more sensitive to root inputs than decomposition of starch, corresponding to the alternative model hypothesis. In the field study, leaf decomposition increased with root density while starch decomposition was unchanged by root density. Microbial biomass and enzyme activity consistently increased with root inputs in CORPSE and the field study. Our field experiment supported the CORPSE simulations with high microbial-substrate affinity. Roots stimulated microbial growth and enzyme production, which increased degradation of more complex substrates such as leaf tissues. Substrates that were easily decomposed, such as starch, may already be degrading at a maximum rate in the absence of rhizosphere influence because their decomposition rate was unchanged by root inputs. We found that the degree to which roots stimulate microbial decomposition depends on the substrate being decomposed, and that root-microbe interactions influenced SOC stocks in both our model and field experiment. Environmental changes that alter root-microbe interactions could, therefore, alter soil C stocks and biogeochemical cycling, and models of these interactions should incorporate differential influence of rhizosphere inputs on different substrates.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Root litter decomposition rates and impacts of drought are regulated by ecosystem legacy

In grassland ecosystems, about two-thirds of productivity is in roots, and therefore roots constitute a major soil organic matter input. However, influences on the rate of root litter decomposition remain unresolved, especially in the context of land-use conversion and climate change. Ecosystem legacy can affect root decomposition rates via impacts on substrate chemistry and soil environments, and this may manifest in responses of decomposition to changing temperature and moisture. Here we investigate the impacts of anthropogenic legacy effects and moderate drought on root litter decomposition rates in five "Land Use History Types": crop fields, cow pastures, remnant tallgrass prairie, and prairie restored from crop fields and pastures. We measured root losses of mass, carbon, and nitrogen over 11 months. Further, soil bulk density was unimportant for decomposition, but soil moisture content and temperature were relevant for decomposition rates while time since disturbance predicted decomposition initiation times. Furthermore, soil moisture and temperature dynamics alone could not explain the responses of decomposition rates to drought, which were positively correlated to time since disturbance. Our findings suggest that anthropogenic legacy impacts decomposition rates in grasslands, especially when soil moisture and temperature dynamics are substantially altered, and mediates soil community responses to drought.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Manganese effects on plant residue decomposition and carbon distribution in soil fractions depend on soil nitrogen availability

Recent studies have highlighted the critical role of manganese (Mn) in plant litter decomposition and soil organic carbon (C) cycling in forest ecosystems. Long term nitrogen (N) deposition and N fertilization can increase soil acidity and mobilize bioavailable Mn (Mn 2+ ) in soil. However, no studies have examined the interactive effect of N and Mn fertilization on litter decomposition and carbon distribution in agricultural soils, despite agroecosystems being subject to both N and Mn management. We hypothesized that increased soil N and Mn availability would accelerate plant residue decomposition and transfer of its C to mineral-associated organic matter (MAOM), and that the combined effect of Mn and N enrichment would be greater than the individual effect. Here, we conducted a laboratory incubation experiment by adding 13 C-labeled residue of perennial grass Glyceria striata (Lam.) to agricultural soils that had received 225 kg N ha –1 yr –1 for 27 years (N 1 ) and comparable soils that received no N (N 0 ). Before the experiment, these soils also received three levels of dissolved Mn 2+ , designated M 0 (no additional Mn), M 1 (50 mg kg –1 ), or M 2 (250 mg kg –1 ). We measured total CO 2 production as well as distribution of 13 C from the residue into CO 2 , particulate organic matter (POM), MAOM, and dissolved organic carbon (DOC) over a 1-year period. Manganese amendments significantly increased CO 2 production from residue decomposition in the N 1 soil, but no such effect was observed in the N 0 soil. Manganese also accelerated the loss of residue-derived C from POM and DOC, but increased its recovery in MAOM. However, the positive effect of added Mn in decomposition and recovery in MAOM in the presence of N fertilization occurred only during the initial 30-day decomposition period, where M 2 showed a 12% increase in cumulative CO 2 production from residue, 8% increase in POM loss, and 43% increase in recovery of residue C in MAOM compared to M 0 . For M 1 , only CO 2 emission from residue was significantly higher than Mo during this period. At 365 days M 2 showed 8% increase in CO 2 production, 1% increase in POM loss, and 16% increase in recovery of residue C in MAOM compared to M 0 , but none of these were statistically significant (p < 0.05). This study adds to the growing evidence that increasing Mn availability enhances plant litter decomposition. However, the occurrence and magnitude of Mn-induced stimulation of decomposition is context specific. Further investigation with greater temporal resolution, involving a multitude of litter and soil types and including microbial compositional and functional characterization, is recommended to fully elucidate the interactive role of Mn and N on C cycling.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Microwave-induced selective decomposition of cellulose: Computational and experimental mechanistic study

Understanding microwave-material interactions will help facilitate the utilization of microwave technology in gasification and renewable energy production. In this study, cellulose was used as a model compound to simulate the organic matter in biomass, and its catalytic decomposition under a microwave (MW) field was studied to identify structural changes from the reaction. The study was conducted using a MW source coupled to a fixed-bed gas-flow reactor, mass spectroscopic, and Fourier transform infrared spectroscopy post-reaction analysis. Zeolite 13X was chosen as a microwave absorber to study the catalytic enhancement of the decomposition of cellulose. Density functional theory (DFT) was used to gain insights into the molecular transformations occurring in the presence of a static electric field, which was used to simulate the electric field component of the microwave electromagnetic radiation. Theoretical calculations demonstrated that both the positive and negative portion of the electric field interact with the permanent dipoles of the cellulose effecting the decomposition through the glycosidic bond breaking mechanism. The theoretical result was verified using infrared spectroscopic analysis of the pure cellulose during microwave heating. The theoretical calculations suggest only the positive electric field component may be active for the cellulose decomposition in the presence of Zeolite 13X. Physically mixing Zeolite 13X with the cellulose led to a significant enhancement in the decomposition rate of the glycosidic bond. Zeolite 13X enhanced the glycosidic O-C decomposition at lower MW power (lower temperatures), whereas the O-H functional group required higher MW power (higher temperature) for its decomposition. The DFT study coupled with the reaction studies revealed that the electric field polarizability is dependent upon both the direction and the orientation of the cellulose. Gas products revealed that applying 250 W of MW power led to the production of CO, H 2 , along with some CO 2 , CH 4 , and benzene at 305 °C. Finally, reaction under 500, 750, and 1000 W of power at constant temperature (305 °C) revealed that higher power led to the complete decomposition of cellulose to mostly CO, H 2 , and CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Modern insights into the mechanisms of neptunium oxalate decomposition

Neptunium oxalate (Np(C 2 O 4 ) 2 ·6H 2 O) is a historically relevant solid phase used in nuclear processing as a precursor for neptunium dioxide (NpO 2 ). Although Np oxalate has been synthesized and used for NpO 2 production for decades, the thermal decomposition mechanism of this phase remains poorly understood and has not been evaluated in over 30 years. Conflicting reports in historical literature suggest either a direct conversion from anhydrous oxalate to NpO 2 or a decomposition that includes the formation of Np carbonate or oxidized Np intermediate phases. In this work, we reexamine the decomposition pathway of Np(C 2 O 4 ) 2 ·6H 2 O using thermal analysis coupled with evolved gas analysis and temperature-dependent Raman spectroscopy to elucidate decomposition mechanisms and intermediate phases using modern analytical techniques. Thermal analysis revealed a three-stage decomposition process, including dehydration below 200 °C, oxalate breakdown between 170 and 370 °C, and NpO 2 formation by 500 °C. However, an unidentified plateau in the thermal data was observed during measurements. Raman spectroscopy confirmed the stages of decomposition, and in the analysis of potential intermediate phases, no carbonate phases or Np 2 O 5 were identified. Raman data suggest that residual oxalate or nonstoichiometric oxide are present during decomposition before pure NpO 2 is formed. These findings clarify aspects of the Np oxalate decomposition mechanism and address longstanding discrepancies in the literature, with a specific focus on Np-specific materials chemistry.

Lawson, Kathryn M. [Oak Ridge National Laboratory ↗
DOE OSTI2021

Coarse woody debris decomposition assessment tool: Model development and sensitivity analysis

Coarse woody debris (CWD) is an important component in forests, hosting a variety of organisms that have critical roles in nutrient cycling and carbon (C) storage. We developed a process-based model using literature, field observations, and expert knowledge to assess woody debris decomposition in forests and the movement of wood C into the soil and atmosphere. The sensitivity analysis was conducted against the primary ecological drivers (wood properties and ambient conditions) used as model inputs. The analysis used eighty-nine climate datasets from North America, from tropical (14.2° N) to boreal (65.0° N) zones, with large ranges in annual mean temperature (26.5°C in tropical to -11.8°C in boreal), annual precipitation (6,143 to 181 mm), annual snowfall (0 to 612 kg m -2 ), and altitude (3 to 2,824 m above mean see level). The sensitivity analysis showed that CWD decomposition was strongly affected by climate, geographical location and altitude, which together regulate the activity of both microbial and invertebrate wood-decomposers. CWD decomposition rate increased with increments in temperature and precipitation, but decreased with increases in latitude and altitude. CWD decomposition was also sensitive to wood size, density, position (standing vs downed), and tree species. The sensitivity analysis showed that fungi are the most important decomposers of woody debris, accounting for over 50% mass loss in nearly all climatic zones in North America. The model includes invertebrate decomposers, focusing mostly on termites, which can have an important role in CWD decomposition in tropical and some subtropical regions. The role of termites in woody debris decomposition varied widely, between 0 and 40%, from temperate areas to tropical regions. Woody debris decomposition rates simulated for eighty-nine locations in North America were within the published range of woody debris decomposition rates for regions in northern hemisphere from 1.6° N to 68.3° N and in Australia.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Castanha et al. 2018: Hopland Lysimeter 13C-Labeled Root Litter Decomposition Study.

The breakdown and decomposition of plant inputs are critical for nutrient cycling, soil development, and climate-ecosystem feedbacks, but uncertainties persist in how the rates and products of litter decomposition are affected by soil temperature, rhizosphere, and depth of input. To elucidate these questions we measured the effects of soil warming (+ 4 °C), rhizosphere, and depth of litter placement on the decomposition of Avena fatua (wild oat grass) root litter in a Mediterranean grassland ecosystem. Field lysimeters were subjected to three environmental treatments (heating, control, and plant removal) and three 13C-labeled root litter addition treatments (to A horizon, to B horizon, and no-addition disturbance control) for each of two harvest time points. We buried root litter in February 2014 and measured loss of 13C in CO2 from the soil surface and in leachate as dissolved organic carbon (DOC) over two growing seasons. At the end of each of the 2014 and 2015 growing seasons we recovered the 13C remaining in the soil. Loss of root litter C occurred almost entirely via heterotrophic respiration, with an estimated < 2% lost as DOC during the initial decay period. The added roots were broken down and incorporated into bulk soil material very quickly; only ~ 30% of added root was visible after 6 months. In the first growing season, decomposition occurred faster in the B than in the A horizon, the latter having greater moisture limitation. Subsequently, there was almost no further decomposition in the B horizon. After two growing seasons, less than 20% of the added root litter C remained in the A or B horizons of all environmental treatments. Heating did not stimulate decomposition, likely because it exacerbated the moisture limitation. However, while plots without plants dried down more slowly than plots with plants, their decomposition rate was not significantly greater, possibly due to the lack of rhizosphere processes such as priming. We conclude that in this Mediterranean grassland ecosystem, soil moisture, which is affected by season, depth, heating, and rhizosphere, plays a dominant role in mediating the effect of those factors on root litter decomposition, which after two seasons did not differ by depth or by treatment.The files in this dataset comprise (1) 13C-labeled litter additions made to each plot, (2) litter recovery after each of 2 growing seasons, (3) periodical soil flux measurements, (4) leachate measurements, and continuously monitored soil (5) temperature and (6) moisture.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Bacterial population-level trade-offs between drought tolerance and resource acquisition traits impact decomposition

Microbes drive fundamental ecosystem processes, such as decomposition. Environmental stressors are known to affect microbes, their fitness, and the ecosystem functions that they perform; yet, understanding the causal mechanisms behind this influence has been difficult. We used leaf litter on soil surface as a model in situ system to assess changes in bacterial genomic traits and decomposition rates for 18 months with drought as a stressor. We hypothesized that genome-scale trade-offs due to investment in stress tolerance traits under drought reduce the capacity for bacterial populations to carry out decomposition, and that these population-level trade-offs scale up to impact emergent community traits, thereby reducing decomposition rates. We observed drought tolerance mechanisms that were heightened in bacterial populations under drought, identified as higher gene copy numbers in metagenome-assembled genomes. A subset of populations under drought had reduced carbohydrate-active enzyme genes that suggested—as a trade-off—a decline in decomposition capabilities. These trade-offs were driven by community succession and taxonomic shifts as distinct patterns appeared in populations. We show that trait–trade-offs in bacterial populations under drought could scale up to reduce overall decomposition capabilities and litter decay rates. Using a trait-based approach to assess the population ecology of soil bacteria, we demonstrate genome-level trade-offs in response to drought with consequences for decomposition rates.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Reparameterizing Litter Decomposition Using a Simplified Monte Carlo Method Improves Litter Decay Simulated by a Microbial Model and Alters Bioenergy Soil Carbon Estimates

Litter decomposition determines soil organic matter (SOM) formation and plant-available nutrient cycles. Therefore, accurate model representation of litter decomposition is critical to improving soil carbon (C) projections of bioenergy feedstocks. Soil C models that simulate microbial physiology (i.e., microbial models) are new to bioenergy agriculture, and their parameterization is often based on small datasets or manual calibration to reach benchmarks. Here, we reparameterized litter decomposition in a microbial soil C model (CORPSE - Carbon, Organisms, Rhizosphere, and Protection in the Soil Environment) using the continental-scale Long-term Inter-site Decomposition Experiment Team (LIDET) dataset which documents decomposition across a range of litter qualities over a decade. Here, we conducted a simplified Monte Carlo simulation that constrained parameter values to reduce computational costs. The LIDET-derived parameters improved modeled C and nitrogen (N) remaining, decomposition rates, and litter mean residence times as compared to Baseline parameters. We applied the LIDET litter decomposition parameters to a microbial bioenergy model (Fixation and Uptake of Nitrogen – Bioenergy Carbon, Rhizosphere, Organisms, and Protection) to examine soil C estimates generated by Baseline and LIDET parameters. LIDET parameters increased estimated soil C in bioenergy feedstocks, with even greater increases under elevated plant inputs (i.e., by increasing residue, N fertilization). This was due to the integrated effects of plant litter quantity, quality, and agricultural practices (tillage, fertilization). Collectively, we developed a simple framework for using large-scale datasets to inform the parameterization of microbial models that impacts projections of soil C for bioenergy feedstocks.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Coarse Woody Debris Decomposition Assessment Tool: Model validation and application

Coarse woody debris (CWD) is a significant component of the forest biomass pool; hence a model is warranted to predict CWD decomposition and its role in forest carbon (C) and nutrient cycling under varying management and climatic conditions. A process-based model, CWDDAT (Coarse Woody Debris Decomposition Assessment Tool) was calibrated and validated using data from the FACE (Free Air Carbon Dioxide Enrichment) Wood Decomposition Experiment utilizing pine ( Pinus taeda ), aspen ( Populous tremuloides ) and birch ( Betula papyrifera ) on nine Experimental Forests (EF) covering a range of climate, hydrology, and soil conditions across the continental USA. The model predictions were evaluated against measured FACE log mass loss over 6 years. Four widely applied metrics of model performance demonstrated that the CWDDAT model can accurately predict CWD decomposition. The R 2 (squared Pearson’s correlation coefficient) between the simulation and measurement was 0.80 for the model calibration and 0.82 for the model validation ( P <0.01). The predicted mean mass loss from all logs was 5.4% lower than the measured mass loss and 1.4% lower than the calculated loss. The model was also used to assess the decomposition of mixed pine-hardwood CWD produced by Hurricane Hugo in 1989 on the Santee Experimental Forest in South Carolina, USA. The simulation reflected rapid CWD decomposition of the forest in this subtropical setting. The predicted dissolved organic carbon (DOC) derived from the CWD decomposition and incorporated into the mineral soil averaged 1.01 g C m -2 y -1 over the 30 years. The main agents for CWD mass loss were fungi (72.0%) and termites (24.5%), the remainder was attributed to a mix of other wood decomposers. These findings demonstrate the applicability of CWDDAT for large-scale assessments of CWD dynamics, and fine-scale considerations regarding the fate of CWD carbon.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Rolling Horizon Based Temporal Decomposition for the Offline Pickup and Delivery Problem with Time Windows

The offline pickup and delivery problem with time windows (PDPTW) is a classical combinatorial optimization problem in the transportation community, which has proven to be very challenging computationally. Due to the complexity of the problem, practical problem instances can be solved only via heuristics, which trade-off solution quality for computational tractability. Among the various heuristics, a common strategy is problem decomposition, that is, the reduction of a large-scale problem into a collection of smaller sub-problems, with spatial and temporal decompositions being two natural approaches. While spatial decomposition has been successful in certain settings, effective temporal decomposition has been challenging due to the difficulty of stitching together the sub-problem solutions across the decomposition boundaries. In this work, we introduce a novel temporal decomposition scheme for solving a class of PDPTWs that have narrow time windows, for which it is able to provide both fast and high-quality solutions. We utilize techniques that have been popularized recently in the context of online dial-a-ride problems along with the general idea of rolling horizon optimization. To the best of our knowledge, this is the first attempt to solve offline PDPTWs using such an approach. To show the performance and scalability of our framework, we use the optimization of paratransit services as a motivating example. Due to the lack of benchmark solvers similar to ours (i.e., temporal decomposition with an online solver), we compare our results with an offline heuristic algorithm using Google OR-Tools. In smaller problem instances (with an average of 129 requests per instance), the baseline approach is as competitive as our framework. However, in larger problem instances (approximately 2,500 requests per instance), our framework is more scalable and can provide good solutions to problem instances of varying degrees of difficulty, while the baseline algorithm often fails to find a feasible solution within comparable compute times.

Kim, Youngseo↗
DOE OSTI2021

A Novel Hollow Fiber Membrane Reactor for High Purity H 2 Generation from Thermal Catalytic NH 3 Decomposition (Final Report)

Ammonia (NH 3 ), as a promising carbon neutral liquid fuel (CNLF) and an effective H 2 source, can be synthesized from air and water (N 2 extracted from air and H 2 from water) using renewable energy sources. To produce H 2 as an intermediate, it is essential to develop effective and economic NH 3 decomposition technologies. We have been developing an innovative hollow fiber membrane reactor for high purity H 2 generation from thermal catalytic NH 3 decomposition. The objective of the proposed research is to fabricate a compact and robust prototype with high energy efficiency (>80%) to deliver high purity (>99%) H2 at high rate per volume (>0.15 g H 2 /h/cm 3 ) from NH3 decomposition at low temperature (<450 °C) and high conversion (>99%). Our overall technical approach is to effectively combine an active catalyst for NH 3 decomposition with a selective H 2 membrane separation process in a novel, compact modular system to generate high purity H 2 and simultaneously achieve high NH 3 conversion and optimize the entire system energy efficiency. This novel integrated membrane reactor design, together with low-cost, highly active Ru-based catalyst, makes it most appropriate for the project objective. The proposed applied research and development work, therefore, represents an innovative and transformational solution to H 2 generation from thermal catalytic NH 3 decomposition. During the course of our research we i) synthesized and characterized ruthenium(Ru)-based catalysts, evaluated their catalytic performance for NH 3 decomposition and optimized the catalyst composition and performance based on machine learning, ii) prepared SAPO-34, MFI membranes on α-alumina hollow fibers and measured their performance for H 2 /N 2 , H 2 /N 2 /NH 3 separation and evaluated carbon molecular sieve (CMS) and Pd/Ag membranes for H 2 /N 2 , H 2 /N 2 /NH 3 separation at different conditions, iii) designed and evaluated several types of membrane reactors for H 2 production from NH 3 decomposition, and iv) evaluated the H 2 delivery cost base on catalysts development, membrane development and membrane reactor. For 3,1,12 RuYK catalyst, H 2 productivity of 6.35 mmol/min/gcat with NH 3 conversion of 95~98% was achieved at 5 bar and 400 °C; for SAPO-34 membrane, the best membrane showed H 2 permeance of 7.56×10 -7 mol/(m 2 ∙s∙Pa) and H 2 /N 2 selectivity of 23.1 at 20 °C; For CMS and Pd/Ag membranes, both showed superior stability for 71%H 2 /24%N 2 /5%NH 3 mixture separation at 450 °C and 7 bar for over 120 h; for the membrane reactor, high H 2 purity of >99.99% with NH 3 conversion of >99.4% were achieved in Pd/Ag membrane reactor at 450 °C, and the NH 3 concentration was always below 10 ppb in H 2 product. The H 2 generation rate was calculated to be as high as 0.47 g/h/cm 3 and the energy efficiency was calculated to be 88%. The membrane reactor showed superior stability for over 370 h and high H 2 purity, H 2 production rate and NH 3 conversion. Based on calculation, the H 2 delivery cost can be as low as $3.66/kg.

08 HYDROGEN↗