Soil carbon dynamics during drying vs. rewetting: Importance of antecedent moisture conditions
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Plant roots and the organisms that surround them are a primary source for stabilized soil organic carbon (SOC). While grassland soils have a large capacity to store organic carbon (C), few field-based studies have quantified the amount of plant-fixed C that moves into soil and persists belowground over multiple years. Yet this characteristic of the soil C cycle is critical to C storage, soil water holding capacity, nutrient provisions, and the management of soil health. Here, we tracked the fate of plant-fixed C following a five-day 13 CO 2 labeling of a Northern California annual grassland, measuring C pools starting at the end of the labeling period, at three days, four weeks, six months, one year, and two years. Soil organic carbon was fractionated using a density-based approach to separate the free-light fraction (FLF), occluded-light fraction (OLF), and heavy fraction (HF). Using isotope ratio mass spectrometry, we measured 13 C enrichment and total C content for plant shoots, roots, soil, soil dissolved organic carbon (DOC), and the FLF, OLF, and HF. The chemical nature of C in the HF was further analyzed by solid state 13 C nuclear magnetic resonance (NMR) spectroscopy.
The persistence of soil organic carbon (SOC) is influenced by soil physicochemical properties, organic matter quality, and climatic conditions that govern its vulnerability to microbial activity. We compared the susceptibility of newly formed SOC to mineralization in two soils (Andosols) that developed under contrasting precipitation regimes. Soil from the high rainfall region (‘high rain ’) had higher SOC and lower iron concentrations than soils exposed to less rainfall (‘low rain ’). We amended soils with 13 C-labeled carbohydrates and measured the amount of substrate-derived SO 13 C mineralized when exposed to dry-wet cycling following months-long incubations. We hypothesized that susceptibility would differ due to iron content and mineralogy, initial SOC, substrate solubility (cellulose versus glucose amendment), and microbial substrate use efficiency (SUE). We found that SO 13 C was less susceptible to dry-wet cycling when more 13 C was assimilated into microbial biomass and co-localized with mineral surfaces than when co-localized with existing organo-mineral surfaces, according to microscale NanoSIMS imaging. Considerably less SO 13 C was susceptible to mineralization in the ferrihydrite-rich (low SOC) low rain soil than the leached (high SOC) high rain soil when C was added as either glucose (7.3-fold less C mineralized) or cellulose (15.2-fold less). Additionally, the SUE of glucose was comparable to cellulose in low rain soil where SO 13 C was less water soluble and coprecipitated with ferrihydrite, and used half as efficiently as cellulose in high rain soil. Our results show that the susceptibility of newly formed SOC to mineralization is modified by the effects of bioavailability on microbial metabolism and the availability of mineral surfaces for forming new organo-mineral complexes.
Lignin decomposition is critically linked to terrestrial carbon (C) cycle due to the enormous C mass of lignin and its importance in controlling overall rates of litter decomposition. Interactions between lignin and iron (Fe) minerals have been increasingly recognized as key mediators of lignin decomposition in experimental studies. However, we still lack a quantitative understanding of how Fe minerals interact with microbes to control lignin decomposition. Here, we leveraged experimental results from an incubation of Fe-rich soil, in which lignin decomposition rates were measured at aerobic conditions after four levels of pre-treated O2 availability, to examine microbe-Fe (MiFe) interactions in lignin decomposition with a MiFe model. We quantified how Fe redox cycling interacted with microbial activities to control lignin decomposition via data-model integration. Our results showed that the MiFe model with time-dependent growth and mortality functions better represented CO2 release from lignin decomposition (R2 ranging from 0.96 to 0.97) than models assuming either first-order or Michaelis-Menten kinetics. Reduction of Fe(III) to Fe(II) after pre-treatments with lower O2 availability stimu-lated the Fenton reaction to break down macro-molecular lignin into small molecules available to microbes. The small molecules of lignin and necromass bounded with oxidized Fe and were protected from decomposition. After 1-year incubation, the model implied that most of C stabilized with Fe minerals was derived from small molecular lignin C. Our quantitative analysis of microbe-Fe interactions sheds new light on lignin decomposition and preservation and helps improve model prediction of soil C persistence under global change.
Large quantities of soil carbon (C) can persist within paleosols for millennia due to burial and subsequent isolation from plant-derived inputs, atmospheric conditions, and microbial activity at the modern surface. Erosion exposes buried soils to modern root-derived C influx via root exudation and root turnover, thus stimulating microbial activity leading to SOC decomposition and accumulation through organo-mineral stabilization of modern C. With this study we aim to quantify how modern root-derived C inputs impact paleosol C decomposition and stabilization across varying degrees of isolation from modern surface conditions in southwestern Nebraska, USA, where hillslope erosion is bringing a buried Late-Pleistocene-early Holocene paleosol (the “Brady Soil”) closer to the modern surface. We collected Brady Soil samples from 0.2m, 0.4m, and 1.2m below the modern surface and conducted two lab-based incubations. Soils were amended with either (1) a lab-synthesized mixture of low molecular weight compounds (12 atom% 13 C), or (2) 13 C enriched root residues (92 atom% 13 C), in 30-day and 240-day incubation experiments, respectively. Here we determined microbial responses to synthetic root exudates and residues by partitioning the 13 C label from Brady Soil C, including measurements of total, root, and primed C respiration, microbial biomass C (MBC), microbial C use efficiency (CUE). To assess the capacity of isolated paleosols to accrue modern plant C, we used Nano-scale Secondary Ion Mass Spectrometry imaging. We found that: (1) adding root-derived C inputs primed Brady Soil C across all depths, and was mediated by depth and composition of root additions; (2) root-derived C inputs stimulated microbial biomass C (MBC) growth similarly across depths, but the magnitude of CUE and MBC varied by chemistry of root-derived additions; (3) new particulate organic matter was incorporated into mineral-associated pools over time; (4) material from the added root residues was found in association with bacterial cells and fungal hyphae as well as with soil aggregate and mineral surfaces. Our study shows that paleosols defy expectations of C content and reactivity with depth, and changes in land cover and climate will expose buried paleosols to modern surface conditions, increasing respired C. This work highlights the importance of evaluating the role resurfacing buried soils through landscape change plays in C cycle feedbacks to the climate system.
Glacial recession is occurring at unprecedented rates resulting in increased sediment accumula-tions in some riverine ecosystems. Increased sediment deposition has implications for ecosystem stability (e.g., floods and river paths) and environmental services (e.g., carbon sequestration). Soils and sediments have an enormous potential to retain carbon (C), predominantly due to sorp-tion to mineral surfaces. However, C persistence may be sensitive to climate-change induced temperature and moisture variations. We coupled ultrahigh resolution organic matter composition classification with bacterial characterization and respiration measurements to test the combined effects of temperature (4 vs 20°C) and moisture (50 vs 100% water-filled pore space) on C turn-over in sediments maintained under different mineralogical conditions (illite-amended vs non-amended). Here we show that the inhibition of CO 2 emissions from the combined effect of in-creased moisture content and illite was reflected in the turnover of key molecular signatures, such as the nominal oxidation state of C, often irrespective of temperature. However, shifts in bacteri-al communities from a coupled moisture-mineral interaction, were temperature-dependent. Our results highlight the importance of moisture in driving mineral-organic interactions and suggest that C in clay-rich, water-saturated sediments is both thermodynamically unfavorable and miner-al-protected from microbial consumption.
Soil rewetting after a dry period results in a surge of activity and succession in both microbial and DNA virus communities. Less is known about the response of RNA viruses to soil rewetting—while they are highly diverse and widely distributed in soil, they remain understudied. We hypothesized that RNA viruses would show temporal succession following rewetting and that phosphate amendment would influence their trajectory, as viral proliferation may cause phosphorus limitation. Using 39 time-resolved metatranscriptomes and amplicon data, 2190 RNA viral populations were identified across five phyla, with 26 % of these predicted to infect bacteria, and 11 % fungi. Only 1.2 % of viral populations had annotated capsid genes, suggesting most persist via intracellular replication without a free virion phase. Phosphate amendment altered RNA viral community composition within the first week and amended vs. unamended communities remained distinguishable for up to three weeks. While the overall host community remained stable, certain bacterial populations showed reduced abundance in phosphate-amended soils, likely due to increased viral lysis, as RNA bacteriophages proliferated significantly. Notably, 60 % of the viruses with increased abundance under phosphate amendment belonged to basal Lenarviricota clades rather than well-known groups like Leviviricetes. We estimate RNA bacteriophage infections may affect 10 7 –10 9 bacteria per gram of soil, aligning with the total bacterial population (10 7 –10 10 g -1 soil), suggesting that RNA phages significantly influence bacterial communities post-wet-up, with phosphorus availability modulating this effect.
Cloud-type impacts present a great challenge to solar forecasting due to diverse and complex cloud-radiation interactions. This third part of our paper sequence seeks to address this challenge by quantifying the forecast accuracies under eight cloud types: cumulus (Cu), stratified clouds (St), altocumulus (Ac), altostratus (As), cirrostratus/anvil (Cr), cirrus (Ci), congestus (Co), deep convective clouds (Dc) across four physics-informed persistence models reported in Part I. To generalize the cloud impacts, the eight cloud types are further grouped into three cloud categories based on their common features: weak convective clouds, stratiform clouds, and strong convective clouds. Here, the decade-long (2001 ~ 2014) collocated measurements of irradiances and cloud types at the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Program South Great Plain (SGP) Central Facility site are used for model evaluation. Results reveal a clear performance hierarchy for global horizontal irradiance (GHI) and direct normal irradiance (DNI): best for weak convective clouds and cirrus, intermediate for stratiform clouds, and worst for strong convective clouds. Performance for diffuse horizontal irradiance (DHI) is less influenced by cloud types. Cloud albedo dominates all three irradiances for Dc, while both cloud albedo and cloud fraction are influential for other cloud types. A 12 %~33 % improvement in accuracy at 6-hour lead time compared to the benchmark smart model confirms the effectiveness of incorporating physics into the models for various cloud types; further improvements are expected by directly integrating cloud type information into forecasting models by modifying the physical formulation of cloud-radiation interaction, and/or using more advanced machine learning models.
Module reliability and service lifetime are critical factors in improving photovoltaic system performance and reducing the levelized cost of electricity (LCOE). Soldering and lamination of the cell impart residual stresses that persist over time and superimpose additional loads during operation. This paper demonstrates the use of X-ray Topography (XRT) to image in-situ the dynamic response of a glass/backsheet mini-module upon drying at elevated temperature after saturation at humidity levels compatible with accelerated testing. The local water content in the encapsulant is also determined in-situ over time via Water Reflectometric Detection (WaRD), with diffusion of water in the front (glass side) and rear (backsheet side) resolved. As water diffuses out from the back of the glass/backsheet module, the cell curves towards the backsheet concomitantly. Here we find that the cell edges deflect 40μm out-of-plane with respect to its center while the encapsulant dries, compared to ~100 μm deflection when heating from 25°C to 85°C. The local cell deflections (changes in cell orientation) are correlated with the dynamic loss of water in the backside encapsulant. We conclude that the observed cell deflections are the result of hygroscopic stress induced by the encapsulant upon moisture outdiffusion. Therefore, the cell experiences a continually changing stress state and curvature dependent on local humidity and temperature. Depending on cell architecture and interconnection, this “breathing” mode of the cell may induce wear out and fatigue of the interconnects, affect the electrical connection of cracked pieces or cause failure near the interconnected edges of two cells.
The study of functional manipulation of graphene is a critical subject, both for fundamental research and practical applications. In this study, we present that the intercalation of 5d transition metals into epitaxial graphene on SiC is a promising strategy for the realization of topologically nontrivial phases with a finite band gap in graphene. Employing first-principles calculations, grounded in density functional theory, we demonstrate that Re- and Ta-intercalated graphene evolve into two-dimensional topological insulators. These exhibit linear Dirac cones and quadratic bands with topological band gaps, respectively. The emergence of these topological states is attributed to the strong spin–orbit coupling strength of the intercalants. We show that the corresponding topological edge states persist within the finite bulk band gap, aligning with the bulk-boundary correspondence. Furthermore, we explore the spin splitting of the band structure, brought about by the inversion symmetry breaking and the spin–orbit coupling. Finally, our study underscores that the intercalation of graphene is an effective and a feasible approach for manipulating the band gap and the topological nature of graphene. Such intercalated graphene systems hold potential utility for spintronics and low-dimensional quantum device applications.
Arctic soil microbial communities may shift with increasing temperatures and water availability from climate change. We examined temperature and volumetric liquid water content (VWC) in the upper 80 cm of permafrost-affected soil over 2 years (2018–2019) at the Bayelva monitoring station, Ny Ålesund, Svalbard. We show VWC increases with depth, whereas in situ temperature is more stable vertically, ranging from -5°C to 5°C seasonally. Prokaryotic metagenome-assembled genomes (MAGs) were obtained at 2–4 cm vertical resolution collected while frozen in April 2018 and at 10 cm vertical resolution collected while thawed in September 2019. The most abundant MAGs were Acidobacteriota, Actinomycetota, and Chloroflexota. Actinomycetota and Chloroflexota increase with depth, while Acidobacteriota classes Thermoanaerobaculia Gp7-AA8, Blastocatellia UBA7656, and Vicinamibacteria Vicinamibacterales are found above 6 cm, below 6 cm, and below 20cm, respectively. All MAGs have diverse carbon-degrading genes, and Actinomycetota and Chloroflexota have autotrophic genes. Further, genes encoding β -glucosidase, N-acetyl-β-D-glucosaminidase, and xylosidase increase with depth, indicating a greater potential for organic matter degradation with higher VWC. Acidobacteriota dominate the top 6 cm with their classes segregating by depth, whereas Actinomycetota and Chloroflexota dominate below ~6 cm. This suggests that Acidobacteriota classes adapt to lower VWC at the surface, while Actinomycetota and Chloroflexota persist below 6cm with higher VWC. This indicates that VWC may be as important as temperature in microbial climate change responses in Arctic mineral soils. Here we describe MAG-based Seqcode type species in the Acidobacteriota, Onstottus arcticum, Onstottus frigus, and Gilichinskyi gelida and in the Actinobacteriota, Mayfieldus profundus.
Intentional nuclear forensics is a concept wherein the deliberate addition of benign and persistent material signatures to nuclear material can be used to reduce the time between the discovery of material outside of regulatory control and determination of its original provenance. One concept within intentional nuclear forensics involves the use of perturbed stable isotopes to generate unique isotope ratio “barcodes” to encode information (e.g., production batch, location, etc.) and track material throughout the nuclear fuel cycle. Synthesis of taggant species of nickel (Ni), molybdenum (Mo), and tungsten (W) was undertaken via a double-spike mechanism, wherein two highly enriched isotopes of interest per elemental taggant were mixed to form an enriched “double-spike” which was subsequently isotopically diluted with bulk material having a natural isotopic composition. Two taggant species perturbing isotopic ratios, alpha (α) and beta (β), for each of Ni, Mo, and W were synthesized. Independent measurements of double spikes and alpha and beta taggant species agreed within uncertainty and are clearly resolvable from natural compositions. High-precision analyses were independently performed by MC-ICP-MS at two U.S. National Laboratories, with consensus values and uncertainties calculated for all samples. Observed isotopic perturbations in the final taggant species measured on the order of hundreds to thousands of permille (‰) with respect to natural for isotope ratios of interest (e.g., 60 Ni/ 58 Ni, 100 Mo/ 98 Mo, 186 W/ 183 W). Discrepancies between modeled and measured isotopic compositions were observed and are largely attributed to imprecise vendor assay values for starting materials. Using measured starting material compositions as inputs for the mixing model improved the level of agreement between predicted and measured α and β taggant isotope ratios. Overall, characterization of all taggant species demonstrates that this “barcode” concept could have viability for use in nuclear forensics. Finally, it is expected that for any two-isotope mixing array dozens of isotopic barcodes could be encoded into a material system and subsequently resolved utilizing modern mass spectrometric methods.
Here, detailed thermal experiments using relative humidity- (RH) and temperature-controlled X-ray diffraction (XRD) and H 2 O adsorption/desorption measurements were applied to understand the dehydration/hydration behaviors of thenardite/mirabilite (Na 2 SO 4 /Na 2 SO 4 ·10H 2 O), tincalconite/borax (Na 2 B 4 O 7 ·5H 2 O/Na 2 B 4 O 7 ·10H 2 O), nahcolite (NaHCO 3 ), and qilianshanite (NaH 4 (BO 3 ) (CO 3 )·2H 2 O or NaHCO 3 ·H 3 BO 3 ·2H 2 O). The thermal behaviors of thenardite/mirabilite and tincalconite/borax were evaluated at room temperature as a function of RH. Hydration of thenardite to mirabilite is very sluggish and does not begin until at least 85 % RH, whereas dehydration of mirabilite to thenardite occurs at ~76 % RH. The reactions are accessible in the solid state and were not completely reversible on the time scale of these measurements. Qilianshanite appears stable under room conditions, as long as the RH is >20 %, supported by 2.5 months of observation during exposure to room air of known RH. Qilianshanite persists metastably for at least two days when exposed to both wet and 0% RH atmospheres at room temperature, observed during environment-controlled XRD. Below 20 % RH, qilianshanite sluggishly reacts to form tincalconite and nahcolite. When heated, qilianshanite broke down at 70 °C based on XRD results, and thermogravimetric analysis (TGA) confirmed a dehydration temperature of ~75 °C. Tincalconite hydrated to borax at 80 % RH, and dehydration from borax to tincalconite occurred at 40–50 % RH, illustrating the effective reversibility of the reaction under room conditions. The minor phase nahcolite originally in qilianshanite remained in the residue of decomposed qilianshanite after heating to 125 °C, demonstrated by continuous XRD measurements, whereas nahcolite was largely dehydrated when heated to ~100 °C during TGA. The difference can be attributed to the slower reaction kinetics in the environmental XRD. These results shed considerable light on the behavior of these minerals in the environment, particularly in evaporite deposits in Antarctica, where all of these minerals are reacting with the atmosphere on a diurnal-to-seasonal basis.
A persistent question in wavenumber analysis in the estimation of thickness from a steady-state wave field is identifying the theoretical sensitivity of the system. Here, a well-known trade-off between spatial frequency/wavenumber resolution and thickness resolution exists. The current work presents a calculation of the Cramer-Rao Lower bound (CRLB), specifically as applied to thickness estimates, for a 2-dimensional multi-mode waveform in Gaussian noise. Cases of near-field and far-field excitation are considered, and transducer position with respect to the scan area is also varied. Additionally, we consider the CRLB in a plate with multiple sources, simulated as sources placed on the boundary of the plate. We conclude by presenting the CRLB values in terms of frequency for various thicknesses, and by presenting optimal excitation frequencies for a nominal thickness, based on the CRLB.
Biofuels from non-recyclable municipal solid waste (NMSW) stand at the forefront of energy sustainability. However, their widespread adoption is hampered by persistent material handling issues stemming from the variability in NMSW material properties. An enhanced understanding of particulated NMSW properties, particularly compressibility and permeability, is essential to address the feedstock handling challenges and optimize the handling equipment. This study measures the compressibility and gas permeability of five streams of NMSW materials (i.e., rigid plastics, cardboard, thin film, paper, and foam) and their mixtures under different stress conditions. The results highlight the significant variability in compressibility and gas permeability among different streams, as well as the impacts of particle sizes. A semi-empirical model capable of predicting the gas permeability of NMSW mixtures is established and validated. Here, the results also highlight that reduced NMSW particle size helps promote consistency in NMSW feedstock’s physical and mechanical properties, which is favored for handling equipment design in waste-to-energy recovery facilities.
This work investigates the chemical changes of the surface of Alloy 800HT during sliding contact under helium atmosphere in the presence of impurities at 750 °C, which is of interest for the nuclear industry. The alloy samples are exposed to helium (He) atmosphere at high temperature for long duration of 500 h to identify the chemical and topographical changes of the alloy surface. The oxidation rate constant is reported based on the weight change data. For the tribo-experimental samples, the surfaces inside and outside the wear track are studied thoroughly using techniques such as secondary electron microscopy, energy dispersive spectroscopy, x-ray diffraction, Raman spectroscopy and secondary ion mass spectroscopy. The formation and evolution of surface oxides are discussed in He atmosphere, compared with air. The presence of Fe-rich thin layer of oxide on top of a thicker Cr-rich oxide and a mixed spinel-based inner layer on the bulk is found. The persistent presence of thicker Fe3O4 in the wear track in high temperature air proved to be the reason of lower friction property. Pre-oxidation of the samples in air or He does not improve but worsen the tribological behavior in He atmosphere.
Preventing spontaneous crystallization of supersaturated solutions by additives is of critical interest to successful process design and implementation, with numerous applications in chemical, pharmaceutical, medical, pigment, and food industries, but challenges remain in laboratory and industry settings and fundamental understanding is lacking. When copresented with antifreeze proteins (AFPs), otherwise spontaneously crystallizing osmolytes are maintained at high supersaturations for months in over-wintering organisms. Thus, we here explore the inhibition phenomenon by AFPs, using persistent crystallization of a common sugar alcohol, D-mannitol, as a case study. We report experimentally that DAFP1, an insect AFP, completely inhibits D-mannitol nucleation. Computer simulations reveal a new mechanism for crystallization inhibition where the population of the crystal-forming conformers are selectively bound and randomized in solution by hydrogen bonding to the protein surface. These results highlight the advantages of using natural polymers to address crystallization inhibition challenges and suggest new strategies in controlling the nucleation processes.
Metallization of quantum spin liquid (QSL) materials has long been considered as a potential route toward unconventional superconductivity. Here, we investigate the pressurization of lithium ytterbium diselenide (LiYbSe 2 ), a three-dimensional QSL candidate with a pyrochlore structure. High-pressure X-ray diffraction (up to 15 GPa) and Raman spectroscopy (up to 48 GPa) reveal no significant structural changes within this pressure range. Remarkably insulating, LiYbSe 2 exhibits a resistance below 10 5 Ω only at pressures exceeding 25 GPa, accompanied by a gradual reduction of band gap upon compression. Interestingly, an insulator-to-metal transition occurs around 68 GPa, and the metallic behavior persists up to 123.5 GPa, the highest pressure achieved in this study. A possible sign of magnetic transitions is also observed. The insulator-to-metal transition in LiYbSe 2 under high pressure presents an ideal platform to explore the pressure effects on QSL candidates of spin-1/2 Yb 3+ systems with various lattice patterns.