Transition-metal dichalcogenides (TMDs) are renowned for their rich and varied bulk properties, while their single-layer variants have become one of the most prominent examples of two-dimensional ...materials beyond graphene. Their disparate ground states largely depend on transition metal d-electron-derived electronic states, on which the vast majority of attention has been concentrated to date. Here, we focus on the chalcogen-derived states. From density-functional theory calculations together with spin- and angle-resolved photoemission, we find that these generically host a co-existence of type-I and type-II three-dimensional bulk Dirac fermions as well as ladders of topological surface states and surface resonances. We demonstrate how these naturally arise within a single p-orbital manifold as a general consequence of a trigonal crystal field, and as such can be expected across a large number of compounds. Already, we demonstrate their existence in six separate TMDs, opening routes to tune, and ultimately exploit, their topological physics.
Methods to generate spin-polarized electronic states in non-magnetic solids are strongly desired to enable all-electrical manipulation of electron spins for new quantum devices. This is generally ...accepted to require breaking global structural inversion symmetry. In contrast, here we report the observation from spin- and angle-resolved photoemission spectroscopy of spin-polarized bulk states in the centrosymmetric transition-metal dichalcogenide WSe2 . Mediated by a lack of inversion symmetry in constituent structural units of the bulk crystal where the electronic states are localized, we show how spin splittings up to thick ~0.5 eV result, with a spin texture that is strongly modulated in both real and momentum space. Through this, our study provides direct experimental evidence for a putative locking of the spin with the layer and valley pseudospins in transition-metal dichalcogenides, of key importance for using these compounds in proposed valleytronic devices.
Soils are a crucial component of the Earth system; they comprise a large portion of terrestrial carbon stocks, mediate the supply and demand of nutrients, and influence the overall response of ...terrestrial ecosystems to perturbations. In this paper, we develop a new soil biogeochemistry model for the Community Land Model, version 4 (CLM4). The new model includes a vertical dimension to carbon (C) and nitrogen (N) pools and transformations, a more realistic treatment of mineral N pools, flexible treatment of the dynamics of decomposing carbon, and a radiocarbon (14C) tracer. We describe the model structure, compare it with site-level and global observations, and discuss the overall effect of the revised soil model on Community Land Model (CLM) carbon dynamics. Site-level comparisons to radiocarbon and bulk soil C observations support the idea that soil C turnover is reduced at depth beyond what is expected from environmental controls for temperature, moisture, and oxygen that are considered in the model. In better agreement with observations, the revised soil model predicts substantially more and older soil C, particularly at high latitudes, where it resolves a permafrost soil C pool. In addition, the 20th century-C dynamics of the model are more realistic than those of the baseline model, with more terrestrial C uptake over the 20th century due to reduced N downregulation and longer turnover times for decomposing C.
Global wetlands are believed to be climate sensitive, and are the largest natural emitters of methane (CH4). Increased wetland CH4 emissions could act as a positive feedback to future warming. The ...Wetland and Wetland CH4 Inter-comparison of Models Project (WETCHIMP) investigated our present ability to simulate large-scale wetland characteristics and corresponding CH4 emissions. To ensure inter-comparability, we used a common experimental protocol driving all models with the same climate and carbon dioxide (CO2) forcing datasets. The WETCHIMP experiments were conducted for model equilibrium states as well as transient simulations covering the last century. Sensitivity experiments investigated model response to changes in selected forcing inputs (precipitation, temperature, and atmospheric CO2 concentration). Ten models participated, covering the spectrum from simple to relatively complex, including models tailored either for regional or global simulations. The models also varied in methods to calculate wetland size and location, with some models simulating wetland area prognostically, while other models relied on remotely sensed inundation datasets, or an approach intermediate between the two. Four major conclusions emerged from the project. First, the suite of models demonstrate extensive disagreement in their simulations of wetland areal extent and CH4 emissions, in both space and time. Simple metrics of wetland area, such as the latitudinal gradient, show large variability, principally between models that use inundation dataset information and those that independently determine wetland area. Agreement between the models improves for zonally summed CH4 emissions, but large variation between the models remains. For annual global CH4 emissions, the models vary by ±40% of the all-model mean (190 Tg CH4 yr−1). Second, all models show a strong positive response to increased atmospheric CO2 concentrations (857 ppm) in both CH4 emissions and wetland area. In response to increasing global temperatures (+3.4 °C globally spatially uniform), on average, the models decreased wetland area and CH4 fluxes, primarily in the tropics, but the magnitude and sign of the response varied greatly. Models were least sensitive to increased global precipitation (+3.9 % globally spatially uniform) with a consistent small positive response in CH4 fluxes and wetland area. Results from the 20th century transient simulation show that interactions between climate forcings could have strong non-linear effects. Third, we presently do not have sufficient wetland methane observation datasets adequate to evaluate model fluxes at a spatial scale comparable to model grid cells (commonly 0.5°). This limitation severely restricts our ability to model global wetland CH4 emissions with confidence. Our simulated wetland extents are also difficult to evaluate due to extensive disagreements between wetland mapping and remotely sensed inundation datasets. Fourth, the large range in predicted CH4 emission rates leads to the conclusion that there is both substantial parameter and structural uncertainty in large-scale CH4 emission models, even after uncertainties in wetland areas are accounted for.
We demonstrate that substrate uptake kinetics in any consumer-substrate network subject to the total quasi-steady-state assumption can be formulated as an equilibrium chemistry (EC) problem. If the ...consumer-substrate complexes equilibrate much faster than other metabolic processes, then the relationships between consumers, substrates, and consumer-substrate complexes are in quasi-equilibrium and the change of a given total substrate (free plus consumer-bounded) is determined by the degradation of all its consumer-substrate complexes. In this EC formulation, the corresponding equilibrium reaction constants are the conventional Michaelis-Menten (MM) substrate affinity constants. When all of the elements in a given network are either consumer or substrate (but not both), we derived a first-order accurate EC approximation (ECA). The ECA kinetics is compatible with almost every existing extension of MM kinetics. In particular, for microbial organic matter decomposition modeling, ECA kinetics explicitly predicts a specific microbe's uptake for a specific substrate as a function of the microbe's affinity for the substrate, other microbes' affinity for the substrate, and the shielding effect on substrate uptake by environmental factors, such as mineral surface adsorption. By taking the EC solution as a reference, we evaluated MM and ECA kinetics for their abilities to represent several differently configured enzyme-substrate reaction networks. In applying the ECA and MM kinetics to microbial models of different complexities, we found (i) both the ECA and MM kinetics accurately reproduced the EC solution when multiple microbes are competing for a single substrate; (ii) ECA outperformed MM kinetics in reproducing the EC solution when a single microbe is feeding on multiple substrates; (iii) the MM kinetics failed, while the ECA kinetics succeeded, in reproducing the EC solution when multiple consumers (i.e., microbes and mineral surfaces) were competing for multiple substrates. We then applied the EC and ECA kinetics to a guild based C-only microbial litter decomposition model and found that both approaches successfully simulated the commonly observed (i) two-phase temporal evolution of the decomposition dynamics; (ii) final asymptotic convergence of the lignocellulose index to a constant that depends on initial litter chemistry and microbial community structure; and (iii) microbial biomass proportion of total organic biomass (litter plus microbes). In contrast, the MM kinetics failed to realistically predict these metrics. We therefore conclude that the ECA kinetics are more robust than the MM kinetics in representing complex microbial, C substrate, and mineral surface interactions. Finally, we discuss how these concepts can be applied to other consumer-substrate networks.
The direction and magnitude of soil organic carbon (SOC) changes in response to climate change depend on the spatial and vertical distributions of SOC. We estimated spatially resolved SOC stocks from ...surface to C horizon, distinguishing active-layer and permafrost-layer stocks, based on geospatial analysis of 472 soil profiles and spatially referenced environmental variables for Alaska. Total Alaska state-wide SOC stock was estimated to be 77 Pg, with 61% in the active-layer, 27% in permafrost, and 12% in non-permafrost soils. Prediction accuracy was highest for the active-layer as demonstrated by highest ratio of performance to deviation (1.5). Large spatial variability was predicted, with whole-profile, active-layer, and permafrost-layer stocks ranging from 1–296 kg C m−2, 2–166 kg m−2, and 0–232 kg m−2, respectively. Temperature and soil wetness were found to be primary controllers of whole-profile, active-layer, and permafrost-layer SOC stocks. Secondary controllers, in order of importance, were found to be land cover type, topographic attributes, and bedrock geology. The observed importance of soil wetness rather than precipitation on SOC stocks implies that the poor representation of high-latitude soil wetness in Earth system models may lead to large uncertainty in predicted SOC stocks under future climate change scenarios. Under strict caveats described in the text and assuming temperature changes from the A1B Intergovernmental Panel on Climate Change emissions scenario, our geospatial model indicates that the equilibrium average 2100 Alaska active-layer depth could deepen by 11 cm, resulting in a thawing of 13 Pg C currently in permafrost. The equilibrium SOC loss associated with this warming would be highest under continuous permafrost (31%), followed by discontinuous (28%), isolated (24.3%), and sporadic (23.6%) permafrost areas. Our high-resolution mapping of soil carbon stock reveals the potential vulnerability of high-latitude soil carbon and can be used as a basis for future studies of anthropogenic and climatic perturbations.
Receptor activator of nuclear factor κB ligand (RANKL) is expressed by a number of cell types to participate in diverse physiological functions. We have previously identified 10 distal RANKL ...enhancers. Earlier studies have shown that RL-D5 is a multifunctional RANKL enhancer. Deletion of RL-D5 from the mouse genome leads to lower skeletal and lymphoid tissue RANKL, causing a high bone mass phenotype. Herein, we determine the physiological role and lineage specificity of 2 additional RANKL enhancers, RL-D6 and RL-T1, which are located 83 and 123 kb upstream of the gene's transcriptional start site, respectively. Lack of RL-D6 or RL-T1 did not alter skeletal RANKL or bone mineral density up to 48 weeks of age. Although both RL-D5 and RL-T1 contributed to activation induction of T-cell RANKL, RL-T1 knockout mice had drastically low lymphocyte and lymphoid tissue RANKL levels, indicating that RL-T1 is the major regulator of lymphocyte RANKL. Moreover, RL-T1 knockout mice had lower circulating soluble RANKL, suggesting that lymphocytes are important sources of circulating soluble RANKL. Under physiological conditions, lack of RL-D6 did not alter RANKL expression. However, lack of RL-D5 or RL-D6, but not of RL-T1, blunted the oncostatin M and lipopolysaccharide induction of RANKL ex vivo and in vivo, suggesting that RL-D5 and RL-D6 coregulate the inflammation-mediated induction of RANKL in osteocytes and osteoblasts while lack of RL-D6 did not alter secondary hyperparathyroidism or lactation induction of RANKL or bone loss. These results suggest that although RL-D5 mediates RANKL expression in multiple lineages, other cell type– or factor-specific enhancers are required for its appropriate control, demonstrating the cell type–specific and complex regulation of RANKL expression.
The fate of currently frozen permafrost carbon as high-latitude climate warms remains highly uncertain and existing models give widely varying estimates of the permafrost carbon-climate feedback. ...This uncertainty is due to many factors, including the role that permafrost thaw-induced transitions in soil hydrologic conditions will have on organic matter decomposition rates and the proportion of aerobic to anaerobic respiration. Large-scale permafrost thaw, as predicted by the Community Land Model (CLM) under an unmitigated greenhouse gas emissions scenario, results in significant soil drying due to increased drainage following permafrost thaw, even though permafrost domain water inputs are projected to rise (net precipitation minus evaporation >0). CLM predicts that drier soil conditions will accelerate organic matter decomposition, with concomitant increases in carbon dioxide (CO2) emissions. Soil drying, however, strongly suppresses growth in methane (CH4) emissions. Considering the global warming potential (GWP) of CO2 and CH4 emissions together, soil drying weakens the CLM projected GWP associated with carbon fluxes from the permafrost zone by more than 50% compared to a non-drying case. This high sensitivity to hydrologic change highlights the need for better understanding and modeling of landscape-scale changes in soil moisture conditions in response to permafrost thaw in order to more accurately assess the potential magnitude of the permafrost carbon-climate feedback.
Metallic transition-metal dichalcogenides (TMDCs) are benchmark systems for studying and controlling intertwined electronic orders in solids, with superconductivity developing from a charge-density ...wave state. The interplay between such phases is thought to play a critical role in the unconventional superconductivity of cuprates, Fe-based and heavy-fermion systems, yet even for the more moderately-correlated TMDCs, their nature and origins have proved controversial. Here, we study a prototypical example, 2H-NbSe2, by spin- and angle-resolved photoemission and first-principles theory. We find that the normal state, from which its hallmark collective phases emerge, is characterized by quasiparticles whose spin is locked to their valley pseudospin. This results from a combination of strong spin-orbit interactions and local inversion symmetry breaking, while interlayer coupling further drives a rich three-dimensional momentum dependence of the underlying Fermi-surface spin texture. These findings necessitate a re-investigation of the nature of charge order and superconducting pairing in NbSe2 and related TMDCs.
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