Solutions and insights for agricultural monitoring, reporting, and verification (MRV) from three consecutive issuances of soil carbon credits.

Regenerative agricultural practice adoption on conventionally managed fields has gained momentum as a climate mitigation strategy, given the ability of these practices to sequester carbon or reduce greenhouse gas emissions. However, the geospatial and temporal variability of the impact of specific practices, such as cover cropping or no-till, pose challenges for scalable quantification of emissions reduction and deploying incentives to drive increased adoption. To quantify impact while accounting for variability and uncertainty at scale, Indigo Ag created a monitoring, reporting, and verification (MRV) pipeline to produce agricultural soil carbon credits produced at large scales (hundreds of thousands of hectares). The pipeline ingests field data from enrolled farmers, checks data quality, uses hybrid soil sampling and biogeochemical modeling to produce estimates of emissions reduction and uncertainty, and then applies deductions based on calculated uncertainty and leakage to quantify total project-wide carbon credits and monitor for durability of carbon. The implementation of a carbon project (CAR1459) from 2018 to 2022 on 553,743 ha of U.S. cropland utilizing the pipeline is estimated to have reduced emissions by 398,408.5 tCO2e, amounting to 296,662 tCO2e of soil carbon credits after uncertainty deductions. This paper explores the effect sizes associated with specific regenerative practice changes across the project domain. Cover cropping consistently resulted in a net positive climate impact and reduced emissions by 1.29 tCO2e per hectare per year, on average. Introduction of no-till was more common in the project, but it had a lower average emissions reduction of 0.38 tCO2e per hectare per year. Effect sizes for no-till vary spatiotemporally and are typically low in the first several years after adoption but increase in subsequent years. Agricultural carbon programs that capture and incentivize the nuance of outcomes of practices rather than the implementation of practices, can promote adoption of the right management practice to be deployed on the right field for maximum environmental benefit.

Direct Observation of Enhanced Electron-Phonon Coupling in Copper Nanoparticles in the Warm-Dense Matter Regime.

Warm dense matter (WDM) represents a highly excited state that lies at the intersection of solids, plasmas, and liquids and that cannot be described by equilibrium theories. The transient nature of this state when created in a laboratory, as well as the difficulties in probing the strongly coupled interactions between the electrons and the ions, make it challenging to develop a complete understanding of matter in this regime. In this work, by exciting isolated ∼8 nm copper nanoparticles with a femtosecond laser below the ablation threshold, we create uniformly excited WDM. Using photoelectron spectroscopy, we measure the instantaneous electron temperature and extract the electron-ion coupling of the nanoparticle as it undergoes a solid-to-WDM phase transition. By comparing with state-of-the-art theories, we confirm that the superheated nanoparticles lie at the boundary between hot solids and plasmas, with associated strong electron-ion coupling. This is evidenced both by a fast energy loss of electrons to ions, and a strong modulation of the electron temperature induced by strong acoustic breathing modes that change the nanoparticle volume. This work demonstrates a new route for experimental exploration of the exotic properties of WDM.

Beyond ecosystem modeling: A roadmap to community cyberinfrastructure for ecological data-model integration.

In an era of rapid global change, our ability to understand and predict Earth's natural systems is lagging behind our ability to monitor and measure changes in the biosphere. Bottlenecks to informing models with observations have reduced our capacity to fully exploit the growing volume and variety of available data. Here, we take a critical look at the information infrastructure that connects ecosystem modeling and measurement efforts, and propose a roadmap to community cyberinfrastructure development that can reduce the divisions between empirical research and modeling and accelerate the pace of discovery. A new era of data-model integration requires investment in accessible, scalable, and transparent tools that integrate the expertise of the whole community, including both modelers and empiricists. This roadmap focuses on five key opportunities for community tools: the underlying foundations of community cyberinfrastructure; data ingest; calibration of models to data; model-data benchmarking; and data assimilation and ecological forecasting. This community-driven approach is a key to meeting the pressing needs of science and society in the 21st century.

Assessment of yield gaps on global grazed-only permanent pasture using climate binning.

To meet rising demands for agricultural products, existing agricultural lands must either produce more or expand in area. Yield gaps (YGs)-the difference between current and potential yield of agricultural systems-indicate the ability to increase output while holding land area constant. Here, we assess YGs in global grazed-only permanent pasture lands using a climate binning approach. We create a snapshot of circa 2000 empirical yields for meat and milk production from cattle, sheep, and goats by sorting pastures into climate bins defined by total annual precipitation and growing degree-days. We then estimate YGs from intra-bin yield comparisons. We evaluate YG patterns across three FAO definitions of grazed livestock agroecosystems (arid, humid, and temperate), and groups of animal production systems that vary in animal types and animal products. For all subcategories of grazed-only permanent pasture assessed, we find potential to increase productivity several-fold over current levels. However, because productivity of grazed pasture systems is generally low, even large relative increases in yield translated to small absolute gains in global protein production. In our dataset, milk-focused production systems were found to be seven times as productive as meat-focused production systems regardless of animal type, while cattle were four times as productive as sheep and goats regardless of animal output type. Sustainable intensification of pasture is most promising for local development, where large relative increases in production can substantially increase incomes or "spare" large amounts of land for other uses. Our results motivate the need for further studies to target agroecological and economic limitations on productivity to improve YG estimates and identify sustainable pathways toward intensification.

Photo-ionization and fragmentation of Sc3N@C80 following excitation above the Sc K-edge.

We have investigated the ionization and fragmentation of a metallo-endohedral fullerene, Sc3N@C80, using ultrashort (10 fs) x-ray pulses. Following selective ionization of a Sc (1s) electron (hν = 4.55 keV), an Auger cascade leads predominantly to either a vibrationally cold multiply charged parent molecule or multifragmentation of the carbon cage following a phase transition. In contrast to previous studies, no intermediate regime of C2 evaporation from the carbon cage is observed. A time-delayed, hard x-ray pulse (hν = 5.0 keV) was used to attempt to probe the electron transfer dynamics between the encapsulated Sc species and the carbon cage. A small but significant change in the intensity of Sc-containing fragment ions and coincidence counts for a delay of 100 fs compared to 0 fs, as well as an increase in the yield of small carbon fragment ions, may be indicative of incomplete charge transfer from the carbon cage on the sub-100 fs time scale.

Nanodrawing of Aligned Single Carbon Nanotubes with a Nanopen.

Single-walled carbon nanotubes (SWCNTs) are considered pivotal components for molecular electronics. Techniques for SWCNT lithography today lack simplicity, flexibility, and speed of direct, oriented deposition at specific target locations. In this paper SWCNTs are directly drawn and placed with chemical identification and demonstrated orientation using fountain pen nanolithography (FPN) under ambient conditions. Placement across specific electrical contacts with such alignment is demonstrated and characterized. The fundamental basis of the drawing process with alignment has potential applications for other related systems such as inorganic nanotubes, polymers, and biological molecules.

Relative Photoionization Cross Sections of Super-Atom Molecular Orbitals (SAMOs) in C60.

The electronic structure and photoinduced dynamics of fullerenes, especially C60, is of great interest because these molecules are model systems for more complex molecules and nanomaterials. In this work we have used Rydberg Fingerprint Spectroscopy to determine the relative ionization intensities from excited SAMO (Rydberg-like) states in C60 as a function of laser wavelength. The relative ionization intensities are then compared to the ratio of the photoionization widths of the Rydberg-like states, computed in time-dependent density functional theory (TD-DFT). The agreement is remarkably good when the same photon order is required to energetically access the excited states. This illustrates the predictive potential of quantum chemistry for studying photoionization of large, complex molecules as well as confirming the assumption that is often made concerning the multiphoton excitation and rapid energy redistribution in the fullerenes.

Dynamics of thermal electron emission from highly excited C60.

Gas-phase fullerenes emit thermal electrons after femtosecond laser excitation in the wavelength range 400-800 nm. We have used angular-resolved photoelectron spectroscopy (PES) to study the influence of the laser's electric field on the dynamics of the thermally emitted electrons. The laser field introduces an asymmetry in the thermal electron distributions with respect to the laser polarization direction, which was confirmed by carrying out experiments at different wavelengths. A simple model could reproduce the trends in measured apparent temperatures in the PES. The asymmetry effect was exploited in a pump-probe experiment to estimate the time scale for thermal electron emission. It was found that, when 400 nm, 120 fs laser pulses of 2 TW cm(-2) intensity are used, thermal electrons are emitted up to ca. 300 fs after the peak of the laser pulse. The pump-probe scheme should be applicable to a wider range of complex molecules and clusters showing thermal electron emission on a femtosecond time scale.

Probing excited electronic states and ionisation mechanisms of fullerenes.

Fullerenes are interesting model systems for probing the complex, fundamental electron dynamics and ionisation mechanisms of large molecules and nanoparticles. In this Tutorial Review we explain how recent experimental and theoretical advances are providing insight into the interesting phenomenon of thermal electron emission from molecular systems and the properties of hydrogenic, diffuse, excited electronic states, known as superatom molecular orbitals, which are responsible for relatively simple, well-resolved structure in fs laser photoelectron spectra of fullerenes. We focus on the application of velocity map imaging combined with fs laser photoionisation to study angular-resolved photoelectron emission.

Electromechanically tunable carbon nanofiber photonic crystal.

We demonstrate an electrically tunable 2D photonic crystal array constructed from vertically aligned carbon nanofibers. The nanofibers are actuated by applying a voltage between adjacent carbon nanofiber pairs grown directly on metal electrodes, thus dynamically changing the form factor of the photonic crystal lattice. The change in optical properties is characterized using optical diffraction and ellipsometry. The experimental results are shown to be in agreement with theoretical predictions and provide a proof-of-principle for rapidly switchable photonic crystals operating in the visible that can be fabricated using standard nanolithography techniques combined with plasma CVD growth of the nanofibers.

Probing rapidly-ionizing super-atom molecular orbitals in C60: a computational and femtosecond photoelectron spectroscopy study.

Super-atom molecular orbitals (SAMOs) are diffuse hydrogen-like orbitals defined by the shallow potential at the centre of hollow molecules such as fullerenes. The SAMO excited states differ from the Rydberg states by the significant electronic density present inside the carbon cage. We provide a detailed computational study of SAMO and Rydberg states and an experimental characterization of SAMO excited electronic states for gas-phase C(60) molecules by photoelectron spectroscopy. A large band of 500 excited states was computed using time-dependent density functional theory. We show that due to their diffuse character, the photoionization widths of the SAMO and Rydberg states are orders of magnitude larger than those of the isoenergetic non-SAMO excited states. Moreover, in the range of kinetic energies experimentally measured, only the SAMO states photoionize significantly on the timescale of the femtosecond laser experiments. Single photon ionization of the SAMO states dominates the photoelectron spectrum for relatively low laser intensities. The computed photoelectron spectra and photoelectron angular distributions are in good agreement with the experimental results.

Hot electron production and diffuse excited states in C70, C82, and Sc3N@C80 characterized by angular-resolved photoelectron spectroscopy.

Angular-resolved photoelectron spectroscopy using wavelength-tuneable femtosecond laser pulses is presented for a series of fullerenes, namely, C70, C82, and Sc3N@C80. The photoelectron kinetic energy distributions for the three molecules show typical thermal electron spectra with a superimposed peak structure that is the result of one-photon ionization of diffuse low-angular momenta states with electron density close to the carbon cage and that are related to so-called super atom molecular orbitals. Photoelectron angular distributions confirm this assignment. The observed structure is less prominent compared to the thermal electron background than what was observed in C60. It can be concluded that hot electron emission is the main ionization channel for the larger and more complex molecules for these excitation conditions.

Determination of the bending rigidity of graphene via electrostatic actuation of buckled membranes.

Classical continuum mechanics is used extensively to predict the properties of nanoscale materials such as graphene. The bending rigidity, κ, is an important parameter that is used, for example, to predict the performance of graphene nanoelectromechanical devices and also ripple formation. Despite its importance, there is a large spread in the theoretical predictions of κ for few-layer graphene. We have used the snap-through behavior of convex buckled graphene membranes under the application of electrostatic pressure to determine experimentally values of κ for double-layer graphene membranes. We demonstrate how to prepare convex-buckled suspended graphene ribbons and fully clamped suspended membranes and show how the determination of the curvature of the membranes and the critical snap-through voltage, using AFM, allows us to extract κ. The bending rigidity of bilayer graphene membranes under ambient conditions was determined to be 35.5−15.0 +20.0 eV. Monolayers are shown to have significantly lower κ than bilayers.

Angular-resolved photoelectron spectroscopy of superatom orbitals of fullerenes.

Photoelectron angular distributions from both C(60) and C(70) were recorded for low laser intensity femtosecond and picosecond pulses. Rich structure is seen for electron kinetic energies that lie below the photon energy. Strong, broad peaks are observed for photoelectron energies corresponding to single-photon ionization of so-called superatom molecular orbitals (SAMOs). The very simple angular distributions measured for these peaks, the close similarity of the spectra observed from C(60) and C(70), and the comparison with time-dependent density functional theory provide strong support for the SAMO hypothesis.

Carbon nanotube field effect transistors with suspended graphene gates.

Novel field effect transistors with suspended graphene gates are demonstrated. By incorporating mechanical motion of the gate electrode, it is possible to improve the switching characteristics compared to a static gate, as shown by a combination of experimental measurements and numerical simulations. The mechanical motion of the graphene gate is confirmed by using atomic force microscopy to directly measure the electrostatic deflection. The device geometry investigated here can also provide a sensitive measurement technique for detecting high-frequency motion of suspended membranes as required, e.g., for mass sensing.

Charge Transport in UV-Oxidized Graphene and Its Dependence on the Extent of Oxidation.

Graphene oxides with different degrees of oxidation are prepared by controlling UV irradiation on graphene, and the charge transport and the evolution of the transport gap are investigated according to the extent of oxidation. With increasing oxygenous defect density nD, a transition from ballistic to diffusive conduction occurs at nD≃1012 cm-2 and the transport gap grows in proportion to nD. Considering the potential fluctuation related to the e-h puddle, the bandgap of graphene oxide is deduced to be Eg≃30nD(1012cm-2) meV. The temperature dependence of conductivity showed metal-insulator transitions at nD≃0.3×1012 cm-2, consistent with Ioffe-Regel criterion. For graphene oxides at nD≥4.9×1012 cm-2, analysis indicated charge transport occurred via 2D variable range hopping conduction between localized sp2 domain. Our work elucidates the transport mechanism at different extents of oxidation and supports the possibility of adjusting the bandgap with oxygen content.

Low-Power Complementary Inverter Based on Graphene/Carbon-Nanotube and Graphene/MoS2 Barristors.

The recent report of a p-type graphene(Gr)/carbon-nanotube(CNT) barristor facilitates the application of graphene barristors in the fabrication of complementary logic devices. Here, a complementary inverter is presented that combines a p-type Gr/CNT barristor with a n-type Gr/MoS2 barristor, and its characteristics are reported. A sub-nW (~0.2 nW) low-power inverter is demonstrated with a moderate gain of 2.5 at an equivalent oxide thickness (EOT) of ~15 nm. Compared to inverters based on field-effect transistors, the sub-nW power consumption was achieved at a much larger EOT, which was attributed to the excellent switching characteristics of Gr barristors.

Initial soil conditions outweigh management in a cool-season dairy farm's carbon sequestration potential.

Pastures and rangelands are a dominant portion of global agricultural land and have the potential to sequester carbon (C) in soils, mitigating climate change. Management intensive grazing (MIG), or high density grazing with rotations through paddocks with long rest periods, has been highlighted as a method of enhancing soil C in pastures by increasing forage production. However, few studies have examined the soil C storage potential of pastures under MIG in the northeastern United States, where the dairy industry comprises a large portion of agricultural use and the regional agricultural economy. Here we present a 12-year study conducted in this region using a combination of field data and the denitrification and decomposition (DNDCv9.5) model to analyze changes in soil C and nitrogen (N) over time, and the climate impacts as they relate to soil carbon dioxide (CO2) and nitrous oxide (N2O) fluxes. Field measurements showed: (1) increases in soil C in grazed fields under MIG (P = 0.03) with no significant increase in hayed fields (P = 0.55); and (2) that the change in soil C was negatively correlated to initial soil C content (P = 0.006). Modeled simulations also showed fields that started with relatively less soil C had significant gains in C over the course of the study, with no significant change in fields with higher initial levels of soil C. Sensitivity analyses showed the physiochemical status of soils (i.e., soil C and clay content) had greater influence over C storage than the intensity of grazing. More extensive grazing methods showed very little change in soil C storage or CO2 and N2O fluxes with modeled continuous grazing trending towards declines in soil C. Our study highlights the importance of considering both initial system conditions as well as management when analyzing the potential for long-term soil C storage.

Indirect Band Gap in Scrolled MoS2 Monolayers.

MoS2 nanoscrolls that have inner core radii of ∼250 nm are generated from MoS2 monolayers, and the optical and transport band gaps of the nanoscrolls are investigated. Photoluminescence spectroscopy reveals that a MoS2 monolayer, originally a direct gap semiconductor (∼1.85 eV (optical)), changes into an indirect gap semiconductor (∼1.6 eV) upon scrolling. The size of the indirect gap for the MoS2 nanoscroll is larger than that of a MoS2 bilayer (∼1.54 eV), implying a weaker interlayer interaction between concentric layers of the MoS2 nanoscroll compared to Bernal-stacked MoS2 few-layers. Transport measurements on MoS2 nanoscrolls incorporated into ambipolar ionic-liquid-gated transistors yielded a band gap of ∼1.9 eV. The difference between the transport and optical gaps indicates an exciton binding energy of 0.3 eV for the MoS2 nanoscrolls. The rolling up of 2D atomic layers into nanoscrolls introduces a new type of quasi-1D nanostructure and provides another way to modify the band gap of 2D materials.