The Role of Wildfires in the Interplay of Forest Carbon Stocks and Wood Harvest in the Contiguous United States During the 20th Century.

Wildfires and land use play a central role in the long-term carbon (C) dynamics of forested ecosystems of the United States. Understanding their linkages with changes in biomass, resource use, and consumption in the context of climate change mitigation is crucial. We reconstruct a long-term C balance of forests in the contiguous U.S. using historical reports, satellite data, and other sources at multiple scales (national scale 1926-2017, regional level 1941-2017) to disentangle the drivers of biomass C stock change. The balance includes removals of forest biomass by fire, by extraction of woody biomass, by forest grazing, and by biomass stock change, their sum representing the net ecosystem productivity (NEP). Nationally, the total forest NEP increased for most of the 20th century, while fire, harvest and grazing reduced total forest stocks on average by 14%, 51%, and 6%, respectively, resulting in a net increase in C stock density of nearly 40%. Recovery from past land-use, plus reductions in wildfires and forest grazing coincide with consistent forest regrowth in the eastern U.S. but associated C stock increases were offset by increased wood harvest. C stock changes across the western U.S. fluctuated, with fire, harvest, and other disturbances (e.g., insects, droughts) reducing stocks on average by 14%, 81%, and 7%, respectively, resulting in a net growth in C stock density of 14%. Although wildfire activities increased in recent decades, harvest was the key driver in the forest C balance in all regions for most of the observed timeframe.

Forest Transitions in the United States, France and Austria: dynamics of forest change and their socio- metabolic drivers.

Understanding the drivers of forest transitions is relevant to inform effective forest conservation. We investigate pathways of forest transitions in the United States (1920-2010), France (1850-2010), and Austria (1830-2010). By combining evidence from forest inventories with the forest model CRAFT, we first quantify how change in forest area (ΔA), maximum biomass density (ΔBdmax ), and actual biomass as fraction of maximum biomass (ΔFmax ) shaped forest dynamics. Second, to investigate the connections between forest change and societal resource use, or social metabolism, we quantify the importance of selected proximate and underlying socio-metabolic drivers. We find that agricultural intensification and reduced forest grazing correlated most with positive ΔA and ΔBdmax . By contrast, change in biomass imports or harvest did not explain forest change. Our findings highlight the importance of forest growth conditions in explaining long-term forest dynamics, and demonstrate the distinct ways in which resource use drove forest change.

Altered growth conditions more than reforestation counteracted forest biomass carbon emissions 1990-2020.

Understanding the carbon (C) balance in global forest is key for climate-change mitigation. However, land use and environmental drivers affecting global forest C fluxes remain poorly quantified. Here we show, following a counterfactual modelling approach based on global Forest Resource Assessments, that in 1990-2020 deforestation is the main driver of forest C emissions, partly counteracted by increased forest growth rates under altered conditions: In the hypothetical absence of changes in forest (i) area, (ii) harvest or (iii) burnt area, global forest biomass would reverse from an actual cumulative net C source of c. 0.74 GtC to a net C sink of 26.9, 4.9 and 0.63 GtC, respectively. In contrast, (iv) without growth rate changes, cumulative emissions would be 7.4 GtC, i.e., 10 times higher. Because this sink function may be discontinued in the future due to climate-change, ending deforestation and lowering wood harvest emerge here as key climate-change mitigation strategies.

Lamellar carbon-aluminosilicate nanocomposites with macroscopic orientation.

Novel preparative approaches towards lamellar nanocomposites of carbon and inorganic materials are relevant for a broad range of technological applications. Here, we describe how to utilize the co-assembly of a liquid-crystalline hexaphenylene amphiphile and an aluminosilicate precursor to prepare carbon-aluminosilicate nanocomposites with controlled lamellar orientation and macroscopic order. To this end, the shear-induced alignment of a precursor phase of the two components resulted in thin films comprising lamellae with periodicities on the order of the molecular length scale, an "edge-on" orientation relative to the substrate and parallel to the shearing direction with order on the centimeter length scale. The lamellar structure, orientation, and macroscopic alignment were preserved in the subsequent pyrolysis that yielded the corresponding carbon-aluminosilicate nanocomposites.

Crystallization and Organic Field-Effect Transistor Performance of a Hydrogen-Bonded Quaterthiophene.

Crystalline thin films of π-conjugated molecules are relevant as the active layers in organic electronic devices. Therefore, materials with enhanced control over the supramolecular arrangement, crystallinity, and thin-film morphology are desirable. Herein, it is reported that hydrogen-bonded substituents serve as additional structure-directing elements that positively affect crystallization, thin-film morphology, and device performance of p-type organic semiconductors. It is observed that a quaterthiophene diacetamide exhibits a denser packing than that of other quaterthiophenes in the single-crystal structure and, as a result, displays enhanced intermolecular electronic interactions. This feature was preserved in crystalline thin films that exhibited a layer-by-layer morphology, with large domain sizes and high internal order. As a result, organic field-effect transistors of these polycrystalline thin films showed mobilities in the range of the best mobility values reported for single-crystalline quaterthiophenes. The use of hydrogen-bonded groups may, thus, provide an avenue for organic semiconducting materials with improved morphology and performance.

Modeling and empirical validation of long-term carbon sequestration in forests (France, 1850-2015).

The development of appropriate tools to quantify long-term carbon (C) budgets following forest transitions, that is, shifts from deforestation to afforestation, and to identify their drivers are key issues for forging sustainable land-based climate-change mitigation strategies. Here, we develop a new modeling approach, CRAFT (CaRbon Accumulation in ForesTs) based on widely available input data to study the C dynamics in French forests at the regional scale from 1850 to 2015. The model is composed of two interconnected modules which integrate biomass stocks and flows (Module 1) with litter and soil organic C (Module 2) and build upon previously established coupled climate-vegetation models. Our model allows to develop a comprehensive understanding of forest C dynamics by systematically depicting the integrated impact of environmental changes and land use. Model outputs were compared to empirical data of C stocks in forest biomass and soils, available for recent decades from inventories, and to a long-term simulation using a bookkeeping model. The CRAFT model reliably simulates the C dynamics during France's forest transition and reproduces C-fluxes and stocks reported in the forest and soil inventories, in contrast to a widely used bookkeeping model which strictly only depicts C-fluxes due to wood extraction. Model results show that like in several other industrialized countries, a sharp increase in forest biomass and SOC stocks resulted from forest area expansion and, especially after 1960, from tree growth resulting in vegetation thickening (on average 7.8 Mt C/year over the whole period). The difference between the bookkeeping model, 0.3 Mt C/year in 1850 and 21 Mt C/year in 2015, can be attributed to environmental and land management changes. The CRAFT model opens new grounds for better quantifying long-term forest C dynamics and investigating the relative effects of land use, land management, and environmental change.

Free-film small-angle neutron scattering: a novel container-free in situ sample environment with minimized H/D exchange.

The development of a container-free sample environment which is particularly well suited for in situ reaction studies of liquid samples by small-angle neutron scattering and related techniques is reported. Hydrogen exchange with the humidity from air is reduced by an encapsulating setup in a bag filled with an inert gas such as He. The effectiveness of this measure is quantitatively accessed by infrared absorption and gravimetry, and further correlated with neutron scattering.

Breakthrough in neutron backscattering spectroscopy: Energy resolution improved by one order of magnitude using the GaAs 200 reflection.

We have developed and tested a demonstrator for a neutron backscattering spectrometer with a tenfold enhanced energy resolution. This is made possible by taking advantage of the narrow intrinsic linewidth of the GaAs 200 Bragg reflection, which is one order of magnitude smaller than the linewidth of the currently used Si 111. First measurements yielded an unprecedented energy resolution of 78 neV FWHM, a factor of 10 narrower than the standard Si 111 configuration and about a factor of 4 smaller than the highest energy resolution currently available with Si 111. These measurements provide proof of concept for the construction of a full-scale user instrument.

A flexible high speed pulse chopper system for an inverted neutron time-of-flight option on backscattering spectrometers.

We present the design and simulation of a high resolution inverted time-of-flight option for a neutron spectrometer with crystal analysers in backscattering, with specific reference to the IN16B spectrometer at the Institut Laue-Langevin, Grenoble. While the conventional configuration with Si 111 crystals provides sub-µeV resolution in an energy range limited to ±30 µeV, the novel BATS option (BATS: Backscattering and Time-of-flight Spectrometer) extends the energy window to 340 µeV with only a slightly increased resolution of 1.2 µeV. Moreover, the observation window can be shifted to inelastic energy transfers. To bring this about, a novel fast chopper system with disks of large diameter and complex slit pattern is used, offering high flexibility in resolution and repetition rate. The chopper system consists out of two counter rotating disk chopper pairs. It provides 7 different pulse lengths, three pulse repetition rates up to 237 Hz and can operate with Si 111 or Si 311 crystal analysers. The latter option is a unique feature which covers a Q-range up to 3.7 Å-1 with a resolution of 6.8 µeV. Extensive ray-tracing simulations have been used to validate the design of the pulse chopper system, set limits on the sample size, and assess the achievable energy resolutions of the different chopper configurations.

Trends in Austrian Resource Efficiency: An Exergy and Useful Work Analysis in Comparison to Material Use, CO2 Emissions, and Land Use.

In the past few years, resource use and resource efficiency have been implemented in the European Union (EU) environmental policy programs as well as international sustainable development programs. In their programs, the EU focuses on four resource types that should be addressed: materials, energy (or carbon dioxide [CO2] emissions), water, and land. In this article, we first discuss different perspectives on energy use and present the results of a long-term exergy and useful work analysis of the Austrian economy for the period 1900-2012, using the methodology developed by Ayres and Warr. Second, we discuss Austrian resource efficiency by comparing the presented exergy and useful work data with material use, CO2 emissions, and land-use data taken from statistical sources. This comparison provides, for the first time, a long-term analysis of Austrian resource efficiency based on a broad understanding thereof and evaluates Austrian development in relation to EU and Austrian policy targets.

The stopped-drop method: a novel setup for containment-free and time-resolved measurements.

A novel setup for containment-free time-resolved experiments at a free-hanging drop is reported. Within a dead-time of 100 ms a drop of mixed reactant solutions is formed and the time evolution of a reaction can be followed from thereon by various techniques. As an example, a small-angle X-ray scattering study on the formation mechanism of EDTA-stabilized CdS both at a synchrotron and a laboratory X-ray source is presented here. While the evolution can be followed with one drop only at a synchrotron source, a stroboscopic mode with many drops is preferable for the laboratory source.

Complementary Molecular Dynamics and X-ray Reflectivity Study of an Imidazolium-Based Ionic Liquid at a Neutral Sapphire Interface.

Understanding the molecular-level behavior of ionic liquids (ILs) at IL-solid interfaces is of fundamental importance with respect to their application in, for example, electrochemical systems and electronic devices. Using a model system, consisting of an imidazolium-based IL ([C2Mim][NTf2]) in contact with a sapphire substrate, we have approached this problem using a complementary combination of high-resolution X-ray reflectivity measurements and atomistic molecular dynamics (MD) simulations. Our strategy enabled us to compare experimental and theoretically calculated reflectivities in a direct manner, thereby critically assessing the applicability of several force-field variants. On the other hand, using the best-matching MD description, we are able to describe the nature of the model IL-solid interface in appreciable detail. More specifically, we find that characteristic interactions between the surface hydroxyl groups and donor and acceptor sites on the IL constituents have a dominant role in inducing a multidimensional layering profile of the cations and anions.

Structural investigations of self-assembled monolayers for organic electronics: results from X-ray reflectivity.

Self-assembled monolayers (SAMs) have been established as crucial interlayers and electronically active layers in organic electronic devices, such as organic light emitting diodes (OLEDs), organic photovoltaics (OPVs), organic thin film transistors (OTFTs), and nonvolatile memories (NVMs). The use of self-assembling functionalized organic molecules is beneficial due to mainly three advantages compared with common thin film deposition approaches. (1) Molecular self-assembly occurs with surface selectivity, determined by the interaction between the functional anchor group of the organic molecules and the target surface. (2) The film thickness of the resulting layers is perfectly controllable on the angstrom scale, due to the self-terminating film formation to only a single molecular layer. And finally, (3) the wide variability in the chemical structure of such molecules enables different SAM functionalities for devices, ranging from electrical insulation to charge storage to charge transport. The SAM approach can be further expanded by employing several functionalized molecules to create mixed SAMs with consequently mixed properties. The function of SAMs in devices depends not only on the chemical structure of the molecules but also on their final arrangement and orientation on the surface. A reliable and nondestructive in-depth characterization of SAMs on nonconductive oxide surfaces is still challenging because of the very small thickness and the impracticality of methods such as scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). In this Account, we illustrate how X-ray reflectivity (XRR) provides analytical access to major questions of SAM composition, morphology, and even formation by means of investigations of pure and mixed SAMs based on phosphonic acids (PAs) of various chain structures on flat alumina (AlOx) surfaces. XRR is an analytical method that provides access to spatially averaged structural depth profiles over a relatively large area of several square micrometers. The key outcome of XRR, the surface-normal electron density profile of the SAMs, leads to precise information on the SAM thickness with subangstrom resolution and allows for the determination of molecular tilt angles and packing densities. We have systematically increased the chemical complexity of PA molecules and the resulting SAMs, utilizing XRR to provide insight into the SAM structures. In SAMs composed of functionalized molecules or complex chain structures, the distribution of electron rich and electron poor signatures is detected and thus the molecular order within the SAM is determined. In mixed SAMs of two different molecular species, electron density profiles reveal the morphology and how the surface-normal structure changes if one component of the mixed SAM is altered. Furthermore, XRR was applied to investigate in situ the self-assembly of functionalized PA molecules from solution by tracking the monolayer growth over time. Even though the results provided by XRR on in-plane molecular arrangement are limited, it presents excellent information on the molecular scale along the surface normal and in addition allows for drawing conclusions on the intermolecular interactions within the SAM.

Nanoscale structure of Si/SiO2/organics interfaces.

X-ray reflectivity measurements of increasingly more complex interfaces involving silicon (001) substrates reveal the existence of a thin low-density layer intruding between the single-crystalline silicon and the amorphous native SiO2 terminating it. The importance of accounting for this layer in modeling silicon/liquid interfaces and silicon-supported monolayers is demonstrated by comparing fits of the measured reflectivity curves by models including and excluding this layer. The inclusion of this layer, with 6-8 missing electrons per silicon unit cell area, consistent with one missing oxygen atom whose bonds remain hydrogen passivated, is found to be particularly important for an accurate and high-resolution determination of the surface normal density profile from reflectivities spanning extended momentum transfer ranges, now measurable at modern third-generation synchrotron sources.

Tuning the molecular order of C60-based self-assembled monolayers in field-effect transistors.

The control of order in organic semiconductor systems is crucial to achieve desired properties in electronic devices. We have studied the order in fullerene functionalized self-assembled monolayers by mixing the active molecules with supporting alkyl phosphonic acids of different chain length. By adjusting the length of the molecules, structural modifications of the alignment of the C60 head groups within the SAM can be tuned in a controlled way. These changes on the sub-nanometre scale were analysed by grazing incidence X-ray diffraction and X-ray reflectivity. To study the electron transport properties across these layers, self-assembled monolayer field-effect transistors (SAMFETs) were fabricated containing only the single fullerene monolayer as semiconductor. Electrical measurements revealed that a high 2D crystalline order is not the only important aspect. If the fullerene head groups are too confined by the supporting alkyl phosphonic acid molecules, defects in the crystalline C60 film, such as grain boundaries, start to strongly limit the charge transport properties. By close interpretation of the results of structural investigations and correlating them to the results of electrical characterization, an optimum chain length of the supporting alkyl phosphonic acids in the range of C10 was determined. With this study we show that minor changes in the order on the sub-nanometre scale, can strongly influence electronic properties of functional self-assembled monolayers.

Region-selective self-assembly of functionalized carbon allotropes from solution.

Approaches for the selective self-assembly of functionalized carbon allotropes from solution are developed and validated for 0D-fullerenes, 1D-carbon nanotubes and 2D-graphene. By choosing the right molecular interaction of self-assembled monolayers (serving the surface) with the functionalization features of carbon materials, which provide the solubility but also serve the driving force for assembly, we demonstrate a region-selective and self-terminating assembly of the materials. Active layers of the carbon allotropes can be selectively deposited in the channel region of thin-film transistor (TFT) devices by this approach. As an example for a 0D system, molecules of C60 functionalized octadecylphosphonic acids are used to realize self-assembled monolayer field-effect transistors (SAMFETs) based on a selective molecular exchange reaction of stearic acid in the channel region. For noncovalently functionalized single-walled carbon nanotubes (SWCNTs) and graphene oxide (GO) flakes, the electrostatic Coulomb interactions between the functional groups of the carbon allotropes and the charged head groups of a SAM dielectric layer are utilized to implement the selective deposition.

Low-voltage self-assembled monolayer field-effect transistors on flexible substrates.

Self-assembled monolayer field-effect transistors (SAMFETs) of BTBT functionalized phosphonic acids are fabricated. The molecular design enables device operation with charge carrier mobilities up to 10(-2) cm(2) V(-1) s(-1) and for the first time SAMFETs which operate on rough, flexible PEN substrates even under mechanical substrate bending.

Micellar crystallization with a hysteresis in temperature.

We have investigated the phase diagram of the triblock copolymer P123 solved in water by viscosity measurements for different concentrations and temperatures. The structures of the different phases were identified by surface sensitive neutron diffraction. We find a pronounced hysteresis between heating and cooling. During heating, a highly viscous crystalline fcc phase is found before melting occurs at 44 °C with a simultaneous drop in viscosity. Upon cooling, first a hexagonal phase with low viscosity develops followed by a highly viscous fcc phase. Phase diagrams for the heating and cooling cycle for different concentrations are provided. The hysteric behavior is discussed in relation to the shape of the micelles.

Non-periodicity in nanoparticles with close-packed structures.

Experimentally it is observed that nanomaterials from II-VI compounds like CdS have a high density of stacking faults. It is argued that these are not crystal defects but rather that they represent a characteristic feature of nanomaterials.

Crystallization of soft crystals.

The crystallization of micelles formed by surfactant F127 solvated by 20% in water was investigated in the vicinity of a hydrophilic interface. Upon entering the crystalline phase from low temperature, a large correlation length develops without preferential texture. Upon heating, the correlation length decreases and Oswald ripening is observed with crystallites orienting with respect to each other while retaining long-range and textured correlation.