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Long-term atmospheric CO2 concentration records have suggested a reduction in the positive effect of warming on high-latitude carbon uptake since the 1990s. A variety of mechanisms have been proposed to explain the reduced net carbon sink of northern ecosystems with increased air temperature, including water stress on vegetation and increased respiration over recent decades. However, the lack of consistent long-term carbon flux and in situ soil moisture data has severely limited our ability to identify the mechanisms responsible for the recent reduced carbon sink strength. In this study, we used a record of nearly 100 site-years of eddy covariance data from 11 continuous permafrost tundra sites distributed across the circumpolar Arctic to test the temperature (expressed as growing degree days, GDD) responses of gross primary production (GPP), net ecosystem exchange (NEE), and ecosystem respiration (ER) at different periods of the summer (early, peak, and late summer) including dominant tundra vegetation classes (graminoids and mosses, and shrubs). We further tested GPP, NEE, and ER relationships with soil moisture and vapor pressure deficit to identify potential moisture limitations on plant productivity and net carbon exchange. Our results show a decrease in GPP with rising GDD during the peak summer (July) for both vegetation classes, and a significant relationship between the peak summer GPP and soil moisture after statistically controlling for GDD in a partial correlation analysis. These results suggest that tundra ecosystems might not benefit from increased temperature as much as suggested by several terrestrial biosphere models, if decreased soil moisture limits the peak summer plant productivity, reducing the ability of these ecosystems to sequester carbon during the summer.

Methane (CH4) is a strong greenhouse gas that accelerates climate change, yet its emissions from wetlands in general and Arctic permafrost-affected wetlands in particular remain very uncertain in the global CH4 budget. Arctic CH4 sources and the expected effect of permafrost thaw on these sources have gained much attention by the public, media, policy makers, and researchers during the past decade, but neither inversion nor process-based models provide clear trends in emissions and there has not been any observational evidence for increasing CH4 emissions from Arctic permafrost ecosystems.Here, we provide this observational evidence. Based on the longest record of direct Arctic CH4 flux observations acquired since 2002 at a Siberian tundra site using the eddy covariance method, we found an increase in the early summer (June and July) CH4 emissions by 1.9 ± 0.7 % yr-1 since 2004 along with a strong increase in June air temperatures of 0.3 ± 0.1 °C yr-1. Although the tundra’s maximum source strength in August has not yet changed and the overall mean annual emissions of 171.5 ± 12.3 mmol m−2 yr−1 remain in the lower half of the published range, the increase in early summer methane emissions shows that atmospheric warming has begun to affect the methane flux dynamics of permafrost-affected ecosystems in the Arctic. This is especially noteworthy, given the very thick and cold continuous permafrost in the study area compared to most other observational sites.While the observed changes clearly happen in the early warm season, we also estimate 39 % of the annual emission to originate from the re-freezing and frozen period, highlighting the importance of the cold season for annual permafrost CH4 emission estimates and the substantial challenges in achieving continuous data coverage in the Arctic winter.

Rewetting drained peatlands is recognized as a leading and effective natural climate solution to curbing greenhouse gas (GHG) emissions. However, CO2 source-to-sink transition is not necessarily detected in years immediately following rewetting and temporal dynamics in carbon budgets can be seen in rewetted systems. Here, we investigate long-term (2008 & 2013 - present) ecosystem flux measurements using the eddy covariance technique, revealing the temporal patterns of annual carbon dioxide (CO2) and methane (CH4) fluxes, in a rewetted peatland site in northeastern Germany. We show that site-level annual emissions presented in this study are only approaching the IPCC default Tier 1 emission factors (EFs) and those suggested for the German national inventory report after 13-16 years of rewetting when the optimum range of water level (close to the soil surface) is reached during the vegetation period. Overall, our results indicate that in addition to annual variation in soil temperature, vegetation development (post-rewetting successional vegetation dynamics) along with water table depth have the greatest effect on the carbon sink function. We further observe a transitional change into a new phase in the ecosystem carbon status throughout the study period that includes a source-to-sink transition of annual CO2 fluxes in 2020. The decreasing trend for CO2 fluxes is estimated at -0.37 t CO2-C ha-1 yr-1 and -44 kg CH4 ha-1 yr-1 for CH4 emissions for the period until 2021. While we found a strong reduction in CH4 emissions in 2019 (following a severe drought), the negative trend in CH4 emissions in the years before the drought event is still statistically significant (-17 kg CH4 ha-1 yr-1). Accordingly, a considerable reduction of the 100-year annual global warming potential (GWP) and sustained-flux global warming potential (SGWP) was observed during the course of the study and potentially approaching a new steady-state phase within the last few years. In Germany, the published long-term datasets from rewetted peatlands only cover a period of ≤10 years after rewetting, thus, the duration of potential phases and development of future emissions are still unclear. This outlines the need for more long-term datasets to cover the source-to-sink transition in rewetted peatlands that also capture the impacts of likely future climate extremes. Here, we aim to establish a baseline to contribute a better understanding of the transitioning, complexity, and climate sensitivity of rewetted systems by analyzing the dynamics within the site and the inter-annual variability via their respective drivers. The introduction, monitoring, and targeted management of an ensemble of site characteristics (coverage/type of dominant vegetation, average water level along with microclimate and microtopographic conditions) is necessary in understanding the transient nature of such systems and further refine the existing static default EFs.

Being the most accurate, direct, and defensible method available to date for studying the ecosystem scale gas exchange, the eddy covariance (EC) method was used to examine the net carbon exchange over an alpine steppe ecosystem near the Nam Co Station for Multi-sphere Observation and Research (NAMORS) on the Tibetan Plateau. EC measurements are site-specific and the values represent the total sum of the relative contribution of fluxes from all the components within the footprint over the measurement time. The scattered and uneven distribution of EC towers and their small footprint demand upscaling of the flux observations to a regional scale for improving understanding of the net exchange of CO2 between the terrestrial biosphere and the atmosphere. Regional scale carbon estimates are highly variable and not fully explored as compared to carbon balance studies at extreme ends of the spatial scale spectrum (large continental scale and small vegetation stand scale). Translating the spatially sparse measurements into consistent, gridded flux estimates at the regional scale is a prerequisite for quantifying the current terrestrial carbon cycle. But the uncertainties caused by the representativeness error in the model grids while quantifying the regional estimates of carbon exchange are not fully investigated due to limited data availability as well as knowledge of flux variability at the grid scale. Rather than extrapolating the point scale and/or site-specific scale measurements by fitting any statistical model to predict ecosystem or earth system processes, a systematic upscaling approach is vital for refining mathematical models and accounting for the grid-scale uncertainties for better policy decisions. As an initial step to this, the net ecosystem exchange (NEE) of carbon estimated at two different measurement heights of 3 m and 19 m, in the early growing period of 2019 were used to quantify and analyze the interdependencies in the flux measurements at two heights and the influence of heterogeneity within the footprint in the measured fluxes.Keywords: Eddy covariance, Carbon flux, Net ecosystem exchange, Tibetan Plateau

The cropland carbon (C) balance at regional scale still contains high uncertainties not the least due to the problem of up-scaling C fluxes of temporarily and spatially highly divers ecosystems. The C-exchange between the terrestrial ecosystem and the atmosphere constitute the largest and most uncertain flux of the cropland C balance, as opposed to C import from organic (manure) and C export through harvest which are lower and less uncertain.Combining satellite data with local eddy covariance CO2-flux data is commonly used to up-scale the C-exchange signal from point to regional scale across global ecosystems. Low spatial resolution products like MODIS limit their applicability and accuracy to larger homogeneous areas involving a high degree of uncertainty rather than detecting and tracing highly dynamic (farm-)field scale CO2-fluxes from space. We are using eddy-covariance CO2-flux data of an arable field in conjunction with Sentinel-2 derived vegetation indices (VI) to assess the ability of the satellite data to monitor daily net-ecosystem exchange (NEE), gross-primary productivity (GPP) and ecosystem respiration (Reco) based on a matched footprint. Simple linear regression models are built to test the ability of a range of VIs (NDVI, GNDVI, EVI, EVI2, SAVI, MNDWI, NDWI, SR, S2REP) to monitor and predict CO2-exchange for croplands. We analyze the correlation between measured CO2-fluxes and VIs over the course of the growing seasons to assess the suitability and accuracy of the VIs along the phenological year. We present a single site analysis to zoom into short-comings of this approach and how the satellite signal relates to vegetation CO2-exchange. VIs generally show a high variability in their predictive power. Still, results suggest a similarly high accuracy as mechanistic modelling approaches for suitable VIs, e.g. the cumulative C-exchange (NEE) of winter wheat of one growing season based on NDVI and GNDVI is over- and under-estimated by only 33 (15%) and 41 (18%) g C m-2 respectively.

Rewetting previously drained peatlands restores the critical function of peatlands as long-term carbon storages and sinks currently threatened by climate change and additional human-induced disturbances. Understanding and projecting the restoration process by rewetting, however, currently face a pressing challenge, the lack of consistent and gap-free records of important carbon cycling indicators of peatlands such as the gross primary production (GPP) over long term. In this study, we reconstructed the GPP in a rewetted peatland called Zarnekow (Fluxnet-ID: DE-Zrk) in Germany from 2000 to 2020 by combining long-term satellite observations and limited-term tower-based eddy covariance (EC) measurements based on Random Forest regression models. The R2 between the reconstructed data and EC data was 0.6. The reasonable reconstruction of long-term GPP enabled trend analysis that identified two distinct periods of decreasing/increasing in GPP due to rewetting and droughts. Rewetting in the winter of 2004 and 2005 stabilized GPP after a decreasing period. A drought in 2018 significantly increased GPP, and GPP remained high over the following two years. Furthermore, the month-specific trends show significant seasonality at this site, specifically, an increasing trend over the 21 years in the growing-season months of June to August and a decreasing trend in the other months. The most important variables for satellite-based estimates of GPP at this site include total evapotranspiration, land surface temperature, enhanced vegetation index and near-infrared reflectance vegetation index. Long-term analyses of carbon fluxes through the combination of satellite observations and EC measurements provide crucial insights into the restoration of carbon sequestration functions in rewetted peatlands.

Nuclear resonant reflectivity (NRR) from an Fe60Al40 film was measured using synchrotron radiation at several grazing angles near the critical angle of total external reflection. Using laterally resolved measurements after irradiation with 20 keV Ne+ ions of gradually varying fluence of 0–3.0 × 1014 ions cm−2, the progressive creation of the ferromagnetic A2 phase with increasing ion fluence was confirmed. The observed depth selectivity of the method has been explained by application of the standing wave approach. From the time spectra of the nuclear resonant scattering in several reflection directions the depth profiles for different hyperfine fields were extracted. The results show that the highest magnetic hyperfine fields (∼18–23 T) are initially created in the central part of the film and partially at the bottom interface with the SiO2 substrate. The evolution of the ferromagnetic onset, commencing at a fixed depth within the film and propagating towards the interfaces, has been directly observed. At higher fluence (3.0 × 1014 ions cm−2) the depth distribution of the ferromagnetic fractions became more homogeneous across the film depth, in accordance with previous results.

Methane (CH4) emissions from natural landscapes constitute roughly half of global CH4 contributions to the atmosphere, yet large uncertainties remain in the absolute magnitude and the seasonality of emission quantities and drivers. Eddy covariance (EC) measurements of CH4 flux are ideal for constraining ecosystem-scale CH4 emissions due to quasi-continuous and high-temporal-resolution CH4 flux measurements, coincident carbon dioxide, water, and energy flux measurements, lack of ecosystem disturbance, and increased availability of datasets over the last decade. Here, we (1) describe the newly published dataset, FLUXNET-CH4 Version 1.0, the first open-source global dataset of CH4 EC measurements (available at https://fluxnet.org/data/fluxnet-ch4-community-product/, last access: 7 April 2021). FLUXNET-CH4 includes half-hourly and daily gap-filled and non-gap-filled aggregated CH4 fluxes and meteorological data from 79 sites globally: 42 freshwater wetlands, 6 brackish and saline wetlands, 7 formerly drained ecosystems, 7 rice paddy sites, 2 lakes, and 15 uplands. Then, we (2) evaluate FLUXNET-CH4 representativeness for freshwater wetland coverage globally because the majority of sites in FLUXNET-CH4 Version 1.0 are freshwater wetlands which are a substantial source of total atmospheric CH4 emissions; and (3) we provide the first global estimates of the seasonal variability and seasonality predictors of freshwater wetland CH4 fluxes. Our representativeness analysis suggests that the freshwater wetland sites in the dataset cover global wetland bioclimatic attributes (encompassing energy, moisture, and vegetation-related parameters) in arctic, boreal, and temperate regions but only sparsely cover humid tropical regions. Seasonality metrics of wetland CH4 emissions vary considerably across latitudinal bands. In freshwater wetlands (except those between 20∘ S to 20∘ N) the spring onset of elevated CH4 emissions starts 3 d earlier, and the CH4 emission season lasts 4 d longer, for each degree Celsius increase in mean annual air temperature. On average, the spring onset of increasing CH4 emissions lags behind soil warming by 1 month, with very few sites experiencing increased CH4 emissions prior to the onset of soil warming. In contrast, roughly half of these sites experience the spring onset of rising CH4 emissions prior to the spring increase in gross primary productivity (GPP). The timing of peak summer CH4 emissions does not correlate with the timing for either peak summer temperature or peak GPP. Our results provide seasonality parameters for CH4 modeling and highlight seasonality metrics that cannot be predicted by temperature or GPP (i.e., seasonality of CH4 peak). FLUXNET-CH4 is a powerful new resource for diagnosing and understanding the role of terrestrial ecosystems and climate drivers in the global CH4 cycle, and future additions of sites in tropical ecosystems and site years of data collection will provide added value to this database. All seasonality parameters are available at https://doi.org/10.5281/zenodo.4672601 (Delwiche et al., 2021). Additionally, raw FLUXNET-CH4 data used to extract seasonality parameters can be downloaded from https://fluxnet.org/data/fluxnet-ch4-community-product/ (last access: 7 April 2021), and a complete list of the 79 individual site data DOIs is provided in Table 2 of this paper.

Permafrost-affected soils contain large quantities of soil organic carbon (SOC). Changes in the SOC pool of a particular ecosystem can be related to its net ecosystem carbon balance (NECB) in which the balance of carbon (C) influxes and effluxes is expressed. For polygonal tundra landscapes, accounts of ecosystem carbon balances in the literature are often solely based on estimates of vertical carbon fluxes. To fill this gap, we present data regarding the lateral export rates of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) from a polygonal tundra site in the north Siberian Lena River delta, Russia. We use water discharge observations in combination with concentration measurements of waterborne carbon to derive the lateral carbon fluxes from one growing season (2 June–8 September 2014 for DOC, 8 June–8 September 2014 for DIC). To put the lateral C fluxes into context, we furthermore present the surface–atmosphere eddy covariance fluxes of carbon dioxide (CO2) and methane (CH4) from this study site. The results show cumulative lateral DIC and DOC fluxes of 0.31–0.38 and 0.06–0.08 g m−2, respectively, during the 93 d observation period (8 June–8 September 2014). Vertical turbulent fluxes of CO2-C and CH4-C accumulated to −19.0 ± 1.2 and 1.0 ± 0.02 g m−2 in the same period. Thus, the lateral C export represented about 2 % of the net ecosystem exchange of (NEE) CO2. However, the relationship between lateral and surface–atmosphere fluxes changed over the observation period. At the beginning of the growing season (early June), the lateral C flux outpaced the surface-directed net vertical turbulent CO2 flux, causing the polygonal tundra landscape to be a net carbon source during this time of the year. Later in the growing season, the vertical turbulent CO2 flux dominated the NECB.

The Tibetan alpine steppe ecosystem covers an area of roughly 800 000 km 2 and contains up to 3.3 % soil organic carbon in the uppermost 30 cm, summing up to 1.93 Pg C for the Tibet Autonomous Region only (472 037 km 2 ). With temperatures rising 2 to 3 times faster than the global average, these carbon stocks are at risk of loss due to enhanced soil respiration. The remote location and the harsh environmental conditions on the Tibetan Plateau (TP) make it challenging to derive accurate data on the ecosystem–atmosphere exchange of carbon dioxide (CO 2 ) and water vapor ( H2O ). Here, we provide the first multiyear data set of CO 2 and H2O fluxes from the central Tibetan alpine steppe ecosystem, measured in situ using the eddy covariance technique. The calculated fluxes were rigorously quality checked and carefully corrected for a drift in concentration measurements. The gas analyzer self-heating effect during cold conditions was evaluated using the standard correction procedure and newly revised formulations ( Burba et al. , 2008 ; Frank and Massman , 2020 ) . A wind field analysis was conducted to identify influences of adjacent buildings on the turbulence regime and to exclude the disturbed fluxes from subsequent computations. The presented CO 2 fluxes were additionally gap filled using a standardized approach. The very low net carbon uptake across the 15-year data set highlights the special vulnerability of the Tibetan alpine steppe ecosystem to become a source of CO 2 due to global warming. The data are freely available at https://doi.org/10.5281/zenodo.3733202 ( Nieberding et al. , 2020 a ) and https://doi.org/10.11888/Meteoro.tpdc.270333 ( Nieberding et al. , 2020 b ) and may help us to better understand the role of the Tibetan alpine steppe in the global carbon–climate feedback.

Arctic permafrost landscapes have functioned as a global carbon sink for millennia. These landscapes are very heterogeneous, and the omnipresent water bodies within them act as a carbon source. Yet, few studies have focused on the impact of these water bodies on the landscape carbon budget. We deepen our understanding of carbon emissions from thermokarst ponds and constrain their impact by comparing carbon dioxide and methane fluxes from these ponds to fluxes from the surrounding tundra. We use eddy covariance measurements from a tower located at the border between a large pond and semi-terrestrial tundra. When we take the open-water areas of thermokarst ponds into account, our results show that the estimated summer carbon uptake of the polygonal tundra is 11 % lower. Further, the data show that open-water methane emissions are of a similar magnitude to polygonal tundra emissions. However, some parts of the pond's shoreline exhibit much higher emissions. This finding underlines the high spatial variability in methane emissions. We conclude that gas fluxes from thermokarst ponds can contribute significantly to the carbon budget of Arctic tundra landscapes. Consequently, changes in the water body distribution of tundra landscapes due to permafrost degradation may substantially impact the overall carbon budget of the Arctic.

Direct feedback from the drilling process will be key to enhance overall drilling performance further, improve steering and will help detect drilling dysfunctions early. This is especially true for demanding drilling applications, such as drilling in difficult geological formations. Faults, hard stringers or borehole instabilities can have a negative impact on rate of penetration (ROP) or even worse can damage equipment and cause non-productive time (NPT). This gets pronounced for extended reach drilling, where long drill strings delay the received feedback from the drilling process or effects along the drill string (e.g friction) skew the results. To overcome these obstacles a near bit sensor was developed to provide real time weight-on-bit (WOB), torque-on-bit (TOB), bending and bending orientation data. It is directly integrated into the steering unit of the rotary steerable system (RSS) with the goal to be simplistic, cost efficient and robust. To discuss potential uses and limitations of the load sensor, the basic design and operational principle are shown. Different usage scenarios of the system are presented in theoretical terms and backed by real-world data. One scenario is the possibility to diagnose reasons for low ROP, for instance weight transfer issues can be distinguished from bit damages if WOB and TOB real time data is available. For early detection of unwanted deflections in directional drilling, for instance due to faults or tilted beds, near bit bending and bending orientation measurements of the RSS system can be used. The near bit sensor design proves to be reliable and cost efficient. It shows high potential to increase ROP and reduce NPT and overall drilling cost.

Arctic warming is affecting snow cover and soil hydrology, with consequences for carbon sequestration in tundra ecosystems. The scarcity of observations in the Arctic has limited our understanding of the impact of covarying environmental drivers on the carbon balance of tundra ecosystems. In this study, we address some of these uncertainties through a novel record of 119 site-years of summer data from eddy covariance towers representing dominant tundra vegetation types located on continuous permafrost in the Arctic. Here we found that earlier snowmelt was associated with more tundra net CO2 sequestration and higher gross primary productivity (GPP) only in June and July, but with lower net carbon sequestration and lower GPP in August. Although higher evapotranspiration (ET) can result in soil drying with the progression of the summer, we did not find significantly lower soil moisture with earlier snowmelt, nor evidence that water stress affected GPP in the late growing season. Our results suggest that the expected increased CO2 sequestration arising from Arctic warming and the associated increase in growing season length may not materialize if tundra ecosystems are not able to continue sequestering CO2 later in the season.

Journal of magnetism and magnetic materials 560, 169663 (2022). doi:10.1016/j.jmmm.2022.169663, This work provides a better understanding and behavior of the metal–organic interface magnetism, which plays a crucial role in organic spin-valve devices. Interface magnetism and topological structure of Fe on organic semiconductor film Tris(8-hydroxyquinolinato) aluminium (Alq$_3$) have been studied and compared with Fe film deposited directly on Si (1 0 0) substrate. To get information of the diffused Fe layer at the Fe/Alq$_3$ interface, grazing incident nuclear resonance scattering (GINRS) measurements are made depth selective by introducing a 95% enriched thin $^{57}$Fe layer at the interface and producing x-ray standing wave within the layered structure. Compared with Fe growth on Si substrate, where film exhibits a hyperfine field value of ∼ 32 T (Bulk Fe), a thick Fe- Alq$_3$ interface has been found with reduced electron density and hyperfine fields providing evidence of deep penetration of Fe atoms into Alq$_3$ film. Due to the soft nature of Alq$_3$, Fe moments relax in the film plane. At the same time, Fe on Si has resultant ∼ 43° out of plane orientation of Fe moments at the interface due to stressed and rough Fe layer near Si. Evolution of magnetism at Fe-Alq$_3$ Interface is monitored using in-situ magneto-optical Kerr effect (MOKE) during growth of Fe on Alq$_3$ surface and small-angle x-ray scattering (SAXS) measurements. It is found that the Fe atom tries to organize into clusters to minimize their surface/interface energy. The origin of the 24 Å thick magnetic dead layer at the interface is attributed to the small Fe clusters of paramagnetic or superparamagnetic nature. Present work provides an understanding of interfacial magnetism at metal–organic interfaces and the topological study using the GI-NRS technique, which is made depth selective to probe magnetism of the diffused ferromagnetic layer, which is otherwise difficult for lab-based techniques., Published by North-Holland Publ. Co., Amsterdam

Physical review research 4(1), 013220 (2022). doi:10.1103/PhysRevResearch.4.013220, In recent years, high-precision x-ray polarimeters have become a key method for the investigation of fundamental physical questions from solid-state physics to quantum optics. Here, we report on the verification of a polarization purity of better than $8×10^{−11}$ at an x-ray free-electron laser, which implies a suppression of the incoming photons to the noise level in the crossed polarizer setting. This purity provides exceptional sensitivity to tiny polarization changes and offers intriguing perspectives for fundamental tests of quantum electrodynamics., Published by APS, College Park, MD

A new family of structurally well-defined molybdenum alkylidyne catalysts for alkyne metathesis, which is distinguished by a tripodal trisilanolate ligand architecture, is presented. Complexes of type 1 combine the virtues of previous generations of silanolate-based catalysts with a significantly improved functional group tolerance. They are easy to prepare on scale; the modularity of the ligand synthesis allows the steric and electronic properties to be fine-tuned and hence the application profile of the catalysts to be optimized. This opportunity is manifested in the development of catalyst 1f, which is as reactive as the best ancestors but exhibits an unrivaled scope. The new catalysts work well in the presence of unprotected alcohols and various other protic groups. The chelate effect entails even a certain stability toward water, which marks a big leap forward in metal alkylidyne chemistry in general. At the same time, they tolerate many donor sites, including basic nitrogen and numerous heterocycles. This aspect is substantiated by applications to polyfunctional (natural) products. A combined spectroscopic, crystallographic, and computational study provides insights into structure and electronic character of complexes of type 1. Particularly informative are a density functional theory (DFT)-based chemical shift tensor analysis of the alkylidyne carbon atom and 95Mo NMR spectroscopy; this analytical tool had been rarely used in organometallic chemistry before but turns out to be a sensitive probe that deserves more attention. The data show that the podand ligands render a Mo-alkylidyne a priori more electrophilic than analogous monodentate triarylsilanols; proper ligand tuning, however, allows the Lewis acidity as well as the steric demand about the central atom to be adjusted to the point that excellent performance of the catalyst is ensured., Journal of the American Chemical Society, 142 (25), ISSN:0002-7863, ISSN:1520-5126

Background and Study Aims The traditional percutaneous placement of dorsal root ganglion (DRG) electrodes may not be eligible for every patient. In this tertiary spine surgery and interventional pain therapy center, alternative neurostimulation implantation techniques were developed and applied where standard percutaneous approaches failed or were contraindicated. Case presentation Three alternative implantation techniques can be used: (1) open surgical placement of DRG leads, (2) two-lead insertion via a lateral to medial transforaminal approach (level L3), and (3) percutaneous approach with two leads close to the spinal nerves L4 (peripheral nerve stimulation). Results The placement of the leads occurred without complications and resulted in similar expected outcomes as with the common percutaneous technique with long-term stable pain suppression at 7 months and 1 year. Conclusions In patients in whom the DRG cannot be approached by the standard percutaneous approach, at least three alternatives may be used in experienced hands resulting in stable pain suppression of similar magnitude.

Ultra-thin Fe film is deposited obliquely on the Tris(8-hydroxyquinolinato) aluminum (Alq3) layer to study the interface magnetism and compared with the normally deposited film of the same thickness. The overall magnetic property of the film, as observed using magneto-optic Kerr effect measurements, is understood precisely through interface resolved grazing incident nuclear resonance scattering (GINRS) measurements under x-ray standing wave (XSW) conditions. To excite XSW modes, the bilayer is deposited between high dense Ag and Pt layers to make a waveguide structure, where the position of the antinode is varied by changing incident angles. The Fe layer is enriched with 57Fe isotope during deposition to make it active for GINRS measurements. Compared with obliquely deposited 57Fe film, reduced hyperfine fields at the interface of normally deposited 57Fe/Alq3 film, providing evidence for the deep penetration of 57Fe atoms into Alq3 film. Due to the large shadowing effect at oblique angle deposition, Fe atoms try to organize into isolated superparamagnetic clusters to minimize their surface/interface energy. On the other hand, besides the relatively deep penetration in the normally deposited thin film, ferromagnetism is observed due to the connecting bigger 57Fe clusters. Our results demonstrate that deposition geometry has a direct and crucial bearing on the interfacial microstructure, which can control diffusion at the Alq3 interfaces and tune magnetic anisotropy in the ferromagnetic layer.

FeCoB/MgO bilayer is prepared to study the interface magnetism and its role in azimuthal angle-dependent magnetic properties. As observed in magneto-optic Kerr effect measurements, unusual hysteresis loops are understood precisely through interface resolved grazing incident nuclear resonance scattering (GINRS) measurements under x-ray standing wave (XSW) conditions. To excite XSW modes, the bilayer is deposited between a Pt waveguide structure, where the position of the anti-nodes is varied by changing incident angles. As GINRS is an isotope sensitive technique, the FeCoB layer is enriched with 57Fe isotope during deposition. The formation of a high-density 57FeCoB layer at the 57FeCoB/MgO interface with a hyperfine field ~34.25 T is found and attributed to the increasing volume of FeCo at the interface. Boron diffusion from 57FeCoB to the MgO layer is found to be responsible for FeCo rich FeCoB layer near the interface. The azimuthal angle-dependent unusual shape of hysteresis loops is described in terms of coupled magnetization reversal between the bulk and interface parts of FeCoB layer. In contrast to some studies in literature, no evidence of the formation of an oxide layer is observed at the interface.

Time series of wetland methane fluxes measured by eddy covariance require gap-filling to estimate daily, seasonal, and annual emissions. Gap-filling methane fluxes is challenging because of high variability and complex responses to multiple drivers. To date, there is no widely established gap-filling standard for wetland methane fluxes, with regards both to the best model algorithms and predictors. This study synthesizes results of different gap-filling methods systematically applied at 17 wetland sites spanning boreal to tropical regions and including all major wetland classes and two rice paddies. Procedures are proposed for: 1) creating realistic artificial gap scenarios, 2) training and evaluating gap-filling models without overstating performance, and 3) predicting half-hourly methane fluxes and annual emissions with realistic uncertainty estimates. Performance is compared between a conventional method (marginal distribution sampling) and four machine learning algorithms. The conventional method achieved similar median performance as the machine learning models but was worse than the best machine learning models and relatively insensitive to predictor choices. Of the machine learning models, decision tree algorithms performed the best in cross-validation experiments, even with a baseline predictor set, and artificial neural networks showed comparable performance when using all predictors. Soil temperature was frequently the most important predictor whilst water table depth was important at sites with substantial water table fluctuations, highlighting the value of data on wetland soil conditions. Raw gap-filling uncertainties from the machine learning models were underestimated and we propose a method to calibrate uncertainties to observations. The python code for model development, evaluation, and uncertainty estimation is publicly available. This study outlines a modular and robust machine learning workflow and makes recommendations for, and evaluates an improved baseline of, methane gap-filling models that can be implemented in multi-site syntheses or standardized products from regional and global flux networks (e.g., FLUXNET). ISSN:0168-1923 ISSN:1873-2240

Arctic permafrost landscapes have functioned as a global carbon sink for millennia. These landscapes are very heterogeneous, and the omnipresent waterbodies are a carbon source within them. Yet, only a few studies focus on the impact of these waterbodies on the landscape carbon budget. We compare carbon dioxide and methane fluxes from small waterbodies to fluxes from the surrounding tundra using eddy covariance measurements from a tower located between a large pond and semi-terrestrial vegetated tundra. When taking the open-water areas of small waterbodies into account, the carbon dioxide sink strength of the landscape was reduced by 11 %. While open-water methane emissions were similar to the tundra emissions, some parts of the studied pond's shoreline exhibited much higher emissions, underlining the high spatial variability of methane emissions. We conclude that gas fluxes from small waterbodies can contribute significantly to the carbon budget of arctic tundra landscapes. Consequently, changes in arctic hydrology and the concomitant changes in the waterbody distribution may substantially impact the overall carbon budget of the Arctic.

The FLUXNET2015 dataset provides ecosystem-scale data on CO2, water, and energy exchange between the biosphere and the atmosphere, and other meteorological and biological measurements, from 212 sites around the globe (over 1500 site-years, up to and including year 2014). These sites, independently managed and operated, voluntarily contributed their data to create global datasets. Data were quality controlled and processed using uniform methods, to improve consistency and intercomparability across sites. The dataset is already being used in a number of applications, including ecophysiology studies, remote sensing studies, and development of ecosystem and Earth system models. FLUXNET2015 includes derived-data products, such as gap-flled time series, ecosystem respiration and photosynthetic uptake estimates, estimation of uncertainties, and metadata about the measurements, presented for the frst time in this paper. In addition, 206 of these sites are for the frst time distributed under a Creative Commons (CC-BY 4.0) license. This paper details this enhanced dataset and the processing methods, now made available as open-source codes, making the dataset more accessible, transparent, and reproducible., European Union (EU), United States Department of Energy (DOE)

Nuclear resonant reflectivity (NRR) from an Fe

International audience; La présente contribution est conçue sous forme d'un rapport d'atelier et donne un premier aperçu concernant le développement d'une approche des phénomènes de frontières et d'espaces frontaliers sur la base des études culturelles. Cette approche tente d'être plus large que celle correspondant aux perspectives jusqu'à présent préconisées par les sciences sociales et appréhende les phénomènes des frontières et des espaces frontaliers en tant qu'entités composées de différentes pratiques et différents discours faisant référence aux frontières et aux différences. Ces entités comprises au sens de bordertextures sont exemplairement illustrées à travers des phénomènes concernant la frontière entre les États-Unis et le Mexique, la frontière franco-allemande et l'Irlande du Nord et elles sont déclinées en différentes dimensions d'analyse. Parmi ces dernières, la corporéalité, la spatialité et la matérialité figurent parmi les approches heuristiques des bordertextures que la présente contribution aborde à titre d'exemples. L'approche relativise la perspective largement répandue correspondant à une conception territoriale de la frontière pour élargir la palette des perspectives analytiques et celles des domaines analysés au sein des Border Studies.

Cross-border cooperation, border regions, soft spaces? This special issue approaches cross-border informal planning processes in cross-border regions by analysing them from a perspective that combines networks, governance and territorialization. Such a relational perspective will be developed by papers which deal with a variety of European cross-border regions and empirical evidence related to the nexus of networks, governance and territorialization.

Methane fluxes on an active flood plain situated in the Siberian Lena River Delta were studied applying the eddy covariance method. During the growing season, the observed fluxes exhibited a great deal of temporal variability, which was largely the result of the pronounced spatial variability of soil and vegetation characteristics within the footprint. Explaining this variability was based on three data-driven modelling approaches: the automatically operating algorithms stepwise regression as well as neural network, and a mechanistic model, which utilised exponential relationships between the methane flux and both flux drivers soil temperature and friction velocity. A substantial improvement in model performance was achieved by applying footprint information in the form of relative contributions of three vegetation classes to the flux signal. This aspect indicates that the vegetation served as an integrated proxy for flux drivers, whose characteristics permanently varied according to the shifting source area. The neural network performed best in explaining the variability of the observed methane fluxes. However, validating the models’ generalisability revealed that the mechanistic model provided the most predictive power suggesting that this model best captured the causality between the methane flux and its drivers. After integrating the gap-filled time series, all models yielded footprint budgets that were similar in magnitude. These budgets, however, lacked representativity due to the sensor location bias, i.e. their strong dependence on tower location, measurement height and wind field conditions. Thus, an unbiased budget of the total area of the flood plain was estimated utilising the mechanistic model. Initially, a downscaling procedure partitioned the observed flux with a seasonal mean of 0.012 μmol m-2 s-1 into three individual vegetation class fluxes accounting for shrubs (0.0004 μmol m-2 s-1), sedges (0.052 μmol m-2 s-1) and intermediate vegetation (0.018 μmol m-2 s-1). These decomposed fluxes in turn formed the basis – in conjunction with a classified high-resolution orthomosaic of the flood plain – for the vegetation class area-weighted upscaling. Alternatively, the straightforward upscaling of the footprint budgets (without the preceding downscaling) yielded budgets that underestimated the methane source strength of the flood plain by roughly 42 %. Hence, the application of fine-scale information on surface characteristics is crucial for both modelling methane flux dynamics and adequately estimating budgets of heterogeneous ecosystems being abundant in the tundra biome.

Iron-sulfur clusters are common building blocks for electron transport and active sites of metalloproteins. Their comprehensive investigation is crucial for understanding these enzymes, which play important roles in modern biomimetic catalysis and biotechnology applications. We address this issue by utilizing (Et4N)3[Fe4Te4(SPh)4], a tellurium modified version of a conventional reduced [4Fe-4S]+ cluster, and performed both 57Fe- and 125Te-NRVS to reveal its characteristic vibrational features. Our analysis exposed major differences in the resulting 57Fe spectrum profile as compared to that of the respective [4Fe-4S] cluster, and between the 57Fe and 125Te profiles. DFT calculations are applied to rationalize structural, electronic, vibrational, and redox-dependent properties of the [4Fe-4Te]+ core. We herein highlight the potential of sulfur/tellurium exchange as a method to isolate the iron-only motion in enzymatic systems.

Given the current call for interdisciplinarity, we reflect on pragmatic methodological implementations of collaborative research – by drawing on empirical evidence from two large-scale cross-disciplinary research projects and by theoretically framing them in trilingual contexts (German, French, and English). These are two major innovations compared to the existing body of literature in this domain. Our empirical analysis shows that multi-, inter- or trans-disciplinary collaboration is an oscillating process along a spectrum of cross-disciplinarity – spanning additive, converging and synthesizing work patterns, i.e. multi-, inter-, and transdisciplinarity. Such an umbrella-term avoids the common amalgamation of ‘interdisciplinarity’ as the overarching category (cross-disciplinarity of whatever form) and one of the relevant subcategories (the specific work form that a research team chooses). Concretely, if the majority of methods are developed through communal negotiation processes, then a truly interdisciplinary analysis of research results can only be guaranteed through recursive self-reflexive loops. Initial research questions may still be additive and interactions can oscillate during the project process between addition und tentative convergence. We label this process situative interdisciplinarity. Multi-, inter- and transdisciplinarity are thus subsumed as a processual entity: flexible, possibly hybrid subforms of cross-disciplinarity. It needs constant reactivation, framing, timing and mediation by project managers. The major challenge lies in the collaborative transfer of concepts, theories, methods and research subjects. This transfer requires translation, explication and transposition of the various disciplinary ‘languages’ and can only be converged in an open-minded, team-oriented and reflexive work environment.

The synthesis and characterization through NMR and X-ray crystallography of a series of N-arylpyridiniophosphines and their corresponding Au(I)-derivatives are reported. Because of their acceptor properties, pyridiniophosphines efficiently enhance the electrophilicity of the Au atom in the complexes they form. In our study, this is translated into higher reactivity of the corresponding Au catalysts, which is demonstrated in two mechanistically differentiated cycloisomerizations. Moreover, the steric protection and probably also the electronic stabilization provided by the N-aryl substituents make the active Au-species more robust and slow down its rate of decay. This allows for an appreciable reduction of the catalyst loadings.

Phonon modes play a vital role in the cooperative phenomenon of light-induced spin transitions in spin crossover (SCO) molecular complexes. Although the cooperative vibrations, which occur over several hundreds of picoseconds to nanoseconds after photoexcitation, are understood to play a crucial role in this phase transition, they have not been precisely identified. Therefore, we have performed a novel optical laser pump-nuclear resonance probe experiment to identify the Fe-projected vibrational density of states (pDOS) during the first few nanoseconds after laser excitation of the mononuclear Fe(II) SCO complex [Fe(PM-BiA)

Methane (CH4) emissions from natural landscapes constitute roughly half of global CH4 contributions to the atmosphere, yet large uncertainties remain in the absolute magnitude and the seasonality of emission quantities and drivers. Eddy covariance (EC) measurements of CH4 flux are ideal for constraining ecosystem-scale CH4 emissions, including their seasonality, due to quasi-continuous and high temporal resolution of flux measurements, coincident measurements of carbon, water, and energy fluxes, lack of ecosystem disturbance, and increased availability of datasets over the last decade. Here, we 1) describe the newly published dataset, FLUXNET-CH4 Version 1.0, the first global dataset of CH4 EC measurements (available at https://fluxnet.org/data/fluxnet-ch4- community-product/). FLUXNET-CH4 includes half-hourly and daily gap-filled and non gap-filled aggregated CH4 fluxes and meteorological data from 79 sites globally: 42 freshwater wetlands, 6 brackish and saline wetlands, 7 formerly drained ecosystems, 7 rice paddy sites, 2 lakes, and 15 uplands. Then, we 2) evaluate FLUXNET-CH4 representativeness for freshwater wetland coverage globally, because the majority of sites in FLUXNET-CH4 Version 1.0 are freshwater wetlands and because freshwater wetlands are a substantial source of total atmospheric CH4 emissions; and 3) provide the first global estimates of the seasonal variability and seasonality predictors of freshwater wetland CH4 fluxes. Our representativeness analysis suggests that the freshwater wetland sites in the dataset cover global wetland bioclimatic attributes (encompassing energy, moisture, and vegetation-related parameters) in arctic, boreal, and temperate regions, but only sparsely cover humid tropical regions. Seasonality metrics of wetland CH4 emissions vary considerably across latitudinal bands. In freshwater wetlands (except those between 20° S to 20° N) the spring onset of elevated CH4 emissions starts three days earlier, and the CH4 emission season lasts 4 days longer, for each degree C increase in mean annual air temperature. On average, the onset of increasing CH4 emissions lags soil warming by one month, with very few sites experiencing increased CH4 emissions prior to the onset of soil warming. In contrast, roughly half of these sites experience the spring onset of rising CH4 emissions prior to the spring increase in gross primary productivity (GPP). The timing of peak summer CH4 emissions does not correlate with the timing for either peak summer temperature or peak GPP. Our results provide seasonality parameters for CH4 modeling, and highlight seasonality metrics that cannot be predicted by temperature or GPP (i.e., seasonality of CH4 peak). The FLUXNET-CH4 dataset provides an open-access resource for CH4 flux synthesis, has a range of applications, and is unique in that it includes coupled measurements of important CH4 drivers such as GPP and temperature. Although FLUXNET-CH4 could certainly be improved by adding more sites in tropical ecosystems and by increasing the number of site-years at existing sites, it is a powerful new resource for diagnosing and understanding the role of terrestrial ecosystems and climate drivers in the global CH4 cycle. All seasonality parameters are available at https://doi.org/10.5281/zenodo.4408468. Additionally, raw FLUXNET-CH4 data used to extract seasonality parameters can be downloaded from https://fluxnet.org/data/fluxnet-ch4-community-product/, and a complete list of the 79 individual site data DOIs is provided in Table 2 in the Data Availability section of this document., Earth System Science Data Discussions, ISSN:1866-3591

Nature / Physical science 590(7846), 401 - 404 (2021). doi:10.1038/s41586-021-03276-x, Coherent control of quantum dynamics is key to a multitude of fundamental studies and applications. In the visible or longer-wavelength domains, near-resonant light fields have become the primary tool with which to control electron dynamics. Recently, coherent control in the extreme-ultraviolet range was demonstrated, with a few-attosecond temporal resolution of the phase control. At hard-X-ray energies (above 5–10 kiloelectronvolts), Mössbauer nuclei feature narrow nuclear resonances due to their recoilless absorption and emission of light, and spectroscopy of these resonances is widely used to study the magnetic, structural and dynamical properties of matter. It has been shown that the power and scope of Mössbauer spectroscopy can be greatly improved using various control techniques. However, coherent control of atomic nuclei using suitably shaped near-resonant X-ray fields remains an open challenge. Here we demonstrate such control, and use the tunable phase between two X-ray pulses to switch the nuclear exciton dynamics between coherent enhanced excitation and coherent enhanced emission. We present a method of shaping single pulses delivered by state-of-the-art X-ray facilities into tunable double pulses, and demonstrate a temporal stability of the phase control on the few-zeptosecond timescale. Our results unlock coherent optical control for nuclei, and pave the way for nuclear Ramsey spectroscopy and spin-echo-like techniques, which should not only advance nuclear quantum optics, but also help to realize X-ray clocks and frequency standards. In the long term, we envision time-resolved studies of nuclear out-of-equilibrium dynamics, which is a long-standing challenge in Mössbauer science., Published by Macmillan28177, London

Die Auffassung, dass Grenzen aus sozialer Praxis hervorgehen und soziale Praxis hervorbringen, hat in den letzten Jahrzehnten für eine Reihe an Ansätzen und Begriffen gesorgt. Der Beitrag versucht diese zu systematisieren und stellt einen processual shift, multiplicity shift und complexitiy shift vor. Diese Trends beschreiben verschiedene analytische Schwerpunktsetzungen und eine zunehmend differenziertere Beschäftigung mit Grenzen. Abschließend wird auf die noch unzureichend bestimmte Kategorie der sozialen Praxis und auf das Potential der Praxistheorien für die Grenzforschung eingegangen.

ZusammenfassungAgile Projektarbeit zieht in immer mehr Branchen Interesse auf sich. Gemeint sind damit unterschiedliche Ansätze (z. B. Scrum), die auf selbstorganisiertes Arbeiten im Team setzen und Nähe zum Kunden versprechen. Agiles Arbeiten birgt für Beschäftigte neben mehr Handlungsspielräumen auch Risiken wie psychische Belastungen. Das Projekt diGAP erforschte, wie Gute agile Projektarbeit unter Bedingungen der Digitalisierung ermöglicht und praxistauglich unterstützt werden kann. Gestützt auf Befragungen, Interviews und Beobachtungen sowie Workshops mit Beschäftigten wurden entscheidende Aspekte agiler Projektarbeit herausgearbeitet. Auf Basis dieser Ergebnisse wurden Gestaltungsfelder, Maßnahmen und Modelle für Gute agile Arbeit entwickelt.