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At least 307 records · Page 17

Groundwater regulates interannual variations in evapotranspiration in a riparian semiarid ecosystem

Dryland ecosystems are an important component of Earth’s carbon, water, and energy budgets. Changes in hydroclimatic conditions can significantly alter land surface fluxes in these ecosystems. In regions with groundwater-river water exchange, land surface fluxes are strongly modulated by groundwater table fluctuations in response to river stage variations; however, interactions between fluxes and groundwater remain poorly understood in drylands. Here, we use eddy covariance data collected in paired upland and riparian semiarid ecosystems during two years with contrasting river flow conditions to examine interactions among river stage conditions, water table dynamics, meteorological drivers, and ecosystem fluxes. Elevated groundwater availability resulting from groundwater-surface water exchange at the riparian site enhanced the latent heat flux (LE, the energy form of evapotranspiration), which was sustained longer in the growing season during both years. At the upland site, mean LE during the dry season differed by less than 2% between the two years. In contrast, at the riparian site contrasting river flow conditions resulted in a 41% difference in peak monthly LE between the two years. The two-year mean LE in the summer at the riparian site was twice that at the upland site. Carbon uptake (NEP) and LE were well correlated at the upland site during both years, but at the riparian site enhanced summertime LE during the high river flow year did not correspond t enhanced NEP. Our results demonstrate that enhanced groundwater availability modulated by river stage variability is a critical driver of land surface fluxes in semiarid riparian ecosystems.

Missik, Justine E.↗

Observations of the Marine Atmospheric Boundary Layer’s Response to a Solar Eclipse

The atmospheric response to the solar eclipse of 8 April 2024 in North America is investigated with a specific focus on the marine atmospheric boundary layer (MABL). We leverage measurements collected during the Third Wind Forecast Improvement Project (WFIP3), including Doppler lidars, sonic anemometers, and thermodynamic profiler data to investigate the atmospheric response across sites that experienced partial eclipse conditions with nearly 90% obscuration. Using these measurements, we examine eclipse-induced changes in key meteorological parameters, such as temperature, wind speed, and turbulent fluxes. Most previous eclipse studies have been conducted over land, whereas this study provides new observations for both coastal and marine environments, offering additional insight into eclipse-driven variability in the MABL. The findings confirm a notable decrease in downwelling shortwave radiation during the eclipse, which results in rapid cooling of surface air. The temperature reduction ranges from $1.2^\circ \text {C}$ to $1.4^\circ \text {C}$ in coastal regions and from $0.3^\circ \text {C}$ to $0.5^\circ \text {C}$ over the ocean. This analysis suggests that the MABL’s higher thermal inertia compared to coastal regions moderates the temperature decrease during the eclipse. Wind speed exhibits a more complex behavior, as it is influenced by both the MABL and preexisting synoptic conditions. Although a reduction in wind speed is observable up to approximately 140 m above ground level (AGL) at more inland sites, at other locations closer to the coast, this reduction is constrained to the lowest 100 m AGL. Turbulence parameters retrieved from sonic anemometers, such as turbulence kinetic energy, turbulent heat flux, and friction velocity, decrease during the eclipse at coastal sites, accompanied by a brief transition of atmospheric stability from unstable to neutral or weakly stable conditions. For the open-ocean sites, the variability in turbulence statistics and atmospheric stability is minimal during the occurrence of the eclipse.

16 TIDAL AND WAVE POWER↗

NGEE Arctic Soil Micro-warming Experiment Temperature Profiles, Council Road Mile Marker 71, Seward Peninsula, Alaska, 2017-2019

The reported soil temperature profile measurements (24 locations - 2 probes with 5 and 6 thermistors, respectively - Fig. 1 and Fig. 2) were initiated as part of a soil micro-warming experiment at the Council Road Mile Marker 71 Site (CN_MM71) in September 2017. From 2017 through August 2019, these were measurements of ambient pre-treatment plot conditions. This tussock tundra site (with underlying permafrost) experiences annual frost heaving that causes a vertical movement of the ground surface, hence causing some of the upper most temperature thermistors to be at surface level or above ground and recorded therefore air temperatures near the surface and not below ground soil temperature (see section on Quality Assurance). After August 2019, these measurements ended in preparation for transitioning to the experimental warming of individual plots. The reported temperature data are nominally 3-hour averages of measurements made at varying frequencies (3-hour maximum) with frequencies that depended upon power (solar) availability to operate the sensors (see section in documentation on Methods). The number of values and the standard deviation for each 3-hour average (where appropriate) are also provided. These measurements are located near the NGEE-Arctic CO2 and CH4 eddy covariance tower at the Council Road Site (US-NGC: NGEE Arctic Council, https://ameriflux.lbl.gov/sites/siteinfo/US-NGC#overview) and auxiliary data at https://doi.org/10.5440/1526749. This dataset contains four *.csv files and one *.pdf file. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

The electrocortical correlates of fluctuating states of attention during vigilance tasks

This study investigated the electrocortical correlates of attention. Sixteen subjects (seven females, nine males) engaged in a forty-minute target detection vigilance task. Task-irrelevant probe tones were presented every 2-4 seconds. While performing the vigilance task, the subjects were asked to press a button if they were daydreaming (i.e. having a task unrelated thought or TUT). Continuous electroencephalograms (EEG's) and event-related potentials (ERP's) were recorded from the subjects during the entire task. The continuous EEG data were analyzed for differences in absolute power throughout the task as well as before and after the subjects indicated that they were daydreaming (TUT response). ERP's elicited by task-irrelevant probe tones were analyzed in the same manner. The results indicated performance decrements as reflected by increased RT to correct detections, and decreased number of hits. Further, as the task progressed, the number of reports of daydreaming increased. The analysis of the EEG data indicated a significant difference in the absolute power of the different frequency bands across periods. The greatest difference was observed at the posterior parietal electrode sites. In addition, when the EEG data was converted into band ratios (beta/alpha and beta/alpha+theta), the pre-TUT conditions were found to be significantly different than the post-TUT conditions in the posterior sites. The ERP components (N1, N2, and P2) were not significantly different before and after a TUT response or across periods. However, the ERP's across periods exhibited amplitudes that were similar to those found in previous studies of vigilance and ERP's.

Cunningham, Stephen G.↗

Observational Constraints Reduce Model Spread but Not Uncertainty in Global Wetland Methane Emission Estimates

The recent rise in atmospheric methane (CH 4 ) concentrations accelerates climate change and offsets mitigation efforts. Although wetlands are the largest natural CH 4 source, estimates of global wetland CH 4 emissions vary widely among approaches taken by bottom-up (BU) process-based biogeochemical models and top-down (TD) atmospheric inversion methods. Here, we integrate in situ measurements, multi-model ensembles, and a machine learning upscaling product into the International Land Model Benchmarking system to examine the relationship between wetland CH 4 emission estimates and model performance. We find that using better-performing models identified by observational constraints reduces the spread of wetland CH 4 emission estimates by 62% and 39% for BU- and TD-based approaches, respectively. However, global BU and TD CH 4 emission estimate discrepancies increased by about 15% (from 31 to 36 TgCH 4 year −1 ) when the top 20% models were used, although we consider this result moderately uncertain given the unevenly distributed global observations. Our analyses demonstrate that model performance ranking is subject to benchmark selection due to large inter-site variability, highlighting the importance of expanding coverage of benchmark sites to diverse environmental conditions. We encourage future development of wetland CH 4 models to move beyond static benchmarking and focus on evaluating site-specific and ecosystem-specific variabilities inferred from observations.

Kuang-Yu Chang↗

Hydrogen Leak Modeling for Development of Smart Distributed Monitoring Under Unintended Releases

Hydrogen is a versatile and clean energy carrier that can be produced from various renewable sources such as wind, solar, and hydropower. Hydrogen has the potential to play a crucial role in decarbonizing industrial processes that are currently reliant on fossil fuels and provide long-duration and/or seasonal energy storage to enable electricity decarbonization. Hydrogen can also be used as a fuel for fuel cell vehicles, providing a zero-emission alternative to traditional internal combustion engines. DOE launched the Hydrogen Energy Earthshot (Hydrogen Shot) in June 2021 to reduce the cost of clean hydrogen by 80% to $1 per 1 kilogram in 1 decade ("1 1 1"). While promising, Hydrogen is highly-flammable, and in the presence of oxygen, it can form explosive mixtures. . Therefore, understanding leak scenarios is essential to evaluate and mitigate the safety risks associated with potential hydrogen leaks. An increased understanding of leak behavior, and having tools to model leaks, can help assess how hydrogen would disperse in different environments, influencing emergency response plans and safety measures, and identify potential issues with materials and design systems that can withstand the challenges posed by hydrogen. Recently, researchers have attempted to study hydrogen leaks for development of risk management strategies. However, the focus has been on closed or semi-closed spaces like storage rooms, vehicles, garages, and fueling stations - all promising locations for future hydrogen infrastructure. In this presentation, the modeling environment extends the span of research further by modeling hydrogen leak in an outdoor, open space. We will present the key challenges with modeling hydrogen leaks in an uncontrollable environment, how they were handled, and how modeling results informed sensor selection and placement. A Hydrogen research facility at the National Renewable Energy Laboratory (NREL) was used as a case study to model hydrogen leaks. In the future, Hydrogen wide area detection methodologies will be developed and tested at this site to monitor for unintended and operational hydrogen releases. The data generated from modeling will be used to develop a predictive model to detect hydrogen leak location based on concentration measured by sensors in this open space. Furthermore, the facility was also chosen because controlled hydrogen releases can be performed. A computational fluid dynamics (CFD) based modeling approach was taken to model hydrogen leak. The full-scale hydrogen facility was modeled with a large ambient domain. The electrolyzer at the facility can produce a controlled release rate of 27 kg-H2/hr. Site-specific atmospheric and weather condition data such as wind direction, wind speed at various altitudes, and temperature were used as inputs to the model. To capture the variability of weather conditions, a subset of the weather conditions experienced during daytime hours without precipitation over the course of three months was generated; using established data clustering techniques, a total of 100 condition sets were chosen. The results show statistical distributions and ranges of hydrogen concentrations at locations throughout the domain. These distributions are compared to experimental data from a constant mass flow, controlled hydrogen release at the facility. The stochastic wind conditions of the release make direct validation difficult, therefore, statistical comparison approaches were used. Wind conditions are found to significantly impact the release behavior, including direction and concentration. Sensor selection and placement is proposed for the facility and is now based on release behavior predicted for the facility given its weather patterns; this is much more informed than without the modeling results. The methodology and analysis procedure can be translated to other facilities using modified geometries and site-specific weather conditions. Hydrogen holds great promise as a renewable energy fuel, but ensuring safety in its production, storage, and use is paramount. Studying potential leak scenarios in an open space will help develop sensors to detect hydrogen on a large spectrum of concentration and eventually build a smart distributed monitoring system.

CFD↗

Reciprocal transplants reveal asymmetric local adaptation of Himalayan Rhododendron approaching elevational range limit

Abstract As plant species expand their upper limits of distribution under current warming, some retain both traditional climate space and biotic environment while others encounter novel conditions. The latter is the case for Rhododendron campanulatum , a woody shrub that grows both above and below treeline at our study site in the Eastern Himalayas where a very conspicuous, stable treeline was defined by a nearly contiguous canopy of tall Abies spectabilis trees, many of which are over a century old. Prior work showed that treeline had remained static in this region while R. campanulatum expanded its elevational range limit. We tested local adaptation of R. campanulatum by performing reciprocal transplants between the species' current elevational range limit (4023 m above sea level [asl]) and just above treeline (3876 m asl). Contrary to expectation, the coldest temperatures of late winter and early mid‐spring were experienced by plants at the lower elevation: R. campanulatum at species' limit (upper site) were covered by snow for a longer period (40 more days) and escaped the coldest temperatures suffered by conspecifics at treeline (lower site). The harsher spring conditions at treeline likely explain why leaves were smaller at treeline (15.3 cm 2 ) than at species limit (21.3 cm 2 ). Contrary to results from equivalent studies in other regions, survival was reduced more by downslope than by upslope movement, again potentially due to extreme cold temperatures observed at treeline in spring. Upslope transplantation had no effect on mortality, but mortality of species limit saplings transplanted downslope was three times higher than that of residents at both sites. A general expectation is that locals should survive better than foreign transplants, but survival of locals and immigrants at our species limit site was identical. However, those species limit saplings that survived the transplant to treeline grew faster than both locals at treeline and the transplants at species limit. Overall, we found asymmetric adaptation: Compared with treeline saplings, those at species limit (147 m above treeline) were more tolerant of extremes in the growing season but less tolerant of extremes in winter and early mid‐spring, displaying local adaptation in a more complex manner than simply home advantage, and complicating predictions about impacts of future regional climate change.

54 ENVIRONMENTAL SCIENCES↗

Another Look at the Optimum Frequencies for a Water Vapor Radiometer

A water vapor radiometer is used to estimate the columnar content of atmospheric water vapor or equivalently the line-of-sight path delay due to water vapor. Two measurement channels are used in order to separate the effects of the liquid and vapor phases of water. The efficiency of the path delay or columnar vapor estimate is dependent on the choice of on-line frequency channel. Previous analysis of this problem has suggested frequencies from 20.3 to 21 GHz. The frequency that yields the minimum error in the inversion algorithm is shown here to be both site and season dependent. Hence, the concept of an optimum frequency must represent an averaging process over the entire range of meteorological conditions that is expected. For a range of sites and condition representing a cross section of the continental United States the optimum on-line frequency seems to be 20.6 GHz.

Resch, G. M.↗

BODY SENSING SYSTEM

System and method for performing one or more relevant measurements at a target site in an animal body, using a probe. One or more of a group of selected internal measurements is performed at the target site, is optionally combined with one or more selected external measurements, and is optionally combined with one or more selected heuristic information items, in order to reduce to a relatively small number the probable medical conditions associated with the target site. One or more of the internal measurements is optionally used to navigate the probe to the target site. Neural net information processing is performed to provide a reduced set of probable medical conditions associated with the target site.

Mah, Robert W.↗

Monitoring the vernal advancement and retrogradation (green wave effect) of natural vegetation

The author has identified the following significant results. A comprehensive review of ERTS-1 MSS color composite imagery, obtained during the autumnal and vernal phases over the Great Plains Corridor test sites, shows that temporal changes in rangeland vegetation can be manually interpreted. The degree to which manual interpretations can be made from the MSS color composites appears to be limited primarily by variations in image reproduction quality. The vernal advancement and other phenophase related phenomena are observable from cycle to cycle and within a single frame for rangeland vegetation. Vegetation changes due to environmental conditions among the test sites and among grazing treatments within test sites are readily observable. An investigation has been initiated which will evaluate band-to-band ratios as an index of rangeland vegetation condition. Data currently available from August 1972 through April 1973 for the five southern test sites are being used to characterize band-to-band ratios as a function of quantity and quality of rangeland vegetation at each of the test sites.

Rouse, J. W., Jr.↗

Global Light System for JEM-EUSO

The Global Light System (GLS) is a network of ground-based Xenon flash lamps and steered UV lasers to validate the key functions of the JEM-EUSO instrument. These functions include triggering efficiency, the accuracy of intrinsic luminosity measurements, and the reconstructed pointing direction accuracy. GLS units will generate benchmark optical signatures in the atmosphere with similar characteristics to the optical signals of cosmic ray EASs. The lasers will generate tracks and the flashers will generate point flashes. But unlike air showers, the number, energy, precise time, direction (lasers) can be specified. JEM-EUSO will reconstruct the pointing directions of the lasers and the energy of the lasers and flash lamps to monitor the detector's triggers, and accuracy of energy and direction reconstruction. 12 GLS units will be deployed at selected sites around the globe. The JEM-EUSO footprint will pass over a GLS unit on average once per (near) moonless night under clear conditions for appropriately selected sites. The 12 units will be supplemented by campaign style measurements with an airborne unit that will be flown over the open ocean at selected altitudes under JEM-EUSO. A GLS prototype in an airplane will support a high-altitude balloon flight in 2014 of a proto-type JEM-EUSO telescope. We will describe the concept and system design and report on the status of prototyping and the selection process for candidates sites.

Christl, Mark↗

Application of Atmospheric Gases and Particulate Matter to the Assessment of Urban Heat Island

Background: Urban heat island (UHI), where built areas are warmer compared to non-urban regions, increases human related diseases and mortality. A key challenge in UHI analysis is the designation of sites as urban or suburban/rural; however, the growing complexity of green spaces in urban areas and the predominance of the transportation sector in nonurban areas creates a dilemma for distinct delineation. Objectives: This study aims to utilize the variability of atmospheric components such as particulate matter (PM), inorganic gases, and volatile organic compounds (VOCs) as direct tracers of the degree of urbanization for ground-based measurements to fully comprehend UHI in convoluted regions with indistinct delineation of urban and nonurban environments. Methods: Atmospheric gases and aerosols were used as direct tracers of urbanization for UHI analysis. Inorganic gases and particulate matter were monitored in two sites in a southeastern US city with varying degrees of urbanization. VOCs were analyzed using a proton transfer reaction time-of-flight mass spectrometer. Results: The more-urbanized site exhibited warmer night conditions and elevated total oxidant levels, leading to the formation of nanometer-sized particles. Machine learning analysis revealed similar atmospheric pollutant profiles for both sites, suggesting comparable sources and variability. Biogenic VOCs were enhanced at the less-urbanized site; however, levels of anthropogenic aromatic VOCs were comparable for both sites. A comprehensive mass spectra analysis revealed distinct molecular backbones per site that further affirmed the applicability of VOCs as indicators of urbanization. Conclusion: This study concludes that VOCs provide more direct and accurate information than typical inorganic gases and PM parameters for characterizing the degree of urbanization. Further exploration of VOCs can enhance our understanding of UHI dynamics and its interaction with vegetation in urban green spaces.

Air quality sensor↗

In Situ/Operando Probing of Dynamic Phase Structures of Alumina‐Supported Ultrasmall Copper‐Gold Alloy Nanoparticles Under Reaction Conditions

Abstract The ability to control phase structures and surface sites of ultrasmall alloy nanoparticles under reaction conditions is essential for preparing catalysts by design. This is, however, challenging due to limited understanding of the atomic‐scale phases and their correlation with the ensemble‐averaged structures and activities of catalysts during catalytic reactions. We reveal here a dynamic structural stability of alumina‐supported ultrasmall and equiatomic copper‐gold alloy nanoparticles under reaction conditions as a model system in the in situ/operando study. In situ atomic‐scale morphological tracking under oxygen reveals temperature‐dependent dynamic crystalline‐amorphous dual‐phase structures, showing dynamic stability over an elevated temperature range. This atomic‐scale dynamic phase stability coincides with a “conversion plateau” observed for carbon monoxide oxidation on the catalyst. It is substantiated by the stable lattice ordering/disordering structures and surface sites with oscillatory characteristics shown by operando ensemble‐average structural tracking of the catalyst during the oxidation reaction. The understanding of the atomic‐scale dynamic phase structures in correlation with the ensemble‐average dynamic ordering/disordering phase structures and surface sites provides fresh insights into the unique synergy of the supported alloy nanoparticles. This understanding has implications for the design and structural tuning of active and stable ultrasmall alloy catalysts under elevated temperatures.

Chemistry↗

Asymmetries in cloud microphysical properties ascribed to sea ice leads via water vapour transport in the central Arctic

To investigate the influence of sea ice openings like leads on wintertime Arctic clouds, the air mass transport is exploited as a heat and humidity feeding mechanism which can modify Arctic cloud properties. Cloud microphysical properties in the central Arctic are analysed as a function of sea ice conditions during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition in 2019–2020. The Cloudnet classification algorithm is used to characterize the clouds based on remote sensing observations and the atmospheric thermodynamic state from the observatory on board the research vessel (RV) Polarstern. To link the sea ice conditions around the observational site with the cloud observations, the water vapour transport (WVT) being conveyed towards RV Polarstern has been utilized as a mechanism to associate upwind sea ice conditions with the measured cloud properties. This novel methodology is used to classify the observed clouds as coupled or decoupled to the WVT based on the location of the maximum vertical gradient of WVT height relative to the cloud-driven mixing layer. Only a conical sub-sector of sea ice concentration (SIC) and the lead fraction (LF) centred on the RV Polarstern location and extending up to 50 km in radius and with an azimuth angle governed by the time-dependent wind direction measured at the maximum WVT is related to the observed clouds. We found significant asymmetries for cases when the clouds are coupled or decoupled to the WVT and selected by LF regimes. Liquid water path of low-level clouds is found to increase as a function of LF, while the ice water path does so only for deep precipitating systems. Clouds coupled to WVT are found to generally have a lower cloud base and larger thickness than decoupled clouds. Thermodynamically, for coupled cases the cloud-top temperature is warmer and accompanied by a temperature inversion at the cloud top, whereas the decoupled cases are found to be closely compliant with the moist adiabatic temperature lapse rate. The ice water fraction within the cloud layer has been found to present a noticeable asymmetry when comparing coupled versus decoupled cases. This novel approach of coupling sea ice to cloud properties via the WVT mechanism unfolds a new tool to study Arctic surface–atmosphere processes. With this formulation, long-term observations can be analysed to enforce the statistical significance of the asymmetries. Furthermore, our results serve as an opportunity to better understand the dynamic linkage between clouds and sea ice and to evaluate its representation in numerical climate models for the Arctic system.

54 ENVIRONMENTAL SCIENCES↗

Structural Features of Zirconium-Based Metal–Organic Frameworks Affecting Radiolytic Stability

Metal–organic frameworks (MOFs) NU-1000 and UiO-66 are herein exposed to two different gamma irradiation doses and dose rates and analyzed to determine the structural features that affect their stability in these environments. MOFs have shown promise for the capture and sensing of off-gases at civilian nuclear energy reprocessing sites, nuclear waste repositories, and nuclear accident locations. However, little is understood about the structural features of MOFs that contribute to their stability levels under the ionizing radiation conditions present at such sites. This study is the first of its kind to explore the structural features of MOFs that contribute to their radiolytic stability. Both NU-1000 and UiO-66 are MOFs that contain Zr metal-centers with the same metal absorption cross section. However, the two MOFs exhibit different linker connectivities, linker aromaticities, node densities, node connectivities, and interligand separations. In this study, NU-1000 and UiO-66 were exposed to high (423.3 Gy/min, 23 min, and 37 s) and low (0.78 Gy/min, 4320 min) dose rates of 60 Co gamma irradiation. NU-1000 displayed insignificant radiation damage under both dose rates due to its high linker connectivity, low node density, and low node connectivity. However, low radiation dose rates caused considerable damage to UiO-66, a framework with lower aromaticity and smaller interligand separation. Finally, results suggest that chronic, low-radiation environments are more detrimental to Zr MOF stability than acute, high-radiation conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Genesis of Active Pt/CeO 2 Catalyst for Dry Reforming of Methane by Reduction and Aggregation of Isolated Platinum Atoms into Clusters

Atomically dispersed metal catalysts offer the advantages of efficient metal utilization and high selectivities for reactions of technological importance. Such catalysts have been suggested to be strong candidates for dry reforming of methane (DRM), offering prospects of high selectivity for synthesis gas without coke formation, which requires ensembles of metal sites and is a challenge to overcome in DRM catalysis. However, investigations of the structures of isolated metal sites on metal oxide supports under DRM conditions are lacking, and the catalytically active sites remain undetermined. Data characterizing the DRM reaction-driven structural evolution of a cerium oxide- supported catalyst, initially incorporating atomically dispersed platinum, and the corresponding changes in catalyst performance are reported. X-ray absorption and infrared spectra show that the reduction and agglomeration of isolated cationic platinum atoms to form small platinum clusters/nanoparticles are necessary for DRM activity. Density functional theory calculations of the energy barriers for methane dissociation on atomically dispersed platinum and on platinum clusters support these observations. Here the results emphasize the need for in-operando experiments to assess the active sites in such catalysts. The inferences about the catalytically active species are suggested to pertain to a broad class of catalytic conversions involving the rate-limiting dissociation of light alkanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stability and Activity of Cobalt Antimonate for Oxygen Reduction in Strong Acid

Guided by computational Pourbaix screening and high-throughput experiments aimed at the development of precious-metal-free fuel cells, we investigate rutile CoSb 2 O 6 as an electrocatalyst for oxygen reduction in 1 M sulfuric acid. Following 4 h of catalyst conditioning at 0.7 V vs RHE, operation at this potential for 20 h yielded an average current density of –0.17 mA cm –2 with corrosion at a rate of 0.04 nm hour –1 that is stoichiometric with catalyst composition. Surface Pourbaix analysis of the (111) surface identified partial H coverage under operating conditions. The Sb active site has an HO* binding free energy of 0.49 eV, which is near the peak of the kinetic 4e – ORR volcano for transition-metal oxides in acidic conditions. Furthermore, the experimental demonstration of operational stability and computational identification of a reaction pathway with favorable energetics place rutile CoSb 2 O 6 among the most promising precious-metal-free electrocatalysts for oxygen reduction in acidic media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Soil resistance and recovery during neotropical forest succession

The recovery of soil conditions is crucial for successful ecosystem restoration and, hence, for achieving the goals of the UN Decade on Ecosystem Restoration. Here, we assess how soils resist forest conversion and agricultural land use, and how soils recover during subsequent tropical forest succession on abandoned agricultural fields. Our overarching question is how soil resistance and recovery depend on local conditions such as climate, soil type and land-use history. For 300 plots in 21 sites across the Neotropics, we used a chronosequence approach in which we sampled soils from two depths in old-growth forests, agricultural fields (i.e. crop fields and pastures), and secondary forests that differ in age (1–95 years) since abandonment. We measured six soil properties using a standardized sampling design and laboratory analyses. Soil resistance strongly depended on local conditions. Croplands and sites on high-activity clay (i.e. high fertility) show strong increases in bulk density and decreases in pH, carbon (C) and nitrogen (N) during deforestation and subsequent agricultural use. Resistance is lower in such sites probably because of a sharp decline in fine root biomass in croplands in the upper soil layers, and a decline in litter input from formerly productive old-growth forest (on high-activity clays). Soil recovery also strongly depended on local conditions. During forest succession, high-activity clays and croplands decreased most strongly in bulk density and increased in C and N, possibly because of strongly compacted soils with low C and N after cropland abandonment, and because of rapid vegetation recovery in high-activity clays leading to greater fine root growth and litter input. Furthermore, sites at low precipitation decreased in pH, whereas sites at high precipitation increased in N and decreased in C : N ratio. Extractable phosphorus (P) did not recover during succession, suggesting increased P limitation as forests age. These results indicate that no single solution exists for effective soil restoration and that local site conditions should determine the restoration strategies.

60 APPLIED LIFE SCIENCES↗