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Root responses to elevated CO 2 , warming and irrigation in a semi-arid grassland: Integrating biomass, length and life span in a 5-year field experiment

Plant roots mediate the impacts of environmental change on ecosystems, yet knowledge of root responses to environmental change is limited because few experiments evaluate multiple environmental factors and their interactions. Inferences about root functions are also limited because root length dynamics are rarely measured. Using a 5-year experiment in a mixed-grass prairie, we report the responses of root biomass, length and life span to elevated carbon dioxide (CO 2 ), warming, elevated CO 2 and warming combined, and irrigation. Root biomass was quantified using soil cores and root length dynamics were assessed using minirhizotrons. By comparing root dynamics with published results for soil resources and above-ground productivity, we provide mechanistic insights into how climate change might impact grassland ecosystems. In the upper soil layer, 0–15 cm depth, both irrigation and elevated CO 2 alone increased total root length by twofold, but irrigation decreased root biomass and elevated CO 2 had only small positive effects on root biomass. The large positive effects of irrigation and elevated CO 2 alone on total root length were due to increases in both root length production and root life span. The increased total root length and life span under irrigation and elevated CO 2 coincided with apparent shifts from water limitation of plant growth to nitrogen limitation. Warming alone had minimal effects on root biomass, length and life span in this shallow soil layer. Warming and elevated CO 2 combined increased root biomass and total root length by c. 25%, but total root length in this treatment was lower than expected if the effects of CO 2 and warming alone were additive. Treatment effects on total root length and root life span varied with soil depth and root diameter. Synthesis. Sub-additive effects of CO 2 and warming suggest studies of elevated CO 2 alone might overestimate the future capacity of grassland root systems to acquire resources. In this mixed-grass prairie, elevated CO 2 with warming stimulated total root length and root life span in deeper soils, likely enhancing plant access to more stable pools of growth-limiting resources, including water and phosphorus. Therefore, these root responses help explain previous observations of higher, and more stable, above-ground productivity in these projected climate conditions.

59 BASIC BIOLOGICAL SCIENCES↗

Subcloud and Cloud-Base Latent Heat Fluxes during Shallow Cumulus Convection

Doppler and Raman lidar observations of vertical velocity and water vapor mixing ratio are used to probe the physics and statistics of subcloud and cloud-base latent heat fluxes during cumulus convection at the ARM Southern Great Plains (SGP) site in Oklahoma, United States. The statistical results show that latent heat fluxes increase with height from the surface up to ~0.8 Z i (where Z i is the convective boundary layer depth) and then decrease to ~0 at Z i . Peak fluxes aloft exceeding 500 W m −2 are associated with periods of increased cumulus cloud cover and stronger jumps in the mean humidity profile. These entrainment fluxes are much larger than the surface fluxes, indicating substantial drying over the 0–0.8 Z i layer accompanied by moistening aloft as the CBL deepens over the diurnal cycle. We also show that the boundary layer humidity budget is approximately closed by computing the flux divergence across the 0–0.8 Z i layer. Composite subcloud velocity and water vapor anomalies show that clouds are linked to coherent updraft and moisture plumes. The moisture anomaly is Gaussian, most pronounced above 0.8 Z i and systematically wider than the velocity anomaly, which has a narrow central updraft flanked by downdrafts. This size and shape disparity results in downdrafts characterized by a high water vapor mixing ratio and thus a broad joint probability density function (JPDF) of velocity and mixing ratio in the upper CBL. We also show that cloud-base latent heat fluxes can be both positive and negative and that the instantaneous positive fluxes can be very large (~10 000 W m −2 ). However, since cloud fraction tends to be small, the net impact of these fluxes remains modest.

54 ENVIRONMENTAL SCIENCES↗

Optical Properties of Individual Tar Balls in the Free Troposphere

Tar balls are brown carbonaceous particles, highly viscous, spherical, amorphous, and light absorbing. They are believed to form in biomass burning smoke plumes during transport in the troposphere. Tar balls are believed to have a significant impact on the Earth’s radiative balance, but due to poorly characterized optical properties, this impact is highly uncertain. Here, we investigate the chemical composition and optical properties of individual tar balls transported in the free troposphere to the Climate Observatory “Ottavio Vittori” on Mt. Cimone, Italy (2165 meters above sea level) using multi-modal micro-spectroscopy. Our results show that tar balls contributed 50% of carbonaceous particles by number in the size range from 0.25 to 1.8 µm. Of those tar balls, 16% were inhomogeneously mixed with other constituents. Using electron energy loss spectroscopy, we retrieved the complex refractive index from 200 to 1200 nm for both inhomogeneously and homogeneously mixed tar balls. We found no significant difference in the average refractive index of inhomogeneously and homogenously mixed tar balls (1.40 - 0.03i, and 1.36 - 0.03i at 550 nm, respectively). Furthermore, we estimated the top of the atmosphere radiative forcing using the Santa Barbara DISORT Atmospheric Radiative Transfer model (SBDART) and found that a layer of only tar balls with an optical depth of 0.1 above vegetation would exert a positive radiative forcing ranging from 2.8 Wm-2 (on a clear sky day) to 9.5 Wm-2 (when clouds are below the aerosol layer). In conclusion, understanding the optical properties of tar balls can help reduce uncertainties associated with the contribution of biomass-burning aerosol in current climate models.

54 ENVIRONMENTAL SCIENCES↗

Mixed-phase Convective Clouds in the Polar Marine Boundary Layer

This proposal, a collaboration between two universities, firstly aims to describe the high-latitude CAO cloud regime using the array of instruments at the NSA (Barrow, Alaska) and at two mobile ARM sites (MARCUS 2017-18, and COMBLE 2020). These ARM data, and the multi-sensor variables we propose to derive, allow detailed descriptions of mesoscale organization of precipitation, thermodynamic profiles, vertical velocity, cloud depth, and cloud and precipitation properties. These observations are key for our second goal, which is to use output from validated cloud- and eddy-resolving simulations to gain insights into the linkages between microphysical processes, the MBL vertical structure, and the MBL dynamics that control cloud macrostructure.

54 ENVIRONMENTAL SCIENCES↗

The MOSAiC Distributed Network: Observing the coupled Arctic system with multidisciplinary, coordinated platforms

Central Arctic properties and processes are important to the regional and global coupled climate system. The Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) Distributed Network (DN) of autonomous ice-tethered systems aimed to bridge gaps in our understanding of temporal and spatial scales, in particular with respect to the resolution of Earth system models. By characterizing variability around local measurements made at a Central Observatory, the DN covers both the coupled system interactions involving the ocean-ice-atmosphere interfaces as well as three-dimensional processes in the ocean, sea ice, and atmosphere. The more than 200 autonomous instruments (“buoys”) were of varying complexity and set up at different sites mostly within 50 km of the Central Observatory. During an exemplary midwinter month, the DN observations captured the spatial variability of atmospheric processes on sub-monthly time scales, but less so for monthly means. They show significant variability in snow depth and ice thickness, and provide a temporally and spatially resolved characterization of ice motion and deformation, showing coherency at the DN scale but less at smaller spatial scales. Ocean data show the background gradient across the DN as well as spatially dependent time variability due to local mixed layer sub-mesoscale and mesoscale processes, influenced by a variable ice cover. The second case (May–June 2020) illustrates the utility of the DN during the absence of manually obtained data by providing continuity of physical and biological observations during this key transitional period. We show examples of synergies between the extensive MOSAiC remote sensing observations and numerical modeling, such as estimating the skill of ice drift forecasts and evaluating coupled system modeling. The MOSAiC DN has been proven to enable analysis of local to mesoscale processes in the coupled atmosphere-ice-ocean system and has the potential to improve model parameterizations of important, unresolved processes in the future.

54 ENVIRONMENTAL SCIENCES↗

Permafrost Active Layer Microbes From Ny Ålesund, Svalbard (79°N) Show Autotrophic and Heterotrophic Metabolisms With Diverse Carbon-Degrading Enzymes

The active layer of permafrost in Ny Ålesund, Svalbard (79°N) around the Bayelva River in the Leirhaugen glacier moraine is measured as a small net carbon sink at the brink of becoming a carbon source. In many permafrost-dominating ecosystems, microbes in the active layers have been shown to drive organic matter degradation and greenhouse gas production, creating positive feedback on climate change. However, the microbial metabolisms linking the environmental geochemical processes and the populations that perform them have not been fully characterized. In this paper, we present geochemical, enzymatic, and isotopic data paired with 10 Pseudomonas sp. cultures and metagenomic libraries of two active layer soil cores (BPF1 and BPF2) from Ny Ålesund, Svalbard, (79°N). Relative to BPF1, BPF2 had statistically higher C/N ratios (15 ± 1 for BPF1 vs. 29 ± 10 for BPF2; n = 30, p < 10 –5 ), statistically lower organic carbon (2% ± 0.6% for BPF1 vs. 1.6% ± 0.4% for BPF2, p < 0.02), statistically lower nitrogen (0.1% ± 0.03% for BPF1 vs. 0.07% ± 0.02% for BPF2, p < 10 –6 ). The d 13 C values for inorganic carbon did not correlate with those of organic carbon in BPF2, suggesting lower heterotrophic respiration. An increase in the δ 13 C of inorganic carbon with depth either reflects an autotrophic signal or mixing between a heterotrophic source at the surface and a lithotrophic source at depth. Potential enzyme activity of xylosidase and N-acetyl-β-D-glucosaminidase increases twofold at 15°C, relative to 25°C, indicating cold adaptation in the cultures and bulk soil. Potential enzyme activity of leucine aminopeptidase across soils and cultures was two orders of magnitude higher than other tested enzymes, implying that organisms use leucine as a nitrogen and carbon source in this nutrient-limited environment. Besides demonstrating large variability in carbon compositions of permafrost active layer soils only ∼84 m apart, results suggest that the Svalbard active layer microbes are often limited by organic carbon or nitrogen availability and have adaptations to the current environment, and metabolic flexibility to adapt to the warming climate.

54 ENVIRONMENTAL SCIENCES↗

A Modeling framework for flocculated cohesive sediment transport in the current bottom boundary layer

Cohesive sediment transport, where its settling velocity is controlled by the flocculation process, is a crucial component in determining biochemical cycles, fate of pollutants, and morphodynamics in many aquatic ecosystems. In this study, a modeling framework is presented to investigate how flocculation influences cohesive sediment transport in the current bottom boundary layer in dilute conditions, consistent with the calibration range of the flocculation model. From a local analysis of floc dynamics in homogenous turbulence, we identify that the floc size distribution is mainly controlled by floc cohesion and yield strength. The uncertainty in fractal dimension plays a minor role for the floc size but it influences the resulting floc density and settling velocity. The transport analysis in the current boundary layer shows that the flocculation process alters the vertical distribution of the settling velocity and hence the sediment concentration with a strong dependence on cohesion, floc yield strength, and floc structure. When the flocs are more susceptible to breaking, a well-mixed concentration profile is obtained. In contrast, for flocs with higher cohesion or yield strength, higher concentration with a sharp gradient is observed close to the bed. Overall, the settling velocity exhibits a low vertical variability within 20 % of the depth-averaged value except near the bed. Further, this suggests that using a depth-averaged settling velocity yields acceptable predictions of the sediment concentration profiles, especially for flocs with lower cohesion.

54 ENVIRONMENTAL SCIENCES↗

Tank 49H solids disturbance analysis

Tank 49H serves as the feed tank for the Salt Waste Processing Facility (SWPF). Transfers into Tank 49H may disturb any solids that have settled to the bottom of the tank, resulting in feed that may exceed the insoluble solids content limit of 1,200 mg/L of the SWPF Waste Acceptance Criteria (WAC). During a transfer into Tank 49H, material that free falls into Tank 49H through a downcomer could potentially disturb any solids on the bottom of the tank and scour or suspend solids from a settled solids layer or turbid region. A previous analysis and report evaluated the potential to disturb solids when transferring into Tank 49H through the B4 riser and recommended a minimum tank level of 120 inches to prevent disturbing any solids in the bottom of the tank. The scope of this task is to perform additional fluid flow analysis to determine whether accounting for disturbed particle settling and particle mixing and dispersion during transfer could allow the minimum liquid level to be reduced below 120 inches. The analysis utilized models from the technical literature to calculate the size and shape of the “plunging jet” as a function of input parameters such as initial velocity, initial jet diameter, elevation of the initial jet, liquid level in the tank, and solids depth. The analysis relied on the M-Star® simulations performed for the previous analysis to provide bounding estimates of the amount of solid particles disturbed and used the MStar® software to calculate the dispersion and mixing of the disturbed solids with other liquid in the tank as the solids are transported to the transfer pump. The analysis showed that with a solid particle size of 5 micron or less, a liquid level of 120 inches should be maintained to prevent significant disturbance of the solid layer at the bottom of Tank 49H.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Methane and nitrous oxide porewater concentrations and surface fluxes of a regulated river

Greenhouse gas (GHG) emissions from rivers are a critical missing component of current global GHG models. Their exclusion is mainly due to a lack of in-situ measurements and a poor understanding of the spatiotemporal dynamics of GHG production and emissions, which prevents optimal model parametrization. We combined simultaneous observations of porewater concentrations along different beach positions and depths, and surface fluxes of methane and nitrous oxide at a plot scale in a large regulated river during three water stages: rising, falling, and low. Our goal was to gain insights into the interactions between hydrological exchanges and GHG emissions and elucidate possible hypotheses that could guide future research on the mechanisms of GHG production, consumption, and transport in the hyporheic zone (HZ). Results indicate that the site functioned as a net source of methane. Surface fluxes of methane during river water stages at three beach positions (shallow intermediate and deep) correlated with porewater concentrations of methane. However, fluxes were significantly higher in the intermediate position during low water stage, suggesting that low residence time increased methane emissions. Vertical profiles of methane peaked at different depths, indicating an influence of the magnitude and direction of the hyporheic mixing during the different river water stages on methane production and consumption. The site acted as either a sink or a source of nitrous oxide depending on the elevation of the water column. Nitrous oxide porewater concentrations peaked at the upper layers of the sediment throughout the different water stages. River hydrological stages significantly influenced porewater concentrations and fluxes of GHG, probably by influencing heterotrophic respiration (production and consumption processes) and transport to and from the HZ. Our results highlight the importance of including dynamic hydrological exchanges when studying and modeling GHG production and consumption in the HZ of large rivers.

54 ENVIRONMENTAL SCIENCES↗

Chamber Flux and Porewater Concentration of CH4, CO2 and N2O, 2018, Columbia River bank at the Hanford site, WA, USA

This is the corresponding observations data for the paper: Jorge A Villa; Garrett J Smith; Yang Ju; Lupita Renteria; Jordan C Angle; Evan Arntzen; Samuel F Harding; Huiying Ren; Xingyuan Chen; Audrey H Sawyer; Emily B Graham; James C Stegen; Kelly C Wrighton; Gil Bohrer (2020) Methane and nitrous oxide porewater concentrations and surface fluxes of a regulated river. Science of the Total Environment.Greenhouse gas (GHG) emissions from rivers are a critical missing component of current global GHG models. Their exclusion is mainly due to a lack of in-situ measurements and a poor understanding of the spatiotemporal dynamics of GHG production and emissions, which prevents optimal model parametrization. We combined simultaneous observations of porewater concentrations along different beach positions and depths, and surface fluxes of methane and nitrous oxide at a plot scale in a large regulated river during three water stages: rising, falling, and low. Our goal was to gain insights into the interactions between hydrological exchanges and GHG emissions and elucidate possible hypotheses that could guide future research on the mechanisms of GHG production, consumption, and transport in the hyporheic zone (HZ). Results indicate that the site functioned as a net source of methane. Surface fluxes of methane during river water stages at three beach positions (shallow, intermediate and deep) correlated with porewater concentrations of methane. However, fluxes were significantly higher in the intermediate position during the low water stage, suggesting that low residence time increased methane emissions. Vertical profiles of methane peaked at different depths, indicating an influence of the magnitude and direction of the hyporheic mixing during the different river water stages on methane production and consumption. The site acted as either a sink or a source of nitrous oxide depending on the elevation of the water column. Nitrous oxide porewater concentrations peaked at the upper layers of the sediment throughout the different water stages. River hydrological stages significantly influenced porewater concentrations and fluxes of GHG, probably by influencing heterotrophic respiration (production and consumption processes) and transport to and from the HZ. Our results highlight the importance of including dynamic hydrological exchanges when studying and modeling GHG production and consumption in the HZ of large rivers.

54 ENVIRONMENTAL SCIENCES↗

Pore-resolved investigation of turbulent open channel flow over a randomly packed permeable sediment bed

Pore-resolved direct numerical simulations are performed to investigate the interactions between streamflow turbulence and groundwater flow through a randomly packed porous sediment bed for three permeability Reynolds numbers, Re K = 2.56 , 5.17 and 8.94, representative of natural stream or river systems. Time–space averaging is used to quantify the Reynolds stress, form-induced stress, mean flow and shear penetration depths, and mixing length at the sediment–water interface (SWI). Here, the mean flow and shear penetration depths increase with Re K and are found to be nonlinear functions of non-dimensional permeability. The peaks and significant values of the Reynolds stresses, form-induced stresses, and pressure variations are shown to occur in the top layer of the bed, which is also confirmed by conducting simulations of just the top layer as roughness elements over an impermeable wall. The probability distribution functions (p.d.f.s) of normalized local bed stress are found to collapse for all Reynolds numbers, and their root-mean-square fluctuations are assumed to follow logarithmic correlations. The fluctuations in local bed stress and resultant drag and lift forces on sediment grains are mainly a result of the top layer; their p.d.f.s are symmetric with heavy tails, and can be well represented by a non-Gaussian model fit. The bed stress statistics and the pressure data at the SWI potentially can be used in providing better boundary conditions in modelling of incipient motion and reach-scale transport in the hyporheic zone.

turbulence simulation↗

Examining conditions supporting the development of anomalous charge structures in supercell thunderstorms in the Southeastern United States

Hypotheses regarding favorable conditions for anomalous charging have primarily resulted from studies within the Great Plains region of the United States, where the efficiency of warm precipitation processes is thought to be fundamental. Rare observations of anomalous charge structures in the Southeastern region challenge existing conceptual models used to explain anomalous charging. As a rigorous evaluation of conditions that support anomalous charge structures, environmental characteristics and bulk kinematic and microphysical properties of two normal and two anomalous supercell thunderstorms observed in the Southeast were compared in this paper. Within the anomalous supercells, greater quantities of precipitation ice were identified at higher altitudes and colder temperatures, suggesting a greater depth of riming growth and increased vertical transport of rimed hydrometeors. Deeper anomalous supercell updrafts were larger and stronger in the upper mixed-phase and glaciated regions. However, normal supercells were characterized by more robust low-level updrafts, resulting in comparable warm cloud residence times that suggested warm precipitation processes were not necessarily less efficient in the anomalous supercells. Indications of enhanced mixed-phase liquid water content in favor of anomalous charging were observed in the anomalous supercells, though contrasts in related environmental parameters were not as large as observed in other comparative studies. Anomalous supercell environments were characterized by increased instability, shallower warm cloud depth, as well as lower relative humidity in the 700 mb to 500 mb layer. Evidence of impacts from dry air in anomalous storm structures suggested that water vapor content may have affected particle-scale charge transfer in support of anomalous charge structure development.

54 ENVIRONMENTAL SCIENCES↗

La 0.6 Sr 0.4 CoO 3−δ Films Under Deoxygenation: Magnetic And Electronic Transitions Are Apart from The Structural Phase Transition

Abstract Topotactic phase transitions induced by changes in the oxygen vacancy concentration can largely alter the physical properties of complex oxides, including electronic and magnetic phases, while maintaining the structural integrity of the crystal lattice. An oxygen‐vacancy‐induced topotactic phase transition from perovskite (PV) to brownmillerite (BM) is achieved in epitaxial La 0.6 Sr 0.4 CoO 3−δ (LSCO) thin films. Two novel intermediate states with different oxygen content are identified by X‐ray diffraction, which involves a single‐phase reduced PV state and a mixed state of co‐existing PV and BM. The combination of depth‐sensitive polarized neutron reflectometry (PNR) and Rutherford backscattering (RBS) allows a quantitative determination of magnetization and the mean oxygen content in all states, revealing a continuous transition from La 0.6 Sr 0.4 CoO 2.97 to La 0.6 Sr 0.4 CoO 2.5 . BM formation is observed for an LSCO layer with an oxygen content of 2.67, while the magnetic and electronic transition already occurs for a layer with a higher oxygen content of 2.77 (and above) and in the absence of a BM signature. These results demonstrate that the physics of electronic metal‐to‐insulator transition (MIT), magnetic ferromagnet‐to‐non‐ferromagnet transition (FM‐to‐non‐FM), and structural PV‐to‐BM phase transition should be considered within the framework of separate but interrelated processes.

36 MATERIALS SCIENCE↗

Nanoscopic cross-grain cation homogenization in perovskite solar cells

Multiscale cation inhomogeneity has been a major hurdle in state-of-the-art formamidinium–caesium (FA–Cs) mixed-cation perovskites for achieving perovskite solar cells with optimal power conversion efficiencies and durability. Although the field has attempted to homogenize the overall distributions of FA–Cs in perovskite films from both plan and cross-sectional views, our understanding of grain-to-grain cation inhomogeneity and ability to tailor it—that is, spatially resolving the FA–Cs compositional difference between individual grains down to the nanoscale—are lacking. Here we reveal that as fundamental building blocks of a perovskite film, individual grains exhibit cationic compositions deviating from the prescribed ideal composition, severely limiting the interfacial optoelectronic properties and perovskite layer durability. This performance-limiting nanoscopic factor is linked to thermodynamic-driven morphological grooving, leading to a segmented surface landscape. At the grain triple junctions, grooves form nanoscale groove traps that hinder the mixing of solid-state cations across grains and thus retard inter-grain FA–Cs mixing. By rationally modulating the heterointerfacial energies, we reduced the depth of these nanoscale groove traps by a factor of three, significantly improving cation homogeneity. Perovskite solar cells with shallower nanoscale groove traps demonstrate enhanced power conversion efficiencies (25.62%) and improved stability under various standardized international protocols. In conclusion, our work highlights the significance of resolving surface nano-morphologies for homogeneous properties of perovskites.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The Chemical and Electronic Properties of Stability-Enhanced, Mixed Ir-TiO x Oxygen Evolution Reaction Catalysts

Iridium has emerged as the leading catalyst material for the anodic oxygen evolution reaction (OER) in acidic media. Often, iridium is mixed with more stable materials such as titanium. For these materials, the electronic structure of titanium plays a crucial role since with varying degrees of oxidation titanium transforms to semiconducting or even insulating phases. Yet, the electronic properties of mixed Ir-TiO x catalysts have never been systematically studied. In this study, we correlate the catalytic performance of mixed Ir-TiO x -based OER catalysts with the electronic structure of the surface layers. For this, a thin film material library with a 20-70 at. % Ir (Ir/[Ir + Ti]) compositional gradient was prepared. We used inductively coupled plasma mass spectrometry to test the OER activity and stability of the set of mixed Ir-TiO x catalyst candidate materials. Complementary, Ti L 2,3 - and O K-edge X-ray absorption spectroscopy and depth-dependent X-ray photoelectron spectroscopy measurements were performed to correlate the catalytic performance with the composition and electronic property profiles of these mixed Ir-TiO x OER anode catalysts. The spectroscopic analysis reveals that titanium is present as an intermixed matrix of semiconductive but stable TiO 2 , conductive but less stable titanium-suboxides (TiO x ), and highly conductive but highly unstable metallic Ti(0). The extent of the titanium oxidation strongly depends on the titanium content, with a lower degree of oxidation observed for lower titanium (and thus higher iridium) contents. For an iridium loading of 70 at. %, the respective mixed Ir-TiO x catalyst showed a similar OER activity to that of the pure metallic iridium (1.74 vs 1.59 VRHE, respectively) but with a 71% lower iridium dissolution rate relative to the pure metallic iridium. This demonstrates the stabilization effect of titanium addition while maintaining high OER activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Combining ToF‐SIMS and Multivariate Analysis to Resolve Active Sites on Ni‐Based HER Catalysts

Unambiguous identification of active sites in heterogeneous catalysis remains a major challenge, particularly for materials with ultrathin, chemically mixed surface layers. Here, we demonstrate a generalizable approach that combines time-of-flight secondary ion mass spectrometry (ToF-SIMS) with multivariate statistical analysis (principal component analysis [PCA] and multivariate curve resolution [MCR]) to resolve catalytically relevant motifs at the nanoscale. Using Ni electrodes as a model system, PCA distinguished hydroxide-enriched domains from oxide- and metal-rich regions, while MCR decomposed depth profiles and 3D images into hydroxide, oxide, and metallic layers with nanometer resolution. A unique secondary-ion fragment, NiO 3 H 3 − (m/z 108.94), emerged as a marker of hydroxide-rich environments and correlated with hydrogen evolution reaction (HER) activity across a series of Ni electrodes. Complementary density functional theory (DFT) calculations revealed that Ni(OH) 2 clusters adjacent to metallic Ni offer the most favorable water dissociation energetics, establishing the structural origin of the marker. While illustrated here for Ni-based HER, this workflow provides a broadly applicable framework to isolate and rank near-surface patterns that govern catalytic activity, thereby extending ToF-SIMS from a qualitative probe to a predictive tool for active site identification.

HER active sites↗

Cosmogenic nuclide and solute flux data from central Cuban rivers emphasize the importance of both physical and chemical mass loss from tropical landscapes

We use 25 new measurements of in situ produced cosmogenic 26 Al and 10 Be in river sand, paired with estimates of dissolved load flux in river water, to characterize the processes and pace of landscape change in central Cuba. Long-term erosion rates inferred from 10 Be concentrations in quartz extracted from central Cuban river sand range from 3.4–189 Mg km –2 yr –1 (mean 59, median 45). Dissolved loads (10–176 Mg km –2 yr –1 ; mean 92, median 97), calculated from stream solute concentrations and modeled runoff, exceed measured cosmogenic- 10 Be-derived erosion rates in 18 of 23 basins. This disparity mandates that in this environment landscape-scale mass loss is not fully represented by the cosmogenic nuclide measurements. The 26 Al / 10 Be ratios are lower than expected for steadystate exposure or erosion in 16 of 24 samples. Depressed 26 Al/ 10 Be ratios occur in many of the basins that have the greatest disparity between dissolved loads (high) and erosion rates inferred from cosmogenic nuclide concentrations (low). Depressed 26 Al/ 10 Be ratios are consistent with the presence of a deep, mixed, regolith layer providing extended storage times on slopes and/or burial and extended storage during fluvial transport. River water chemical analyses indicate that many basins with lower 26 Al/ 10 Be ratios and high 10 Be concentrations are underlain at least in part by evaporitic rocks that rapidly dissolve. Our data show that when assessing mass loss in humid tropical landscapes, accounting for the contribution of rock dissolution at depth is particularly important. In such warm, wet climates, mineral dissolution can occur many meters below the surface, beyond the penetration depth of most cosmic rays and thus the production of most cosmogenic nuclides. Our data suggest the importance of estimating solute fluxes and measuring paired cosmogenic nuclides to better understand the processes and rates of mass transfer at a basin scale.

54 ENVIRONMENTAL SCIENCES↗

Observed Sensitivity of Low-Cloud Radiative Effects to Meteorological Perturbations over the Global Oceans

Understanding how marine low clouds and their radiative effects respond to changing meteorological conditions is crucial to constrain low-cloud feedbacks to greenhouse warming and internal climate variability. In this paper, we use observations to quantify the low-cloud radiative response to meteorological perturbations over the global oceans to shed light on physical processes governing low-cloud and planetary radiation budget variability in different climate regimes. We assess the independent effect of perturbations in sea surface temperature, estimated inversion strength, horizontal surface temperature advection, 700-hPa relative humidity, 700-hPa vertical velocity, and near-surface wind speed. Stronger inversions and stronger cold advection greatly enhance low-level cloudiness and planetary albedo in eastern ocean stratocumulus and midlatitude regimes. Warming of the sea surface drives pronounced reductions of eastern ocean stratocumulus cloud amount and optical depth, and hence reflectivity, but has a weaker and more variable impact on low clouds in the tropics and middle latitudes. By reducing entrainment drying, higher free-tropospheric relative humidity enhances low-level cloudiness. At low latitudes, where cold advection destabilizes the boundary layer, stronger winds enhance low-level cloudiness; by contrast, wind speed variations have weak influence at midlatitudes where warm advection frequently stabilizes the marine boundary layer, thus inhibiting vertical mixing. These observational constraints provide a framework for understanding and evaluating marine low-cloud feedbacks and their simulation by models.

54 ENVIRONMENTAL SCIENCES↗