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At least 253 records · Page 14

Seasonal drivers of dissolved oxygen across a tidal creek–marsh interface revealed by machine learning

Abstract Dissolved oxygen (DO) is a key biogeochemical control in coastal systems, and its concentration and drivers vary markedly through time and space. This makes it difficult to accurately represent coastal DO and associated biogeochemical processes in models, limiting our ability to predict how these systems will respond to global change. We obtained high‐frequency (5‐min) in situ measurements of DO collected at three locations across the interface of a tidal creek and coastal marsh in the Pacific Northwest, USA. Random Forest machine learning models quantified the importance of three categories of environmental drivers (Aquatic, Climatic, and Terrestrial) of DO variability across the creek–marsh interface. We selected two 4‐month datasets representing Summer and Winter seasonal periods to test two hypotheses on the dominant drivers of DO at the coastal interface. We found that the Terrestrial driver—characterized by long periods of anaerobic conditions and episodic pulses in DO after floods—was most important during the Winter, whereas the Aquatic driver—characterized by variability over tidal, diel, and lunar cycles—was most important during the Summer. We explored how future climate change scenarios could alter the drivers of DO variability using a cumulative sums driver–response framework. Our results suggest that under climate change, Aquatic and Climatic drivers may increase in importance during the Summer, potentially linked to changing metabolic regimes and sea level, with Terrestrial driver importance potentially increasing during the Winter. Our approach highlights useful methods for understanding the spatiotemporal complexity of oxygen across coastal interfaces and quantifying the relative importance of distinct environmental drivers.

54 ENVIRONMENTAL SCIENCES↗

Diel variation in CO 2 flux is substantial in many lakes

Lakes play a significant role in the global carbon cycle, acting as sources and sinks of carbon dioxide (CO 2 ). In situ measurements of CO 2 flux (FCO 2 ) from lakes have generally been collected during daylight, despite indications of significant diel variability. This introduces bias when scaling up to whole-lake annual aquatic carbon budgets. We conducted an international sampling program to ascertain the extent of diel variation in FCO 2 across lakes. We sampled 21 lakes over 41 campaigns and measured FCO 2 at 4-h intervals over a full diel cycle. Rates of FCO 2 ranged from −3.16 to 4.39 mmol m −2 h −1 . Integrated over a day, FCO 2 ranged from −381.68 to 878.49 mg C m −2 d −1 (mean = 76.54) across campaigns. We identified three characteristic diel patterns in FCO 2 related to trophic status and show that for half of the campaigns, daily flux estimates were biased by > 50% if based on a single (daytime) measurement.

de Eyto, Elvira [Marine Institute, Mayo (Ireland)]↗

Haze–cloud correlations mediated by supersaturation fluctuations

Atmospheric aerosol particles that contain water-soluble components can absorb water vapor in humid environments and form either haze particles or cloud droplets, depending on supersaturation conditions. Laboratory and in situ measurements have shown that haze particles and cloud droplets often coexist and compete for available water vapor in shallow clouds and fogs, especially under polluted conditions. It is expected that more aerosol particles can form more haze particles and cloud droplets, so that the haze and cloud number concentrations are positively correlated. However, recent large-eddy simulations show that haze and cloud number concentration can be negatively correlated under extremely polluted conditions. Haze–cloud interactions across different environmental settings remain poorly understood. In this study, experiments in a convection cloud chamber with the same aerosol injection rate show that, as supersaturation forcing increases (i.e., changing from polluted to clean conditions), the covariance between haze and cloud droplet number concentration changes from negative to positive and finally to zero. Large-eddy simulations (LES) of the cloud chamber with a fixed supersaturation forcing but varying aerosol injection rates show a similar result for the haze–cloud correlation: near zero in clean, mean-supersaturation-dominated activation conditions; positive in moderate, supersaturation-fluctuation-influenced activation conditions; and negative in polluted, supersaturation-fluctuation-dominated activation conditions. A theoretical covariance framework was developed to interpret this behavior based on the relative magnitude and signs of the correlations between supersaturation and the populations of haze and cloud droplets. Significantly, experiments, LES, and theory all yield the same three-regime behavior for the sign of the haze–cloud covariance. Furthermore, our results show that the haze–cloud covariance remains robust and easily measurable, thereby providing a useful metric for regime identification in the atmosphere, improving regime-aware parameterizations, and informing aerosol interventions such as fog dispersion, rainfall enhancement, and albedo modification.

54 ENVIRONMENTAL SCIENCES↗

Spatially Enhanced Electrostatic Doping in Graphene Realized via Heterointerfacial Precipitated Metals

Forming heavily-doped regions in 2D materials, like graphene, is a steppingstone to the design of emergent devices and heterostructures. Here, a selective-area approach is presented to tune the work-function and carrier density in monolayer graphene by spatially synthesizing sub-monolayer gallium beneath the 2D-solid. The localized metallic gallium is formed via precipitation from an underlying diamond-like carbon (DLC) film that is spatially implanted with gallium-ions. By controlling the interfacial precipitation process with annealing temperature, spatially precise ambipolar tuning of the graphene work-function is achieved, and the tunning effect preserved upon cooling to ambient conditions. Consequently, charge carrier densities from ≈1.8 × 10 10 cm -2 (hole-doped) to ≈7 × 10 13 cm -2 (electron-doped) are realized, confirmed by in situ and ex situ measurements. The theoretical studies corroborated the role of gallium at the heterointerface on charge transfer and electrostatic doping of the graphene overlayer. Specifically, sub-monolayer gallium facilitates heavy n-doping in graphene. Extending this doping strategy to other implantable elements in DLC provides a new means of exploring the physics and chemistry of highly-doped 2D materials.

36 MATERIALS SCIENCE↗

Jupiter missions as probes of dark matter

Jupiter, the fascinating largest planet in the solar system, has been visited by nine spacecraft, which have collected a significant amount of data about Jovian properties. In this paper, we show that one type of the in situ measurements on the relativistic electron fluxes could be used to probe dark matter (DM) and dark mediator between the dark sector and our visible world. Jupiter, with its immense weight and cool core, could be an ideal capturer for DM with masses around the GeV scale. The captured DM particles could annihilate into long-lived dark mediators such as dark photons, which subsequently decay into electrons and positrons outside Jupiter. The charged particles, trapped by the Jovian magnetic field, have been measured in Jupiter missions such as the Galileo probe and the Juno orbiter. We use the data available to set upper bounds on the cross section of DM scattering off nucleons, σ χn , for dark mediators with lifetime of order $O$ (0.1–1) s. The results show that data from Jupiter missions already probe regions in the parameter space un- or under-explored by existing DM searches, e.g., constrain σχn of order (10 –41 –10 –39 ) cm 2 for 1 GeV DM dominantly annihilating into e + e – through dark mediators. This study serves as an example and an initial step to explore the full physics potential of the large planetary datasets from Jupiter missions. We also outline several other potential directions related to secondary products of electrons, positron signals and solar axions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Image Processing Pipeline for Fluoroelastomer Crystallite Detection in Atomic Force Microscopy Images

Phase transformations in materials systems can be tracked using atomic force microscopy (AFM), enabling the examination of surface properties and macroscale morphologies. In situ measurements investigating phase transformations generate large datasets of time-lapse image sequences. The interpretation of the resulting image sequences, guided by domain-knowledge, requires manual image processing using handcrafted masks. Here this approach is time-consuming and restricts the number of images that can be processed. Her in this study, we developed an automated image processing pipeline which integrates image detection and segmentation methods. We examine five time-series AFM videos of various fluoroelastomer phase transformations. The number of image sequences per video ranges from a hundred to a thousand image sequences. The resulting image processing pipeline aims to automatically classify and analyze images to enable batch processing. Using this pipeline, the growth of each individual fluoroelastomer crystallite can be tracked through time. We incorporated statistical analysis into the pipeline to investigate trends in phase transformations between different fluoroelastomer batches. Understanding these phase transformations is crucial, as it can provide valuable insights into manufacturing processes, improve product quality, and possibly lead to the development of more advanced fluoroelastomer formulations.

36 MATERIALS SCIENCE↗

Remote sensing of seasonal variation of LAI and fAPAR in a deciduous broadleaf forest

Climate change is affecting the phenology of terrestrial ecosystems. In deciduous forests, phenology in leaf area index (LAI) is the primary driver of seasonal variation in the fraction of absorbed photosynthetically active radiation (fAPAR), which drives photosynthesis. Remote sensing has been widely used to estimate LAI and fAPAR. However, while many studies have examined both empirical and model-based relationships among LAI, fAPAR, and spectral vegetation indices (SVI) from remote sensing, few studies have systematically and empirically examined how relationships among these variables change over the growing season. In this study, we examine how and why seasonal-scale covariation differs among time series of remotely sensed SVIs and both LAI and fAPAR based on current understanding and theory. To do this we use newly available remote sensing data sets in combination with time series of in-situ measurements and a canopy radiative transfer model to analyze how seasonal variation in canopy and environmental conditions affect relationships among remotely sensed SVIs, LAI, and fAPAR at a temperate deciduous forest site in central Massachusetts. Our results show that accounting for seasonal variation in canopy shadowing, which is driven by variation in solar zenith angle, improved remote sensing-based estimates of LAI, fAPAR, and daily total APAR. Specifically, we show that the phenology of SVIs is strongly influenced by seasonal variation in near infrared (NIR) reflectance arising from systematic variation in the canopy shadow fraction that is independent of changes in LAI or fAPAR. Therefore, results of this work provide a refined basis for understanding how remote sensing can be used to monitor and model the phenology of LAI, fAPAR, APAR, and gross primary productivity in temperate deciduous forests.

54 ENVIRONMENTAL SCIENCES↗

Influence of thermal treatment on structure and catalytic performance of ceria-zirconia supported copper oxide (CuO x /Ce y Zr 1-y O 2 ) catalysts for CO oxidation

Copper oxide (CuO x ) supported on ceria-zirconia (Ce y Zr 1-y O 2 , y = 1.0, 0.5, 0.0) catalysts were investigated to elucidate the effects of thermal treatment on their physicochemical properties and catalytic performance in carbon monoxide (CO) oxidation. Here, the catalysts were synthesized via a one-pot chemical vapor deposition (OP-CVD) method at 700˚C and 900˚C with controlled Cu loading. Characterization techniques, including synchrotron X-ray diffraction (S-XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma spectroscopy (ICP), and N 2 adsorption-desorption, were implemented to probe the crystalline structure, molecular and electronic structure, oxygen vacancies, specific surface area (SSA) and metal loading. CO oxidation was chosen as a model reaction to explore the structure-catalytic performance relationship. A ∼100% CO conversion was achieved at < 150˚C, particularly with the CuO x /CeO 2 catalyst calcined at 700˚C. In contrast, calcination at 900˚C caused a ∼90% decrease in SSA and a ∼24% increase in T 50 . Activity tests revealed that increasing ZrO 2 content lowered CO oxidation activity despite generating more defect sites. In-situ measurement of the 700 °C calcined samples revealed the presence of stable and unstable defects in CuO x /Ce 0.5 Zr 0.5 O 2 and CeO 2 respectively, which play a key role in the activity of the catalysts. The results highlight that catalytic performance is closely related to the SSA. Furthermore, an optimum calcination temperature favor significant oxygen vacancy formation with required CuO x -support interactions, enhancing redox properties and catalytic performance.

36 MATERIALS SCIENCE↗

CO2 partial pressure and fluxes in the Amazon River Plume using in situ and remote sensing data

Estimations of the global carbon budget include a quantitative understanding of the evolving processes that occur along river-to-ocean gradients. However, high spatiotemporal resolution observations of these processes are limited. Here we present in situ measurements of the partial pressure of CO2 (pCO2) made through the Amazon River plume (ARP) during different discharge seasons, from 2010-2012. We evaluated the spatiotemporal distribution of pCO2 using Soil Moisture and Ocean Salinity (SMOS) satellite observations for each hydrologic period in the ARP. Regression models were used to estimate pCO2 at the ARP for the period of 2010-2014. From these distributions we calculated sea-air gas exchange of CO2 between the plume waters and the atmosphere (F_co2^sea). Intra-annual variability of F_co2^sea was related to discharge at the river mouth and ocean currents as well as trade winds in the plume. Climatic events during the study period had a significant impact on the F_co2^sea. Including the plume area closer to the river mouth makes the ARP a net source of CO2 with an annual net sea-air flux of 8.6 ±7.1 Tg C y-1 from 2011-2014.

Amazon↗

MITgcm-AD v2: Open source tangent linear and adjoint modeling framework for the oceans and atmosphere enabled by the Automatic Differentiation tool Tapenade

The Massachusetts Institute of Technology General Circulation Model (MITgcm) is widely used by the climate science community to simulate planetary atmosphere and ocean circulations. A defining feature of the MITgcm is that it has been developed to be compatible with an algorithmic differentiation (AD) tool, TAF, enabling the generation of tangent-linear and adjoint models. These provide gradient information which enables dynamics-based sensitivity and attribution studies, state and parameter estimation, and rigorous uncertainty quantification. Importantly, gradient information is essential for computing comprehensive sensitivities and performing efficient large-scale data assimilation, ensuring that observations collected from satellites and in-situ measuring instruments can be effectively used to optimize a large uncertain control space. As a result, the MITgcm forms the dynamical core of a key data assimilation product employed by the physical oceanography research community: Estimating the Circulation and Climate of the Ocean (ECCO) state estimate. Although MITgcm and ECCO are used extensively within the research community, the AD tool TAF is proprietary and hence inaccessible to a large proportion of these users. The new version 2 (MITgcm-AD v2) framework introduced here is based on the source-to-source AD tool Tapenade, which has recently been open-sourced. Another feature of Tapenade is that it stores required variables by default (instead of recomputing them) which simplifies the implementation of efficient, AD-compatible code. The framework has been integrated with the MITgcm model’s main branch and is now freely available.

Adjoints↗

Titanium isotope systematics of refractory inclusions: Echoes of molecular cloud heterogeneity

Calcium-aluminum-rich inclusions (CAIs) are highly refractory objects found in different chondrite groups and represent some of the oldest known solids of the Solar System. As such, CAIs provide key information regarding the conditions prevailing in the solar protoplanetary disk as well as subsequent mixing and transport processes. Many studies have investigated CAIs for their isotopic compositions and reported nucleosynthetic isotope anomalies in numerous elements, which are typically explained by the variable incorporation of isotopically highly anomalous presolar phases. However, with the exception of 54 Cr-enriched nanospinels, the exact presolar phases responsible for the isotopic heterogeneities are yet to be identified. To address this issue, we here present in-situ Ti isotopic analyses obtained on a diverse set of CAIs from various CV3 chondrites. In this work, the in-situ measurements were performed by targeting individual mineral phases of 15 CAIs with laser-ablation mass spectrometry and indicate significant inter- and intra-CAI isotopic heterogeneity in the neutron-rich isotope 50 Ti. This is particularly pronounced for primitive fine-grained CAIs, whereas coarse-grained CAIs, which have been subject to melting, exhibit smaller degrees of Ti isotopic heterogeneity. To further investigate this Ti isotopic heterogeneity, we additionally obtained Ti isotopic compositions of sequential acid leachates from two fine-grained and two coarse-grained CAIs derived from CV3 chondrites. In contrast to potential expectations from the first part of the study, we do not observe any significant intra-CAI Ti isotopic heterogeneity between the different leaching steps. The lack of intra-CAI Ti isotopic heterogeneity in the acid leachate samples of this study likely reflects that the leaching procedure is unable to efficiently separate the carriers of isotopically anomalous Ti in CAIs. By comparing the bulk CAI Ti isotope compositions with Ti isotope data for hibonite-rich objects from the literature, we find that the range of Ti isotope compositions recorded by CAIs from various chondrite groups can be accounted for by the averaging of hibonite grains. In turn, the variable Ti isotope compositions of hibonite grains can be explained by the averaging of isotopically diverse presolar grains present in the Sun’s parental molecular cloud. This effect of averaging is statistically supported by the central limit theorem, and the concept has the potential to be useful for other isotopic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A hydrogeophysical framework to assess infiltration during a simulated ecosystem-scale flooding experiment

This study presents a framework to quantify changes in soil saturation in response to flooding caused by extreme hydrologic perturbation on coastal ecosystems at the interfaces and transition between terrestrial and aquatic systems. Subsurface heterogeneity limits the use of in situ measurements to quantify subsurface flow during flooding due to the spatial discontinuity in the measured data. While geophysical methods, including time-lapse electrical resistivity imaging (ERI), are increasingly used to monitor soil hydrological processes, their abilities to parameterize flow models have been underutilized. This study combines background ERI, ground penetrating radar (GPR), time-lapse ERI, soil characterization, and a numerical flow model developed using an Advanced Terrestrial Simulator (ATS) code to quantify the infiltration pathway and describe the hydrological dynamics during a simulated flooding experiment. We assessed the use of two conceptual models developed using [1] ERI and GPR data that described the stratigraphic distribution, and time-lapse ERI that mapped permeability contrast, and [2] information from a national soil database for capturing changes in saturation. Combining the ERI and GPR results with soil core data revealed the stratigraphic heterogeneity at the site with a silty clay layer from 1 to 2 m between an overlying loamy topsoil and an underlying saturated silty sand. This silty clay layer could restrict deep infiltration. The time-lapse ERI showed up to a 35% decrease in resistivity, which correlated with soil moisture data (R 2 value > 0.53) and revealed preferential infiltration zones used to inform the flow model. Numerical simulation results from both the geophysics- and soil database-informed models quantified changes in soil saturation with calculated soil moistures that agreed with field data. The geophysics-informed model captured more of the system’s variability, reflective of shallow subsurface heterogeneities. The framework presented will serve as a precursor for a robust ecohydrological model that can describe the impacts of extreme events induced by climate change on coastal ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Radial burnup characteristics of spent fuel pellets by zirconium analysis

Resonance ionization mass spectrometry is a powerful tool for in-situ measurements of elemental ratios in micrometer-sized spent fuel samples. By measuring the concentration of the fission product Zr we provide a framework for determining fuel burnup while simultaneously considering the 239 Pu fission fraction. Here, the analyzed spent fuel samples were taken from different fuels and distances from the fuel pellets’ edge. Results show a burnup enhancement at the edge of a fuel pellet of 180–220% compared to the center of the pellet. By comparing the concentration of the anthropogenic 93 Zr to the naturally occurring Zr isotopes, any influence of non-fissiogenic Zr or disturbing neutron capture reactions can be ruled out. This established 93 Zr as a new tool to measure fuel burnup.

Burnup↗

Identification and demonstration of roGFP2 as an environmental sensor for cryogenic correlative light and electron microscopy

Cryogenic correlative light and electron microscopy (cryo-CLEM) seeks to leverage orthogonal information present in two powerful imaging modalities. While recent advances in cryogenic electron microscopy (cryo-EM) allow for the visualization and identification of structures within cells at the nanometer scale, information regarding the cellular environment, such as pH, membrane potential, ionic strength, etc., which influences the observed structures remains absent. Fluorescence microscopy can potentially be used to reveal this information when specific labels, known as fluorescent biosensors, are used, but there has been minimal use of such biosensors in cryo-CLEM to date. Here we demonstrate the applicability of one such biosensor, the fluorescent protein roGFP2, for cryo-CLEM experiments. At room temperature, the ratio of roGFP2 emission brightness when excited at 425 nm or 488 nm is known to report on the local redox potential. When samples containing roGFP2 are rapidly cooled to 77 K in a manner compatible with cryo-EM, the ratio of excitation peaks remains a faithful indicator of the redox potential at the time of freezing. Using purified protein in different oxidizing/reducing environments, we generate a calibration curve which can be used to analyze in situ measurements. As a proof-of-principle demonstration, we investigate the oxidation/reduction state within vitrified Caulobacter crescentus cells. The polar organizing protein Z (PopZ) localizes to the polar regions of C. crescentus where it is known to form a distinct microdomain. Finally, by expressing an inducible roGFP2-PopZ fusion we visualize individual microdomains in the context of their redox environment.

59 BASIC BIOLOGICAL SCIENCES↗

Pu(IV) quantification via visible–near-infrared absorption spectroscopy: tackling interferences using D-optimal design and partial least squares

Here, this study presents a novel analytical approach for quantifying Pu(IV) in glove box environments using fiber-optic-based visible–near-infrared absorption spectroscopy in combination with partial least squares regression (PLSR) and design of experiments. The method addresses significant challenges posed by overlapping spectral features arising from Nd(III), which is a common fission product impurity, and the speciation variability of Pu(IV) nitrato complexes in HNO 3 concentrations ranging from 2.5 to 11 M. A curated training set consisting of data from 20 samples was developed via D-optimal design to enable robust PLSR model calibration for Pu(IV) using the near-infrared band near 1050 nm. The training set was acquired from samples in cuvettes with a 1-cm path length and was used to build the PLSR model. The robustness of the model was validated with data collected using a dip probe with a 1-cm path length and varying Pu(IV) concentrations. The strong performance of the model indicates good model transfer from cuvette to dip probe and highlights the potential for in situ measurements and online monitoring of reactions in a crystallization reactor vessel. The results demonstrate that this combined spectroscopic and chemometric approach can accurately and simultaneously quantify Pu(IV) and HNO 3 , thereby offering a promising tool for real-time monitoring in process environments.

Actinide↗

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↗

Chemical state of nickel nanoparticles during the oxygen evolution reaction in a carbonate-bicarbonate buffer solution

The chemical state of nickel anodes during the oxygen evolution reaction can impact their electrocatalytic performance. Here, X-ray photoelectron and absorption spectroscopies reveal the chemical state of nickel nanoparticles under oxygen evolution reaction conditions in amildly alkaline carbonate-bicarbonate buffer solution. Ni 2+ and Ni 3+ species are observed at the reaction onset potential with a 7:4 ratio, with no remaining metallic nickel. These species include NiO, which increasingly converts to other Ni 2+ and Ni 3+ species once the potential is increased above the onset potential. Conversely, when a 20-nm-thick nickel film is used instead of nickel nanoparticles, a significant amount of metallic nickel remains in the inner layers. Nickel nanoparticles also undergo significant morphological and structural changes during the reaction, as evidenced by ex situ transmission electron microscopy. Amorphization of the nanoparticles is attributed to significant H 2 O incorporation, with the oxygen intensity increasing both in operando and ex situ measurements.

36 MATERIALS SCIENCE↗