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At least 721 records · Page 40

Impacts of climate and disturbance on nutrient fluxes and stoichiometry in mixed-conifer forests

Elucidating climatic impacts on stream nutrient export and stoichiometry will improve the understanding of forest carbon (C) storage in a warmer world. We constructed C, nitrogen (N), and phosphorus (P) budgets in four watersheds within a rain-snow transition site and another four within a higher-elevation, snow-dominated site, in California’s mixed-conifer zone. We used these two sites in a space-for-time substitution to assess the potential effects of warming on nutrient cycles in currently snow-dominated areas that will become more rain-dominated. During a non-drought period (water year (WY) 2004 – 2011), mean annual stream exports of C and N in particulate forms at the transition site were double that at the snow-dominated site, suggesting that sediment-associated nutrient losses may increase with warming. The transition site had 12% lower N but double the P content in mineral horizons, lower N:P mass ratios in organic horizons, and lower stream export of dissolved inorganic N than the snow-dominated site. Furthermore, these differences suggest that montane forests may receive lower supply of N relative to P with warming. In addition, given strong interests in forest thinning to increase drought resiliency, we examined changes in stream nutrient export after thinning and during a major drought period (WY 2013 – 2015). Stream exports of C, N, and P were similar between unthinned and thinned watersheds during drought, suggesting negligible thinning impacts on stream nutrient export during excessively dry periods. Taken together, our results suggest that as the climate warms, California’s montane forests may lose more nutrients through erosion and receive less N input than P.

54 ENVIRONMENTAL SCIENCES↗

Influence of the Rheology Behavior of Water-Soluble Polyacrylamides and Their Efficiency of Flocculation

Organic polymers such as water-soluble polyacrylamides that are used as flocculants in solid–liquid separations, have their flocculation efficiency determined by the behavior of their macromolecules in solution. This behavior is affected by its intrinsic characteristics, especially the presence of ionic groups in its macromolecules. In this context, the present work aimed to characterize three water-soluble polyacrylamides. The effect of the intrinsic properties of each polymer on the behavior of the polymer chains in aqueous solution was compared in different environments. Beside this, the polymers behavior effect on the destabilization of particles was evaluated through kaolin particle aggregation studies. Viscosity results show that the conformation of the macromolecules in solution is altered according to the amount of ionized groups present. This variation, together with other factors such as the affinity with the kaolin particles and the excess of ions in solution, reflects in the flocculation efficiency of kaolin particles, in the flocs size and the flocs sedimentation rate. Graphic Abstract: .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Offshore application of landslide susceptibility mapping using gradient-boosted decision trees: a Gulf of Mexico case study

Abstract Among natural hazards occurring offshore, submarine landslides pose a significant risk to offshore infrastructure installations attached to the seafloor. With the offshore being important for current and future energy production, there is a need to anticipate where future landslide events are likely to occur to support planning and development projects. Using the northern Gulf of Mexico (GoM) as a case study, this paper performs Landslide Susceptibility Mapping (LSM) using a gradient-boosted decision tree (GBDT) model to characterize the spatial patterns of submarine landslide probability over the United States Exclusive Economic Zone (EEZ) where water depths are greater than 120 m. With known spatial extents of historic submarine landslides and a Geographic Information System (GIS) database of known topographical, geomorphological, geological, and geochemical factors, the resulting model was capable of accurately forecasting potential locations of sediment instability. Results of a permutation modelling approach indicated that LSM accuracy is sensitive to the number of unique training locations with model accuracy becoming more stable as the number of training regions was increased. The influence that each input feature had on predicting landslide susceptibility was evaluated using the SHapely Additive exPlanations (SHAP) feature attribution method. Areas of high and very high susceptibility were associated with steep terrain including salt basins and escarpments. This case study serves as an initial assessment of the machine learning (ML) capabilities for producing accurate submarine landslide susceptibility maps given the current state of available natural hazard-related datasets and conveys both successes and limitations.

Dyer, Alec S. (ORCID:0000000219813904)↗

Extending TOUGH + HYDRATE with a parallel particle transport simulator: numerical investigation of sand production during gas production from hydrate deposits

A new parallel code for simulating particle transport in porous media is integrated with the TOUGH + HYDRATE simulator to investigate sand production associated with gas production from unconsolidated gas hydrate-bearing sediments (HBS). Here, the parallel coupled simulator is named THMPT and uses the integral finite difference method to describe the Darcian and non-Darcian flow of fluids and heat transport, the finite element method to describe the associated geomechanical changes, and the discrete element method to track the trajectory of individual sand particles within the HBS. The THMPT simulator is written in Fortran, incorporates multiple optimized algorithms, and can comprehensively address the coupled flow, thermal, chemical, geomechanical, and particle transport processes that characterize the system behaviors during gas production from HBS. The simulator can capture all processes involved in sand particle transport in porous media, including sand detachment, collision, clogging (i.e., bridging), and migration. A benchmark case study of sand production in the course of depressurization-induced gas production from a representative HBS reveals various distinct microscopic particle migration mechanisms and the adverse impact of sand particle detachment, transport, and clogging. The numerical investigation also examines the effect of bottomhole pressure on mitigating sand production. The simulation results indicate that sand clogging near the wellbore significantly reduces permeability, decreasing gas production by at least 50%. Lastly, the efficiency of gravel packing in mitigating sand production is numerically evaluated, revealing that the structure of the porous media appears to profoundly influence the macroscopic motion behavior of sand particles and sand clogging characteristics.

discrete element method↗

Petrology and geochemistry of the Middle Pennsylvanian (Langsettian) Clintwood coalbed, Pike County, Kentucky

Abstract The Middle Pennsylvanian, Langsettian sub-stage Clintwood coal, along with its correlatives, was one of the more important energy resources in eastern Kentucky. The coal thickens from the NE-SW-trending Belfry anticline in central Pike County to the southeast, towards the Virginia-Kentucky border. Much of the thickness increase is in the bright lithotypes below a dull lithology. The bright lithologies transition from a bright clarain + vitrain + fusain lithology to a clarain + fusain lithology to the southeast. Half of the lithotypes in the three analyzed sections exceed 1000-µg/g Rare earth elements + Y + Sc (REYSc) (ash basis). The La N /Sm N vs. Gd N /Yb N and La N /Sm N vs. Ce N /Ce N * plots suggest that the top lithotype may have had best indication of an oxidizing environment. Positive Gd N /Gd N * and Eu N /Eu N * in some of the lithologies suggests that there may have been a hydrothermal influence in the sediment sources and/or in the diagenesis of the coal. Consideration of La N /Sm N and Zr (µg/g; ash basis), Zr vs. Sr, and V/Cr vs. inertinite/(inertinite + vitrinite) indicates that the dull lithotypes existed in a distinct geochemical environment compared to the brighter lithotypes. The isolation of the dull lithotypes from the bright lithotypes is supported by principal components analysis on inertinite/(inertinite + vitrinite), La N /Sm N , V/Cr, Sr, and either Zr or Ln(100(TiO 2 )/Al 2 O 3 ).

Hower, James C. (ORCID:0000000346942776)↗

High sensitivity measurement of femtogram-level 238 Pu by thermal ionization mass spectrometry with correction of background 238 U

Low-concentration plutonium isotopic measurements provide a valuable fingerprint to identify possible material origins in the context of environmental contamination monitoring, environmental tracing, nuclear safeguards, nuclear forensics, and treaty monitoring. Thermal ionization mass spectrometry (TIMS) has long been recognized as one of the most sensitive techniques for plutonium isotopic measurement, but has not generally been utilized for 238 Pu determination, especially at low concentrations, due to an isobaric interference from 238 U, prevalent as background. Here, this work demonstrates a new analytical technique for correction of background 238 U from the 238 Pu counts collected during a TIMS analysis. The technique takes advantage of the higher ionization temperature of U relative to Pu and uses a 235 U tracer added after plutonium purification chemistry for 238 U semi-quantitative determination. This technique has been successfully applied to the determination of 238 Pu concentration and the 238 Pu/ 239 Pu ratio in sample types including single-isotope standards, isotopic certified reference materials, matrix-containing environmental reference materials, and simulated nuclear detonation debris. The results have been directly compared on a sample-by-sample basis to alpha spectrometry results. The detection limit by this new technique is 0.23 fg 238 Pu, which was previously unachievable by mass spectrometry and is possible in around 1 h of analysis time post-chemistry compared to weeks of required counting time by alpha spectrometry (at the same atom amount). We also present original, high precision data for Pu isotope concentrations in IAEA-384, Fangataufa Sediment, including 242 Pu results for the first time. The new technique allows measurement of a key isotope, 238 Pu, that was previously not measured in small environmental or nuclear forensics collections.

238Pu↗

Localization and functional exploration of leiomodin-2’s C-terminal binding sites

Striated muscle contraction occurs through interactions between overlapping myosin-based thick and actin-based thin filaments within the sarcomere. For effective contraction to occur, the length of the thin filament must be maintained to allow for sufficient overlap with the thick filament. The proteins leiomodin and tropomodulin compete for binding at the pointed end of thin filaments to regulate their length, utilizing their homologous N-terminal actin and tropomyosin binding sites. Leiomodin also has a region called the C-terminal extension, absent in tropomodulin. In this region, the cardiac isoform (leiomodin-2) contains additional actin-binding sites that enable it to bind along the sides of thin filaments in a Ca2+-dependent manner. Here, using nuclear magnetic resonance spectroscopy, we localize the regions of the C-terminal extension that contain residues involved in thin filament side-binding. Using co-sedimentation assays, we reveal that these regions can independently bind thin filaments and discover that the poly-proline region plays a role as a linker, maintaining an adequate distance between two of the regions required for effective interaction to occur. In addition to its role in side-binding, we provide direct evidence that the poly-proline region interacts with profilin and propose a new mechanism by which leiomodin-2 may assist in the polymerization of profilin-bound actin at thin filament pointed ends.

ACTIN-BINDING PROTEINS↗

Mitigation of spatial nonstationarity with vision transformers

Spatial nonstationarity, the location variance of features’ statistical distributions, is ubiquitous in many natural settings. For example, in geological reservoirs rock matrix porosity varies vertically due to geomechanical compaction trends, in mineral deposits grades vary due to sedimentation and concentration processes, in hydrology rainfall varies due to the atmosphere and topography interactions, and in metallurgy crystalline structures vary due to differential cooling. Conventional geostatistical modeling workflows rely on the assumption of stationarity to be able to model spatial features for geostatistical inference. Nevertheless, this is often not a realistic assumption when dealing with nonstationary spatial data and this has motivated a variety of nonstationary spatial modeling workflows such as trend and residual decomposition, cosimulation with secondary features, and spatial segmentation and independent modeling over stationary subdomains. The advent of deep learning technologies has enabled new workflows for modeling spatial relationships. However, there is a paucity of demonstrated best practice and general guidance on mitigation of spatial nonstationarity with deep learning in the geospatial context. We demonstrate the impact of two common types of geostatistical spatial nonstationarity on deep learning model prediction performance and propose the mitigation of such impacts using self-attention (vision transformer) models. We demonstrate the utility of vision transformers for the mitigation of nonstationarity with relative errors as low as 10%, exceeding the performance of alternative deep learning methods such as convolutional neural networks. We establish best practice by demonstrating the ability of self-attention networks for modeling large-scale spatial relationships in the presence of commonly observed geospatial nonstationarity.

58 GEOSCIENCES↗

Additive manufacturing of complexly shaped SiC with high density via extrusion-based technique – Effects of slurry thixotropic behavior and 3D printing parameters

Here, additive manufacturing of dense SiC parts was achieved via an extrusion-based process followed by electrical-field assisted pressure-less sintering. The aim of this research was to study the effect of the rheological behavior of SiC slurry on the printing process and quality, as well as the influence of 3D printing parameters on the dimensions of the extruded filament, which are directly related to the printing precision and quality. Different solid contents and dispersant- Darvan 821A concentrations were studied to optimize the viscosity, thixotropy and sedimentation rate of the slurry. The optimal slurry was composed of 77.5 wt% SiC, Y 2 O 3 and Al 2 O 3 powders, 0.25 wt% dispersant and 0.01 wt% defoamer. The printing parameters studied included extrusion pressure, nozzle size, layer height and printing speed; the one that had the most prominent effect on filament width and height was indicated as layer height. The nozzle inner diameter of 1.04 mm, speed of 350 mm/min, layer height of 0.7 mm and extrusion air pressure of 0.31 MPa were the optimal printing parameters. Furthermore, the relationship between the printing parameters and the filament dimensions was successfully predicted by using machine learning and grey system theory. Finally, the relative density of the printed SiC parts sintered at 1900 oC reached 94.7±1.5%.

36 MATERIALS SCIENCE↗

Phase distribution in Fischer-Tropsch mimicked slurry bubble column via computed tomography

This study aims to investigate the phases distribution and hydrodynamics in an air-Therminol LT-glass beads slurry bubble column reactor in bubbly and churn-turbulent flow regimes by implementing a gamma-ray computed tomography. It is found that gas holdup increases with increasing superficial gas velocity and operating pressure while increasing solids loading has an opposite effect on gas holdup measurements. It is noticed that the pressure effect is more significant at high solids loading and the solids loading is relatively more substantial at lower pressure. Solids loading has the most significant a stronger effect on the solids holdup profile than on the gas holdup profile. Current results were compared with the Sedimentation-Dispersion Model (SDM) predictions. Overall, the findings of this study advance the knowledge of the true behavior of phases distribution in FT mimicked slurry bubble columns which are pertinent in designing such reactors.

42 ENGINEERING↗

Epitaxial growth mechanism of heterogeneous catalytic oxidation of Mn(II) on manganite under oxic conditions

Manganese oxides are ubiquitous in soils and sediments, and their formation and transformation processes affect the migration and transformation of heavy metals and organic pollutants. Most previous work has been focused the oxidation of Mn(II) on Mn(IV) oxide surface, but it remains poorly understood how Mn(II) interacts with manganite under oxic conditions. Here, the interactions between manganite and dissolved Mn(II) within pH 5.0–9.0 under oxic conditions were systematically studied. The results indicated that adsorbed Mn(II) was directly oxidized to manganite on the surface, and the oxidation rate increased with increasing pH and oxygen partial pressure. Electrons are likely transferred in bulk manganite during the oxidation process of Mn(II). Although manganite induced Mn(II) oxidation and the epitaxial growth of bulk particles, there was no obvious change in mineral phase. Dissolved oxygen accelerated the growth of manganite in Mn(II) solution. Compared with the absence of manganite, the presence of manganite inhibited the formation of hausmannite from Mn(II) oxidation by oxygen in air. Furthermore, this study reveals the catalytic oxidation process and mechanism of Mn(II) on manganite surface, and improves the understanding of manganite crystal growth in supergene environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Co doping on the structure and physicochemical properties of hausmannite (Mn 3 O 4 ) and its transformation during aging

Hausmannite is a common low-valence manganese oxide mineral with a distorted spinel structure in surficial sediments. Although natural Mn oxides often contain various transition metal (TM) impurities, few studies have addressed the substitution mechanisms of TMs, such as cobalt (Co), with hausmannite and induced changes in the mineral physicochemical properties. In this study, Co-doped hausmannites with final Co/Mn molar ratios of 0.05 and 0.11 were synthesized and characterized by wet chemical analysis, powder X-ray diffraction (XRD), Fourier transformed infrared spectra (FTIR), high resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure spectroscopy (XAFS). Co-doped samples have larger crystallite sizes and smaller specific surface areas than those of the hausmannite without Co. The Co cations exist in a mixed-valence of +3 and + 2. Powder XRD and acid dissolution experiments indicate that Co incorporates into the mineral structures, and increases the mineral structural stability. Co K-edge extended X-ray adsorption fine structure (EXAFS) analysis demonstrates that Co likely substitutes for lattice Mn(III). After aging at room temperature for three years, 14.1 ± 1.9% of pure hausmannite is transformed to manganite while only 2.6 ± 0.7% of manganite appears in the aged Co-doped sample with an initial Co/Mn molar ratio of 0.10. Finally, these results provide new insights into the incorporation mechanisms of TMs into low valence Mn oxides, and the stability of these minerals in natural environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spatially resolved X-ray imaging and molecular characterisation of sulfur and iron in organic- and sulfur-rich hydrocarbon source mudstones

Sulfurisation of organic matter (OM) is a prominent preservation mechanism, however iron sulfide precipitation, particularly pyrite (FeS2), can counteract this mechanism. There is a dearth of high-resolution, spatially-resolved spectroscopic (redox) information on sulfur and iron inventories within organic-rich rocks that would improve our understanding of prevailing environmental conditions during deposition. Here, state-of-the-art synchrotron-based X-ray absorption and fluorescence analyses of key organic- and sulfur-rich mudstones demonstrate the potential of these techniques to non-destructively map and produce detailed spectroscopic information. Detailed high-resolution analyses (μm- to mm-scale) reveal the presence of widespread sulfurised OM in the Blackstone Band of the Kimmeridge Clay Formation, in line with a persistence of euxinia over a long temporal span and low reactive iron input, facilitating the preservation of OM through sulfurisation. In contrast, the presence of sulfurised OM was transitional in the Monterey Formation, consistent with fluctuating water column redox conditions, and is less significant in the Whitby Mudstone Formation, likely due to the high reactive iron concentrations outcompeting sulfurised OM formation. Analyses of sulfur species using model compounds further indicate that the Whitby Formation is strongly enriched in inorganic reduced sulfur minerals, while both the Kimmeridge Clay and Monterey Formations are dominated by organic sulfur species. These synchrotron-based observations improve our understanding of environmental conditions during the time of deposition of these mudstones and thus show great promise in the study of organic-rich sediments, especially in allowing their depositional settings to be more accurately reconstructed.

Kimmeridge Clay Formation↗

The Co-Transport of PFAS and Cr(VI) in porous media

PFAS and Cr are present at some sites as co-contaminants. Here, the objective of this research was to investigate the co-transport behavior of per- and polyfluoroalkyl substances (PFAS) and hexavalent chromium (Cr(VI)) in porous media. Miscible-displacement experiments were conducted using two soils and an aquifer sediment with different geochemical properties. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were employed as model PFAS. The retardation of PFOS was decreased in the presence of Cr(VI). Conversely, the transport and retardation of PFOA was not affected by the presence of Cr(VI). The reduction of PFOS retardation caused by Cr(VI) is likely due to sorption competition for both organic-carbon and inorganic (metal-oxides and clay minerals) domains. The relative contributions of the three soil constituents to PFOS sorption and the potential for competition between PFOS and Cr(VI) is a function of the geochemical composition of the porous media (i.e., organic carbon, metal-oxides and clay minerals). The PFAS had minimal impact on the retention and transport of Cr(VI). To our knowledge, the results presented herein represent the first reported data for PFOS and Cr(VI) co-transport in porous media. The results of this study indicate that the presence of Cr(VI) has the potential to increase the migration potential of PFOS in soil and groundwater, which should be considered when characterizing electroplating facilities, leather tanning facilities, and other co-contaminated sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical impacts of subsurface CO 2 and brine on shallow groundwater quality

Leakage from geologic CO 2 sequestration (GCS) sites to overlying shallow drinking water aquifers is a tangible risk. A primary purpose of this study is to assess the potential impacts of CO 2 leakage into a fresh-water aquifer with associated CO 2 -water-sediment interactions. Here, the study site is the Ogallala aquifer overlying an active demonstration-scale GCS site in north Texas, USA. Using the results of combined batch experiments and reactive transport simulations, we discuss the effects of salinity on potential trace metal release and the potential for groundwater quality recovery after leakage ceases.

54 ENVIRONMENTAL SCIENCES↗

Association of uranium with macerals in marine black shales: Insights from the Upper Devonian New Albany Shale, Illinois Basin

We report marine organic-rich shales generally have high uranium content associated with sedimentary organic matter. However, organic matter in black shales is not homogeneous, but instead a mixture of different macerals. The uranium content and organic petrographic composition of 27 New Albany Shale samples indicate differential contributions of macerals to the uranium content in the Upper Devonian New Albany Shale of the Illinois Basin. Specifically, uranium is mainly associated with amorphous organic matter (microbially degraded phytoplankton, zooplankton, and bacterial biomass), where an average uranium content of approximately 550 ppm has been estimated. The amorphous organic matter's lack of structure, as well as admixed with mineral grains (<7.8 μm) suggest that it originated via microbial degradation in surficial sediments. Uranium may have been incorporated into amorphous organic matter during phytoplankton degradation and amorphous kerogen formation early in diagenesis. Pore-water redox conditions and pH control the reduction of uranium (VI) and its incorporation into amorphous organic matter. Alginite derived from Tasmanites algae (average uranium content <10 ppm) contributes minimally to uranium content. Terrestrial organic matter in the New Albany Shale contains on average ~ 20 ppm uranium, and because it accounts for <10% of total organic matter in the New Albany Shale, its contribution is equally negligible.

58 GEOSCIENCES↗

Assessing the thermal maturity of black shales using vitrinite reflectance: Insights from Devonian black shales in the eastern United States

Thermal maturity of source rocks indicated by vitrinite reflectance (R o ) is an important and reliable parameter to determine the petroleum potential of sedimentary basins. Originally, R o was used to characterize the degree of coalification of coals and thus works well for coal seams, but it has limitations when used to determine the thermal maturity of black shale successions. A suite of six coal-shale pairs from the Upper Devonian black shale formations in the eastern United States (New Albany Shale, Ohio Shale, Dunkirk Shale, and Rhinestreet Shale) was selected to study the applicability of R o in assessing the thermal maturity of black shale successions. The results show that vitrinite in the studied coal samples is dominated by collotelinite, whereas vitrinite in black shales occurs as small dispersed particles (~5 μm) in the mineral matrix. When comparing the size and morphology of dispersed vitrinite particles in shales and collotelinite fragments in coals, vitrinite in shales and adjacent coals should have the same origin. The measured mean random R o of vitrinite in coals ranges from 0.51–0.68%, and is 0.04–0.11% (average 0.07%) lower than that of dispersed vitrinite particles in enclosing shales. This observation contrasts with previously reported R o suppression in liptinite-rich black shales. A high standard deviation of R o measurements indicates a highly heterogeneous nature of vitrinite in black shales. Three mechanisms can be envisioned to contribute to the higher R o of dispersed vitrinite particles in black shales relative to enclosed coals. First, small vitrinite particles may become more oxidized because small particles are more frequently suspended during transport to the site of deposition and reworking of bottom sediments after deposition than large pieces of driftwood that will turn into enclosed coal lenses during burial diagenesis. Second, misidentification of zooclast (e.g., chitinozoan) fragments as vitrinite due to loss of diagnostic morphology. Third, various macerals in the vitrinite group (e.g., corpogelinite and collotelinite) may have had different original reflectance values. Based on the petrographic characteristics of vitrinite and vitrinite-like particles, caution should be applied when using the R o values of dispersed vitrinite and vitrinite-like particles in black shales as indicators of thermal maturity.

58 GEOSCIENCES↗

Microbial spies and bloggers: programming cells to convert environmental information into discernible signals

Microbes regulate their dynamic behaviors using the chemical and physical characteristics of their environment. The ability of microbes to continuously convert this physicochemical information into biochemical information and to use organic matter in the environment as a power source makes these organisms attractive as chassis for building sensors. However, most biosensors have severe limitations when considering applications in hard-to-image settings like soils, sediments, and wastewater. Emerging technologies at the interface of biomolecular design, microbiome engineering, and synthetic biology offer new tools to program cells and communities as biosensors for these settings. Here, in this review, we describe innovations in biosensor outputs that are enabling new applications in complex environments, including reporters that are read out using electrochemical, gas chromatography, hyperspectral imaging, and next-generation sequencing methods. We also discuss computational advances that are accelerating the diversification of sensing components by mining metagenomics data for new transcriptional regulators and by designing allosteric protein switches that directly regulate reporter outputs using analytes. We highlight emerging opportunities for programming undomesticated microbes in communities to function as distributed sensors in the environment. Finally, we discuss the need for responsible biosensor development and to modernize regulatory frameworks to support evidence-based assessment of environmental biosensors.

analyte↗