Probing Compositional Variation within Hybrid Nanostructures

We present a detailed analysis of the structural and magnetic properties of solution-grown PtCo-CdS hybrid structures in comparison to similar free-standing PtCo alloy nanoparticles. X-ray absorption spectroscopy is utilized as a sensitive probe for identifying subtle differences in the structure of the hybrid materials. We found that the growth of bimetallic tips on a CdS nanorod substrate leads to a more complex nanoparticle structure composed of a PtCo alloy core and thin CoO shell. The core-shell architecture is an unexpected consequence of the different nanoparticle growth mechanism on the nanorod tip, as compared to free growth in solution. Magnetic measurements indicate that the PtCo-CdS hybrid structures are superparamagnetic despite the presence of a CoO shell. The use of X-ray spectroscopic techniques to detect minute differences in atomic structure and bonding in complex nanosystems makes it possible to better understand and predict catalytic or magnetic properties for nanoscale bimetallic hybrid materials

Selenium Biotransformations in an Engineered Aquatic Ecosystem for Bioremediation of Agricultural Wastewater via Brine Shrimp Production

An engineered aquatic ecosystem was specifically designed to bioremediate selenium (Se), occurring as oxidized inorganic selenate from hypersalinized agricultural drainage water while producing brine shrimp enriched in organic Se and omega-3 and omega-6 fatty acids for use in value added nutraceutical food supplements. Selenate was successfully bioremediated by microalgal metabolism into organic Se (seleno-amino acids) and partially removed via gaseous volatile Se formation. Furthermore, filterfeeding brine shrimp that accumulated this organic Se were removed by net harvest. Thriving in this engineered pond system, brine shrimp (Artemia franciscana Kellogg) and brine fly (Ephydridae sp.) have major ecological relevance as important food sources for large populations of waterfowl, breeding, and migratory shore birds. This aquatic ecosystem was an ideal model for study because it mimics trophic interactions in a Se polluted wetland. Inorganic selenate in drainage water was metabolized differently in microalgae, bacteria, and diatoms where it was accumulated and reduced into various inorganic forms (selenite, selenide, or elemental Se) or partially incorporated into organic Se mainly as selenomethionine. Brine shrimp and brine fly larva then bioaccumulated Se from ingesting aquatic microorganisms and further metabolized Se predominately into organic Se forms. Importantly, adult brine flies, which hatched from aquatic larva, bioaccumulated the highest Se concentrations of all organisms tested

Iron Speciation in PM2.5 from Urban, Agriculture, and Mixed Environments in Colorado, USA

Atmospheric iron solubility varies depending on whether the particles are collected in rural or urban areas, with urban areas showing increased iron solubility. In this study, we investigate if the iron species present in different environments affects its ultimate solubility. Field data are presented from the Platte River Air Pollution and Photochemistry Experiment (PRAPPE), aimed at understanding the interactions between organic carbon and trace elements in atmospheric particulate matter (PM). 24-hr PM2.5 samples were collected during the summer and winter (2016–2017), at three different sites on the Eastern Colorado plains: an urban, agricultural, and a mixed site. Downtown Denver had an average total and water-soluble iron air concentration of 181.2 and 7.7 ng m−3, respectively. Platteville, the mixed site, had an average of total iron of 76.1 ng m−3, with average water-soluble iron concentration of 9.1 ng m−3. Jackson State Park (rural/agricultural) had the lowest total iron average of 31.5 ng m−3 and the lowest water-soluble iron average, 1.3 ng m−3. The iron oxidation state and chemical speciation of 97 samples across all sites and seasons was probed by X-ray absorption near edge structure (XANES) spectroscopy. The most common iron phases observed were almandine (Fe₃Al₂Si₃O₁₂) (Denver 21%, Platteville 16%, Jackson 24%), magnetite (Fe3O4) (Denver 9%, Platteville 4%, Jackson 5%) and Fe (III)dextran (Denver 5%, Platteville 13%, Jackson 5%), a surrogate for Fe-organic complexes. Additionally, native iron [Fe(0)] was found in significant amounts at all sites. No correlation was observed between iron solubility and iron oxidation state or chemical speciation

Mixing fraction of inner solar system material in comet 81P/Wild2

The presence of crystalline silicates in the comae of comets, inferred through infrared observations, has been a long-standing puzzle. Crystalline silicates are unexpectedif comets are composed of pristine interstellar material, since interstellar silicates are almost entirely amorphous. Heating to> 1100 K can anneal silicates to crystallinity,but no protoplanetary heating sources have been identified that were sufficiently strong to heat materials in the outer nebula to such high temperatures. This conundrum led to the suggestion that large-scalemixing was important in theprotoplanetary disk. Reports of refractory calcium - aluminum-rich inclusion-like objects and large concentrations of noble gases in Stardust samples underscore the need for such mixing. However, the evidence from the Stardust samples until now has been largely anecdotal, and it has not been possible to place quantitative constraints on the mixing fraction. Here we report synchrotron-based X-ray microprobe measurements of the relative concentrations of the chemical state of iron in material from a known comet, the Jupiter-family comet 81P/Wild2. We find that the comet is rich in iron sulfides. The elemental S/Fe ratio based on the sulfide concentration, S/Fe> 0.31(2 sigma), is higher than in most chondritic meteorites. We also found that Fe-bearing silicates are at least 50percent crystalline. Based on these measurements, we estimate the fraction psi of inner nebular material in 81P/Wild2. With the lower bound on the crystalline Fe-bearing silicate fraction, we find that psi> 0.5. If the observed S depletion in the inner solar system predated or was contemporaneous with large-scale mixing, our lower bound on the S/Fe ratio gives an upper bound on psi of ~;; 0.65. This measurement may be used to test mixing models of the early solar system

Experimental Preservation of Muscle Tissue in Quartz Sand and Kaolinite

Siliciclastic sediments of the Ediacaran Period contain exceptionally preserved fossils of macroscopic organisms, including three-dimensional casts and molds commonly found in sandstones and siltstones and some two-dimensional compressions reported in shales. The sporadic and variable associations of these exceptionally preserved macroscopic fossils with pyrite, clay minerals, and microbial fossils and textures complicate our understanding of fossilization processes. This hinders inferences about the evolutionary histories, tissue types, original morphologies, and lifestyles of the enigmatic Ediacara biota. Here, we investigate the delayed decay of scallop muscles buried in quartz sand or kaolinite for 45 days. This process occurs in the presence of microbial activity in mixed redox environments, but in the absence of thick, sealing microbial mats. Microbial processes that mediate organic decay and release the highest concentrations of silica and Fe(II) into the pore fluids are associated with the most extensive tissue decay. Delayed decay and the preservation of thick muscles in sand are associated with less intense microbial iron reduction and the precipitation of iron oxides and iron sulfides that contain Fe(II) or Fe(III). In contrast, muscles buried in kaolinite are coated only by <10 μm-thick clay veneers composed of kaolinite grains and newly formed K- and Fe(II)-rich aluminosilicate phases. Muscles that undergo delayed decay in kaolinite lose more mass relative to the muscles buried in sand and undergo vertical collapse. These findings show that the composition of minerals that coat or precipitate within the tissues and the vertical dimension of the preserved features can depend on the type of sediment that buries the muscles. Similar processes in the zone of oscillating redox likely facilitated the formation of exceptionally preserved macrofossils in Ediacaran siliciclastic sediments

Selenium tolerance, accumulation, localization and speciation in a Cardamine hyperaccumulator and a non-hyperaccumulator

Cardamine violifolia (family Brassicaceae) is the first discovered selenium hyperaccumulator from the genus Cardamine with unique properties in terms of selenium accumulation, i.e., high abundance of selenolanthionine. In our study, a fully comprehensive experiment was conducted with the comparison of a non-hyperaccumulator Cardamine species, Cardamine pratensis, covering growth characteristics, chlorophyll fluorescence, spatial selenium/sulfur distribution patterns through elemental analyses (synchrotron-based X-Ray Fluorescence and ICP-OES) and speciation data through selenium K-edge micro X-ray absorption near-edge structure analysis (μXANES) and strong cation exchange (SCX)-ICP-MS. The results revealed remarkable differences in contrast to other selenium hyperaccumulators as neither Cardamine species showed evidence of growth stimulation by selenium. Also, selenite uptake was not inhibited by phosphate for either of the Cardamine species. Sulfate inhibited selenate uptake, but the two Cardamine species did not show any difference in this respect. However, μXRF derived speciation maps and selenium/sulfur uptake characteristics provided results that are similar to other formerly reported hyperaccumulator and non-hyperaccumulator Brassicaceae species. μXANES showed organic selenium, "C-Se-C", in seedlings of both species and also in mature C. violifolia plants. In contrast, selenate-supplied mature C. pratensis contained approximately half "C-Se-C" and half selenate. SCX-ICP-MS data showed evidence of the lack of selenocystine in any of the Cardamine plant extracts. Thus, C. violifolia shows clear selenium-related physiological and biochemical differences compared to C. pratensis and other selenium hyperaccumulators

Getting to the Root of Selenium Hyperaccumulation—Localization and Speciation of Root Selenium and Its Effects on Nematodes

Elemental hyperaccumulation protects plants from many aboveground herbivores. Little is known about effects of hyperaccumulation on belowground herbivores or their ecological interactions. To examine effects of plant selenium (Se) hyperaccumulation on nematode root herbivory, we investigated spatial distribution and speciation of Se in hyperaccumulator roots using X-ray microprobe analysis, and effects of root Se concentration on root-associated nematode communities. Perennial hyperaccumulators Stanleya pinnata and Astragalus bisulcatus, collected from a natural seleniferous grassland contained 100–1500 mg Se kg−1 root dry weight (DW). Selenium was concentrated in the cortex and epidermis of hyperaccumulator roots, with lower levels in the stele. The accumulated Se consisted of organic (C-Se-C) compounds, indistinguishable from methyl-selenocysteine. The field-collected roots yielded 5–400 nematodes g−1 DW in Baermann funnel extraction, with no correlation between root Se concentration and nematode densities. Even roots containing \u3e 1000 mg Se kg−1 DW yielded herbivorous nematodes. However, greenhouse-grown S. pinnata plants treated with Se had fewer total nematodes than those without Se. Thus, while root Se hyperaccumulation may protect plants from non-specialist herbivorous nematodes, Se-resistant nematode taxa appear to associate with hyperaccumulators in seleniferous habitats, and may utilize high-Se hyperaccumulator roots as food source. These findings give new insight into the ecological implications of plant Se (hyper)accumulation

Selenium hyperaccumulation offers protection from cell disruptor herbivores

<p>Abstract</p> <p>Background</p> <p>Hyperaccumulation, the rare capacity of certain plant species to accumulate toxic trace elements to levels several orders of magnitude higher than other species growing on the same site, is thought to be an elemental defense mechanism against herbivores and pathogens. Previous research has shown that selenium (Se) hyperaccumulation protects plants from a variety of herbivores and pathogens. Selenium hyperaccumulating plants sequester Se in discrete locations in the leaf periphery, making them potentially more susceptible to some herbivore feeding modes than others. In this study we investigate the protective function of Se in the Se hyperaccumulators <it>Stanleya pinnata </it>and <it>Astragalus bisulcatus </it>against two cell disrupting herbivores, the western flower thrips (<it>Frankliniella occidentalis</it>) and the two-spotted spider mite (<it>Tetranychus urticae</it>).</p> <p>Results</p> <p><it>Astragalus bisulcatus </it>and <it>S. pinnata </it>with high Se concentrations (greater than 650 mg Se kg^-1) were less subject to thrips herbivory than plants with low Se levels (less than 150 mg Se kg^-1). Furthermore, in plants containing elevated Se levels, leaves with higher concentrations of Se suffered less herbivory than leaves with less Se. Spider mites also preferred to feed on low-Se <it>A. bisulcatus </it>and <it>S. pinnata </it>plants rather than high-Se plants. Spider mite populations on <it>A. bisulcatus </it>decreased after plants were given a higher concentration of Se. Interestingly, spider mites could colonize <it>A. bisulcatus </it>plants containing up to 200 mg Se kg^-1dry weight, concentrations which are toxic to many other herbivores. Selenium distribution and speciation studies using micro-focused X-ray fluorescence (μXRF) mapping and Se K-edge X-ray absorption spectroscopy revealed that the spider mites accumulated primarily methylselenocysteine, the relatively non-toxic form of Se that is also the predominant form of Se in hyperaccumulators.</p> <p>Conclusions</p> <p>This is the first reported study investigating the protective effect of hyperaccumulated Se against cell-disrupting herbivores. The finding that Se protected the two hyperaccumulator species from both cell disruptors lends further support to the elemental defense hypothesis and increases the number of herbivores and feeding modes against which Se has shown a protective effect. Because western flower thrips and two-spotted spider mites are widespread and economically important herbivores, the results from this study also have potential applications in agriculture or horticulture, and implications for the management of Se-rich crops.</p

Experimental Preservation of Muscle Tissue in Quartz Sand and Kaolinite

Siliciclastic sediments of the Ediacaran Period contain exceptionally preserved fossils of macroscopic organisms, including three-dimensional casts and molds commonly found in sandstones and siltstones and some two-dimensional compressions reported in shales. The sporadic and variable associations of these exceptionally preserved macroscopic fossils with pyrite, clay minerals, and microbial fossils and textures complicate our understanding of fossilization processes. This hinders inferences about the evolutionary histories, tissue types, original morphologies, and lifestyles of the enigmatic Ediacara biota. Here, we investigate the delayed decay of scallop muscles buried in quartz sand or kaolinite for 45 days. This process occurs in the presence of microbial activity in mixed redox environments, but in the absence of thick, sealing microbial mats. Microbial processes that mediate organic decay and release the highest concentrations of silica and Fe(II) into the pore fluids are associated with the most extensive tissue decay. Delayed decay and the preservation of thick muscles in sand are associated with less intense microbial iron reduction and the precipitation of iron oxides and iron sulfides that contain Fe(II) or Fe(III). In contrast, muscles buried in kaolinite are coated only by <10 μm-thick clay veneers composed of kaolinite grains and newly formed K- and Fe(II)-rich aluminosilicate phases. Muscles that undergo delayed decay in kaolinite lose more mass relative to the muscles buried in sand and undergo vertical collapse. These findings show that the composition of minerals that coat or precipitate within the tissues and the vertical dimension of the preserved features can depend on the type of sediment that buries the muscles. Similar processes in the zone of oscillating redox likely facilitated the formation of exceptionally preserved macrofossils in Ediacaran siliciclastic sediments