The adsorption of metals and other elements onto environmental plastics has been previously quantified and is known to be enhanced by surface-weathering and development of biofilms. However, further ...biofilm-adsorption characterisation is needed with respect to the fate of radionuclides. This study uses spectroscopy, microscopy and radiotracer methods to investigate the adsorption capacity of relatively strong and weak cations onto different microplastic sample types that were conditioned in freshwater, estuarine and marine conditions although marine data were limited. Fourier-transform infrared spectroscopy confirmed that surface oxidation chemistry changes induced by gamma irradiation were similar to those resulting from environmental exposures. Microscopy elemental mapping revealed patchy biofilm development, which contained Si, Al, and O, consistent with microbial-facilitated capture of clays. The plastics+biofilm of all sample types had measurable adsorption for Cs and Sr radiotracers, suggesting environmental plastics act broadly as a sink for the key pervasive environmental radionuclides of 137Cs and 90Sr associated with releases from nuclear activities. Adsorption onto high-density polyethylene plastic types was greater than that on polypropylene. However, in most cases, the adsorption rates of all types of plastic+biofilm were much lower than those of reference sediments and roughly consistent with their relative exchangeable surface areas.
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•Differing types of microplastics were deployed in various aquatic systems.•Surface weathering by gamma irradiation simulated environmental exposures.•Microscopy revealed patchy biofilm development on microplastic surfaces.•The elements associated with biofilm were dominated by the clay indicators Al, Si, and O.•The plastics+biofilm adsorbed Cs and Sr cations, but not as strongly as sediments.
Leaf trichomes are not part of the primary pathway through which foliar-applied Zn fertilizer moves across the leaf surface in soybean and tomato.
Abstract
The present study investigated the role of ...trichomes in absorption of foliar-applied zinc fertilizers in soybean and tomato. Using synchrotron-based X-ray fluorescence microscopy for in situ analyses of hydrated leaves, we found that upon foliar application of ZnSO4, Zn accumulated within 15 min in some non-glandular trichomes in soybean, but not in tomato. However, analyses of cross-sections of soybean leaves did not show any marked accumulation of Zn in tissues surrounding trichomes. Furthermore, when near-isogenic lines of soybean differing 10-fold in trichome density were used to compare Zn absorption, it was found that foliar Zn absorption was not related to trichome density. Therefore, it is suggested that trichomes are not part of the primary pathway through which foliar-applied Zn moves across the leaf surface in soybean and tomato. However, this does not preclude trichomes being important in other plant species, as they are known to be highly diverse. We also compared the absorption of Zn when supplied as either ZnSO4, nano-ZnO, or bulk-ZnO, and found that absorption from ZnSO4 was about 10-fold higher than from nano- and bulk-ZnO, suggesting that it was mainly absorbed as soluble Zn. This study improves our understanding of the absorption of foliar-applied nutrients.
Metals and metalloids play a key role in plant and other biological systems as some of them are essential to living organisms and all can be toxic at high concentrations. It is therefore important to ...understand how they are accumulated, complexed and transported within plants. In situ imaging of metal distribution at physiological relevant concentrations in highly hydrated biological systems is technically challenging. In the case of roots, this is mainly due to the possibility of artifacts arising during sample preparation such as cross sectioning. Synchrotron x-ray fluorescence microtomography has been used to obtain virtual cross sections of elemental distributions. However, traditionally this technique requires long data acquisition times. This has prohibited its application to highly hydrated biological samples which suffer both radiation damage and dehydration during extended analysis. However, recent advances in fast detectors coupled with powerful data acquisition approaches and suitable sample preparation methods can circumvent this problem. We demonstrate the heightened potential of this technique by imaging the distribution of nickel and zinc in hydrated plant roots. Although 3D tomography was still impeded by radiation damage, we successfully collected 2D tomograms of hydrated plant roots exposed to environmentally relevant metal concentrations for short periods of time. To our knowledge, this is the first published example of the possibilities offered by a new generation of fast fluorescence detectors to investigate metal and metalloid distribution in radiation-sensitive, biological samples.
The infrared and near-infrared spectra of acetylacetone, acetylacetone-d 8, and hexafluoroacetylacetone are characterized from experiment and computations at different levels. In the fundamental ...region, the intramolecular hydrogen bonded OH-stretching transition is clearly observed as a very broad band with substantial structure and located at significantly lower frequency compared to common OH-stretching frequencies. There is no clear evidence for OH-stretching overtone transitions in the near-infrared region, which is dominated by the CH-stretching overtones of the methine and methyl CH bonds. From molecular dynamics (MD) simulations, with a potential energy surface previously validated for tunneling splittings, the infrared spectra are determined and used in assigning the experimentally measured ones. It is found that the simulated spectrum in the region associated with the proton transfer mode is exquisitely sensitive to the height of the barrier for proton transfer. Comparison of the experimental and the MD simulated spectra establishes that the barrier height is around 2.5 kcal/mol, which favorably compares with 3.2 kcal/mol obtained from high-level electronic structure calculations.
Consumption of rice (Oryza sativa) is the major dietary source of cadmium (Cd) for populations with rice as the staple. Little is known about the distribution and chemical speciation of Cd in rice ...grain, which is critical in determining the bioavailability of Cd to humans. We used synchrotron-based techniques for analyses of the speciation and distribution of Cd in rice grain. The majority of the Cd in rice grain was present as Cd–thiolate complexes (66–92%), likely in the form of Cd bound with thiol-rich proteins. The remainder was present as Cd–carboxyl compounds and Cd–histidine. Elemental mapping showed two different patterns of Cd distribution, one with an even distribution throughout the entire grain and the other with a preferential distribution in the outer tissues (aleurone layer and outer starchy endosperm). The distribution pattern is important as it affects the removal of Cd during milling. On average, milling reduced grain Cd concentrations by 23.5% (median of 27.5%), although the range varied widely from a 64.7% decrease to a 22.2% increase, depending upon the concentration of Cd in the bran. We found that the variation in the distribution pattern of Cd in the rice grain was due to a temporal change in the supply of Cd from the soil porewater during grain filling. These results have important implications for Cd bioavailability in human diets.
Soil acidity and waterlogging increase manganese (Mn) in leaf tissues to potentially toxic concentrations, an effect reportedly alleviated by increased silicon (Si) and phosphorus (P) supply.
Effects ...of Si and P on Mn toxicity were studied in four plant species using synchrotron-based micro X-ray fluorescence (μ-XRF) and nanoscale secondary ion mass spectrometry (NanoSIMS) to determine Mn distribution in leaf tissues and using synchrotron-based X-ray absorption spectroscopy (XAS) to measure Mn speciation in leaves, stems and roots.
A concentration of 30 μM Mn in solution was toxic to cowpea and soybean, with 400 μM Mn toxic to sunflower but not white lupin. Unexpectedly, μ-XRF analysis revealed that 1.4mMSi in solution decreased Mn toxicity symptoms through increased Mn localization in leaf tissues. NanoSIMS showed Mn and Si co-localized in the apoplast of soybean epidermal cells and basal cells of sunflower trichomes. Concomitantly, added Si decreased oxidation of Mn(II) to Mn(III) and Mn(IV). An increase from 5 to 50 μMP in solution changed some Mn toxicity symptoms but had little effect on Mn distribution or speciation.
We conclude that Si increases localized apoplastic sorption of Mn in cowpea, soybean and sunflower leaves thereby decreasing free Mn2+ accumulation in the apoplast or cytoplasm.
A novel binding layer (BL) as part of the diffusive gradients in thin films (DGT) technique was developed for the two-dimensional visualization and quantification of labile phosphorus (P) in soils. ...This BL was designed for P detection by synchrotron-based X-ray fluorescence microscopy (XFM). It differs from the conventional DGT BL as the hydrogel is eliminated to overcome the issue that the fluorescent X-rays of P are detected mainly from shallow sample depths. Instead, the novel design is based on a polyimide film (Kapton) onto which finely powdered titanium dioxide-based P binding agent (Metsorb) was applied, resulting in superficial P binding only. The BL was successfully used for quantitative visualization of P diffusion from three conventional P fertilizers applied to two soils. On a selection of samples, XFM analysis was confirmed by quantitative laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The XFM method detected significant differences in labile P concentrations and P diffusion zone radii with the P fertilizer incubation, which were explained by soil and fertilizer properties. This development paves the way for fast XFM analysis of P on large DGT BLs to investigate in situ diffusion of labile P from fertilizers and to visualize large-scale P cycling processes at high spatial resolution.
The XFM beamline at the Australian Synchrotron Howard, Daryl L.; de Jonge, Martin D.; Afshar, Nader ...
Journal of synchrotron radiation,
September 2020, 2020-09-01, 20200901, Letnik:
27, Številka:
5
Journal Article
Recenzirano
The X‐ray fluorescence microscopy (XFM) beamline is an in‐vacuum undulator‐based X‐ray fluorescence (XRF) microprobe beamline at the 3 GeV Australian Synchrotron. The beamline delivers hard X‐rays in ...the 4–27 keV energy range, permitting K emission to Cd and L and M emission for all other heavier elements. With a practical low‐energy detection cut‐off of approximately 1.5 keV, low‐Z detection is constrained to Si, with Al detectable under favourable circumstances. The beamline has two scanning stations: a Kirkpatrick–Baez mirror microprobe, which produces a focal spot of 2 µm × 2 µm FWHM, and a large‐area scanning `milliprobe', which has the beam size defined by slits. Energy‐dispersive detector systems include the Maia 384, Vortex‐EM and Vortex‐ME3 for XRF measurement, and the EIGER2 X 1 Mpixel array detector for scanning X‐ray diffraction microscopy measurements. The beamline uses event‐mode data acquisition that eliminates detector system time overheads, and motion control overheads are significantly reduced through the application of an efficient raster scanning algorithm. The minimal overheads, in conjunction with short dwell times per pixel, have allowed XFM to establish techniques such as full spectroscopic XANES fluorescence imaging, XRF tomography, fly scanning ptychography and high‐definition XRF imaging over large areas. XFM provides diverse analysis capabilities in the fields of medicine, biology, geology, materials science and cultural heritage. This paper discusses the beamline status, scientific showcases and future upgrades.
The X‐ray fluorescence microscopy (XFM) beamline at the Australian Synchrotron specializes in the spatially resolved detection and speciation determination of elements at the micrometre length scale. The status of its various operational modes and future upgrades are presented.
The choroid plexus and cerebral ventricles are critical structures for the production of cerebral spinal fluid (CSF) and play an important role in regulating ion and metal transport in the brain, ...however many aspects of its roles in normal physiology and disease states, such as psychiatric illness, remain unknown. The choroid plexus is difficult to examine in vivo, and in situ ex vivo, and as such has typically been examined indirectly with radiolabeled tracers or ex vivo stains, making measurements of the endogenous K+, Cl-, and Ca+ distributions unreliable. In the present study, we directly examined the distribution of endogenous ions and biologically relevant transition metals in the choroid plexus and regions surrounding the ventricles (ventricle wall, cortex, corpus callosum, striatum) using X-ray fluorescence imaging (XFI). We find that the choroid plexus was rich in Cl- and Fe while K+ levels increase further from the ventricle as Cl- levels decrease, consistent with the known role of ion transporters in the choroid plexus CSF production. A polyI:C offspring displayed enlarged ventricles, elevated Cl- surrounding the ventricles, and intraventricular calcifications. These observations fit with clinical findings in patients with schizophrenia and suggest maternal treatment with polyI:C may lead to dysfunctional ion regulation in offspring. This study demonstrates the power of XFI for examining the endogenous elemental distributions of the ventricular system in healthy brain tissue as well as disease models.
The distribution and substitution mechanism of Ge in the Ge-rich sphalerite from the Tres Marias Zn deposit, Mexico, was studied using a combination of techniques at μm- to atomic scales. Trace ...element mapping by Laser Ablation Inductively Coupled Mass Spectrometry shows that Ge is enriched in the same bands as Fe, and that Ge-rich sphalerite also contains measurable levels of several other minor elements, including As, Pb and Tl. Micron- to nanoscale heterogeneity in the sample, both textural and compositional, is revealed by investigation using Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) combined with Synchrotron X-ray Fluorescence mapping and High-Resolution Transmission Electron Microscopy imaging of FIB-prepared samples. Results show that Ge is preferentially incorporated within Fe-rich sphalerite with textural complexity finer than that of the microbeam used for the X-ray Absorption Near Edge Structure (XANES) measurements. Such heterogeneity, expressed as intergrowths between 3C sphalerite and 2H wurtzite on zones, could be the result of either a primary growth process, or alternatively, polystage crystallization, in which early Fe-Ge-rich sphalerite is partially replaced by Fe-Ge-poor wurtzite. FIB-SEM imaging shows evidence for replacement supporting the latter. Transformation of sphalerite into wurtzite is promoted by (111)* twinning or lattice-scale defects, leading to a heterogeneous ZnS sample, in which the dominant component, sphalerite, can host up to ~20% wurtzite. Ge K-edge XANES spectra for this sphalerite are identical to those of the germanite and argyrodite standards and the synthetic chalcogenide glasses GeS2 and GeSe2, indicating the Ge formally exists in the tetravalent form in this sphalerite. Fe K-edge XANES spectra for the same sample indicate that Fe is present mainly as Fe2+, and Cu K-edge XANES spectra are characteristic for Cu+. Since there is no evidence for coupled substitution involving a monovalent element, we propose that Ge4+ substitutes for (Zn2+, Fe2+) with vacancies in the structure to compensate for charge balance. This study shows the utility of synchrotron radiation combined with electron beam micro-analysis in investigating low-level concentrations of minor metals in common sulfides.
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