High Energy Resolution-X-ray Absorption Near Edge Structure Spectroscopy Reveals Zn Ligation in Whole Cell Bacteria

Identifying the zinc (Zn) ligation and coordination environment in complex biological and environmental systems is crucial to understand the role of Zn as a biologically essential but sometimes toxic metal. Most studies on Zn coordination in biological or environmental samples rely on the extended X-ray absorption fine structure (EXAFS) region of a Zn K-edge X-ray absorption spectroscopy (XAS) spectrum. However, EXAFS analysis cannot identify unique nearest neighbors with similar atomic number (i.e., O versus N) and provides little information on Zn ligation. Herein, we demonstrate that high energy-resolution X-ray absorption near edge structure (HR-XANES) spectroscopy enables the direct determination of Zn ligation in whole cell bacteria, providing additional insights lost from EXAFS analysis at a fraction of the scan time and Zn concentration. HR-XANES is a relatively new technique that has improved our understanding of trace metals (e.g., Hg, Cu, and Ce) in dilute systems. This study is the first to show that HR-XANES can unambiguously detect Zn coordination to carboxyl, phosphoryl, imidazole, and/or thiol moieties in model microorganisms

Uptake and speciation of zinc in edible plants grown in smelter contaminated soils

Heavy metal accumulation in edible plants grown in contaminated soils poses a major environmental risk to humans and grazing animals. This study focused on the concentration and speciation of Zn in different edible plants grown in soils contaminated with smelter wastes (Spelter, WV, USA) containing high levels of the metals Zn, Cu, Pb, Cd. Their accumulation was examined in different parts (roots, stem, and leaves) of plants and as a function of growth stage (dry seed, sprouting seed, cotyledon, and leaves) in the root vegetables radish, the leafy vegetable spinach and the legume clover. Although the accumulation of metals varied significantly with plant species, the average metal concentrations were [Zn] > [Pb] > [Cu] > [Cd]. Metal uptake studies were complemented with bulk and micro X-ray absorption spectroscopy (XAS) at Zn K-edge and micro X-ray fluorescence (μXRF) measurements to evaluate the speciation and distribution of Zn in these plant species. Dynamic interplay between the histidine and malate complexation of Zn was observed in all plant species. XRF mapping of spinach leaves at micron spatial resolution demonstrated the accumulation of Zn in vacuoles and leaf tips. Radish root showed accumulation of Zn in root hairs, likely as ZnS nanoparticles. At locations of high Zn concentration in spinach leaves, μXANES suggests Zn complexation with histidine, as opposed to malate in the bulk leaf. These findings shed new light on the dynamic nature of Zn speciation in plants

Cellular Mercury Coordination Environment, and Not Cell Surface Ligands, Influence Bacterial Methylmercury Production

The conversion of inorganic mercury (Hg(II)) to methylmercury (MeHg) is central to the understanding of Hg toxicity in the environment. Hg methylation occurs in the cytosol of certain obligate anaerobic bacteria and archaea possessing the hgcAB gene cluster. However, the processes involved in Hg(II) biouptake and methylation are not well understood. Here, we examined the role of cell surface thiols, cellular ligands with the highest affinity for Hg(II) that are located at the interface between the outer membrane and external medium, on the sorption and methylation of Hg(II) by Geobacter sulfurreducens. The effect of added cysteine (Cys), which is known to greatly enhance Hg(II) biouptake and methylation, was also explored. By quantitatively blocking surface thiols with a thiol binding ligand (qBBr), we show that surface thiols have no significant effect on Hg(II) methylation, regardless of Cys addition. The results also identify a significant amount of cell-associated Hg-S₃/S₄ species, as studied by high energy-resolution X-ray absorption near edge structure (HR-XANES) spectroscopy, under conditions of high MeHg production (with Cys addition). In contrast, Hg-S₂ are the predominant species during low MeHg production. Hg-S₃/S₄ species may be related to enhanced Hg(II) biouptake or the ability of Hg(II) to become methylated by HgcAB and should be further explored in this context

Chitosan-coated mesoporous MIL-100(Fe) nanoparticles as improved bio-compatible oral nanocarriers

Nanometric biocompatible Metal-Organic Frameworks (nanoMOFs) are promising candidates for drug delivery. Up to now, most studies have targeted the intravenous route, related to pain and severe complications; whereas nanoMOFs for oral administration, a commonly used non-invasive and simpler route, remains however unexplored. We propose here the biofriendly preparation of a suitable oral nanocarrier based on the benchmarked biocompatible mesoporous iron(III) trimesate nanoparticles coated with the bioadhesive polysaccharide chitosan (CS). This method does not hamper the textural/ structural properties and the sorption/release abilities of the nanoMOFs upon surface engineering. The interaction between the CS and the nanoparticles has been characterized through a combination of high resolution soft X-ray absorption and computing simulation, while the positive impact of the coating on the colloidal and chemical stability under oral simulated conditions is here demonstrated. Finally, the intestinal barrier bypass capability and biocompatibility of CS-coated nanoMOF have been assessed in vitro, leading to an increased intestinal permeability with respect to the noncoated material, maintaining an optimal biocompatibility. In conclusion, the preservation of the interesting physicochemical features of the CS-coated nanoMOF and their adapted colloidal stability and progressive biodegradation, together with their improved intestinal barrier bypass, make these nanoparticles a promising oral nanocarrier

Preservation of iron(II) by carbon-rich matrices in a hydrothermal plume

Hydrothermal venting associated with mid-ocean ridge volcanism is globally widespread. This venting is responsible for a dissolved iron flux to the ocean that is approximately equal to that associated with continental riverine runoff. For hydrothermal fluxes, it has long been assumed that most of the iron entering the oceans is precipitated in inorganic forms. However, the possibility of globally significant fluxes of iron escaping these mass precipitation events and entering open-ocean cycles is now being debated, and two recent studies suggest that dissolved organic ligands might influence the fate of hydrothermally vented metals. Here we present spectromicroscopic measurements of iron and carbon in hydrothermal plume particles at the East Pacific Rise mid-ocean ridge. We show that organic carbon-rich matrices, containing evenly dispersed iron(II)-rich materials, are pervasive in hydrothermal plume particles. The absence of discrete iron(II) particles suggests that the carbon and iron associate through sorption or complexation. We suggest that these carbon matrices stabilize iron(II) released from hydrothermal vents in the region, preventing its oxidation and/or precipitation as insoluble minerals. Our findings have implications for deep-sea biogeochemical cycling of iron, a widely recognized limiting nutrient in the oceans

Chemically and Geographically distinct solid-phase iron pools in the Southern Ocean

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Kinetic and thermal decomposition of ettringite synthesized from aqueous solutions

The kinetics of the thermal decomposition of a synthetic ettringite sample was studied between 298 and 820 K in an inert atmosphere for the present work. The ettringite and its thermal decomposition products were characterized using X-ray diffraction, infrared spectroscopy, and scanning electron microscopy. Four endothermic events were observed with thermogravimetry curves, the maxima of which occurred at 366, 397, 537, and 641 K. All events were associated with the loss of water molecules with different degrees of interaction within the ettringite structure. Chemical equations for each decomposition step were proposed based on the percentages of mass loss observed. In addition, for the first time, the activation energies of each ettringite decomposition events were determined by the isoconversional methods of Ozawa–Flynn–Wall, Friedman, and Kissinger–Akahira– Sunose. The modeling revealed that the activation energy varied from *50 kJ mol-1, characteristic of mass transfer control steps, to *150 kJ mol-1, which is typical of chemical control, as the temperature increased and the ettringite structure lost water. A total of 32 mol of water was released equivalent to 43.1 % of the initial sample mass