Zinc Sorption to Three Gram-Negative Bacteria: Combined Titration, Modeling, and EXAFS Study

The acid-base and Zn sorption properties of three bacteria, Cupriavidus metallidurans CH34, Pseudomonas putida ATCC12633, and Escherichia coli K12DH5R, were investigated through an original combination of extended X-ray absorption fine structure (EXAFS) spectroscopy and equilibrium titration studies. Acid-base titration curves of the three strains were fitted with a model accounting for three conceptual reactive sites: an acidic (carboxyl and/ or phosphodiester), a neutral (phosphomonoester), and a basic (amine and/or hydroxyl) group. Calculated proton and Zn equilibrium constants and site densities compare with literature data. The nature of Zn binding sites was studied by EXAFS spectroscopy. Phosphoester, carboxyl, and unexpectedly sulfhydryl ligands were identified. Their proportions depended on Zn loading and bacterial strain and were consistent with the titration results. These findings were compared to the structure and site density of the major cell wall components. It appeared that the cumulated theoretical site density of these structures (<2 Zn nm-2) was much lower than the total site density of the investigated strains (16-56 Zn nm-2). These results suggest a dominant role of extracellular polymeric substances in Zn retention processes, although Zn binding to inner cell components cannot be excluded

Chemical forms of selenium in the metal-resistant bacterium Ralstonia metallidurans CH34 exposed to selenite and selenate

International audienceRalstonia metallidurans CH34, a soil bacterium resistant to a variety of metals, is known to reduce selenite to intracellular granules of elemental selenium (Se0). We have studied the kinetics of selenite (SeIV) and selenate (SeVI) accumulation and used X-ray absorption spectroscopy to identify the accumulated form of selenate, as well as possible chemical intermediates during the transformation of these two oxyanions. When introduced during the lag phase, the presence of selenite increased the duration of this phase, as previously observed. Selenite introduction was followed by a period of slow uptake, during which the bacteria contained Se0 and alkyl selenide in equivalent proportions. This suggests that two reactions with similar kinetics take place: an assimilatory pathway leading to alkyl selenide, and a slow detoxification pathway leading to Se0. Subsequently, selenite uptake strongly increased (up to 340 mg Se per g of proteins), and Se0 was the predominant transformation product, suggesting an activation of selenite transport and reduction systems after several hours of contact. Exposure to selenate did not induce an increase in the lag phase duration and the bacteria accumulated approximately 25 fold less Se than when exposed to selenite. SeIV was detected as transient species in the first 12 hours after selenate introduction, Se0 also occurred as minor species, and the major accumulated form was alkyl selenide. Thus, in the present experimental conditions selenate mostly follows an assimilatory pathway, and the reduction pathway is not activated upon selenate exposure. These results show that R. metallidurans CH34 may be suitable for the remediation of selenite - but not selenate -contaminated environments

Zinc distribution and speciation in Arabidopsis halleri x Arabidopsis lyrata progenies presenting various zinc accumulation capacities

The definitive version is available at http://www.blackwell-synergy.com/loi/nphInternational audienceThe purpose of this study was to investigate the relationship between the chemical form and localization of zinc (Zn) in plant leaves and their Zn accumulation capacity. * An interspecific cross between Arabidopsis halleri sp. halleri and Arabidopsis lyrata sp. petrea segregating for Zn accumulation was used. Zinc (Zn) speciation and Zn distribution in the leaves of the parent plants and of selected F1 and F2 progenies were investigated by spectroscopic and microscopic techniques and chemical analyses. * A correlation was observed between the proportion of Zn being in octahedral coordination complexed to organic acids and free in solution (Zn-OAs + Znaq) and Zn content in the leaves. This pool varied between 40% and 80% of total leaf Zn depending on the plant studied. Elemental mapping of the leaves revealed different Zn partitioning between the veins and the leaf tissue. The vein : tissue fluorescence ratio was negatively correlated with Zn accumulation. * The higher proportion of Zn-OAs + Znaq and the depletion of the veins in the stronger accumulators are attributed to a higher xylem unloading and vacuolar sequestration in the leaf cells. Elemental distributions in the trichomes were also investigated, and results support the role of carboxyl and ⁄ or hydroxyl groups as major Zn ligands in these cells

Zinc distribution and speciation in Arabidopsis halleri x Arabidops is lyrata progenies presenting various zinc accumulation capacities

- The purpose of this study was to investigate the relationship between the chemical form and localization of zinc (Zn) in plant leaves and their Zn accumulation capacity. - An interspecific cross between Arabidopsis halleri sp. halleri and Arabidopsis lyrata sp. petrea segregating for Zn accumulation was used. Zinc (Zn) speciation and Zn distribution in the leaves of the parent plants and of selected F1 and F2 progenies were investigated by spectroscopic and microscopic techniques and chemical analyses. - A correlation was observed between the proportion of Zn being in octahedral coordination complexed to organic acids and free in solution (Zn?OAs + Znaq) and Zn content in the leaves. This pool varied between 40percent and 80percent of total leaf Zn depending on the plant studied. Elemental mapping of the leaves revealed different Zn partitioning between the veins and the leaf tissue. The vein : tissue fluorescence ratio was negatively correlated with Zn accumulation. - The higher proportion of Zn?OAs + Znaq and the depletion of the veins in the stronger accumulators are attributed to a higher xylem unloading and vacuolar sequestration in the leaf cells. Elemental distributions in the trichomes were also investigated, and results support the role of carboxyl and ⁄ or hydroxyl groups as major Zn ligands in these cells

Comment on “Speciation and fate of toxic cadmium in contaminated paddy soils and rice using XANES/EXAFS spectroscopy”

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Sampling, defining, characterising and modelling the rhizosphere - The soils science toolbox

International audienceWe review methods and models that help to assess how root activity changes soil properties and affects the fluxes of matter in the soil. Subsections discuss (1) experimental systems including plant treatments in artificial media, studying the interaction of model root and microbial exudates with soil constituents, and microcosms to distinguish between soil compartments differing in root influence, (2) the sampling and characterization of rhizosphere soil and solution, focusing on the separation of soil at differentdistances from roots and the spatially resolved sampling of soil solution, (3) cutting-edge methodologies to study chemical effects in soil, including the estimation of bioavailable element or ion contents (biosensors, diffusive gradients in thin-films), studying the ultrastructure of soil components, localizing elements and determining their chemical form (microscopy, diffractometry, spectroscopy), tracing the compartmentalization of substances in soils (isotope probing, autoradiography), and imaging gradients insitu with micro electrodes or gels or filter papers containing dye indicators, (4) spectroscopic and geophysical methods to study the plants influence on the distribution of water in soils, and (5) the modeling of rhizosphere processes. Macroscopic models with a rudimentary depiction of rhizosphere processes are used to predict water or nutrient requirements by crops and forests, to estimate biogeochemical element cycles, to calculate soil water transport on a profile scale, or to simulate the development of root systems. Microscopic or explanatory models are based on mechanistic or empirical relations that describe processes on a single root or root system scale and/or chemical reactions in soil solution. We conclude that in general we have the tools at hand to assess individual processes on the microscale under rather artificial conditions. Microscopic, spectroscopic and tracer methods to look at processes in small “aliquots” of naturally structured soil seem to step out of their infancy and have become promising tools to better understand the complex interactions between plant roots, soil and microorganisms. On the field scale, while there are promising first results on using non-invasive geophysical methods to assess the plant's influence on soil moisture, there are no such tools in the pipeline to assess the spatial heterogeneity of chemical properties and processes in the field. Here, macroscopic models have to be used, or model results on the microscopic level have to be scaled up to the whole plant or plot scale. Upscaling is recognized as a major challenge

A critical review on the impacts of nanoplastics and microplastics on aquatic and terrestrial photosynthetic organisms

International audienceMicroplastic and nanoplastic contamination is widespread and affects aquatic and terrestrial ecosystems. Photosynthetic organisms are present in both media, they are primary producers, sink for CO2, and they represent a major point of entry in the food chain. Here, the current knowledge on the fate and impacts of microplastics and nanoplastics in interaction with these organisms has been reviewed. As a general trend, plastic characteristics (smaller size and positive charge) play a crucial role in their toxicity towards photosynthetic organisms. Plastic leachates (containing additives) represent also a major source of toxicity, and some harmful compounds such as phthalate esters have been shown to accumulate in plants and generate a risk for the consumers. Adsorption of plastic particles has been evidenced for each type of photosynthetic organism, and uptake and translocation in terrestrial plants was evidenced for nanoplastics, leading to concerns for trophic chain contamination. The available techniques for the detection of microplastics and nanoplastics and their secondary products in biological samples and media are also listed. Finally, the current gaps of knowledge, specific challenges, and future research directions were also discussed

Changes of Cadmium Storage Forms and Isotope Ratios in Rice During Grain Filling

International audienceRice poses a major source of the toxic contaminant cadmium (Cd) for humans. Here, we elucidated the role of Cd storage forms (i.e., the chemical Cd speciation) on the dynamics of Cd within rice. In a pot trial, we grew rice on a Cd-contaminated soil in upland conditions and sampled roots and shoots parts at flowering and maturity. Cd concentrations, isotope ratios, Cd speciation (X-ray absorption spectroscopy), and micronutrient concentrations were analyzed. During grain filling, Cd and preferentially light Cd isotopes were strongly retained in roots where the Cd storage form did not change (Cd bound to thiols, Cd–S = 100%). In the same period, no net change of Cd mass occurred in roots and shoots, and the shoots became enriched in heavy isotopes (Δ 114/110 Cd maturity–flowering = 0.14 ± 0.04‰). These results are consistent with a sequestration of Cd in root vacuoles that includes strong binding of Cd to thiol containing ligands that favor light isotopes, with a small fraction of Cd strongly enriched in heavy isotopes being transferred to shoots during grain filling. The Cd speciation in the shoots changed from predominantly Cd–S (72%) to Cd bound to O ligands (Cd–O, 80%) during grain filling. Cd–O may represent Cd binding to organic acids in vacuoles and/or binding to cell walls in the apoplast. Despite this change of ligands, which was attributed to plant senescence, Cd was largely immobile in the shoots since only 0.77% of Cd in the shoots were transferred into the grains. Thus, both storage forms (Cd–S and Cd–O) contributed to the retention of Cd in the straw. Cd was mainly bound to S in nodes I and grains (Cd–S &gt; 84%), and these organs were strongly enriched in heavy isotopes compared to straw (Δ 114/110 Cd grains/nodes– straw = 0.66–0.72‰) and flag leaves (Δ 114/110 Cd grains/nodes–flag leaves = 0.49–0.52‰). Hence, xylem to phloem transfer in the node favors heavy isotopes, and the Cd–S form may persist during the transfer of Cd from node to grain. This study highlights the importance of Cd storage forms during its journey to grain and potentially into the food chain

Zinc distribution and speciation in roots of various genotypes of tobacco exposed to Zn

International audienceCell walls of roots have a great reactivity towards metals, and may act as a barrier limiting the entry of metals, especially in non-hyperaccumulating species. The aim of this study was to determine the localization and speciation of Zn in roots of tobacco (Nicotiana tabacum) grown in Zn-contaminated substrates. Chemical extractions and EXAFS spectroscopy were applied on whole roots and on isolated cell walls of roots. Our results show that cell walls of roots exhibited a distribution of Zn affinity sites, from water-soluble to non-exchangeable Zn. In whole roots, Zn was bound with oxalate and other COOH/OH groups: the first species was probably intracellular while the second was attributed to Zn bound to the cell walls and, to a lesser extent, to intracellular organic acids. Moreover, Zn-phosphate was also identified, and this species was CuSO4-extractable. It probably resulted from chemical precipitation in the apoplasm, and explained the steady increase in exchangeable root Zn observed in root of tobacco during the culture. This study shows the strength of combining EXAFS and chemical extractions for studying localization and speciation of metals in plant

Lung distribution, quantification, co-localization and speciation of silver nanoparticles after lung exposure in mice

Large knowledge gaps still exist on the toxicological mechanisms of silver (Ag) engineered nanoparticles (ENPs); a comprehensive understanding of the sources, biodistribution, toxicity and transformation of Ag ENPs along their life cycle and after transfer in living organisms is needed. In a previous study, mice were pulmonary exposed to Ag ENPs and local (lung) and systemic toxic effects together with biodistribution to organs including heart, liver, spleen and kidney were investigated. Here, Ag lung distribution, local concentration, co-localization with other elements such as Fe, Cu and S, and speciation were determined after lung exposure to Ag ENPs using micro X-ray fluorescence (μXRF), micro X-ray absorption near edge structure spectroscopy (μXANES) and micro proton-induced X-ray emission (μPIXE) techniques. We found that approximately a quarter of all macrophages in the lumen of the airways contained ENPs. High local concentrations of Ag were also detected in the lung tissue, probably phagocytized by macrophages. The largest part of the ENPs was dissolved and complexed to thiol-containing molecules. Increased concentrations of Fe and Cu observed in the Ag-rich spots suggest that these molecules are metallothioneins (MTs). These results give more insights on the behavior of Ag ENPs in the lung in vivo and will help in the understanding of the toxicological mechanisms of Ag ENPs.publisher: Elsevier articletitle: Lung distribution, quantification, co-localization and speciation of silver nanoparticles after lung exposure in mice journaltitle: Toxicology Letters articlelink: http://dx.doi.org/10.1016/j.toxlet.2015.07.001 content_type: article copyright: Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.status: publishe