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Environmental science & technology 57(7), 2768 - 2778 (2023). doi:10.1021/acs.est.2c06985, Rare earth elements (REEs) are strategic metals strongly involved in low-carbon energy conversion. However, these emerging contaminants are increasingly disseminated into ecosystems, raising concern regarding their toxicity. REE-accumulating plants are crucial subjects to better understand REE transfer to the trophic chain but are also promising phytoremediation tools. In this analysis, we deciphered REE accumulation sites in the REE-accumulating fern Dryopteris erythrosora by synchrotron X-ray μfluorescence (μXRF). This technique allows a high-resolution and in situ analysis of fresh samples or frozen-hydrated cross sections of different organs of the plant. In the sporophyte, REEs were translocated from the roots to the fronds by the xylem sap and were stored within the xylem conductive system. The comparison of REE distribution and accumulation levels in the healthy and necrotic parts of the frond shed light on the differential mobility between light and heavy REEs. Furthermore, the comparison emphasized that necrotized areas were not the main REE-accumulating sites. Finally, the absence of cell-to-cell mobility of REEs in the gametophyte suggested the absence of REE-compatible transporters in photosynthetic tissues. These results provide valuable knowledge on the physiology of REE-accumulating ferns to understand the REE cycle in biological systems and the expansion of phytotechnologies for REE-enriched or REE-contaminated soils., Published by American Chemical Society, Columbus, Ohio

While our awareness of the toxicity of rare earth elements to aquatic organisms increases, our understanding of their direct interaction and accumulation remains limited. This study describes the acute toxicity...

International audience; Silver biodistribution and gut toxicity of two commercially available colloidal silver products, Mesosilver™ and AgC, were evaluated in male mice. AgC is composed solely of ionic silver (Ag+) while Mesosilver™ contains a mix of silver nanoparticles (AgNPs) and Ag+ ions. After high-dose (approximately 3 mg per kg body weight (bw) per day) sub-chronic exposure, silver accumulation was close for Mesosilver™ and AgC. The combination of micro X-ray fluorescence and micro X-ray absorption spectroscopy showed that metallic AgNPs and Ag+ ions initially contained in Mesosilver™ were subjected to physicochemical modifications during their fate in the gut. In the colon, most Ag atoms were oxidized and dissolved to form Ag complexes with thiol groups (-SH) of proteins and/or peptides. Sub-chronic exposure at lower dose (150 μg per kg bw per day) led to a moderate impact on the gut barrier for both colloidal silver products. An increase in colonic LCN-2 was observed only after AgC exposure. For gut microbiota at the genus level, exposure to Mesosilver™ led to a decrease in Ruminococcus and Anaerosporobacter, while Intestinimonas increased. Exposure to AgC resulted in an increase in Clostridium sp. ASF356 and Tyzzerella, while the relative abundance of Anaerosporobacter decreased. In addition, the Saccharomycetes fungal population increased. Near-infrared spectroscopy was able to satisfactorily discriminate the Mesosilver™-vs. AgC-exposed mice for both exposure doses. This study highlights the applicability of biophysics-based methodologies for providing novel insights into colloidal silver uptake, fate and toxicological effects after oral exposure

Since the 1980's the uses, and thus mining, of Rare EarthElements (REE) have grown exponentially. This has led toquestions about the impact of REE on the environment, and REEbeing designated emerging pollutants. Currently, knowledgeabout the behaviour of REE in the environment is stillincomplete. For example, there are few studies on REEadsorption on iron (Fe) (oxy)hydroxides, which are consideredkey carriers of metal pollution, and on the other factorscontrolling this adsorption [1-4]. Knowing that in natural(oxy)hydroxides, Fe is frequently substituted by other elementsin the environment in which they form, we were interested in theeffect of these substitutions on the adsorption capacity of(oxy)hydroxides towards REE.This study focusses on aluminium (Al, common in naturalenvironments and easily substituted into Fe-oxyhydroxides) andgallium (Ga, chemical analogue to Al) substitutions in goethite(Goe), representative of commonly found Fe-(oxy)hydroxideswhose well-defined structure allows for modelling of sorptionand surface interactions. For this purpose, experiments of REEwere conducted on pure and substituted goethites (Goe) withvarying Al and Ga content.A characterisation of these goethites, shows that thesubstitution does not affect the shape, size, and specific surfacearea significantly. Nevertheless, the REE adsorption patterns areaffected by substitutions: 5% substitution decreases the sorptioncapacity of the goethite, and at 10% substitution the preferredadsorption of the mid and heavy REE diminishes, resulting in a'flatter' pattern. Meanwhile, the Neodymium (Nd) L3-edgeEXAFS experiments show no modification of its binding modeto the Goe surfaces, forming corner sharing bidentate-binuclearcomplexes regardless of the substitution rate. However, TEMobservations and Cerium (Ce) L 3-edge XANES experimentsdemonstrate that the Ga substitution favours a higher Ce(IV)O2adsorption, while the Al substitution favours Ce(III) adsorptioncompared to the pure Goe.These results reveal the large impact of substitutions on thereactivity of goethite towards REE.

International audience; In this study, we investigate the interactions between the cellulose surface and Ag nanoparticles (AgNPs) for the purpose of manufacturing hybrid nanomaterials using bacterial cellulose nanocrystals (BCNs) as a model substrate. We focus on the role of the BCN surface chemistry on the AgNP nucleation obtained by chemical reduction of Ag+ ions. Homogeneous hybrid suspensions of BCN/AgNP are produced, regardless of whether the BCNs are quasi-neutral, negatively (TBCNs) or positively charged (ABCNs). The characterization of BCN/AgNP hybrids identifies the –OH surface groups as nucleation points for AgNPs, of about 20 nm revealing that surface charges only improve the accessibility to OH groups. X-ray Absorption technics (XANES and EXAFS) revealed a high metallic Ag0 content ranging from 88% to 97%. Moreover, the grafting of hydrophobic molecules on a BCN surface (HBCNs) does not prevent AgNP nucleation, illustrating the versatility of our method and the possibility to obtain bifunctional NPs. A H2O2 redox post-treatment on the hybrid induces an increase in AgNPs size, up to 90 nm as well as a shape variation (i.e., triangular). In contrast, H2O2 induces no size/shape variation for aggregated hybrids, emphasizing that the accessibility to –OH groups ensures the nucleation of bigger Ag nano-objects.

International audience; Iron-organic matter (Fe-OM) aggregates are a key factor in the control of pollutant mobility. Their physical and structural organization depends on the prevailing physicochemical conditions during their formation and on subsequent exposure to variations in porewater goechemistry. Among these conditions, calcium (Ca) could be a major parameter given its high concentrations in the environment and its affinity for OM. Mimetic environmental Fe-OM-Ca associations were synthesized at various Fe/organic carbon (OC) and Ca/Fe molar ratios using Leonardite humic acid as OM model. The impact of Ca on Fe-OM aggregates was studied by a combination of X-ray absorption spectroscopy, small angle X-ray and neutron scattering and imaging techniques (TEM, cryo-TEM and cryo-TXM). Iron phases are constituted of Fe(III)-oligomers, Fe(III)-nanoparticles and ferrihydrite (Fh), all bound or embedded by OM. Iron phases exhibit a fractal organization with Fe-primary beads aggregated as Fe-primary aggregates (Fe-PA) which themselves are embedded in an OM aggregates. For Ca/OC (mol/mol) < 0.026, Fe-PA aggregate in a third level as a Fe-secondary aggregate. For Ca/OC ≥ 0.026, OM forms a large Ca-branched network in which Ca is bound as a dimer to OM carboxylic sites. In such conditions, Fe-PA are distributed in the OM network, distant from each other. All these structural transitions are driven by Ca which partially screens the Fe-OM interactions. The formation of such micrometric network should impact both the surface reactivity of the Fe phases as well as the mobility of Fe, OM and associated elements, notably in the soil porosity where they are produced under natural conditions.

International audience; Flax (Linum usitatissimum) lodging is an issue of great interest for industrial producers due to its economic impact; despite a strong varietal selection over around one century, this plant remains sensitive to lodging which represents a main technico-economic issue. To better understand lodging effects at the cell wall and stem scale, the cell wall composition dynamics during cell wall development and after a 90 degrees tilt bending stress is reported. Deep-UltraViolet (DUV) fluorescence emission dynamics recorded at the Synchrotron SOLEIL-DISCO beamline by multichannel autofluorescence imaging is addressed for five cellular wall types of flax stems after an artificially induced gravitropic reaction. The quantitative fluorescent profile intensities were computed after image analysis, and compared to the control flax stems, we reported a systematically higher average intensity fluorescence (probability >95%) for the 90 degrees tilted plants. Moreover, the average stem fluorescence intensities were significantly different among the 3 developmental stages, with the youngest stage (VS) exhibiting on average 30% and 20% less fluorescence than the medium (FG) and mature (M) stages, respectively. The flax stem response to tilt impacted the xylem cellular type, while the bast fibres were arguably less affected by the protein, and hydroxycinnamate contents. A complementary investigation was carried out on bast fibres by infrared microspectroscopy to explore the polysaccharide components not detected in DUV fluorescence, and significant modifications were monitored.

There is a demand for nanoparticles that are environmentally acceptable, but simultaneously efficient and low cost. We prepared silver nanoparticles (AgNPs) grafted on a native bio-based substrate (cellulose nanocrystals, CNCs) with high biocidal activity and no toxicological impact. AgNPs of 10 nm are nucleated on CNCs in aqueous suspension with content from 0.4 to 24.7 wt%. XANES experiments show that varying the NaBH4/AgNO3 molar ratio affects the AgNP oxidation state, while maintaining an fcc structure. AgNPs transition from 10 nm spherical NPs to 300 nm triangular-shaped AgNPrisms induced by H2O2 post-treatment. The 48 h biocidal activity of the hybrid tested on B. Subtilis is intensified with the increase of AgNP content irrespective of the Ag+/Ag0 ratio in AgNPs, while the AgNSphere−AgNPrism transition induces a significant reduction of biocidal activity. A very low minimum inhibitory concentration of 0.016 mg AgNP/mL is determined. A new long-term biocidal activity test (up to 168 h) proved efficiency favorable to the smaller AgNPs. Finally, it is shown that AgNPs have no impact on the phagocytic capacity of mammalian cells.

International audience; Titanium dioxide is a food additive that has raised some concerns for humans due to the presence of nanoparticles. We were interested in knowing the fate of TiO2 particles in the gastro-intestinal tract and their potential effect on digestive enzymes. For this purpose, we analysed the behaviour of two different food grade TiO2 samples (E171) and one nano-sized TiO2 sample (P25) through a standardized static in vitro digestion protocol simulating the oral, gastric and intestinal phases with appropriate juices including enzymes. Both E171 and P25 TiO2 particles remained intact in the digestive fluids but formed large agglomerates, and especially in the intestinal fluid where up to 500 mu m sized particles have been identified. The formation of these agglomerates is mediated by the adsorption of mainly alpha-amylase and divalent cations. Pepsin was also identified to adsorb onto TiO2 particles but only in the case of silica-covered E171. In the salivary conditions, TiO2 exerted an inhibitory action on the enzymatic activity of alpha-amylase. The activity was reduced by a factor dependent on enzyme concentrations (up to 34% at 1 mg mL(-1)) but this inhibitory effect was reduced to hardly 10% in the intestinal fluid. In the gastric phase, pepsin was not affected by any form of TiO2. Our results hint that food grade TiO2 has a limited impact on the global digestion of carbohydrates and proteins. However, the reduced activity specifically observed in the oral phase deserves deeper investigation to prevent any adverse health effects related to the slowdown of carbohydrate metabolism.

International audience; Rare Earth Elements (REEs) are essential components of many high-tech products. In industrial materials, REEs come at 90% from Southern China ion-adsorption deposits, from which they are recovered by heap leaching using ammonium sulfate. Such large-scale process leads to severe environmental damage, and produces large tailings. Elucidating the nature of REE-bearing phases in these mine tailings is critical for predicting REE dynamics and designing a successful sustainable reclamation strategy, phyto-stabilization being currently tested.First investigations on the tailings soils revealed their high heterogeneous mineral composition, supporting the need for micro-scale investigation. XRD and TEM-EDXS identified quartz, K-feldspars and kaolinite as major phases, and optical microscope observations evidenced Fe-rich weathered layers surrounding particles, as well as organic material that might play a role in REEs distribution.X-ray spectromicroscopy analyses of soil thin sections (bare and planted) were performed at SSRL (beamline 2-3) and SOLEIL (LUCIA). We targeted the most concentrated REEs in the bulk soil, i.e., La, Ce and Nd. Overlaps in the fluorescence lines of REEs and transition metals (Ba, Ti) obliged us to perform fitting of the fluorescence signal in each pixel of the maps. Then, µXANES spectra at REE L-edges were collected to confirm the presence of REEs. The use of µXANES allowed us to detect very low quantities of REEs that were not detectable in global fluorescence maps. The combination of spectromicroscopy and fluorescence mapping was crucial and powerful to detect low levels of REEs in heterogeneous material.We evidenced the co-localization of REEs with Fe oxides, and, in reclaimed and vegetated samples, with roots. The high number of measurements performed on LUCIA beamline showed us that Ce speciation was predominantly Ce4+ when not accompanied by others REEs. In contrast, Ce3+ is systematically associated with Nd3+ and La3+.This work is, to our knowledge, the first to address REE distribution and speciation in soils. It provides significantly enhanced understanding of processes governing REE behaviour in mine tailings and will help designing successful reclamation techniques of contaminated land. It will contribute to validate process-based geochemical models describing REE behaviour, allowing to predict REE fate with ongoing reclamation.

Flax lodging is an issue of great interest for producers due to its economic impact. To better understand its effects at the cell wall and stem scale, new knowledge regarding the cell wall composition dynamics during cell wall development and after a 90° tilt bending stress is reported. Deep-Ultra Violet fluorescence emission (DUV) dynamics recorded at the Synchrotron SOLEIL-DISCO beamline by multichannel autofluorescence imaging is reported for five cellular wall types of flax stems after an artificially induced gravitropic reaction. Three flax growth development stages, namely, the vegetative stage (VS), the fast growth (FG) and the mature stage (MS), were selected in normal plants, referred to as the control plants, or in gravitropic-induced response plants, referred to as 90° tilted plants.

• Grevillea meisneri, an endemic New Caledonian Mn-hyperaccumulator, is used in rehabilitation of degraded mining sites on the island. Large-scale programs require transplanting nursery-grown seedlings, but effects of the nursery environment on Mn tolerance of transplants and their capacity to hyper-accumulate Mn are unknown, slowing rehabilitation efforts.• We studied tissue-level distribution of Mn and other elements in different tissues of G. meisneri using micro-X-Ray Fluorescence spectroscopy (μXRF), comparing nursery-grown plants transplanted into the site and sampled seven years later, and similar-sized plants that had grown spontaneously in the site. • Mirroring patterns in other Mn-hyperaccumulators, Mn was preferentially accumulated in leaves but was also present in roots. Concentrations were highest in leaf epidermal tissues, in cortex and vascular tissues of stems and primary roots, and in phloem and pericycle-endodermis of parent cluster roots. Although abundant in soil, Ni was absent from all tissues of G. meisneri. Ca was always co-localised with Mn. Preferential uptake of Mn vs Ni in roots implies as-yet-uncharacterized specific Mn-transporters, while Ca and Mn co-localisation suggests shared transport pathways. • No differences were observed in concentration and distribution of Mn in transplanted and spontaneously-growing plants. Nursery-grown transplants should be highly suitable for large-scale, high-throughput rehabilitation programs.

Calcareous nannofossils are micrometric calcite platelets secreted by the photosynthetic algae named coccolithophores and incertae sedis. Calcareous nannoplankton inhabit the photic zone from coast to open-ocean and have left an abundant fossil record since the Triassic. Therefore, they constitute an interesting material for geochemical studies although they have been overlooked in comparison to foraminifera. We have analyzed manganese distribution and valence in six calcareous nannofossil species representing different ages (Recent to Jurassic) and geological settings (land sections and deep ocean core-tops) and with different structures to assess the potential of Mn as a paleobiological or paleoenvironmental proxy. Nano x -Ray Fluorescence ( xrf ) maps were established at the esrf id 22 ni and id 21 beamlines and Mn k -edge x -Ray Absorption Near Edge Structure ( xanes ) at id 21. Mn is more abundant in nannofossils from pre-Quaternary rock samples than from core-top samples. In nannofossil rock samples, Mn nano xrf maps show distributions correlated with primary crystalline organization whereas in nannofossil core-top samples, Mn is either absent or does not follow the crystal organization. X anes analyses show that Mn is in the form of MnCO3. All these observations argue for Mn incorporation within calcareous nannofossils controlled by diagenesis through overgrowth of secondary calcite (Ca, Mn)CO3. Crusts grew along the original crystal growth directions. The incorporation of Mn in some core-top samples highlights potential early diagenesis input when the detached platelet lies on the seafloor or is still in the water column. Mn should therefore be considered a critical tool to identify diagenetic overgrowth rather than primary environmental conditions.

Our understanding of plant responses to climate change, and their feedbacks to the climate system, rely heavily on consistent long-term observations. Yet, measuring tropical plant species is particularly demanding and results in a lack of spatial and temporal coverage to build relationships between forest dynamics and climatology in the central Congo Basin. Here dendrochronology and wood chemical analyses might provide important ecophysiological information addressing this knowledge gap, especially in tropical forests where the lack of a pronounced seasonality often makes it difficult to discern variability in xylem cell size and density. Conventional optical dendrochronology measurements therefore have strong limitations within these ecosystems, however chemical and elemental analysis can provide additional information. For example, seasonal fluctuations in the carbon (δ13C) and oxygen (δ18O) stable isotope composition of cellulose is linked to variations in local climate and changes in physiological function. A fewstudies have shown that intra-annual and inter-annual variations in the content of calcium [Ca] in tropical tree rings can be used to age tropical trees without rings, constraining estimates of biomass accumulation. Other studies have linked calcium accumulation in different plant organs to the rate of transpiration in trees making it a powerful predictor of inter-annual variability in rainfall for monsoon regions and a strong novel proxy for drought stress.Here we present the first results of X-ray Fluorescence (XRF) measurements conducted at the SOLEIL synchrotron and analysis of [Ca] and [Sr], combined with ancillary data such as anatomical, stable isotope and climatological measurements for three tropical tree species. Most species show variability in calcium corresponding to previous proxy measurements, corroborating previous results and showing the potential of non-destructive XRF measurements of wood samples in support of ecophysiological research. The potential of high throughput scanning, in contrast to stable isotope measurements, opens possibilities to gather data on the large scale required to understand diverse tropical forest ecosystems and their responses to (drought) disturbances.

Hybrid nanoparticles involving 10-nm silver nanoparticles (AgNPs) nucleated on unmodified rod-like cellulose nanocrystals (CNCs) were prepared by chemical reduction. H2O2 used as a post-treatment induced a size-shape transition following a redox mechanism, passing from 10-nm spherical AgNPs to 300-nm triangular or prismatic NPs (AgNPrisms), where CNCs are the only stabilizers for AgNPs and AgNPrisms. We investigated the role of the H2O2/AgNP mass ratio (&alpha, ) on AgNPs. At &alpha, values above 0.20, the large amount of H2O2 led to extensive oxidation that produced numerous nucleation points for AgNPrisms on CNCs. On the contrary, for &alpha, below 0.20, primary AgNPs are only partially oxidized, releasing a reduced amount of Ag+ ions and thus preventing the formation of AgNPrisms and reforming spherical AgNPs. While XRD and EXAFS reveal that the AgNP fcc crystal structure is unaffected by the H2O2 treatment, the XANES spectra proved that the AgNP&ndash, AgNPrism transition is always associated with an increase in the metallic Ag fraction (Ag0). In contrast, the formation of new 15-nm spherical AgNPs keeps the initial Ag0/Ag+ ratio unmodified. For the first time, we introduce a complete guide map for the fully-controlled preparation of aqueous dispersed AgNPs using CNC as a template.

Iron-Organic Matter (Fe-OM) aggregates produced by redox alternation in wetlands are a key factor in the control of metallic pollutants mobility. Their ability to adsorb metal(loid)s depends on the size, morphology and structural arrangement between Fe and OM phases, which are mainly controlled by the OM occurrence. The physical, chemical and morphological organization of such aggregates is influenced by the physico-chemical conditions prevailing in the environment. Calcium (Ca) is a common major ion in natural waters which exhibits high affinity for OM. It can thus modify the size and the structural organization of Fe-OM aggregates and, subsequently, their ability to bind metal(loid)s. Among metal(loids), arsenic (As) is of major importance because of its high toxicity and its high affinity towards Fe(III)-oxyhydroxides. Moreover, Fe-OM aggregates are an important factor controlling the mobility of arsenic (As) in the environment.Mimetic natural Fe-OM aggregates were synthesized at various Fe/OM and Ca/Fe ratios. After a fine characterization of the size and structural organization, Fe-OM-Ca associations were used to perform As binding sorption experiments at 2 As/Fe ratios. The suspensions were stirred during 24h and subsequently filtrated ant ultra-filtrated.Our study demonstrates that Ca strongly influences the Fe-OM aggregates physical organisation. For low Ca/Fe ratio, Fe phases exhibit a fractal organization in which Fe phases are composed of oligomers, and primary nano-aggregates (around 6 nm) which aggregate in larger Fe secondary aggregates (>200 nm). Both are embedded in the OM matrix composed of isolated molecules and OM aggregates. For high Ca/Fe ratios, OM, Fe oligomers and primary nano-aggregates form a large continuous network where Fe phases are connected by OM large molecules. With the increasing Ca/Fe ratio, the amount of Fe oligomers decreases to the benefit of larger primary nano-aggregates (increase of their geometrical radius). Ultrafiltration experiments demonstrated that DOC, Fe, Ca and As follow the same size distribution. Surprisingly, As sorption increases with the increasing size and amount of primary nano-aggregates and the formation of the large network. SAXS analyses revealed that in such network, the distance between primary nano-aggregates increases as compared to their distance in secondary aggregates. All this results suggest that, with the increasing Ca/Fe ratio, although the primary nano-aggregates size increase, their structural distance allows to rise the availability of their binding site for As.This study demonstrates that Ca not only controls the Fe-OM structural organization but also its subsequent capacity to bind toxic elements such as As. These results are of major importance since such parameter was never so clearly evidence. They show that the actual representation of the physical organisation of Fe-OM aggregates and its reactivity have to be renewed as well as the geochemical models.

International audience; Metallic ions were quantified and mapped at the tissue and the cell scales in two texture and phenolic content contrasted cider apples by atomic absorption spectroscopy, ion chromatography and synchrotron cryo X-ray fluorescence imaging. Metallic ions content and gradient distribution from the cuticle to the inner tissue significantly varied between years of harvest (1-294 % of differences between years). The content of non-esterified uronic acid in the cell wall pectin was also measured (3.1 and 4.9 mol kg(-1) of dry weight fruit) and found higher than the total metallic ions in the two varieties (0.22 and 0.27 mol kg(-1) of dry weight fruit). Calcium content and cell wall pectin methyl-esterification were not determinants distinguishing firm from soft apples. The results are discussed with regard to the co-location of metallic ions with the phenolic compounds which questions their role in oxidative mechanisms during fruit development and processing, affecting particularly the colour and taste of fruit products.

The main storage components of the maize endosperm are starch, proteins and lipids. Starch and proteins are heterogeneously deposited, leading to the formation of vitreous and floury regions at the periphery and at the centre of the endosperm. The vitreous/floury mass ratio is a key physical parameter of maize end-uses for the food, feed and non-food sectors, as well as for the resistance of seeds to environmental aggressions. To improve maize breeding for vitreousness, one of the main issues is to finely delineate the molecular and physicochemical mechanisms associated with the formation of endosperm texture. In this context, we use scanning transmission X-ray microscopy at the C K-edge on maize endosperm resin-embedded ultrathin sections. The combination of local near edge X-ray absorption fine structure (NEXAFS) spectroscopy and high-resolution images enable us to achieve a quantitative fine description of the spatial distribution of the main components within the endosperm.

Dust deposition is an important source of phosphorus (P) to many ecosystems. However, there is little evidence of dust-derived P-containing minerals in soils. Here we studied P forms along a well-described climatic gradient on Hawaii, which is also a dust deposition gradient. Soil mineralogy and soil P forms from six sites along the climatic gradient were analyzed with bulk (X-ray diffraction and P K-edge X-ray absorption near edge structure) and microscale (X-ray fluorescence, P K-edge X-ray absorption near edge structure, and Raman) analysis methods. In the wettest soils, apatite grains ranging from 5 to 30 µm in size were co-located at the micro-scale with quartz, a known continental dust indicator suggesting recent atmospheric deposition. In addition to co-location with quartz, further evidence of dust-derived P included backward trajectory modeling indicating that dust particles could be brought to Hawaii from the major global dust-loading areas in central Asia and northern Africa. Although it is not certain whether the individual observed apatite grains were derived from long-distance transport of dust, or from local dust sources such as volcanic ash or windblown fertilizer, these observations offer direct evidence that P-containing minerals have reached surface layers of highly-weathered grassland soils through atmospheric deposition., Geoderma, 381, ISSN:0016-7061, ISSN:1872-6259

Sulfur (S) and phosphorus (P) are essential elements for plant growth and physiological functioning. Their deficiency can limit N

Through a mutualistic relationship with woody plant roots, ectomycorrhizal fungi provide growth-limiting nutrients, including inorganic phosphate (Pi), to their host. Reciprocal trades occur at the Hartig net, which is the symbiotic interface of ectomycorrhizas where the two partners are symplasmically isolated. Fungal Pi must be exported to the symbiotic interface, but the proteins facilitating this transfer are unknown. In the present study, we combined transcriptomic, microscopy, whole plant physiology, X-ray fluorescence mapping, 32 P labeling and fungal genetic approaches to unravel the role of HcPT2, a fungal Pi transporter, during the Hebeloma cylindrosporum-Pinus pinaster ectomycorrhizal association. We localized HcPT2 in the extra-radical hyphae and the Hartig net and demonstrated its determinant role for both the establishment of ectomycorrhizas and Pi allocation towards P. pinaster. We showed that the host plant induces HcPT2 expression and that the artificial overexpression of HcPT2 is sufficient to significantly enhance Pi export towards the central cylinder. Together, our results reveal that HcPT2 plays an important role in ectomycorrhizal symbiosis, affecting both Pi influx in the mycelium and efflux towards roots under the control of P. pinaster.

Background The in vivo observation of diffusible components, such as ions and small phenolic compounds, remains a challenge in turgid plant organs. The analytical techniques used to localize such components in water-rich tissue with a large field of view are lacking. It remains an issue to limit compound diffusion during sample preparation and observation processes. Results An experimental setup involving the infusion staining of plant tissue and the cryo-fixation and cryo-sectioning of tissue samples followed by fluorescence cryo-observation by laser scanning confocal microscopy (LSCM) was developed. This setup was successfully applied to investigate the structure of the apple fruit cortex and table grape berry and was shown to be relevant for localizing calcium, potassium and flavonoid compounds. Conclusion The cryo-approach was well adapted and opens new opportunities for imaging other diffusible components in hydrated tissues.

In order to better understand the behaviour of Fe3+ during partial melting of a mid-ocean-ridge-basalt (MORB) mantle source, we performed partial melting experiments of a spinel peridotite at 1.5 GPa, between 1320 and 1450 °C, and over a range of oxygen fugacities (fO2) varying from FMQ-3.5 to FMQ+6 (log-units relative to FMQ = Fayalite-Magnetite-Quartz oxygen buffer). Changes in fO2 were achieved using different capsule materials and by varying the oxidation state of the starting material. Fe3+ contents of spinels and glasses were examined using Fe K-edge X-ray Absorption Near Edge Structure (XANES) spectroscopy in full-field mode. Our results show that this method allows Fe3+/ƩFe measurements to be made of spinels in our experimental charges but is not suitable for quantifying Fe3+/ƩFe of glasses, particularly at relatively low fO2 where melt Fe2O3 contents are small. We therefore employed several methods (Fe3+/ƩFe ratios of spinels measured by XANES and calculated by stoichiometry, and Fe-alloy sliding redox sensors) to assess the fO2 of the samples. These were then used to calculate the Fe3+/ƩFe ratios of glasses using published models, which were further constrained by Mossbauer spectroscopy measurements on an additional set of partial melting experiments. For a particular initial redox state, the Fe3+/ΣFe ratio in melts remains approximately constant with partial melting degree. This is explained by a slight decrease of the bulk partition coefficient of Fe2O3 ( D Fe 2 O 3 peridotite - m e l t ) as the degree of partial melting increases. The Fe3+/ΣFe ratios of resulting melts are thus restricted to a relatively narrow range over large degrees of melting, as observed for global MORB glass analyses. This observation is also confirmed by pMELTS calculations employing different bulk Fe3+/ΣFe ratios. We conclude that the Fe2O3 content in MORB can be accounted for through partial melting of a mantle source containing 0.1–0.5 wt% Fe2O3 and a bulk D Fe 2 O 3 peridotite - m e l t ranging from 0.3 to 0.1.

Nano-silicon dioxide (SiO2) is used nowadays in several biomedical applications such as drug delivery and cancer therapy, and is produced on an industrial scale as additive to paints and coatings, cosmetics and food. Data regarding the long-term biokinetics of SiO2 engineered nanoparticles (ENPs) is lacking. In this study, the whole-body biodistribution of SiO2 core-shell ENPs containing a paramagnetic core of Fe3O4 was investigated after a single exposure via intravenous injection or intratracheal instillation in mice. The distribution and accumulation in different organs was evaluated for a period of 84 days using several techniques, including magnetic resonance imaging, inductively coupled plasma mass spectrometry, X-ray fluorescence and X-ray absorption near edge structure spectroscopy. We demonstrated that intravenously administered SiO2 ENPs mainly accumulate in the liver, and are retained in this tissue for over 84 days. After intratracheal instillation, an almost complete particle clearance from the lung was seen after 84 days with distribution to spleen and kidney. Furthermore, we have strong evidence that the ENPs retain their original core-shell structure during the whole observation period. This work gives an insight into the whole-body biodistribution of SiO2 ENPs and will provide guidance for further toxicity studies.

Phosphorus (P) is an essential nutrient for plants but its low availability often necessitates amendments for agronomical issues. Objectives were to determine P spatial distribution and speciation that remain poorly understood in cultivated soils. Aquic Argiudoll soil samples developed on a calcareous loam glacial till were collected from experimental plots submitted to contrasting crop rotations and amendments. Micro-X-ray fluorescence (μ-XRF) maps were collected on undisturbed samples. X-ray absorption near edge structure (XANES) spectra were collected on bulk samples and on fractions thereof, and on points of interests selected from μ-XRF maps. Results were compared with chemical analyses and extraction techniques results. Chemical analyses show variations in total and exchangeable P contents depending on the samples but no significant difference is observed in terms of P distribution and speciation. P distribution is dominated by a low-concentration diffuse background with a minor contribution from minute hot spots. P speciation is dominated by phosphate groups bound to clay-humic complexes. No modification of P distribution and speciation is observed close to roots. This study evidenced minor effect of cropping and fertilizing practices on P speciation in cultivated soils. Despite analytical challenges, the combined use of μ-XRF and XANES provides relevant information on P speciation in heterogeneous soil media.

A pot experiment was carried out with maize to determine the phosphorus (P) plant-availability of different secondary P-fertilizers derived from wastewater. We analyzed the respective soils by P K-edge X-ray absorption near-edge structure (XANES) spectroscopy to determine the P chemical forms that were present and determine the transformation processes. Macro- and micro-XANES spectroscopy were used to determine the chemical state of the overall soil P and identify P compounds in P-rich spots. Mainly organic P and/or P adsorbed on organic matter or other substrates were detected in unfertilized and fertilized soils. In addition, there were indications for the formation of ammonium phosphates in some fertilized soils. However, this effect was not seen in the maize yield of all P-fertilizers. The observed reactions between phosphate from secondary P-fertilizers and co-fertilized nitrogen compounds should be further investigated. Formation of highly plant-available compounds such as ammonium phosphates could make secondary P-fertilizers more competitive to commercial phosphate rock-based fertilizers with positive effects on resources conservation. Electronic supplementary material The online version of this article (10.1007/s13280-017-0973-z) contains supplementary material, which is available to authorized users.

Soils comprise various heterogeneously distributed pools of lithogenic, free organic, occluded, adsorbed, and precipitated phosphorus (P) forms, which differ depending on soil forming factors. Small-scale heterogeneity of element distributions recently has received increased attention in soil science due to its influence on soil functions and soil fertility. We investigated the micro-scale distribution of total P and different specific P binding forms in aggregates taken from a high-P clay-rich soil and a low-P sandy soil by combining advanced spectrometric and spectroscopic techniques to introduce new insights on P accessibility and availability in soils. Here we show that soil substrate and soil depth determine micro-scale P heterogeneity in soil aggregates. In P-rich areas of all investigated soil aggregates, P was predominantly co-located with aluminium and iron oxides and hydroxides, which are known to strongly adsorb P. Clay minerals were co-located with P only to a lesser extent. In the low-P topsoil aggregate, the majority of the P was bound organically. Aluminium and iron phosphate predominated in the quartz-rich low-P subsoil aggregate. Sorbed and mineral P phases determined P speciation in the high-P top- and subsoil, and apatite was only detected in the high-P subsoil aggregate. Our results indicate that micro-scale spatial and chemical heterogeneity of P influences P accessibility and bioavailability.

Marine sediment records suggest that episodes of major atmospheric CO2 drawdown during the last glacial period were linked to iron (Fe) fertilization of subantarctic surface waters. The principal source of this Fe is thought to be dust transported from southern mid-latitude deserts. However, uncertainty exists over contributions to CO2 sequestration from complementary Fe sources, such as the Antarctic ice sheet, due to the difficulty of locating and interrogating suitable archives that have the potential to preserve such information. Here we present petrographic, geochemical and microbial DNA evidence preserved in precisely dated subglacial calcites from close to the East Antarctic Ice-Sheet margin, which together suggest that volcanically-induced drainage of Fe-rich waters during the Last Glacial Maximum could have reached the Southern Ocean. Our results support a significant contribution of Antarctic volcanism to subglacial transport and delivery of nutrients with implications on ocean productivity at peak glacial conditions., Contributions of iron sources to Southern Ocean CO2 sequestration during the last glacial period remain uncertain. Here, based on the biogeochemical analysis of subglacial calcites, the authors propose Antarctic volcanism, via subglacial drainage of Fe-rich waters, as a key contributor.

International audience; The ID21 beamline (European Synchrotron Radiation facility, France) is a multi micro-analytical platform combining X-ray and infrared micro-probes, for characterization of elements, species, molecular groups and crystalline structures in complex materials. Applications are mainly in the fields of cultural heritage, life science, environmental and earth sciences, materials sciences. Here, we first present the status of instruments: (i) the scanning micro-spectroscopy end-station, operating from 2.0 to 9.2 keV, under vacuum and offering cryo conditions, for the acquisition of 2D micro X-ray fluorescence (μXRF) maps, single point micro X-ray Absorption Near Edge Structure (μXANES) spectra and speciation maps with sub-micrometric resolution; (ii) the XANES full-field end-station, operating in the same vacuum and energy conditions, for the acquisition of hyper-spectral radiographs of thin concentrated samples, resulting in speciation maps with micrometric resolution and millimetric field of view; (iii) the scanning micro-X-ray diffraction (μXRD)/μXRF end-station, operating at 8.5 keV, in air, for the acquisition of 2D crystalline phase maps, with micrometric resolution; and (iv) the scanning infrared microscope, operating in the mid-infrared range for the acquisition of molecular maps and some structural maps with micrometric resolution. Recent hardware and software developments are presented, as well as new protocols for improved sample preparation of thin sections. Secondly, a review of recent applications for the study of cultural heritage is presented, illustrated by various examples: determination of the origin of the color in blue Chinese porcelains and in brown Sèvres porcelains; detection of lead in ink on Herculaneum papyri; identification and degradation of modeling materials used by Auguste Rodin and of chrome yellow pigments used by Vincent van Gogh. Cryo capabilities are illustrated by the analysis of plants exposed to chromate solutions. These examples show the variety of materials analyzed, of questions tackled, and particularly the multiple advantages of the ID21 analytical platform for the analysis of ancient and artistic materials.

International audience; Sulfur has been recognized in biogenic calcites for a long time. However, its structural position is matter of debate. For some authors, sulfur is a marker of the organic matrix while it is part of the calcite structure itself for others. To better understand the place of sulfur in calcite, sulfated magnesian calcites (S-MgCalcite) have been synthetized at high pressure and temperature and studied by μ-XANES spectroscopy. S-MgCalcite XANES spectra show two different types of sulfur: sulfate (SO42−) as a predominant species and a small contribution of sulfite (SO32−), both substituting for carbonate ions in the calcite structure. To address the question of the position of sulfur in biogenic calcites, the oxidation states of sulfur in the skeleton and organic tissues of Corallium rubrum have been investigated by micro X-ray fluorescence (μ-XRF) and sulfur K-edge micro X-ray absorption near edge structure (μ-XANES) spectroscopy at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) on beamline ID21. In the skeleton, sulfur is mainly present as oxidized sulfur SO42− (+VI), plus a weak sulfite contribution. XANES spectra indicate that sulfur is inorganically incorporated as sulfur structurally substituted to carbonate ions (SSS). Although an organic matrix is present in the red coral skeleton, reduced organic sulfur could not be detected by μ-XANES spectroscopy in the skeleton probably due to low organic/inorganic sulfur ratio. In the organic tissues surrounding the skeleton, several sulfur oxidation states have been detected including disulfide (S–S), thioether (R–S–CH3), sulfoxide (SO2), sulfonate (SO2O−) and sulfate (SO42−). The unexpected occurrence of inorganic sulfate within the organic tissues suggests the presence of pre-organized organic/inorganic complexes in the circulatory system of the red coral, precursors to biomineralization ahead of the growth front.

We investigate the relationship between sulfur and oxygen fugacity at Erta Ale and Masaya volcanoes. Oxygen fugacity was assessed utilizing Fe3+/Sigma Fe and major element compositions measured in olivine-hosted melt inclusions and matrix glasses. Erta Ale melts have Fe3+/Sigma Fe of 0.15-0.16, reflecting fO(2) of Delta QFM 0.0 +/- 0.3, which is indistinguishable from fO(2) calculated from CO2/CO ratios in high-temperature gases. Masaya is more oxidized at Delta QFM + 1.7 +/- 0.4, typical of arc settings. Sulfur isotope compositions of gases and scoria at Erta Ale (delta S-34(gas) - 0.5 parts per thousand; delta S-34(scoria) + 0.9 parts per thousand) and Masaya (delta S-34(gas) + 4.8 parts per thousand; delta S-34(scoria) + 7.4 parts per thousand) reflect distinct sulfur sources, as well as isotopic fractionation during degassing (equilibrium and kinetic fractionation effects). Sulfur speciation in melts plays an important role in isotope fractionation during degassing and S6+/Sigma S is 0.67 in Masaya melt inclusions. No change is observed in Fe3+/Sigma Fe or S6+/Sigma S with extent of S degassing at Erta Ale, indicating negligible effect on fO(2), and further suggesting that H2S is the dominant gas species exsolved from the S2--rich melt (i.e., no redistribution of electrons). High SO2/H2S observed in Erta Ale gas emissions is due to gas re-equilibration at low pressure and fixed fO(2). Sulfur budget considerations indicate that the majority of S injected into the systems is emitted as gas, which is therefore representative of the magmatic S isotope composition. The composition of the Masaya gas plume (+4.8 parts per thousand) cannot be explained by fractionation effects but rather reflects recycling of high delta S-34 oxidized sulfur through the subduction zone

Phosphorus (P) is an essential element for all forms of life and is applied as fertilizer in agriculture. The P availability for plants may be highly dependent on the chemical state of P in fertilizers and soils; however, the nature of this dependence remains obscure due to the limitations of generally applied wet chemical and instrumental analytical approaches. This paper focuses on recently developed infrared, Raman, ultraviolet and X-ray microspectroscopic techniques for the characterization of P in soil. Microspectroscopic techniques have the advantage that discrete P phases can be distinguished and characterized even if their mass fractions are very low. However, only small volumes of soil can be analyzed by microspectroscopic methods hence a combination of macro- and microspectroscopic techniques is a promising concept.

Nano-silicon dioxide (SiO2) is used nowadays in several biomedical applications such as drug delivery and cancer therapy, and is produced on an industrial scale as additive to paints and coatings, cosmetics and food. Data regarding the long-term biokinetics of SiO2 engineered nanoparticles (ENPs) is lacking. In this study, the whole-body biodistribution of SiO2 core-shell ENPs containing a paramagnetic core of Fe3O4 was investigated after a single exposure via intravenous injection or intratracheal instillation in mice. The distribution and accumulation in different organs was evaluated for a period of 84 days using several techniques, including magnetic resonance imaging, inductively coupled plasma mass spectrometry, X-ray fluorescence and X-ray absorption near edge structure spectroscopy. We demonstrated that intravenously administered SiO2 ENPs mainly accumulate in the liver, and are retained in this tissue for over 84 days. After intratracheal instillation, an almost complete particle clearance from the lung was seen after 84 days with distribution to spleen and kidney. Furthermore, we have strong evidence that the ENPs retain their original core-shell structure during the whole observation period. This work gives an insight into the whole-body biodistribution of SiO2 ENPs and will provide guidance for further toxicity studies.

International audience; To better understand the reaction mechanisms involved at the Fe(0)/clay minerals interface, we investigate in the present study the reaction between an Fe(0) surface and a clay suspension extracted from the Callovo-Oxfordian claystone (COx). Batch experiments were carried out under anoxic conditions in sealed autoclave, at 90 degrees C to mimic predicted radioactive waste disposal conditions. An Fe(0) foil was introduced into the autoclave so that the lower part of the foil was immersed in the clay suspension while the upper part was contacted with the atmosphere of the experimental setup. After two months, the mineralogical deposits that precipitated at the surface of the Fe(0) foil were analyzed using multiple techniques, namely X-ray diffraction (XRD), scanning/transmission electron microscopy associated to microanalysis (SEM/TEM-EDXS), and micro-spectroscopic measurements (l-FTIR and l-Raman). Both parts of the Fe(0) foil were then shown to react: magnetite was the main resulting mineral formed at the Fe(0) surface in the atmospheric conditions whereas serpentine 1:1 phyllosilicates were the main end-products in the clay suspension. The analyses performed on the immersed part of the foil revealed a spatial heterogeneity in both serpentine cristallochemistry and morphology, with a gradient from the Fe(0) contact point toward the clay suspension. A pure Fe-Si phyllosilicate ring was observed at the direct contact point with the Fe(0) foil and a progressive incorporation of Al instead of Fe into the clay phases was identified as deposit thickness increased from the Fe(0) surface to the clay suspension. Our findings suggest that reaction mechanisms include several steps, corresponding to successive regimes depending on the availability of the main reactive elements at the Fe(0)/solution interface, namely Fe, Si and Al. Thus, our results provide new information to support the understanding of both mineral organization and composition at the clay/Fe(0) interface.

International audience; In order to better understand the possible interactions between steel canisters and a claystone host rock, in this case the Callovo-Oxfordian rock (COx), the present study investigated in detail, under conditions relevant to high-level radioactive waste repositories (anoxic conditions, temperature of 90°C), the reactions between metallic iron and: (1) COx; (2) the clay fraction extracted from COx (CF); and (3) mixtures of CF with quartz, calcite, or pyrite. Batch experiments were then carried out in the presence of NaCl-CaCl2 background electrolyte, for durations of 1, 3, and 9 months. Solid and liquid end-products were characterized by a combination of techniques including liquid analyses, transmission and scanning electron microscopies, X-ray diffraction, N2 adsorption at 77 K, and Mössbauer spectroscopy. The interaction between CF and metallic iron appeared to proceed by means of pathways similar to those illustrated in previous studies on interactions between metallic iron and purified clays. In spite of the many similarities with previous studies, significant differences were observed between the behavior of COx and CF, particularly in terms of pH and Eh evolution, iron consumption, chemical composition of the neoformed particles, and textural evolution. Such differences demonstrate the important role played by non-clay minerals in reaction pathways. The addition of carbonates or pyrite to CF did not lead to significant change in reactivity. In contrast, under the conditions used in the present study, i.e. for relatively low iron:clay ratios, the presence of quartz strongly influenced reaction pathways. In the presence of quartz, magnetite was observed only in trace abundances whereas the amounts of magnetite were significant in experiments without quartz. Furthermore, filamentous serpentine particles with a small Al:Si ratio appeared which could develop from an FeSiAl gel that only forms in the presence of quartz. Considering that most clay rocks currently being considered for radioactive waste disposal contain significant amounts of quartz, the results obtained in the present study may be of significant interest for predicting the long-term behavior of clay barriers in such sites.

International audience; This study was conducted to determine phosphorus (P) species captured in a vertical-flow constructed wetland (VFCW) system combining a trickling filter followed by FeCl3 injection for phosphate coagulation. Suspended solids (SS) thus formed accumulated over time at the VFCW surface and transformed into a sludge deposit layer, which was shown to concentrate most of the P captured in the system. In order to investigate the effect of aging on P species, representative SS and sludge samples were taken from a wastewater treatment plant that had been in operation for 8 years and analyzed using P fractionation, solution 31P NMR spectroscopy and P and Fe K-edge XANES spectroscopy. A partial mineralization of organic matter was shown by comparing organic carbon contents of SS and sludge materials. Chemical fractionations combined with P and Fe K-edge XANES spectroscopy showed that P was predominantly bound to iron within both samples in the form of ferric phosphate, rather than adsorbed onto ferric oxyhydroxide. Calcium-bound P was more significantly observed in sludge than in SS, suggesting that aging induced the recombination of part of the organic and iron-bound P species into calcium-bound forms, as a possible consequence of the partial mineralization of organic matter.

International audience; In the context of radioactive waste repository in geological formation, kaolinite-metallic iron interaction in chlorine solution was conducted in batch experiments, under anoxic conditions at 90 degrees C during 9 months. After a mineralogical characterization at a global scale, products were analyzed at the micrometer and nanometer scales by X-ray absorption spectroscopic techniques (XAS and STXM). Absorption at Al, Si and Fe edges was investigated to have a complete overview of the distribution and status of constituting elements. Whereas Si K-edge results do not evidence significant evolution of silicon status, investigations at Al K-edge and Fe L-edges demonstrate variations at aggregate and particle scales of Al-IV:Al-VI and Fe2+:Fe3+ ratios. Spectroscopic data evidence the systematic crystallization of Fe-serpentines onto the remaining particles of kaolinite and the absence of pure species (kaolinite or Fe-serpentines). Combination of spatially resolved spectroscopic analyses and TEM-EDXS elemental distribution aims to calculate unit cell formulae of Fe-serpentines layers and abundance of each species in mixed particles. For most of the investigated particles, results reveal that the variations of particles composition are directly linked to the relative contributions of kaolinite and Fe-berthierine in mixed particles. However, for some particles, microscale investigations evidence crystallization of two other Fe-serpentines species, devoid of aluminum, cronstedtite and greenalite.