Are nano-colloids controlling rare earth elements mobility or is it the opposite? Insight from A4F-UV-QQQ-ICP-MS.

Rare earth element (REE) mobility in the environment is expected to be controlled by colloids. Recent research has detailed the structure of iron-organic colloids (Fe-OM colloids), which include both large colloids and smaller nano-colloids. To assess how these nano-colloids affect REE mobility, their interactions with REE and calcium (Ca) were investigated at pH 4 and 6. Using Asymmetric Flow Field Flow Fractionation (A4F) combined with UV and Triple Quadrupole Inductively Coupled Plasma Mass Spectrometry (QQQ-ICP-MS), Fe-OM nano-colloids were separated from bulk Fe-OM colloids and their REE and Ca content were analyzed. Without REE and Ca, nano-colloids had an average diameter of approximately 25 nm. Their structure is pH-dependent, with aggregation increasing as pH decreases. At high REE loadings (REE/Fe ≥ 0.05), REE induced a size increase of nano-colloids, regardless of pH. Heavy REE (HREE), with their high affinity for organic matter, formed strong complexes with Fe-OM colloids, resulting in large aggregates. In contrast, light REE (LREE), which bind less strongly to organic molecules, were associated with the smallest nano-colloids. Low REE loading did not cause noticeable fractionation. Calcium further enhanced the aggregation process at both pH levels by neutralizing the charges on nano-colloids. These findings indicate that REE can act as aggregating agent controlling their own mobility, and regulating colloid transfer.

Association of rare earth elements with secondary mineral phases formed during alkalinization of acid mine drainage.

Rare Earth Elements (REE) are present in acid mine drainage (AMD) in micromolar concentrations and AMD discharge may lead to an environmental risk. Alkaline Passive Treatment Systems (PTS) are often used to treat AMD and trap toxic trace elements. This study was set up to identify mechanisms by which REE are trapped in or on secondary phases formed in a PTS. Batch alkalinization experiments were performed to simulate PTS by sequentially increasing the pH of AMD collected from the Tharsis mining area inside the Iberian Pyrite Belt and synthetic AMD water samples via CaCO3 addition. The solids that precipitated up to pH ~4 and between pH 4-6 were collected and characterized by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) in combination with Scanning Electron Microscope/Energy Dispersive X-ray spectroscopy (SEM/EDX) and synchrotron-based X-ray Absorption Spectroscopy (XAS) and synchrotron-based Micro-X-ray Fluorescence (µ-XRF). Results reveal that REE are mostly scavenged between pH 4-6 in association with Al and Fe phases, whereas a smaller fraction is scavenged at pH ~4 by association with gypsum. Synchrotron-based analysis evidences the incorporation of La3+ into the gypsum structure by substituting Ca2+, indicating a co-precipitation mechanism with gypsum occurring mainly at low pH. Results from parallel adsorption and co-precipitation tests suggest that the REE scavenging between pH 4-6 could be due to a combination of adsorption and co-precipitation on Al(OH)3 and ferrihydrite. This implies that in PTS, REE would be mainly found in Al- (and Fe-) oxyhydroxides occurring in deeper layers of the PTS, i.e., where higher pH-values occur, though a small fraction, especially the light REE, could also be found incorporated into gypsum in the upper layers.

Nonclassical Growth Mechanism of Double-Walled Metal-Oxide Nanotubes Implying Transient Single-Walled Structures.

The formation of imogolite nanotubes is reported to be a kinetic process involving intermediate roof-tile nanostructures. Here, the structural evolution occurring during the synthesis of aluminogermanate double-walled imogolite nanotubes is in situ monitored, thanks to an instrumented autoclave allowing the control of the temperature, the continuous measurement of pH and pressure, and the regular sampling of gas and solution. Chemical analyses confirm the completion of the precursor's conversion with the release of CO2, ethanol, and dioxane as main side products. The combination of microscopic observations, infrared, and absorption spectroscopies with small and wide-angle X-ray scattering experiments unravel a unique growth mechanism implying transient single-walled nanotubes instead of the self-assembly of stacked proto-imogolite tiles. The growth formation of these transient nanotubes is followed at the molecular level by Quick-X-ray absoprtion specotrscopy experiments. Multivariate data analysis evidences that the near neighboring atomic environment of Ge evolves from monotonous to a more complex one as the reaction progresses. The following transformation into a double-walled nanotube takes place at a nearly constant mean radius, as demonstrated by the simulation of X-ray scattering diagrams. Overall, transient nanotubes appear to serve for the anchoring of a new wall, corresponding to a mechanism radically different from that proposed in the literature.

Ti-Modified Imogolite Nanotubes as Promising Photocatalyst 1D Nanostructures for H2 Production.

Imogolite nanotubes (INTs) are predicted as a unique 1D material with spatial separation of conduction and valence band edges but their large band gaps have inhibited their use as photocatalysts. The first step toward using these NTs in photocatalysis and exploiting the polarization-promoted charge separation across their walls is to reduce their band gap. Here, the modification of double-walled aluminogermanate INTs by incorporation of titanium into the NT walls is explored. The precursor ratio x = [Ti]/([Ge]+[Ti]) is modulated between 0 and 1. Structural and optical properties are determined at different scales and the photocatalytic performance is evaluated for H2 production. Although the incorporation of Ti atoms into the structure remains limited, the optimal condition is found around x = 0.4 for which the resulting NTs reveal a remarkable hydrogen production of ≈1500 µmol g-1 after 5 h for a noble metal-free photocatalyst, a 65-fold increase relative to a commercial TiO2 -P25. This is correlated to a lowering of the recombination rate of photogenerated charge carriers for the most active structures. These results confirm the theoretical predictions regarding the potential of modified INTs as photoactive nanoreactors and pave the way for investigating and exploiting their polarization properties for energy applications.

Determination of the distribution of rare earth elements La and Gd in Daphnia magna via micro and nano-SXRF imaging.

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 of lanthanum (La) and gadolinium (Gd) in Daphnia magna neonates and discusses potential modes of action on the basis of the respective patterns of biodistribution. Ecotoxicological bioassays for acute toxicity were conducted and dissolved metal concentrations at the end of the tests were determined. The results showed a significant difference in nominal EC50 (immobility) between La (>30 mg L-1) and Gd (13.93 (10.92 to 17.38) mg L-1). Daphnids that were then exposed to a concentration close to the determined EC50 of Gd (15 mg L-1, nominal concentration) for 48 h and 72 h were studied by synchrotron micro and nano-X-ray fluorescence to evaluate the biodistribution of potentially accumulated metals. X-ray fluorescence analyses showed that La was mainly found in the intestinal track and appeared to accumulate in the hindgut. This accumulation might be explained by the ingestion of solid La precipitates formed in the media. In contrast, Gd could only be detected in a small amount, if at all, in the intestinal tract, but was present at a much higher concentration in the tissues and became more pronounced with longer exposure time. The solubility of Gd is higher in the media used, leading to higher dissolved concentrations and uptake into tissue in ionic form via common metal transporting proteins. By studying La and Gd biodistribution in D. magna after an acute exposure, the present study has demonstrated that different uptake pathways of solid and dissolved metal species may lead to different accumulation patterns and toxicity.

Locked up Inside the Vessels: Rare Earth Elements Are Transferred and Stored in the Conductive Tissues of the Accumulating Fern Dryopteris erythrosora.

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.

Innovative in situ remediation of mine waters using a layered double hydroxide-biochar composite.

The current demand for alternative water sources requires the incorporation of low-cost composites in remediation technologies. These represent a sustainable alternative to more expensive, commercially used adsorbents. The main objective of this comprehensive field-scale study was to incorporate the layered double hydroxides (LDHs) into the hybrid biochar-based composites and apply an innovative material to remediate As/Sb-rich mine waters. The presence of hydrous Fe oxides (HFOs) within the composite enhanced the total adsorption efficiency of the composite for As(V) and Sb(V). The kinetic data fitted a pseudo-second order model. Equilibrium experiments confirmed that the composite had a stronger interaction with As(V) than with Sb(V). The efficient removal of As(V) from mine water was achieved in both batch and continuous flow column systems, reaching up to 98% and 80%, respectively. Sb(V) showed different behavior to As(V) during mine water treatment, reaching adsorption efficiencies of up to 39% and 26% in batch and column experiments, respectively. The migration of Sb(V) in mine water was mostly attributed to its dispersion before it was able to show affinity to the composite. In general, the proposed column technology is suitable for the field remediation of small volumes of contaminated water, and thus has significant commercial potential.

Macrophage autophagy protects mice from cerium oxide nanoparticle-induced lung fibrosis.

BACKGROUND: Cerium (Ce) is a rare earth element, rapidly oxidizing to form CeO2, and currently used in numerous commercial applications, especially as nanoparticles (NP). The potential health effects of Ce remain uncertain, but literature indicates the development of rare earth pneumoconiosis accompanied with granuloma formation, interstitial fibrosis and inflammation. The exact underlying mechanisms are not yet completely understood, and we propose that autophagy could be an interesting target to study, particularly in macrophages. Therefore, the objective of our study was to investigate the role of macrophagic autophagy after pulmonary exposure to CeO2 NP in mice. Mice lacking the early autophagy gene Atg5 in their myeloid lineage and their wildtype counterparts were exposed to CeO2 NP by single oropharyngeal administration and sacrificed up to 1 month after. At that time, lung remodeling was thoroughly characterized (inflammatory cells infiltration, expression of fibrotic markers such as αSMA, TGFß1, total and type I and III collagen deposition), as well as macrophage infiltration (quantification and M1/M2 phenotype). RESULTS: Such pulmonary exposure to CeO2 NP induces a progressive and dose-dependent lung fibrosis in the bronchiolar and alveolar walls, together with the activation of autophagy. Blockage of macrophagic autophagy protects from alveolar but not bronchiolar fibrosis, via the modulation of macrophage polarization towards M2 phenotype. CONCLUSION: In conclusion, our findings bring novel insight on the role of macrophagic autophagy in lung fibrogenesis, and add to the current awareness of pulmonary macrophages as important players in the disease.

How crucial is the impact of calcium on the reactivity of iron-organic matter aggregates? Insights from arsenic.

Environmental iron-organic matter (Fe-OM) aggregates play a major role in the dynamic of pollutants. Nowadays, there is a lack of information about the control exerted by their structural organization on their reactivity towards metal(loid)s and in particular, the impact of major ions, such as calcium. The sorption capacity of mimetic environmental Fe-OM-Ca aggregates was investigated relative to the Fe/organic carbon (OC) and Ca/Fe ratios using As as a probe. It was shown that Fe speciation is the key factor controlling the reactivity of Fe-OM-Ca aggregates regarding the high affinity of Fe(III)-oligomers towards As and the high sorption capacity of ferrihydrite-like nanoparticles. Moreover, when it occurs at high concentration, Ca competes with Fe for OM binding leading to an increase in the amount of ferrihydrite-like nanoparticles and binding site availability. As a consequence, Ca not only impacts the ionic strength but it also has a dramatic impact on the structural organization of Fe-OM aggregates at several scales of organization, resulting in an increase of their sorption capacity. In the presence of high amounts of Ca, Fe-OM-Ca aggregates could immobilize pollutants in the soil porous media as they form a micrometric network exhibiting a strong sorption capacity.

The microfluidic laboratory at Synchrotron SOLEIL.

A microfluidic laboratory recently opened at Synchrotron SOLEIL, dedicated to in-house research and external users. Its purpose is to provide the equipment and expertise that allow the development of microfluidic systems adapted to the beamlines of SOLEIL as well as other light sources. Such systems can be used to continuously deliver a liquid sample under a photon beam, keep a solid sample in a liquid environment or provide a means to track a chemical reaction in a time-resolved manner. The laboratory provides all the amenities required for the design and preparation of soft-lithography microfluidic chips compatible with synchrotron-based experiments. Three examples of microfluidic systems that were used on SOLEIL beamlines are presented, which allow the use of X-ray techniques to study physical, chemical or biological phenomena.

Mapping Chemical Elements and Iron Oxidation States in the Substantia Nigra of 6-Hydroxydopamine Lesioned Rats Using Correlative Immunohistochemistry With Proton and Synchrotron Micro-Analysis.

Brain metal homeostasis is altered in neurodegenerative diseases and the concentration, the localization and/or the chemical speciation of the elements can be modified compared to healthy individuals. These changes are often specific to the brain region affected by the neurodegenerative process. For example, iron concentration is increased in the substantia nigra (SN) of Parkinson's disease patients and iron redox reactions might be involved in the pathogenesis. The identification of the molecular basis behind metal dyshomeostasis in specific brain regions is the subject of intensive research and chemical element imaging methods are particularly useful to address this issue. Among the imaging modalities available, Synchrotron X-ray fluorescence (SXRF) and particle induced X-ray emission (PIXE) using focused micro-beams can inform about the quantitative distribution of metals in specific brain regions. Micro-X-ray absorption near edge spectroscopy (XANES) can in addition identify the chemical species of the elements, in particular their oxidation state. However, in order to bring accurate information about metal changes in specific brain areas, these chemical imaging methods must be correlated to brain tissue histology. We present a methodology to perform chemical element quantitative mapping and speciation on well-identified brain regions using correlative immunohistochemistry. We applied this methodology to the study of an animal model of Parkinson's disease, the 6-hydroxydopamine (6-OHDA) lesioned rat. Tyrosine hydroxylase immunohistochemical staining enabled to identify the SN pars compacta (SNpc) and pars reticulata (SNpr) as well as the ventral tegmental area (VTA). Using PIXE we found that iron content was higher respectively in the SNpr > SNpc > VTA, but was not statistically significantly modified by 6-OHDA treatment. In addition, micro-SXRF revealed the higher manganese content in the SNpc compared to the SNpr. Using micro-XANES we identified Fe oxidation states in the SNpr and SNpc showing a spectral similarity comparable to ferritin for all brain regions and exposure conditions. This study illustrates the capability to correlate immunohistochemistry and chemical element imaging at the brain region level and this protocol can now be widely applied to other studies of metal dyshomeostasis in neurology.

Influence of crystallographic environment on scandium K-edge X-ray absorption near-edge structure spectra.

The absence of an extensive series of Sc K-edge X-ray absorption near-edge structure spectroscopy (XANES) reference spectra and the scarcity of direct structural data on Sc are major hurdles to develop our understanding of Sc chemistry. However, this first step is essential to develop new Sc-based applications and to better understand the formation of Sc deposits. Here, we present a detailed comparative study of Sc K-edge XANES spectra of three Sc-bearing compounds: a garnet (Ca3Sc2Si3O12), an oxide (Sc2O3) and a phosphate (ScPO4·2H2O). First-principles calculations have been performed to interpret the origin of the K pre-edge spectral features. We demonstrate the validity of our approach by reproducing satisfyingly the experimental spectra. The densities of states projected on the absorbing Sc atom and its first neighbours give the possibility to interpret the position and intensity of the pre-edge XANES features in terms of Sc local environment. The pre-edge features provide information on p-d mixing of the absorber orbitals giving clues on the centrosymmetry of the site and on the mixing of the empty 4p orbitals of the absorber with empty 3d orbitals of the neighbours via the empty p orbitals of the ligands. We also show that these features give a first estimate of the crystal-field splitting energy (ca. 1.5 eV), inaccessible using other spectroscopic methods. Comparisons with K-edge spectra of other 3d0 ions from the literature reveal the specificities of the Sc pre-edge, indicating that core-hole screening is weaker than for Ti4+-bearing compounds. This study provides a dataset of spectral signatures and a theoretical basis for their interpretation, a requirement for future studies on Sc chemical form in synthetic and natural systems.

Experimental evidence of REE size fraction redistribution during redox variation in wetland soil.

The evolution of rare earth element (REE) speciation between reducing and oxidizing conditions in a riparian wetland soil was studied relative to the size fractionation of the solution. In all size fractions obtained from the reduced and oxidized soil solutions, the following analyses were carried out: organic matter (OM) characterization, transmission electron microscopy (TEM) observations as well as major and trace element analyses. Significant REE redistribution and speciation evolution between the various size fractions were observed. Under reducing conditions, the REEs were bound to colloidal and dissolved OM (<2µm size fractions). By contrast, under oxidizing conditions, they were distributed in particulate (>2µm size fraction), colloidal (<2µm size fraction), organic and Fe-enriched fractions. In the particulate size fraction, the REEs were bound to humic and bacterial OM embedding Fe nano-oxides. The resulting REE pattern showed a strong enrichment in heavy REEs (HREEs) in response to REE binding to specific bacterial OM functional groups. In the largest colloidal size fraction (0.2µm-30kDa), the REEs were bound to humic substances (HS). The lowest colloidal size fraction (<30kDa) is poorly concentrated in the REEs and the REE pattern showed an increase in the middle REEs (MREEs) and heavy REEs (HREEs) corresponding to a low REE loading on HS. A comparison of the REE patterns in the present experimental and field measurements demonstrated that, in riparian wetlands, under a high-water level, reducing conditions are insufficient to allow for the dissolution of the entire Fe nano-oxide pool formed during the oxidative period. Therefore, even under reducing conditions, Fe(III) seems to remain a potential scavenger of REEs.

Pulmonary exposure to metallic nanomaterials during pregnancy irreversibly impairs lung development of the offspring.

Due to the growing commercial applications of manufactured nanoparticles (NPs), toxicological studies on NPs, especially during the critical window of development, are of major importance. The aim of the study was to assess the impact of respiratory exposure to metallic and metal oxide NPs during pregnancy on lung development of the offspring and to determine the key parameters involved in lung alterations. Pregnant mice were exposed to weekly doses of 100 µg (total dose 300 µg) of titanium dioxide (TiO2), cerium oxide (CeO2), silver (Ag) NPs or saline solution by nonsurgical intratracheal instillation. The offspring lungs were analyzed at different stages of lung development: fetal stage (gestational day 17.5), pulmonary alveolarization (post-delivery day 14.5) and lung maturity (post-delivery day 49.5). Regardless of the type of NP, maternal exposure during gestation induced long-lasting impairment of lung development of the offspring. This effect was accompanied by: i) decreased placental efficiency together with the presence of NPs in placenta, ii) no increase of inflammatory mediators present in amniotic fluid, placenta or offspring lungs and iii) decreased pulmonary expression of vascular endothelial growth factor-α (VEGF-α) and matrix metalloproteinase 9 (MMP-9) at the fetal stage, and fibroblast growth factor-18 (FGF-18) at the alveolarization stage. Respiratory exposure to metallic NPs during pregnancy induces stereotyped impairment of lung development with a lasting effect in adult mice, independently of the chemical nature of the NP.

Fate of cadmium in the rhizosphere of Arabidopsis halleri grown in a contaminated dredged sediment.

In regions impacted by mining and smelting activities, dredged sediments are often contaminated with metals. Phytotechnologies could be used for their management, but more knowledge on the speciation of metals in the sediment and on their fate after colonization by plant roots is needed. This work was focused on a dredged sediment from the Scarpe river (North of France), contaminated with Zn and Cd. Zn, Cd hyperaccumulating plants Arabidopsis halleri from metallicolous and non-metallicolous origin were grown on the sediment for five months in a pot experiment. The nature and extent of the modifications in Cd speciation with or without plant were determined by electron microscopy, micro X-ray fluorescence and bulk and micro X-ray absorption spectroscopy. In addition, changes in Cd exchangeable and bioavailable pools were evaluated, and Cd content in leachates was measured. Finally, Cd plant uptake and plant growth parameters were monitored. In the original sediment, Cd was present as a mixed Zn, Cd, Fe sulfide. After five months, although pots still contained reduced sulfur, Cd-bearing sulfides were totally oxidized in vegetated pots, whereas a minor fraction (8%) was still present in non-vegetated ones. Secondary species included Cd bound to O-containing groups of organic matter and Cd phosphates. Cd exchangeability and bioavailability were relatively low and did not increase during changes in Cd speciation, suggesting that Cd released by sulfide oxidation was readily taken up with strong interactions with organic matter and phosphate ligands. Thus, the composition of the sediment, the oxic conditions and the rhizospheric activity (regardless of the plant origin) created favorable conditions for Cd stabilization. However, it should be kept in mind that returning to anoxic conditions may change Cd speciation, so the species formed cannot be considered as stable on the long term.

Evidence of various mechanisms of Cd sequestration in the hyperaccumulator Arabidopsis halleri, the non-accumulator Arabidopsis lyrata, and their progenies by combined synchrotron-based techniques.

Arabidopsis halleri is a model plant for Zn and Cd hyperaccumulation. The objective of this study was to determine the relationship between the chemical forms of Cd, its distribution in leaves, and Cd accumulation and tolerance. An interspecific cross was carried out between A. halleri and the non-tolerant and non-hyperaccumulating relative A. lyrata providing progenies segregating for Cd tolerance and accumulation. Cd speciation and distribution were investigated using X-ray absorption spectroscopy and microfocused X-ray fluorescence. In A. lyrata and non-tolerant progenies, Cd was coordinated by S atoms only or with a small contribution of O groups. Interestingly, the proportion of O ligands increased in A. halleri and tolerant progenies, and they were predominant in most of them, while S ligands were still present. Therefore, the binding of Cd with O ligands was associated with Cd tolerance. In A. halleri, Cd was mainly located in the xylem, phloem, and mesophyll tissue, suggesting a reallocation process for Cd within the plant. The distribution of the metal at the cell level was further discussed. In A. lyrata, the vascular bundles were also Cd enriched, but the epidermis was richer in Cd as compared with the mesophyll. Cd was identified in trichomes of both species. This work demonstrated that both Cd speciation and localization were related to the tolerance character of the plant.

Interactions between natural organic matter, sulfur, arsenic and iron oxides in re-oxidation compounds within riparian wetlands: nanoSIMS and X-ray adsorption spectroscopy evidences.

Arsenic (As) is a toxic and ubiquitous element which can be responsible for severe health problems. Recently, Nano-scale Secondary Ions Mass Spectrometry (nanoSIMS) analysis has been used to map organomineral assemblages. Here, we present a method adapted from Belzile et al. (1989) to collect freshly precipitated compounds of the re-oxidation period in a natural wetland environment using a polytetrafluoroethylene (PTFE) sheet scavenger. This method provides information on the bulk samples and on the specific interactions between metals (i.e. As) and the natural organic matter (NOM). Our method allows producing nanoSIMS imaging on natural colloid precipitates, including (75)As(-), (56)Fe(16)O(-), sulfur ((32)S(-)) and organic matter ((12)C(14)N) and to measure X-ray adsorption of sulfur (S) K-edge. A first statistical treatment on the nanoSIMS images highlights two main colocalizations: (1) (12)C(14)N(-), (32)S(-), (56)Fe(16)O(-) and (75)As(-), and (2) (12)C(14)N(-), (32)S(-) and (75)As(-). Principal component analyses (PCAs) support the importance of sulfur in the two main colocalizations firstly evidenced. The first component explains 70% of the variance in the distribution of the elements and is highly correlated with the presence of (32)S(-). The second component explains 20% of the variance and is highly correlated with the presence of (12)C(14)N(-). The X-ray adsorption near edge spectroscopy (XANES) on sulfur speciation provides a quantification of the organic (55%) and inorganic (45%) sulfur compositions. The co-existence of reduced and oxidized S forms might be attributed to a slow NOM kinetic oxidation process. Thus, a direct interaction between As and NOM through sulfur groups might be possible.

Interaction of Fe(III) and Al(III) during hydroxylation by forced hydrolysis: the nature of Al-Fe oxyhydroxy co-precipitates.

Al-Fe oxyhydroxy co-precipitates were synthesised by forced hydrolysis of Fe(NO3)3·9H2O and Al(NO3)3·9H2O solutions. Solids containing 0, 1, 10, 25, 50, 75, 90 mol% Al were characterised for composition, texture, mineral structure and local atomic environment. Cation substitution in the hydrous oxides was not observed. The solids consisted of hydrous ferric oxide (HFO) nuclei surrounded by Al-hydroxide. Below 50 mol% Al, unit particle size, high specific surface area and microporosity of HFO were preserved. Al-K-edge XANES showed ordered arrangements of Al-octahedra suggesting that some Al bound specifically to HFO surface sites. Above 50 mol%, Al precipitated in multiple layers around the nuclei and also as individual entities. The HFO nuclei exhibited the general characteristics of a 2-line ferrihydrite. However, as Al increased, the structure was slightly modified. While the symmetry of the FeO6 octahedra improved, the number of Fe-Fe linkages decreased, suggesting less polymerisation. An organisation of the Fe-octahedra, faintly resembling akaganeite, was expressed in Raman spectra. These changes in HFO structure were attributed to hindrance in the progressive olation/oxolation of the primary Fe-hydroxypolymers, caused by Al bound to the surface of nuclei. The presence of nitrate is suspected to have favoured the structural changes.

Investigation of the discoloration of smalt pigment in historic paintings by micro-X-ray absorption spectroscopy at the Co K-edge.

Smalt was commonly used as a pigment by artists between the 16th and 18th centuries. It is a powdered blue potash glass colored by cobalt ions and often degrades causing dramatic changes in the appearance of paintings. The aim of the work presented in this paper was to investigate the changes in the structure and environment around the cobalt ion on deterioration, to further our understanding of the basis of the loss of color. Particles of well-preserved and altered smalt in microsamples from paintings in the National Gallery, London, and the Louvre, Paris, were analyzed using synchrotron micro-X-ray absorption spectroscopy at the Co K-edge. X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) measurements showed that in intense blue particles the cobalt is predominantly present as Co(2+) in tetrahedral coordination, whereas in colorless altered smalt the Co(2+) coordination number in the glass structure is increased and there is a shift from tetrahedral toward octahedral coordination. The extent of this shift correlates clearly with the alkali content, indicating that it is caused by leaching of potassium cations, which act as charge compensators and stabilize the tetrahedral coordination of the cobalt ions that is responsible for the blue color.

Spatial distribution and speciation of lead around corroding bullets in a shooting range soil studied by micro-X-ray fluorescence and absorption spectroscopy.

We investigated the spatial distribution and speciation of Pb in the weathering crust and soil surrounding corroding metallic Pb bullets in a shooting range soil. The soil had a neutral pH, loamy texture, and was highly contaminated with Pb, with total Pb concentrations in the surface soil up to 68 000 mg kg(-1). Undisturbed soil samples containing corroding bullets were collected and embedded in resin, and polished sections were prepared for micro-X-ray fluorescence (micro-XRF) elemental mapping and micro-X-ray absorption near edge structure (micro-XANES) spectroscopy. Bullet weathering crust material was separated from the metallic Pb cores and analyzed by powder X-ray diffraction analysis. Our results show a steep decrease in total Pb concentrations from the bullet weathering crust into the surrounding soil matrix. The weathering crust consisted of a mixture of litharge [alpha-PbO], hydrocerussite [Pb3(CO3)2-(OH)2], and cerussite [PbCO3], with litharge dominating near the metallic Pb core and cerussite dominating in the outer crust, which is in contact with the soil matrix. On the basis of these results and thermodynamic considerations, we propose that the transition of Pb species after oxidation of Pb(O) to Pb(II) follows the sequence litharge --> hydrocerussite --> cerussite. Consequently, the solubility of cerussite limits the activity of Pb2+ in the soil solution in contact with weathering bullets to < or =1.28 x 10(-6) at pH 7, assuming that the CO2 partial pressure (PCO2) in the soil is equal or larger than in the atmosphere (PCO2 > or = 0.000 35 atm).