Hyper-accumulation of vanadium in animals: Two sponges compete with urochordates.

Vanadium (V) concentrations in organisms are usually very low. To date, among animals, only some urochordate and annelid species contain very high levels of V in their tissues. A new case of hyper-accumulation of V in a distinct animal phylum (Porifera), namely, the two homoscleromorph sponge species Oscarella lobularis and O. tuberculata is reported. The measured concentrations (up to 30 g/kg dry weight) exceed those reported previously and are not found in all sponge classes. In both Oscarella species, V is mainly accumulated in the surface tissues, and in mesohylar cells, as V(IV), before being partly reduced to V(III) in the deeper tissues. Candidate genes from Bacteria and sponges have been identified as possibly being involved in the metabolism of V. This finding provides clues for the development of bioremediation strategies in marine ecosystems and/or bioinspired processes to recycle this critical metal.

Multiscale imaging on Saxifraga paniculata provides new insights into yttrium uptake by plants.

Yttrium (Y) has gained importance in high tech applications and, together with the other rare earth elements (REEs), is also considered to be an emerging environmental pollutant. The alpine plant Saxifraga paniculata was previously shown to display high metal tolerance and an intriguing REE accumulation potential. In this study, we analysed soil grown commercial and wild specimens of Saxifraga paniculata to assess Y accumulation and shed light on the uptake pathway. Laser ablation inductively coupled plasma mass spectrometry and synchrotron-based micro X-ray fluorescence spectroscopy was used to localise Y within the plant tissues and identify colocalized elements. Y was distributed similarly in commercial and wild specimens. Within the roots, Y was mostly located in the epidermis region. Translocation was low, but wild individuals accumulated significantly more Y than commercial ones. In plants of both origins, we observed consistent colocalization of Al, Fe, Y and Ce in all plant parts except for the hydathodes. This indicates a shared pathway during translocation and could explained by the formation of a stable organic complex with citrate, for example. Our study provides important insights into the uptake pathway of Y in S. paniculata, which can be generalised to other plants.

Uptake patterns of critical metals in alpine plant species growing in an unimpaired natural site.

The range of metals used for industrial purposes - electrical engineering, solar panels, batteries - has increased substantially over the last twenty years. Some of these emerging metals are the subject of geopolitical conflict and are considered critical as their unique properties make them irreplaceable. Many of these elements are poorly studied and their biogeochemical cycles still raise many questions. Aim of this study is to analyse the soil-to-plant transfer of some of these chemical elements and to shed light on their uptake pathways. For this purpose, the geological site of Jas Roux (France) was chosen as this alpine site is naturally rich in critical and potentially toxic elements such as As, Sb, Ba and Tl, but nevertheless is host to a high diversity of plants. Elemental concentrations were analysed in the topsoil and in 12 selected alpine plant species sampled in situ. Statistical tools were used to detect species dependent characteristics in elemental uptake. Our analyses revealed accumulation of rare earth elements by Saxifraga paniculata, selective oxyanion absorption by Hippocrepis comosa, accumulation of Tl by Biscutella laevigata and Galium corrudifolium and an exclusion strategy in Juniperus communis. These findings advance our understanding of the environmental behaviour of critical metals and metalloids such as V, As, Y, Sb, Ce, Ba and Tl and might bare valuable information for phytoremediation applications.

X-ray absorption spectroscopy evidence of sulfur-bound cadmium in the Cd-hyperaccumulator Solanum nigrum and the non-accumulator Solanum melongena.

It has been proposed that non-protein thiols and organic acids play a major role in cadmium phytoavailability and distribution in plants. In the Cd-hyperaccumulator Solanum nigrum and non-accumulator Solanum melongena, the role of these organic ligands in the accumulation and detoxification mechanisms of Cd are debated. In this study, we used X-ray absorption spectroscopy to investigate Cd speciation in these plants (roots, stem, leaves) and in the soils used for their culture to unravel the plants responses to Cd exposure. The results show that Cd in the 100 mg kg-1 Cd-doped clayey loam soil is sorbed onto iron oxyhydroxides. In both S. nigrum and S. melongena, Cd in roots and fresh leaves is mainly bound to thiol ligands, with a small contribution of inorganic S ligands in S. nigrum leaves. We interpret the Cd binding to sulfur ligands as detoxification mechanisms, possibly involving the sequestration of Cd complexed with glutathione or phytochelatins in the plant vacuoles. In the stems, results show an increase binding of Cd to -O ligands (>50% for S. nigrum). We suggest that Cd is partly complexed by organic acids for transportation in the sap.

Accumulation, speciation and localization of silver nanoparticles in the earthworm Eisenia fetida.

The use of silver nanoparticles (AgNPs) in agriculture and many consumer products has led to a significant release of Ag in the environment. Although Ag toxicity in terrestrial organisms has been studied extensively, very little is known about the accumulation capacity and coping mechanisms of organisms in Ag-contaminated soil. In this context, we exposed Eisenia fetida earthworms to artificial OECD soil spiked with a range of concentrations of Ag (AgNPs or AgNO3). The main aims were to (1) identify the location and form of accumulation of Ag in the exposed earthworms and (2) better understand the physiological mechanisms involved in Ag detoxification. The results showed that similar doses of AgNPs or AgNO3 did not have the same effect on E. fetida survival. The two forms of Ag added to soil exhibited substantial differences in speciation at the end of exposure, but the Ag speciation and content of Ag in earthworms were similar, suggesting that biotransformation of Ag occurred. Finally, 3D images of intact earthworms obtained by X-ray micro-computed tomography revealed that Ag accumulated preferentially in the chloragogen tissue, coelomocytes, and nephridial epithelium. Thus, E. fetida bioaccumulates Ag, but a regulation mechanism limits its impact in a very efficient manner. The location of Ag in the organism, the competition between Ag and Cu, and the speciation of internal Ag suggest a link between Ag and the thiol-rich proteins that are widely present in these tissues, most probably metallothioneins, which are key proteins in the sequestration and detoxification of metals.

Medium-term effects of Ag supplied directly or via sewage sludge to an agricultural soil on Eisenia fetida earthworm and soil microbial communities.

The widespread use of silver nanoparticles (AgNPs) in consumer products that release Ag throughout their life cycle has raised potential environmental concerns. AgNPs primarily accumulate in soil through the spreading of sewage sludge (SS). In this study, the effects of direct exposure to AgNPs or indirect exposure via SS contaminated with AgNPs on the earthworm Eisenia fetida and soil microbial communities were compared, through 3 scenarios offering increasing exposure concentrations. The effects of Ag speciation were analyzed by spiking SS with AgNPs or AgNO3 before application to soil. SS treatment strongly impacted Ag speciation due to the formation of Ag2S species that remained sulfided after mixing in the soil. The life traits and expression of lysenin, superoxide dismutase, cd-metallothionein genes in earthworms were not impacted by Ag after 5 weeks of exposure, but direct exposure to Ag without SS led to bioaccumulation of Ag, suggesting transfer in the food chain. Ag exposure led to a decrease in potential carbon respiration only when directly added to the soil. The addition of SS had a greater effect on soil microbial diversity than the form of Ag, and the formation of Ag sulfides in SS reduced the impact of AgNPs on E. fetida and soil microorganisms compared with direct addition.

Screening of Native Plants Growing on a Pb/Zn Mining Area in Eastern Morocco: Perspectives for Phytoremediation.

Screening of native plant species from mining sites can lead to identify suitable plants for phytoremediation approaches. In this study, we assayed heavy metals tolerance and accumulation in native and dominant plants growing on abandoned Pb/Zn mining site in eastern Morocco. Soil samples and native plants were collected and analyzed for As, Cd, Cu, Ni, Sb, Pb, and Zn concentrations. Bioconcentration factor (BCF), translocation factor (TF), and biological accumulation coefficient (BAC) were determined for each element. Our results showed that soils present low organic matter content combined with high levels of heavy metals especially Pb and Zn due to past extraction activities. Native and dominant plants sampled in these areas were classified into 14 species and eight families. Principal components analysis separated Artemisia herba-alba with high concentrations of As, Cd, Cu, Ni, and Pb in shoots from other species. Four plant species, namely, Reseda alba, Cistus libanotis, Stipa tenacissima, and Artemisia herba-alba showed strong capacity to tolerate and hyperaccumulate heavy metals, especially Pb, in their tissues. According to BCF, TF, and BAC, these plant species could be used as effective plants for Pb phytoextraction. Stipa tenacissima and Artemisia herba-alba are better suited for phytostabilization of Cd/Cu and Cu/Zn, respectively. Our study shows that several spontaneous and native plants growing on Pb/Zn contaminated sites have a good potential for developing heavy metals phytoremediation strategies.

How to assess trace elements bioavailability for benthic organisms in lowly to moderately contaminated coastal sediments?

The bioavailability of trace elements (As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Zn) in lowly to moderately contaminated coastal sediments from the Berre lagoon, France, was assessed by comparing their potentially bioavailable concentrations and bioaccumulated concentrations in the polychaete Alitta succinea. No linear correlations were observed contrarily to what is generally observed in similar works in areas with highly contaminated sediment. Correlations between trace and major elements (Fe, Ca, S, Mg, P, Al) in Alitta succinea tissues and their distribution in organism tissues show that, in such lowly to moderately contaminated sediments, biological variabilities should be considered. Normalization procedures allow to take into account these variabilities and to identify that sediment contamination is partly involved in the benthic ecosystem degradation of the Berre lagoon. Alitta succinea cannot be used as relevant bioindicator for Zn and Co bioavailability in sediment, since these elements are regulated by this organism.

Drastic Change in Zinc Speciation during Anaerobic Digestion and Composting: Instability of Nanosized Zinc Sulfide.

Zinc (Zn) is a potentially toxic trace element that is present in large amounts in organic wastes (OWs) spread on agricultural lands as fertilizer. Zn speciation in OW is a crucial parameter to understand its fate in soil after spreading and to assess the risk associated with agricultural recycling of OW. Here, we investigated changes in Zn speciation from raw OWs up to digestates and/or composts for a large series of organic wastes sampled in full-scale plants. Using extended X-ray absorption fine structure, we show that nanosized Zn sulfide (nano-ZnS) is a major Zn species in raw liquid OWs and a minor species in raw solid OWs. Whatever the characteristics of the raw OW, anaerobic digestion always favors the formation of nano-ZnS (>70% of zinc in digestates). However, after 1 to 3 months of composting of OWs, nano-ZnS becomes a minor species (<10% of zinc). In composts, Zn is mostly present as amorphous Zn phosphate and Zn sorbed to ferrihydrite. These results highlight (i) the influence of OW treatment on Zn speciation and (ii) the chemical instability of nano-ZnS formed in OW in anaerobic conditions.

Non-linear release dynamics for a CeO2 nanomaterial embedded in a protective wood stain, due to matrix photo-degradation.

The release of CeO2-bearing residues during the weathering of an acrylic stain enriched with CeO2 nanomaterial designed for wood protection (Nanobyk brand additive) was studied under two different scenarios: (i) a standard 12-weeks weathering protocol in climate chamber, that combined condensation, water spraying and UV-visible irradiation and (ii) an alternative accelerated 2-weeks leaching batch assay relying on the same weathering factors (water and UV), but with a higher intensity of radiation and immersion phases. Similar Ce released amounts were evidenced for both scenarios following two phases: one related to the removal of loosely bound material with a relatively limited release, and the other resulting from the degradation of the stain, where major release occurred. A non-linear evolution of the release with the UV dose was evidenced for the second phase. No stabilization of Ce emissions was reached at the end of the experiments. The two weathering tests led to different estimates of long-term Ce releases, and different degradations of the stain. Finally, the photo-degradations of the nanocomposite, the pure acrylic stains and the Nanobyk additive were compared. The incorporation of Nanobyk into the acrylic matrix significantly modified the response of the acrylic stain to weathering.

Respiratory hazard of Li-ion battery components: elective toxicity of lithium cobalt oxide (LiCoO2) particles in a mouse bioassay.

Rechargeable Li-ion batteries (LIB) are increasingly produced and used worldwide. LIB electrodes are made of micrometric and low solubility particles, consisting of toxicologically relevant elements. The health hazard of these materials is not known. Here, we investigated the respiratory hazard of three leading LIB components (LiFePO4 or LFP, Li4Ti5O12 or LTO, and LiCoO2 or LCO) and their mechanisms of action. Particles were characterized physico-chemically and elemental bioaccessibility was documented. Lung inflammation and fibrotic responses, as well as particle persistence and ion bioavailability, were assessed in mice after aspiration of LIB particles (0.5 or 2 mg); crystalline silica (2 mg) was used as reference. Acute inflammatory lung responses were recorded with the 3 LIB particles and silica, LCO being the most potent. Inflammation persisted 2 m after LFP, LCO and silica, in association with fibrosis in LCO and silica lungs. LIB particles persisted in the lungs after 2 m. Endogenous iron co-localized with cobalt in LCO lungs, indicating the formation of ferruginous bodies. Fe and Co ions were detected in the broncho-alveolar lavage fluids of LFP and LCO lungs, respectively. Hypoxia-inducible factor (HIF) -1α, a marker of fibrosis and of the biological activity of Co ions, was upregulated in LCO and silica lungs. This study identified, for the first time, the respiratory hazard of LIB particles. LCO was at least as potent as crystalline silica to induce lung inflammation and fibrosis. Iron and cobalt, but not lithium, ions appear to contribute to LFP and LCO toxicity, respectively.

Multi-scale X-ray computed tomography to detect and localize metal-based nanomaterials in lung tissues of in vivo exposed mice.

In this methodological study, we demonstrated the relevance of 3D imaging performed at various scales for the ex vivo detection and location of cerium oxide nanomaterials (CeO2-NMs) in mouse lung. X-ray micro-computed tomography (micro-CT) with a voxel size from 14 µm to 1 µm (micro-CT) was combined with X-ray nano-computed tomography with a voxel size of 63 nm (nano-CT). An optimized protocol was proposed to facilitate the sample preparation, to minimize the experimental artifacts and to optimize the contrast of soft tissues exposed to metal-based nanomaterials (NMs). 3D imaging of the NMs biodistribution in lung tissues was consolidated by combining a vast variety of techniques in a correlative approach: histological observations, 2D chemical mapping and speciation analysis were performed for an unambiguous detection of NMs. This original methodological approach was developed following a worst-case scenario of exposure, i.e. high dose of exposure with administration via intra-tracheal instillation. Results highlighted both (i) the non-uniform distribution of CeO2-NMs within the entire lung lobe (using large field-of-view micro-CT) and (ii) the detection of CeO2-NMs down to the individual cell scale, e.g. macrophage scale (using nano-CT with a voxel size of 63 nm).

Nanoscale Coloristic Pigments: Upper Limits on Releases from Pigmented Plastic during Environmental Aging, In Food Contact, and by Leaching.

The life cycle of nanoscale pigments in plastics may cause environmental or human exposure by various release scenarios. We investigated spontaneous and induced release with mechanical stress during/after simulated sunlight and rain degradation of polyethylene (PE) with organic and inorganic pigments. Additionally, primary leaching in food contact and secondary leaching from nanocomposite fragments with an increased surface into environmental media was examined. Standardized protocols/methods for release sampling, detection, and characterization of release rate and form were applied: Transformation of the bulk material was analyzed by Scanning Electron Microscopy (SEM), X-ray-tomography and Fourier-Transform Infrared spectroscopy (FTIR); releases were quantified by Inductively Coupled Plasma Mass Spectrometry (ICP-MS), single-particle-ICP-MS (sp-ICP-MS), Transmission Electron Microscopy (TEM), Analytical Ultracentrifugation (AUC), and UV/Vis spectroscopy. In all scenarios, the detectable particulate releases were attributed primarily to contaminations from handling and machining of the plastics, and were not identified with the pigments, although the contamination of 4 mg/kg (Fe) was dwarfed by the intentional content of 5800 mg/kg (Fe as Fe2O3 pigment). We observed modulations (which were at least partially preventable by UV stabilizers) when comparing as-produced and aged nanocomposites, but no significant increase of releases. Release of pigments was negligible within the experimental error for all investigated scenarios, with upper limits of 10 mg/m2 or 1600 particles/mL. This is the first holistic confirmation that pigment nanomaterials remain strongly contained in a plastic that has low diffusion and high persistence such as the polyolefin High Density Polyethylene (HDPE).

Nanoparticle Uptake in Plants: Gold Nanomaterial Localized in Roots of Arabidopsis thaliana by X-ray Computed Nanotomography and Hyperspectral Imaging.

Terrestrial plants can internalize and translocate nanoparticles (NPs). However, direct evidence for the processes driving the NP uptake and distribution in plants is scarce at the cellular level. Here, NP-root interactions were investigated after 10 days of exposure of Arabidopsis thaliana to 10 mg·L-1 of negatively or positively charged gold NPs (∼12 nm) in gels. Two complementary imaging tools were used: X-ray computed nanotomography (nano-CT) and enhanced dark-field microscopy combined with hyperspectral imaging (DF-HSI). The use of these emerging techniques improved our ability to detect and visualize NP in plant tissue: by spectral confirmation via DF-HSI, and in three dimensions via nano-CT. The resulting imaging provides direct evidence that detaching border-like cells (i.e., sheets of border cells detaching from the root) and associated mucilage can accumulate and trap NPs irrespective of particle charge. On the contrary, border cells on the root cap behaved in a charge-specific fashion: positively charged NPs induced a higher mucilage production and adsorbed to it, which prevented translocation into the root tissue. Negatively charged NPs did not adsorb to the mucilage and were able to translocate into the apoplast. These observations provide direct mechanistic insight into NP-plant interactions, and reveal the important function of border cells and mucilage in interactions of plants with charged NPs.

Silver Nanoparticles and Wheat Roots: A Complex Interplay.

Agricultural soils are major sinks of silver nanoparticles in the environment, and crops are directly exposed to these emerging contaminants. A clear picture of their chemical transformations, uptake and transport mechanisms, and phytotoxic impacts is still lacking. In this work, wheat plants were exposed to pristine metallic (Ag-NPs) and sulfidized (Ag2S-NPs) silver nanoparticles and ionic Ag. Data on Ag distribution and speciation, phytotoxicity markers, and gene expression were studied. A multi-technique and multi-scale approach was applied, combining innovating tools at both the laboratory and synchrotron. Various chemical transformations were observed on the epidermis and inside roots, even for Ag2S-NPs, leading to an exposure to multiple Ag forms, which likely evolve over time. Genes involved in various functions including oxidative stress, defense against pathogens, and metal homeostasis were impacted in different ways depending upon the Ag source. This study illustrates the complexity of the toxicity pattern for plants exposed to Ag-NPs, the necessity of monitoring several markers to accurately evaluate the toxicity, and the interest of interpreting the toxicity pattern in light of the distribution and speciation of Ag.

Effect of phytoliths for mitigating water stress in durum wheat.

The role of silicon (Si) in alleviating biotic and abiotic stresses in crops is well evidenced by empirical studies; however, the mechanisms by which it works are still poorly known. The aim of this study is to determine whether or not phytolith composition and distribution in wheat are affected by drought and, if so, why. Durum wheat was grown using hydroponics in the presence of polyethylene glycol (PEG)-6000 to perform a water-stress simulation. We developed an original method for in situ analysis of phytoliths in leaves via X-ray imaging. PEG was efficient in inhibiting water uptake by roots and creating stress, and prevented a small fraction of Si from being accumulated in the shoots. The application of Si with PEG maintained shoot and root fresh weights (FW) and relative water content at higher values than for plants without Si, especially at PEG 12%. Our data show that, under water stress in the presence of Si, accumulation of phytoliths over the veins provides better support to the leaf, thus allowing for a better development of the whole plant than in the absence of Si. The development of silicified trichomes in durum wheat depends primarily on the availability of Si in soil and is not an adaptation to water stress.

Environmental exposure to TiO2 nanomaterials incorporated in building material.

Nanomaterials are increasingly being used to improve the properties and functions of common building materials. A new type of self-cleaning cement incorporating TiO2 nanomaterials (TiO2-NMs) with photocatalytic properties is now marketed. This promising cement might provide air pollution-reducing properties but its environmental impact must be validated. During cement use and aging, an altered surface layer is formed that exhibits increased porosity. The surface layer thickness alteration and porosity increase with the cement degradation rate. The hardened cement paste leaching behavior has been fully documented, but the fate of incorporated TiO2-NMs and their state during/after potential release is currently unknown. In this study, photocatalytic cement pastes with increasing initial porosity were leached at a lab-scale to produce a range of degradation rates concerning the altered layer porosity and thickness. No dissolved Ti was released during leaching, only particulate TiO2-NM release was detected. The extent of release from this batch test simulating accelerated worst-case scenario was limited and ranged from 18.7 ± 2.1 to 33.5 ± 5.1 mg of Ti/m2 of cement after 168 h of leaching. TiO2-NMs released into neutral aquatic media (simulate pH of surface water) were not associated or coated by cement minerals. The TiO2-NM release mechanism is suspected to start from freeing of TiO2-NMs in the altered layer pore network due to partial cement paste dissolution followed by diffusion into the bulk pore solution to the surface. The extent of TiO2-NM release was not solely related to the cement degradation rate.

Effect of pH and Pressure on Uranium Removal from Drinking Water Using NF/RO Membranes.

Groundwater is becoming an increasingly important drinking water source. However, the use of groundwater for potable purposes can lead to chronic human exposure to geogenic contaminants, for example, uranium. Nanofiltration (NF) and reverse osmosis (RO) processes are used for drinking water purification, and it is important to understand how contaminants interact with membranes since accumulation of contaminants to the membrane surface can lead to fouling, performance decline and possible breakthrough of contaminants. During the current study laboratory experiments were conducted using NF (TFC-SR2) and RO (BW30) membranes to establish the behavior of uranium across pH (3-10) and pressure (5-15 bar) ranges. The results showed that important determinants of uranium-membrane sorption interactions were (i) the uranium speciation (uranium species valence and size in relation to membrane surface charge and pore size) and (ii) concentration polarization, depending on the pH values. The results show that it is important to monitor sorption of uranium to membranes, which is controlled by pH and concentration polarization, and, if necessary, adjust those parameters controlling uranium sorption.

Increased zinc and copper availability in organic waste amended soil potentially involving distinct release mechanisms.

This study aimed at determining the fate of trace elements (TE) following soil organic waste (OW) application. We used a unique combination of X-ray absorption spectroscopy analyses, to determine TE speciation, with incubation experiments for in situ monitoring of TE availability patterns over a time course with the technique of the diffusive gradients in thin films (DGT). We showed that copper (Cu) and zinc (Zn) availability were both increased in OW-amended soil, but their release was controlled by distinct mechanisms. Zn speciation in OW was found to be dominated by an inorganic species, i.e. Zn sorbed on Fe oxides. Zn desorption from Fe oxides could explain the increase in Zn availability in OW-amended soil. Cu speciation in OW was dominated by organic species. Cu release through the mineralization of organic carbon from OW was responsible for the increase in Cu availability.

Microbial and mineral evolution in zero valent iron-based permeable reactive barriers during long-term operations.

Impacts of subsurface biogeochemical processes over time have always been a concern for the long-term performance of zero valent iron (Fe(0))-based permeable reactive barriers (PRBs). To evaluate the biogeochemical impacts, laboratory experiments were performed using flow-through glass columns for 210 days at controlled temperature (20 °C). Two different particle sizes of Fe(0) were used in the columns, and to simulate indigenous microbial activity, extra carbon source was provided in the two columns (biotic columns) and the remaining two columns were kept abiotic using gamma radiations. Heavy metals (Zn, As) were removed efficiently in all the columns, and no exhaustion of treatment capability or clogging was observed during our experimental duration. Newly formed Fe mineral phases and precipitates were characterized using X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), and micro-XRF techniques in solid phase at the end of the experiment. In addition, 16S rRNA gene extraction was used for microbial community identification in biotic columns. During the incubation, microbial population shifted in favor of Desulfosporosinus species (sulfate-reducing bacteria) from initial dominance of Acidithiobacillus ferrooxidans in sediments. Dominant mineral phases detected in biotic columns were mackinawite (FeS) and sulfate green rust, while in abiotic columns, magnetite/maghemite phases were more prevalent.