Immobilisation of contaminants by 'green'-synthesized magnetite as a remediation approach to the phosphogypsum waste leachates model solution.

Contaminant removal from (waste)waters by magnetite is a promising technology. In the present experimental study, a magnetite recycled from the steel industry waste (zero-valent iron powder) was used to investigate the sorption of As, Sb and U in phosphate-free and -rich suspensions, i.e. as a remediation for the acidic phosphogypsum leachates derived from the phosphate fertilizer industry. The results showed up to 98% U removal under controlled pH conditions, while phosphate did not hinder this immobilisation. In contrast, the results confirmed the limited uptake of As and Sb oxyanions by magnetite in presence of phosphate as the competing anion, displaying only 7-11% removal, compared to 83-87% in the phosphate-free sorption experiments. To limit this wastewater problem, raw ZVI anaerobic oxidation was examined as mechanism to increase the pH and as a source of Fe2+ in a first step, and in a second step to remove phosphate via vivianite precipitation, therefore prior to the reaction with magnetite. UV-Vis, XRD and SEM-EDS showed that vivianite precipitation is feasible at pH > 4.5, mainly depending on the phosphate concentration. The higher the [PO43-], the lower is the pH at which vivianite precipitates and the higher the % removal of phosphate from solution. It is anticipated that an optimum 3-steps design with separate reactors controlling the conditions of ZVI oxidation, followed by vivianite precipitation and finally, reaction with magnetite, can achieve high contaminant uptake in field applications.

Redox Interaction between Selenite and Mackinawite in Cement Pore Water.

In cement-rich radioactive waste repositories, mackinawite (FeS) forms at the steel corrosion interface within reinforced concrete and potentially retards the transport of redox-sensitive radionuclides (e.g., 79Se) in porous cement media. Redox interactions between selenite and mackinawite under hyperalkaline conditions remain unclear and require further investigations. Here, using comprehensive characterization on both aqueous and solid speciation, we successfully monitored the whole interaction process between selenite and mackinawite under hyperalkaline conditions. The results show similar chemical environments for SeO32- and S2-/Sn2- at the mackinawite-water interface, verifying an immediate reduction. After 192 h of reaction, SeO32- was reduced to solid Se0 and SeS2 species, accompanied by the oxidation of S2-/Sn2- to S2O32- and Fe(II) to Fe(III) in mackinawite. Aqueous speciation results showed that ∼99% of aqueous selenium was present as Se4S nanoparticles due to the dissolution of Se from the solid. In parallel, ∼62% of S2-/Sn2- was released into the solution, with mackinawite transforming into magnetite, Fe(OH)3 and FeS2O3+ complexed to Cl- or OH- species, and magnetite subsequently dispersed in the solution. This study provides valuable data about the retardation mechanisms of redox-sensitive radionuclides by soluble iron sulfides, which is critical to advance our understanding of reactive concrete barriers used in nuclear waste disposal systems.

Selenium Nanowire Formation by Reacting Selenate with Magnetite.

The mobility of 79Se, a fission product of 235U and long-lived radioisotope, is an important parameter in the safety assessment of radioactive nuclear waste disposal systems. Nonradioactive selenium is also an important contaminant of drainage waters from black shale mountains and coal mines. Highly mobile and soluble in its high oxidation states, selenate (Se(VI)O42-) and selenite (Se(IV)O32-) oxyanions can interact with magnetite, a mineral present in anoxic natural environments and in steel corrosion products, thereby being reduced and consequently immobilized by forming low-solubility solids. Here, we investigated the sorption and reduction capacity of synthetic nanomagnetite toward Se(VI) at neutral and acidic pH, under reducing, oxygen-free conditions. The additional presence of Fe(II)aq, released during magnetite dissolution at pH 5, has an effect on the reduction kinetics. X-ray absorption spectroscopy analyses revealed that, at pH 5, trigonal gray Se(0) formed and that sorbed Se(IV) complexes remained on the nanoparticle surface during longer reaction times. The Se(0) nanowires grew during the reaction, which points to a complex transport mechanism of reduced species or to active reduction sites at the tip of the Se(0) nanowires. The concomitant uptake of aqueous Fe(II) and Se(VI) ions is interpreted as a consequence of small pH oscillations that result from the Se(VI) reduction, leading to a re-adsorption of aqueous Fe(II) onto the magnetite, renewing its reducing capacity. This effect is not observed at pH 7, where we observed only the formation of Se(0) with slow kinetics due to the formation of an oxidized maghemite layer. This indicates that the presence of aqueous Fe(II) may be an important factor to be considered when examining the environmental reactivity of magnetite.

Ab initio modeling of H2S dissociative chemisorption on Ag(100).

Natural sulfidation of silver nanomaterials can passivate the surface, while preserving desirable optical and electrical properties, which is beneficial for limiting Ag+ release and cytotoxicity. But little is known at the atomic scale about silver sulfidation mechanisms, particularly on different crystallographic terminations. Using density functional theory (DFT) calculations, we examined the process of H2S sorption and reaction on Ag(100) surfaces relevant to Ag nanowires (AgNWs). DFT energy minimizations predict a strong dissociative chemisorption of H2S on the surface yielding co-adsorbed sulfide and hydrogen atoms in specific surface sites. However, nudged elastic band (NEB) calculations suggest relatively large activation energies for both the first and second dissociation steps, due in part to overcoming the energy to cleave the S-H bond and attendant site migration from an on-top Ag site position to a hollow site position of the bound S atom. The large barriers associated with the dissociative chemisorption reaction for gas-phase H2S points to the importance of including thermochemical contributions and the influence of other components in more complex environmental media such as air or water to help complete the mechanistic picture of silver sulfidation and passivation for realistic systems.

Crumpling of silver nanowires by endolysosomes strongly reduces toxicity.

Fibrous particles interact with cells and organisms in complex ways that can lead to cellular dysfunction, cell death, inflammation, and disease. The development of conductive transparent networks (CTNs) composed of metallic silver nanowires (AgNWs) for flexible touchscreen displays raises new possibilities for the intimate contact between novel fibers and human skin. Here, we report that a material property, nanowire-bending stiffness that is a function of diameter, controls the cytotoxicity of AgNWs to nonimmune cells from humans, mice, and fish without deterioration of critical CTN performance parameters: electrical conductivity and optical transparency. Both 30- and 90-nm-diameter AgNWs are readily internalized by cells, but thinner NWs are mechanically crumpled by the forces imposed during or after endocytosis, while thicker nanowires puncture the enclosing membrane and release silver ions and lysosomal contents to the cytoplasm, thereby initiating oxidative stress. This finding extends the fiber pathology paradigm and will enable the manufacture of safer products incorporating AgNWs.

Influence of Silica Coatings on Magnetite-Catalyzed Selenium Reduction.

The reactivity of iron(II/III) oxide surfaces may be influenced by their interaction with silica, which is ubiquitous in aquatic systems. Understanding the structure-reactivity relationships of Si-coated mineral surfaces is necessary to describe the complex surface behavior of nanoscale iron oxides. Here, we use Si-adsorption isotherms and Fourier transform infrared spectroscopy to analyze the sorption and polymerization of silica on slightly oxidized magnetite nanoparticles (15% maghemite and 85% magnetite, i.e., ∼2 maghemite surface layers), showing that Si adsorption follows a Langmuir isotherm up to 2 mM dissolved Si, where surface polymerization occurs. Furthermore, the effects of silica surface coatings on the redox-catalytic ability of magnetite are analyzed using selenium as a molecular probe. The results show that for partially oxidized nanoparticles and even under different Si surface coverages, electron transfer is still occurring. The results indicate anion exchange between silicate and the sorbed SeIV and SeVI. X-ray absorption near-edge structure analyses of the reacted Se indicate the formation of a mixed selenite/Se0 surface phase. We conclude that neither partial oxidation nor silica surface coatings block the sorption and redox-catalytic properties of magnetite nanoparticles, a result with important implications to assess the reactivity of mixed-valence phases in environmental settings.

Selenite Sorption on Hydrated CEM-V/A Cement in the Presence of Steel Corrosion Products: Redox vs Nonredox Sorption.

Reinforced cementitious structures in nuclear waste repositories will act as barriers that limit the mobility of radionuclides (RNs) in case of eventual leakage. CEM-V/A cement, a ternary blended cement with blast furnace slag (BFS) and fly ash (FA), could be qualified and used in nuclear waste disposal. Chemical interactions between the cement and RNs are critical but not completely understood. Here, we combined wet chemistry methods, synchrotron-based X-ray techniques, and thermodynamic modeling to explore redox interactions and nonredox sorption processes in simulated steel-reinforced CEM-V/A hydration systems using selenite as a molecular probe. Among all of the steel corrosion products analyzed, only the addition of Fe0 can obviously enhance the reducing ability of cement toward selenite. In comparison, steel corrosion products showed stronger reducing power in the absence of cement hydrates. Selenium K-edge X-ray absorption spectroscopy (XAS) revealed that selenite immobilization mechanisms included nonredox inner-/outer-sphere complexations and reductive precipitations of FeSe and/or Se(0). Importantly, the hydrated pristine cement showed a good reducing ability, driven by ferrous phases and (bi)sulfides (as shown by sulfur K-edge XAS) originated from BFS and FA. The overall redox potential imposed by hydrated CEM-V/A was determined, hinting to a redox shift in underground cementitious structures.

Influence of Surface Compositions on the Reactivity of Pyrite toward Aqueous U(VI).

Pyrite plays a significant role in governing the mobility of toxic uranium in an anaerobic environment via an oxidation-reduction process occurring at the mineral-water interface, but the factors influencing the reaction kinetics remain poorly understood. In this study, natural pyrites with different impurities (Pb, As, and Si) and different surface pretreatments were used to react with aqueous U(VI) from pH ∼3.0 to ∼9.5. Both aqueous and solid results indicated that freshly crushed pyrites, which do have more surface Fe2+/Fe3+ and S2- sites that were generated from breakage of Fe(S)-S bonds during ball milling, exhibited a much stronger reactivity than those treated with acid washing. Besides, U(VI) reduction which involves the possible intermediate U(V) and the formation of hyperstoichiometric UO2+x(s) was found to preferentially occur at Pb- and As-rich spots on the pyrite surface, suggesting that the incorporated impurities could act as reactive sites because of the generation of lattice defects and galena- and arsenopyrite-like local configurations. These reactive surface sites can be removed by acid washing, leaving a pyrite surface nearly inert toward aqueous U(VI). Thus, reactivity of pyrite toward U(VI) is largely governed by its surface compositions, which provides an insight into the chemical behavior of both pyrite and uranium in various environments.

Selenium nanoparticles trigger alterations in ovarian cancer cell biomechanics.

High dose selenium acts as a cytotoxic agent, with potential applications in cancer treatment. However, clinical trials have failed to show any chemotherapeutic value of selenium at safe and tolerated doses (<90 µg/day). To enable the successful exploitation of selenium for cancer treatment, we evaluated inorganic selenium nanoparticles (SeNP), and found them effective in inhibiting ovarian cancer cell growth. In both SKOV-3 and OVCAR-3 ovarian cancer cell types SeNP treatment resulted in significant cytotoxicity. The two cell types displayed contrasting nanomechanical responses to SeNPs, with decreased surface roughness and membrane stiffness, characteristics of OVCAR-3 cell death. In SKOV-3, cell membrane surface roughness and stiffness increased, both properties associated with decreased metastatic potential. The beneficial effects of SeNPs on ovarian cancer cell death appear cell type dependent, and due to their low in vivo toxicity offer an exciting opportunity for future cancer treatment.

XANES-Based Determination of Redox Potentials Imposed by Steel Corrosion Products in Cement-Based Media.

The redox potential (Eh) in a cementitious nuclear waste repository is critical to the retardation behavior of redox-sensitive radionuclides (RNs), and largely controlled by embedded steel corrosion but hard to be determined experimentally. Here, we propose an innovative Eh determination method based on chemical/spectroscopic measurements. Oxidized nuclides (UVI, SeIV, MoVI, and SbV) were employed as species probes to detect the Eh values imposed by steel (Fe0) and steel corrosion products (magnetite/hematite, and magnetite/goethite couples) in cement pore water. Nuclides showed good sorption affinity, especially toward Fe0, in decreasing Kd order for U > Sb > Se > Mo under both N2 and H2 atmospheres. The reduced nuclide species were identified as UO2, U4O9, FeSe, FeSe2, Se0, Sb0, and Sb2O3, but no redox transformation occurred for Mo. Eh values were obtained by using the Nernst equation. Remarkably, their values fell in a small range centered around -456 mV at pH ∼ 13.5 for both Fe0 and Fe-oxyhydroxides couples. This Eh value appears to be controlled by the nanocrystalline Fe(OH)2/Fe(OH)3 or (Fe1- x,Ca x)(OH)2/Fe(OH)3 couple, whose presence was confirmed by pair distribution function analyses. This approach could pave the way for describing the Eh gradient in reinforced concrete where traditional Eh measurements are not feasible.

Arsenic Speciation in Mekong Delta Sediments Depends on Their Depositional Environment.

Arsenic contamination in groundwater is pervasive throughout deltaic regions of Southeast Asia and threatens the health of millions. The speciation of As in sediments overlying contaminated aquifers is poorly constrained. Here, we investigate the chemical and mineralogical compositions of sediment cores collected from the Mekong Delta in Vietnam, elucidate the speciation of iron and arsenic, and relate them to the sediment depositional environment. Gradual dissolution of ferric (oxyhydr)oxides with depth is observed down to 7 m, corresponding to the establishment of reducing conditions. Within the reduced sediment, layers originating from marine, coastal or alluvial depositional environments are identified and their age is consistent with a late Holocene transgression in the Mekong Delta. In the organic matter- and sulfur-rich layers, arsenic is present in association with organic matter through thiol-bonding and in the form of arsenian pyrite. The highest arsenic concentration (34-69 ppm) is found in the peat layer at 16 m and suggests the accumulation of arsenic due to the formation of thiol-bound trivalent arsenic (40-55%) and arsenian pyrite (15-30%) in a paleo-mangrove depositional environment (∼8079 yr BP). Where sulfur is limited, siderite is identified, and oxygen- and thiol-bound trivalent arsenic are the predominant forms. It is also worth noting that pentavalent arsenic coordinated to oxygen is ubiquitous in the sediment profile, even in reduced sediment layers. But the identity of the oxygen-bound arsenic species remains unknown. This work shows direct evidence of thiol-bound trivalent arsenic in the Mekong Delta sediments and provides insight to refine the current model of the origin, deposition, and release of arsenic in the alluvial aquifers of the Mekong Delta.

Selenite Uptake by Ca-Al LDH: A Description of Intercalated Anion Coordination Geometries.

Layered double hydroxides (LDHs) are anion exchangers with a strong potential to scavenge anionic contaminants in aquatic environments. Here, the uptake of selenite (SeO32-) by Ca-Al LDHs was investigated as a function of Se concentration. Thermodynamic modeling of batch sorption isotherms shows that the formation of SeO32--intercalated AFm (hydrated calcium aluminate monosubstituent) phase, AFm-SeO3, is the dominant mechanism controlling the retention of Se at medium loadings. AFm-Cl2 shows much stronger affinity and larger distribution ratio (Rd ∼ 17800 L kg-1) toward SeO32- than AFm-SO4 (Rd ∼ 705 L kg-1). At stoichiometric SeO32- loading for anion exchange, the newly formed AFm-SeO3 phase results in two basal spacing, i.e., 9.93 ± 0.06 Å and ∼11.03 ± 0.03 Å. Extended X-ray absorption fine structure (EXAFS) spectra indicate that the intercalated SeO32- forms inner-sphere complexes with the Ca-Al-O layers. In situ X-ray diffraction (XRD) shows that basal spacing of Ca-Al LDHs have a remarkable linear relationship with the size of hydrated intercalated anions (i.e., Cl-, SO42-, MoO42-, and SeO32-). Contrary to AFm-SeO3 with inner-sphere SeO32- complexes in the interlayer, the phase with hydrogen-bonded inner-sphere complexed SeO32- is kinetically favored but thermodynamically unstable. This work offers new insights about the determination of intercalated anion coordination geometries via XRD analyses.

Evidence of Multiple Sorption Modes in Layered Double Hydroxides Using Mo As Structural Probe.

Layered double hydroxides (LDHs) have been considered as effective phases for the remediation of aquatic environments, to remove anionic contaminants mainly through anion exchange mechanisms. Here, a combination of batch isotherm experiments and X-ray techniques was used to examine molybdate (MoO42-) sorption mechanisms on CaAl LDHs with increasing loadings of molybdate. Advanced modeling of aqueous data shows that the sorption isotherm can be interpreted by three retention mechanisms, including two types of edge sites complexes, interlayer anion exchange, and CaMoO4 precipitation. Meanwhile, Mo geometry evolves from tetrahedral to octahedral on the edge, and back to tetrahedral coordination at higher Mo loadings, indicated by Mo K-edge X-ray absorption spectra. Moreover, an anion exchange process on both CaAl LDHs was followed by in situ time-resolved synchrotron-based X-ray diffraction, remarkably agreeing with the sorption isotherm. This detailed molecular view shows that different uptake mechanisms-edge sorption, interfacial dissolution-reprecipitation-are at play and control anion uptake under environmentally relevant conditions, which is contrast to the classical view of anion exchange as the primary retention mechanism. This work puts all these mechanisms in perspective, offering a new insight into the complex interplay of anion uptake mechanisms by LDH phases, by using changes in Mo geometry as powerful molecular-scale probe.

On-off mobilization of contaminants in soils during redox oscillations.

Near-surface biogeochemical systems can oscillate between oxic and anoxic conditions. Under such periodic changes many redox-sensitive inorganic contaminants undergo speciation, mobility and toxicity changes. We investigated the changes to chromium (Cr), arsenic (As), selenium (Se), antimony (Sb) and uranium (U) mobility during a series of laboratory experiments where argillaceous substrates were subjected to successive cycles of oxidizing and reducing conditions. The EH oscillated between -320 and +470 mV, induced via both abiotic and microbial forcings. Chemically induced cycles of oxidation and reduction were achieved via a combination of gas (N2:CO2 vs compressed air) and carbon (ethanol) addition, to stimulate the metabolism of a natively present microbial community. The contaminants were added either alone or as contaminant mixtures. Results show clear on-off switch mobility behavior for both major elements such as carbon (C), iron (Fe) and manganese (Mn) and for contaminants. Mn, Fe, and As were mobilized under anoxic conditions, whereas Sb, Se, and U were mobilized under oxic conditions. While As, Sb, and U were reversibly sorbed, Se and Cr were irreversibly sequestered via reductive precipitation. When present in aqueous solutions at high concentrations, Cr(VI) prevented the reduction of Mn and Fe, and inhibited the mobilization of elements with lower EH(o). To improve remediation strategies for multiple contaminants in redox-dynamic environments, we propose a mixed kinetic-equilibrium biogeochemical model that can be forced by oscillating boundary conditions and that uses literature rates and constants to capture the key processes responsible for the mobilization of contaminants in soils.

Inhibition of U(VI) reduction by synthetic and natural pyrite.

Reductive precipitation is an effective method of attenuating the mobility of uranium (U) in subsurface environments. The reduction of U(VI) by synthetic and naturally occurring pyrite was investigated at pH 3.0-9.5. In contrast to thermodynamic calculations that were used to predict UO2(s) precipitation, a mixed U(IV) and U(VI) product (e.g., U3O8/U4O9/U3O7) was only observed at pH 6.21-8.63 and 4.52-4.83 for synthetic and natural pyrite, respectively. Under acidic conditions, the reduction of UO2(2+) by surface-associated Fe(2+) may not be favored because the mineral surface is nearly neutral or not negative enough. At high pH, the sorption of negatively charged U(VI) species is not favored on the negatively charged mineral surface. Thus, the redox reaction is not favored. Trace elements generally contained within the natural pyrite structure can affect the reactivity of pyrite and lead to a different result between the natural and synthetic pyrite. Because UO2(s) is extremely redox-sensitive toward U(VI), the observed UO2+x(s) phase reduction product indicates a surface reaction that is largely controlled by reaction kinetics and pyrite surface chemistry. These factors may explain why most laboratory experiments have observed incomplete U(VI) reduction on Fe(II)-bearing minerals.

Interstratification patterns from the pH-dependent intercalation of a tetracycline antibiotic within montmorillonite layers.

Little is known about the distribution of the intercalated molecules within the interstratified layers resulting from the pH-dependent interlayer adsorption of ionizable organic molecules, including antibiotics, within smectite-type clay minerals. Here we employed experimental and simulated X-ray diffraction (XRD) to characterize interstratification (or mixed layering) from the intercalation of oxytetracycline (OTC), a commonly used tetracycline antibiotic, within Na-montmorillonite layers at pHs 4, 5, 6, and 8. Our XRD data reveal that OTC is distributed nonrandomly in the interlayers such that Na- and OTC-saturated interlayers coexist. The profile of the full width at half-maximum intensity (fwhm), monitored as a function of increasing layer-to-layer distance (d001), resulting from an increasing amount of intercalated OTC, reflects such mixed-layer crystals under the acidic pH conditions. A minimum in fwhm occurs at a d spacing of about 1.8 nm, which is to be the optimal d001 for OTC-saturated layers, in agreement with molecular modeling results. Using the coordinates of the thermodynamically favorable configuration of the adsorptives in a model montmorillonite interlayer, we simulated XRD profiles to unravel the different patterns of interstratification from the experimental data. At both pHs 4 and 5, Na- and OTC-interlayers are randomly interstratified, whereas at pH 6, these layers are clustered, as characterized by a segregated interstratification pattern. The theoretical layer stacking sequences of the simulated XRD illustrate, as pH increases, the clustering of similar layer types with the exclusion of OTC intercalation from clay populations enriched in Na. At pH 8, both fwhm and d001 indicate OTC adsorption primarily on external surface sites, not within interlayers. Our findings imply that, in addition to chemical speciation, a pH-dependent formation of montmorillonite crystallites with unexfoliated layers may be responsible both for the decreased OTC intercalation and for the increased binding on external sites, thus resulting in the different patterns of interstratification as a function of increasing pH.

Exploring carbonate rock wettability across scales: Role of (bio)minerals.

HYPOTHESIS: The wettability of carbonate rocks is expected to be affected by the organic components of biominerals which are complex, nanostructured organo-mineral assemblages. Elucidating the nanoscale mechanisms driving the wettability of solid surfaces will enable a better understanding of the role of biominerals in the wetting properties of carbonate rocks to control various geological, environmental and industrial processes. EXPERIMENTS: Using Atomic Force Microscopy and Spectroscopy (AFM/AFS) we probed the wettability properties of carbonate rocks with different amounts of organic material. The adhesion properties of two types of limestones were determined in liquid environments at different length scales (nm to mm) using functionalized tips with different chemical groups to determine the extent of surface hydrophobic and hydrophilic organo-mineral interactions. FINDINGS: We observed homogeneous hydrophobic areas at length scales below < 5 µm. The origin of this hydrophobicity is linked to the presence of organics, whose amount and spatial distribution depend on the rock composition. Specifically, our results reveal that the biogenic vs non-biogenic origin of the mineral grains is the main rock property controlling the wettability of the solid surface. Overall, our methodology offers a multi-scale approach to unravel the role that organic moieties and biominerals play in controlling the wettability of rock-water interfaces.

Selenium nanoparticles modulate histone methylation via lysine methyltransferase activity and S-adenosylhomocysteine depletion.

At physiological levels, the trace element selenium plays a key role in redox reactions through the incorporation of selenocysteine in antioxidant enzymes. Selenium has also been evaluated as a potential anti-cancer agent, where selenium nanoparticles have proven effective, and are well tolerated in vivo at doses that are toxic as soluble Se. The use of such nanoparticles, coated with either serum albumin or the naturally occurring alkaline polysaccharide chitosan, also serves to enhance biocompatibility and bioavailability. Here we demonstrate a novel role for selenium in regulating histone methylation in ovarian cancer cell models treated with inorganic selenium nanoparticles coated with serum albumin or chitosan. As well as inducing thioredoxin reductase expression, ROS activity and cancer cell cytotoxicity, coated nanoparticles caused significant increases in histone methylation. Specifically, selenium nanoparticles triggered an increase in the methylation of histone 3 at lysines K9 and K27, histone marks involved in both the activation and repression of gene expression, thus suggesting a fundamental role for selenium in these epigenetic processes. This direct function was confirmed using chemical inhibitors of the histone lysine methyltransferases EZH2 (H3K27) and G9a/EHMT2 (H3K9), both of which blocked the effect of selenium on histone methylation. This novel role for selenium supports a distinct function in histone methylation that occurs due to a decrease in S-adenosylhomocysteine, an endogenous inhibitor of lysine methyltransferases, the metabolic product of methyl-group transfer from S-adenosylmethionine in the one-carbon metabolism pathway. These observations provide important new insights into the action of selenium nanoparticles. It is now important to consider both the classic antioxidant and novel histone methylation effects of this key redox element in its development in cancer therapy and other applications.

Intracellular Fate of Sub-Toxic Concentration of Functionalized Selenium Nanoparticles in Aggressive Prostate Cancer Cells.

Selenium 0 (Se0) is a powerful anti-proliferative agent in cancer research. We investigated the impact of sub-toxic concentrations of Se0 functionalized nanoparticles (SeNPs) on prostate cancer PC-3 cells and determined their intracellular localization and fate. An in-depth characterization of functionalized selenium nanoparticles composition is proposed to certify that no chemical bias relative to synthesis issues might have impacted the study. Selenium is an extremely diluted element in the biological environment and therefore requires high-performance techniques with a very low detection limit and high spatial resolution for intracellular imaging. This was explored with state-of-the-art techniques, but also with cryopreparation to preserve the chemical and structural integrity of the cells for spatially resolved and speciation techniques. Monodisperse solutions of SeNPs capped with bovine serum albumin (BSA) were shown to slow down the migration capacity of aggressive prostate cancer cells compared to polydisperse solutions of SeNPs capped with chitosan. BSA coating could prevent interactions between the reactive surface of the nanoparticles and the plasma membrane, mitigating the generation of reactive oxygen species. The intracellular localization showed interaction with mitochondria and also a localization in the lysosome-related organelle. The SeNPs-BSA localization in mitochondria constitute a possible explanation for our result showing a very significant dampening of the PC-3 cell proliferation capabilities. The purpose of the use of sublethal compound concentrations was to limit adverse effects resulting from high cell death to best evaluate some cellular changes and the fate of these SeNPs on PC-3. Our findings provide new insight to further study the various mechanisms of cytotoxicity of SeNPs.

Adsorption of hydrogen gas and redox processes in clays.

In order to assess the adsorption properties of hydrogen gas and reactivity of adsorbed hydrogen, we measured H(2)(g) adsorption on Na synthetic montmorillonite-type clays and Callovo-Oxfordian (COx) clayrock using gas chromatography. Synthetic montmorillonites with increasing structural Fe(III) substitution (0 wt %, 3.2 wt %, and 6.4 wt % Fe) were used. Fe in the synthetic montmorillonites is principally present as structural Fe(III) ions. We studied the concomitant reduction of structural Fe(III) in the clays using (57)Fe Mössbauer spectrometry. The COx, which mainly contains smectite/illite and calcite minerals, is also studied together with the pure clay fraction of this clayrock. Experiments were performed with dry clay samples which were reacted with hydrogen gas at 90 and 120 °C for 30 to 45 days at a hydrogen partial pressure close to 0.45 bar. Results indicate that up to 0.11 wt % of hydrogen is adsorbed on the clays at 90 °C under 0.45 bar of relative pressure. (57)Fe Mössbauer spectrometry shows that up to 6% of the total structural Fe(III) initially present in these synthetic clays is reduced upon adsorption of hydrogen gas. No reduction is observed with the COx sample in the present experimental conditions.