Pentavalent U Reactivity Impacts U Isotopic Fractionation during Reduction by Magnetite.

Meaningful interpretation of U isotope measurements relies on unraveling the impact of reduction mechanisms on the isotopic fractionation. Here, the isotope fractionation of hexavalent U [U(VI)] was investigated during its reductive mineralization by magnetite to intermediate pentavalent U [U(V)] and ultimately tetravalent U [U(IV)]. As the reaction proceeded, the remaining aqueous phase U [containing U(VI) and U(V)] systematically carried light isotopes, whereas in the bicarbonate-extracted solution [containing U(VI) and U(V)], the δ238U values varied, especially when C/C0 approached 0. This variation was interpreted as reflecting the variable relative contribution of unreduced U(VI) (δ238U < 0‰) and bicarbonate-extractable U(V) (δ238U > 0‰). The solid remaining after bicarbonate extraction included unextractable U(V) and U(IV), for which the δ238U values consistently followed the same trend that started at 0.3-0.5‰ and decreased to ∼0‰. The impact of PIPES buffer on isotopic fractionation was attributed to the variable abundance of U(V) in the aqueous phase. A few extremely heavy bicarbonate-extracted δ238U values were due to mass-dependent fractionation resulting from several hypothesized mechanisms. The results suggest the preferential accumulation of the heavy isotope in the reduced species and the significant influence of U(V) on the overall isotopic fractionation, providing insight into the U isotope fractionation behavior during its abiotic reduction process.

Implantation of Bacillus pseudomycoides Chromate Transporter Increases Chromate Tolerance in Bacillus subtilis.

Chromium of anthropogenic origin contaminates the environment worldwide. The toxicity of chromium, a group I human carcinogen, is greatest when it is in a hexavalent oxidation state, Cr(VI). Cr(VI) is actively transported into the cell, triggering oxidative damage intracellularly. Due to the abundance of unspecific intracellular reductants, any microbial species is capable of bio-transformation of toxic Cr(VI) to innocuous Cr(III), however, this process is often lethal. Only some bacterial species are capable of sustaining the vegetative growth in the presence of a high concentration of Cr(VI) and thus operate as self-sustainable bioremediation agents. One of the successful microbial Cr(VI) detoxification strategies is the activation of chromate efflux pumps. This work describes transplantation of the chromate efflux pump from the potentially pathogenic but highly Cr resistant Bacillus pseudomycoides environmental strain into non-pathogenic but only transiently Cr tolerant Bacillus subtilis strain. In our study, we compared the two Bacillus spp. strains harboring evolutionarily diverged chromate efflux proteins. We have found that individual cells of the Cr-resistant B. pseudomycoides environmental strain accumulate less Cr than the cells of B. subtilis strain. Further, we found that survival of the B. subtilis strain during the Cr stress can be increased by the introduction of the chromate transporter from the Cr resistant environmental strain into its genome. Additionally, the expression of B. pseudomycoides chromate transporter ChrA in B. subtilis seems to be activated by the presence of chromate, hinting at versatility of Cr-efflux proteins. This study outlines the future direction for increasing the Cr-tolerance of non-pathogenic species and safe bioremediation using soil bacteria.

Persistence of the Isotopic Signature of Pentavalent Uranium in Magnetite.

Uranium isotopic signatures can be harnessed to monitor the reductive remediation of subsurface contamination or to reconstruct paleo-redox environments. However, the mechanistic underpinnings of the isotope fractionation associated with U reduction remain poorly understood. Here, we present a coprecipitation study, in which hexavalent U (U(VI)) was reduced during the synthesis of magnetite and pentavalent U (U(V)) was the dominant species. The measured δ238U values for unreduced U(VI) (∼-1.0‰), incorporated U (96 ± 2% U(V), ∼-0.1‰), and extracted surface U (mostly U(IV), ∼0.3‰) suggested the preferential accumulation of the heavy isotope in reduced species. Upon exposure of the U-magnetite coprecipitate to air, U(V) was partially reoxidized to U(VI) with no significant change in the δ238U value. In contrast, anoxic amendment of a heavy isotope-doped U(VI) solution resulted in an increase in the δ238U of the incorporated U species over time, suggesting an exchange between incorporated and surface/aqueous U. Overall, the results support the presence of persistent U(V) with a light isotope signature and suggest that the mineral dynamics of iron oxides may allow overprinting of the isotopic signature of incorporated U species. This work furthers the understanding of the isotope fractionation of U associated with iron oxides in both modern and paleo-environments.

Biological Reduction of a U(V)-Organic Ligand Complex.

Metal-reducing microorganisms such as Shewanella oneidensis MR-1 reduce highly soluble species of hexavalent uranyl (U(VI)) to less mobile tetravalent uranium (U(IV)) compounds. The biologically mediated immobilization of U(VI) is being considered for the remediation of U contamination. However, the mechanistic underpinnings of biological U(VI) reduction remain unresolved. It has become clear that a first electron transfer occurs to form pentavalent (U(V)) intermediates, but it has not been definitively established whether a second one-electron transfer can occur or if disproportionation of U(V) is required. Here, we utilize the unusual properties of dpaea2- ((dpaeaH2═bis(pyridyl-6-methyl-2-carboxylate)-ethylamine)), a ligand forming a stable soluble aqueous complex with U(V), and investigate the reduction of U(VI)-dpaea and U(V)-dpaea by S. oneidensis MR-1. We establish U speciation through time by separating U(VI) from U(IV) by ion exchange chromatography and characterize the reaction end-products using U M4-edge high resolution X-ray absorption near-edge structure (HR-XANES) spectroscopy. We document the reduction of solid phase U(VI)-dpaea to aqueous U(V)-dpaea but, most importantly, demonstrate that of U(V)-dpaea to U(IV). This work establishes the potential for biological reduction of U(V) bound to a stabilizing ligand. Thus, further work is warranted to investigate the possible persistence of U(V)-organic complexes followed by their bioreduction in environmental systems.

Nanoscale mechanism of UO2 formation through uranium reduction by magnetite.

Uranium (U) is a ubiquitous element in the Earth's crust at ~2 ppm. In anoxic environments, soluble hexavalent uranium (U(VI)) is reduced and immobilized. The underlying reduction mechanism is unknown but likely of critical importance to explain the geochemical behavior of U. Here, we tackle the mechanism of reduction of U(VI) by the mixed-valence iron oxide, magnetite. Through high-end spectroscopic and microscopic tools, we demonstrate that the reduction proceeds first through surface-associated U(VI) to form pentavalent U, U(V). U(V) persists on the surface of magnetite and is further reduced to tetravalent UO2 as nanocrystals (~1-2 nm) with random orientations inside nanowires. Through nanoparticle re-orientation and coalescence, the nanowires collapse into ordered UO2 nanoclusters. This work provides evidence for a transient U nanowire structure that may have implications for uranium isotope fractionation as well as for the molecular-scale understanding of nuclear waste temporal evolution and the reductive remediation of uranium contamination.

Effect of Aging on the Stability of Microbially Reduced Uranium in Natural Sediment.

Reductive immobilization of uranium has been explored as a remediation strategy for the U-contaminated subsurface. Via the in situ biostimulation of microbial processes, hexavalent U is reduced to less soluble tetravalent species, which are immobilized within the sediment. Although the mineral uraninite (UO2) was initially considered the dominant product of biological reduction, non-crystalline U(IV) species (NCU(IV)) are found to be abundant in the environment despite their greater susceptibility to oxidation and remobilization. However, it has been recently proposed that, through aging, NCU(IV) might transform into UO2, which would potentially enhance the stability of the reduced U pool. In this study, we performed column experiments to produce NCU(IV) species in natural sediment mimicking the environmental conditions during bioremediation. Bioreduced sediment retrieved from the columns and harboring NCU(IV) was incubated in static microcosms under anoxic conditions to allow the systematic monitoring of U coordination by X-ray absorption spectroscopy (XAS) over 12 months. XAS revealed that, under the investigated conditions, the speciation of U(IV) does not change over time. Thus, because NCU(IV) is the dominant species in the sediment, bioreduced U(IV) species remain vulnerable to oxidation and remobilization in the aqueous phase even after a 12-month aging period.

Colloidal Size and Redox State of Uranium Species in the Porewater of a Pristine Mountain Wetland.

Uranium (U) speciation was investigated in anoxically preserved porewater samples of a natural mountain wetland in Gola di Lago, Ticino, Switzerland. U porewater concentrations ranged from less than 1 µg/L to tens of µg/L, challenging the available analytical approaches for U speciation in natural samples. Asymmetrical flow field-flow fractionation coupled with inductively coupled plasma mass spectrometry allowed the characterization of colloid populations and the determination of the size distribution of U species in the porewater. Most of the U was associated with three fractions: <0.3 kDa, likely including dissolved U and very small U colloids; a 1-3 kDa fraction containing humic-like organic compounds, dispersed Fe, and, to a small extent, Fe nanoparticles; and a third fraction (5-50 nm), containing a higher amount of Fe and a lower amount of organic matter and U relative to the 1-3 kDa fraction. The proportion of U associated with the 1-3 kDa colloids varied spatially and seasonally. Using anion exchange resins, we also found that a significant proportion of U occurs in its reduced form, U(IV). Tetravalent U was interpreted as occurring within the colloidal pool of U. This study suggests that U(IV) can occur as small (1-3 kDa), organic-rich, and thus potentially mobile colloidal species in naturally reducing wetland environments.

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.

Variability in DPA and Calcium Content in the Spores of Clostridium Species.

Spores of a number of clostridial species, and their resistance to thermal treatment is a major concern for the food industry. Spore resistance to wet heat is related to the level of spore hydration, which is inversely correlated with the content of calcium and dipicolinic acid (DPA) in the spore core. It is widely believed that the accumulation of DPA and calcium in the spore core is a fundamental component of the sporulation process for all endospore forming species. We have noticed heterogeneity in the heat resistance capacity and overall DPA/calcium content among the spores of several species belonging to Clostridium sensu stricto group: two C. acetobutylicum strains (DSM 792 and 1731), two C. beijerinckii strains (DSM 791 and NCIMB 8052), and a C. collagenovorans strain (DSM 3089). A C. beijerinckii strain (DSM 791) and a C. acetobutylicum strain (DSM 792) display low Ca and DPA levels. In addition, these two species, with the lowest average Ca/DPA content amongst the strains considered, also exhibit minimal heat resistance. There appears to be no correlation between the Ca/DPA content and the phylogenetic distribution of the C. acetobutylicum and C. beijerinckii species based either on the 16S rRNA or the spoVA gene. This finding suggests that a subset of Clostridium sensu stricto species produce spores with low resistance to wet heat. Additionally, analysis of individual spores using STEM-EDS and STXM revealed that DPA and calcium levels can also vary amongst individual spores in a single spore population.

Products of in Situ Corrosion of Depleted Uranium Ammunition in Bosnia and Herzegovina Soils.

Hundreds of tons of depleted uranium (DU) ammunition were used in previous armed conflicts in Iraq, Bosnia and Herzegovina, and Serbia/Kosovo. The majority (>90%) of DU penetrators miss their target and, if left in the environment, corrode in these postconflict zones. Thus, the best way to understand the fate of bulk DU material in the environment is to characterize the corrosion products of intact DU penetrators under field conditions for extended periods of time. However, such studies are scarce. To fill this knowledge gap, we characterized corrosion products formed from two intact DU penetrators that remained in soils in Bosnia and Herzegovina for over seven years. We used a combination of X-ray powder diffraction, electron microscopy, and X-ray absorption spectroscopy. The results show that metaschoepite (UO3(H2O)2) was a main component of the two DU corrosion products. Moreover, studtite ((UO2)O2(H2O)2·2(H2O)) and becquerelite (Ca(UO2)6O4(OH)6·8(H2O)) were also identified in the corrosion products. Their formation through transformation of metaschoepite was a result of the geochemical conditions under which the penetrators corroded. Moreover, we propose that the transformation of metaschoepite to becquerelite or studtite in the DU corrosion products would decrease the potential for mobilization of U from corroded DU penetrators exposed to similar environments in postconflict areas.

Electronic interactions between "pea" and "pod": the case of oligothiophenes encapsulated in carbon nanotubes.

One of the most challenging strategies to achieve tunable nanophotonic devices is to build robust nanohybrids with variable emission in the visible spectral range, while keeping the merits of pristine single-walled carbon nanotubes (SWNTs). This goal is realized by filling SWNTs ("pods") with a series of oligothiophene molecules ("peas"). The physical properties of these peapods are depicted by using aberration-corrected high-resolution transmission electron microscopy, Raman spectroscopy, and other optical methods including steady-state and time-resolved measurements. Visible photoluminescence with quantum yields up to 30% is observed for all the hybrids. The underlying electronic structure is investigated by density functional theory calculations for a series of peapods with different molecular lengths and tube diameters, which demonstrate that van der Waals interactions are the bonding mechanism between the encapsulated molecule and the tube.

Surfactant-free synthesis of mesoporous and hollow silica nanoparticles with an inorganic template.

A surfactant-free synthesis of mesoporous and hollow silica nanoparticles is reported in which boron acts as the templating agent. Using such a simple and mild procedure as a treatment with water, the boron-rich phase is selectively removed, affording mesoporous pure silica nanoparticles with wormhole-like pores or, depending on the synthetic conditions, silica nanoshells.