Neptunium and manganese biocycling in nuclear legacy sediment systems

Understanding the behaviour of the highly radiotoxic, long half-life radionuclide neptunium in the environment is important for the management of radioactively contaminated land and the safe disposal of radioactive wastes. Recent studies have identified that microbial reduction can reduce the mobility of neptunium via reduction of soluble Np(V) to poorly soluble Np(IV), with coupling to both Mn- and Fe(III)- reduction implicated in neptunyl reduction. To further explore these processes Mn(IV) as δMnO2 was added to sediment microcosms to create a sediment microcosm experiment "poised" under Mn-reducing conditions. Enhanced removal of Np(V) from solution occurred during Mn-reduction, and parallel X-ray absorption spectroscopy (XAS) studies confirmed Np(V) reduction to Np(IV) commensurate with microbially-mediated Mn-reduction. Molecular ecology analysis of the XAS systems, which contained up to 0.2 mM Np showed no significant impact of elevated Np concentrations on the microbial population. These results demonstrate the importance of Mn cycling on Np biogeochemistry, and clearly highlight new pathways to reductive immobilisation for this highly radiotoxic actinide

Microbial Reduction of U(VI) under Alkaline Conditions: Implications for Radioactive Waste Geodisposal

Although there is consensus that microorganisms significantly influence uranium speciation and mobility in the subsurface under circumneutral conditions, microbiologically mediated U(VI) redox cycling under alkaline conditions relevant to the geological disposal of cementitious intermediate level radioactive waste, remains unexplored. Here, we describe microcosm experiments that investigate the biogeochemical fate of U(VI) at pH 10–10.5, using sediments from a legacy lime working site, stimulated with an added electron donor, and incubated in the presence and absence of added Fe(III) as ferrihydrite. In systems without added Fe(III), partial U(VI) reduction occurred, forming a U(IV)-bearing non-uraninite phase which underwent reoxidation in the presence of air (O2) and to some extent nitrate. By contrast, in the presence of added Fe(III), U(VI) was first removed from solution by sorption to the Fe(III) mineral, followed by bioreduction and (bio)magnetite formation coupled to formation of a complex U(IV)-bearing phase with uraninite present, which also underwent air (O2) and partial nitrate reoxidation. 16S rRNA gene pyrosequencing showed that Gram-positive bacteria affiliated with the Firmicutes and Bacteroidetes dominated in the post-reduction sediments. These data provide the first insights into uranium biogeochemistry at high pH and have significant implications for the long-term fate of uranium in geological disposal in both engineered barrier systems and the alkaline, chemically disturbed geosphere

Robo-AO M-dwarf Multiplicity Survey: Catalog

We analyze observations from Robo-AO's field M dwarf survey taken on the 2.1 m Kitt Peak telescope and perform a multiplicity comparison with Gaia DR2. Through its laser-guided, automated system, the Robo-AO instrument has yielded the largest adaptive optics M dwarf multiplicity survey to date. After developing an interface to visually identify and locate stellar companions, we selected 11 low-significance Robo-AO detections for follow-up on the Keck II telescope using NIRC2. In the Robo-AO survey we find 553 candidate companions within 4'' around 534 stars out of 5566 unique targets, most of which are new discoveries. Using a position cross-match with DR2 on all targets, we assess the binary recoverability of Gaia DR2 and compare the properties of multiples resolved by both Robo-AO and Gaia. The catalog of nearby M dwarf systems and their basic properties presented here can assist other surveys which observe these stars, such as the NASA TESS mission

Retention of immobile Se(0) in flow-through aquifer column systems during bioreduction and oxic-remobilization

Selenium (Se) is a toxic contaminant with multiple anthropogenic sources, including Se-79 from nuclear fission. Se mobility in the geosphere is generally governed by its oxidation state, therefore understanding Se speciation under variable redox conditions is important for the safe management of Se contaminated sites. Here, we investigate Se behavior in sediment groundwater column systems. Experiments were conducted with environmentally relevant Se concentrations, using a range of groundwater compositions, and the impact of electron-donor (i.e., biostimulation) and groundwater sulfate addition was examined over a period of 170 days. X-Ray Absorption Spectroscopy and standard geochemical techniques were used to track changes in sediment associated Se concentration and speciation. Electron-donor amended systems with and without added sulfate retained up to 90% of added Se(VI)(aq), with sediment associated Se speciation dominated by trigonal Se(0) and possibly trace Se(-II); no Se colloid formation was observed. The remobilization potential of the sediment associated Se species was then tested in reoxidation and seawater intrusion perturbation experiments. In all treatments, sediment associated Se (i.e., trigonal Se(0)) was largely resistant to remobilization over the timescale of the experiments (170 days). However, in the perturbation experiments, less Se was remobilized from sulfidic sediments, suggesting that previous sulfate-reducing conditions may buffer Se against remobilization and migration.Peer reviewe

Strontium sorption and precipitation behaviour during bioreduction in nitrate impacted sediments

AbstractThe behaviour of strontium (Sr2+) during microbial reduction in nitrate impacted sediments was investigated in sediment microcosm experiments relevant to nuclear sites. Although Sr2+ is not expected to be influenced directly by redox state, bioreduction of nitrate caused reduced Sr2+ solubility due to an increase in pH during bioreduction and denitrification. Sr2+ removal was greatest in systems with the highest initial nitrate loading and consequently more alkaline conditions at the end of denitrification. After denitrification, a limited re-release of Sr2+ back into solution occurred coincident with the onset of metal (Mn(IV) and Fe(III)) reduction which caused minor pH changes in all microcosms with the exception of the bicarbonate buffered system with initial nitrate of 100mM and final pH>9. In this system ~95% of Sr2+ remained associated with the sediment throughout the progression of bioreduction. Analysis of this pH 9 system using X-ray absorption spectroscopy (XAS) and electron microscopy coupled to thermodynamic modelling showed that Sr2+ became partially incorporated within carbonate phases which were formed at higher pH. This is in contrast to all other systems where final pH was <9, here XAS analysis showed that outer sphere Sr2+ sorption predominated. These results provide novel insight into the likely environmental fate of the significant radioactive contaminant, 90Sr, during changes in sediment biogeochemistry induced by bioreduction in nitrate impacted nuclear contaminated environments

Knowledge practices in design: The role of visual representations as 'epistemic objects'

We use a detailed study of the knowledge work around visual representations to draw attention to the multidimensional nature of `objects'. Objects are variously described in the literatures as relatively stable or in flux; as abstract or concrete; and as used within or across practices. We clarify these dimensions, drawing on and extending the literature on boundary objects, and connecting it with work on epistemic and technical objects. In particular, we highlight the epistemic role of objects, using our observations of knowledge work on an architectural design project to show how, in this setting, visual representations are characterized by a `lack' or incompleteness that precipitates unfolding. The conceptual design of a building involves a wide range of technical, social and aesthetic forms of knowledge that need to be developed and aligned. We explore how visual representations are used, and how these are meaningful to different stakeholders, eliciting their distinct contributions. As the project evolves and the drawings change, new issues and needs for knowledge work arise. These objects have an `unfolding ontology' and are constantly in flux, rather than fully formed. We discuss the implications for wider understandings of objects in organizations and for how knowledge work is achieved in practice

Calculating energy levels of isomerizing tetra-atomic molecules. II. The vibrational states of acetylene and vinylidene

A general, full-dimensional computational method for the accurate calculation of rotationally and vibrationally excited states of tetra-atomic molecules is further developed. The resulting computer program may be run in serial and parallel modes and is particularly appropriate for molecules executing wide-amplitude motions and isomerizations. An application to the isomerizing acetylene∕vinylidene system is presented. Large-scale calculations using a coordinate system based on orthogonal satellite vectors have been performed in six dimensions and vibrational term values and wave functions for acetylene and vinylidene states up to ≈23000cm−1 above the potential minimum have been determined. This has permitted the characterization of acetylene and vinylidene states at and above the isomerization barrier. These calculations employ more extensive vibrational basis sets and hence consider a much higher density of states than in any variational calculations reported hitherto for this system. Comparison of the calculated density of states with that determined empirically suggests that our calculations are the most realistic achieved for this system to date. Indeed more states have been converged than in any previous study of this system. Calculations on lower lying excited states of acetylene based on HC–CH diatom-diatom coordinates give nearly identical results to those based on orthogonal satellite vectors. Comparisons are also made with calculations based on HH–CC diatom-diatom coordinates

Protostellar and Protoplanetary Disk Masses in the Serpens Region

We present the results from an Atacama Large Millimeter/Submillimeter Array (ALMA) 1.3 mm continuum and $^{12}$CO ($J=2-1$) line survey spread over 10 square degrees in the Serpens star-forming region of 320 young stellar objects, 302 of which are likely members of Serpens (16 Class I, 35 Flat spectrum, 235 Class II, and 16 Class III). From the continuum data, we derive disk dust masses and show that they systematically decline from Class I to Flat spectrum to Class II sources. Grouped by stellar evolutionary state, the disk mass distributions are similar to other young ($<3$ Myr) regions, indicating that the large scale environment of a star-forming region does not strongly affect its overall disk dust mass properties. These comparisons between populations reinforce previous conclusions that disks in the Ophiuchus star-forming region have anomalously low masses at all evolutionary stages. Additionally, we find a single deeply embedded protostar that has not been documented elsewhere in the literature and, from the CO line data, 15 protostellar outflows which we catalog here.Comment: 14 pages, 9 figures, 3 tables, accepted to Ap

Biogeochemical Cycling of 99Tc in Alkaline Sediments

99Tc will be present in significant quantities in radioactive wastes including intermediate-level waste (ILW). The internationally favored concept for disposing of higher activity radioactive wastes including ILW is via deep geological disposal in an underground engineered facility located ∼200–1000 m deep. Typically, in the deep geological disposal environment, the subsurface will be saturated, cement will be used extensively as an engineering material, and iron will be ubiquitous. This means that understanding Tc biogeochemistry in high pH, cementitious environments is important to underpin safety case development. Here, alkaline sediment microcosms (pH 10) were incubated under anoxic conditions under “no added Fe(III)” and “with added Fe(III)” conditions (added as ferrihydrite) at three Tc concentrations (10–11, 10–6, and 10–4 mol L–1). In the 10–6 mol L–1 Tc experiments with no added Fe(III), ∼35% Tc(VII) removal occurred during bioreduction. Solvent extraction of the residual solution phase indicated that ∼75% of Tc was present as Tc(IV), potentially as colloids. In both biologically active and sterile control experiments with added Fe(III), Fe(II) formed during bioreduction and >90% Tc was removed from the solution, most likely due to abiotic reduction mediated by Fe(II). X-ray absorption spectroscopy (XAS) showed that in bioreduced sediments, Tc was present as hydrous TcO2-like phases, with some evidence for an Fe association. When reduced sediments with added Fe(III) were air oxidized, there was a significant loss of Fe(II) over 1 month (∼50%), yet this was coupled to only modest Tc remobilization (∼25%). Here, XAS analysis suggested that with air oxidation, partial incorporation of Tc(IV) into newly forming Fe oxyhydr(oxide) minerals may be occurring. These data suggest that in Fe-rich, alkaline environments, biologically mediated processes may limit Tc mobility.Peer reviewe