Technetium Chemistry in High-Level Waste

Tc contamination is found within the DOE complex at those sites whose mission involved extraction of plutonium from irradiated uranium fuel or isotopic enrichment of uranium. At the Hanford Site, chemical separations and extraction processes generated large amounts of high level and transuranic wastes that are currently stored in underground tanks. The waste from these extraction processes is currently stored in underground High Level Waste (HLW) tanks. However, the chemistry of the HLW in any given tank is greatly complicated by repeated efforts to reduce volume and recover isotopes. These processes ultimately resulted in mixing of waste streams from different processes. As a result, the chemistry and the fate of Tc in HLW tanks are not well understood. This lack of understanding has been made evident in the failed efforts to leach Tc from sludge and to remove Tc from supernatants prior to immobilization. Although recent interest in Tc chemistry has shifted from pretreatment chemistry to waste residuals, both needs are served by a fundamental understanding of Tc chemistry

Speciation, Dissolution, and Redox Reactions of Chromium Relevant to Pretreatment and Separation of High-Level Tank Wastes (First Year of Funding: FY 1998)

Chromium, one of the problematic elements in tank sludges, is presently considered to be the most important constituent in defining the total volume of HLW glass to be produced from the Hanford tank wastes. This is because (1) it greatly complicates the vitrification process by forming separate phases in the molten glass and, (2) more importantly, current sludge washing processes are not effective in removing Cr. Inadequate removal of chromium from sludges could result in production of an unacceptably large volume of HLW glass. The removal of Cr from tank sludges is complicated by factors including the complex chemistry of Cr, lack of fundamental data applicable to the HLW chemical systems (high heterogeneity, high ionic strength, high alkalinity and the presence of inorganic and organic ligands, etc.), and the need to avoid processes that may adversely enhance the solubility of Pu and other actinides. Significant gaps exist in the fundamental understanding of Cr chemistry in tank-like environments. Without such data/understanding, these strategies cannot be appropriately evaluated or optimized. The primary objective of the research being carried out under this project is to develop such data/understanding for HLW tank processing. Pacific Northwest and Lawrence Berkeley National Laboratories in collaboration with Washington State University are developing fundamental data on the precipitation/dissolution reactions of Cr(III) compounds and the kinetics of oxidation of Cr(III) to Cr(VI) at room and elevated temperatures and under conditions relevant to high-level waste processing. This integrated approach involving measurement of solubility and oxidation rate constants and spectroscopic characterization of aqueous and solid species as a function of ionic strength, alkalinity, redox conditions and temperature will provide thermodynamic and kinetic data. These data are necessary to predict changes in Cr solubility and speciation in response to changes in pretreatment strategies or to develop cost effective tank waste processing technologies that result from reducing the total amount of Cr in processed waste

Technetium Chemistry in HLW

Tc contamination is found within the DOE complex at those sites whose mission involved extraction of plutonium from irradiated uranium fuel or isotopic enrichment of uranium. At the Hanford Site, chemical separations and extraction processes generated large amounts of high level and transuranic wastes that are currently stored in underground tanks. The waste from these extraction processes is currently stored in underground High Level Waste (HLW) tanks. However, the chemistry of the HLW in any given tank is greatly complicated by repeated efforts to reduce volume and recover isotopes. These processes ultimately resulted in mixing of waste streams from different processes. As a result, the chemistry and the fate of Tc in HLW tanks are not well understood. This lack of understanding has been made evident in the failed efforts to leach Tc from sludge and to remove Tc from supernatants prior to immobilization. Although recent interest in Tc chemistry has shifted from pretreatment chemistry to waste residuals, both needs are served by a fundamental understanding of Tc chemistry

Aligning the Measurement of Microbial Diversity with Macroecological Theory

The number of microbial operational taxonomic units (OTUs) within a community is akin to species richness within plant/animal (“macrobial”) systems. A large literature documents OTU richness patterns, drawing comparisons to macrobial theory. There is, however, an unrecognized fundamental disconnect between OTU richness and macrobial theory: OTU richness is commonly estimated on a per-individual basis, while macrobial richness is estimated per-area. Furthermore, the range or extent of sampled environmental conditions can strongly influence a study's outcomes and conclusions, but this is not commonly addressed when studying OTU richness. Here we (i) propose a new sampling approach that estimates OTU richness per-mass of soil, which results in strong support for species energy theory, (ii) use data reduction to show how support for niche conservatism emerges when sampling across a restricted range of environmental conditions, and (iii) show how additional insights into drivers of OTU richness can be generated by combining different sampling methods while simultaneously considering patterns that emerge by restricting the range of environmental conditions. We propose that a more rigorous connection between microbial ecology and macrobial theory can be facilitated by exploring how changes in OTU richness units and environmental extent influence outcomes of data analysis. While fundamental differences between microbial and macrobial systems persist (e.g., species concepts), we suggest that closer attention to units and scale provide tangible and immediate improvements to our understanding of the processes governing OTU richness and how those processes relate to drivers of macrobial species richness

Untargeted metabolomic profiling of Sphagnum fallax reveals novel antimicrobial metabolites

Sphagnum mosses dominate peatlands by employing harsh ecosystem tactics to prevent vascular plant growth and microbial degradation of these large carbon stores. Knowledge about Sphagnum-produced metabolites, their structure and their function, is important to better understand the mechanisms, underlying this carbon sequestration phenomenon in the face of climate variability. It is currently unclear which compounds are responsible for inhibition of organic matter decomposition and the mechanisms by which this inhibition occurs. Metabolite profiling of Sphagnum fallax was performed using two types of mass spectrometry (MS) systems and 1H nuclear magnetic resonance spectroscopy (1H NMR). Lipidome profiling was performed using LC-MS/MS. A total of 655 metabolites, including one hundred fifty-two lipids, were detected by NMR and LC-MS/MS-329 of which were novel metabolites (31 unknown lipids). Sphagum fallax metabolite profile was composed mainly of acid-like and flavonoid glycoside compounds, that could be acting as potent antimicrobial compounds, allowing Sphagnum to control its environment. Sphagnum fallax metabolite composition comparison against previously known antimicrobial plant metabolites confirmed this trend, with seventeen antimicrobial compounds discovered to be present in Sphagnum fallax, the majority of which were acids and glycosides. Biological activity of these compounds needs to be further tested to confirm antimicrobial qualities. Three fungal metabolites were identified providing insights into fungal colonization that may benefit Sphagnum. Characterizing the metabolite profile of Sphagnum fallax provided a baseline to understand the mechanisms in which Sphagnum fallax acts on its environment, its relation to carbon sequestration in peatlands, and provide key biomarkers to predict peatland C store changes (sequestration, emissions) as climate shifts.Microbiomes in Transition; Office of Biological and Environmental ResearchOpen access journalThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Deciphering ocean carbon in a changing world

Author Posting. © The Author(s), 2016. This is the author's version of the work. It is posted here for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences of the United States of America 113 (2016): 3143-3151, doi:10.1073/pnas.1514645113.Dissolved organic matter (DOM) in the oceans is one of the largest pools of reduced carbon on Earth, comparable in size to the atmospheric CO2 reservoir. A vast number of compounds are present in DOM and they play important roles in all major element cycles, contribute to the storage of atmospheric CO2 in the ocean, support marine ecosystems, and facilitate interactions between organisms. At the heart of the DOM cycle lie molecular-level relationships between the individual compounds in DOM and the members of the ocean microbiome that produce and consume them. In the past, these connections have eluded clear definition because of the sheer numerical complexity of both DOM molecules and microorganisms. Emerging tools in analytical chemistry, microbiology and informatics are breaking down the barriers to a fuller appreciation of these connections. Here we highlight questions being addressed using recent methodological and technological developments in those fields and consider how these advances are transforming our understanding of some of the most important reactions of the marine carbon cycle.Support was provided by National Science Foundation grants OCE1356010, OCE1154320, and OCE1356890, and Gordon and Betty Moore Foundation Grant #3304

Science To Support DOE Site Cleanup: The Pacific Northwest National Laboratory Environmental Management Science Program Awards

Pacific Northwest National Laboratory (PNNL) was awarded ten Environmental Management Science Program (EMSP) research grants in fiscal year 1996, six in fiscal year 1997, nine in fiscal year 1998, seven in fiscal year 1999, and five in fiscal year 2000. All of the fiscal year 1996 award projects have published final reports. The 1997 and 1998 award projects have been completed or are nearing completion. Final reports for these awards will be published, so their annual updates will not be included in this document. This section summarizes how each of the 1999 and 2000 grants address significant U.S. Department of Energy (DOE) cleanup issues, including those at the Hanford Site. The technical progress made to date in each of these research projects is addressed in more detail in the individual progress reports contained in this document. The 1999 and 2000 EMSP awards at PNNL are focused primarily in two areas: Tank Waste Remediation, and Soil and Groundwater Cleanup

Regional and scale-specific effects of land use on amphibian diversity [poster]

Background/Question/Methods Habitat loss and degradation influence amphibian distributions and are important drivers of population declines. Our previous research demonstrated that road disturbance, development and wetland area consistently influence amphibian richness across regions of the U.S. Here, we examined the relative importance of these factors in different regions and at multiple spatial scales. Understanding the scales at which habitat disturbance may be affecting amphibian distributions is important for conservation planning. Specifically, we asked: 1) Over what spatial scales do distinct landscape features affect amphibian richness? and 2) Do road types (non-rural and rural) have similar effects on amphibian richness? This is the second year of a collaborative, nationwide project involving 11 U.S. colleges integrated within undergraduate biology curricula. We summarized North American Amphibian Monitoring Program data in 13 Eastern and Central U.S states and used geographic information systems to extract landscape data for 471 survey locations. We developed models to quantify the influence of landscape variables on amphibian species richness and site occupancy across five concentric buffers ranging from 300m to 10,000m. Results/Conclusions Across spatial scales, development, road density and agriculture were the best predictors of amphibian richness and site occupancy by individual species. Across regions, we found that scale did not exert a large influence on how landscape features influenced amphibian richness as effects were largely comparable across buffers. However, development and percent impervious surface had stronger influence on richness at smaller spatial scales. Richness was lower at survey locations with higher densities of non-rural and rural roads, and non-rural road density had a larger negative effect at smaller scales. Within regions, landscape features driving patterns of species richness varied. The scales at which these factors were associated with richness were highly variable within regions, suggesting the scale effects may be region specific. Our project demonstrates that networks of undergraduate students can collaborate to compile and analyze large ecological data sets, while engaging students in authentic and inquiry-based learning in landscape-scale ecology

An international laboratory comparison of dissolved organic matter composition by high resolution mass spectrometry: Are we getting the same answer?

High-resolution mass spectrometry (HRMS) has become a vital tool for dissolved organic matter (DOM) characterization. The upward trend in HRMS analysis of DOM presents challenges in data comparison and interpretation among laboratories operating instruments with differing performance and user operating conditions. It is therefore essential that the community establishes metric ranges and compositional trends for data comparison with reference samples so that data can be robustly compared among research groups. To this end, four identically prepared DOM samples were each measured by 16 laboratories, using 17 commercially purchased instruments, using positive-ion and negative-ion mode electrospray ionization (ESI) HRMS analyses. The instruments identified ~1000 common ions in both negative- and positive-ion modes over a wide range of m/z values and chemical space, as determined by van Krevelen diagrams. Calculated metrics of abundance-weighted average indices (H/C, O/C, aromaticity, and m/z) of the commonly detected ions showed that hydrogen saturation and aromaticity were consistent for each reference sample across the instruments, while average mass and oxygenation were more affected by differences in instrument type and settings. In this paper we present 32 metric values for future benchmarking. The metric values were obtained for the four different parameters from four samples in two ionization modes and can be used in future work to evaluate the performance of HRMS instruments

Adjuvanted Fusion Protein Vaccine Induces Durable Immunity to Onchocerca volvulus in Mice and Non-Human Primates

Onchocerciasis remains a debilitating neglected tropical disease. Due to the many challenges of current control methods, an effective vaccine against the causative agent Onchocerca volvulus is urgently needed. Mice and cynomolgus macaque non-human primates (NHPs) were immunized with a vaccine consisting of a fusion of two O. volvulus protein antigens, Ov-103 and Ov-RAL-2 (Ov-FUS-1), and three different adjuvants: Advax-CpG, alum, and AlT4. All vaccine formulations induced high antigen-specific IgG titers in both mice and NHPs. Challenging mice with O. volvulus L3 contained within subcutaneous diffusion chambers demonstrated that Ov-FUS-1/Advax-CpG-immunized animals developed protective immunity, durable for at least 11 weeks. Passive transfer of sera, collected at several time points, from both mice and NHPs immunized with Ov-FUS-1/Advax-CpG transferred protection to naïve mice. These results demonstrate that Ov-FUS-1 with the adjuvant Advax-CpG induces durable protective immunity against O. volvulus in mice and NHPs that is mediated by vaccine-induced humoral factors