Microbial Transformations of TRU and Mixed Wastes: Actinide Speciation and Waste Volume Reduction

Cellosic samples were prepared 1/29/92 at BNL from various sources, including white and brown paper towel, and Kimwipes. The mixed cellulosics were cut into 1 cm x 1 cm squares and transferred to glass serum bottles and various treatments were conducted: unamended (U) samples were filled with nitrogen-purged brine from G-Seep (4.1 M Na+ and 5.1 Cl- with minor amounts of Mg, K, and Ca and 0.3 M sulfate (Brush, 1990)); unamended/inoculated (UI) samples were filled with bacteria-containing surface lake water, sediment, and halite from the underground at the WIPP site; amended/inoculated (AI) samples were inoculated in this fashion and amended with nutrients; and amended/inoculated/excess nitrate (AINO3) samples were inoculated with excess nitrate in the form of KNO3 (5 g L-1 (49.5 mM)). Further information on sample preparation is available. All samples were analyzed by Fourier transform infrared spectroscopy (FTIR) at SBU to identify any transformations in cellulosic material which may have occurred during treatment and storage

Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species

<p>Abstract</p> <p>Background</p> <p>Quantum mechanical calculations were performed on a variety of uranium species representing U(VI), U(V), U(IV), U-carbonates, U-phosphates, U-oxalates, U-catecholates, U-phosphodiesters, U-phosphorylated N-acetyl-glucosamine (NAG), and U-2-Keto-3-doxyoctanoate (KDO) with explicit solvation by H₂O molecules. These models represent major U species in natural waters and complexes on bacterial surfaces. The model results are compared to observed EXAFS, IR, Raman and NMR spectra.</p> <p>Results</p> <p>Agreement between experiment and theory is acceptable in most cases, and the reasons for discrepancies are discussed. Calculated Gibbs free energies are used to constrain which configurations are most likely to be stable under circumneutral pH conditions. Reduction of U(VI) to U(IV) is examined for the U-carbonate and U-catechol complexes.</p> <p>Conclusion</p> <p>Results on the potential energy differences between U(V)- and U(IV)-carbonate complexes suggest that the cause of slower disproportionation in this system is electrostatic repulsion between UO₂[CO₃]₃^5-ions that must approach one another to form U(VI) and U(IV) rather than a change in thermodynamic stability. Calculations on U-catechol species are consistent with the observation that UO₂²⁺can oxidize catechol and form quinone-like species. In addition, outer-sphere complexation is predicted to be the most stable for U-catechol interactions based on calculated energies and comparison to ¹³C NMR spectra. Outer-sphere complexes (i.e., ion pairs bridged by water molecules) are predicted to be comparable in Gibbs free energy to inner-sphere complexes for a model carboxylic acid. Complexation of uranyl to phosphorus-containing groups in extracellular polymeric substances is predicted to favor phosphonate groups, such as that found in phosphorylated NAG, rather than phosphodiesters, such as those in nucleic acids.</p

Assessing the role of EO in biodiversity monitoring: options for integrating in-situ observations with EO within the context of the EBONE concept

The European Biodiversity Observation Network (EBONE) is a European contribution on terrestrial monitoring to GEO BON, the Group on Earth Observations Biodiversity Observation Network. EBONE’s aims are to develop a system of biodiversity observation at regional, national and European levels by assessing existing approaches in terms of their validity and applicability starting in Europe, then expanding to regions in Africa. The objective of EBONE is to deliver: 1. A sound scientific basis for the production of statistical estimates of stock and change of key indicators; 2. The development of a system for estimating past changes and forecasting and testing policy options and management strategies for threatened ecosystems and species; 3. A proposal for a cost-effective biodiversity monitoring system. There is a consensus that Earth Observation (EO) has a role to play in monitoring biodiversity. With its capacity to observe detailed spatial patterns and variability across large areas at regular intervals, our instinct suggests that EO could deliver the type of spatial and temporal coverage that is beyond reach with in-situ efforts. Furthermore, when considering the emerging networks of in-situ observations, the prospect of enhancing the quality of the information whilst reducing cost through integration is compelling. This report gives a realistic assessment of the role of EO in biodiversity monitoring and the options for integrating in-situ observations with EO within the context of the EBONE concept (cfr. EBONE-ID1.4). The assessment is mainly based on a set of targeted pilot studies. Building on this assessment, the report then presents a series of recommendations on the best options for using EO in an effective, consistent and sustainable biodiversity monitoring scheme. The issues that we faced were many: 1. Integration can be interpreted in different ways. One possible interpretation is: the combined use of independent data sets to deliver a different but improved data set; another is: the use of one data set to complement another dataset. 2. The targeted improvement will vary with stakeholder group: some will seek for more efficiency, others for more reliable estimates (accuracy and/or precision); others for more detail in space and/or time or more of everything. 3. Integration requires a link between the datasets (EO and in-situ). The strength of the link between reflected electromagnetic radiation and the habitats and their biodiversity observed in-situ is function of many variables, for example: the spatial scale of the observations; timing of the observations; the adopted nomenclature for classification; the complexity of the landscape in terms of composition, spatial structure and the physical environment; the habitat and land cover types under consideration. 4. The type of the EO data available varies (function of e.g. budget, size and location of region, cloudiness, national and/or international investment in airborne campaigns or space technology) which determines its capability to deliver the required output. EO and in-situ could be combined in different ways, depending on the type of integration we wanted to achieve and the targeted improvement. We aimed for an improvement in accuracy (i.e. the reduction in error of our indicator estimate calculated for an environmental zone). Furthermore, EO would also provide the spatial patterns for correlated in-situ data. EBONE in its initial development, focused on three main indicators covering: (i) the extent and change of habitats of European interest in the context of a general habitat assessment; (ii) abundance and distribution of selected species (birds, butterflies and plants); and (iii) fragmentation of natural and semi-natural areas. For habitat extent, we decided that it did not matter how in-situ was integrated with EO as long as we could demonstrate that acceptable accuracies could be achieved and the precision could consistently be improved. The nomenclature used to map habitats in-situ was the General Habitat Classification. We considered the following options where the EO and in-situ play different roles: using in-situ samples to re-calibrate a habitat map independently derived from EO; improving the accuracy of in-situ sampled habitat statistics, by post-stratification with correlated EO data; and using in-situ samples to train the classification of EO data into habitat types where the EO data delivers full coverage or a larger number of samples. For some of the above cases we also considered the impact that the sampling strategy employed to deliver the samples would have on the accuracy and precision achieved. Restricted access to European wide species data prevented work on the indicator ‘abundance and distribution of species’. With respect to the indicator ‘fragmentation’, we investigated ways of delivering EO derived measures of habitat patterns that are meaningful to sampled in-situ observations

Lymphovascular and perineural invasion as selection criteria for adjuvant therapy in intrahepatic cholangiocarcinoma: a multi-institution analysis

AbstractObjectivesCriteria for the selection of patients for adjuvant chemotherapy in intrahepatic cholangiocarcinoma (IHCC) are lacking. Some authors advocate treating patients with lymph node (LN) involvement; however, nodal assessment is often inadequate or not performed. This study aimed to identify surrogate criteria based on characteristics of the primary tumour.MethodsA total of 58 patients who underwent resection for IHCC between January 2000 and January 2010 at any of three institutions were identified. Primary outcome was overall survival (OS).ResultsMedian OS was 23.0months. Median tumour size was 6.5cm and the median number of lesions was one. Overall, 16% of patients had positive margins, 38% had perineural invasion (PNI), 40% had lymphovascular invasion (LVI) and 22% had LN involvement. A median of two LNs were removed and a median of zero were positive. Lymph nodes were not sampled in 34% of patients. Lymphovascular and perineural invasion were associated with reduced OS [9.6months vs. 32.7months (P= 0.020) and 10.7months vs. 32.7months (P= 0.008), respectively]. Lymph node involvement indicated a trend towards reduced OS (10.7months vs. 30.0months; P= 0.063). The presence of either LVI or PNI in node-negative patients was associated with a reduction in OS similar to that in node-positive patients (12.1months vs. 10.7months; P= 0.541). After accounting for adverse tumour factors, only LVI and PNI remained associated with decreased OS on multivariate analysis (hazard ratio4.07, 95% confidence interval 1.60–10.40; P= 0.003).ConclusionsLymphovascular and perineural invasion are separately associated with a reduction in OS similar to that in patients with LN-positive disease. As nodal dissection is often not performed and the number of nodes retrieved is frequently inadequate, these tumour-specific factors should be considered as criteria for selection for adjuvant chemotherapy

A photosynthesis-specific rubredoxin-like protein is required for efficient association of the D1 and D2 proteins during the initial steps of photosystem II assembly

Oxygenic photosynthesis relies on accessory factors to promote the assembly and maintenance of the photosynthetic apparatus in the thylakoid membranes. The highly conserved membrane-bound rubredoxin-like protein RubA has previously been implicated in the accumulation of both photosystem I (PSI) and photosystem II (PSII) but its mode of action remains unclear. Here we show that RubA in the cyanobacterium Synechocystis sp. PCC 6803 is required for photoautotrophic growth in fluctuating light and acts early in PSII biogenesis by promoting the formation of the heterodimeric D1/D2 reaction center complex, the site of primary photochemistry. We find that RubA, like the accessory factor Ycf48, is a component of the initial D1 assembly module as well as larger PSII assembly intermediates and that the redox-responsive rubredoxinlike domain is located on the cytoplasmic surface of PSII complexes. Fusion of RubA to Ycf48 still permits normal PSII assembly suggesting a spatiotemporal proximity of both proteins during their action. RubA is also important for the accumulation of PSI but this is an indirect effect stemming from the downregulation of light-dependent chlorophyll biosynthesis induced by PSII deficiency. Overall our data support the involvement of RubA in the redox control of PSII biogenesis

The catalytic role of uranyl in formation of polycatechol complexes

To better understand the association of contaminant uranium with natural organic matter (NOM) and the fate of uranium in ground water, spectroscopic studies of uranium complexation with catechol were conducted. Catechol provides a model for ubiquitous functional groups present in NOM. Liquid samples were analyzed using Raman, FTIR, and UV-Vis spectroscopy. Catechol was found to polymerize in presence of uranyl ions. Polymerization in presence of uranyl was compared to reactions in the presence of molybdate, another oxyion, and self polymerization of catechol at high pH. The effect of time and dissolved oxygen were also studied. It was found that oxygen was required for self-polymerization at elevated pH. The potential formation of phenoxy radicals as well as quinones was monitored. The benzene ring was found to be intact after polymerization. No evidence for formation of ether bonds was found, suggesting polymerization was due to formation of C-C bonds between catechol ligands. Uranyl was found to form outer sphere complexes with catechol at initial stages but over time (six months) polycatechol complexes were formed and precipitated from solution (forming humic-like material) while uranyl ions remained in solution. Our studies show that uranyl acts as a catalyst in catechol-polymerization

Meta-analysis of multidecadal biodiversity trends in Europe

Local biodiversity trends over time are likely to be decoupled from global trends, as local processes may compensate or counteract global change. We analyze 161 long-term biological time series (15-91 years) collected across Europe, using a comprehensive dataset comprising similar to 6,200 marine, freshwater and terrestrial taxa. We test whether (i) local long-term biodiversity trends are consistent among biogeoregions, realms and taxonomic groups, and (ii) changes in biodiversity correlate with regional climate and local conditions. Our results reveal that local trends of abundance, richness and diversity differ among biogeoregions, realms and taxonomic groups, demonstrating that biodiversity changes at local scale are often complex and cannot be easily generalized. However, we find increases in richness and abundance with increasing temperature and naturalness as well as a clear spatial pattern in changes in community composition (i.e. temporal taxonomic turnover) in most biogeoregions of Northern and Eastern Europe. The global biodiversity decline might conceal complex local and group-specific trends. Here the authors report a quantitative synthesis of longterm biodiversity trends across Europe, showing how, despite overall increase in biodiversity metric and stability in abundance, trends differ between regions, ecosystem types, and taxa.peerReviewe