Field observation of sequestration of uranium in iron-rich sediments under sequential reduction-oxidation conditions at the DOE Oak Ridge IFRC

At the U.S. DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site, the iron content of shallow subsurface materials (i.e. weathered saprolite) is relatively high (up to 5-6% as w/w), and therefore, the forms of the iron species present plays a critical role in the long-term sequestration of uranium. A long term pilot-scale study of the bioreduction and reoxidation of uranium conducted at the ORIFRC area 3 site, adjacent to the former S-3 disposal ponds (source zone), has provided us with the opportunity to study the impact of iron species on the sequestration of U(VI). The aqueous U(VI) concentrations at the site were decreased to below the EPA MCL through the intermittent injection of ethanol as the electron donor. Previous field tests indicated that both oxygen and nitrate could oxidize the bioreduced U(IV) and cause a short-term rebound of aqueous phase uranium concentration after the oxidative agents were delivered directly to the bioreduced zone.

A field test has been conducted to examine the long-term effect of exposure of bioreduced sediments to nitrate in contaminated groundwater for more than 1,380 days at the Area 3 site. Contaminated groundwater was allowed to invade the previously bioreduced zone via the natural groundwater gradient after an extended period in which reducing conditions were maintained and the bioreduced zone was protected from the influx of upgradient contaminated groundwater. The geochemical response to the invasion of contaminated groundwater was dependent on whether the monitoring location is in the middle or the fringe of the previously bioreduced zone. In general, the nitrate concentrations in the previously bioreduced area, increased gradually from near zero to ~50-300 mM within 200 days and then stabilized. The pH declined from bioreduced levels of 6.2-6.7 to below 5.0. Uranium concentrations rebounded in all monitoring wells but at different rates. At most locations U concentrations rebounded, declined and then rebounded again. Methane gas disappeared while a significant level (20,000 to 44,000 ppmv) N2O was found in the groundwater of monitoring wells after three years of reoxidization.

The U(IV) in sediments was mainly reoxidized to U(VI) species. Based on XANES analysis, the predominate uranium in all samples after re-oxidation was similar to a uranyl nitrate form. But the U content in the sediment remained as high as that determined after bioreduction activates were completed, indicating that much of the U is still sequestrated in situ. SEM observations of surged fine sediments revealed that clusters of colloidal-sized (200-500nm) U-containing precipitates appeared to have formed in situ, regardless from sample of FW106 in non-bioactivity control area or of pre-bioreduced FW101-2 and FW102-3. Additionally, SEM-EDS and microprobe analysis, showed that the U-containing precipitates (~1% U) in FW106 are notably higher in Fe, compared to the precipitates (~1-2.5% U) from FW101-2 and FW102-3. However, XRF analysis indicated that the U content was remained as high as 2180 and 1810 mg/kg with U/Fe ratio at 0.077 and 0.055 vs 0.037 g/g, respectively in pre-bioreduced FW101-2 and FW102-3, suggesting more U sequestrated by Fe in pre-bioreduced sediments.

The Interlaboratory Robustness Of Next-Generation Sequencing (IRON) Study Phase II: Deep-Sequencing Analyses Of Hematological Malignancies Performed In 8,867 Cases By An International Network Involving 27 Laboratories

Introduction: Amplicon deep-sequencing using second-generation sequencing technology is an innovative molecular diagnostic technique and enables a highly-sensitive detection of mutations. As an international consortium we had investigated previously the robustness, precision, and reproducibility of 454 amplicon next-generation sequencing (NGS) across 10 laboratories from 8 countries (Leukemia, 2011;25:1840-8).

Aims: In Phase II of the study, we established distinct working groups for various hematological malignancies, i.e. acute myeloid leukemia (AML), acute lymphoblastic leukemia (ALL), chronic lymphocytic leukemia (CLL), chronic myelogenous leukemia (CML), myelodysplastic syndromes (MDS), myeloproliferative neoplasms (MPN), and multiple myeloma. Currently, 27 laboratories from 13 countries are part of this research consortium. In total, 74 gene targets were selected by the working groups and amplicons were developed for a NGS deep-sequencing assay (454 Life Sciences, Branford, CT). A data analysis pipeline was developed to standardize mutation interpretation both for accessing raw data (Roche Amplicon Variant Analyzer, 454 Life Sciences) and variant interpretation (Sequence Pilot, JSI Medical Systems, Kippenheim, Germany).

Results: We will report on the design, standardization, quality control aspects, landscape of mutations, as well as the prognostic and predictive utility of this assay in a cohort of 8,867 cases. Overall, 1,146 primer sequences were designed and tested. In detail, for example in AML, 924 cases had been screened for CEBPA mutations. RUNX1 mutations were analyzed in 1,888 cases applying the deep-sequencing read counts to study the stability of such mutations at relapse and their utility as a biomarker to detect residual disease. Analyses of DNMT3A (n=1,041) were focused to perform landscape investigations and to address the prognostic relevance. Additionally, this working group is focusing on TET2, ASXL1, and TP53 analyses. A novel prognostic model is being developed allowing stratification of AML into prognostic subgroups based on molecular markers only. In ALL, 1,124 pediatric and adult cases have been screened, including 763 assays for TP53 mutations both at diagnosis and relapse of ALL. Pediatric and adult leukemia expert labs developed additional content to study the mutation incidence of other B and T lineage markers such as IKZF1, JAK2, IL7R, PAX5, EP300, LEF1, CRLF2, PHF6, WT1, JAK1, PTEN, AKT1, IL7R, NOTCH1, CREBBP, or FBXW7. Further, the molecular landscape of CLL is changing rapidly. As such, a separate working group focused on analyses including NOTCH1, SF3B1, MYD88, XPO1, FBXW7 and BIRC3. Currently, 922 cases were screened to investigate the range of mutational burden of NOTCH1 mutations for their prognostic relevance. In MDS, RUNX1 mutation analyses were performed in 977 cases. The prognostic relevance of TP53 mutations in MDS was assessed in additional 327 cases, including isolated deletions of chromosome 5q. Next, content was developed targeting genes of the cellular splicing component, e.g. SF3B1, SRSF2, U2AF1, and ZRSR2. In BCR-ABL1-negative MPN, nine genes of interest (JAK2, MPL, TET2, CBL, KRAS, EZH2, IDH1, IDH2, ASXL1) have been analyzed in a cohort of 155 primary myelofibrosis cases searching for novel somatic mutations and addressing their relevance for disease progression and leukemia transformation. Moreover, an assay was developed and applied to CMML cases allowing the simultaneous analysis of 25 leukemia-associated target genes in a single sequencing run using just 20 ng of starting DNA. Finally, nine laboratories are studying CML, applying ultra-deep sequencing of the BCR-ABL1 tyrosine kinase domain. Analyses were performed on 615 cases investigating the dynamics of expansion of mutated clones under various tyrosine kinase inhibitor therapies.

Conclusion: Molecular characterization of hematological malignancies today requires high diagnostic sensitivity and specificity. As part of the IRON-II study, a network of laboratories analyzed a variety of disease entities applying amplicon-based NGS assays. Importantly, the consortium not only standardized assay design for disease-specific panels, but also achieved consensus on a common data analysis pipeline for mutation interpretation. Distinct working groups have been forged to address scientific tasks and in total 8,867 cases had been analyzed thus far.

Physical properties of a new Deep Eutectic Solvent based on lithium bis[(trifluoromethyl)sulfonyl]imide and N-methylacetamide as superionic suitable electrolyte for lithium ion batteries and electric double layer capacitors

Herein we present a study on the physical/chemical properties of a new Deep Eutectic Solvent (DES) based on N-methylacetamide (MAc) and lithium bis[(trifluoromethyl)sulfonyl]imide (LiTFSI). Due to its interesting properties, such as wide liquid-phase range from -60°C to 280°C, low vapor pressure, and high ionic conductivity up to 28.4mScm at 150°C and at x=1/4, this solution can be practically used as electrolyte for electrochemical storage systems such as electric double-layer capacitors (EDLCs) and/or lithium ion batteries (LiBs). Firstly, relationships between its transport properties (conductivity and viscosity) as a function of composition and temperature were discussed through Arrhenius' Law and Vogel-Tamman-Fulcher (VTF) equations, as well as by using the Walden classification. From this investigation, it appears that this complex electrolyte possesses a number of excellent transport properties, like a superionic character for example. Based on which, we then evaluated its electrochemical performances as electrolyte for EDLCs and LiBs applications by using activated carbon (AC) and lithium iron phosphate (LiFePO) electrodes, respectively. These results demonstrate that this electrolyte has a good compatibility with both electrodes (AC and LiFePO) in each testing cell driven also by excellent electrochemical properties in specific capacitance, rate and cycling performances, indicating that the LiTFSI/MAc DES can be a promising electrolyte for EDLCs and LiBs applications especially for those requiring high safety and stability. © 2013 Elsevier Ltd.

Thermolyzable polymer networks and star polymers containing a novel, compact, degradable acylal-based dimethacrylate cross-linker: Synthesis, characterization, and thermolysis

A compact, cleavable acylal dimethacrylate cross-linker, 1,1-ethylenediol dimethacrylate (EDDMA), was synthesized from the anhydrous iron(III) chloride-catalyzed reaction between methacrylic anhydride and acetaldehyde. The ability of EDDMA to act as cross-linker was demonstrated by using it for the preparation of one neat cross-linker network, four star polymers of methyl methacrylate (MMA), and four randomly cross-linked MMA polymer networks using group transfer polymerization (GTP). For comparison, the corresponding polymer structures based on the commercially available ethylene glycol dimethacrylate (EGDMA) cross-linker (isomer of EDDMA) were also prepared via GTR The number of arms of the EDDMA-based star polymers was lower than that of the corresponding EGDMA polymers, whereas the degrees of swelling in tetrahydrofuran of the EDDMA-based MMA networks were higher than those of their EGDMA-based counterparts. Although none of the EDDMA-containing polymers could be cleanly hydrolyzed under basic or acidic conditions, they could be thermolyzed at 200 degrees C within 1 day giving lower molecular weight products.

Experimental and discrete element modelling of cohesive iron ore fines

In this study, the behaviour of iron ore fines with varying levels of adhesion was investigated using a confined compression test and a uniaxial test. The uniaxial test was conducted using the semi-automated uniaxial EPT tester in which the cohesive strength of a bulk solid is evaluated from an unconfined compression test following a period of consolidation to a pre-defined vertical stress. The iron ore fines were also tested by measuring both the vertical and circumferential strains on the cylindrical container walls under vertical loading in a separate confined compression tester - the K0 tester, to determine the lateral pressure ratio. Discrete Element Method simulations of both experiments were carried out and the predictions were compared with the experimental observations. A recently developed DEM contact model for cohesive solids, an Elasto-Plastic Adhesive model, was used. This particle contact model uses hysteretic non-linear loading and unloading paths and an adhesion parameter which is a function of the maximum contact overlap. The model parameters for the simulations are phenomenologically based to reproduce the key bulk characteristics exhibited by the solid. The simulation results show a good agreement in capturing the stress history dependent behaviour depicted by the flow function of the cohesive iron ore fines while also providing a reasonably good match for the lateral pressure ratio observed during the confined compression K0 tests. This demonstrates the potential for the DEM model to be used in the simulation of bulk handling applications.

Characteristics, complications, and gaps in evidence-based interventions in rheumatic heart disease: the Global Rheumatic Heart Disease Registry (the REMEDY study)

AIMS: Rheumatic heart disease (RHD) accounts for over a million premature deaths annually; however, there is little contemporary information on presentation, complications, and treatment.

METHODS AND RESULTS: This prospective registry enrolled 3343 patients (median age 28 years, 66.2% female) presenting with RHD at 25 hospitals in 12 African countries, India, and Yemen between January 2010 and November 2012. The majority (63.9%) had moderate-to-severe multivalvular disease complicated by congestive heart failure (33.4%), pulmonary hypertension (28.8%), atrial fibrillation (AF) (21.8%), stroke (7.1%), infective endocarditis (4%), and major bleeding (2.7%). One-quarter of adults and 5.3% of children had decreased left ventricular (LV) systolic function; 23% of adults and 14.1% of children had dilated LVs. Fifty-five percent (n = 1761) of patients were on secondary antibiotic prophylaxis. Oral anti-coagulants were prescribed in 69.5% (n = 946) of patients with mechanical valves (n = 501), AF (n = 397), and high-risk mitral stenosis in sinus rhythm (n = 48). However, only 28.3% (n = 269) had a therapeutic international normalized ratio. Among 1825 women of childbearing age (12-51 years), only 3.6% (n = 65) were on contraception. The utilization of valvuloplasty and valve surgery was higher in upper-middle compared with lower-income countries.

CONCLUSION: Rheumatic heart disease patients were young, predominantly female, and had high prevalence of major cardiovascular complications. There is suboptimal utilization of secondary antibiotic prophylaxis, oral anti-coagulation, and contraception, and variations in the use of percutaneous and surgical interventions by country income level.

Peroxide-based hybrid and prodrug antimalarials to deliver cysteine protease inhibitors into the parasitic food vacuole

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2014

Low-loss austempered ductile iron gears: experimental evaluation comparing materials and lubricants

An experimental study to evaluate the power dissipation of gears was performed. Three low-loss gear models were manufactured using standard 20° pressure angle tools. Austempered ductile iron (ADI) and 20MnCr5 carburized steel gears were tested in an FZG gear test machine using mineral, ester and polyalphaolephine (PAO)-based oils. The results compare power dissipation, the influence of different tooth flank geometries, materials and lubricants. This work concludes that conventional power-transmission gears can be replaced by these improved and more efficient low–loss models, which can be produced using common tools and that steel gears can be successfully replaced by austempered ductile iron gears.

The Gandarela Mountain Range and the “resistance space” against iron ore mining threat: a focus on the contrapositions

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Investigations on The Finite Size Effects of Some Inverse Spinels and Studies on Their Composites Based on Nitrile Rubber

Magnetism and magnetic materials have been an ever-attractive subject area for engineers and scientists alike because of its versatility in finding applications in useful devices. They find applications in a host of devices ranging from rudimentary devices like loud speakers to sophisticated gadgets like waveguides and Magnetic Random Access Memories (MRAM).The one and only material in the realm of magnetism that has been at the centre stage of applications is ferrites and in that spinel ferrites received the lions share as far as practical applications are concerned.It has been the endeavour of scientists and engineers to remove obsolescence and improve upon the existing so as to save energy and integrate in to various other systems. This has been the hallmark of material scientists and this has led to new materials and new technologies.In the field of ferrites too there has been considerable interest to devise new materials based on iron oxides and other compounds. This means synthesising ultra fine particles and tuning its properties to device new materials. There are various preparation techniques ranging from top- down to bottom-up approaches. This includes synthesising at molecular level, self assembling,gas based condensation. Iow temperature eo-precipitation, solgel process and high energy ball milling. Among these methods sol-gel process allows good control of the properties of ceramic materials. The advantage of this method includes processing at low temperature. mixing at the molecular level and fabrication of novel materials for various devices.Composites are materials. which combine the good qualities of one or more components. They can be prepared in situ or by mechanical means by the incorporation of fine particles in appropriate matrixes. The size of the magnetic powders as well as the nature of matrix affect the processability and other physical properties of the final product. These plastic/rubber magnets can in turn be useful for various applications in different devices. In applications involving ferrites at high frequencies, it is essential that the material possesses an appropriate dielectric permittivity and suitable magnetic permeability. This can be achieved by synthesizing rubber ferrite composites (RFC's). RFCs are very useful materials for microwave absorptions. Hence the synthesis of ferrites in the nanoregirne.investigations on their size effects on the structural, magnetic, and electrical properties and the incorporation of these ferrites into polymer matrixes assume significance.In the present study, nano particles of NiFe204, Li(!5Fe2S04 and Col-e-O, are prepared by sol gel method. By appropriate heat treatments, particles of different grain sizes are obtained. The structural, magnetic and electrical measurements are evaluated as a function of grain size and temperature. NiFel04 prepared in the ultrafine regime are then incorporated in nitrile rubber matrix. The incorporation was carried out according to a specific recipe and for various loadings of magnetic fillers. The cure characteristics, magnetic properties, electrical properties and mechanical properties of these elastomer blends are carried out. The electrical permittivity of all the rubber samples in the X - band are also conducted.

Studies on the structural, electrical and magnetic properties of composites based on spinel ferrites

This thesis mainly deals with the preparation and studies on magnetic composites based on spinel ferrites prepared both chemically and mechanically. Rubber ferrite composites (RFC) are chosen because of their mouldability and flexibility and the ease with which the dielectric and magnetic properties can be manipulated to make them as useful devices. Natural rubber is chosen as the Matrix because of its local availability and possible value addition. Moreover, NR represents a typical unsaturated nonpolar matrix. The work can be thought of as two parts. Part l concentrates on the preparation and characterization of nanocomposites based on y-Fe203. Part 2 deals with the preparation and characterization of RFCs containing Nickel zinc ferrit In the present study magnetic nanocomposites have been prepared by ionexchange method and the preparation conditions have been optimized. The insitu incorporation of the magnetic component is carried out chemically. This method is selected as it is the easiest and simplest method for preparation of nanocomposite. Nanocomposite samples thus prepared were studied using VSM, Mossbauer spectroscopy, Iron content estimation, and ESR spectroscopy. For the preparation of RFCs, the filler material namely nickel zinc ferrite having the general formula Ni)_xZnxFez04, where x varies from 0 to 1 in steps of 0.2 have been prepared by the conventional ceramic techniques. The system of Nil_xZn"Fe204 is chosen because of their excellent high frequency characteristics. After characterization they are incorporated into the polymer matrix of natural rubber by mechanical method. The incorporation is done according to a specific recipe and for various Loadings of magnetic fillers and also for all compositions. The cure characteristics, magnetic properties and dielectric properties of these composites are evaluated. The ac electrical conductivity of both ceramic nickel zinc ferrites and rubber ferrite composites are also calculated using a simple relation. The results are correlated.

On the Tailoring of Magnetic Properties of Fe-Based Alloy Thin Films by Swift Heavy Ion Irradiation and Thermal Annealing

The development of new materials has been the hall mark of human civilization. The quest for making new devices and new materials has prompted humanity to pursue new methods and techniques that eventually has given birth to modern science and technology. With the advent of nanoscience and nanotechnology, scientists are trying hard to tailor materials by varying their size and shape rather than playing with the composition of the material. This, along with the discovery of new and sophisticated imaging tools, has led to the discovery of several new classes of materials like (3D) Graphite, (2D) graphene, (1D) carbon nanotubes, (0D) fullerenes etc. Magnetic materials are in the forefront of applications and have beencontributing their share to remove obsolescence and bring in new devices based on magnetism and magnetic materials. They find applications in various devices such as electromagnets, read heads, sensors, antennas, lubricants etc. Ferromagnetic as well as ferrimagnetic materials have been in use in the form of various devices. Among the ferromagnetic materials iron, cobalt and nickel occupy an important position while various ferrites finds applications in devices ranging from magnetic cores to sensors.

Effect of cycling on the magnetization of ion exchanged magnetic nanocomposite based on polystyrene

Magnetic nanocomposites containing iron oxide particles embedded in a polymer matrix have been synthesized using the method of ion exchange. They have been characterized by using low temperature and room temperature magnetic measurements and Mo¨ ssbauer spectroscopy. The iron content in these samples has also been determined. The results have been analysed and explained. The physical and chemical properties of these nanocomposite materials are different from those of the bulk. Some of the unique properties of these materials find application in information storage, color imaging, ferrofluids and magnetic refrigeration

On the synthesis and magnetic properties of multiwall carbon nanotube– superparamagnetic iron oxide nanoparticle nanocomposites

Multiwall carbon nanotubes (MWCNTs) possessing an average inner diameter of 150 nm were synthesized by template assisted chemical vapor deposition over an alumina template. Aqueous ferrofluid based on superparamagnetic iron oxide nanoparticles (SPIONs) was prepared by a controlled co-precipitation technique, and this ferrofluid was used to fill the MWCNTs by nanocapillarity. The filling of nanotubes with iron oxide nanoparticles was confirmed by electron microscopy. Selected area electron diffraction indicated the presence of iron oxide and graphitic carbon from MWCNTs. The magnetic phase transition during cooling of the MWCNT–SPION composite was investigated by low temperature magnetization studies and zero field cooled (ZFC) and field cooled experiments. The ZFC curve exhibited a blocking at ∼110 K. A peculiar ferromagnetic ordering exhibited by the MWCNT–SPION composite above room temperature is because of the ferromagnetic interaction emanating from the clustering of superparamagnetic particles in the constrained volume of an MWCNT. This kind of MWCNT–SPION composite can be envisaged as a good agent for various biomedical applications

Bioinspired iron and manganese catalysts for the effective and selective oxidation of alkanes and alkenes

La gran eficiència, selectivitat i les condicions suaus exhibides per les reaccions que tenen lloc al centre actiu de les metal·looxigenases són la font d'inspiració per la present dissertació. Amb l'objectiu de dissenyar catalitzadors d'oxidació eficients hem fet ús de dues estratègies: la primera consisteix en el disseny de complexos amb baix pes molecular inspirats en aspectes estructurals de la primera esfera de coordinació del centre metàl·lic d'enzims de ferro i de manganès. Aquests complexos s'han estudiat com a catalitzadors en l'oxidació selectiva d'alcans i d'alquens fent servir oxidants "verds" com ara l'H2O2. La segona estratègia està basada en l'ús de la química supramolecular per tal de desenvolupar estructures moleculars auto-acoblades amb la forma i les propietats químiques desitjades. Concretament, la construcció de nanocontenidors amb un catalitzador d'oxidació incrustat a la seva estructura ens permetria dur a terme reaccions més selectives, tal com passa en les reaccions catalitzades per enzims.