Use of soft heterocyclic N‑donor ligands to separate actinides and lanthanides

The removal of the most long-lived radiotoxic elements from used nuclear fuel, minor actinides, is foreseen as an essential step toward increasing the public acceptance of nuclear energy as a key component of a low-carbon energy future. Once removed from the remaining used fuel, these elements can be used as fuel in their own right in fast reactors or converted into shorter-lived or stable elements by transmutation prior to geological disposal. The SANEX process is proposed to carry out this selective separation by solvent extraction. Recent efforts to develop reagents capable of separating the radioactive minor actinides from lanthanides as part of a future strategy for the management and reprocessing of used nuclear fuel are reviewed. The current strategies for the reprocessing of PUREX raffinate are summarized, and some guiding principles for the design of actinide-selective reagents are defined. The development and testing of different classes of solvent extraction reagent are then summarized, covering some of the earliest ligand designs right through to the current reagents of choice, bis(1,2,4-triazine) ligands. Finally, we summarize research aimed at developing a fundamental understanding of the underlying reasons for the excellent extraction capabilities and high actinide/lanthanide selectivities shown by this class of ligands and our recent efforts to immobilize these reagents onto solid phases.

Classification and fault detection methods for fuel cell monitoring and quality control

In this paper, various types of fault detection methods for fuel cells are compared. For example, those that use a model based approach or a data driven approach or a combination of the two. The potential advantages and drawbacks of each method are discussed and comparisons between methods are made. In particular, classification algorithms are investigated, which separate a data set into classes or clusters based on some prior knowledge or measure of similarity. In particular, the application of classification methods to vectors of reconstructed currents by magnetic tomography or to vectors of magnetic field measurements directly is explored. Bases are simulated using the finite integration technique (FIT) and regularization techniques are employed to overcome ill-posedness. Fisher's linear discriminant is used to illustrate these concepts. Numerical experiments show that the ill-posedness of the magnetic tomography problem is a part of the classification problem on magnetic field measurements as well. This is independent of the particular working mode of the cell but influenced by the type of faulty behavior that is studied. The numerical results demonstrate the ill-posedness by the exponential decay behavior of the singular values for three examples of fault classes.

A reprocessing for climate of sea surface temperature from the Along-Track Scanning Radiometers: initial validation, accounting for skin and diurnal variability

An initial validation of the Along Track Scanning Radiometer (ATSR) Reprocessing for Climate (ARC) retrievals of sea surface temperature (SST) is presented. ATSR-2 and Advanced ATSR (AATSR) SST estimates are compared to drifting buoy and moored buoy observations over the period 1995 to 2008. The primary ATSR estimates are of skin SST, whereas buoys measure SST below the surface. Adjustment is therefore made for the skin effect, for diurnal stratification and for differences in buoy–satellite observation time. With such adjustments, satellite-in situ differences are consistent between day and night within ~ 0.01 K. Satellite-in situ differences are correlated with differences in observation time, because of the diurnal warming and cooling of the ocean. The data are used to verify the average behaviour of physical and empirical models of the warming/cooling rates. Systematic differences between adjusted AATSR and in-situ SSTs against latitude, total column water vapour (TCWV), and wind speed are less than 0.1 K, for all except the most extreme cases (TCWV < 5 kg m–2, TCWV > 60 kg m–2). For all types of retrieval except the nadir-only two-channel (N2), regional biases are less than 0.1 K for 80% of the ocean. Global comparison against drifting buoys shows night time dual-view two-channel (D2) SSTs are warm by 0.06 ± 0.23 K and dual-view three-channel (D3) SSTs are warm by 0.06 ± 0.21 K (day-time D2: 0.07 ± 0.23 K). Nadir-only results are N2: 0.03 ± 0.33 K and N3: 0.03 ± 0.19 K showing the improved inter-algorithm consistency to ~ 0.02 K. This represents a marked improvement from the existing operational retrieval algorithms for which inter-algorithm inconsistency is > 0.5 K. Comparison against tropical moored buoys, which are more accurate than drifting buoys, gives lower error estimates (N3: 0.02 ± 0.13 K, D2: 0.03 ± 0.18 K). Comparable results are obtained for ATSR-2, except that the ATSR-2 SSTs are around 0.1 K warm compared to AATSR

A reprocessing for climate of sea surface temperature from the Along-Track Scanning Radiometers: a new retrieval scheme

We present a new coefficient-based retrieval scheme for estimation of sea surface temperature (SST) from the Along Track Scanning Radiometer (ATSR) instruments. The new coefficients are banded by total column water vapour (TCWV), obtained from numerical weather prediction analyses. TCWV banding reduces simulated regional retrieval biases to < 0.1 K compared to biases ~ 0.2 K for global coefficients. Further, detailed treatment of the instrumental viewing geometry reduces simulated view-angle related biases from ~ 0.1 K down to < 0.005 K for dual-view retrievals using channels at 11 and 12 μm. A novel analysis of trade-offs related to the assumed noise level when defining coefficients is undertaken, and we conclude that adding a small nominal level of noise (0.01 K) is optimal for our purposes. When applied to ATSR observations, some inter-algorithm biases appear as TCWV-related differences in SSTs estimated from different channel combinations. The final step in coefficient determination is to adjust the offset coefficient in each TCWV band to match results from a reference algorithm. This reference uses the dual-view observations of 3.7 and 11 μm. The adjustment is independent of in situ measurements, preserving independence of the retrievals. The choice of reference is partly motivated by uncertainty in the calibration of the 12 μm of Advanced ATSR. Lastly, we model the sensitivities of the new retrievals to changes to TCWV and changes in true SST, confirming that dual-view SSTs are most appropriate for climatological applications

A reprocessing for climate of sea surface temperature from the Along-Track Scanning Radiometers: basis in radiative transfer

We present new radiative transfer simulations to support determination of sea surface temperature (SST) from Along Track Scanning Radiometer (ATSR) imagery. The simulations are to be used within the ATSR Reprocessing for Climate project. The simulations are based on the “Reference Forward Model” line-by-line model linked with a sea surface emissivity model that accounts for wind speed and temperature, and with a discrete ordinates scattering model (DISORT). Input to the forward model is a revised atmospheric profile dataset, based on full resolution ERA-40, with a wider range of high-latitude profiles to address known retrieval biases in those regions. Analysis of the radiative impacts of atmospheric trace gases shows that geographical and temporal variation of N2O, CH4, HNO3, and CFC-11 and CFC-12 have effects of order 0.05, 0.2, 0.1 K on the 3.7, 11, 12 μm channels respectively. In addition several trace gases, neglected in previous studies, are included using fixed profiles contributing ~ 0.04 K to top-of-atmosphere BTs. Comparison against observations for ATSR2 and AATSR indicates that forward model biases have been reduced from 0.2 to 0.5 K for previous simulations to ~ 0.1 K.

Multiwavelength Observations of EXO 0748-676. I. Reprocessing of X-Ray Bursts

We present high time-resolution multiwavelength observations of X-ray bursts in the low-mass X-ray binary UY Vol. Strong reprocessed signals are present in the ultraviolet and optical, lagged and smeared with respect to the X-rays. The addition of far-ultraviolet coverage for one burst allows much tighter constraints on the temperature and geometry of the reprocessing region than previously possible. A blackbody reprocessing model for this burst suggests a rise in temperatures during the burst from 18,000 to 35,000 K and an emitting area comparable to that expected for the disk and/or irradiated companion star. The lags are consistent with those expected. The single-zone blackbody model cannot reproduce the ratio of optical to ultraviolet flux during the burst, however. The discrepancy seems too large to explain with deviations from a local blackbody spectrum and more likely indicates that a range of reprocessing temperatures are required. Comparable results are derived from other bursts, and in particular the lag and smearing both appear shorter when the companion star is on the near side of the disk as predicted. The burst observed by HST also yielded a spectrum of the reprocessed light. It is dominated by continuum, with a spectral shape consistent with the temperatures derived from lightcurve modeling. Taken as a whole, our observations confirm the standard paradigm of prompt reprocessing distributed across the disk and companion star, with the response dominated by a thermalized continuum rather than by emission lines.

On the reprocessing and reanalysis of observations for climate

The long observational record is critical to our understanding of the Earth’s climate, but most observing systems were not developed with a climate objective in mind. As a result, tremendous efforts have gone into assessing and reprocessing the data records to improve their usefulness in climate studies. The purpose of this paper is to both review recent progress in reprocessing and reanalyzing observations, and summarize the challenges that must be overcome in order to improve our understanding of climate and variability. Reprocessing improves data quality through more scrutiny and improved retrieval techniques for individual observing systems, while reanalysis merges many disparate observations with models through data assimilation, yet both aim to provide a climatology of Earth processes. Many challenges remain, such as tracking the improvement of processing algorithms and limited spatial coverage. Reanalyses have fostered significant research, yet reliable global trends in many physical fields are not yet attainable, despite significant advances in data assimilation and numerical modeling. Oceanic reanalyses have made significant advances in recent years, but will only be discussed here in terms of progress toward integrated Earth system analyses. Climate data sets are generally adequate for process studies and large-scale climate variability. Communication of the strengths, limitations and uncertainties of reprocessed observations and reanalysis data, not only among the community of developers, but also with the extended research community, including the new generations of researchers and the decision makers is crucial for further advancement of the observational data records. It must be emphasized that careful investigation of the data and processing methods are required to use the observations appropriately.

Flow synthesis using gaseous ammonia in a Teflon AF-2400 tube-in-tube reactor: Paal–Knorr pyrrole formation and gas concentration measurement by inline flow titration

Using a simple and accessible Teflon AF-2400 based tube-intube reactor, a series of pyrroles were synthesised in flow using the Paal–Knorr reaction of 1,4-diketones with gaseous ammonia. An inline flow titration technique allowed measurement of the ammonia concentration and its relationship to residence time and temperature.

Continuous-flow processing of gaseous ammonia using a Teflon AF-2400 tube-in-tube reactor: synthesis of thioureas and in-line titrations

A simple tube-in-tube reactor based on the gas-permeable membrane Teflon AF-2400 was used in the continuous flow reaction of gaseous ammonia with isothiocyanates and one isocyanate. A colourimetric in-line titration technique is also reported as a simple method to quantify the amount of ammonia taken up by the solvent in the system.

Tagged phosphine reagents to assist reaction work-up by phase-switched scavenging using a modular flow reactor

The use of three orthogonally tagged phosphine reagents to assist chemical work-up via phase-switch scavenging in conjunction with a modular flow reactor is described. These techniques (acidic, basic and Click chemistry) are used to prepare various amides and tri-substituted guanidines from in situ generated iminophosphoranes.

[3 + 2] Cycloaddition of acetylenes with azides to give 1,4-disubstituted 1,2,3-triazoles in a modular flow reactor

The cycloaddition of acetylenes with azides to give the corresponding 1,4-disubstituted 1,2,3-triazoles is reported using immobilised reagents and scavengers in pre-packed glass tubes in a modular flow reactor.

A modular flow reactor for performing Curtius rearrangements as a continuous flow process

The use of a mesofluidic flow reactor is described for performing Curtius rearrangement reactions of carboxylic acids in the presence of diphenylphosphoryl azide and trapping of the intermediate isocyanates with various nucleophiles.