Steric effects on uranyl complexation: synthetic, structural, and theoretical studies of carbamoyl pyrazole compounds of the uranyl(VI) ion

New bifunctional pyrazole based ligands of the type [C3HR2N2CONR'] (where R = H or CH3; R' = CH3, C2H5, or (C3H7)-C-i) were prepared and characterized. The coordination chemistry of these ligands with uranyl nitrate and uranyl bis(dibenzoyl methanate) was studied with infrared (IR), H-1 NMR, electrospray-mass spectrometry (ES-MS), elemental analysis, and single crystal X-ray diffraction methods. The structure of compound [UO2(NO3)(2)(C3H3N2CON{C2H5}(2))] (2) shows that the uranium(VI) ion is surrounded by one nitrogen atom and seven oxygen atoms in a hexagonal bipyramidal geometry with the ligand acting as a bidentate chelating ligand and bonds through both the carbamoyl oxygen and pyrazolyl nitrogen atoms. In the structure of [UO2(NO3)(2)(H2O)(2)(C5H7N2CON {C2H5}(2))(2)], (5) the pyrazole figand acts as a second sphere ligand and hydrogen bonds to the water molecules through carbamoyl oxygen and pyrazolyl nitrogen atoms. The structure of [UO2(DBM)(2)C3H3N2CON{C2H5}(2)] (8) (where DBM = C6H5COCHCOC6H5) shows that the pyrazole ligand acts as a monodentate ligand and bonds through the carbamoyl oxygen to the uranyl group. The ES-MS spectra of 2 and 8 show that the ligand is similarly bonded to the metal ion in solution. Ab initio quantum chemical studies show that the steric effect plays the key role in complexation behavior.

Liquid AP-UV-MALDI enables stable ion yields of multiply charged peptide and protein ions for sensitive analysis by mass spectrometry

In biological mass spectrometry (MS), two ionization techniques are predominantly employed for the analysis of larger biomolecules, such as polypeptides. These are nano-electrospray ionization [1, 2] (nanoESI) and matrix-assisted laser desorption/ionization [3, 4] (MALDI). Both techniques are considered to be “soft”, allowing the desorption and ionization of intact molecular analyte species and thus their successful mass-spectrometric analysis. One of the main differences between these two ionization techniques lies in their ability to produce multiply charged ions. MALDI typically generates singly charged peptide ions whereas nanoESI easily provides multiply charged ions, even for peptides as low as 1000 Da in mass. The production of highly charged ions is desirable as this allows the use of mass analyzers, such as ion traps (including orbitraps) and hybrid quadrupole instruments, which typically offer only a limited m/z range (< 2000–4000). It also enables more informative fragmentation spectra using techniques such as collisioninduced dissociation (CID) and electron capture/transfer dissociation (ECD/ETD) in combination with tandem MS (MS/MS). [5, 6] Thus, there is a clear advantage of using ESI in research areas where peptide sequencing, or in general, the structural elucidation of biomolecules by MS/MS is required. Nonetheless, MALDI with its higher tolerance to contaminants and additives, ease-of-operation, potential for highspeed and automated sample preparation and analysis as well as its MS imaging capabilities makes it an ionization technique that can cover bioanalytical areas for which ESI is less suitable. [7, 8] If these strengths could be combined with the analytical power of multiply charged ions, new instrumental configurations and large-scale proteomic analyses based on MALDI MS(/MS) would become feasible.

Changes in storm track and cyclone activity in three SRES ensemble experiments with the ECHAM5/MPI-OM1 GCM

Synoptic activity over the Northern Hemisphere is evaluated in ensembles of ECHAM5/MPI-OM1 simulations for recent climate conditions (20C) and for three climate scenarios (following SRES A1B, A2, B1). A close agreement is found between the simulations for present day climate and the respective results from reanalysis. Significant changes in the winter mid-tropospheric storm tracks are detected in all three scenario simulations. Ensemble mean climate signals are rather similar, with particularly large activity increases downstream of the Atlantic storm track over Western Europe. The magnitude of this signal is largely dependent on the imposed change in forcing. However, differences between individual ensemble members may be large. With respect to the surface cyclones, the scenario runs produce a reduction in cyclonic track density over the mid-latitudes, even in the areas with increasing mid-tropospheric activity. The largest decrease in track densities occurs at subtropical latitudes, e.g., over the Mediterranean Basin. An increase of cyclone intensities is detected for limited areas (e.g., near Great Britain and Aleutian Isles) for the A1B and A2 experiments. The changes in synoptic activity are associated with alterations of the Northern Hemisphere circulation and background conditions (blocking frequencies, jet stream). The North Atlantic Oscillation index also shows increased values with enhanced forcing. With respect to the effects of changing synoptic activity, the regional change in cyclone intensities is accompanied by alterations of the extreme surface winds, with increasing values over Great Britain, North and Baltic Seas, as well as the areas with vanishing sea ice, and decreases over much of the subtropics.

Double jeopardy: the potential for problems when bats interact with breathable roofing membranes in the United Kingdom

In order to reduce environmental impacts and achieve sustainability, it is important to balance the interactions between the built and natural environment. The construction industry is becoming more aware of ecological concerns and the importance that biodiversity and maintenance ecosystem services has for sustainability. Bats constitute an important component of urban biodiversity and several species in the UK are highly dependent on buildings, making them particularly vulnerable to anthropogenic and environmental changes. Many buildings suitable for use as bat roosts often require re-roofing as they age and traditional bituminous roofing felts are frequently being replaced with breathable roofing membranes (BRMs). In the UK new building regulations and modern materials may substantially reduce the viability of existing roosts, yet at thesame time building regulations require that materials be fit for purpose. Reports suggest that both bats and BRMs may experience problems when the two interact. Such information makes it important to understand how house dwelling bats and BRMs may be affected. This paper considers the possible ways in which bats and BRMs may interact, how this could affect existing bat roosts within buildings and the implications for BRM service life predictions and warranties. Keywords –Breathable Roofing Membranes, Bats in Buildings, Material Deterioration, Sustainability, Conservation, Biodiversit

How large are projected 21st century storm track changes?

Projected changes in the extra-tropical wintertime storm tracks are investigated using the multi-model ensembles from both the third and fifth phases of the World Climate Research Programme's Coupled Model Intercomparison Project (CMIP3 and CMIP5). The aim is to characterize the magnitude of the storm track responses relative to their present-day year-to-year variability. For the experiments considered, the ‘middle-of-the-road’ scenarios in each CMIP, there are regions of the Northern Hemisphere where the responses of up to 40% of the models exceed half of the inter-annual variability, and for the Southern Hemisphere there are regions where up to 60% of the model responses exceed half of the inter-annual variability.

A twenty-year independent record of sea surface temperature for climate from Along-track Scanning Radiometers

A new record of sea surface temperature (SST) for climate applications is described. This record provides independent corroboration of global variations estimated from SST measurements made in situ. Infrared imagery from Along-Track Scanning Radiometers (ATSRs) is used to create a 20 year time series of SST at 0.1° latitude-longitude resolution, in the ATSR Reprocessing for Climate (ARC) project. A very high degree of independence of in situ measurements is achieved via physics-based techniques. Skin SST and SST estimated for 20 cm depth are provided, with grid cell uncertainty estimates. Comparison with in situ data sets establishes that ARC SSTs generally have bias of order 0.1 K or smaller. The precision of the ARC SSTs is 0.14 K during 2003 to 2009, from three-way error analysis. Over the period 1994 to 2010, ARC SSTs are stable, with better than 95% confidence, to within 0.005 K yr−1(demonstrated for tropical regions). The data set appears useful for cleanly quantifying interannual variability in SST and major SST anomalies. The ARC SST global anomaly time series is compared to the in situ-based Hadley Centre SST data set version 3 (HadSST3). Within known uncertainties in bias adjustments applied to in situ measurements, the independent ARC record and HadSST3 present the same variations in global marine temperature since 1996. Since the in situ observing system evolved significantly in its mix of measurement platforms and techniques over this period, ARC SSTs provide an important corroboration that HadSST3 accurately represents recent variability and change in this essential climate variable.

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.

An infrared desert dust index for the Along-Track Scanning Radiometers

A new aerosol index for the Along-Track Scanning Radiometers (ATSRs) is presented that provides a means to detect desert dust contamination in infrared SST retrievals. The ATSR Saharan dust index (ASDI) utilises only the thermal infrared channels and may therefore be applied consistently to the entire ATSR data record (1991 to present), for both day time and night time observations. The derivation of the ASDI is based on a principal component (PC) analysis (PCA) of two unique pairs of channel brightness temperature differences (BTDs). In 2-D space (i.e. BTD vs BTD), it is found that the loci of data unaffected by aerosol are confined to a single axis of variability. In contrast, the loci of aerosol-contaminated data fall off-axis, shifting in a direction that is approximately orthogonal to the clear-sky axis. The ASDI is therefore defined to be the second PC, where the first PC accounts for the clear-sky variability. The primary ASDI utilises the ATSR nadir and forward-view observations at 11 and 12 μm (ASDI2). A secondary, three-channel nadir-only ASDI (ASDI3) is also defined for situations where data from the forward view are not available. Empirical and theoretical analyses suggest that ASDI is well correlated with aerosol optical depth (AOD: correlation r is typically > 0.7) and provides an effective tool for detecting desert mineral dust. Overall, ASDI2 is found to be more effective than ASDI3, with the latter being sensitive only to very high dust loading. In addition, use of ASDI3 is confined to night time observations as it relies on data from the 3.7 μm channel, which is sensitive to reflected solar radiation. This highlights the benefits of having data from both a nadir- and a forward-view for this particular approach to aerosol detection.

Deriving a sea surface temperature record suitable for climate change research from the along-track scanning radiometers

We describe the approach to be adopted for a major new initiative to derive a homogeneous record of sea surface temperature for 1991–2007 from the observations of the series of three along-track scanning radiometers (ATSRs). This initiative is called (A)RC: (Advanced) ATSR Re-analysis for Climate. The main objectives are to reduce regional biases in retrieved sea surface temperature (SST) to less than 0.1 K for all global oceans, while creating a very homogenous record that is stable in time to within 0.05 K decade−1, with maximum independence of the record from existing analyses of SST used in climate change research. If these stringent targets are achieved, this record will enable significantly improved estimates of surface temperature trends and variability of sufficient quality to advance questions of climate change attribution, climate sensitivity and historical reconstruction of surface temperature changes. The approach includes development of new, consistent estimators for SST for each of the ATSRs, and detailed analysis of overlap periods. Novel aspects of the approach include generation of multiple versions of the record using alternative channel sets and cloud detection techniques, to assess for the first time the effect of such choices. There will be extensive effort in quality control, validation and analysis of the impact on climate SST data sets. Evidence for the plausibility of the 0.1 K target for systematic error is reviewed, as is the need for alternative cloud screening methods in this context.

Equator-to-pole temperature differences and the extra-tropical storm track responses of the CMIP5 climate models

This paper aims to understand the physical processes causing the large spread in the storm track projections of the CMIP5 climate models. In particular, the relationship between the climate change responses of the storm tracks, as measured by the 2–6 day mean sea level pressure variance, and the equator-to-pole temperature differences at upper- and lower-tropospheric levels is investigated. In the southern hemisphere the responses of the upper- and lower-tropospheric temperature differences are correlated across the models and as a result they share similar associations with the storm track responses. There are large regions in which the storm track responses are correlated with the temperature difference responses, and a simple linear regression model based on the temperature differences at either level captures the spatial pattern of the mean storm track response as well explaining between 30 and 60 % of the inter-model variance of the storm track responses. In the northern hemisphere the responses of the two temperature differences are not significantly correlated and their associations with the storm track responses are more complicated. In summer, the responses of the lower-tropospheric temperature differences dominate the inter-model spread of the storm track responses. In winter, the responses of the upper- and lower-temperature differences both play a role. The results suggest that there is potential to reduce the spread in storm track responses by constraining the relative magnitudes of the warming in the tropical and polar regions.

Variability of the North Atlantic summer storm track: mechanisms and impacts on European climate

The summertime variability of the extratropical storm track over the Atlantic sector and its links to European climate have been analysed for the period 1948–2011 using observations and reanalyses. The main results are as follows. (1) The dominant mode of the summer storm track density variability is characterized by a meridional shift of the storm track between two distinct paths and is related to a bimodal distribution in the climatology for this region. It is also closely related to the Summer North Atlantic Oscillation (SNAO). (2) A southward shift is associated with a downstream extension of the storm track and a decrease in blocking frequency over the UK and northwestern Europe. (3) The southward shift is associated with enhanced precipitation over the UK and northwestern Europe and decreased precipitation over southern Europe (contrary to the behaviour in winter). (4) There are strong ocean–atmosphere interactions related to the dominant mode of storm track variability. The atmosphere forces the ocean through anomalous surface fluxes and Ekman currents, but there is also some evidence consistent with an ocean influence on the atmosphere, and that coupled ocean–atmosphere feedbacks might play a role. The ocean influence on the atmosphere may be particularly important on decadal timescales, related to the Atlantic Multidecadal Oscillation (AMO).

Linking Northern Hemisphere blocking and storm track biases in the CMIP5 climate models

The relationship between biases in Northern Hemisphere (NH) atmospheric blocking frequency and extratropical cyclone track density is investigated in 12 CMIP5 climate models to identify mechanisms underlying climate model biases and inform future model development. Biases in the Greenland blocking and summer Pacific blocking frequencies are associated with biases in the storm track latitudes while biases in winter European blocking frequency are related to the North Atlantic storm track tilt and Mediterranean cyclone density. However, biases in summer European and winter Pacific blocking appear less related with cyclone track density. Furthermore, the models with smaller biases in winter European blocking frequency have smaller biases in the cyclone density in Europe, which suggests that they are different aspects of the same bias. This is not found elsewhere in the NH. The summer North Atlantic and the North Pacific mean CMIP5 track density and blocking biases might therefore have different origins.

Transient receptor potential ion channels V4 and A1 contribute to pancreatitis pain in mice.

The mechanisms of pancreatic pain, a cardinal symptom of pancreatitis, are unknown. Proinflammatory agents that activate transient receptor potential (TRP) channels in nociceptive neurons can cause neurogenic inflammation and pain. We report a major role for TRPV4, which detects osmotic pressure and arachidonic acid metabolites, and TRPA1, which responds to 4-hydroxynonenal and cyclopentenone prostaglandins, in pancreatic inflammation and pain in mice. Immunoreactive TRPV4 and TRPA1 were detected in pancreatic nerve fibers and in dorsal root ganglia neurons innervating the pancreas, which were identified by retrograde tracing. Agonists of TRPV4 and TRPA1 increased intracellular Ca(2+) concentration ([Ca(2+)](i)) in these neurons in culture, and neurons also responded to the TRPV1 agonist capsaicin and are thus nociceptors. Intraductal injection of TRPV4 and TRPA1 agonists increased c-Fos expression in spinal neurons, indicative of nociceptor activation, and intraductal TRPA1 agonists also caused pancreatic inflammation. The effects of TRPV4 and TRPA1 agonists on [Ca(2+)](i), pain and inflammation were markedly diminished or abolished in trpv4 and trpa1 knockout mice. The secretagogue cerulein induced pancreatitis, c-Fos expression in spinal neurons, and pain behavior in wild-type mice. Deletion of trpv4 or trpa1 suppressed c-Fos expression and pain behavior, and deletion of trpa1 attenuated pancreatitis. Thus TRPV4 and TRPA1 contribute to pancreatic pain, and TRPA1 also mediates pancreatic inflammation. Our results provide new information about the contributions of TRPV4 and TRPA1 to inflammatory pain and suggest that channel antagonists are an effective therapy for pancreatitis, when multiple proinflammatory agents are generated that can activate and sensitize these channels.