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.

Enhanced seasonal forecast skill following stratospheric sudden warmings

Advances in seasonal forecasting have brought widespread socio-economic benefits. However, seasonal forecast skill in the extratropics is relatively modest, prompting the seasonal forecasting community to search for additional sources of predictability. For over a decade it has been suggested that knowledge of the state of the stratosphere can act as a source of enhanced seasonal predictability; long-lived circulation anomalies in the lower stratosphere that follow stratospheric sudden warmings are associated with circulation anomalies in the troposphere that can last up to two months. Here, we show by performing retrospective ensemble model forecasts that such enhanced predictability can be realized in a dynamical seasonal forecast system with a good representation of the stratosphere. When initialized at the onset date of stratospheric sudden warmings, the model forecasts faithfully reproduce the observed mean tropospheric conditions in the months following the stratospheric sudden warmings. Compared with an equivalent set of forecasts that are not initialized during stratospheric sudden warmings, we document enhanced forecast skill for atmospheric circulation patterns, surface temperatures over northern Russia and eastern Canada and North Atlantic precipitation. We suggest that seasonal forecast systems initialized during stratospheric sudden warmings are likely to yield significantly greater forecast skill in some regions.

Quantifying the contributions to stratospheric ozone changes from ozone depleting substances and greenhouse gases

A state-of-the-art chemistry climate model coupled to a three-dimensional ocean model is used to produce three experiments, all seamlessly covering the period 1950–2100, forced by different combinations of long-lived Greenhouse Gases (GHGs) and Ozone Depleting Substances (ODSs). The experiments are designed to quantify the separate effects of GHGs and ODSs on the evolution of ozone, as well as the extent to which these effects are independent of each other, by alternately holding one set of these two forcings constant in combination with a third experiment where both ODSs and GHGs vary. We estimate that up to the year 2000 the net decrease in the column amount of ozone above 20 hPa is approximately 75% of the decrease that can be attributed to ODSs due to the offsetting effects of cooling by increased CO2. Over the 21st century, as ODSs decrease, continued cooling from CO2 is projected to account for more than 50% of the projected increase in ozone above 20 hPa. Changes in ozone below 20 hPa show a redistribution of ozone from tropical to extra-tropical latitudes with an increase in the Brewer-Dobson circulation. In addition to a latitudinal redistribution of ozone, we find that the globally averaged column amount of ozone below 20 hPa decreases over the 21st century, which significantly mitigates the effect of upper stratospheric cooling on total column ozone. Analysis by linear regression shows that the recovery of ozone from the effects of ODSs generally follows the decline in reactive chlorine and bromine levels, with the exception of the lower polar stratosphere where recovery of ozone in the second half of the 21st century is slower than would be indicated by the decline in reactive chlorine and bromine concentrations. These results also reveal the degree to which GHGrelated effects mute the chemical effects of N2O on ozone in the standard future scenario used for the WMO Ozone Assessment. Increases in the residual circulation of the atmosphere and chemical effects from CO2 cooling more than halve the increase in reactive nitrogen in the mid to upper stratosphere that results from the specified increase in N2O between 1950 and 2100.

Seasonal persistence of northern low- and middle-latitude anomalies of ozone and other trace gases in the upper stratosphere

Analysis of observed ozone profiles in Northern Hemisphere low and middle latitudes reveals the seasonal persistence of ozone anomalies in both the lower and upper stratosphere. Principal component analysis is used to detect that above 16 hPa the persistence is strongest in the latitude band 15–45°N, while below 16 hPa the strongest persistence is found over 45–60°N. In both cases, ozone anomalies persist through the entire year from November to October. The persistence of ozone anomalies in the lower stratosphere is presumably related to the wintertime ozone buildup with subsequent photochemical relaxation through summer, as previously found for total ozone. The persistence in the upper stratosphere is more surprising, given the short lifetime of Ox at these altitudes. It is hypothesized that this “seasonal memory” in the upper stratospheric ozone anomalies arises from the seasonal persistence of transport-induced wintertime NOy anomalies, which then perturb the ozone chemistry throughout the rest of the year. This hypothesis is confirmed by analysis of observations of NO2, NOx, and various long-lived trace gases in the upper stratosphere, which are found to exhibit the same seasonal persistence. Previous studies have attributed much of the year-to-year variability in wintertime extratropical upper stratospheric ozone to the Quasi-Biennial Oscillation (QBO) through transport-induced NOy (and hence NO2) anomalies but have not identified any statistical connection between the QBO and summertime ozone variability. Our results imply that through this “seasonal memory,” the QBO has an asynchronous effect on ozone in the low to midlatitude upper stratosphere during summer and early autumn.

Transport in the middle atmosphere

An overview is provided of the current understanding of transport in the middle atmosphere. Over the past quarter century this subject has evolved from a basic recognition of the Brewer-Dobson circulation to a detailed appreciation of many key features of transport such as the stratospheric surf zone, mixing barriers and the dynamics of filamentation. Whilst the elegant theoretical framework for middle atmosphere transport that emerged roughly twenty years ago never fulfilled its promise, useful phenomenological models have been developed together with innovative diagnostic methods. These advances were made possible by the advent of plenty of satellite and aircraft observations of long-lived chemical species together with developments in data assimilation and numerical modeling, and have been driven in large measure by the problem of stratospheric ozone depletion. This review is primarily focused on the stratosphere, where both the interest and the knowledge are the greatest, but a few remarks are also made on the mesosphere.

Summertime stratospheric processes at northern mid-latitudes: comparisons between MANTRA balloon measurements and the Canadian Middle Atmosphere Model

In this paper we report on a study conducted using the Middle Atmospheric Nitrogen TRend Assessment (MANTRA) balloon measurements of stratospheric constituents and temperature and the Canadian Middle Atmosphere Model (CMAM). Three different kinds of data are used to assess the inter-consistency of the combined dataset: single profiles of long-lived species from MANTRA 1998, sparse climatologies from the ozonesonde measurements during the four MANTRA campaigns and from HALOE satellite measurements, and the CMAM climatology. In doing so, we evaluate the ability of the model to reproduce the measured fields and to thereby test our ability to describe mid-latitude summertime stratospheric processes. The MANTRA campaigns were conducted at Vanscoy, Saskatchewan, Canada (52◦ N, 107◦ W)in late August and early September of 1998, 2000, 2002 and 2004. During late summer at mid-latitudes, the stratosphere is close to photochemical control, providing an ideal scenario for the study reported here. From this analysis we find that: (1) reducing the value for the vertical diffusion coefficient in CMAM to a more physically reasonable value results in the model better reproducing the measured profiles of long-lived species; (2) the existence of compact correlations among the constituents, as expected from independent measurements in the literature and from models, confirms the self-consistency of the MANTRA measurements; and (3) the 1998 measurements show structures in the chemical species profiles that can be associated with transport, adding to the growing evidence that the summertime stratosphere can be much more disturbed than anticipated. The mechanisms responsible for such disturbances need to be understood in order to assess the representativeness of the measurements and to isolate longterm trends.

Normal mode Rossby waves and their effects on chemical composition in the late summer stratosphere

During past MANTRA campaigns, ground-based measurements of several long-lived chemical species have revealed quasi-periodic fluctuations on time scales of several days. These fluctuations could confound efforts to detect long-term trends from MANTRA, and need to be understood and accounted for. Using the Canadian Middle Atmosphere Model, we investigate the role of dynamical variability in the late summer stratosphere due to normal mode Rossby waves and the impact of this variability on fluctuations in chemical species. Zonal wavenumber 1, westward travelling waves are considered with average periods of 5, 10 and 16 days. Time-lagged correlations between the temperature and nitrous oxide, methane and ozone fields are calculated in order to assess the possible impact of these waves on the chemical species. Using Fourier-wavelet decomposition and correlating the fluctuations between the temperature and chemical fields, we determine that variations in the chemical species are well-correlated with the 5- and 10-day waves between 30 and 60 km, although the nature of the correlations depend strongly on altitude. Interannual variability of the waves is also examined.

Satellite observations and modeling of transport in the upper troposphere through the lower mesosphere during the 2006 major stratospheric sudden warming

An unusually strong and prolonged stratospheric sudden warming (SSW) in January 2006 was the first major SSW for which globally distributed long-lived trace gas data are available covering the upper troposphere through the lower mesosphere. We use Aura Microwave Limb Sounder (MLS), Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) data, the SLIMCAT Chemistry Transport Model (CTM), and assimilated meteorological analyses to provide a comprehensive picture of transport during this event. The upper tropospheric ridge that triggered the SSW was associated with an elevated tropopause and layering in trace gas profiles in conjunction with stratospheric and tropospheric intrusions. Anomalous poleward transport (with corresponding quasi-isentropic troposphere-to-stratosphere exchange at the lowest levels studied) in the region over the ridge extended well into the lower stratosphere. In the middle and upper stratosphere, the breakdown of the polar vortex transport barrier was seen in a signature of rapid, widespread mixing in trace gases, including CO, H2O, CH4 and N2O. The vortex broke down slightly later and more slowly in the lower than in the middle stratosphere. In the middle and lower stratosphere, small remnants with trace gas values characteristic of the pre-SSW vortex lingered through the weak and slow recovery of the vortex. The upper stratospheric vortex quickly reformed, and, as enhanced diabatic descent set in, CO descended into this strong vortex, echoing the fall vortex development. Trace gas evolution in the SLIMCAT CTM agrees well with that in the satellite trace gas data from the upper troposphere through the middle stratosphere. In the upper stratosphere and lower mesosphere, the SLIMCAT simulation does not capture the strong descent of mesospheric CO and H2O values into the reformed vortex; this poor CTM performance in the upper stratosphere and lower mesosphere results primarily from biases in the diabatic descent in assimilated analyses.

Determination of a lower bound on Earth’s climate sensitivity

Transient and equilibrium sensitivity of Earth's climate has been calculated using global temperature, forcing and heating rate data for the period 1970–2010. We have assumed increased long-wave radiative forcing in the period due to the increase of the long-lived greenhouse gases. By assuming the change in aerosol forcing in the period to be zero, we calculate what we consider to be lower bounds to these sensitivities, as the magnitude of the negative aerosol forcing is unlikely to have diminished in this period. The radiation imbalance necessary to calculate equilibrium sensitivity is estimated from the rate of ocean heat accumulation as 0.37±0.03W m^−2 (all uncertainty estimates are 1−σ). With these data, we obtain best estimates for transient climate sensitivity 0.39±0.07K (W m^−2)^−1 and equilibrium climate sensitivity 0.54±0.14K (W m^−2)^−1, equivalent to 1.5±0.3 and 2.0±0.5K (3.7W m^−2)^−1, respectively. The latter quantity is equal to the lower bound of the ‘likely’ range for this quantity given by the 2007 IPCC Assessment Report. The uncertainty attached to the lower-bound equilibrium sensitivity permits us to state, within the assumptions of this analysis, that the equilibrium sensitivity is greater than 0.31K (W m^−2)^−1, equivalent to 1.16K(3.7W m^−2)^−1, at the 95% confidence level.

A Lagrangian analysis of ice-supersaturated air over the North Atlantic

Understanding the nature of air parcels that exhibit ice-supersaturation is important because they are the regions of potential formation of both cirrus and aircraft contrails, which affect the radiation balance. Ice-supersaturated air parcels in the upper troposphere and lower stratosphere over the North Atlantic are investigated using Lagrangian trajectories. The trajectory calculations use ERA-Interim data for three winter and three summer seasons, resulting in approximately 200,000 trajectories with ice-supersaturation for each season. For both summer and winter, the median duration of ice-supersaturation along a trajectory is less than 6 hours. 5% of air which becomes ice-supersaturated in the troposphere, and 23% of air which becomes ice-supersaturated in the stratosphere will remain ice-supersaturated for at least 24 hours. Weighting the ice-supersaturation duration with the observed frequency indicates the likely overall importance of the longer duration ice-supersaturated trajectories. Ice-supersaturated air parcels typically experience a decrease in moisture content while ice-supersaturated, suggesting that cirrus clouds eventually form in the majority of such air. A comparison is made between short-lived (less than 24 h) and long-lived (greater than 24 h) ice-supersaturated air flows. For both air flows, ice-supersaturation occurs around the northernmost part of the trajectory. Short-lived ice-supersaturated air flows show no significant differences in speed or direction of movement to subsaturated air parcels. However, long-lived ice-supersaturated air occurs in slower moving air flows, which implies that they are not associated with the fastest moving air through a jet stream.

Characterizing sampling bias in the trace gas climatologies of the SPARC Data Initiative

Monthly zonal mean climatologies of atmospheric measurements from satellite instruments can have biases due to the nonuniform sampling of the atmosphere by the instruments. We characterize potential sampling biases in stratospheric trace gas climatologies of the Stratospheric Processes and Their Role in Climate (SPARC) Data Initiative using chemical fields from a chemistry climate model simulation and sampling patterns from 16 satellite-borne instruments. The exercise is performed for the long-lived stratospheric trace gases O3 and H2O. Monthly sampling biases for O3 exceed 10% for many instruments in the high-latitude stratosphere and in the upper troposphere/lower stratosphere, while annual mean sampling biases reach values of up to 20% in the same regions for some instruments. Sampling biases for H2O are generally smaller than for O3, although still notable in the upper troposphere/lower stratosphere and Southern Hemisphere high latitudes. The most important mechanism leading to monthly sampling bias is nonuniform temporal sampling, i.e., the fact that for many instruments, monthly means are produced from measurements which span less than the full month in question. Similarly, annual mean sampling biases are well explained by nonuniformity in the month-to-month sampling by different instruments. Nonuniform sampling in latitude and longitude are shown to also lead to nonnegligible sampling biases, which are most relevant for climatologies which are otherwise free of biases due to nonuniform temporal sampling.

Social innovation in local food in Japan: Choku-bai-jo markets and Teikei cooperative practices

The working paper depicts two innovative examples from Japan of the direct supply of food, which involves the development of closer producer-consumer relations, as well as closer producer-producer networks. Choku-bai-jo and Teikei networks are considered as examples of practices implicated in alternative food networks (AFNs). One example has become a quasi-public endeavour and is seen by the Japanese state as a legitimate part of rural development and is promoted in support of small producers. The other is borne from consumer concern over food quality and, despite its long-lived status, this arrangement remains marginal and with little institutional or governmental support. A model which blends the organization and aims of both examples holds potential for a more sustainable eco-economic future.

The potential impact of changes in lower stratospheric water vapour on stratospheric temperatures over the past 30 years

This study investigates the potential contribution of observed changes in lower stratospheric water vapour to stratospheric temperature variations over the past three decades using a comprehensive global climate model (GCM). Three case studies are considered. In the first, the net increase in stratospheric water vapour (SWV) from 1980–2010 (derived from the Boulder frost-point hygrometer record using the gross assumption that this is globally representative) is estimated to have cooled the lower stratosphere by up to ∼0.2 K decade−1 in the global and annual mean; this is ∼40% of the observed cooling trend over this period. In the Arctic winter stratosphere there is a dynamical response to the increase in SWV, with enhanced polar cooling of 0.6 K decade−1 at 50 hPa and warming of 0.5 K decade−1 at 1 hPa. In the second case study, the observed decrease in tropical lower stratospheric water vapour after the year 2000 (imposed in the GCM as a simplified representation of the observed changes derived from satellite data) is estimated to have caused a relative increase in tropical lower stratospheric temperatures by ∼0.3 K at 50 hPa. In the third case study, the wintertime dehydration in the Antarctic stratospheric polar vortex (again using a simplified representation of the changes seen in a satellite dataset) is estimated to cause a relative warming of the Southern Hemisphere polar stratosphere by up to 1 K at 100 hPa from July–October. This is accompanied by a weakening of the westerly winds on the poleward flank of the stratospheric jet by up to 1.5 m s−1 in the GCM. The results show that, if the measurements are representative of global variations, SWV should be considered as important a driver of transient and long-term variations in lower stratospheric temperature over the past 30 years as increases in long-lived greenhouse gases and stratospheric ozone depletion.

Meteorological factors controlling low-level continental pollutant outflow across a coast

Coastal outflow describes the horizontal advection of pollutants from the continental boundary layer across a coastline into a layer above the marine boundary layer. This process can ventilate polluted continental boundary layers and thus regulate air quality in highly populated coastal regions. This paper investigates the factors controlling coastal outflow and quantifies its importance as a ventilation mechanism. Tracers in the Met Office Unified Model (MetUM) are used to examine the magnitude and variability of coastal outflow over the eastern United States for a 4 week period during summer 2004. Over the 4 week period, ventilation of tracer from the continental boundary layer via coastal outflow occurs with the same magnitude as vertical ventilation via convection and advection. The relative importance of tracer decay rate, cross-coastal advection rate, and a parameter based on the relative continental and marine boundary layer heights, on coastal outflow is assessed by reducing the problem to a time-dependent box-model. The ratio of the advection rate and decay rate is a dimensionless parameter which determines whether tracers are long-lived or short-lived. Long- and short-lived tracers exhibit different behaviours with respect to coastal outflow. For short-lived tracers, increasing the advection rate increases the diurnally averaged magnitude of coastal outflow, but has the opposite effect for very long-lived tracers. Short-lived tracers exhibit large diurnal variability in coastal outflow but long-lived tracers do not. By combining the MetUM and box-model simulations a landwidth is determined which represents the distance inland over which emissions contribute significantly to coastal outflow. A landwidth of between 100 and 400 km is found to be representative for a tracer with a lifetime of 24 h.

Ice supersaturation and the potential for contrail formation in a changing climate

Ice supersaturation (ISS) in the upper troposphere and lower stratosphere is important for the formation of cirrus clouds and long-lived contrails. Cold ISS (CISS) regions (taken here to be ice-supersaturated regions with temperature below 233 K) are most relevant for contrail formation.We analyse projected changes to the 250 hPa distribution and frequency of CISS regions over the 21st century using data from the Representative Concentration Pathway 8.5 simulations for a selection of Coupled Model Intercomparison Project Phase 5 models. The models show a global-mean, annual-mean decrease in CISS frequency by about one-third, from 11 to 7% by the end of the 21st century, relative to the present-day period 1979–2005. Changes are analysed in further detail for three subregions where air traffic is already high and increasing (Northern Hemisphere mid-latitudes) or expected to increase (tropics and Northern Hemisphere polar regions). The largest change is seen in the tropics, where a reduction of around 9 percentage points in CISS frequency by the end of the century is driven by the strong warming of the upper troposphere. In the Northern Hemisphere mid-latitudes the multi-model-mean change is an increase in CISS frequency of 1 percentage point; however the sign of the change is dependent not only on the model but also on latitude and season. In the Northern Hemisphere polar regions there is an increase in CISS frequency of 5 percentage points in the annual mean. These results suggest that, over the 21st century, climate change may have large impacts on the potential for contrail formation; actual changes to contrail cover will also depend on changes to the volume of air traffic, aircraft technology and flight routing.