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.

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.

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.

Atmospheric chemistry and physics in the atmosphere of a developed megacity (London): an overview of the REPARTEE experiment and its conclusions

The REgents PARk and Tower Environmental Experiment (REPARTEE) comprised two campaigns in London in October 2006 and October/November 2007. The experiment design involved measurements at a heavily trafficked roadside site, two urban background sites and an elevated site at 160–190 m above ground on the BT Tower, supplemented in the second campaign by Doppler lidar measurements of atmospheric vertical structure. A wide range of measurements of airborne particle physical metrics and chemical composition were made as well as measurements of a considerable range of gas phase species and the fluxes of both particulate and gas phase substances. Significant findings include (a) demonstration of the evaporation of traffic-generated nanoparticles during both horizontal and vertical atmospheric transport; (b) generation of a large base of information on the fluxes of nanoparticles, accumulation mode particles and specific chemical components of the aerosol and a range of gas phase species, as well as the elucidation of key processes and comparison with emissions inventories; (c) quantification of vertical gradients in selected aerosol and trace gas species which has demonstrated the important role of regional transport in influencing concentrations of sulphate, nitrate and secondary organic compounds within the atmosphere of London; (d) generation of new data on the atmospheric structure and turbulence above London, including the estimation of mixed layer depths; (e) provision of new data on trace gas dispersion in the urban atmosphere through the release of purposeful tracers; (f) the determination of spatial differences in aerosol particle size distributions and their interpretation in terms of sources and physico-chemical transformations; (g) studies of the nocturnal oxidation of nitrogen oxides and of the diurnal behaviour of nitrate aerosol in the urban atmosphere, and (h) new information on the chemical composition and source apportionment of particulate matter size fractions in the atmosphere of London derived both from bulk chemical analysis and aerosol mass spectrometry with two instrument types.

Counteracting the climate effects of volcanic eruptions using short-lived greenhouse gases

A large volcanic eruption might constitute a climate emergency, significantly altering global temperature and precipitation for several years. Major future eruptions will occur, but their size or timing cannot be predicted. We show, for the first time, that it may be possible to counteract these climate effects through deliberate emissions of short-lived greenhouse gases, dampening the abrupt impact of an eruption. We estimate an emission pathway countering a hypothetical eruption 3 times the size of Mount Pinatubo in 1991. We use a global climate model to evaluate global and regional responses to the eruption, with and without counteremissions. We then raise practical, financial, and ethical questions related to such a strategy. Unlike the more commonly discussed geoengineering to mitigate warming from long-lived greenhouse gases, designed emissions to counter temporary cooling would not have the disadvantage of needing to be sustained over long periods. Nevertheless, implementation would still face significant challenges.

Potential of Brassic rapa, Cannabis sativa, Helianthus annuus and Zea mays for phytoextraction of heavy metals from calcareous dredged sediment derived soils

Remediation of soil pollution is one of the many current environmental challenges. Anthropogenic activity has resulted in the contamination of extended areas of land, the remediation of which is both invasive and expensive by conventional means. Phytoextraction of heavy metals from contaminated soils has the prospect of being a more economic in situ alternative. In addition, phytoextraction targets ecotoxicologically the most relevant soil fraction of these metals, i.e. the bioavailable fraction. Greenhouse experiments were carried out to evaluate the potential of four high biomass crop species in their potential for phytoextraction of heavy metals, with or without with the use of soil amendments (EDTA or EDDS). A calcareous dredged sediment derived surface soil, with high organic matter and clay content and moderate levels of heavy metal pollution, was used in the experiments. No growth depression was observed in EDTA or EDDS treated pots in comparison to untreated controls. Metal accumulation was considered to be low for phytoextraction purposes, despite the use of chelating agents. The low observed shoot concentrations of heavy metals were attributed to the low phytoavailability of heavy metals in this particular soil substrate. The mobilising effects induced by EDTA in the soil were found to be too long-lived for application as a soil amendment in phytoextraction. Although EDDS was found to be more biodegradable, higher effect half lives were observed than reported in literature or observed in previous experiments. These findings caution against the use of any amendment, biodegradable or otherwise, without proper investigation of its effects and the longevity thereof. (C) 2005 Elsevier Ltd. All rights reserved.

Excess open solar magnetic flux from satellite data: 1. Analysis of the third perihelion Ulysses pass

We use the third perihelion pass by the Ulysses spacecraft to illustrate and investigate the “flux excess” effect, whereby open solar flux estimates from spacecraft increase with increasing heliocentric distance. We analyze the potential effects of small-scale structure in the heliospheric field (giving fluctuations in the radial component on timescales smaller than 1 h) and kinematic time-of-flight effects of longitudinal structure in the solar wind flow. We show that the flux excess is explained by neither very small-scale structure (timescales < 1 h) nor by the kinematic “bunching effect” on spacecraft sampling. The observed flux excesses is, however, well explained by the kinematic effect of larger-scale (>1 day) solar wind speed variations on the frozen-in heliospheric field. We show that averaging over an interval T (that is long enough to eliminate structure originating in the heliosphere yet small enough to avoid cancelling opposite polarity radial field that originates from genuine sector structure in the coronal source field) is only an approximately valid way of allowing for these effects and does not adequately explain or account for differences between the streamer belt and the polar coronal holes.

Some new strategies for the chemical separation of actinides and lanthanides

A future goal in nuclear fuel reprocessing is the conversion or transmutation of the long-lived radioisotopes of minor actinides, such as americium, into short-lived isotopes by irradiation with neutrons. In order to achieve this transmutation, it is necessary to separate the minor actinides(III), [An(Ill)], from the lanthanides(III), [Ln(Ill)], by solvent extraction (partitioning), because the lanthanides absorb neutrons too effectively and hence limit neutron capture by the transmutable actinides. Partitioning using ligands containing only carbon, hydrogen, nitrogen and oxygen atoms is desirable because they are completely incinerable and thus the final volume of waste is minimised [1]. Nitric acid media will be used in the extraction experiments because it is envisaged that the An(III)/Ln(III) separation process could take place after the PUREX process. There is no doubt that the correct design of a molecule that is capable of acting as a ligand or extraction reagent is required for the effective separation of metal ions such as actinides(III) from lanthanides. Recent attention has been directed towards heterocyclic ligands with for the preferential separation of the minor actinides. Although such molecules have a rich chemistry, this is only now becoming sufficiently well understood in relation to the partitioning process [2]. The molecules shown in Figures I and 2 will be the principal focus of this study. Although the examples chosen here are used rather specific, the guidelines can be extended to other areas such as the separation of precious metals [3].

Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Solar cycle 24: what is the sun up to?

March 2012 brought the first solar and geomagnetic disturbances of any note during solar cycle 24. But perhaps what was most remarkable about these events was how unremarkable they were compared to others during the space-age, attracting attention only because solar activity had been so quiet. This follows an exceptionally low and long-lived solar cycle minimum, and so the current cycle looks likely to extend a long-term decline in solar activity that started around 1985 and that could even lead to conditions similar to the Maunder minimum within 40 years from now, with implications for solar-terrestrial science and the mitigation of space weather hazards and maybe even for climate in certain regions and seasons.

Impact of duration thresholds on Atlantic tropical cyclone counts*

Records of Atlantic basin tropical cyclones (TCs) since the late nineteenth century indicate a very large upward trend in storm frequency. This increase in documented TCs has been previously interpreted as resulting from anthropogenic climate change. However, improvements in observing and recording practices provide an alternative interpretation for these changes: recent studies suggest that the number of potentially missed TCs is sufficient to explain a large part of the recorded increase in TC counts. This study explores the influence of another factor—TC duration—on observed changes in TC frequency, using a widely used Atlantic hurricane database (HURDAT). It is found that the occurrence of short-lived storms (duration of 2 days or less) in the database has increased dramatically, from less than one per year in the late nineteenth–early twentieth century to about five per year since about 2000, while medium- to long-lived storms have increased little, if at all. Thus, the previously documented increase in total TC frequency since the late nineteenth century in the database is primarily due to an increase in very short-lived TCs. The authors also undertake a sampling study based upon the distribution of ship observations, which provides quantitative estimates of the frequency of missed TCs, focusing just on the moderate to long-lived systems with durations exceeding 2 days in the raw HURDAT. Upon adding the estimated numbers of missed TCs, the time series of moderate to long-lived Atlantic TCs show substantial multidecadal variability, but neither time series exhibits a significant trend since the late nineteenth century, with a nominal decrease in the adjusted time series. Thus, to understand the source of the century-scale increase in Atlantic TC counts in HURDAT, one must explain the relatively monotonic increase in very short-duration storms since the late nineteenth century. While it is possible that the recorded increase in short-duration TCs represents a real climate signal, the authors consider that it is more plausible that the increase arises primarily from improvements in the quantity and quality of observations, along with enhanced interpretation techniques. These have allowed National Hurricane Center forecasters to better monitor and detect initial TC formation, and thus incorporate increasing numbers of very short-lived systems into the TC database.

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.

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.