A synchrotron powder X-ray diffraction study of the skutterudite-related phases AB1.5Te1.5 (A=Co, Rh, Ir; B= Ge, Sn)

X-ray resonant scattering has been exploited to investigate the crystal structure of the AB1.5Te1.5 phases (A = Co, Rh, Ir; B = Ge, Sn). Analysis of the diffraction data reveals that CoGe1.5Te1.5 and ASn1.5Te1.5 adopt a rhombohedral skutterudite-related structure, containing diamond-shape B2Te2 rings, in which the B and Te atoms are ordered and trans to each other. Anion ordering is however incomplete, and with increasing the size of both cations and anions, the degree of anion ordering decreases. By contrast, the diffraction data of IrGe1.5Te1.5 are consistent with an almost statistical distribution of the anions over the available sites, although some ordered domains may be present. The thermoelectric properties of these materials are discussed in the light of these results.

Interdecadal enhancement of the Walker circulation over the Tropical Pacific in the late 1990s

The Walker circulation is one of the major components of the large-scale tropical atmospheric circulation and variations in its strength are critical to equatorial Pacific Ocean circulation. It has been argued in the literature that during the 20th century the Walker circulation weakened, and that this weakening was attributable to anthropogenic climate change. By using updated observations, we show that there has been a rapid interdecadal enhancement of the Walker circulation since the late 1990s. Associated with this enhancement is enhanced precipitation in the tropical western Pacific, anomalous westerlies in the upper troposphere, descent in the central and eastern tropical Pacific, and anomalous surface easterlies in the western and central tropical Pacific. The characteristics of associated oceanic changes are a strengthened thermocline slope and an enhanced zonal SST gradient across the tropical Pacific. Many characteristics of these changes are similar to those associated with the mid-1970s climate shift with an opposite sign. We also show that the interdecadal variability of the Walker circulation in the tropical Pacific is inversely correlated to the interdecadal variability of the zonal circulation in the tropical Atlantic. An enhancement of the Walker circulation in the tropical Pacific is associated with a weakening zonal circulation in the tropical Atlantic and vise versa, implying an inter-Atlantic-Pacific connection of the zonal overturning circulation variation. Whether these recent changes will be sustained is not yet clear, but our research highlights the importance of understanding the interdecadal variability, as well as the long-term trends, that influence tropical circulation.

Multi-season eddy covariance observations of energy, water and carbon fluxes over a suburban area in Swindon, UK

Eddy covariance measurements of the turbulent sensible heat, latent heat and carbon dioxide fluxes for 12 months (2011–2012) are reported for the first time for a suburban area in the UK. The results from Swindon are comparable to suburban studies of similar surface cover elsewhere but reveal large seasonal variability. Energy partitioning favours turbulent sensible heat during summer (midday Bowen ratio 1.4–1.6) and latent heat in winter (0.05–0.7). A significant proportion of energy is stored (and released) by the urban fabric and the estimated anthropogenic heat flux is small but non-negligible (0.5–0.9 MJ m−2 day−1). The sensible heat flux is negative at night and for much of winter daytimes, reflecting the suburban nature of the site (44% vegetation) and relatively low built fraction (16%). Latent heat fluxes appear to be water limited during a dry spring in both 2011 and 2012, when the response of the surface to moisture availability can be seen on a daily timescale. Energy and other factors are more relevant controls at other times; at night the wind speed is important. On average, surface conductance follows a smooth, asymmetrical diurnal course peaking at around 6–9 mm s−1, but values are larger and highly variable in wet conditions. The combination of natural (vegetative) and anthropogenic (emission) processes is most evident in the temporal variation of the carbon flux: significant photosynthetic uptake is seen during summer, whilst traffic and building emissions explain peak release in winter (9.5 g C m−2 day−1). The area is a net source of CO2 annually. Analysis by wind direction highlights the role of urban vegetation in promoting evapotranspiration and offsetting CO2 emissions, especially when contrasted against peak traffic emissions from sectors with more roads. Given the extent of suburban land use, these results have important implications for understanding urban energy, water and carbon dynamics.

Vertical distribution and radiative effects of mineral dust and biomass burning aerosol over West Africa during DABEX

This paper presents measurements of the vertical distribution of aerosol extinction coefficient over West Africa during the Dust and Biomass-burning Aerosol Experiment (DABEX)/African Monsoon Multidisciplinary Analysis dry season Special Observing Period Zero (AMMA-SOP0). In situ aircraft measurements from the UK FAAM aircraft have been compared with two ground-based lidars (POLIS and ARM MPL) and an airborne lidar on an ultralight aircraft. In general, mineral dust was observed at low altitudes (up to 2 km), and a mixture of biomass burning aerosol and dust was observed at altitudes of 2–5 km. The study exposes difficulties associated with spatial and temporal variability when intercomparing aircraft and ground measurements. Averaging over many profiles provided a better means of assessing consistent errors and biases associated with in situ sampling instruments and retrievals of lidar ratios. Shortwave radiative transfer calculations and a 3-year simulation with the HadGEM2-A climate model show that the radiative effect of biomass burning aerosol was somewhat sensitive to the vertical distribution of aerosol. In particular, when the observed low-level dust layer was included in the model, the absorption of solar radiation by the biomass burning aerosols increased by 10%. We conclude that this absorption enhancement was caused by the dust reflecting solar radiation up into the biomass burning aerosol layer. This result illustrates that the radiative forcing of anthropogenic absorbing aerosol can be sensitive to the presence of natural aerosol species.

Comparison of the radiative properties and direct radiative effect of aerosols from a global aerosol model and remote sensing data over ocean

A global aerosol transport model (Oslo CTM2) with main aerosol components included is compared to five satellite retrievals of aerosol optical depth (AOD) and one data set of the satellite-derived radiative effect of aerosols. The model is driven with meteorological data for the period November 1996 to June 1997 which is the time period investigated in this study. The modelled AOD is within the range of the AOD from the various satellite retrievals over oceanic regions. The direct radiative effect of the aerosols as well as the atmospheric absorption by aerosols are in both cases found to be of the order of 20 Wm−2 in certain regions in both the satellite-derived and the modelled estimates as a mean over the period studied. Satellite and model data exhibit similar patterns of aerosol optical depth, radiative effect of aerosols, and atmospheric absorption of the aerosols. Recently published results show that global aerosol models have a tendency to underestimate the magnitude of the clear-sky direct radiative effect of aerosols over ocean compared to satellite-derived estimates. However, this is only to a small extent the case with the Oslo CTM2. The global mean direct radiative effect of aerosols over ocean is modelled with the Oslo CTM2 to be –5.5 Wm−2 and the atmospheric aerosol absorption 1.5 Wm−2.

Modelling of urban sensible heat flux at multiple spatial scales : a demonstration using airborne hyperspectral imagery of Shanghai and a temperature–emissivity separation approach

Urbanization related alterations to the surface energy balance impact urban warming (‘heat islands’), the growth of the boundary layer, and many other biophysical processes. Traditionally, in situ heat flux measures have been used to quantify such processes, but these typically represent only a small local-scale area within the heterogeneous urban environment. For this reason, remote sensing approaches are very attractive for elucidating more spatially representative information. Here we use hyperspectral imagery from a new airborne sensor, the Operative Modular Imaging Spectrometer (OMIS), along with a survey map and meteorological data, to derive the land cover information and surface parameters required to map spatial variations in turbulent sensible heat flux (QH). The results from two spatially-explicit flux retrieval methods which use contrasting approaches and, to a large degree, different input data are compared for a central urban area of Shanghai, China: (1) the Local-scale Urban Meteorological Parameterization Scheme (LUMPS) and (2) an Aerodynamic Resistance Method (ARM). Sensible heat fluxes are determined at the full 6 m spatial resolution of the OMIS sensor, and at lower resolutions via pixel aggregation and spatial averaging. At the 6 m spatial resolution, the sensible heat flux of rooftop dominated pixels exceeds that of roads, water and vegetated areas, with values peaking at ∼ 350 W m− 2, whilst the storage heat flux is greatest for road dominated pixels (peaking at around 420 W m− 2). We investigate the use of both OMIS-derived land surface temperatures made using a Temperature–Emissivity Separation (TES) approach, and land surface temperatures estimated from air temperature measures. Sensible heat flux differences from the two approaches over the entire 2 × 2 km study area are less than 30 W m− 2, suggesting that methods employing either strategy maybe practica1 when operated using low spatial resolution (e.g. 1 km) data. Due to the differing methodologies, direct comparisons between results obtained with the LUMPS and ARM methods are most sensibly made at reduced spatial scales. At 30 m spatial resolution, both approaches produce similar results, with the smallest difference being less than 15 W m− 2 in mean QH averaged over the entire study area. This is encouraging given the differing architecture and data requirements of the LUMPS and ARM methods. Furthermore, in terms of mean study QH, the results obtained by averaging the original 6 m spatial resolution LUMPS-derived QH values to 30 and 90 m spatial resolution are within ∼ 5 W m− 2 of those derived from averaging the original surface parameter maps prior to input into LUMPS, suggesting that that use of much lower spatial resolution spaceborne imagery data, for example from Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) is likely to be a practical solution for heat flux determination in urban areas.

An assessment of observed vertical flux divergence in long-term eddy-covariance measurements over two Midwestern forest ecosystems

Vertical divergence of CO2 fluxes is observed over two Midwestern AmeriFlux forest sites. The differences in ensemble averaged hourly CO2 fluxes measured at two heights above canopy are relatively small (0.2–0.5 μmol m−2 s−1), but they are the major contributors to differences (76–256 g C m−2 or 41.8–50.6%) in estimated annual net ecosystem exchange (NEE) in 2001. A friction velocity criterion is used in these estimates but mean flow advection is not accounted for. This study examines the effects of coordinate rotation, averaging time period, sampling frequency and co-spectral correction on CO2 fluxes measured at a single height, and on vertical flux differences measured between two heights. Both the offset in measured vertical velocity and the downflow/upflow caused by supporting tower structures in upwind directions lead to systematic over- or under-estimates of fluxes measured at a single height. An offset of 1 cm s−1 and an upflow/downflow of 1° lead to 1% and 5.6% differences in momentum fluxes and nighttime sensible heat and CO2 fluxes, respectively, but only 0.5% and 2.8% differences in daytime sensible heat and CO2 fluxes. The sign and magnitude of both offset and upflow/downflow angle vary between sonic anemometers at two measurement heights. This introduces a systematic and large bias in vertical flux differences if these effects are not corrected in the coordinate rotation. A 1 h averaging time period is shown to be appropriate for the two sites. In the daytime, the absolute magnitudes of co-spectra decrease with height in the natural frequencies of 0.02–0.1 Hz but increase in the lower frequencies (<0.01 Hz). Thus, air motions in these two frequency ranges counteract each other in determining vertical flux differences, whose magnitude and sign vary with averaging time period. At night, co-spectral densities of CO2 are more positive at the higher levels of both sites in the frequency range of 0.03–0.4 Hz and this vertical increase is also shown at most frequencies lower than 0.03 Hz. Differences in co-spectral corrections at the two heights lead to a positive shift in vertical CO2 flux differences throughout the day at both sites. At night, the vertical CO2 flux differences between two measurement heights are 20–30% and 40–60% of co-spectral corrected CO2 fluxes measured at the lower levels of the two sites, respectively. Vertical differences of CO2 flux are relatively small in the daytime. Vertical differences in estimated mean vertical advection of CO2 between the two measurement heights generally do not improve the closure of the 1D (vertical) CO2 budget in the air layer between the two measurement heights. This may imply the significance of horizontal advection. However, a reliable assessment of mean advection contributions in annual NEE estimate at these two AmeriFlux sites is currently an unsolved problem.

Reconstruction of geomagnetic activity and near-Earth interplanetary conditions over the past 167 yr – Part 1: A new geomagnetic data composite

We present a new composite of geomagnetic activity which is designed to be as homogeneous in its construction as possible. This is done by only combining data that, by virtue of the locations of the source observatories used, have similar responses to solar wind and IMF (interplanetary magnetic field) variations. This will enable us (in Part 2, Lockwood et al., 2013a) to use the new index to reconstruct the interplanetary magnetic field, B, back to 1846 with a full analysis of errors. Allowance is made for the effects of secular change in the geomagnetic field. The composite uses interdiurnal variation data from Helsinki for 1845–1890 (inclusive) and 1893–1896 and from Eskdalemuir from 1911 to the present. The gaps are filled using data from the Potsdam (1891–1892 and 1897–1907) and the nearby Seddin observatories (1908–1910) and intercalibration achieved using the Potsdam–Seddin sequence. The new index is termed IDV(1d) because it employs many of the principles of the IDV index derived by Svalgaard and Cliver (2010), inspired by the u index of Bartels (1932); however, we revert to using one-day (1d) means, as employed by Bartels, because the use of near-midnight values in IDV introduces contamination by the substorm current wedge auroral electrojet, giving noise and a dependence on solar wind speed that varies with latitude. The composite is compared with independent, early data from European-sector stations, Greenwich, St Petersburg, Parc St Maur, and Ekaterinburg, as well as the composite u index, compiled from 2–6 stations by Bartels, and the IDV index of Svalgaard and Cliver. Agreement is found to be extremely good in all cases, except two. Firstly, the Greenwich data are shown to have gradually degraded in quality until new instrumentation was installed in 1915. Secondly, we infer that the Bartels u index is increasingly unreliable before about 1886 and overestimates the solar cycle amplitude between 1872 and 1883 and this is amplified in the proxy data used before 1872. This is therefore also true of the IDV index which makes direct use of the u index values.

Reconstruction of geomagnetic activity and near-Earth interplanetary conditions over the past 167 yr – Part 2: A new reconstruction of the interplanetary magnetic field

We present a new reconstruction of the interplanetary magnetic field (IMF, B) for 1846–2012 with a full analysis of errors, based on the homogeneously constructed IDV(1d)composite of geomagnetic activity presented in Part 1 (Lockwood et al., 2013a). Analysis of the dependence of the commonly used geomagnetic indices on solar wind parameters is presented which helps explain why annual means of interdiurnal range data, such as the new composite, depend only on the IMF with only a very weak influence of the solar wind flow speed. The best results are obtained using a polynomial (rather than a linear) fit of the form B = χ · (IDV(1d) − β)α with best-fit coefficients χ = 3.469, β = 1.393 nT, and α = 0.420. The results are contrasted with the reconstruction of the IMF since 1835 by Svalgaard and Cliver (2010).

A comparative performance analysis of TRMM 3B42 (TMPA) versions 6 and 7 for hydrological applications over Andean-Amazon river basins

The Tropical Rainfall Measuring Mission 3B42 precipitation estimates are widely used in tropical regions for hydrometeorological research. Recently, version 7 of the product was released. Major revisions to the algorithm involve the radar refl ectivity - rainfall rates relationship, surface clutter detection over high terrain, a new reference database for the passive microwave algorithm, and a higher quality gauge analysis product for monthly bias correction. To assess the impacts of the improved algorithm, we compare the version 7 and the older version 6 product with data from 263 rain gauges in and around the northern Peruvian Andes. The region covers humid tropical rainforest, tropical mountains, and arid to humid coastal plains. We and that the version 7 product has a significantly lower bias and an improved representation of the rainfall distribution. We further evaluated the performance of versions 6 and 7 products as forcing data for hydrological modelling, by comparing the simulated and observed daily streamfl ow in 9 nested Amazon river basins. We find that the improvement in the precipitation estimation algorithm translates to an increase in the model Nash-Sutcliffe effciency, and a reduction in the percent bias between the observed and simulated flows by 30 to 95%.

'Penetrating' foreign lands: contestations over African landscape. A case study from Eastern Zimbabwe

While it was happening, European expansion was often legitimised by evoking frontier images: pioneers setting off from the metropolis, penetrating wilderness in order to open access to resources, like minerals, living-space, and fertile lands. Central to the ideology of the frontier is the notion of 'no-man's land'. These 'pioneers', however, often had to face local inhabitants and their interpretations and uses of this land. Thus it will be argued that contestations over landscape were at the same time battles over the legitimation of European expansion, as well as over local perceptions of this process. Ideologically, contestations by Europeans and Africans become apparent in the sexualisation of landscape. This paper is based on the case study of a Valley in eastern Zimbabwe on the border with Mozambique, and more specifically of two tea estates which were established in the rainforest. Unusually late for the region, European influence in this remote area only began to become significant in the 1950s which were an important turning point regarding land and landscape in the area. These years of great change will be analysed in order to map out different strands of interest by the main parties involved. It will be demonstrated that their readings of landscape translated into contestations over land. A recent example of such a conflict will be given.

The gravity wave momentum flux in hydrostatic flow with directional shear over elliptical mountains

Semi-analytical expressions for the momentum flux associated with orographic internal gravity waves, and closed analytical expressions for its divergence, are derived for inviscid, stationary, hydrostatic, directionally-sheared flow over mountains with an elliptical horizontal cross-section. These calculations, obtained using linear theory conjugated with a third-order WKB approximation, are valid for relatively slowly-varying, but otherwise generic wind profiles, and given in a form that is straightforward to implement in drag parametrization schemes. When normalized by the surface drag in the absence of shear, a quantity that is calculated routinely in existing drag parametrizations, the momentum flux becomes independent of the detailed shape of the orography. Unlike linear theory in the Ri → ∞ limit, the present calculations account for shear-induced amplification or reduction of the surface drag, and partial absorption of the wave momentum flux at critical levels. Profiles of the normalized momentum fluxes obtained using this model and a linear numerical model without the WKB approximation are evaluated and compared for two idealized wind profiles with directional shear, for different Richardson numbers (Ri). Agreement is found to be excellent for the first wind profile (where one of the wind components varies linearly) down to Ri = 0.5, while not so satisfactory, but still showing a large improvement relative to the Ri → ∞ limit, for the second wind profile (where the wind turns with height at a constant rate keeping a constant magnitude). These results are complementary, in the Ri > O(1) parameter range, to Broad’s generalization of the Eliassen–Palm theorem to 3D flow. They should contribute to improve drag parametrizations used in global weather and climate prediction models.

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.