Pyrene-Modified quartz crystal microbalance for the detection of polynitroaromatic compounds

The synthesis of a dithiol-functionalized pyrene derivative is reported, together with studies of interactions between this receptor (and other related pyrenes) and nitroaromatic compounds (NACs), in both solution and in the solid state. Spectroscopic analysis in solution and X-ray crystallographic analysis of cocrystals of pyrene and NACs in the solid state indicate that supramolecular interactions lead to the formation of defined pi-pi stacked complexes. The dithiolfunctionalized pyrene derivative can be used to modify the surface of a gold quartz crystal microbalance (QCM) to create a unique π-electron rich surface, which is able to interact with electron poor aromatic compounds. For example, exposure of the modified QCM surface to the nitroaromatic compound 2,4-dinitrotoluene (DNT) in solution results in a reduction in the resonant frequency of the QCM as a result of supramolecular interactions between the electron-rich pyrenyl surface layer and the electron-poor DNT molecules. These results suggest the potential use of such modified QCM surfaces for the detection of explosive NACs.

Prediction of the thermal performance of horizontal-coupled ground source heat exchangers

The thermal performance of a horizontal-coupled ground-source heat pump system has been assessed both experimentally and numerically in a UK climate. A numerical simulation of thermal behaviour of the horizontal-coupled heat exchanger for combinations of different ambient air temperatures, wind speeds, refrigerant temperature and soil thermal properties was studied using a validated 2D transient model. The specific heat extraction by the heat exchanger increased with ambient temperature and soil thermal conductivity, however it decreased with increasing refrigerant temperature. The effect of wind speed was negligible.

Assessment of CloudSat reflectivity measurements and ice cloud properties using ground-based and airborne cloud radar observations

A quantitative assessment of Cloudsat reflectivities and basic ice cloud properties (cloud base, top, and thickness) is conducted in the present study from both airborne and ground-based observations. Airborne observations allow direct comparisons on a limited number of ocean backscatter and cloud samples, whereas the ground-based observations allow statistical comparisons on much longer time series but with some additional assumptions. Direct comparisons of the ocean backscatter and ice cloud reflectivities measured by an airborne cloud radar and Cloudsat during two field experiments indicate that, on average, Cloudsat measures ocean backscatter 0.4 dB higher and ice cloud reflectivities 1 dB higher than the airborne cloud radar. Five ground-based sites have also been used for a statistical evaluation of the Cloudsat reflectivities and basic cloud properties. From these comparisons, it is found that the weighted-mean difference ZCloudsat − ZGround ranges from −0.4 to +0.3 dB when a ±1-h time lag around the Cloudsat overpass is considered. Given the fact that the airborne and ground-based radar calibration accuracy is about 1 dB, it is concluded that the reflectivities of the spaceborne, airborne, and ground-based radars agree within the expected calibration uncertainties of the airborne and ground-based radars. This result shows that the Cloudsat radar does achieve the claimed sensitivity of around −29 dBZ. Finally, an evaluation of the tropical “convective ice” profiles measured by Cloudsat has been carried out over the tropical site in Darwin, Australia. It is shown that these profiles can be used statistically down to approximately 9-km height (or 4 km above the melting layer) without attenuation and multiple scattering corrections over Darwin. It is difficult to estimate if this result is applicable to all types of deep convective storms in the tropics. However, this first study suggests that the Cloudsat profiles in convective ice need to be corrected for attenuation by supercooled liquid water and ice aggregates/graupel particles and multiple scattering prior to their quantitative use.

The evaluation of CloudSat and CALIPSO ice microphysical products using ground-based cloud radar and lidar observations

In this paper, the statistical properties of tropical ice clouds (ice water content, visible extinction, effective radius, and total number concentration) derived from 3 yr of ground-based radar–lidar retrievals from the U.S. Department of Energy Atmospheric Radiation Measurement Climate Research Facility in Darwin, Australia, are compared with the same properties derived using the official CloudSat microphysical retrieval methods and from a simpler statistical method using radar reflectivity and air temperature. It is shown that the two official CloudSat microphysical products (2B-CWC-RO and 2B-CWC-RVOD) are statistically virtually identical. The comparison with the ground-based radar–lidar retrievals shows that all satellite methods produce ice water contents and extinctions in a much narrower range than the ground-based method and overestimate the mean vertical profiles of microphysical parameters below 10-km height by over a factor of 2. Better agreements are obtained above 10-km height. Ways to improve these estimates are suggested in this study. Effective radii retrievals from the standard CloudSat algorithms are characterized by a large positive bias of 8–12 μm. A sensitivity test shows that in response to such a bias the cloud longwave forcing is increased from 44.6 to 46.9 W m−2 (implying an error of about 5%), whereas the negative cloud shortwave forcing is increased from −81.6 to −82.8 W m−2. Further analysis reveals that these modest effects (although not insignificant) can be much larger for optically thick clouds. The statistical method using CloudSat reflectivities and air temperature was found to produce inaccurate mean vertical profiles and probability distribution functions of effective radius. This study also shows that the retrieval of the total number concentration needs to be improved in the official CloudSat microphysical methods prior to a quantitative use for the characterization of tropical ice clouds. Finally, the statistical relationship used to produce ice water content from extinction and air temperature obtained by the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) satellite is evaluated for tropical ice clouds. It is suggested that the CALIPSO ice water content retrieval is robust for tropical ice clouds, but that the temperature dependence of the statistical relationship used should be slightly refined to better reproduce the radar–lidar retrievals.

The statistical properties of tropical ice clouds generated by the West-African and Australian monsoons from ground-based radar-lidar observations

In the present paper we characterize the statistical properties of non-precipitating tropical ice clouds (deep ice anvils resulting from deep convection and cirrus clouds) over Niamey, Niger, West Africa, and Darwin, northern Australia, using ground-based radar–lidar observations from the Atmospheric Radiation Measurement (ARM) programme. The ice cloud properties analysed in this paper are the frequency of ice cloud occurrence, cloud fraction, the morphological properties (cloud-top height, base height, and thickness), the microphysical and radiative properties (ice water content, visible extinction, effective radius, terminal fall speed, and concentration), and the internal cloud dynamics (in-cloud vertical air velocity). The main highlight of the paper is that it characterizes for the first time the probability density functions of the tropical ice cloud properties, their vertical variability and their diurnal variability at the same time. This is particularly important over West Africa, since the ARM deployment in Niamey provides the first vertically resolved observations of non-precipitating ice clouds in this crucial area in terms of redistribution of water and energy in the troposphere. The comparison between the two sites also provides an additional observational basis for the evaluation of the parametrization of clouds in large-scale models, which should be able to reproduce both the statistical properties at each site and the differences between the two sites. The frequency of ice cloud occurrence is found to be much larger over Darwin when compared to Niamey, and with a much larger diurnal variability, which is well correlated with the diurnal cycle of deep convective activity. The diurnal cycle of the ice cloud occurrence over Niamey is also much less correlated with that of deep convective activity than over Darwin, probably owing to the fact that Niamey is further away from the deep convective sources of the region. The frequency distributions of cloud fraction are strongly bimodal and broadly similar over the two sites, with a predominance of clouds characterized either by a very small cloud fraction (less than 0.3) or a very large cloud fraction (larger than 0.9). The ice clouds over Darwin are also much thicker (by 1 km or more statistically) and are characterized by a much larger diurnal variability than ice clouds over Niamey. Ice clouds over Niamey are also characterized by smaller particle sizes and fall speeds but in much larger concentrations, thereby carrying more ice water and producing more visible extinction than the ice clouds over Darwin. It is also found that there is a much larger occurrence of downward in-cloud air motions less than 1 m s−1 over Darwin, which together with the larger fall speeds retrieved over Darwin indicates that the life cycle of ice clouds is probably shorter over Darwin than over Niamey.

The variability of tropical ice cloud properties as a function of the large-scale context from ground-based radar-lidar observations over Darwin, Australia

The high complexity of cloud parameterizations now held in models puts more pressure on observational studies to provide useful means to evaluate them. One approach to the problem put forth in the modelling community is to evaluate under what atmospheric conditions the parameterizations fail to simulate the cloud properties and under what conditions they do a good job. It is the ambition of this paper to characterize the variability of the statistical properties of tropical ice clouds in different tropical "regimes" recently identified in the literature to aid the development of better process-oriented parameterizations in models. For this purpose, the statistical properties of non-precipitating tropical ice clouds over Darwin, Australia are characterized using ground-based radar-lidar observations from the Atmospheric Radiation Measurement (ARM) Program. The ice cloud properties analysed are the frequency of ice cloud occurrence, the morphological properties (cloud top height and thickness), and the microphysical and radiative properties (ice water content, visible extinction, effective radius, and total concentration). The variability of these tropical ice cloud properties is then studied as a function of the large-scale cloud regimes derived from the International Satellite Cloud Climatology Project (ISCCP), the amplitude and phase of the Madden-Julian Oscillation (MJO), and the large-scale atmospheric regime as derived from a long-term record of radiosonde observations over Darwin. The vertical variability of ice cloud occurrence and microphysical properties is largest in all regimes (1.5 order of magnitude for ice water content and extinction, a factor 3 in effective radius, and three orders of magnitude in concentration, typically). 98 % of ice clouds in our dataset are characterized by either a small cloud fraction (smaller than 0.3) or a very large cloud fraction (larger than 0.9). In the ice part of the troposphere three distinct layers characterized by different statistically-dominant microphysical processes are identified. The variability of the ice cloud properties as a function of the large-scale atmospheric regime, cloud regime, and MJO phase is large, producing mean differences of up to a factor 8 in the frequency of ice cloud occurrence between large-scale atmospheric regimes and mean differences of a factor 2 typically in all microphysical properties. Finally, the diurnal cycle of the frequency of occurrence of ice clouds is also very different between regimes and MJO phases, with diurnal amplitudes of the vertically-integrated frequency of ice cloud occurrence ranging from as low as 0.2 (weak diurnal amplitude) to values in excess of 2.0 (very large diurnal amplitude). Modellers should now use these results to check if their model cloud parameterizations are capable of translating a given atmospheric forcing into the correct statistical ice cloud properties.

Coppicing shifts CO2 stimulation of poplar productivity to above-ground pools: a synthesis of leaf to stand level results from the POP/EUROFACE experiment

A poplar short rotation coppice (SRC) grown for the production of bioenergy can combine carbon (C) storage with fossil fuel substitution. Here, we summarize the responses of a poplar (Populus) plantation to 6 yr of free air CO2 enrichment (POP/EUROFACE consisting of two rotation cycles). We show that a poplar plantation growing in nonlimiting light, nutrient and water conditions will significantly increase its productivity in elevated CO2 concentrations ([CO2]). Increased biomass yield resulted from an early growth enhancement and photosynthesis did not acclimate to elevated [CO2]. Sufficient nutrient availability, increased nitrogen use efficiency (NUE) and the large sink capacity of poplars contributed to the sustained increase in C uptake over 6 yr. Additional C taken up in high [CO2] was mainly invested into woody biomass pools. Coppicing increased yield by 66% and partly shifted the extra C uptake in elevated [CO2] to above-ground pools, as fine root biomass declined and its [CO2] stimulation disappeared. Mineral soil C increased equally in ambient and elevated [CO2] during the 6 yr experiment. However, elevated [CO2] increased the stabilization of C in the mineral soil. Increased productivity of a poplar SRC in elevated [CO2] may allow shorter rotation cycles, enhancing the viability of SRC for biofuel production.

A child’s burial in unconsecrated ground in early modern Dorchester

Re-examination of a child burial found during excavations in advance of the construction of new offices for Dorset County Council in the north-west quarter of Dorchester in 1937 indicates that it is of early modern, rather than of Roman date, as originally believed at the time of excavation. A possible context is explored for the burial of a child in unconsecrated ground in the 17th century.

Enhanced viability of corneal epithelial cells for efficient transport/storage using a structurally-modified calcium alginate hydrogel

Aims: Therapeutic limbal epithelial stem cells could be managed more efficiently if clinically validated batches were transported for ‘on-demand’ use. Materials & methods: In this study, corneal epithelial cell viability in calcium alginate hydrogels was examined under cell culture, ambient and chilled conditions for up to 7 days. Results: Cell viability improved as gel internal pore size increased, and was further enhanced with modification of the gel from a mass to a thin disc. Ambient storage conditions were optimal for supporting cell viability in gel discs. Cell viability in gel discs was significantly enhanced with increases in pore size mediated by hydroxyethyl cellulose. Conclusion: Our novel methodology of controlling alginate gel shape and pore size together provides a more practical and economical alternative to established corneal tissue/cell storage methods.

The study of chiral adsorption systems using synchrotron- based structural and spectroscopic techniques: stereospecific adsorption of serine on Au-modified chiral Cu{531} surfaces

We apply modern synchrotron-based structural techniques to the study of serine adsorbed on the pure andAumodified intrinsically chiral Cu{531} surface. XPS and NEXAFS data in combination with DFT show that on the pure surface both enantiomers adsorb in l4 geometries (with de-protonated b-OH groups) at low coverage and in l3 geometries at saturation coverage. Significantly larger enantiomeric differences are seen for the l4 geometries, which involve substrate bonds of three side groups of the chiral center, i.e. a three-point interaction. The l3 adsorption geometry, where only the carboxylate and amino groups form substrate bonds, leads to smaller but still significant enantiomeric differences, both in geometry and the decomposition behavior. When Cu{531} is modified by the deposition of 1 and 2ML Au the orientations of serine at saturation coverage are significantly different from those on the clean surface. In all cases, however, a l3 bond coordination is found at saturation involving different numbers of Au atoms, which leads to relatively small enantiomeric differences.

Interactions between the physical soil environment and a horizontal ground coupled heat pump, for a domestic site in the UK

There is currently an increased interest of Government and Industry in the UK, as well as at the European Community level and International Agencies (i.e. Department of Energy, American International Energy Agency), to improve the performance and uptake of Ground Coupled Heat Pumps (GCHP), in order to meet the 2020 renewable energy target. A sound knowledge base is required to help inform the Government Agencies and advisory bodies; detailed site studies providing reliable data for model verification have an important role to play in this. In this study we summarise the effect of heat extraction by a horizontal ground heat exchanger (installed at 1 m depth) on the soil physical environment (between 0 and 1 m depth) for a site in the south of the UK. Our results show that the slinky influences the surrounding soil by significantly decreasing soil temperatures. Furthermore, soil moisture contents were lower for the GCHP soil profile, most likely due to temperature-gradient related soil moisture migration effects and a decreased hydraulic conductivity, the latter as a result of increased viscosity (caused by the lower temperatures for the GCHP soil profile). The effects also caused considerable differences in soil thermal properties. This is the first detailed mechanistic study conducted in the UK with the aim to understand the interactions between the soil, horizontal heat exchangers and the aboveground environment. An increased understanding of these interactions will help to achieve an optimum and sustainable use of the soil heat resources in the future. The results of this study will help to calibrate and verify a simulation model that will provide UK-wide recommendations to improve future GCHP uptake and performance, while safeguarding the soil physical resources.

A study of the arrival over the United Kingdom in April 2010 of the Eyjafjallajökull ash cloud using ground-based lidar and numerical simulations

We make a qualitative and quantitative comparison of numericalsimulations of the ashcloud generated by the eruption of Eyjafjallajökull in April2010 with ground-basedlidar measurements at Exeter and Cardington in southern England. The numericalsimulations are performed using the Met Office’s dispersion model, NAME (Numerical Atmospheric-dispersion Modelling Environment). The results show that NAME captures many of the features of the observed ashcloud. The comparison enables us to estimate the fraction of material which survives the near-source fallout processes and enters into the distal plume. A number of simulations are performed which show that both the structure of the ashcloudover southern England and the concentration of ash within it are particularly sensitive to the height of the eruption column (and the consequent estimated mass emission rate), to the shape of the vertical source profile and the level of prescribed ‘turbulent diffusion’ (representing the mixing by the unresolved eddies) in the free troposphere with less sensitivity to the timing of the start of the eruption and the sedimentation of particulates in the distal plume.