Synthesis of different gold nanostructures by solar radiation and their SERS spectroscopy

In this article, a simple and novel photochemical synthesis of different gold nanostructures is proposed using solar radiation. This method is rapid, convenient and of low cost, and can be performed under ambient conditions. By adjusting the concentration of sodium acetate (NaAc), different morphologies of the products can be easily obtained. Without NaAc, the products obtained are mainly polyhedral gold particles; lower concentration of NaAc (0.05 and 0.1 M) accelerates the formation of flowerlike gold nanostructures; while higher concentration of NaAc (0.5 M) facilitates the formation of a variety of gold nanowires and nanobelts. It is found that the morphology change of gold nanaostructures is the result of the synergistic effect of poly(diallyl dimethylammonium) chloride (PDDA), Ac- ions, and the pH value. In addition, the different gold nanostructures thus obtained were used as substrates for surface-enhanced Raman scattering (SERS) with p-aminothiophenol (p-ATP) as the probe molecule.

A toolkit approach to solar radiation modelling.

Considerable effort is required to implement solar radiation models in software. Many existing implementations have efficiency as their main priority rather than re-usability, and this can adversely affect their further development since the relationships between the software and physical quantities may be obscured. The Solar Toolkit is an attempt to overcome such barriers by exploiting the current abundance of computing resource, and the availability of user-oriented tools such as Microsoft Excel®. The Solar Toolkit takes the form of a set of functions written in Visual Basic for Applications® (VBA) made available under the Academic Free Licence. Transparency is the overriding priority throughout the implementation so that the Toolkit can provide a platform for further modelling initiatives.

Photodegradation of sertraline by solar radiation and influencing factors

Photodegradation is considered to be one of the most important processes of elimination of pharmaceutical drugs from natural water matrices. The high consumption and discharge of these substances, in particular antidepressants, to the aquatic environment supports the need to study degradation processes. This dissertation aimed at studying the direct and indirect photodegradation of sertraline, an antidepressant known for its persistence in the environment, and the evaluation of the influence of environmentally relevant factors in its photodegradation. The photodegradation experiments were developed under simulated solar light and the irradiation times converted to summer sunny days (SSD), an equivalent time in natural environmental conditions. The direct photodegradation was evaluated in solutions of sertraline prepared in ultrapure water and the indirect photodegradation was studied through the addition of photosensitizers (humic substances, Fe(III), nitrates and oxygen). Further irradiation studies were perfomed in aqueous samples collected from two wastewater treatment plants, Vouga river and Ria de Aveiro. The samples were chemically characterized (dissolved organic carbon, nitrates and nitrites and iron determination and UV/Vis spectroscopy). The quantification of sertraline was done by HPLC-UV and photoproducts from direct photodegradation were identified by electrospray mass spectrometry. An observed direct photodegradation rate of sertraline of 0.0062 h-1 was determined, corresponding to a half-life time of 111 h (equivalent to 29 SSD). A significant influence of photosensitizers was observed, the best results being achieved in irradiations of sertraline with humic acids, obtaining a half-life time of 12 h. This was attributed to the hydrophobicity of this substance and higher absortivity in the UV/Vis wavelength, which promote processes of indirect photodegradation. The degradation of sertraline in natural samples was also enhanced comparatively to the direct photodegradation, achieving half-life times between 10 and 25h; the best results were achieved in samples from the primary treatment of a wastewater treatment plant and Ria de Aveiro, with half-life times of 10 and 16 h, respectively. A total of six photoproducts formed during the direct photodegradation of sertraline were identified, three of which were not yet identified in the literature. The main factors contributing to the degradation of sertraline were analysed but this was not fully accomplished, requiring further studies of the composition of the natural matrices and the combined influence of distinct photosensitizers during the irradiation. Nevertheless, it was concluded that the photodegradation of sertraline is greatly influenced by indirect photodegradation processes, promoted by the presence of photosensitizers.

Prediction of the solar radiation using RBF neural networks and ground-to-sky images

In this study, Artificial Neural Networks are applied to multistep long term solar radiation prediction. The networks are trained as one-step-ahead predictors and iterated over time to obtain multi-step longer term predictions. Auto-regressive and Auto-regressive with exogenous inputs solar radiationmodels are compared, considering cloudiness indices as inputs in the latter case. These indices are obtained through pixel classification of ground-to-sky images. The input-output structure of the neural network models is selected using evolutionary computation methods.

Estimating surface net solar radiation by use of Landsat-5 TM and digital elevation models

The ground surface net solar radiation is the energy that drives physical and chemical processes at the ground surface. In this paper, multi-spectral data from the Landsat-5 TM, topographic data from a gridded digital elevation model, field measurements, and the atmosphere model LOWTRAN 7 are used to estimate surface net solar radiation over the FIFE site. Firstly an improved method is presented and used for calculating total surface incoming radiation. Then, surface albedo is integrated from surface reflectance factors derived from remotely sensed data from Landsat-5 TM. Finally, surface net solar radiation is calculated by subtracting surface upwelling radiation from the total surface incoming radiation.

Assessment of the consistency of near-infrared water vapor line intensities using high-spectral-resolution ground-based Fourier transform measurements of solar radiation

Calculations of the absorption of solar radiation by atmospheric gases, and water vapor in particular, are dependent on the quality of databases of spectral line parameters. There has been increasing scrutiny of databases such as HITRAN in recent years, but this has mostly been performed on a band-by-band basis. We report nine high-spectral-resolution (0.03 cm(-1)) measurements of the solar radiation reaching the surface in southern England over the wave number range 2000 to 12,500 cm(-1) (0.8 to 5 mm) that allow a unique assessment of the consistency of the spectral line databases over this entire spectral region. The data are assessed in terms of the modeled water vapor column that is required to bring calculations and observations into agreement; for an entirely consistent database, this water vapor column should be constant with frequency. For the HITRAN01 database, the spread in water vapor column is about 11%, with distinct shifts between different spectral regions. The HITRAN04 database is in significantly better agreement (about 5% spread) in the completely updated 3000 to 8000 cm(-1) spectral region, but inconsistencies between individual spectral regions remain: for example, in the 8000 to 9500 cm(-1) spectral region, the results indicate an 18% (+/- 1%) underestimate in line intensities with respect to the 3000 to 8000 cm(-1) region. These measurements also indicate the impact of isotopic fractionation of water vapor in the 2500 to 2900 cm(-1) range, where HDO lines dominate over the lines of the most abundant isotope of H2O.

RAMI4PILPS: An intercomparison of formulations for the partitioning of solar radiation in land surface models

[1] Remotely sensed, multiannual data sets of shortwave radiative surface fluxes are now available for assimilation into land surface schemes (LSSs) of climate and/or numerical weather prediction models. The RAMI4PILPS suite of virtual experiments assesses the accuracy and consistency of the radiative transfer formulations that provide the magnitudes of absorbed, reflected, and transmitted shortwave radiative fluxes in LSSs. RAMI4PILPS evaluates models under perfectly controlled experimental conditions in order to eliminate uncertainties arising from an incomplete or erroneous knowledge of the structural, spectral and illumination related canopy characteristics typical for model comparison with in situ observations. More specifically, the shortwave radiation is separated into a visible and near-infrared spectral region, and the quality of the simulated radiative fluxes is evaluated by direct comparison with a 3-D Monte Carlo reference model identified during the third phase of the Radiation transfer Model Intercomparison (RAMI) exercise. The RAMI4PILPS setup thus allows to focus in particular on the numerical accuracy of shortwave radiative transfer formulations and to pinpoint to areas where future model improvements should concentrate. The impact of increasing degrees of structural and spectral subgrid variability on the simulated fluxes is documented and the relevance of any thus emerging biases with respect to gross primary production estimates and shortwave radiative forcings due to snow and fire events are investigated.

Absolute high spectral resolution measurements of surface solar radiation for detection of water vapour continuum absorption

Solar-pointing Fourier transform infrared (FTIR) spectroscopy offers the capability to measure both the fine scale and broadband spectral structure of atmospheric transmission simultaneously across wide spectral regions. It is therefore suited to the study of both water vapour monomer and continuum absorption behaviours. However, in order to properly address this issue, it is necessary to radiatively calibrate the FTIR instrument response. A solar-pointing high-resolution FTIR spectrometer was deployed as part of the ‘Continuum Absorption by Visible and Infrared radiation and its Atmospheric Relevance’ (CAVIAR) consortium project. This paper describes the radiative calibration process using an ultra-high-temperature blackbody and the consideration of the related influence factors. The result is a radiatively calibrated measurement of the solar irradiation at the ground across the IR region from 2000 to 10 000 cm−1 with an uncertainty of between 3.3 and 5.9 per cent. This measurement is shown to be in good general agreement with a radiative-transfer model. The results from the CAVIAR field measurements are being used in ongoing studies of atmospheric absorbers, in particular the water vapour continuum.

Modelled and observed changes in aerosols and surface solar radiation over Europe between 1960 and 2009

Substantial changes in anthropogenic aerosols and precursor gas emissions have occurred over recent decades due to the implementation of air pollution control legislation and economic growth. The response of atmospheric aerosols to these changes and the impact on climate are poorly constrained, particularly in studies using detailed aerosol chemistry–climate models. Here we compare the HadGEM3-UKCA (Hadley Centre Global Environment Model-United Kingdom Chemistry and Aerosols) coupled chemistry–climate model for the period 1960–2009 against extensive ground-based observations of sulfate aerosol mass (1978–2009), total suspended particle matter (SPM, 1978–1998), PM10 (1997–2009), aerosol optical depth (AOD, 2000–2009), aerosol size distributions (2008–2009) and surface solar radiation (SSR, 1960–2009) over Europe. The model underestimates observed sulfate aerosol mass (normalised mean bias factor (NMBF) = −0.4), SPM (NMBF = −0.9), PM10 (NMBF = −0.2), aerosol number concentrations (N30 NMBF = −0.85; N50 NMBF = −0.65; and N100 NMBF = −0.96) and AOD (NMBF = −0.01) but slightly overpredicts SSR (NMBF = 0.02). Trends in aerosol over the observational period are well simulated by the model, with observed (simulated) changes in sulfate of −68 % (−78 %), SPM of −42 % (−20 %), PM10 of −9 % (−8 %) and AOD of −11 % (−14 %). Discrepancies in the magnitude of simulated aerosol mass do not affect the ability of the model to reproduce the observed SSR trends. The positive change in observed European SSR (5 %) during 1990–2009 ("brightening") is better reproduced by the model when aerosol radiative effects (ARE) are included (3 %), compared to simulations where ARE are excluded (0.2 %). The simulated top-of-the-atmosphere aerosol radiative forcing over Europe under all-sky conditions increased by > 3.0 W m−2 during the period 1970–2009 in response to changes in anthropogenic emissions and aerosol concentrations.

Coordinated weather balloon solar radiation measurements during a solar eclipse

Solar eclipses provide a rapidly changing solar radiation environment. These changes can be studied using simple photodiode sensors, if the radiation reaching the sensors is unaffected by cloud.Transporting the sensors aloft using standard meteorological instrument packages modified to carry extra sensors, provides one promising but hitherto unexploited possibility for making solar eclipse radiation measurements. For the 20th March 2015 solar eclipse, a coordinated campaign of balloon-carried solar radiation measurements was undertaken from Reading (51.44N, 0.94W), Lerwick (60.15N, 1.13W) and Reykjavik (64.13N, 21.90W), straddling the path of the eclipse.The balloons reached sufficient altitude at the eclipse time for eclipse-induced variations in solar radiation and solar limb darkening to be measured above cloud. Because the sensor platforms were free to swing, techniques have been evaluated to correct the measurements for their changing orientation. In the swing-averaged technique, the mean value across a set of swings was used to approximate the radiation falling on a horizontal surface; in the swing-maximum technique, the direct beam was estimated by assuming the sensing surface becomes normal to the solar beam direction at a maximum swing. Both approaches, essentially independent,give values that agree with theoretical expectations for the eclipse-induced radiation changes.

Large contribution of supercooled liquid clouds to the solar radiation budget of the Southern Ocean

The Southern Ocean is a critical region for global climate, yet large cloud and solar radiation biases over the Southern Ocean are a long-standing problem in climate models and are poorly understood, leading to biases in simulated sea surface temperatures. This study shows that supercooled liquid clouds are central to understanding and simulating the Southern Ocean environment. A combination of satellite observational data and detailed radiative transfer calculations is used to quantify the impact of cloud phase and cloud vertical structure on the reflected solar radiation in the Southern Hemisphere summer. It is found that clouds with supercooled liquid tops dominate the population of liquid clouds. The observations show that clouds with supercooled liquid tops contribute between 27% and 38% to the total reflected solar radiation between 40° and 70°S, and climate models are found to poorly simulate these clouds. The results quantify the importance of supercooled liquid clouds in the Southern Ocean environment and highlight the need to improve understanding of the physical processes that control these clouds in order to improve their simulation in numerical models. This is not only important for improving the simulation of present-day climate and climate variability, but also relevant for increasing confidence in climate feedback processes and future climate projections.

The role of clouds in improving the regression model for hourly values of diffuse solar radiation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)