Mercury Redox Chemistry in the Negro River Basin, Amazon: The Role of Organic Matter and Solar Light

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Global and diffuse solar irradiances in urban and rural areas in southeast Brazil

The seasonal evolution of daily and hourly values of global and diffuse solar radiation at the surface are compared for the cities of São Paulo and Botucatu, both located in Southeast Brazil and representative of urban and rural areas, respectively. The comparisons are based on measurements of global and diffuse solar irradiance carried out at the surface during a six year simultaneous period in these two cities. Despite the similar latitude and altitude, the seasonal evolution of daily values indicate that São Paulo receives, during clear sky days, 7.8% less global irradiance in August and 5.1% less in June than Botucatu. on the other hand, São Paulo receives, during clear sky days, 3.6% more diffuse irradiance in August and 15.6% more in June than Botucatu. The seasonal variation of the diurnal cycle confirms these differences and indicates that they are more pronounced during the afternoon. The regional differences are related to the distance from the Atlantic Ocean, systematic penetration of the sea breeze and daytime evolution of the particulate matter in São Paulo. An important mechanism controlling the spatial distribution of solar radiation, on a regional scale, is the sea breeze penetration in São Paulo, bringing moisture and maritime aerosol that in turn further increases the solar radiation scattering due to pollution and further reduces the intensity of the direct component of solar radiation at the surface. Surprisingly, under clear sky conditions the atmospheric attenuation of solar radiation in Botucatu during winter - the biomass burning period due to the sugar cane harvest - is equivalent to that at São Paulo City, indicating that the contamination during sugar cane harvest in Southeast Brazil has a large impact in the solar radiation field at the surface.

Solar energy budgets in central Amazonian ecosystems: a comparison between natural forest and bare soil areas

In order to estimate the deforestation consequences on the actual solar energy budget of the Central Amazon Region, two ecosystems of different characteristics were compared. The present conditions of the region were represented by a typical 'terra firme' forest cover located at INPA's Ducke Forest Reserve, where the measurements necessary to evaluate its solar energy balance were carried out. The second ecosystem, simulating a deforested area, was represented by an area about 1.0 ha without natural vegetation and situated in the same Reserve. In this area lysimeters were placed, two of them filled with yellow latosol and two others with quartzose sand soil. Both soils are representative soils in the region. Their water balances were taken into account as well as the other parameters necessary to compute the solar energy balances. The results showed that water loss by evaporation was about 41.8% of the total precipitation in the yellow latosol lysimeters and about 26.4% for the quartzose sand ones. For the forest cover it was estimated an evapotranspiration of 67.9% of the rainfall amount. In relation to solar energy balance calculated for the forest cover, it was found that 83.1% of the total energy incoming to this ecosystem was used by the evapotranspiration process, while the remaining of 16.9% can be taken as sensible heat. For bare soils, 55.1% and 31.8% of the total energy were used as latent heat by yellow latosol and quartzose sand soils, respectively. So, the remaining amounts of 44.9% and 68.2% were related to sensible heat and available to atmospheric air heating of these ecosystems. Such results suggest that a large deforestation of the Amazon Region would have direct consequences on their water and solar radiation balances, with an expected change on the actual climatic conditions of the region. © 1993.

Solar photodegradation of dichloroacetic acid and 2,4-dichlorophenol using an enhanced photo-Fenton process

The photo-Fenton process using potassium ferrioxalate as a mediator was investigated for the photodegradation of dichloracetic acid (DCA) and 2,4-dichlorophenol (DCP) in aqueous medium using solar light as source of irradiation. The influence of the solution depth, the light intensity and the effect of stirring the solution during irradiation process were evaluated using DCA as a model compound. A negligible influence of stirring the solution was observed when the concentration of ferrioxalate (FeOx) was 0.8 mM and solution depth was 4.5 or 14 cm. The optimum FeOx concentration determined for solution depths between 4.5 and 14 cm was 0.8 mM considering total organic carbon (TOC) removal during DCA irradiation. The high efficiency of the photo-Fenton process was demonstrated on summer days, when only 10 min of exposition (around noon) were sufficient to completely destroy the organic carbon of a 1.0 mM DCA solution in the presence of 0.8 mM FeOx and 6.0 mM H2O2 using a solution depth of 4.5 cm. It was observed that the photodegradation efficiency increases linearly with the solar light intensity up to values around 15 Wm-2 but this linear relationship does not hold above this value showing a square root dependence. The photodegradation of a solution of DCP/FeOx showed a lower TOC removal rate than that observed for DCA/FeOx, achieving ∼90% after 35 min irradiation under 19 Wm-2, while under this light intensity, the same TOC removal of DCA/FeOx was achieved in only 10 min irradiation. © 2002 Elsevier Science Ltd. All rights reserved.

Evaluation of the combined solar TiO2/photo-Fenton process using multivariate analysis

The effect of combining the photocatalytic processes using TiO 2 and the photo-Fenton reaction with Fe3+ or ferrioxalate as a source of Fe2+ was investigated in the degradation of 4-chlorophenol (4CP) and dichloroacetic acid (DCA) using solar irradiation. Multivariate analysis was used to evaluate the role of three variables: iron, H2O2 and TiO2 concentrations. The results show that TiO2 plays a minor role when compared to iron and H2O2 in the solar degradation of 4CP and DCA in the studied conditions. However, its presence can improve TOC removal when H2O2 is totally consumed. Iron and peroxide play major roles, especially when Fe(NO3)3 used in the degradation of 4CP. No significant synergistic effect was observed by the addition of TiO 2 in this process. On the other hand, synergistic effects were observed between FeOx and TiO2 and between H 2O2 and TiO2 in the degradation of DCA. © IWA Publishing 2004.

Annual and monthly mean global, direct and diffuse solar irradiation in Botucatu/SP/Brazil

This paper presents a climatic and statistical analysis of global, direct horizontal and diffuse radiation from a database of solar radiation measured from 1996 to 2006 in the city of Botucatu, SP, Brazil. Variation intervals of hourly and daily irradiation, annual mean 〈H̄G〉, 〈H̄bh〉 and 〈H̄d〉 irradiation, monthly mean 〈H̄G〉, 〈H̄ bh〉 and 〈H̄d〉 irradiation and monthly mean 〈K̄t〉, 〈K̄bh〉 and 〈K̄d〉 fractions were determined. Results showed that values of hourly and daily annual mean irradiation were as follows: 〈H̄G〉=1.49MJ/m2 and 〈H̄ G〉=17.74MJ/m2; 〈H̄bh〉=0. 90MJ/m2 and 〈H̄bh〉=10.33MJ/m2 and 〈H̄d〉=0.57 MJ/m2 and 〈H̄d〉=7.09MJ/m2, respectively. Variation intervals of hourly monthly mean irradiation were as follows: 〈H̄G〉 ranged from 1.65MJ/m2 in March to 1.16MJ/m2 in June; 〈H̄bh〉 ranged from 1.06MJ/m2 in April to 0.79MJ/m2 in June, and 〈H̄d〉 ranged from 0.70MJ/m2 in January to 0.37MJ/m2 in June and July. Similarly, daily 〈H̄ G〉 irradiation ranged from 21.35MJ/m2 in November to 12.94MJ/m2 in June; 〈H̄bh〉 ranged from 11.83MJ/m2 in April to 8.49MJ/m2 in June, and 〈H̄d〉 ranged from 10.29MJ/m2 in December to 4.38MJ/m2 in June. Variation intervals of hourly monthly mean fractions were as follows: 〈K̄t〉 ranged from 43.5% in January to 54.2% in April; 〈K̄bh〉 ranged from 33.6% in January to 58.0% in April and 〈K̄d〉 ranged from 66.4% in January to 42.0% in April. In the same way, daily 〈K̄ t〉 fractions ranged from 45.5% in January to 59.8% in August; 〈K̄bh〉 ranged from 38.9% in January to 62.0% in August and 〈K̄d〉 ranged from 61.1% in January to 37.7% in July.

Radiation balance at the surface in the city of So Paulo, Brazil: diurnal and seasonal variations

The main goal of this work is to describe the diurnal and seasonal variations of the radiation balance components at the surface in the city of So Paulo based on observations carried out during 2004. Monthly average hourly values indicate that the amplitudes of the diurnal cycles of net radiation (Q*), downwelling and upwelling shortwave radiation (SW(DW), SW(UP)), and longwave radiations (LW(DW), LW(UP)) in February were, respectively, 37%, 14%, 19%, 11%, and 5% larger than they were in August. The monthly average daily values indicate a variation of 60% for Q*, with a minimum in June and a maximum in December; 45% for SW(DW), with a minimum in May and a maximum in September; 50% for SW(UP), with a minimum in June and a maximum in September; 13% for LW(DW), with a minimum in July and a maximum in January; and 9% for LW(UP), with a minimum in July and a maximum in February. It was verified that the atmospheric broadband transmissivity varied from 0.36 to 0.57; the effective albedo of the surface varied from 0.08 to 0.10; and the atmospheric effective emissivity varied from 0.79 to 0.92. The surface effective emissivity remained approximately constant and equal to 0.96. The albedo and surface effective emissivity for So Paulo agreed with those reported for urban areas in Europe and North America cities. This indicates that material and geometric effects on albedo and surface emissivity in So Paulo are similar to ones observed in typical middle latitudes cities. On the other hand, it was found that So Paulo city induces an urban heat island with daytime maximum intensity varying from 2.6A degrees C in July (16:00 LT) to 5.5A degrees C in September (15:00 LT). The analysis of the radiometric properties carried out here indicate that this daytime maximum is a primary response to the seasonal variation of daily values of net solar radiation at the surface.

Nitrate reduces the negative effect of UV radiation on photosynthesis and pigmentation in Gracilaria tenuistipitata (Rhodophyta): the photoprotection role of mycosporine-like amino acids

Photoprotection of the agarophyte red alga Gracilaria tenuistipitata against ultraviolet radiation (UVR) was investigated in algae submitted for 1 week to photosynthetically active radiation (PAR, 260 mu mol photons m(-2) s(-1)) or PAR + UVR (UV-A, 8.13 W m(-2) and UV-B, 0.42 W m(-2)) under different nitrogen concentrations: 0, 0.1, and 0.5 mM of NO3-. Photosynthetic pigments decreased during the time of the experiment mainly under low nitrogen supply and UVR. Incubation under high nitrogen supply (0.5 mM) sustained the photosynthetic levels over time. In contrast, mycosporine-like amino acids (MAAs) increased up to eightfold in the presence of UVR and 0.5 mM NO3-. Under PAR + UVR, maximal quantum yield was positively correlated to MAA abundance, whereas under PAR no correlation was found. The photosynthetic yield of algae cultivated during seven days under PAR + UVR was less affected by a 30-min exposure of high UVR (16 W m(-2)) and fully recovered after transferring to low PAR irradiances, whereas algae kept under PAR were more affected by UV exposure and no full recovery was observed. Growth rates decreased after three days in the presence of UVR and under low nitrate supply. However, these rates were similar when compared with treatments of PAR and PAR + UVR after seven days, with the exception of samples in 0 mM NO3-, indicating that the acclimation after one week's exposure is related to nitrate supply. In conclusion, the lowest negative effect of UVR on photosynthesis and growth rate in high N-supply-grown algae could be explained by the stimulation of photoprotection mechanisms, such as accumulation of MAAs. Photostimulation of MAA accumulation by UVR under high N supply was observed in G. tenuistipitata even after 20 years in culture without the induction of this photomorphogenic light signal.

Martian sub-surface ionising radiation: biosignature and geology

The surface of Mars, unshielded by thick atmosphere or global magnetic field, is exposed to high levels of cosmic radiation. This ionising radiation field is deleterious to the survival of dormant cells or spores and the persistence of molecular biomarkers in the subsurface, and so its characterisation is of prime astrobiological interest. Here, we present modelling results of the absorbed radiation dose as a function of depth through the Martian subsurface, suitable for calculation of biomarker persistence. A second major implementation of this dose accumulation rate data is in application of the optically stimulated luminescence technique for dating Martian sediments. We present calculations of the dose-depth profile in the Martian subsurface for various scenarios: variations of surface composition (dry regolith, ice, layered permafrost), solar minimum and maximum conditions, locations of different elevation (Olympus Mons, Hellas basin, datum altitude), and increasing atmospheric thickness over geological history. We also model the changing composition of the subsurface radiation field with depth compared between Martian locations with different shielding material, determine the relative dose contributions from primaries of different energies, and discuss particle deflection by the crustal magnetic fields.

Impact of a potential 21st century “grand solar minimum” on surface temperatures and stratospheric ozone

We investigate the effects of a recently proposed 21st century Dalton minimum like decline of solar activity on the evolution of Earth's climate and ozone layer. Three sets of two member ensemble simulations, radiatively forced by a midlevel emission scenario (Intergovernmental Panel on Climate Change RCP4.5), are performed with the atmosphere-ocean chemistry-climate model AOCCM SOCOL3-MPIOM, one with constant solar activity, the other two with reduced solar activity and different strength of the solar irradiance forcing. A future grand solar minimum will reduce the global mean surface warming of 2 K between 1986–2005 and 2081–2100 by 0.2 to 0.3 K. Furthermore, the decrease in solar UV radiation leads to a significant delay of stratospheric ozone recovery by 10 years and longer. Therefore, the effects of a solar activity minimum, should it occur, may interfere with international efforts for the protection of global climate and the ozone layer.

Impact of Earth radiation pressure on LAGEOS orbits and on the global scale

The indirect solar radiation pressure caused by reflected or re-emitted radiation by the Earth’s surface is an important non-gravitational force perturbing the orbits of geodetic satellites (Rubincam and Weiss, 1986; Martin and Rubincam, 1996). In the case of LAGEOS this acceleration is of the order of 15% of the direct solar radiation pressure. Therefore, Earth radiation pressure has a non-negligible impact not only on LAGEOS orbits, but also on the SLR-derived terrestrial reference frame. We investigate the impact of the Earth radiation pressure on LAGEOS orbits and on the SLR-derived parameters. Earth radiation pressure has a remarkable impact on the semi-major axes of the LAGEOS satellites, causing a systematic reduction of 1.5 mm. The infrared Earth radiation causes a reduction of about 1.0 mm and the Earth’s reflectivity of 0.5 mm of the LAGEOS’ semi-major axes. The global scale defined by the SLR network is changed by 0.07 ppb, when applying Earth radiation pressure. The resulting station heights differ by 0.5-0.6 mm in the solution with and without Earth radiation pressure. However, when range biases are estimated, the height differences are absorbed by the range biases, and thus, the station heights are not shifted.

Upconverter materials and upconversion solar-cell devices: simulation and characterization with broad solar spectrum illumination

Upconverter materials and upconverter solar devices were recently investigated with broad-band excitation revealing the great potential of upconversion to enhance the efficiency of solar cell at comparatively low solar concentration factors. In this work first attempts are made to simulate the behavior of the upconverter β-NaYF4 doped with Er3+ under broad-band excitation. An existing model was adapted to account for the lower absorption of broader excitation spectra. While the same trends as observed for the experiments were found in the simulation, the absolute values are fairly different. This makes an upconversion model that specifically considers the line shape function of the ground state absorption indispensable to achieve accurate simulations of upconverter materials and upconverter solar cell devices with broadband excitations, such as the solar radiation.

Pasture degradation modifies the water and carbon cycles of the Tibetan highlands

The Tibetan Plateau has a significant role with regard to atmospheric circulation and the monsoon in particular. Changes between a closed plant cover and open bare soil are one of the striking effects of land use degradation observed with unsustainable range management or climate change, but experiments investigating changes of surface properties and processes together with atmospheric feedbacks are rare and have not been undertaken in the world's two largest alpine ecosystems, the alpine steppe and the Kobresia pygmaea pastures of the Tibetan Plateau. We connected measurements of micro-lysimeter, chamber, 13C labelling, and eddy covariance and combined the observations with land surface and atmospheric models, adapted to the highland conditions. This allowed us to analyse how three degradation stages affect the water and carbon cycle of pastures on the landscape scale within the core region of the Kobresia pygmaea ecosystem. The study revealed that increasing degradation of the Kobresia turf affects carbon allocation and strongly reduces the carbon uptake, compromising the function of Kobresia pastures as a carbon sink. Pasture degradation leads to a shift from transpiration to evaporation while a change in the sum of evapotranspiration over a longer period cannot be confirmed. The results show an earlier onset of convection and cloud generation, likely triggered by a shift in evapotranspiration timing when dominated by evaporation. Consequently, precipitation starts earlier and clouds decrease the incoming solar radiation. In summary, the changes in surface properties by pasture degradation found on the highland have a significant influence on larger scales.

Solar irradiance over and under seasonal land-fast sea ice off Barrow, Alaska, in 2010

The amount of solar radiation transmitted through Arctic sea ice is determined by the thickness and physical properties of snow and sea ice. Light transmittance is highly variable in space and time since thickness and physical properties of snow and sea ice are highly heterogeneous on variable time and length scales. We present field measurements of under-ice irradiance along transects under undeformed land-fast sea ice at Barrow, Alaska (March, May, and June 2010). The measurements were performed with a spectral radiometer mounted on a floating under-ice sled. The objective was to quantify the spatial variability of light transmittance through snow and sea ice, and to compare this variability along its seasonal evolution. Along with optical measurements, snow depth, sea ice thickness, and freeboard were recorded, and ice cores were analyzed for chlorophyll a and particulate matter. Our results show that snow cover variability prior to onset of snow melt causes as much relative spatial variability of light transmittance as the contrast of ponded and white ice during summer. Both before and after melt onset, measured transmittances fell in a range from one third to three times the mean value. In addition, we found a twentyfold increase of light transmittance as a result of partial snowmelt, showing the seasonal evolution of transmittance through sea ice far exceeds the spatial variability. However, prior melt onset, light transmittance was time invariant and differences in under-ice irradiance were directly related to the spatial variability of the snow cover.

Basic and other measurements of radiation from the Baseline Surface Radiation Network (BSRN) Station Ny-Ålesund in the years 1992 to 2013, reference list of 253 datasets

At Ny-Ålesund (78.9° N), Svalbard, surface radiation measurements of up- and downward short- and longwave radiation are operated since August 1992 in the frame of the Baseline Surface Radiation Network (BSRN), complemented with surface and upper air meteorology since August 1993. The long-term observations are the base for a climatological presentation of the surface radiation data. Over the 21-year observation period, ongoing changes in the Arctic climate system are reflected. Particularly, the observations indicate a strong seasonality of surface warming and related changes in different radiation parameters. The annual mean temperature at Ny-Ålesund has risen by +1.3 ± 0.7 K per decade, with a maximum seasonal increase during the winter months of +3.1 ± 2.6 K per decade. At the same time, winter is also the season with the largest long-term changes in radiation, featuring an increase of +15.6 ± 11.6 W/m**2 per decade in the downward longwave radiation. Furthermore, changes in the reflected solar radiation during the months of snow melt indicate an earlier onset of the warm season by about 1 week compared to the beginning of the observations. The online available dataset of Ny-Ålesund surface radiation measurements provides a valuable data source for the validation of satellite instruments and climate models.