Radiation-transfer modeling of snow-pack photochemical processes during ALERT 2000

The delta-Eddington radiation transfer model is used to calculate actinic fluxes and photolysis rates within the snow pack during the ALERT 2000 field campaign. Actinic fluxes are enhanced within the snow pack due to the high albedo of snow and conversion of direct light to diffuse light. The conversion of direct to diffuse light is highly dependent on the solar zenith angle, as demonstrated by model calculations. The optical properties of Alert snow are modeled as 100 μm radius ice spheres with impurity added to increase the absorption coefficient over that of pure water ice. Using these optical properties, the model achieves good agreement with observations of irradiance within the snow pack. The model is used to calculate the total actinic flux as a function of solar zenith angle and depth for either clear sky or cloudy conditions. The actinic flux is then used to calculate photochemical production of nitrogen oxides from nitrate photolysis assuming that nitrate in snow has the same absorption cross section and quantum yield in snow as in aqueous solution. Assuming all photo-produced nitrogen oxides are released to the gas phase, we derive a maximal flux of nitrogen oxides (NO_x+HONO and possibly other products) from the snow pack. The value of this maximal flux depends critically on the assumed quantum yield for production of NO₂, which is unknown in ice. Depending on the assumed quantum yield, the calculated maximal flux varies between values four times smaller than the observed NO_x+HONO flux to five times larger than the NO_x+HONO flux. Therefore, it appears that the calculated flux is in approximate agreement with the observations with a great need for improved understanding of nitrogen photochemistry in snow.     

Canada’s Mobile Sources Air Pollution Control Program

The chemical and optical properties of particle emissions from onroad vehicles were investigated at the Allegheny Tunnel on the Pennsylvania Turnpike during July 1981. The optical results are in agreement with earlier data: (1) in terms of light extinction per km driven, diesel particle emissions are at least an order of magnitude more important than particle emissions from spark-ignition vehicles; (2) for diesel particle emissions, light absorption is about twice as efficient as light scattering. Chemical analyses showed that: (1) 24% of the vehicle aerosol was extractable material, (2) 75% of the total mass was carbon, (3) 55% of the total mass was unextractable (elemental) carbon, and (4) the stoichiometry of the extractable fraction of the diesel particle emissions was C_nH_t.7nN_0.05n , i.e., the extractable material was composed predominantly of alkanes. The results of the chemical analyses allow the calculation of the massspecific light absorption coefficient for the elemental carbon component of the diesel particle emissions, i.e., 10.9 ± 1.8 m²/g (500 nm).     

Spectroscopic study of organic coatings on fine particles,exposed to ozone and simulated sunlight

This work intends to quantify the variation in optical properties of aerosol by in-situ spectroscopic monitoring the ozonolysis of a mixture of typical biomass burning compounds. The reaction occurs on silica and glass particles in the presence of simulated sunlight.Fused silica particles (Aerosil) were coated with a thin film of a 1:1 mixure of 4-phenoxyphenol with 4-carboxyphenone as a photosensitizer. UV–VIS spectra of dichloromethane extracts from the particles recorded before and after treatment, show development of a new band after prolonged ozone and light exposure.Changes in optical properties are reported, and variations of spectroscopic features are discussed. We show that the ozone-induced heterogeneous photochemical reaction does produce species absorbing light in the solar spectral range. Further, we demonstrate that the heterogeneous photosensitized reactions at 200 ppb ozone (strongly ozone polluted regions) for a time period of 7 h aging process, can increase light absorption of atmospheric aerosols in the tropospheric actinic window (>290 nm) by 0.4 absorption units ng-C^?1 O₃ ppm^?1 in the region 290–358 nm and by 1.0 absorption units ng-C^?1 O₃ ppm^?1 in the region 360–448 nm.Chemical changes of such surface films were identified by diffuse reflectance infrared Fourier transform spectroscopy of coated glass spheres, and we suggest formation of humic-like substances comparable to those reported in continental aerosol.     

State of mixture of atmospheric submicrometer black carbon particles and its effect on particulate light absorption

The state of mixture of light-absorbing carbonaceous particles was investigated in relation to light absorption properties using electron microscopic examinations, black carbon (BC) analyses of quartz filter by thermal/optical reflectance (TOR) method, measurements with two continuous light-absorbing photometers at a suburban site of Tsukuba, about 60 km northeast of Tokyo. The volume fraction of water-soluble material (?) in individual particles is important for assessing particulate light-absorbing and/or scattering of atmospheric aerosols. The values of ? in BC particles were evaluated by electron micrographs before and after dialysis (extraction) of water-soluble material. The mass absorption coefficient (MAC in units of m² g^?1) tended to increase with increasing the average ? in BC particles with the radius range of 0.05–0.5 μm. Thus, our results indicate that coatings of water-soluble material around BC particles can enhance the absorption of solar radiation. Moreover, the single scattering albedo (SSA) will increase because a large amount of coating material will scatter more light.     

Aerosol light absorption measurement techniques: Analysis and intercomparisons

A controlled study was carried out to evaluate three measurement techniques used for the determination of aerosol light absorption coefficients from aerosol samples collected on various filter substrates. These techniques were found to agree within about 10–30% when applied to a range of filter loading obtained for a laboratory generated calibration aerosol. Microphysical properties of the calibration aerosol were used to model its optical effects using Mie theory. The measured and modeled optical properties were found to differ by less than 30%. Qualitative and quantitative agreement of these techniques indicate that they provide a reasonable indirect method for the determination of atmospheric aerosol absorption coefficients and the related concentration of elemental carbon aerosol.     

Light absorption by water-soluble organic carbon in atmospheric fine particles in the central Tibetan Plateau

Environmental Science and Pollution Research - Brown carbon (BrC) has recently received much attention because of its light absorption features. The chemical compositions, optical properties, and...     

Design of graphene-based TiO2 photocatalysts—a review

There is a recent increase in the interest of designing high-performance photocatalysts using graphene-based materials. This review gathers some important aspects of graphene?CTiO₂, graphene oxide?CTiO₂, and reduced graphene oxide?CTiO₂ composites, which are of especial relevance as next generation photocatalysts. The methods used for the preparation of these materials, the associated mechanistic fundamentals, and the application of graphene-based composites on the photocatalytic degradation of pollutants are reviewed. Some structural, textural, and chemical properties of these materials and other photo-assisted applications, such as hydrogen production from water splitting and dye-sensitized solar cells, are also briefly included.     

Variability in ultraviolet total optical depth during the Southern California Ozone Study (SCOS97)

Formation of photochemical air pollution is governed in part by the solar ultraviolet actinic radiation flux, but wavelength-resolved measurements of UV radiation in polluted urban atmospheres are rarely available. As part of the 1997 Southern California Ozone Study, cosine weighted solar irradiance was measured continuously at seven UV wavelengths (300, 306, 312, 318, 326, 333 and 368 nm) at two sites during the period 1 July to 1 November 1997. The first site was at Riverside (260 m a.s.l.) in the Los Angeles metropolitan area, which frequently experiences severe air pollution episodes. The second site was at Mt Wilson (1725 m a.s.l.), approximately 70 km northwest of Riverside, and located above much of the urban haze layer. Measurements of direct (i.e., total minus diffuse) solar irradiance were used to compute total atmospheric optical depths. At 300 nm, optical depths (mean±1 S.D.) measured over the entire study period were 4.3±0.3 at Riverside and 3.7±0.2 at Mt Wilson. Optical depth decreased with increasing wavelength, falling at 368 nm to values of 0.8±0.2 at Riverside and 0.5±0.1 at Mt Wilson. At all wavelengths, both the mean and the relative standard deviation of optical depths were larger at Riverside than at Mt Wilson. At 300 nm, the difference between the smallest and largest observed optical depths corresponds to over a factor 2 increase in the direct beam irradiance for overhead sun, and over a factor 7 increase for a solar zenith angle of 60°. Principal component analysis was used to reveal underlying factors contributing to variability in optical depths. PCA showed that a single factor (component) was responsible for the major part of the variability. At Riverside, the first component was responsible for 97% of the variability and the second component for 2%. At Mt Wilson, 89% of the variability could be attributed to the first component and 10% to the second. Dependence of the component contributions on wavelength allowed identification of probable physical causes: the first component is linked to light scattering and absorption by atmospheric aerosols, and the second component is linked to light absorption by ozone. These factors are expected to contribute to temporal and spatial variability in solar actinic flux and photodissociation rates of species including ozone, nitrogen dioxide, and formaldehyde.     

Solar energy for electricity and fuels

Solar energy conversion into electricity by photovoltaic modules is now a mature technology. We discuss the need for materials and device developments using conventional silicon and other materials, pointing to the need to use scalable materials and to reduce the energy payback time. Storage of solar energy can be achieved using the energy of light to produce a fuel. We discuss how this can be achieved in a direct process mimicking the photosynthetic processes, using synthetic organic, inorganic, or hybrid materials for light collection and catalysis. We also briefly discuss challenges and needs for large-scale implementation of direct solar fuel technologies.     

Review on fabrication methodologies and its impacts on performance of dye-sensitized solar cells

This review highlights and summarizes the impact of different fabrication processes on the efficiency of dye-sensitized solar cells (DSSCs). Energy conversion efficiency of cell depends upon semiconductor, sensitizer, electrolyte, and counter electrode. Efficiency of DSSCs can be enhanced by properly selecting the optimum significance of various parameters of fabrications process. Major challenges of these solar cells are non-vegetal, noxious, extreme sensitizers. Application of natural dyes in this field plays a significant role. An optimized CdSe-TiO₂ photoanode showed a power conversion efficiency (PCE) of 13.29% and short circuit current density of 15.30 mA cm^?2 for the DSSC. Power conversion efficiency of 3.26% was achieved by using TTO electrode for DSSC device that is ascribed to the improved electrical and optical properties due to doping with Ta element. Absorbance of betalain was shown in the visible range of 530–535 nm for betanin while 450–559 nm for anthocyanin pigment. The natural dyes are economical, readily available, and environmentally friendly. This compilation would be beneficial for researchers working on dye solar cell.

     

On the relation between the size and chemical composition of aerosol particles and their optical properties

The light scattering and absorption coefficients of fine atmospheric aerosol particles were recorded in Hungary under rural conditions in 1998–1999 by an integrating nephelometer and particle soot absorption photometer, respectively. In some cases optical properties in the fine size range were compared to those in the coarse particles. Results obtained indicate, as expected, that fine particles control the scattering and absorption caused by the aerosol. In 1999 the size distribution of aerosol particles was also monitored by means of an electric low pressure impactor (ELPI). This makes it possible the study of the relationship between the number, surface and mass concentration in the size range of 0.1–1.0 μm and the optical characteristics by also considering the chemical composition of the particles.     

Spectroscopic measurement of horizontal atmospheric extinction and its practical application

At a suburban location in southern Korea, the optical properties of the atmosphere were characterized over a horizontal light path of 1.5 km (in two ways) from 22 October to 19 November 2002. This was achieved by measuring light extinction with a long path differential optical absorption spectrometer system in the ultraviolet and visible wavelength region. The extinction coefficients were obtained relatively as a ratio of a target air spectrum to a defined reference spectrum measured over the same light path (290–760 nm). To assess the measured extinction coefficients, the extinction coefficients at 550 nm were compared to those measured with a commercial long-path transmissometer.To avoid the absorption of known gases (H₂O, NO₂, and O₃), extinction coefficients at the spectral bands of 325, 394, 472, 550, 580, 680, and 753 nm, with 3 nm window widths, were selected and analyzed for the purpose of the study of the aerosol properties. Importantly, the atmospheric physical properties during the episodes (such as a biomass burning or a dust storm) were investigated by means of the Angstrom parameters and the mass ratio of fine-to-coarse particles. In addition, it was found that the Angstrom exponents decrease monotonously for relative humidity above 50%.     

Comparison of continuous and filter-based carbon measurements at the Fresno supersite

Results from six continuous and semicontinuous black carbon (BC) and elemental carbon (EC) measurement methods are compared for ambient samples collected from December 2003 through November 2004 at the Fresno Supersite in California. Instruments included a multi-angle absorption photometer (MAAP; lambda = 670 nm); a dual-wavelength (lambda = 370 and 880 nm) aethalometer; seven-color (lambda = 370, 470, 520, 590, 660, 880, and 950 nm) aethalometers; the Sunset Laboratory carbon aerosol analysis field instrument; a photoacoustic light absorption analyzer (lambda = 1047 nm); and the R&P 5400 ambient carbon particulate monitor. All of these acquired BC or EC measurements over periods of 1 min to 1 hr. Twenty-four-hour integrated filter samples were also acquired and analyzed by the Interagency Monitoring of Protected Visual Environments (IMPROVE) thermal/optical reflectance carbon analysis protocol. Site-specific mass absorption efficiencies estimated by comparing light absorption with IMPROVE EC concentrations were 5.5 m2/g for the MAAP, 10 m2/g for the aethalometer at a wavelength of 880 nm, and 2.3 m2/g for the photoacoustic analyzer; these differed from the default efficiencies of 6.5, 16.6, and 5 m2/g, respectively. Scaling absorption by inverse wavelength did not provide equivalent light absorption coefficients among the instruments for the Fresno aerosol measurements. Ratios of light absorption at 370 nm to those at 880 nm from the aethalometer were nearly twice as high in winter as in summer. This is consistent with wintertime contributions from vehicle exhaust and from residential wood combustion, which is believed to absorb more shorter-wavelength light. To reconcile BC and EC measurements obtained by different methods, a better understanding is needed of the wavelength dependence of light-absorption and mass-absorption efficiencies and how they vary with different aerosol composition.     

Humic-like substances extracted from composts can promote the photodegradation of Irgarol 1051 in solar light

Humic-like substances (HLS) were extracted from a mixture of sewage sludges and trimmings (70-30%, w/w) after different times of composting (0, 70 days and 130 days). HLS were analyzed by elemental analysis, UV-visible and fluorescence spectroscopy and also tested for their ability to photosensitize the degradation of Irgarol. The rate of Irgarol photodegradation in artificial solar light was found to be 2.5- to 4.3-fold higher in the presence of HLS than in buffered Milli-Q water. These results were confirmed by experiments in solar light that evidenced the photodegrading properties of HLS in a more striking way. Using 2-propanol as hydroxyl radical scavenger, we could show that hydroxyl radicals contributed to the photosensitized Irgarol degradation for about 25%. The photodegrading activity of HLS, their absorbance and their emissive properties were all found to increase between 0 and 70 days of composting and to remain quite constant between 70 and 130 days. The degree of humification varied in the same way, linking all these properties to the humification process.     

Fractionation and spectroscopic properties of fulvic acid and its extract

Novel results were obtained when a fulvic acid was isolated from Acros humic acid and fractionated by traditional preparative thin-layer chromatography. Eight colorful bands were directly viewed and analyzed showing very different fluorescence and absorption properties. The fluorescence quantum yield of the bands ranged from 2% to 9.4%, significantly higher than that of natural humic substances. An aqueous fulvic acid solution was also extracted with methylene chloride (CH(2)Cl(2)) by continuous liquid-liquid extraction. The CH(2)Cl(2) extract was further fractionated by thin-layer chromatography. Eleven highly fluorescent colorful bands and six weakly fluorescent bands were observed and examined. UV-vis absorption and fluorescence (including 3D matrix) spectra and fluorescence quantum yields revealed that each band still represented a mixture of compounds. Moreover, substantial differences in optical properties were observed among bands. A single band possessed the highest fluorescence quantum yield (6%) and highest specific fluorescence (fluorescence/mass), and accounted for 21% of the total fluorescence of the extract. The mass of individual bands varied from 1.6% to 14.1% of the total materials recovered. Components of all fractions were grouped into 11 fluorophore families according to their maxima on 3D matrix fluorescence spectra. No component is dominant in the whole fulvic acid or extracted portion in terms of optical properties. Over 40 natural products are proposed for model chromophores.     

Fusion of SeaWiFS and TOMS satellite data with surface observations and topographic data during extreme aerosol events.

Spaceborne sensors allow near-continuous aerosol monitoring throughout the world. This paper illustrates the fusion of Sea-Viewing Wide Field-of-View Sensor (SeaWiFS) and TOMS satellite data with surface observations and topographic data during four extreme aerosol events: (1) the April 1998 Asian dust storm that impacted the west coast of North America, (2) the May 1998 Central American forest fire smoke that impacted eastern North America, (3) the intense fall 1999 northern California fires, and (4) the massive February 2000 Sahara dust storm. During these dust and smoke events, the aerosol was visualized on true color SeaWiFS images as a distinct yellowish dye, the result of the aerosol increasing the reflectance of darker surfaces (ocean and land) and decreasing the reflectance of clouds. TOMS imagery also indicated increased aerosol absorption in the affected areas, while surface monitors measured major reductions in visual range. Fusing these data aids in the determination of the aerosol's spatial, temporal, and optical properties and provides supporting evidence for characterizing what is being visualized as dust or smoke. A 3-dimensional perspective of the events is obtained when incorporating topographic data and provides insight into the vertical properties of the aerosol plumes.     

Ultra-high efficiency photovoltaic cells for large scale solar power generation

The primary targets of our project are to drastically improve the photovoltaic conversion efficiency and to develop new energy storage and delivery technologies. Our approach to obtain an efficiency over 40% starts from the improvement of III-V multi-junction solar cells by introducing a novel material for each cell realizing an ideal combination of bandgaps and lattice-matching. Further improvement incorporates quantum structures such as stacked quantum wells and quantum dots, which allow higher degree of freedom in the design of the bandgap and the lattice strain. Highly controlled arrangement of either quantum dots or quantum wells permits the coupling of the wavefunctions, and thus forms intermediate bands in the bandgap of a host material, which allows multiple photon absorption theoretically leading to a conversion efficiency exceeding 50%. In addition to such improvements, microfabrication technology for the integrated high-efficiency cells and the development of novel material systems that realizes high efficiency and low cost at the same time are investigated.     

Ultra-High Efficiency Photovoltaic Cells for Large Scale Solar Power Generation

The primary targets of our project are to drastically improve the photovoltaic conversion efficiency and to develop new energy storage and delivery technologies. Our approach to obtain an efficiency over 40% starts from the improvement of III–V multi-junction solar cells by introducing a novel material for each cell realizing an ideal combination of bandgaps and lattice-matching. Further improvement incorporates quantum structures such as stacked quantum wells and quantum dots, which allow higher degree of freedom in the design of the bandgap and the lattice strain. Highly controlled arrangement of either quantum dots or quantum wells permits the coupling of the wavefunctions, and thus forms intermediate bands in the bandgap of a host material, which allows multiple photon absorption theoretically leading to a conversion efficiency exceeding 50%. In addition to such improvements, microfabrication technology for the integrated high-efficiency cells and the development of novel material systems that realizes high efficiency and low cost at the same time are investigated.     

Fusion of SeaWiFS and TOMS Satellite Data with Surface Observations and Topographic Data during Extreme Aerosol Events

ABSTRACT

Spaceborne sensors allow near-continuous aerosol monitoring throughout the world. This paper illustrates the fusion of Sea-Viewing Wide Field-of-View Sensor (SeaWiFS) and TOMS satellite data with surface observations and topographic data during four extreme aerosol events: (1) the April 1998 Asian dust storm that impacted the west coast of North America, (2) the May 1998 Central American forest fire smoke that impacted eastern North America, (3) the intense fall 1999 northern California fires, and (4) the massive February 2000 Sahara dust storm. During these dust and smoke events, the aerosol was visualized on true color SeaWiFS images as a distinct yellowish dye, the result of the aerosol increasing the reflectance of darker surfaces (ocean and land) and decreasing the reflectance of clouds. TOMS imagery also indicated increased aerosol absorption in the affected areas, while surface monitors measured major reductions in visual range. Fusing these data aids in the determination of the aerosol's spatial, temporal, and optical properties and provides supporting evidence for characterizing what is being visualized as dust or smoke. A 3-dimensional perspective of the events is obtained when incorporating topographic data and provides insight into the vertical properties of the aerosol plumes.     

Effect of Nb doping on structural, optical and photocatalytic properties of flame-made TiO2 nanopowder

TiO₂:Nb nanopowders within a dopant concentration in the range of 0.1?C15?at.% were prepared by one-step flame spray synthesis. Effect of niobium doping on structural, optical and photocatalytic properties of titanium dioxide nanopowders was studied. Morphology and structure were investigated by means of Brunauer?CEmmett?CTeller isotherm, X-ray diffraction and transmission electron microscopy. Diffuse reflectance and the resulting band gap energy were determined by diffuse reflectance spectroscopy. Photocatalytic activity of the investigated nanopowders was revised for the photodecomposition of methylene blue (MB), methyl orange (MO) and 4-chlorophenol under UVA and VIS light irradiation. Commercial TiO₂-P25 nanopowder was used as a reference. The specific surface area of the powders was ranging from 42.9?m²/g for TiO₂:0.1?at.% Nb to 90.0?m²/g for TiO₂:15?at.% Nb. TiO₂:Nb particles were nanosized, spherically shaped and polycrystalline. Anatase was the predominant phase in all samples. The anatase-related transition was at 3.31?eV and rutile-related one at 3.14?eV. TiO₂:Nb nanopowders exhibited additional absorption in the visible range. In comparison to TiO₂-P25, improved photocatalytic activity of TiO₂:Nb was observed for the degradation of MB and MO under both UVA and VIS irradiation, where low doping level (Nb?<?1?at.%) was the most effective. Niobium doping affected structural, optical and photocatalytic properties of TiO₂. Low dopant level enhanced photocatalytic performance under UVA and VIS irradiation. Therefore, TiO₂:Nb (Nb?<?1?at.%) can be proposed as an efficient selective solar light photocatalyst.