Bidirectional reflectance spectroscopy: 6. Effects of porosity

It is well known that the bidirectional reflectance of a particulate medium such as a planetary regolith depends on the porosity, in contrast to predictions of models based on the equation of radiative transfer as usually formulated. It is shown that this failure to predict porosity dependence arises from an incorrect treatment of the light that passes between the particles. In this paper a more physically correct treatment that takes account of the necessity of preventing particles from interpenetrating is used together with the two-stream approximation to solve the radiative transfer equation and derive improved expressions for the bidirectional and directional-hemispherical reflectances. It is found that increasing the filling factor (decreasing the porosity) increases the reflectance of low and medium albedo powders, but decreases it for ones with very high albedos. The model agrees qualitatively with measured data.     

Photochemical Degradation of Hydrophilic Xenobiotics in the UV/H2O2-process. Influence of Bicarbonate on the Degradation Rate of EDTA, 2-Amino-1-naphthalenesulfonate,Diphenyl-4-sulfonate,and 4,4′-Diaminostilbene-2,2′-disulfonate

Hydrophilic xenobiotics can be eliminated in the UV/H₂O₂-process. The oxidation in this process is enhanced by the photolytically generated HO radicals. Bicarbonate is able to scavenge HO radicals. So it was expected that the degradation rates of the investigated xenobiotics were affected by the influence of bicarbonate. In contrast to the widely described decrease of the degradation rate, a much more complex situation was found in this investigation. The degradation rates of 2-amino-1-naphthalenesulfonate and diphenyl-4-sulfonate were decreased and reached for high concentrations of bicarbonate the values of the photolytical degradation rate. The degradation of 4,4′-diaminostilbene-2,2′-disulfonate was accelerated significantly in the presence of bicarbonate. The degradation rate of EDTA was increased at small concentrations of bicarbonate and decreased at higher concentrations.     

昆明地面生物有效紫外辐照度的初步计算

近年来，大气平流层臭氧含量普遍呈下降趋势。这将对人类的生存环境构成极大威胁， 应当引起人们的高度重视。 其中，太阳紫外辐射是一大因素。 太阳紫外光（ UVB和UVA，尤其是波长为280～320 nm）对动植物生长及人类健康具有重要的生物学效应 。但太阳光在大气中的传输过程极其复杂，涉及到大气臭氧吸收、空气分子散射、 气溶胶颗粒以及云滴的散射等作用。 针对昆明地处低纬高原、季风云系影响显著等特点 ， 本文在同时考虑上述几种情况下， 用二流模式（two-stream model）方法对太阳紫外辐射传输问题进行了研究，得出了一些有意义的计算结果，并对其作了讨论。     

Temperature-dependence of ultraviolet absorption cross-sections of alternative chlorofluoroethanes

The absorption cross-sections of HCFC-123 (CF₃–CHCl₂), HCFC-141b (CH₃–CFCl₂) and HCFC-142b (CH₃–CF₂Cl) are measured between 170 and 250 nm for temperatures ranging from 295 to 210 K with uncertainties between 2 and 4%. They are compared with other available determinations. Temperature effects are discussed and parametrical formulae are proposed to compute the absorption cross-section for wavelengths and temperatures useful in atmospheric modelling calculations. Photodissociation coefficients are presented and their temperature-dependence is discussed.     

Measurement of Solar and Cosmic Radiation during Spaceflight

The external platform of the International Space Station (ISS) will provide aunique opportunity for exobiological studies under space conditions, e.g., spacevacuum, solar UV radiation, cosmic radiation, and temperature extremes. In orderto facilitate this research, ESA is developing the EXPOSE facility to be attachedto the External Pallet of the truss structure of the ISS. The experiment is plannedfor a duration of 18 months during the ISS early utilization period. Experimentson the ``Responses of Organisms to the Space Environment (ROSE)' will studythe survival of spores from bacteria, fungi, ferns, etc., under space conditions andthus investigate whether life could potentially survive extended travel through space.In parallel to the exposure of the biological material, the charged particle and solarextraterrestrial radiation will be measured with a multichannel dosimeter. Thisinstrument is based on two separate developments. The dosimeter which determinessolar radiation in four channels is based on the ground-based ELDONET (Europeanlight dosimeter network) instrument which has been developed to measure solar UVand visible radiation in three channels. The other part of the instrument is based on a256 channel dosimeter of cosmic radiation which was developed and used on theRussian space station Mir. A final miniature prototype has been developed to fit thespace available. The instrument incorporates the latest technologies such as SurfaceMounted Devices (SMDs), switchable amplifiers, as well as on-board microprocessorcontrol. Several software packages have been developed to record the solar visible andUV, and charged particle, radiations, to display them in graphical form and to store them for future analysis. All recorded data will be made available to the public via the Internet.     

Mie scattering and charge transfer phenomena as causes of the UV edge in the absorption spectra of natural and synthetic almandine garnets

 The UV edge in the electronic absorption spectra of minerals, in many cases influencing their colour, is generally interpreted as the low-energy wing of very strong UV bands caused by ligand–metal charge transfer (CT) transitions (e.g. Burns 1993). However, Mie scattering theory shows that the presence of randomly distributed submicroscopic inclusions with narrow size distribution and a refractive index n _i in a matrix with different refractive index n _m may give rise to a λ-dependent, band-like scattering (e.g. Kortüm 1969). Such scattering bands have so far not been considered as contributing to the UV edge. Single-crystal electronic absorption spectra of eight natural almandine-rich garnets (Alm₆₀–Alm₈₈), two synthetic almandine samples (Alm₁₀₀), all of different colours, and synthetic spessartine were studied by means of a Zeiss microscope-spectrometer in the range 40 000–20 000 cm⁻¹. Special techniques of spectral measurements with crossed analyzer and polarizer, which enable the registration of the scattering effect directly, were used as well. Four of the above garnets were also investigated using transmission electron microscopy. Different types of inclusions, from 10 to several 100 nm in size, were observed in the garnet matrices. They are abundant in cores of synthetic garnets, but very rare in most natural almandines studied. Electronic absorption spectra of the natural almandine garnets show largely varying UV edge position and, hence, intensity at a given wavenumber which correlates with the intensities of spin-forbidden dd bands of Fe³⁺ ions at 27 000 and 28 000 cm⁻¹, superimposed on the long energy slope of the UV absorption. There are also positive correlations between Ti⁴⁺ and Fe³⁺ content, the latter recalculated on the basis of garnet stoichiometry, and UV edge intensity. Thus, the presence of Ti⁴⁺ and Fe³⁺ ions in octahedra, even in very low concentrations (0.0n at. pfu), leads to CT phenomena, that probably involve Fe²⁺ ions in edge-shared dodecahedral position and intensifies ligand- to-metal CT. The different colours of natural almandine garnets with similar Fe²⁺ contents studied here are caused by this effect. Consistent with the absence of inclusions in most natural garnets studied, λ-dependent scattering plays no role in their UV absorption. In contrast, in synthetic almandine and spessartine crystals, a different intensity of UV absorption was observed in inclusion-free rims and inclusion-enriched cores. Some of the latter demonstrate typical scattering patterns when measured at crossed polarizers. Received: 10 April 2001 / Accepted: 27 September 2001     

DOAS Zenith Sky Observations: 1. BrO Measurements over Bremen (53°N) 1993–1994

Observations of stratospheric BrO over Bremen (53°N) are reported for winter and early spring periods of 1993 and 1993/94. The BrO was observed by ground-based near-UV absorption spectroscopy of sunlight scattered in the zenith. Differential slant column densities for solar zenith angles 90°/80° in the range of9× 10¹³ (detection limit) to 4.5×10¹⁴ molecules/cm² having a high day-to-day variability were found. For the majority of the measurements no significant difference was observed between the morning and evening behaviour of BrO. Exceptions are the morning measurements from the winter of 1992/93 where an accelerated production of BrO was observed. We believe the latter best to be explained by the early morning rapid photolysis of elevated amounts of photo-labile Br-reservoirs formed during the night. The largest differential slant column densities of BrO were measured in December 1993 when the temperatures at 30 hPa dropped below 205 K. This might be an indication of heterogeneous conversion of bromine compounds on sulfate and other aerosols.     

Degradation of Aqueous Atrazine and Metazachlor Solutions by UV and UV/H2O2 — Influence of pH and Herbicide Concentration Abbau von Atrazin und Metazachlor in wäßriger Lösung durch UV und UV/H2O2 — Einfluß von pH und Herbizid-Konzentration

The degradation of two pesticides: atrazine and metazachlor was investigated in aqueous solution under UV-irradiation with and without H₂O₂. Rate constants of the photochemical degradation were determined applying a first order kinetics and quantum yields of the processes were calculated. This approach leads to an apparent decrease of the quantum yield with increasing initial pesticide concentration. At low H₂O₂ initial concentrations, the pesticide degradation was shown to be much more efficient than the degradation under UV-irradiation only. However, at high H₂O₂ concentrations (>2 mmol L^?1), the efficiency of the UV/H₂O₂ system dropped down and the quantum yields of degradation were lower than for the direct photolysis. In the absence of H₂O₂, no influence of the pH value on the photodegradation of the pesticides could be noticed in a range between pH 3 and pH 11. At low H₂O₂ initial concentrations, the photochemical degradation of the pesticides was much faster at pH 3 and pH 7 compared with the degradation at pH 11. The results emphasize the potential of optimized reaction conditions in advanced oxidation.