Calculation of the UV Absorption Spectra of As(III) Oxo- and Thio- Acids and Anions in Aqueous Solution and of PF3 in the Gas-phase

Changes in the UV spectra of As(OH)₃ solutions with variations in pH and temperature have recently been used to determine the temperature dependence of the pK_a of the acid. In previous studies I used quantum mechanical techniques to study changes in structure and vibrational spectra as a function of pH for arsenites and thioarsenites. I previously calculated UV spectra for ``molecular' minerals, like realgar As₄S₄. Here I use a number of different quantum mechanical methods, both Hartree-Fock and density functional theory based, to calculate the UV spectra for both a related simple well-characterized gas-phase molecule PF₃ and for As(OH)₃ and As(SH)₃ and their conjugate anions and some neutral and anionic oligomers in aqueous solution. For the monomeric species small numbers of water molecules have been explicitly included, in a supermolecule or microsolvation approach. I find that UV absorption energies accurate to a few tenths of an eV can be obtained both for gas- phase PF₃ and for neutral arsenious acid in aqueous solution, for which the UV absorption maximum is calculated to occur around 6.5 eV, consistent with experiment. Accurate calculation of the UV energies for arsenite anions in aqueous solution is much more difficult, since basis set size and solvation effects are considerably larger than for the neutral molecules, but fairly reliable results can still be obtained. Deprotonation is found to reduce the lowest calculated UV transition energy by about half an eV. Oligomerization also reduces the lowest calculated UV energy by at least half an eV. Replacement of one or all the –OH groups by –SH groups reduces the lowest calculated UV energies by about 2 eV. UV excitation energies have been calculated for oligomeric species as large as As₃E₃(EH)₃ and As₄E₆, where E = O, S, and may be useful for identifying such species in solution.     

Influence of Clouds on UV Irradiance at Ground Level and Backscattered Exittance

The influence of various cloud parameters and the interactions with the ground albedo and the solar zenith angle have been studied by means of model simulations. The radiative transfer model suitable for a cloudy atmosphere as well as for a clear atmosphere has been developed on the basis of the Discrete Ordinate Method. This study leads to a general understanding for cloudy atmospheres: in the presence of a uniform cloud, the cloud scattering is dominant to molecular and aerosol scattering, and it is also wavelength-independent; the ratio of transmitted irradiance in a cloudy atmosphere to that in the background clear atmosphere is independent of cloud height and solar zenith angle. That’s to say, the radiation downwelling out of a cloud is quite isotropic; it decreases approximately exponentially with the cloud optical depth at a rate related to the ground albedo; the reflected irradiance at the top of the atmosphere is dependent on cloud optical depth as well as on solar zenith angle, but not on ground albedo for clouds of not very thin optical depth.     

The NO2 absorption spectrum. III: The 200–300 nm region at ambient temperature

Absorption cross-section measurements of NO₂ performed in our laboratory have been extended to the 200–300 nm region at ambient temperature. Low pressures have been used, limiting the effects of the dimer N₂O₄ which has an absorption cross-section from one to two orders of magnitude larger than that of NO₂ in this region. The results have been compared to those of previous authors and are now available for atmospheric purposes at 0.01 nm intervals.Unité de Recherche Associée au CNRS.     

SSBUV and NOAA-11 SBUV/2 Solar Variability Measurements

The Shuttle SBUV (SSBUV) and NOAA-11 SBUV/2 instruments measured solar spectral UV irradiance during the maximum and declining phase of solar cycle 22. The SSBUV data accurately represent the absolute solar UV irradiance between 200–405 nm, and also show the long-term variations during eight flights between October 1989 and January 1996. These data have been used to correct long-term sensitivity changes in the NOAA-11 SBUV/2 data, which provide a near-daily record of solar UV variations over the 170–400 nm region between December 1988 and October 1994. The NOAA-11 data demonstrate the evolution of short-term solar UV activity during solar cycle 22.     

XMM–Newton observations of soft gamma-ray repeaters

All the confirmed Soft Gamma-ray Repeaters have been observed with the EPIC instrument on the XMM–Newton satellite. We review the results obtained in these observations, providing the most accurate spectra on the persistent X-ray emission in the 1–10 keV range for these objects, and discuss them in the context of the magnetar interpretation.      

Unveiling soft gamma-ray repeaters with INTEGRAL

Thanks to INTEGRAL’s long exposures of the Galactic Plane, the two brightest Soft Gamma-Ray Repeaters, SGR 1806-20 and SGR 1900+14, have been monitored and studied in detail for the first time at hard-X/soft gamma rays. This has produced a wealth of new scientific results, which we will review here. Since SGR 1806-20 was particularly active during the last two years, more than 300 short bursts have been observed with INTEGRAL and their characteristics have been studied with unprecedented sensitivity in the 15–200 keV range. A hardness-intensity anticorrelation within the bursts has been discovered and the overall Number-Intensity distribution of the bursts has been determined. In addition, a particularly active state, during which 100 bursts were emitted in 10 minutes, has been observed on October 5 2004, indicating that the source activity was rapidly increasing. This eventually led to the Giant Flare of December 27th 2004, for which a possible soft gamma-ray (>80 keV) early afterglow has been detected. The deep observations allowed us to discover the persistent emission in hard X-rays (20–150 keV) from 1806-20 and 1900+14, the latter being in a quiescent state, and to directly compare the spectral characteristics of all Magnetars (two SGRs and three Anomalous X-ray Pulsars) detected with INTEGRAL. D.G. acknowledges the French Space Agency (CNES) for financial support. Based on observations with INTEGRAL, an ESA project with instruments and the science data centre funded by ESA member states (especially the PI countries: Denmark, France, Germany, Italy, Switzerland, Spain), Czech Republic and Poland, and with the participation of Russia and the USA. ISGRI has been realized and maintained in flight by CEA-Saclay/DAPNIA with the support of CNES. K.H. is grateful for support under NASA’s INTEGRAL U.S. Guest Investigator program, Grants NAG5-13738 and NNG05GG35G.     

Survey of cyanomyovirus abundance in Shantou coastal waters by g20

To understand the genetic diversity and population changes in cyanophages in the coastal waters of Shantou,northeast South China Sea,we used the capsid assembly protein gene g 20 as a marker of the abundance and phylogeny of natural cyanomyovirus communities. The abundance of total viruses,heterotrophic bacteria,and picophytoplankton in the coastal waters was monitored with flow cytometry. Hydrological parameters(NO ˉ 3,NO ˉ 2,NH 3,soluble reactive phosphorus,total dissolved nitrogen,total dissolved phosphorus,dissolved oxygen,chemical oxygen demand,temperature,salinity,and chlorophyll a concentration) and microbial abundance(total viruses,total bacteria,P rochlorococcus,Synechococcus,and eukaryotes) were measured in the upper and lower layers at four sampling sites in the research area. In the direct viral counts,cyanomyoviruses accounted for 1.92% to 10% of the total viral community. A phylogenetic analysis showed that the g 20 sequences in the Shantou coastal waters were very diverse,distributed in eight distinct operational taxonomic units,including the newly formed Cluster W. The g 20 gene copies inferred from real time PCR assay indicated that cyanomyoviruses were correlated significantly with the heterotrophic bacteria numbers and the nitrate and chlorophyll a concentrations. These results suggest that cyanomyoviruses are ubiquitous and are an abundant component of the virioplankton in Shantou coastal waters.     

Europa’s disk-resolved ultraviolet spectra: Relationships with plasma flux and surface terrains

The full set of high-resolution observations from the Galileo Ultraviolet Spectrometer (UVS) is analyzed to look for spectral trends across the surface of Europa. We provide the first disk-resolved map of the 280 nm SO₂ absorption feature and investigate its relationship with sulfur and electron flux distributions as well as with surface features and relative surface ages. Our results have implications for exogenic and endogenic sources. The large-scale pattern in SO₂ absorption band depth is again shown to be similar to the pattern of sulfur ion implantation, but with strong variations in band depth based on terrain. In particular, the young chaos units show stronger SO₂ absorption bands than expected from the average pattern of sulfur ion flux, suggesting a local source of SO₂ in those regions, or diapiric heating that leads to a sulfur-rich lag deposit.While the SO₂ absorption feature is confined to the trailing hemisphere, the near UV albedo (300-310 nm) has a global pattern with a minimum at the center of the trailing hemisphere and a maximum at the center of the leading hemisphere. The global nature of the albedo pattern is suggestive of an exogenic source, and several possibilities are discussed. Like the SO₂ absorption, the near UV albedo also has local variations that depend on terrain type and age.