Stratospheric Photolysis Frequencies: Impact of an Improved Numerical Solution of the Radiative Transfer Equation

Numerical schemes for the calculation of photolysis rates are usually employed in simulations of stratospheric chemistry. Here, we present an improvement of the treatment of the diffuse actinic flux in a widely used stratospheric photolysis scheme (Lary and Pyle, 1991). We discuss both the consequences of this improvement and the correction of an error present in earlier applications of this scheme on the calculation of stratospheric photolysis frequencies. The strongest impact of both changes to the scheme is for small solar zenith angles. The effect of the improved treatment of the diffuse flux is most pronounced in the lower stratosphere and in the troposphere. Overall, the change in the calculated photolysis frequencies in the region of interest in the stratosphere is below about 20%, although larger deviations are found for H₂O, O₂, NO, N₂O, and HCl.     

A Database for Volatile Organic Compounds

The database for volatile organic compounds (VOC data base) was created with the aim of providing an overview of tropospheric hydrocarbon measurements. The data base contains 202 substances, for which atmospheric and useful kinetic data such as rate coefficients, photolysis frequencies, mixing ratios, emission data and ozone formation potentials are compiled from available literature. The database file can be downloaded without charge from http://www.physchem.uni-wuppertal.de/voc-database. Registered users will be informed about the appearance of updates.     

A proposed new type of arsenian pyrite: Composition, nanostructure and geological significance

This report describes a new form of arsenian pyrite, called As³⁺-pyrite, in which As substitutes for Fe [(Fe,As)S₂], in contrast to the more common form of arsenian pyrite, As¹⁻-pyrite, in which As¹⁻ substitutes for S [Fe(As,S)₂]. As³⁺-pyrite has been observed as colloformic overgrowths on As-free pyrite in a hydrothermal gold deposit at Yanacocha, Peru. XPS analyses of the As³⁺-pyrite confirm that As is present largely as As³⁺. EMPA analyses show that As³⁺-pyrite incorporates up to 3.05 at % of As and 0.53 at. %, 0.1 at. %, 0.27 at. %, 0.22 at. %, 0.08 at. % and 0.04 at. % of Pb, Au, Cu, Zn, Ni, and Co, respectively. Incorporation of As³⁺ in the pyrite could be written like: As³⁺+yAu⁺+1-y(□)⇔2Fe²⁺; where Au⁺ and vacancy (□) help to maintain the excess charge. HRTEM observations reveal a sharp boundary between As-free pyrite and the first overgrowth of As³⁺-pyrite (20-40 nm thick) and co-linear lattice fringes indicating epitaxial growth of As³⁺-pyrite on As-free pyrite. Overgrowths of As³⁺-pyrite onto As-free pyrite can be divided into three groups on the basis of crystal size, 8-20 nm, 100-300 nm and 400-900 nm, and the smaller the crystal size the higher the concentration of toxic arsenic and trace metals. The Yanacocha deposit, in which As³⁺-pyrite was found, formed under relatively oxidizing conditions in which the dominant form of dissolved As in the stability field of pyrite is As³⁺; in contrast, reducing conditions are typical of most environments that host As¹⁻-pyrite. As³⁺-pyrite will likely be found in other oxidizing hydrothermal and diagenetic environments, including high-sulfidation epithermal deposits and shallow groundwater systems, where probably kinetically controlled formation of nanoscale crystals such as observed here would be a major control on incorporation and release of As³⁺ and toxic heavy metals in oxidizing natural systems.     

Chemical and structural characterization of As immobilization by nanoparticles of mackinawite (FeSm)

The mobility and availability of arsenite, As(III), in anoxic environments is largely controlled by adsorption onto iron sulfides and/or precipitation of arsenic in solid phases. The interaction of As(III) with synthetic mackinawite (FeS_m) in pH 5 and 9 suspensions was investigated using high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM), STEM elemental mapping, high resolution TEM, and X-ray photoelectron spectroscopy (XPS). At pH 5, arsenic sulfide phases precipitate among the FeS_m particles as discrete particles that are an amorphous hydrous phase of arsenic sulfide. The oxidation state of As in the surface layers of the arsenic sulfide precipitates is ‘realgar-like’ based on XPS results showing that > 75% of the As 3d peak area is due to As with oxidation states between 0 and 2+. Discrete, arsenic sulfide precipitates are absent at pH 9, but elemental mapping in STEM-EDX mode shows that arsenic is uniformly distributed on the FeS_m, suggesting that uptake is caused by the sorption of As(III) oxyanions and/or the precipitation of highly dispersed arsenic sulfides on FeS_m. XPS also revealed that the FeS_m that equilibrated without As(III) has a more oxidized surface composition than the sample at pH 9, as indicated by the higher concentration of O ( three times greater than that at pH 9) and the larger fraction of Fe(III) species making up the total Fe (2p_3/2) peak. These findings provide a better understanding of redox processes and phase transitions upon As(III) adsorption on iron sulfide substrates.     

Fractionation,hybridisation and magma-mixing in the Kialineq centre East Greenland

The igneous rocks of the Kialineq centre on the coast of East Greenland at 67°N include a number of quartz syenite and granite plutons intruded 35my BP. These are subvolcanic bodies emplaced by cauldron subsidence and with ring-dike and bell-jar form. Associated with the major intrusions is an extensive acid-basic mixed magma complex. Two-liquid structures, chilling of basic against acid magma, pillows of basic in acid, and net-veining of basic by acid magma, are superbly displayed. The basic magma was of a transitional or alkaline type and underwent varying degrees of fractionation in a regime of repeated intrusions and diverse chambers. Heterogeneous hybrid rocks intermediate between basalt and quartz syenite are strongly developed and were formed by repeated mechanical mixing of contrasting magmas. The energy for this mixing probably came in the main from cauldron-block subsidence. The quartz syenite magma, which itself fractionated towards granite, has initial ⁸⁷Sr/⁸⁶Sr ratios the same as the basic magma and is itself believed to be a fractionation product of alkali basalt magma.     

Nitrogen and noble gases in a glass sample from the LEW88516 shergottite

Abstract— A glass separate from the LEW88516 shergottite was analyzed by step-wise combustion for N and noble gases to determine whether it contained trapped gas similar in composition to the martian atmosphere-like component previously observed in lithology C of EETA79001. Excesses of ⁴⁰Ar and ¹²⁹Xe were in fact observed in this glass, although the amounts of these excesses are ≤20% of those seen in the latter meteorite, and are comparable to the amounts seen in whole-rock analyses of LEW88516. The isotopic composition of N in LEW88516 does not show an enrichment in ¹⁵N commensurate with the amount of isotopically-heavy N expected from the noble gases excesses. One must posit some extreme assumptions about the nature of the N components present in LEW88516 in order to allow the presence of the trapped nitrogen component. Alternatively, the N has somehow been decoupled from the noble gases, and was either never present or has been lost.     

Solar wind noble gases and nitrogen in metal from lunar soil 68501

Abstract Noble gases and N were analyzed in handpicked metal separates from lunar soil 68501 by a combination of step-wise combustions and pyrolyses. Helium and Ne were found to be unfractionated with respect to one another when normalized to solar abundances, for both the bulk sample and for all but the highest temperature steps. However, they are depleted relative to Ar, Kr and Xe by at least a factor of 5. The heavier gases exhibit mass-dependent fractionation relative to solar system abundance ratios but appear unfractionated, both in the bulk metal and in early temperature steps, when compared to relative abundances derived from lunar ilmenite 71501 by chemical etching, recently put forward as representing the abundance ratios in solar wind. Estimates of the contribution of solar energetic particles (SEP) to the originally implanted solar gases, derived from a basic interpretation of He and Ne isotopes, yield values of about 10%. Analysis of the Ar isotopes requires a minimum of 20% SEP, and Kr isotopes, using our preferred composition for solar wind Kr, yield a result that overlaps both of these values. It is possible to reconcile the data from these gases if significant loss of solar wind Ar, Kr and presumably Xe has occurred relative to the SEP component, most likely by erosive processes that are mass independent, although mass-dependent losses (Ar > Kr > Xe) cannot be excluded. If such losses did occur, the SEP contribution to the solar implanted gases must have been no more than a few percent. Nitrogen is a mixture of indigenous meteoritic N, whose isotopic composition is inferred to be relatively light, and implanted solar N, which has probably undergone diffusive redistribution and fractionation. If the heavy noble gases have not undergone diffusive loss, then N/Ar in the solar wind can be inferred to be at least several times the accepted solar ratio. The solar wind N appears, even after correction for fractionation effects, to have a minimum δ¹⁵N value ≥+150‰ and a more probable value ≥+200‰.     

Relative-rate study of the gas-phase reaction of hydroxy radicals with difunctional organic nitrates at 298 K and atmospheric pressure

Rate coefficients for the reactions of difunctional nitrates with atmospherically important OH radicals are not currently available in the literature. This study represents the first determination of rate coefficients for a number of C(3) and C(4) carbonyl nitrates and dinitrates with OH radicals in a 38 l glass reaction chamber at 1000 mbar total pressure of synthetic air by 298±2 K using a relative kinetic technique.The following rate coefficients (in units of 10^-12 cm³ molecule^-1 s^-1) were obtained: 1,2-propandiol dinitrate, <0.31; 1,2-butandiol dinitrate, 1.70±0.32; 2,3-butandiol dinitrate, 1.07±0.26; -nitrooxyacetone, <0.43; 1-nitrooxy-2-butanone, 0.91±0.16; 3-nitrooxy-2-butanone, 1.27±0.14; 1,4-dinitrooxy-2-butene, 15.10±1.45; 3,4-dinitrooxy-1-butene, 10.10±0.50.The possible importance of reaction of OH as an atmospheric sink for the compounds compared to other loss processes is considered.