Technical Note: VUV photodesorption rates from water ice in the 120-150 K temperature range - significance for Noctilucent Clouds

Laboratory studies have been carried out with the aim to improve our understanding of physicochemical processes which take place at the water ice/air interface initiated by solar irradiation with a wavelength of 121.6 nm. It was intended to mimic the processes of ice particles characteristic of Noctilucent Clouds (NLCs). The experimental set-up used includes a high-vacuum chamber, a gas handling system, a cryostat with temperature controller, an FTIR spectrometer, a vacuum ultraviolet hydrogen lamp, and a microwave generator. We report the first results of measurements of the absolute photodesorption rate (loss of substance due to the escape of photoproducts into gas phase) from thin (20–100 nm) water ice samples kept in the temperature range of 120–150 K. The obtained results show that a flow of photoproducts into the gas phase is considerably lower than presumed in the recent study by Murray and Plane (2005). The experiments indicate that almost all photoproducts remain in the solid phase, and the principal chemical reaction between them is the recombination reaction H + OH → H<sub>2</sub>O which is evidently very fast. This means that direct photolysis of mesospheric ice particles seems to have no significant impact on the gas phase chemistry of the upper mesosphere

Steam turbine materials and corrosion

Ultra-supercritical (USC) power plants offer the promise of higher efficiencies and lower emissions. Current goals of the U.S. Department of Energy’s Advanced Power Systems Initiatives include power generation from coal at 60% efficiency, which would require steam temperatures of up to 760°C. This project examines the steamside oxidation of candidate alloys for use in USC systems, with emphasis placed on applications in high- and intermediate-pressure turbines. As part of this research a concern has arisen about the possibility of high chromia evaporation rates of protective scales in the turbine. A model to calculate chromia evaporation rates is presented

Phosphine and methylphosphine production by simulated lightning - s study for the volatile phosphorus cycle and cloud formation in the earth atmosphere

Phosphine (PH3), was recently found worldwide even in the remote atmosphere (Naturwissenschaften 83 (1996a,131, Atmos. Environ. 37 (2003) 2429). It is of interest to find natural mechanisms which could produce phosphine gas and drive a volatile link of the atmospheric phosphorus cycle and the formation of phosphoric acid as possible condensation nuclei for clouds.Here we report on simulated lightning exposing sodium phosphate in a reducing medium (methane model atmosphere or organic matter) for 5 seconds to a spark induced by microwave. The gas product analyzed by gas chromatography contained phosphine (yield up to 0.6 g per kg phosphate P) and methylphosphine (CH3)PH2 (yield up to 0.02 g per kg phosphate P).We suggest a plasma-chemical formation mechanism where organic compounds or methane or secondary hydrogen thereof reduce phosphate to phosphine of which a small fraction can subsequently react with methyl radicals to form methylphosphine. A small yield of 6 mg phosphine per kg phosphate P was even obtained in methane free medium, by simple plasmatic recombination of inorganic phosphorus. We believe that methane and hydrogen are useful model substances of pyrolytic gases with high reducing power which may form if lightning strikes biomass, soil and aerosol.These results suggest evidence that phosphine and methylphosphine (detectable in the field by intense garlic odor) are produced when atmospheric lightning strikes the ground or aerosol which is containing oxidized forms of phosphorus and chemical reductants.Additional reviewed data show that laboratory lightning was able to reduce a much more significant portion of phosphate to phosphite (up to 25% yield), methylphosphonic acid (up to 8.5% yield) and traces of hyposphosphite in a matter of seconds

Correlation between equatorial Kelvin waves and the occurrence of extremely thin ice clouds at the tropical tropopause

A number of field-campaigns in the tropics have been conducted in recent years with two different LIDAR systems at Paramaribo (5.8° N, 55.2° W), Suriname. The lidars detect particles in the atmosphere with high vertical and temporal resolution and are capable of detecting extremely thin cloud layers which frequently occur in the tropical tropopause layer (TTL). Radiosonde as well as operational ECMWF analysis showed that equatorial Kelvin waves propagated in the TTL and greatly modulated its temperature structure. We found a clear correlation between the temperature anomalies introduced by these waves and the occurrence of thin cirrus in the TTL. In particular we found that extremely thin ice clouds form regularly where cold anomalies shift the tropopause to high altitudes. These findings suggest an influence of Kelvin wave activity on the dehydration in the TTL and thus on the global stratospheric water vapour concentration