A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

International audienceA new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl sulfide, NOx, and O3 in the MBL

Low Temperature Ground States and Field-Induced Phase Transitions in α-(BEDT-TTF)_2-MHg(XCN)_4 (M=K, Tl, Rb, NH_4; X=S, Se) (Research in High Magnetic Fields)

There have been observed in a series of isostructural α-(BEDT-TTF)_2MHg(XCN)_4\u27s a variety of ground states such as spin-density-wave metallic state (M=K, Tl, Rb; X=S), superconducting one (M=NH_4; X=S), and simple metallic one (M=K, Tl; X=Se). Current status of these researches is outlined, including the magnetic field effects on the first group which appear in high fields more than 20T at low temperatures

The role of snow in the thickening processes of lake ice at Lake Abashiri, Hokkaido, Japan

To clarify the properties of lake ice at mid-latitudes subject to moderate air temperature, heavy snow and abundant solar radiation even in winter, we conducted field observations at Lake Abashiri in Japan for three winters and developed a one-dimensional (1-D) thermo-dynamical ice growth model. Using this model with meteorological data-sets, we examined the role of snow in the ice thickening process, as well as the Lake Abashiri ice phenology (including the interannual trend) for the past 55 years to compare with high latitude lakes. The ice was composed of two distinct layers: a snow ice (SI) layer and a congelation ice layer. The SI layer occupied a much greater fraction of total ice thickness than that at high latitude lakes. In-situ observations served to demonstrate the validity of the model. Freeze-up and break-up dates supplied by satellite imagery enabled further model validation prior to the availability of field data (2000/01–2015/16). Based on both observations and numerical experiments, it was found that one important role of snow is to moderate the variability of ice thickness caused by changes in meteorological conditions. Furthermore, ice thickness is more sensitive to snow depth than air temperature. When applied to an extended 55-year period (1961/62–2015/16) for which local meteorological observations are available, the mean dates of freeze-up and break-up, ice cover duration and ice thickness in February were estimated to be 12 December (no significant trend), 17 April (−1.7 d/decade), 127 d (−2.4 d/decade) and 43 cm (−1.4 cm/decade). For this long-term period, while snow still played an important role in ice growth, the surface air temperature warming trend was found to be a strong factor influencing ice growth, as reported for the high latitude lakes