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

Observation of strong electron dephasing in disordered Cu93_{93}Ge4_4Au3_3 thin films

We report the observation of strong electron dephasing in a series of disordered Cu$_{93}$Ge$_4$Au$_3$ thin films. A very short electron dephasing time possessing very weak temperature dependence around 6 K, followed by an upturn with further decrease in temperature below 4 K, is found. The upturn is progressively more pronounced in more disordered samples. Moreover, a ln$T$ dependent, but high-magnetic-field-insensitive, resistance rise persisting from above 10 K down to 30 mK is observed in the films. These results suggest a nonmagnetic dephasing process which is stronger than any known mechanism and may originate from the coupling of conduction electrons to dynamic defects.Comment: to appear in Phys. Rev. Let

Chemical transport model ozone simulations for spring 2001 over the western Pacific:comparisons with TRACE-P lidar, ozonesondes, and Total Ozone Mapping Spectrometer columns

Two closely related chemical transport models (CTMs) employing the same high-resolution meteorological data (similar to180 km x similar to180 km x similar to600 m) from the European Centre for Medium-Range Weather Forecasts are used to simulate the ozone total column and tropospheric distribution over the western Pacific region that was explored by the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) measurement campaign in February-April 2001. We make extensive comparisons with ozone measurements from the lidar instrument on the NASA DC-8, with ozonesondes taken during the period around the Pacific Rim, and with TOMS total column ozone. These demonstrate that within the uncertainties of the meteorological data and the constraints of model resolution, the two CTMs (FRSGC/UCI and Oslo CTM2) can simulate the observed tropospheric ozone and do particularly well when realistic stratospheric ozone photochemistry is included. The greatest differences between the models and observations occur in the polluted boundary layer, where problems related to the simplified chemical mechanism and inadequate horizontal resolution are likely to have caused the net overestimation of about 10 ppb mole fraction. In the upper troposphere, the large variability driven by stratospheric intrusions makes agreement very sensitive to the timing of meteorological features

Precise measurement of HFS of positronium

The ground state hyperfine splitting in positronium, $\Delta _{\mathrm{HFS}}$, is sensitive to high order corrections of QED. A new calculation up to $O(\alpha ^3)$ has revealed a $3.9 \sigma$ discrepancy between the QED prediction and the experimental results. This discrepancy might either be due to systematic problems in the previous experiments or to contributions beyond the Standard Model. We propose an experiment to measure $\Delta_{\mathrm{HFS}}$ employing new methods designed to remedy the systematic errors which may have affected the previous experiments. Our experiment will provide an independent check of the discrepancy. The measurement is in progress and a preliminary result of $\Delta_{\mathrm{HFS}} = 203.399 \pm 0.029 \mathrm{GHz} (143 \mathrm{ppm})$ has been obtained. A measurement with a precision of O(1) ppm is expected within a few years.Comment: 5 pages, 6 figures, contributed to POSMOL 2009, will be published in J. Phys.: Conf. Serie

Distributed specific sediment yield estimations in Japan attributed to extreme-rainfall-induced slope failures under a changing climate

The objective of this study was to estimate the potential sediment yield distribution in Japan attributed to extreme-rainfall-induced slope failures in the future. For this purpose, a regression relationship between the slope failure probability and the subsequent sediment yield was developed by using sediment yield observations from 59 dams throughout Japan. The slope failure probability accounts for the effects of topography (as relief energy), geology and hydro-climate variations (hydraulic gradient changes due to extreme rainfall variations) and determines the potential slope failure occurrence with a 1-km resolution. The applicability of the developed relationship was then validated by comparing the simulated and observed sediment yields in another 43 dams. To incorporate the effects of a changing climate, extreme rainfall variations were estimated by using two climate change scenarios (the MRI-RCM20 Ver.2 model A2 scenario and the MIROC A1B scenario) for the future and by accounting for the slope failure probability through the effect of extreme rainfall on the hydraulic gradient. Finally, the developed slope failure hazard-sediment yield relationship was employed to estimate the potential sediment yield distribution under a changing climate in Japan. <br><br> Time series analyses of annual sediment yields covering 15–20 years in 59 dams reveal that extreme sedimentation events have a high probability of occurring on average every 5–7 years. Therefore, the extreme-rainfall-induced slope failure probability with a five-year return period has a statistically robust relationship with specific sediment yield observations (with <i>r</i><sup>2</sup> = 0.65). The verification demonstrated that the model is effective for use in simulating specific sediment yields with <i>r</i><sup>2</sup> = 0.74. The results of the GCM scenarios suggest that the sediment yield issue will be critical in Japan in the future. When the spatially averaged sediment yield for all of Japan is considered, both scenarios produced an approximately 17–18% increase around the first half of the 21st century as compared to the present climate. For the second half of the century, the MIROC and MRI-RCM20 scenarios predict increased sediment yields of 22% and 14%, respectively, as compared to present climate estimations. On a regional scale, both scenarios identified several common areas prone to increased sediment yields in the future. Substantially higher specific sediment yield changes (over 1000 m<sup>3</sup>/km<sup>2</sup>/year) were estimated for the Hokuriku, Kinki and Shikoku regions. Out of 105 river basins in Japan, 96 will have an increasing trend of sediment yield under a changing climate, according to the predictions. Among them, five river basins will experience an increase of more than 90% of the present sediment yield in the future. This study is therefore expected to guide decision-makers in identifying the basins that are prone to sedimentation hazard under a changing climate in order to prepare and implement appropriate mitigation measures to cope with the impacts

Performance of MAX-DOAS measurements of aerosols at Tsukuba, Japan: a comparison with lidar and sky radiometer measurements

International audienceGround-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements were performed at Tsukuba, Japan (36.1° N, 140.1° E), in November?December 2006. The measured spectra of scattered sunlight are analyzed by DOAS and optimal estimation methods to retrieve the aerosol optical depth (?) and the vertical profile of the aerosol extinction coefficient (?) at 476 nm in the lower troposphere. We characterize these retrieved quantities through comparisons with coincident lidar and sky radiometer measurements. The retrieved ? values for layers of 0?1 and 1?2 km agree with lidar data to within 30% and 60%, respectively, for most cases, including partly cloudy conditions. Results similar to ? at 0?1 km are obtained for the retrieved ? values, demonstrating that MAX-DOAS provides the new, unique aerosol dataset in the lower troposphere