Products and Mechanism of the Gas Phase Reaction of Ozone with β-Pinene

Gas phase ozonolysis of -pinene was performedin a 570 l static reactor at 730 Torr and 296 K insynthetic air and the products were analysed by acombination of gas phase FTIR spectroscopy, HPLC andIC analyses of gas phase and aerosol samples,respectively. The reaction mechanism was investigatedby adding HCHO, HCOOH and H₂O as Criegeeintermediate scavenger and cyclohexane as OH radicalscavenger. Main identified products (yields inparentheses) in the presence of cyclohexane as OHradical scavenger were HCHO (0.65 ± 0.04),nopinone (0.16 ± 0.04), 3-hydroxy-nopinone (0.15± 0.05), CO₂ (0.20 ± 0.04), CO (0.030± 0.002), HCOOH (0.020 ± 0.002), the secondaryozonide of -pinene (0.16 ± 0.05), andcis-pinic acid (0.02 ± 0.01). The decompositionof the primary ozonide was found to yieldpredominantly the excited C₉-Criegee intermediateand HCHO (0.84 ± 0.04) and to a minor extent theexcited CH₂OO intermediate and nopinone (0.16± 0.04). Roughly 40% of the excitedC₉-Criegee intermediate becomes stabilised andcould be shown to react with HCHO, HCOOH and H₂O. The atmospherically important reaction of thestabilised C₉-Criegee intermediate with H₂Owas found to result in a nopinone increase of (0.35± 0.05) and in the formation of H₂O₂(0.24 ± 0.03). Based on the observed products,the unimolecular decomposition/isomerisationchannels of the C₉-Criegee intermediate arediscussed in terms of the hydroperoxide and esterchannels. Subsequent reactions of the nopinonylradical, formed in the hydroperoxide channel, lead tomajor products like 3-hydroxy-nopinone but also tominor products like cis-pinic acid. A mechanismfor the formation of this dicarboxylic acid isproposed and its possible role in aerosol formationprocesses discussed.     

The ALOMAR Rayleigh/Mie/Raman lidar: objectives, configuration, and performance

We report on the development and current capabilities of the ALOMAR Rayleigh/Mie/Raman lidar. This instrument is one of the core instruments of the international ALOMAR facility, located near Andenes in Norway at 69°N and 16°E. The major task of the instrument is to perform advanced studies of the Arctic middle atmosphere over altitudes between about 15 to 90 km on a climatological basis. These studies address questions about the thermal structure of the Arctic middle atmosphere, the dynamical processes acting therein, and of aerosols in the form of stratospheric background aerosol, polar stratospheric clouds, noctilucent clouds, and injected aerosols of volcanic or anthropogenic origin. Furthermore, the lidar is meant to work together with other remote sensing instruments, both ground- and satellite-based, and with balloon- and rocket-borne instruments performing in situ observations. The instrument is basically a twin lidar, using two independent power lasers and two tiltable receiving telescopes. The power lasers are Nd:YAG lasers emitting at wavelengths 1064, 532, and 355 nm and producing 30 pulses per second each. The power lasers are highly stabilized in both their wavelengths and the directions of their laser beams. The laser beams are emitted into the atmosphere fully coaxial with the line-of-sight of the receiving telescopes. The latter use primary mirrors of 1.8 m diameter and are tiltable within 30° off zenith. Their fields-of-view have 180 rad angular diameter. Spectral separation, filtering, and detection of the received photons are made on an optical bench which carries, among a multitude of other optical components, three double Fabry-Perot interferometers (two for 532 and one for 355 nm) and one single Fabry-Perot interferometer (for 1064 nm). A number of separate detector channels also allow registration of photons which are produced by rotational-vibrational and rotational Raman scatter on N₂ and N₂+O₂ molecules, respectively. Currently, up to 36 detector channels simultaneously record the photons collected by the telescopes. The internal and external instrument operations are automated so that this very complex instrument can be operated by a single engineer. Currently the lidar is heavily used for measurements of temperature profiles, of cloud particle properties such as their altitude, particle densities and size distributions, and of stratospheric winds. Due to its very effective spectral and spatial filtering, the lidar has unique capabilities to work in full sunlight. Under these conditions it can measure temperatures up to 65 km altitude and determine particle size distributions of overhead noctilucent clouds. Due to its very high mechanical and optical stability, it can also employed efficiently under marginal weather conditions when data on the middle atmosphere can be collected only through small breaks in the tropospheric cloud layers.     

The role of sodium bicarbonate in the nucleation of noctilucent clouds

It is proposed that a component of meteoric smoke, sodium bicarbonate (NaHCO₃), provides particularly effective condensation nuclei for noctilucent clouds. This assertion is based on three conditions being met. The first is that NaHCO₃ is present at sufficient concentration (10⁴ cm^–3) in the upper mesosphere between 80 and 90 km. It is demonstrated that there is strong evidence for this based on recent laboratory measurements coupled with atmospheric modelling. The second condition is that the thermodynamics of NaHCO₃(H₂O)_n cluster formation allow spontaneous nucleation to occur under mesospheric conditions at temperatures below 140 K. The Gibbs free energy changes for forming clusters with n = 1 and 2 were computed from quantum calculations using hybrid density functional/Hartree-Fock (B3LYP) theory and a large basis set with added polarization and diffuse functions. The results were then extrapolated to higher n using an established dependence of the free energy on cluster size and the free energy for the sublimation of H₂O to bulk ice. A 1-dimensional model of sodium chemistry was then employed to show that spontaneous nucleation to form ice particles (n > 100) should occur between 84 and 89 km in the high-latitude summer mesosphere. The third condition is that other metallic components of meteoric smoke are less effective condensation nuclei, so that the total number of potential nuclei is small relative to the amount of available H₂O. Quantum calculations indicate that this is probably the case for major constituents such as Fe(OH)₂, FeO₃ and MgCO₃.     

Experimental determination of saltating glass particle dispersion in a turbulent boundary layer

A horizontal saltation layer of glass particles in air is investigated experimentally over a flat bed and also over a triangular ridge in a wind tunnel. Particle concentrations are measured by light scattering diffusion (LSD) and digital image processing, and velocities using particle image velocimetry (PIV). All the statistical moments of the particle concentration are determined such as mean concentration, root mean square concentration fluctuations, skewness and flatness coefficients. Over the flat bed, it is confirmed that the mean concentration decreases exponentially with height, the mean dispersion height being a significant length scale. It is shown that the concentration distribution follows quite well a lognormal distribution. Over the ridge, measurements were made at the top of the ridge and in the cavity region and are compared with measurements without the ridge. On the hill crest, particles are retarded, the saltation layer decreases in thickness and concentration is increased. Downwind of the ridge, particle flow behaves like a jet, in particular no particle return flow is observed. Copyright © 2006 John Wiley & Sons, Ltd.     

生物质燃烧颗粒物有机示踪化合物的测定和应用

使用气相色谱-质谱法对2002年7月-2003年7月的北京市大气粗、细颗粒物样品中的左旋葡聚糖等糖类化合物进行了测定。结果表明，左旋葡聚糖主要存在于细颗粒中，可以作为示踪化合物来研究生物质燃烧现象。生物质燃烧对北京市大气颗粒物有较重要的贡献。对应于12％-40％的PM2.5有机碳和10％-33％的PM10有机碳。北京市在2002年10月和11月受到明显的生物质燃烧的影响，可能由于农田秸杆焚烧和秋季落叶焚烧。2003年5月7日颗粒物样品受到直线距离约为1000km以外的内蒙古自治区呼伦贝尔市大兴安岭林区森林大火烟雾的影响。生物质燃烧事件具有突发性，可以长距离传输；生物质作为农村生物燃料的使用其燃烧排放具有经常性和持久性的特征。     

Characteristics of Aerosol Ionic Compositions in Summer 2003 at Lin''''an of Yangtze Delta Region

With the size-resolved aerosol mass and ion composition data obtained at Lin'an regional atmospheric pollution monitoring station in July 2003, the size distributions of aerosol mass and ionic components, and the correlations between major ion pairs were analyzed. The primary results indicate that in the period of in-situ measurement, the aerosols are mainly composed of fine particles. The mass of aerosols with size less than 2.1μm accounts for 66% of the total mass of all size ranges, in which about 50% of the mass is contributed by the particles with size less than 0.65μm. Similar to the size distributions of aerosol mass, the water-soluble ions are mainly concentrated in the size range of <0.65μm, accounting for about 77% of the sum of analyzed ions, and the ions within the range of <2.1μm reach 88%. The sulfate, ammonium, and potassium are the dominant ionic components in fine particles (particle size less than 2.1μm). Ion correlation analysis suggests that the sulfates in fine particles are mostly in the compounds of (NH4)2SO4, Na2SO4, and K2SO4, but for submicron particles the sulfates are mainly in the form of (NH4)2SO4.     

EFFECT OF FLOW CONDITIONS ON 3D MOVEMENT CHARACTERISTICS OF PARTICLES

1 INTRODUCTION The mechanism of particle movement in the flow is one of basic problems of sediment transport research. The conventional measurement approaches usually disturb the structure of the flow, consequently inducing errors. With the development of…     

Atmospheric Electrification in the Solar System

Atmospheric electrification is not a purely terrestrial phenomenon: all Solar System planetary atmospheres become slightly electrified by cosmic ray ionisation. There is evidence for lightning on Jupiter, Saturn, Uranus and Neptune, and it is possible on Mars, Venus and Titan. Controversy surrounds the role of atmospheric electricity in physical climate processes on Earth; here, a comparative approach is employed to review the role of electrification in the atmospheres of other planets and their moons. This paper reviews the theory, and, where available, measurements, of planetary atmospheric electricity which is taken to include ion production and ion–aerosol interactions. The conditions necessary for a planetary atmospheric electric circuit similar to Earth’s, and the likelihood of meeting these conditions in other planetary atmospheres, are briefly discussed. Atmospheric electrification could be important throughout the solar system, particularly at the outer planets which receive little solar radiation, increasing the relative significance of electrical forces. Nucleation onto atmospheric ions has been predicted to affect the evolution and lifetime of haze layers on Titan, Neptune and Triton. Atmospheric electrical processes on Titan, before the arrival of the Huygens probe, are summarised. For planets closer to Earth, heating from solar radiation dominates atmospheric circulations. However, Mars may have a global circuit analogous to the terrestrial model, but based on electrical discharges from dust storms. There is an increasing need for direct measurements of planetary atmospheric electrification, in particular on Mars, to assess the risk for future unmanned and manned missions. Theoretical understanding could be increased by cross-disciplinary work to modify and update models and parameterisations initially developed for a specific atmosphere, to make them more broadly applicable to other planetary atmospheres.     

Correlation of atmospheric visibility with chemical composition of Kaohsiung aerosols

The objective of this study was to investigate the correlation of visibility with chemical composition of Kaohsiung aerosols. Daytime visibility was observed around noon at two observation sites in metropolitan Kaohsiung, Taiwan in the years of 1999 and 2000. Both seasonal and diurnal variation patterns of visibility were observed in the region. Ambient aerosols were sampled and analyzed for 11 constituents, including water-soluble ionic species (Cl⁻, NO₃⁻, SO₄⁻², NH₄⁺, K⁺, Na⁺, Ca⁺², and Mg⁺²) and carbonaceous contents (OC, EC, and TC), to characterize the chemical composition of Kaohsiung aerosols. Furthermore, a stepwise multiple linear regression model was developed to elucidate the influence of aerosol species on visibility impairments. The results showed that sulfate was the dominant species that affected both light scattering coefficient and visibility. On average, the percentage contributions of visibility degrading species to light scattering coefficient were 29% for sulfate, 28% for nitrate, 22% for total carbon, and 21% for PM_2.5-remainder. An empirical regression model of visibility based on sulfate, nitrate, and relative humidity was also developed. The model showed that sulfate in PM_2.5 was the most sensitive species to visibility variation, suggesting that the reduction of sulfate in PM_2.5 could effectively improve the visibility of metropolitan Kaohsiung. During the investigation period, an event of Asian dusts intruded metropolitan Kaohsiung and dramatically increased the aerosol loadings, especially in the coarse particles. However, local visual air quality did not degrade accordingly during the Asian dust event because both visibility and light scattering coefficient are affected mainly by the fine particles. The results are discussed in detail in the paper.     

Fog and rain water chemistry at Mt. Fuji: A case study during the September 2002 campaign

Measurements of fog and rain water chemistry at the summit of Mt. Fuji, the highest peak in Japan, as well as at Tarobo, the ESE slope of Mt. Fuji in September 2002. The pH of fog and rain water sampled at Mt. Fuji varied over a range of 4.0–6.8. Acidic fogs (pH < 5.0) were observed at the summit when the air mass came from the industrial regions on the Asian continent. The ratio of [SO₄²⁻]/[NO₃⁻] in the fog water was lower at Tarobo than at the summit. High concentrations of Na⁺ and Cl⁻ were determined in the rain water sampled at the summit, possibly because of the long-range transport of sea-salt particles raised by a typhoon through the middle troposphere. The vertical transport of sea-salt particles would influence the cloud microphysical properties in the middle troposphere. Significant loss of Mg²⁺ was seen in the rain water at the summit. The concentrations of peroxides in the fog and rain water were relatively large (10–105 μM). The potential capacity for SO₂ oxidation seems to be strong from summer to early autumn at Mt. Fuji. The fog water peroxide concentrations displayed diurnal variability. The peroxide concentrations in the nighttime were significantly higher than those in the daytime.