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Detailed PSC formation in a two-dimensional chemical transport model of the stratosphere

A new two-dimensional zonal model of the stratosphere, based on a formulation in an isentropic framework, with complete chemistry has been coupled with a high resolution detailed microphysical model for polar stratospheric clouds (PSCs). The 2D model chemistry includes all presently known heterogeneous processes on sulfate aerosols and PSCs. The coupling of these two models, with inherently different time scales, is discussed. It is demonstrated that in order to obtain a realistic interrelationship between NOy and N2O an accurate simulation of the sedimentation by PSC particles is necessary. A good agreement of model PSC presence and observations is found for the Antarctic polar winter without the need to impose additional artificial temperature variations in the model. The calculated occurrence of polar stratospheric clouds and resulting heterogeneous chemistry during the Antarctic winter are discussed. Sensitivity of the polar stratospheric chemical composition and cloud formation for different perturbations is investigated by studying the effects of transport across the polar vortex boundary and heterogeneous processing by an enhanced sulfate aerosol load. The importance of including sedimentation for all cases is also discussed.
A numerical study of the transport and diffusion of coastal pollutants during the breeze cycle in the Island of Mallorca

An Eulerian study of the distribution over the Island of Mallorca of a non-reactive pollutant (SO2) emitted from an electric power plant operating at present on the north coast is performed using a meso-β numerical model, paying particular attention to the diffusive physical mechanisms. The study is applied to the conditions of sea-land breeze development. This is a local circulation that dominates the flow during the summer and favours transporting pollutants from the coast toward the centre of the island. Results indicate that values of the ground-level concentration higher than 5 μ g/m3 are restricted over a limited and mountainous region during the whole diurnal cycle. However, when the simulation is carried out with the inclusion of a twin electric plant which may be built on the south coast, the affected area becomes larger, especially early in the morning, when air over the island is sinking as a consequence of the land breeze development. The inclusion of dry deposition in the simulations does not produce important changes in the spatial and temporal evolution of the ground-level concentration.
Seasonal variations in the occurrence of geomagnetic storms

Seasonal variations in the onset of magnetic storms are investigated. For the purposes of this study storms have been defined as events in which Dst falls below –50 nT for at least four consecutive hours. The storms have been classified as either storm sudden commencements (SSCs; storms initiated by a sudden commencement) or as storm gradual commencements (SGCs; all other storms). It is found that the semi-annual variation of magnetic activity is reflected in the occurrence statistics of SGC events only, indicative that the solar wind origin is different for SSCs and SGCs. It is suggested that the heliospheric latitude model of seasonal magnetic activity is relatively ineffective in modulating the previously observed seasonal variations in the occurrence of magnetic storms.
Effects of neutral wind on the electron temperature at a height of 600 km in the low latitude region

Electron temperature observed by the Hinotori satellite with the low inclination at the height of ~600 km was studied in terms of local time, season, latitude, magnetic declination and solar flux intensity during a 16-month period from 1981 to 1982. The electron temperatures show steep rise in the early morning (well known as morning overshoot), decrease after that and again increase at ~18 hours (hereafter named as evening overshoot). Generally the morning overshoot becomes more enhanced in the winter hemisphere and for higher solar fluxes. The evening overshoot becomes more pronounced in the mid-latitude in all seasons and more enhanced in the winter hemisphere in the same way as the morning overshoot. A difference is seen between 210°–285° and 285°–360° longitudes where magnetic declination is different. The longitudinal dependence of electron temperature indicates that the neutral wind also contributes to the thermal structure in the low latitude ionosphere.
Observations of gravity waves in the upper and lower stratosphere by lidar and ozonesondes

Lidar observations of Rayleigh backscatter and temperature profiles measured by ozonesondes have been used to investigate gravity waves in the upper and lower stratosphere, respectively, over Aberystwyth (52.4°N, 4.1°W). Both data sets have been used to investigate the vertical wavenumber spectrum of the wave field at high wavenumbers. Similar analytic techniques applied to each data set enable direct comparison of the spectra. The possibility of laminar structures generated by differential advection contaminating gravity-wave fields deduced from temperature and/or density measurement is discussed and the behaviour of the wave-field mean potential energy reveals a seasonal cycle throughout the stratosphere with a late winter maximum and a summer minimum.
Nonlinear interaction between acoustic gravity waves

The resonant interaction between three acoustic gravity waves is considered. We improve on the results of previous authors and write the new coupling coefficients in a symmetric form. Particular attention is paid to the low-frequency limit.
Seasonal change in CO2 and H2O exchange between grassland and atmosphere

The seasonal change in CO2 flux over an artificial grassland was analyzed from the ecological and meteorological point of view. This grassland contains C3 and C4 plants; the three dominant species belonging to the Gramineae; Festuca elatior (C3) dominated in early spring, and Imperata cylindrica (C4) and Andropogon virginicus (C4) grew during early summer and became dominant in mid-summer. CO2 flux was measured by the gradient method, and the routinely observed data for the surface-heat budget were used to analyze the CO2 and H2O exchange between the grassland and atmosphere. From August to October in 1993, CO2 flux was reduced to around half under the same solar-radiation conditions, while H2O flux decreased 20% during the same period. The monthly values of water use efficiency, i.e., ratio of CO2 flux to H2O flux decreased from 5.8 to 3.3 mg CO2/g H2O from August to October, the Bowen ratio increased from 0.20 to 0.30, and the ratio of the bulk latent heat transfer coefficient CE to the sensible heat transfer coefficient CH was maintained around 0.40-0.50. The increase in the Bowen ratio was explained by the decrease in air temperature from 22.3 °C in August to 16.6 °C in October without considering biological effects such as stomatal closure on the individual leaves. The nearly constant CE/CH ratios suggested that the contribution ratio of canopy resistance to aerodynamic resistance did not change markedly, although the meteorological conditions changed seasonally. The decrease in the water use efficiency, however, suggested that the photosynthetic rate decreased for individual leaves from August to October under the same radiation conditions. Diurnal variations of CO2 exchange were simulated by the multi-layer canopy model taking into account the differences in the stomatal conductance and photosynthetic pathway between C3 and C4 plants. The results suggested that C4 plants played a major role in the CO2 exchange in August, the contribution of C4 plants decreased in September, and daily variations of CO2 exchange were mainly due to C3 plants in October. The results also suggested that the decrease in the net canopy CO2 exchange from August to October was induced partly by the decrease of net photosynthesis on the individual leaves in both C4 and C3 plants, which could be due to aging of the leaves.
Isotopic composition for source identification of mercury in atmospheric fine particles

The usefulness of mercury (Hg) isotopes for tracing the sources and pathways of Hg (and its vectors) in atmospheric fine particles (PM2.5) is uncertain. Here, we measured Hg isotopic compositions in 30 potential source materials and 23 PM2.5 samples collected in four seasons from the megacity Beijing (China) and combined the seasonal variation in both mass-dependent fractionation (represented by the ratio 202Hg ∕ 198Hg, δ202Hg) and mass-independent fractionation of isotopes with odd and even mass numbers (represented by Δ199Hg and Δ200Hg, respectively) with geochemical parameters and meteorological data to identify the sources of PM2.5-Hg and possible atmospheric particulate Hg transformation. All PM2.5 samples were highly enriched in Hg and other heavy metals and displayed wide ranges of both δ202Hg (−2.18 to 0.51 ‰) and Δ199Hg (−0.53 to 0.57 ‰), as well as small positive Δ200Hg (0.02 to 0.17 ‰). The results indicated that the seasonal variation in Hg isotopic composition (and elemental concentrations) was likely derived from variable contributions from anthropogenic sources, with continuous input due to industrial activities (e.g., smelting, cement production and coal combustion) in all seasons, whereas coal combustion dominated in winter and biomass burning mainly found in autumn. The more positive Δ199Hg of PM2.5-Hg in spring and early summer was likely derived from long-range-transported Hg that had undergone extensive photochemical reduction. The study demonstrated that Hg isotopes may be potentially used for tracing the sources of particulate Hg and its vectors in the atmosphere.
Heterogeneous photochemistry of imidazole-2-carboxaldehyde: HO2 radical formation and aerosol growth

The multiphase chemistry of glyoxal is a source of secondary organic aerosol (SOA), including its light-absorbing product imidazole-2-carboxaldehyde (IC). IC is a photosensitizer that can contribute to additional aerosol ageing and growth when its excited triplet state oxidizes hydrocarbons (reactive uptake) via H-transfer chemistry. We have conducted a series of photochemical coated-wall flow tube (CWFT) experiments using films of IC and citric acid (CA), an organic proxy and H donor in the condensed phase. The formation rate of gas-phase HO2 radicals (PHO2) was measured indirectly by converting gas-phase NO into NO2. We report on experiments that relied on measurements of NO2 formation, NO loss and HONO formation. PHO2 was found to be a linear function of (1) the [IC]  ×  [CA] concentration product and (2) the photon actinic flux. Additionally, (3) a more complex function of relative humidity (25 %  <  RH  <  63 %) and of (4) the O2 ∕ N2 ratio (15 %  <  O2 ∕ N2  <  56 %) was observed, most likely indicating competing effects of dilution, HO2 mobility and losses in the film. The maximum PHO2 was observed at 25–55 % RH and at ambient O2 ∕ N2. The HO2 radicals form in the condensed phase when excited IC triplet states are reduced by H transfer from a donor, CA in our system, and subsequently react with O2 to regenerate IC, leading to a catalytic cycle. OH does not appear to be formed as a primary product but is produced from the reaction of NO with HO2 in the gas phase. Further, seed aerosols containing IC and ammonium sulfate were exposed to gas-phase limonene and NOx in aerosol flow tube experiments, confirming significant PHO2 from aerosol surfaces. Our results indicate a potentially relevant contribution of triplet state photochemistry for gas-phase HO2 production, aerosol growth and ageing in the atmosphere.
Heterogeneous kinetics of H2O, HNO3 and HCl on HNO3 hydrates (α-NAT, β-NAT, NAD) in the range 175–200 K

Experiments on the title compounds have been performed using a multidiagnostic stirred-flow reactor (SFR) in which the gas phase as well as the condensed phase has been simultaneously investigated under stratospheric temperatures in the range 175–200 K. Wall interactions of the title compounds have been taken into account using Langmuir adsorption isotherms in order to close the mass balance between deposited and desorbed (recovered) compounds. Thin solid films at 1 µm typical thickness have been used as a proxy for atmospheric ice particles and have been deposited on a Si window of the cryostat, with the optical element being the only cold point in the deposition chamber. Fourier transform infrared (FTIR) absorption spectroscopy in transmission as well as partial and total pressure measurement using residual gas mass spectrometry (MS) and sensitive pressure gauges have been employed in order to monitor growth and evaporation processes as a function of temperature using both pulsed and continuous gas admission and monitoring under SFR conditions. Thin solid H2O ice films were used as the starting point throughout, with the initial spontaneous formation of α-NAT (nitric acid trihydrate) followed by the gradual transformation of α- to β-NAT at T > 185 K. Nitric acid dihydrate (NAD) was spontaneously formed at somewhat larger partial pressures of HNO3 deposited on pure H2O ice. In contrast to published reports, the formation of α-NAT proceeded without prior formation of an amorphous HNO3 ∕ H2O layer and always resulted in β-NAT. For α- and β-NAT, the temperature-dependent accommodation coefficient α(H2O) and α(HNO3), the evaporation flux Jev(H2O) and Jev(HNO3) and the resulting saturation vapor pressure Peq(H2O) and Peq(HNO3) were measured and compared to binary phase diagrams of HNO3 ∕ H2O in order to afford a thermochemical check of the kinetic parameters. The resulting kinetic and thermodynamic parameters of activation energies for evaporation (Eev) and standard heats of evaporation ΔHev0 of H2O and HNO3 for α- and β-NAT, respectively, led to an estimate for the relative standard enthalpy difference between α- and β-NAT of −6.0 ± 20 kJ mol−1 in favor of β-NAT, as expected, despite a significantly larger value of Eev for HNO3 in α-NAT. This in turn implies a substantial activation energy for HNO3 accommodation in α- compared to β-NAT where Eacc(HNO3) is essentially zero. The kinetic (α(HCl), Jev(HCl)) and thermodynamic (Peq(HCl)) parameters of HCl-doped α- and β-NAT have been determined under the assumption that HCl adsorption did not significantly affect α(H2O) and α(HNO3) as well as the evaporation flux Jev(H2O). Jev(HCl) and Peq(HCl) on both α- and β-NAT are larger than the corresponding values for HNO3 across the investigated temperature range but significantly smaller than the values for pure H2O ice at T < 200 K.