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Wavelength dependence of isotope fractionation in N2O photolysis

In previous reports on isotopic fractionation in the ultraviolet photolysis of nitrous oxide (N2O) only enrichments of heavy isotopes in the remaining N2O fraction have been found. However, most direct photolysis experiments have been performed at wavelengths far from the absorption maximum at 182 nm. Here we present high-precision measurements of the 15N and 18O fractionation constants (ε) in photolysis at 185 nm. Small, but statistically robust depletions of heavy isotopes for the terminal atoms in the linear N2O molecule are found. This means that the absorption cross sections σ(15N 14N 16O) and σ(14N218O) are larger than σ(14N216O) at this specific wavelength. In contrast, the central N atom becomes enriched in 15N. The corresponding fractionation constants (±1 standard deviation) are 15ε1 = σ(15N 14N 16O)/σ(14N2 16O) - 1 = (3.7±0.2) %o 18ε = σ(14N218O)/σ(14N216O) - 1 = (4.5±0.2) %o  and 15ε2 = σ(14N 15N 16O)/σ(14N216O) - 1 = (-18.6±0.5) %o To our knowledge, this is the first documented case of such a heavy isotope depletion in the photolysis of N2O which supports theoretical models and pioneering vacuum ultraviolet spectroscopic measurements of 15N substituted N2O species that predict fluctuations of ε around zero in this spectral region (Selwyn and Johnston, 1981). Such a variability in isotopic fractionation could have consequences for atmospheric models of N2O isotopes since actinic flux varies also strongly over narrow wavelength regions between 175 and 200 nm due to the Schumann-Runge bands of oxygen. However, the spacing between maxima and minima of the fractionation constants and of the actinic flux differ by two orders of magnitude in the wavelength domain. The wavelength dependence of fractionation constants in N2O photolysis can thus be approximated by a linear fit with negligible consequences on the actual value of the spectrally averaged fractionation constant. In order to establish this linear fit, additional measurements at wavelengths other than 185 nm were made using broadband light sources, namely D2, Hg/Xe and Sb lamps. The latter lamp was used in conjunction with various interference filters to shift the peak photolysis rate to longer wavelengths. From these experiments and existing data in the literature, a comprehensive picture of the wavelength dependence of N2O photolysis near room-temperature is created.
Emission of ions and charged soot particles by aircraft engines

In this article, a model which examines the formation and evolution of chemiions in an aircraft engine is proposed. This model which includes chemiionisation, electron thermo-emission, electron attachment to soot particles and to neutral molecules, electron-ion and ion-ion recombination, ion-soot interaction, allows the determination of the ion concentration at the exit of the combustor and at the nozzle exit of the engine. It also allows the determination of the charge of the soot particles. For the engine considered, the upper limit for the ion emission index EIi is of the order of (2-5) x1016 ions/kg-fuel if ion-soot interactions are ignored and the introduction of ion-soot interactions lead about to a 50% reduction. The results also show that most of the soot particles are either positively or negatively charged, the remaining neutral particles representing approximately 20% of the total particles. A comparison of the model results with the available ground-based experimental data obtained on the ATTAS research aircraft engines during the SULFUR experiments (Schumann, 2002) shows an excellent agreement.
Fluxes of nitrates between snow surfaces and the atmosphere in the European high Arctic

Measurements of atmospheric and snow mixing ratios of nitrates and nitrites and their fluxes above the snow surface were made during two intensive campaigns during spring time 2001 at Ny-Ålesund, Svalbard as part of the EU project  "`The NItrogen Cycle and Effects on the oxidation of atmospheric trace species at high latitudes" (NICE). At this coastal site close to the unseasonably unfrozen fjord, of the measured nitrogen species, only HNO3 showed a significant flux on to the snow surface; a mean deposition of -8.7 nmol h-1 m-2 was observed in late April / early May 2001. These fluxes may be due to the reaction of HNO3 with sea salt, and especially NaCl, or may be simply uptake of HNO3 by ice, which is alkaline because of the sea salt in our marine environment. During snowfall periods dry deposition of HNO3 may contribute up to 10% of the N budget in the snow; however, the main source for N is wet deposition in falling snow. The surface snow at Ny-Ålesund showed very complex stratigraphy; the NO3- mixing ratio in snow varied between 65 and 520 ng g-1, the total NO3- content of the snowpack was on the order of 2700 ng cm-2. In comparison the atmospheric boundary layer column showed a NO3- content of only 8 ng cm-2. The limited exchange, however, between the snow and the atmosphere was attributed to low mobility of NO3- in the observed snow. Contrary to other Arctic sites (i.e. Alert, Nunavut or Summit, Greenland) deposition of sea salt and crustal aerosols in this marine environment made the surface snow alkaline; snow NO3- was associated with heavier cations and was not readily available for physical exchange or photochemical reactions.
The impact of mid-latitude intrusions into the polar vortex on ozone loss estimates

Current stratospheric chemical model simulations underestimate substantially the large ozone loss rates that are derived for the Arctic from ozone sondes for January of some years. Until now, no explanation for this discrepancy has been found. Here, we examine the influence of intrusions of mid-latitude air into the polar vortex on these ozone loss estimates. This study focuses on the winter 1991/92, because during this winter the discrepancy between simulated and experimentally derived ozone loss rates is reported to be the largest. Also during the considered period the vortex was disturbed by a strong warming event with large-scale intrusions of mid-latitude air into the polar vortex, which is quite unusual for this time of the year. The study is based on simulations performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS). Two methods for determination the ozone loss are investigated, the so-called vortex average approach and the Match method. The simulations for January 1992 show that the intrusions induce a reduction of vortex average ozone mixing ratio corresponding to a systematic offset of the ozone loss rate of about 12 ppb per day. This should be corrected for in the vortex average method. The simulations further suggest, that these intrusions do not cause a significant bias for the Match method due to effective quality control measures in the Match technique.
Twilight tropospheric and stratospheric photodissociation rates derived from balloon borne radiation measurements

A new ligthweight multichannel moderate bandwidth filter instrument designed to be flown on balloons, is described. The instrument measures the radiation field within the short UV (center wavelength at 312 nm) and long UV (center wavelength at 340 nm). The angular and spectral characteristics of the instrument are discussed and the calibration procedure outlined. Measurements made during a stratospheric balloon flight at twilight conditions from Gap-Tallard, France, are presented and compared with state-of-the-art radiative transfer model simulations. The model simulations and the measurements agree within ±10% (±20%) for solar zenith angles smaller than 93° (90°) for the 340 (312) nm channel. Based on the model simulations of the measured radiation, actinic flux spectra are reconstructed. These are used to calculate various photodissociation rates.
The Hohenpeissenberg aerosol formation experiment (HAFEX): a long-term study including size-resolved aerosol, H2SO4, OH, and monoterpenes measurements

Ambient aerosol size distributions (>3 nm) and OH, H2SO4, and terpene concentrations were measured from April 1998 to August 2000 at a rural continental site in southern Germany. New particle formation (NPF) events were detected on 18% of all days, typically during midday hours under sunny and dry conditions. The number of newly formed particles correlated significantly with solar irradiance and ambient levels of H2SO4. A pronounced anti-correlatation of NPF events with the pre-existing particle surface area was identified in the cold season, often associated with the advection of dry and relatively clean air masses from southerly directions (Alps). Estimates of the particle formation rate based on observations were around 1 cm-3 s-1, being in agreement with the predictions of ternary homogeneous H2SO4-NH3-H2O nucleation within a few orders of magnitude. The experimentally determined nucleation mode particle growth rates were on average 2.6 nm h-1, with a fraction of 0.7 nm h-1 being attributed to the co-condensation of H2SO4-H2O-NH3. The magnitude of nucleation mode particle growth was neither significantly correlated to H2SO4, nor to the observed particle formation rate. Turn-over rate calculations of measured monoterpenes and aromatic hydrocarbons suggest that especially the oxidation products of monoterpenes have the capacity to contribute to the growth of nucleation mode particles. Although a large number of precursor gases, aerosol and meteorological parameters were measured, the ultimate key factors controlling the occurence of NPF events could not be identified.
Factors controlling Arctic denitrification in cold winters of the 1990s

Denitrification of the Arctic winter stratosphere has been calculated using a 3-D microphysical model for the winters 1994/95, 1995/96, 1996/97 and 1999/2000. Denitrification is assumed to occur through the sedimentation of low number concentrations of large nitric acid trihydrate (NAT) particles (as inferred by e.g. Fahey et al., 2001). We examine whether the meteorological conditions that allowed particles to grow to the very large sizes observed in 1999/2000 also occurred in the other cold winters. The results show that winter 1999/2000 had conditions that were optimum for denitrification by large NAT particles, which are a deep concentric NAT area and vortex. Under these conditions, NAT particles can circulate in the NAT-supersaturated air for several days, reaching several micrometres in radius and leading to a high downward flux of nitric acid. The other winters had shorter periods with optimum conditions for denitrification. However, we find that NAT particles could have grown to large sizes in all of these winters and could have caused significant denitrification. We define the quantity "closed-flow area' (the fraction of the NAT area in which air parcel trajectories can form closed loops) and show that it is a very useful indicator of possible denitrification. We find that even with a constant NAT nucleation rate throughout the NAT area, the average NAT number concentration and size can vary by up to a factor of 10 in response to this meteorological quantity. These changes in particle properties account for a high degree of variability in denitrification between the different winters. This large meteorologically induced variability in denitrification rate needs to be compared with that which could arise from a variable nucleation rate of NAT particles, which remains an uncertain quantity in models. Sensitivity studies show that although denitrification was likely approaching asymptotic minimum values throughout much of the 1999/2000 vortex, decreases in the volume-averaged nucleation rate would have substantially reduced the denitrification.
Intercontinental transport of nitrogen oxide pollution plumes

We describe the first satellite observation of intercontinental transport of nitrogen oxides emitted by power plants, verified by simulations with a particle tracer model. The analysis of such episodes shows that anthropogenic NOx plumes may influence the atmospheric chemistry thousands of kilometers away from its origin, as well as the ocean they traverse due to nitrogen fertilization. This kind of monitoring became possible by applying an improved algorithm to extract the tropospheric fraction of NO2 from the spectral data coming from the GOME instrument. As an example we show the observation of NO2 in the time period 4--14 May, 1998, from the South African Plateau to Australia which was possible due to favourable weather conditions during that time period which availed the satellite measurement. This episode was also simulated with the Lagrangian particle dispersion model FLEXPART which uses NOx emissions taken from an inventory for industrial emissions in South Africa and is driven with analyses from the European Centre for Medium-Range Weather Forecasts. Additionally lightning emissions were taken into account by utilizing Lightning Imaging Sensor data. Lightning was found to contribute probably not more than 25% of the resulting concentrations. Both, the measured and simulated emission plume show matching patterns while traversing the Indian Ocean to Australia and show great resemblance to the aerosol and CO2 transport observed by Piketh et al. (2000).
Aircraft measurements of nitrogen oxides, ozone, and carbon monoxide during MINOS 2001: distributions and correlation analyses

We present mean altitude profiles of NOx, NOy, O3, and CO as measured by the DLR Falcon aircraft during the MINOS 2001 campaign over the Mediterranean in August 2001 and compare the data with results from other aircraft campaigns, namely the SIL 1996 (North Atlantic flight corridor), the POLINAT-2 (North Atlantic flight corridor), and the EXPORT 2000 (central Europe) campaigns. The MINOS NOy, O3, and CO mixing ratios in the free troposphere, especially between 4–8 km, are very similar to those measured during the EXPORT 2000 campaign. However, compared to the other campaigns the MINOS O3 and CO were significantly higher in the boundary layer, by about 20 ppbV and 50 ppbV, respectively. In the second part of the paper the D[O3]/D[NOy], D[O3]/D[CO], D[CO]/D[NOy], and D[NOx]/D[NOy] trace gas correlations were calculated for the MINOS 2001 campaign. It was found that, within the scatter of the data, the overall average altitude profiles of the correlations compared well with data from a literature survey. The analysis of the mean vertical correlation profiles as measured during MINOS 2001 does therefore not single out special meteorological conditions and air mass origins over the Mediterranean in summer but reflects a more general condition of the free troposphere in the northern hemisphere. Correlation analyses for single flights at different altitudes, however, unambiguously identify air masses influenced by the stratosphere, whereas pollution plumes could only be identified with the help of back trajectories.
On the use of mass-conserving wind fields in chemistry-transport models

A new method has been developed that provides mass-conserving wind fields for global chemistry-transport models. In previous global Eulerian modeling studies a mass-imbalance was found between the model mass transport and the surface pressure tendencies. Several methods have been suggested to correct for this imbalance, but so far no satisfactory solution has been found. Our new method solves these problems by using the wind fields in a spherical harmonical form (divergence and vorticity) by mimicing the physics of the weather forecast model as closely as possible. A 3-D chemistry-transport model was used to show that the calculated ozone fields with the new processing method agree remarkably better with ozone observations in the upper troposphere and lower stratosphere. In addition, the calculated age of air in the lower stratosphere show better agreement with observations, although the air remains still too young in the extra-tropical stratosphere.