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Measurement-based modeling of bromine chemistry in the Dead Sea boundary layer – Part 2: The influence of NO2 on bromine chemistry at mid-latitude areas

Understanding the interaction between anthropogenic air pollution and Reactive Halogen Species (RHS) activity has had only limited support from direct field measurements, due to the fact that past field measurements of RHS have been mainly performed in Polar Regions. The present paper investigates the interaction between NO2 and Reactive Bromine Species (RBS) activity by model simulations based on extensive field measurements performed in the Dead Sea area, as described in a companion paper (Tas et al., 2006). The Dead Sea is an excellent natural laboratory for this investigation since elevated mixing ratios of BrO (up to more than 150 pptv) are frequently observed, while the average levels of NO2 are around several ppb. The results of the present study show that under the chemical mechanisms that occur at the Dead Sea, higher levels of NO2 lead to higher daily average mixing ratios of BrOx. This is the result of an increase in the rate of the heterogeneous decomposition of BrONO2, which in turn causes an increase in the rate of the "Bromine Explosion" mechanism. However, above a certain threshold level of NO2 (daily average mixing ratios of 0.2 ppbv during RBS activity), the daily average mixing ratios of BrOx decrease for a further increase in the NO2 mixing ratios. This investigation shows that the influence of NO2 on BrOx production clearly reflects an enhancement of RBS activity caused by anthropogenic activity.
Effects of sea surface winds on marine aerosols characteristics and impacts on longwave radiative forcing over the Arabian Sea

Collocated measurements of spectral aerosol optical depths (AODs), total and BC mass concentrations, and number size distributions of near surface aerosols, along with sea surface winds, made onboard a scientific cruise over southeastern Arabian Sea, are used to delineate the effects of changes in the wind speed on aerosol properties and its implication on the shortwave and longwave radiative forcing. The results indicated that an increase in the sea-surface wind speed from calm to moderate (<1 to 8 m s−1) values results in a selective increase of the particle concentrations in the size range 0.5 to 5 μm, leading to significant changes in the size distribution, increase in the mass concentration, decrease in the BC mass fraction, a remarkable increase in AODs in the near infrared and a flattening of the AOD spectrum. The consequent increase in the longwave direct radiative forcing almost entirely offsets the corresponding increase in the short wave direct radiative forcing (or even overcompensates) at the top of the atmosphere; while the surface forcing is offset by about 50%.
Intercomparison of erythemal broadband radiometers calibrated by seven UV calibration facilities in Europe and the USA

A bi-lateral intercomparison of erythemal broadband radiometers was performed between seven UV calibration facilities. The calibrations provided by the instruments owners were compared relative to the characterisation and calibration performed at PMOD/WRC in Davos, Switzerland. The calibration consisted in the determination of the spectral and angular response of the radiometer, followed by an absolute calibration performed outdoors relative to a spectroradiometer which provided the absolute reference. The characterization of the detectors in the respective laboratories are in good agreement: The determinations of the angular responses have deviations below ±4% and the spectral responses agree within ±20%. A "blind" intercomparison of the erythemally weighted irradiances derived by the respective institutes and PMOD/WRC showed consistent measurements to within ±2% for the majority of institutes. One institute showed slightly larger deviation of 10%. The differences found between the different instrument calibrations are all within the combined uncertainty of the calibration.
Multiphase modeling of nitrate photochemistry in the quasi-liquid layer (QLL): implications for NOx release from the Arctic and coastal Antarctic snowpack

We utilize a multiphase model, CON-AIR (Condensed Phase to Air Transfer Model), to show that the photochemistry of nitrate (NO3−) in and on ice and snow surfaces, specifically the quasi-liquid layer (QLL), can account for NOx volume fluxes, concentrations, and [NO]/[NO2] (γ=[NO]/[NO2]) measured just above the Arctic and coastal Antarctic snowpack. Maximum gas phase NOx volume fluxes, concentrations and γ simulated for spring and summer range from 5.0×104 to 6.4×105 molecules cm−3 s−1, 5.7×108 to 4.8×109 molecules cm−3, and ~0.8 to 2.2, respectively, which are comparable to gas phase NOx volume fluxes, concentrations and γ measured in the field. The model incorporates the appropriate actinic solar spectrum, thereby properly weighting the different rates of photolysis of NO3− and NO2−. This is important since the immediate precursor for NO, for example, NO2−, absorbs at wavelengths longer than nitrate itself. Finally, one-dimensional model simulations indicate that both gas phase boundary layer NO and NO2 exhibit a negative concentration gradient as a function of height although [NO]/[NO2] are approximately constant. This gradient is primarily attributed to gas phase reactions of NOx with halogens oxides (i.e. as BrO and IO), HOx, and hydrocarbons, such as CH3O2.
Ship plume dispersion rates in convective boundary layers for chemistry models

Detailed ship plume simulations in various convective boundary layer situations have been performed using a Lagrangian Dispersion Model driven by a Large Eddy Simulation Model. The simulations focus on the early stage (1–2 h) of plume dispersion regime and take into account the effects of plume rise on dispersion. Results are presented in an attempt to provide to atmospheric chemistry modellers a realistic description of characteristic dispersion impact on exhaust ship plume chemistry. Plume dispersion simulations are used to derive analytical dilution rate functions. Even though results exhibit striking effects of plume rise parameter on dispersion patterns, it is shown that initial buoyancy fluxes at ship stack have a minor effect on plume dilution rate. After initial high dispersion regimes a simple characteristic dilution time scale can be used to parameterize the subgrid plume dilution effect in large-scale chemistry models. The results show that this parameter is directly related to the typical turn-over time scale of the convective boundary layer.
Global error maps of aerosol optical properties: an error propagation analysis

Among the numerous atmospheric constituents, aerosols play a unique role on climate, due to their scattering and absorbing capabilities, visibility degradation and their effect on incoming and outgoing radiation. The most important optical properties are the aerosol optical depth (AOD), the asymmetry parameter (g) and the single scattering albedo (SSA). Uncertainties in aerosol microphysics in global models, which in turn affect their optical properties, propagate to uncertainties on the effect of aerosols on climate. This study aims to estimate the uncertainty of AOD, g and SSA attributable to the aerosol representation in models, namely mixing state, aerosol size and aerosol associated water. As a reference, the monthly mean output of the general circulation model LMDz-INCA from the international comparison exercise AEROCOM B was used. For the optical properties calculations, aerosols were considered either externally mixed, homogeneously internally mixed or coated spheres. The radius was allowed to vary by ±20% (with 2% intervals) and the aerosol water content by ±50% (with 5% intervals) with respect to the reference model output. All of these possible combinations were assumed to be equally likely and the optical properties were calculated for each one of them. A probability density function (PDF) was constructed at each model grid point for AOD, g and SSA. From this PDF, the 1σ and 2σ uncertainties of the AOD, g and SSA were calculated and are available as global maps for each month. For the range of the cases studied, we derive a maximum 2σ uncertainty range in AOD of 70%, while for g and SSA the maxima reach 18% and 28% respectively. The mixing state was calculated to be important, with the aerosol absorption and SSA being the most affected properties when absorbing aerosols are present.
A quasi-Lagrangian coordinate system based on high resolution tracer observations: implementation for the Antarctic polar vortex

In order to quantitatively analyse the chemical and dynamical evolution of the polar vortex it has proven extremely useful to work with coordinate systems that follow the vortex flow. We propose here a two-dimensional quasi-Lagrangian coordinate system {χi, Δχi}, based on the mixing ratio of a long-lived stratospheric trace gas i, and its systematic use with i = N2O, in order to describe the structure of a well-developed Antarctic polar vortex. In the coordinate system {χi, Δχi} the mixing ratio χi is the vertical coordinate and Δχi = χi(Θ)−χivort(Θ) is the meridional coordinate (χivort(Θ) being a vertical reference profile in the vortex core). The quasi-Lagrangian coordinates {χi, Δχi} persist for much longer time than standard isentropic coordinates, potential temperature Θ and equivalent latitude φe, do not require explicit reference to geographic space, and can be derived directly from high-resolution in situ measurements. They are therefore well-suited for studying the evolution of the Antarctic polar vortex throughout the polar winter with respect to the relevant chemical and microphysical processes. By using the introduced coordinate system {χN2O, ΔχN2O} we analyze the well-developed Antarctic vortex investigated during the APE-GAIA (Airborne Polar Experiment – Geophysica Aircraft in Antarctica – 1999) campaign (Carli et al., 2000). A criterion, which uses the local in-situ measurements of χi=χi(Θ) and attributes the inner vortex edge to a rapid change (δ-step) in the meridional profile of the mixing ratio χi, is developed to determine the (Antarctic) inner vortex edge. In turn, we suggest that the outer vortex edge of a well-developed Antarctic vortex can be attributed to the position of a local minimum of the χH2O gradient in the polar vortex area. For a well-developed Antarctic vortex, the ΔχN2O-parametrization of tracer-tracer relationships allows to distinguish the tracer inter-relationships in the vortex core, vortex boundary region and surf zone and to examine their meridional variation throughout these regions. This is illustrated by analyzing the tracer-tracer relationships χi : χN2O obtained from the in-situ data of the APE-GAIA campaign for i = CFC-11, CFC-12, H-1211 and SF6. A number of solitary anomalous points in the CFC-11 : N2O correlation, observed in the Antarctic vortex core, are interpreted in terms of small-scale cross-isentropic dispersion.
Direct detection of OH formation in the reactions of HO2 with CH3C(O)O2 and other substituted peroxy radicals

This work details the first direct observation of OH as a product from (R1): HO2+CH3C(O)O2→(products), which has generally been considered an atmospheric radical termination process. The technique of pulsed laser photolysis radical generation, coupled to calibrated laser induced fluorescence detection was used to measure an OH product yield for (R1) of α1(298 K)=(0.5±0.2). This study of (R1) included the measurement of a rate coefficient k1(298 K)=(1.4±0.5)×10−11cm3 molecule−1 s−1, substantially reducing the uncertainties in modelling this important atmospheric reaction. OH was also detected as a product from the reactions of HO2 with three other carbonyl-containing peroxy radicals, albeit at smaller yield, e.g. (R2): HO2+CH3C(O)CH2O2→(products), α2≈0.15. By contrast, OH was not observed (α<0.06) as a major product from reactions where carbonyl functionality was absent, e.g. HO2+HOCH2CH2O2 (R8), and HO2+CH3CH(OH)CH2O2 (R9).
Vertical profile of peroxyacetyl nitrate (PAN) from MIPAS-STR measurements over Brazil in February 2005 and its contribution to tropical UT NOy partitioning

We report on the retrieval of PAN (CH3C(O)OONO2) in the upper tropical troposphere from limb measurements by the remote-sensor MIPAS-STR on board the Russian high altitude research aircraft M55-Geophysica. The measurements were performed close to Araçatuba, Brazil, on 17 February 2005. The retrieval was made in the spectral range 775–820 cm−1 where PAN exhibits its strongest feature but also more than 10 species interfere. Especially trace gases such as CH3CCl3, CFC-113, CFC-11, and CFC-22, emitting also in spectrally broad not-resolved branches, make the processing of PAN prone to errors. Therefore, the selection of appropriate spectral windows, the separate retrieval of several interfering species and the careful handling of the water vapour profile are part of the study presented. The retrieved profile of PAN has a maximum of about 0.14 ppbv at 10 km altitude, slightly larger than the lowest reported values (<0.1 ppbv) and much lower than the highest reported in the literature (0.65 ppbv). Besides the NOy constituents measured by MIPAS-STR (HNO3, ClONO2, HO2NO2, PAN), the in situ instruments aboard the Geophysica provide simultaneous measurements of NO, NO2, and the sum NOy. Comparing the sum of in-situ and remotely derived NO+NO2+HNO3+ClONO2+HO2NO2+PAN with total NOy a deficit of 30–40% (0.2–0.3 ppbv) in the troposphere remains unexplained whereas the values fit well in the stratosphere.
The role of atmospheric ions in aerosol nucleation – a review

Atmospheric aerosols affect climate and yet the reason for many observed events of new aerosol formation is not understood. One of the theories put forward to explain these events is that the presence of ions can enhance the formation of aerosols. The theory is called Ion Induced Nucleation and in this paper the state of observations, theory and experiments within the field will be reviewed. While evidence for Ion Induced Nucleation is accumulating the exact mechanism is still not known and more research is required to understand and quantify the effect.