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Summertime NOx measurements during the CHABLIS campaign: can source and sink estimates unravel observed diurnal cycles?

NOx measurements were conducted at the Halley Research Station, coastal Antarctica, during the austral summer period 1 January–10 February 2005. A clear NOx diurnal cycle was observed with minimum concentrations close to instrumental detection limit (5 pptv) measured between 04:00–05:00 GMT. NOx concentrations peaked (24 pptv) between 19:00–20:00 GMT, approximately 5 h after local solar noon. An optimised box model of NOx concentrations based on production from in-snow nitrate photolysis and chemical loss derives a mean noon emission rate of 3.48 × 108 molec cm−2 s−1, assuming a 100 m boundary layer mixing height, and a relatively short NOx lifetime of ~6.4 h. This emission rate compares to directly measured values ranging from 2.1 to 12.6 × 108 molec cm−2 s−1 made on 3 days at the end of the study period. Calculations of the maximum rate of NO2 loss via a variety of conventional HOx and halogen oxidation processes show that the lifetime of NOx is predominantly controlled by halogen processing, namely BrNO3 and INO3 gas-phase formation and their subsequent heterogeneous uptake. Furthermore the presence of halogen oxides is shown to significantly perturb NOx concentrations by decreasing the NO/NO2 ratio. We conclude that in coastal Antarctica, the potential ozone production efficiency of NOx emitted from the snowpack is mitigated by the more rapid NOx loss due to halogen nitrate hydrolysis.
Influence of the North Atlantic Oscillation on air pollution transport

We examined the influence of the North Atlantic Oscillation (NAO) on the atmospheric dispersion of pollution by computing the emission, transport and removal of idealized insoluble gaseous and water-soluble aerosol tracers, tagged by the continent of origin. We simulated a period of 50 yr (1960–2010), using the ECHAM5/MESSy1 atmospheric chemistry (EMAC) general circulation model. The model accounts for anthropogenic, biogenic and biomass burning sources, removal of trace gases through OH oxidation, and precipitation, sedimentation and deposition of aerosols. The model is shown to reproduce the observed spatial features of the NAO, moisture transports and precipitation. During high NAO phase seasons the axis of maximum westerly North American trace gas transports extends relatively far to the north and east over Europe. The NAO phase is significantly correlated with North American insoluble gas and soluble aerosol tracer concentrations over the northwestern Atlantic Ocean and across northern Europe, and with European trace gases and aerosols over Africa and north of the Arctic circle. We find a strong anti-correlation between the phase of the NAO and European pollutant gas concentration over western and central Europe.
Atmospheric ice nuclei in the Eyjafjallajökull volcanic ash plume

We have sampled atmospheric ice nuclei (IN) and aerosol in Germany and in Israel during spring 2010. IN were analyzed by the static vapor diffusion chamber FRIDGE, as well as by electron microscopy. During the Eyjafjallajökull volcanic eruption of April 2010 we have measured the highest ice nucleus number concentrations (>600 l−1) in our record of 2 yr of daily IN measurements in central Germany. Even in Israel, located about 5000 km away from Iceland, IN were as high as otherwise only during desert dust storms. The fraction of aerosol activated as ice nuclei at −18 °C and 119% rhice and the corresponding area density of ice-active sites per aerosol surface were considerably higher than what we observed during an intense outbreak of Saharan dust over Europe in May 2008. Pure volcanic ash accounts for at least 53–68% of the 239 individual ice nucleating particles that we collected in aerosol samples from the event and analyzed by electron microscopy. Volcanic ash samples that had been collected close to the eruption site were aerosolized in the laboratory and measured by FRIDGE. Our analysis confirms the relatively poor ice nucleating efficiency (at −18 °C and 119% ice-saturation) of such "fresh" volcanic ash, as it had recently been found by other workers. We find that both the fraction of the aerosol that is active as ice nuclei as well as the density of ice-active sites on the aerosol surface are three orders of magnitude larger in the samples collected from ambient air during the volcanic peaks than in the aerosolized samples from the ash collected close to the eruption site. From this we conclude that the ice-nucleating properties of volcanic ash may be altered substantially by aging and processing during long-range transport in the atmosphere, and that global volcanism deserves further attention as a potential source of atmospheric ice nuclei.
Advances and limitations of atmospheric boundary layer observations with GPS occultation over southeast Pacific Ocean

The typical atmospheric boundary layer (ABL) over the southeast (SE) Pacific Ocean is featured with a strong temperature inversion and a sharp moisture gradient across the ABL top. The strong moisture and temperature gradients result in a sharp refractivity gradient that can be precisely detected by the Global Positioning System (GPS) radio occultation (RO) measurements. In this paper, the Constellation Observing System for Meteorology, Ionosphere & Climate (COSMIC) GPS RO soundings, radiosondes and the high-resolution ECMWF analysis over the SE Pacific are analyzed. COSMIC RO is able to detect a wide range of ABL height variations (1–2 km) as observed from the radiosondes. However, the ECMWF analysis systematically underestimates the ABL heights. The sharp refractivity gradient at the ABL top frequently exceeds the critical refraction (e.g., −157 N-unit km−1) and becomes the so-called ducting condition, which results in a systematic RO refractivity bias (or called N-bias) inside the ABL. Simulation study based on radiosonde profiles reveals the magnitudes of the N-biases are vertical resolution dependent. The $N$-bias is also the primary cause of the systematically smaller refractivity gradient (rarely exceeding −110 N-unit km−1) at the ABL top from RO measurement. However, the N-bias seems not affect the ABL height detection. Instead, the very large RO bending angle and the sharp refractivity gradient due to ducting allow reliable detection of the ABL height from GPS RO. The seasonal mean climatology of ABL heights derived from a nine-month composite of COSMIC RO soundings over the SE Pacific reveals significant differences from the ECMWF analysis. Both show an increase of ABL height from the shallow stratocumulus near the coast to a much higher trade wind inversion further off the coast. However, COSMIC RO shows an overall deeper ABL and reveals different locations of the minimum and maximum ABL heights as compared to the ECMWF analysis. At low latitudes, despite the decreasing number of COSMIC RO soundings and the lower percentage of soundings that penetrate into the lowest 500-m above the mean-sea-level, there are small sampling errors in the mean ABL height climatology. The difference of ABL height climatology between COSMIC RO and ECMWF analysis over SE Pacific is significant and requires further studies.
Distributions and regional budgets of aerosols and their precursors simulated with the EMAC chemistry-climate model

The new global anthropogenic emission inventory (EDGAR-CIRCE) of gas and aerosol pollutants has been incorporated in the chemistry general circulation model EMAC (ECHAM5/MESSy Atmospheric Chemistry). A relatively high horizontal resolution simulation is performed for the years 2005–2008 to evaluate the capability of the model and the emissions to reproduce observed aerosol concentrations and aerosol optical depth (AOD) values. Model output is compared with observations from different measurement networks (CASTNET, EMEP and EANET) and AODs from remote sensing instruments (MODIS and MISR). A good spatial agreement of the distribution of sulfate and ammonium aerosol is found when compared to observations, while calculated nitrate aerosol concentrations show some discrepancies. The simulated temporal development of the inorganic aerosols is in line with measurements of sulfate and nitrate aerosol, while for ammonium aerosol some deviations from observations occur over the USA, due to the wrong temporal distribution of ammonia gas emissions. The calculated AODs agree well with the satellite observations in most regions, while negative biases are found for the equatorial area and in the dust outflow regions (i.e. Central Atlantic and Northern Indian Ocean), due to an underestimation of biomass burning and aeolian dust emissions, respectively. Aerosols and precursors budgets for five different regions (North America, Europe, East Asia, Central Africa and South America) are calculated. Over East-Asia most of the emitted aerosols (precursors) are also deposited within the region, while in North America and Europe transport plays a larger role. Further, it is shown that a simulation with monthly varying anthropogenic emissions typically improves the temporal correlation by 5–10% compared to one with constant annual emissions.
A hybrid bin scheme to solve the condensation/evaporation equation using a cubic distribution function

A computationally efficient method is proposed to replace the piecewise linear number distribution in a hybrid bin scheme with a piecewise cubic polynomial. When the linear distribution is replaced by a cubic, the errors generated in solutions to the condensation/evaporation equation are reduced by a factor of two to three. Alternatively, using the cubic distribution function allows reducing the number of bins by 20 ± 5% when solving the condensation/evaporation problem without sacrificing accuracy.
Interaction of NO2 with TiO2 surface under UV irradiation: measurements of the uptake coefficient

The interaction of NO2 with TiO2 solid films was studied under UV irradiation using a low pressure flow reactor (1–10 Torr) combined with a modulated molecular beam mass spectrometer for monitoring of the gaseous species involved. The NO2 to TiO2 reactive uptake coefficient was measured from the kinetics of NO2 loss on TiO2 coated Pyrex rods as a function of NO2 concentration, irradiance intensity (JNO2 = 0.002–0.012 s−1), relative humidity (RH = 0.06–69 %), temperature (T = 275–320 K) and partial pressure of oxygen (0.001–3 Torr). TiO2 surface deactivation upon exposure to NO2 was observed. The initial uptake coefficient of NO2 on illuminated TiO2 surface (with 90 ppb of NO2 and JNO2&cong;0.006 s−1) was found to be γ0 = (1.2±0.4) ×10−4 (calculated using BET surface area) under dry conditions at T = 300 K. The steady state uptake, γ, was several tens of times lower than the initial one, independent of relative humidity, and was found to decrease in the presence of molecular oxygen. In addition, it was shown that γ is not linearly dependent on the photon flux and seems to level off under atmospheric conditions. Finally, the following expression for γ was derived, γ = 2.3×10−3 exp(−1910/T)/(1 + P0.36) (where P is O2 pressure in Torr), and recommended for atmospheric applications (for any RH, near 90 ppb of NO2 and JNO2 = 0.006 s−1).
The scale problem in quantifying aerosol indirect effects

A wide range of estimates exists for the radiative forcing of the aerosol effect on cloud albedo. We argue that a component of this uncertainty derives from the use of a wide range of observational scales and platforms. Aerosol influences cloud properties at the microphysical scale, or the "process scale", but observations are most often made of bulk properties over a wide range of resolutions, or "analysis scales". We show that differences between process and analysis scales incur biases in quantification of the albedo effect through the impact that data aggregation and computational approach have on statistical properties of the aerosol or cloud variable, and their covariance. Measures made within this range of scales are erroneously treated as equivalent, leading to a large uncertainty in associated radiative forcing estimates. Issues associated with the coarsening of observational resolution particular to quantifying the albedo effect are discussed. Specifically, the omission of the constraint on cloud liquid water path and the separation in space of cloud and aerosol properties from passive, space-based remote sensors dampen the measured strength of the albedo effect. We argue that, because of this lack of constraints, many of these values are in fact more representative of the full range of aerosol-cloud interactions and their associated feedbacks. Based on our understanding of these biases we propose a new observationally-based and process-model-constrained, method for estimating aerosol-cloud interactions that can be used for radiative forcing estimates as well as a better characterization of the uncertainties associated with those estimates.
Polar-night O3, NO2 and NO3 distributions during sudden stratospheric warmings in 2003–2008 as seen by GOMOS/Envisat

Sudden stratospheric warmings (SSW) are large-scale transient events, which have a profound effect on the Northern Hemisphere stratospheric circulation in winter. During the SSW events the temperature in stratosphere increases by several tens of Kelvins and zonal winds decelerate or reverse in direction. Changes in temperature and dynamics significantly affect the chemical composition of the middle atmosphere. In this paper, the response of the middle-atmosphere trace gases during several sudden stratospheric warmings in 2003–2008 is investigated using measurements from the GOMOS (Global Ozone Monitoring by Occultation of Stars) instrument on board the Envisat satellite. We have analyzed spatial and temporal changes of NO2 and NO3 in the stratosphere, and of ozone in the whole middle atmosphere. To facilitate our analyses, we have used the temperature profiles data from the MLS (Microwave Limb Sounder) instrument on board the Aura satellite, as well as simulations by the FinROSE chemistry-transport model and the Sodankylä Ion and Neutral Chemistry model (SIC). NO3 observations in the polar winter stratosphere during SSWs are reported for the first time. Changes in chemical composition are found not to be restricted to the stratosphere, but to extend to mesosphere and lower thermosphere. They often exhibit a complicated structure, because the distribution of trace gases is affected by changes in both chemistry and dynamics. The tertiary ozone maximum in the mesosphere often disappears with the onset of SSW, probably because of strong mixing processes. The strong horizontal mixing with outside-vortex air is well observed also in NO2 data, especially in cases of enhanced NO2 inside the polar vortex before SSW. Almost in all of the considered events, ozone near the secondary maximum decreases with onset of SSW. In both experimental data and FinROSE modelling, ozone changes are positively correlated with temperature changes in the lower stratosphere in the dynamically controlled region below ~35 km, and they are negatively correlated with temperature in the upper stratosphere (altitudes 35–50 km), where chemical processes play a significant role. Large enhancements of stratospheric NO3, which strongly correlate with temperature enhancements, are observed for all SSWs, as expected by the current understanding of temperature-dependence of NO3 concentrations and simulations with the CTM.
Attributing and quantifying carbon monoxide sources affecting the Eastern Mediterranean: a combined satellite, modelling, and synoptic analysis study

Pollutants from global sources are known to affect the Eastern Mediterranean Shore (EMS). However, there has been no previous study explicitly locating the European sources, characterizing their transport pathways, and quantifying their contribution to local concentrations in the EMS. In the current study, spatially tagged carbon monoxide was used as a tracer for pollutant transport from Europe to the EMS over five consecutive years (2003–2007) using the global chemical transport model MOZART-4. The model results were compared against NOAA/GMD ground station data and remotely sensed data from the Terra/MOPITT satellite and found to agree well on monthly basis but do not agree on daily basis. On synoptic scale, there is agreement between MOZART and GMD during July to August. A budget analysis reveals the role of CO from hydrocarbon oxidation on CO concentration during summer. European anthropogenic emissions were found to significantly influence EM surface concentrations, while European biomass burning (BB) emissions were found to have only a small impact on EM surface concentrations. Over the five simulated years, only two European biomass burning episodes contributed more than 10 ppb to surface CO concentrations in the EM. CO enhancement in the EM during the summer was attributed to synoptic conditions prone to favorable transport from Turkey and Eastern Europe towards the EM rather than increased emissions. We attribute the apparently misleading association between CO emitted from European BB and CO enhancements over the EM to typical summer synoptic conditions caused by the lingering of an anticyclone positioned over the Western and Central Mediterranean Basin that lead to forest fires in the area. Combined with a barometric trough over the eastern part of the Mediterranean Basin, this generates a prevailing transport of air masses from Eastern Europe to the EMS. Synoptic scale variations are shown to change the transport pathways from Europe towards the EMS having an overall small affect. CO concentration over the EMS can be describe as having 3 components: the seasonal cycle, the cycle of CO produced from hydrocarbon oxidation and a synoptic variation.