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BrO, blizzards, and drivers of polar tropospheric ozone depletion events

The source of bromine that drives polar boundary layer ozone depletion events (ODEs) is still open to some debate. While ODEs are generally noted to form under conditions of a shallow stable boundary layer, observations of depleted air under high wind conditions are taken as being transport-related. Here we report observations from Antarctica in which an unusually large cloud of BrO formed over the Weddell Sea. The enhanced BrO was observed over Halley station in coastal Antarctica, providing an opportunity to probe the conditions within an active "bromine explosion" event. On this occasion, enhanced BrO and depleted boundary layer ozone coincided with high wind speeds and saline blowing snow. We derive a simple model to consider the environmental conditions that favour ODEs and find two maxima, one at low wind/stable boundary layer and one at high wind speeds with blowing snow. Modelling calculations aiming to reproduce the wider regional or global impacts of ODEs, either via radiative effects or as a halogen source, will also need to account for high wind speed mechanisms.
Time span and spatial scale of regional new particle formation events over Finland and Southern Sweden

We investigated the time span and spatial scale of regional new particle formation (NPF) events in Finland and Southern Sweden using measured particle number size distributions at five background stations. We define the time span of a NPF event as the time period from the first moment when the newly formed mode of aerosol particles is observable below 25 nm until the newly formed mode is not any more distinguishable from other background modes of aerosol particles after growing to bigger sizes. We identify the spatial scale of regional NPF events based on two independent approaches. The first approach is based on the observation within a network of stationary measurement stations and the second approach is based on the time span and the history of air masses back-trajectories. According to the second approach, about 60% and 28% of the events can be traced to distances longer than 220 km upwind from where the events were observed in Southern Finland (Hyytiälä) and Northern Finland (Värriö), respectively. The analysis also showed that the observed regional NPF events started over the continents but not over the Atlantic Ocean. The first approach showed that although large spatial scale NPF events are frequently observed at several locations simultaneously, they are rarely identical (similar characteristics and temporal variations) due to differences in the initial meteorological and geographical conditions between the stations. The growth of the newly formed particles during large spatial scale events can be followed for more than 30 h where the newly formed aerosol particles end up in the Aitken mode (diameter 25–100 nm) and accumulation mode size ranges (diameter 0.1–1 μm). This study showed clear evidence that regional NPF events can pose a significant source for accumulation mode particles over the Scandinavian continent provided that these findings can be generalized to many of the air masses traveling over the European continent.
Aerosol size-dependent below-cloud scavenging by rain and snow in the ECHAM5-HAM

Wet deposition processes are highly efficient in the removal of aerosols from the atmosphere, and thus strongly influence global aerosol concentrations, and clouds, and their respective radiative forcings. In this study, physically detailed size-dependent below-cloud scavenging parameterizations for rain and snow are implemented in the ECHAM5-HAM global aerosol-climate model. Previously, below-cloud scavenging by rain in the ECHAM5-HAM was simply a function of the aerosol mode, and then scaled by the rainfall rate. The below-cloud scavenging by snow was a function of the snowfall rate alone. The global mean aerosol optical depth, and sea salt burden are sensitive to the below-cloud scavenging coefficients, with reductions near to 15% when the more vigorous size-dependent below-cloud scavenging by rain and snow is implemented. The inclusion of a prognostic rain scheme significantly reduces the fractional importance of below-cloud scavenging since there is higher evaporation in the lower troposphere, increasing the global mean sea salt burden by almost 15%. Thermophoretic effects are shown to produce increases in the global and annual mean number removal of Aitken size particles of near to 10%, but very small increases (near 1%) in the global mean below-cloud mass scavenging of carbonaceous and sulfate aerosols. Changes in the assumptions about the below-cloud scavenging by rain of particles with radius smaller than 10 nm do not cause any significant changes to the global and annual mean aerosol mass or number burdens, despite a change in the below-cloud number removal rate for nucleation mode particles by near to five-fold. Annual and zonal mean nucleation mode number concentrations are enhanced by up to 30% in the lower troposphere with the more vigourous size-dependent below-cloud scavenging. Closer agreement with different observations is found when the more physically detailed below-cloud scavenging parameterization is employed in the ECHAM5-HAM model.
Significant variations of trace gas composition and aerosol properties at Mt. Cimone during air mass transport from North Africa – contributions from wildfire emissions and mineral dust

High levels of trace gas (O3 and CO) and aerosol (BC, fine and coarse particle volumes), as well as high scattering coefficient (σp) values, were recorded at the regional GAW-WMO station of Mt. Cimone (CMN, 2165 m a.s.l., Italy) during the period 26–30 August 2007. Analysis of air-mass circulation, aerosol chemical characterization and trace gas and aerosol enhancement ratios (ERs), showed that high O3 and aerosol levels were likely linked to (i) the transport of anthropogenic pollution from northern Italy, and (ii) the advection of air masses rich in mineral dust and biomass burning (BB) products from North Africa. In particular, during the advection of air masses from North Africa, the CO and aerosol levels (CO: 175 ppbv, BC: 1015 ng/m3, fine particle volume: 3.00 μm3 cm−3, σp: 84.5 Mm−1) were even higher than during the pollution event (CO: 138 ppbv, BC: 733 ng/m3, fine particles volume: 1.58 μm3 cm−3, σp: 44.9 Mm<sup−). Moreover, despite the presence of mineral dust able to affect significantly the O3 concentration, the analysis of ERs showed that the BB event represented an efficient source of fine aerosol particles (e.g. BC), but also of the O3 recorded at CMN. In particular, the calculated O3/CO ERs (0.10–0.17 ppbv/ppbv) were in the range of values found in literature for relatively aged (2–4 days) BB plumes and suggested significant photochemical O3 production during the air-mass transport. For fine particles and σp, the calculated ERs was higher in the BB plumes than during the anthropogenic pollution events, stressing the importance of the identified BB event as a source of atmospheric aerosol able to affect the atmospheric radiation budget. These results suggest that episodes of mineral dust mobilization and wildfire emissions over North Africa could significantly influence radiative properties (as deduced from σp observations at CMN) and air quality over the Mediterranean basin and northern Italy.
Simulation of Mexico City plumes during the MIRAGE-Mex field campaign using the WRF-Chem model

The quantification of tropospheric O3 production in the downwind of the Mexico City plume is a major objective of the MIRAGE-Mex field campaign. We used a regional chemistry-transport model (WRF-Chem) to predict the distribution of O3 and its precursors in Mexico City and the surrounding region during March 2006, and compared the model with in-situ aircraft measurements of O3, CO, VOCs, NOx, and NOy concentrations. The comparison shows that the model is capable of capturing the timing and location of the measured city plumes, and the calculated variability along the flights is generally consistent with the measured results, showing a rapid increase in O3 and its precursors when city plumes are detected. However, there are some notable differences between the calculated and measured values, suggesting that, during transport from the surface of the city to the outflow plume, ozone mixing ratios are underestimated by about 0–25% during different flights. The calculated O3-NOx, O3-CO, and O3-NOz correlations generally agree with the measured values, and the analyses of these correlations suggest that photochemical O3 production continues in the plume downwind of the city (aged plume), adding to the O3 already produced in the city and exported with the plume. The model is also used to quantify the contributions to OH reactivity from various compounds in the aged plume. This analysis suggests that oxygenated organics (OVOCs) have the highest OH reactivity and play important roles for the O3 production in the aging plume. Furthermore, O3 production per NOx molecule consumed (O3 production efficiency) is more efficient in the aged plume than in the young plume near the city. The major contributor to the high O3 production efficiency in the aged plume is the reaction RO2+NO. By contrast, the reaction of HO2+NO is rather uniformly distributed in the plume.
Long-term study of VOCs measured with PTR-MS at a rural site in New Hampshire with urban influences

A long-term, high time-resolution volatile organic compound (VOC) data set from a ground site that experiences urban, rural, and marine influences in the Northeastern United States is presented. A proton-transfer-reaction mass spectrometer (PTR-MS) was used to quantify 15 VOCs: a marine tracer dimethyl sulfide (DMS), a biomass burning tracer acetonitrile, biogenic compounds (monoterpenes, isoprene), oxygenated VOCs (OVOCs: methyl vinyl ketone (MVK) plus methacrolein (MACR), methanol, acetone, methyl ethyl ketone (MEK), acetaldehyde, and acetic acid), and aromatic compounds (benzene, toluene, C8 and C9 aromatics). Time series, overall and seasonal medians, with 10th and 90th percentiles, seasonal mean diurnal profiles, and inter-annual comparisons of mean summer and winter diurnal profiles are shown. Methanol and acetone exhibit the highest overall median mixing ratios 1.44 and 1.02 ppbv, respectively. Comparing the mean diurnal profiles of less well understood compounds (e.g., MEK) with better known compounds (e.g., isoprene, monoterpenes, and MVK + MACR) that undergo various controls on their atmospheric mixing ratios provides insight into possible sources of the lesser known compounds. The constant diurnal value of ~0.7 for the toluene:benzene ratio in winter, may possibly indicate the influence of wood-based heating systems in this region. Methanol exhibits an initial early morning release in summer unlike any other OVOC (or isoprene) and a dramatic late afternoon mixing ratio increase in spring. Although several of the OVOCs appear to have biogenic sources, differences in features observed between isoprene, methanol, acetone, acetaldehyde, and MEK suggest they are produced or emitted in unique ways.
Satellite observations and modeling of transport in the upper troposphere through the lower mesosphere during the 2006 major stratospheric sudden warming

An unusually strong and prolonged stratospheric sudden warming (SSW) in January 2006 was the first major SSW for which globally distributed long-lived trace gas data are available covering the upper troposphere through the lower mesosphere. We use Aura Microwave Limb Sounder (MLS), Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) data, the SLIMCAT Chemistry Transport Model (CTM), and assimilated meteorological analyses to provide a comprehensive picture of transport during this event. The upper tropospheric ridge that triggered the SSW was associated with an elevated tropopause and layering in trace gas profiles in conjunction with stratospheric and tropospheric intrusions. Anomalous poleward transport (with corresponding quasi-isentropic troposphere-to-stratosphere exchange at the lowest levels studied) in the region over the ridge extended well into the lower stratosphere. In the middle and upper stratosphere, the breakdown of the polar vortex transport barrier was seen in a signature of rapid, widespread mixing in trace gases, including CO, H2O, CH4 and N2O. The vortex broke down slightly later and more slowly in the lower than in the middle stratosphere. In the middle and lower stratosphere, small remnants with trace gas values characteristic of the pre-SSW vortex lingered through the weak and slow recovery of the vortex. The upper stratospheric vortex quickly reformed, and, as enhanced diabatic descent set in, CO descended into this strong vortex, echoing the fall vortex development. Trace gas evolution in the SLIMCAT CTM agrees well with that in the satellite trace gas data from the upper troposphere through the middle stratosphere. In the upper stratosphere and lower mesosphere, the SLIMCAT simulation does not capture the strong descent of mesospheric CO and H2O values into the reformed vortex; this poor CTM performance in the upper stratosphere and lower mesosphere results primarily from biases in the diabatic descent in assimilated analyses.
East Asian SO2 pollution plume over Europe – Part 2: Evolution and potential impact

We report on the first observation-based case study of an aged East Asian anthropogenic SO2 pollution plume over Europe. Our airborne measurements in that plume detected highly elevated SO2 mole fractions (up to 900 pmol/mol) between about 5000 and 7000 m altitude. Here, we focus on investigations of the origin, dispersion, evolution, conversion, and potential impact of the observed excess SO2. In particular, we investigate SO2 conversion to gas-phase sulfuric acid and sulfuric acid aerosols. Our FLEXPART and LAGRANTO model simulations, along with additional trace gas measurements, suggest that the plume originated from East Asian fossil fuel combustion sources and, 8–7 days prior to its arrival over Europe, ascended over the coast region of central East Asia to 9000 m altitude, probably in a cyclonic system with an associated warm conveyor belt. During this initial plume ascent a substantial fraction of the initially available SO2 must have escaped from removal by cloud processes. Hereafter, while mostly descending slowly, the plume experienced advection across the North Pacific, North America and the North Atlantic. During its upper troposphere travel, clouds were absent in and above the plume and OH-induced gas-phase conversion of SO2 to gas-phase sulfuric acid (GSA) was operative, followed by GSA nucleation and condensation leading to sulfuric acid aerosol formation and growth. Our AEROFOR model simulations indicate that numerous large sulfuric acid aerosol particles were formed, which at least temporarily, caused substantial horizontal visibility degradation, and which have the potential to act as water vapor condensation nuclei in liquid water cloud formation, already at water vapor supersaturations as low as about 0.1%. Our AEROFOR model simulations also indicate that those fossil fuel combustion generated soot particles, which have survived cloud induced removal during the initial plume ascent, have experienced extensive H2SO4/H2O-coating, during upper troposphere plume travel. This coating may have dramatically altered the morphology and markedly increased the light absorption efficiency of soot particles.
East Asian SO2 pollution plume over Europe – Part 1: Airborne trace gas measurements and source identification by particle dispersion model simulations

A large SO2-rich pollution plume of East Asian origin was detected by aircraft based CIMS (Chemical Ionization Mass Spectrometry) measurements at 3–7.5 km altitude over the North Atlantic. The measurements, which took place on 3 May 2006 aboard of the German research aircraft Falcon, were part of the INTEX-B (Intercontinental Chemical Transport Experiment-B) campaign. Additional trace gases (NO, NOy, CO, H2O) were measured and used for comparison and source identification. The atmospheric SO2 mole fraction was markedly increased inside the plume and reached up to 900 pmol/mol. Accompanying lagrangian FLEXPART particle dispersion model simulations indicate that the probed pollution plume originated at low altitudes from densely populated and industrialized regions of East Asia, primarily China, about 8–12 days prior to the measurements.
First year of upper tropospheric integrated content of CO2 from IASI hyperspectral infrared observations

Simultaneous observations from the Infrared Atmospheric Sounding Interferometer (IASI) and from the Advanced Microwave Sounding Unit (AMSU), launched together onboard the European MetOp platform in October 2006, are used to retrieve an upper tropospheric content of carbon dioxide (CO2) covering the range 11–15 km (100–300 hPa), in clear-sky conditions, in the tropics, over sea, for the first year of operation of MetOp (January 2008–December 2008). With its very high spectral resolution, IASI provides fourteen channels in the 15 μm band highly sensitive to CO2 with reduced sensitivities to other atmospheric variables. IASI observations, sensitive to both CO2 and temperature, are used in conjunction with AMSU observations, only sensitive to temperature, to decorrelate both signals through a non-linear inference scheme based on neural networks. A key point of this approach is that no use is made of prior information in terms of CO2 seasonality, trend, or geographical patterns. The precision of the retrieval is estimated to be about 2.0 ppmv (~0.5%) for a 5°×5° spatial resolution on a monthly time scale. Features of the retrieved CO2 space-time distribution include: (1) a strong seasonal cycle of 4 ppmv in the northern tropics with a maximum in June–July and a minimum in September–October. This cycle is characterized by a backward two-months lag as compared to the surface, by a backward one-month lag as compared to measurements performed at 11 km, and by a forward one-month lag as compared to observations performed at the tropopause (16 km). This is likely due to the time-lag of CO2 cycle while transported from the surface to the upper troposphere; (2) a more complex seasonal cycle in the southern tropics, in agreement with in-situ measurements; (3) a latitudinal variation of CO2 shifting from a South-to-North increase of 3.5 ppmv in boreal spring to a South-to-North decrease of 1.5 ppmv in the fall, in excellent agreement with tropospheric aircraft measurements; (4) signatures of CO2 emissions transported to the upper troposphere. In addition to bringing an improved view of CO2 distribution, these results from IASI should provide an additional means to observe and understand atmospheric transport pathways of CO2 from the surface to the upper troposphere.