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Corrigendum to "Quantifying the uncertainty in simulating global tropospheric composition due to the variability in global emission estimates of Biogenic Volatile Organic Compounds" published in Atmos. Chem. Phys., 13, 2857–2891, 2013
CH4 and CO distributions over tropical fires during October 2006 as observed by the Aura TES satellite instrument and modeled by GEOS-Chem

Tropical fires represent a highly uncertain source of atmospheric methane (CH4) because of the variability of fire emissions and the dependency of the fire CH4 emission factors (g kg−1 dry matter burned) on fuel type and combustion phase. In this paper we use new observations of CH4 and CO in the free troposphere from the Aura Tropospheric Emission Sounder (TES) satellite instrument to place constraints on the role of tropical fire emissions versus microbial production (e.g. in wetlands and livestock) during the (October) 2006 El Niño, a time of significant fire emissions from Indonesia. We first compare the global CH4 distributions from TES using the GEOS-Chem model. We find a mean bias between the observations and model of 26.3 ppb CH4 that is independent of latitude between 50° S and 80° N, consistent with previous validation studies of TES CH4 retrievals using aircraft measurements. The slope of the distribution of CH4 versus CO as observed by TES and modeled by GEOS-Chem is consistent (within the TES observation error) for air parcels over the Indonesian peat fires, South America, and Africa. The CH4 and CO distributions are correlated between R = 0.42 and R = 0.46, with these correlations primarily limited by the TES random error. Over Indonesia, the observed slope of 0.13 (ppb ppb−1) ±0.01, as compared to a modeled slope of 0.153 (ppb ppb−1) ±0.005 and an emission ratio used within the GEOS-Chem model of approximately 0.11 (ppb ppb−1), indicates that most of the observed methane enhancement originated from the fire. Slopes of 0.47 (ppb ppb−1) ±0.04 and 0.44 (ppb ppb−1) ±0.03 over South America and Africa show that the methane in the observed air parcels primarily came from microbial-generated emissions. Sensitivity studies using GEOS-Chem show that part of the observed correlation for the Indonesian observations and most of the observed correlations over South America and Africa are a result of transport and mixing of the fire and nearby microbial-generated emissions into the observed air parcels. Differences between observed and modeled CH4 distributions over South America and southern Africa indicate that the magnitude of the methane emissions for this time period are inconsistent with observations even if the relative distribution of fire versus biotic emissions are consistent. This study shows the potential for estimation of CH4 emissions over tropical regions using joint satellite observations of CH4 and CO.
Detection and characterization of volcanic ash plumes over Lille during the Eyjafjallajökull eruption

Routine sun-photometer and micro-lidar measurements were performed in Lille, northern France, in April and May 2010 during the Eyjafjallajökull volcanic eruption. The impact of such an eruption emphasized significance of hazards for human activities and importance of observations of the volcanic aerosol particles. This paper presents the main results of a joint micro-lidar/sun-photometer analysis performed in Lille, where volcanic ash plumes were observed during at least 22 days, whenever weather conditions permitted. Aerosol properties retrieved from automatic sun-photometer measurements (AERONET) were strongly changed during the volcanic aerosol plumes transport over Lille. In most cases, the aerosol optical depth (AOD) increased, whereas Ångström exponent decreased, thus indicating coarse-mode dominance in the volume size distribution. Moreover, the non-spherical fraction retrieved by AERONET significantly increased. The real part of the complex refractive index was up to 1.55 at 440 nm during the eruption, compared to background data of about 1.46 before the eruption. Collocated lidar data revealed that several aerosol layers were present between 2 and 5 km, all originating from the Iceland region as confirmed by backward trajectories. The volcanic ash AOD was derived from lidar extinction profiles and sun-photometer AOD, and its maximum was estimated around 0.37 at 532 nm on 18 April 2010. This value was observed at an altitude of 1700 m and corresponds to an ash mass concentration (AMC) slightly higher than 1000 μg m−3 (±50%). An effective lidar ratio of ash particles of 48 sr was retrieved at 532 nm for 17 April during the early stages of the eruption, a value which agrees with several other studies carried out on this topic. Even though the accuracy of the retrievals is not as high as that obtained from reference multiwavelength lidar systems, this study demonstrates the opportunity of micro-lidar and sun-photometer joint data processing for deriving volcanic AMC. It also outlines the fact that a network of combined micro-lidars and sun photometers can be a powerful tool for routine monitoring of aerosols, especially in the case of such hazardous volcanic events.
Exploring the atmospheric chemistry of O2SO3− and assessing the maximum turnover number of ion-catalysed H2SO4 formation

It has recently been demonstrated that the O2SO3− ion forms in the atmosphere as a natural consequence of ionizing radiation. Here, we present a density functional theory-based study of the reactions of O2SO3− with O3. The most important reactions are (a) oxidation to O2SO3− and (b) cluster decomposition into SO3, O2 and O3−. The former reaction is highly exothermic, and the nascent O2SO3− will rapidly decompose into SO4− and O2. If the origin of O2SO3− is SO2 oxidation by O3−, the latter reaction closes a catalytic cycle wherein SO2 is oxidized to SO3. The relative rate between the two major sinks for O2SO3− is assessed, thereby providing a measure of the maximum turnover number of ion-catalysed SO2 oxidation, i.e. how many SO2 can be oxidized per free electron. The rate ratio between reactions (a) and (b) is significantly altered by the presence or absence of a single water molecule, but reaction (b) is in general much more probable. Although we are unable to assess the overall importance of this cycle in the real atmosphere due to the unknown influence of CO2 and NOx, we roughly estimate that ion-induced catalysis may contribute with several percent of H2SO4 levels in typical CO2-free and low NOx reaction chambers, e.g. the CLOUD chamber at CERN.
Sources, trends and regional impacts of fine particulate matter in southern Mississippi valley: significance of emissions from sources in the Gulf of Mexico coast

The sources of fine particles over a 10 yr period at Little Rock, Arkansas, an urban area in the southern Mississippi Valley, were identified by positive matrix factorization. The annual trends of PM2.5 and its sources, and their associations with the pathways of air mass backward trajectories were examined. Seven sources were apportioned, namely, primary traffic particles, secondary nitrate and sulphate, biomass burning, diesel particles, aged/contaminated sea salt and mineral/road dust, accounting for more than 90% of measured PM2.5 (particles with aerodynamic diameter less than 2.5 μm) mass. The declining trend of PM2.5 mass (0.4 μg m−3 per year) was related to lower levels of SO42− (0.2 μg m−3 per year) due to SO2 reductions from point and mobile sources. The slower decline for NO3− particles (0.1 μg m−3 per year) was attributed to the increasing NH3 emissions in the Midwest. The annual variation of biomass burning particles was associated with fires in the southeast and northwest US. Of the four regions within 500 km from the receptor site, the Gulf Coast and the southeast US accounted cumulatively for more than 65% of PM2.5 mass, nitrate, sulphate and biomass burning aerosol. Overall, more than 50% of PM2.5 and its components originated from sources outside the state. Sources within the Gulf Coast and western Gulf of Mexico include 65% of the busiest ports in the US, intense marine traffic within 400 km of the coast burning rich in S diesel, and a large number of offshore oil and natural gas platforms and many refineries. This approach allowed for the quantitative assessment of the impacts of transport from regions representing diverse mixtures of sources and weather conditions for different types of particles. The findings of this effort demonstrated the influences of emission controls on SO2 and NOx on PM2.5 mass, the potential effect of events (i.e. fires) sensitive to climate change phenomena on air pollution and the potential of offshore activities and shipping emissions to influence air quality in urban areas located more than 1000 km away from the sources.
Effective aerosol optical depth from pyranometer measurements of surface solar radiation (global radiation) at Thessaloniki, Greece

Pyranometer measurements of the solar surface radiation (SSR) are available at many locations worldwide, often as long time series covering several decades into the past. These data constitute a potential source of information on the atmospheric aerosol load. Here, we present a method for estimating the aerosol optical depth (AOD) using pyranometer measurements of the SSR together with total water vapor column information. The method, which is based on radiative transfer simulations, was developed and tested using recent data from Thessaloniki, Greece. The effective AOD calculated using this method was found to agree well with co-located AERONET measurements, exhibiting a correlation coefficient of 0.9 with 2/3 of the data found within ±20% or ±0.05 of the AERONET AOD. This is similar to the performance of current satellite aerosol methods. Differences in the AOD as compared to AERONET can be explained by variations in the aerosol properties of the atmosphere that are not accounted for in the idealized settings used in the radiative transfer simulations, such as variations in the single scattering albedo and Ångström exponent. Furthermore, the method is sensitive to calibration offsets between the radiative transfer simulations and the pyranometer SSR. The method provides an opportunity of extending our knowledge of the atmospheric aerosol load to locations and times not covered by dedicated aerosol measurements.
Pollution transport from North America to Greenland during summer 2008

Ozone pollution transported to the Arctic is a significant concern because of the rapid, enhanced warming in high northern latitudes, which is caused, in part, by short-lived climate forcers, such as ozone. Long-range transport of pollution contributes to background and episodic ozone levels in the Arctic. However, the extent to which plumes are photochemically active during transport, particularly during the summer, is still uncertain. In this study, regional chemical transport model simulations are used to examine photochemical production of ozone in air masses originating from boreal fire and anthropogenic emissions over North America and during their transport toward the Arctic during early July 2008. Model results are evaluated using POLARCAT aircraft data collected over boreal fire source regions in Canada (ARCTAS-B) and several days downwind over Greenland (POLARCAT-France and POLARCAT-GRACE). Model results are generally in good agreement with the observations, except for certain trace gas species over boreal fire regions, in some cases indicating that the fire emissions are too low. Anthropogenic and biomass burning pollution (BB) from North America was rapidly uplifted during transport east and north to Greenland where pollution plumes were observed in the mid- and upper troposphere during POLARCAT. A model sensitivity study shows that CO levels are in better agreement with POLARCAT measurements (fresh and aged fire plumes) upon doubling CO emissions from fires. Analysis of model results, using ΔO3/ΔCO enhancement ratios, shows that pollution plumes formed ozone during transport towards the Arctic. Fresh anthropogenic plumes have average ΔO3/ΔCO enhancement ratios of 0.63 increasing to 0.92 for aged anthropogenic plumes, indicating additional ozone production during aging. Fresh fire plumes are only slightly enhanced in ozone (ΔO3/ΔCO=0.08), but form ozone downwind with ΔO3/ΔCO of 0.49 for aged BB plumes (model-based run). We estimate that aged anthropogenic and BB pollution together made an important contribution to ozone levels with an average contribution for latitudes >55° N of up to 6.5 ppbv (18%) from anthropogenic pollution and 3 ppbv (5.2%) from fire pollution in the model domain in summer 2008.
Montreal Protocol Benefits simulated with CCM SOCOL

Ozone depletion is caused by the anthropogenic increase of halogen-containing species in the atmosphere, which results in the enhancement of the concentration of reactive chlorine and bromine in the stratosphere. To reduce the influence of anthropogenic ozone-depleting substances (ODS), the Montreal Protocol was agreed by Governments in 1987, with several Amendments and Adjustments adopted later. In order to assess the benefits of the Montreal Protocol and its Amendments and Adjustments (MPA) on ozone and UV radiation, two different runs of the chemistry-climate model (CCM) SOCOL have been carried out. The first run was driven by the emission of ozone depleting substances (ODS) prescribed according to the restrictions of the MPA. For the second run we allow the ODS to grow by 3% annually. We find that the MPA would have saved up to 80% of the global annual total ozone by the end of the 21st century. Our calculations also show substantial changes of the stratospheric circulation pattern as well as in surface temperature and precipitations that could occur in the world without MPA implementations. To illustrate the changes in UV radiation at the surface and to emphasise certain features, which can only be seen for some particular regions if the influence of the cloud cover changes is accounted for, we calculate geographical distribution of the erythemally weighted irradiance (Eery). For the no Montreal Protocol simulation Eery increases by factor of 4 to 16 between the 1970s and 2100. For the scenario including the Montreal Protocol it is found that UV radiation starts to decrease in 2000, with continuous decline of 5% to 10% at middle latitudes in the both Northern and Southern Hemispheres.
Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols

The formation of carboxylic acids and dimer esters from α-pinene oxidation was investigated in a smog chamber and in ambient aerosol samples collected during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX). Chamber experiments of α-pinene ozonolysis in dry air and at low NOx concentrations demonstrated formation of two dimer esters, pinyl-diaterpenyl (MW 358) and pinonyl-pinyl dimer ester (MW 368), under both low- and high-temperature conditions. Concentration levels of the pinyl-diaterpenyl dimer ester were lower than the assumed first-generation oxidation products cis-pinic and terpenylic acids, but similar to the second-generation oxidation products 3-methyl-1,2,3-butane tricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). Dimer esters were observed within the first 30 min, indicating rapid production simultaneous to their structural precursors. However, the sampling time resolution precluded conclusive evidence regarding formation from gas- or particle-phase processes. CCN activities of the particles formed in the smog chamber displayed a modest variation during the course of experiments, with κ values in the range 0.06–0.09 (derived at a supersaturation of 0.19%). The pinyl-diaterpenyl dimer ester was also observed in ambient aerosol samples collected above a ponderosa pine forest in the Sierra Nevada Mountains of California during two seasonally distinct field campaigns in September 2007 and July 2009. The pinonyl-pinyl ester was observed for the first time in ambient air during the 2009 campaign, and although present at much lower concentrations, it was correlated with the abundance of the pinyl-diaterpenyl ester, suggesting similarities in their formation. The maximum concentration of the pinyl-diaterpenyl ester was almost 10 times higher during the warmer 2009 campaign relative to 2007, while the concentration of cis-pinic acid was approximately the same during both periods, and lack of correlation with levels of cis-pinic and terpenylic acids for both campaigns indicate that the formation of the pinyl-diaterpenyl ester was not controlled by their ambient abundance. In 2009 the concentration of the pinyl-diaterpenyl ester was well correlated with the concentration of DTAA, a supposed precursor of diaterpenylic acid, suggesting that the formation of pinyl-diaterpenyl dimer was closely related to DTAA. Generally, the pinyl-diaterpenyl ester was found at higher concentrations under higher temperature conditions, both in the smog-chamber study and in ambient air aerosol samples, and exhibited much higher concentrations at night relative to daytime in line with previous results. We conclude that analysis of pinyl dimer esters provides valuable information on pinene oxidation processes and should be included in studies of formation and photochemical aging of biogenic secondary organic aerosols, especially at high temperatures.
Oxidation of SO2 by stabilized Criegee intermediate (sCI) radicals as a crucial source for atmospheric sulfuric acid concentrations

The effect of increased reaction rates of stabilized Criegee intermediates (sCIs) with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012) increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO) with SO2 according to the values recommended by Welz et al. (2012) increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.