ALBERT

Description: Methane plays an important role in the Earth’s atmospheric chemistry and radiative balance being the second most important greenhouse gas after carbon dioxide. Methane is released to the atmosphere by a wide number of sources, both natural and anthropogenic, with the latter being twice as large as the former (IPCC, 2007). It has recently been established that significant amounts of geological methane, produced within the Earth’s crust, are currently released naturally into the atmosphere (Etiope, 2004). Active or recent volcanic/geothermal areas represent one of these sources of geological methane. But due to the fact that methane flux measurements are laboratory intensive, very few data have been collected until now and the contribution of this source has been generally indirectly estimated (Etiope et al., 2007). The Greek territory is geodynamically very active and has many volcanic and geothermal areas. Here we report on methane flux measurements made at two volcanic/geothermal systems along the South Aegean volcanic arc: Sousaki and Nisyros. The former is an extinct volcanic area of Plio-Pleistocene age hosting nowadays a low enthalpy geothermal field. The latter is a currently quiescent active volcanic system with strong fumarolic activity due to the presence of a high enthalpy geothermal system. Both systems have gas manifestations that emit significant amounts of hydrothermal methane and display important diffuse carbon dioxide emissions from the soils. New data on methane isotopic composition and higher hydrocarbon contents point to an abiogenic origin of the hydrothermal methane in the studied systems. Measured methane flux values range from –48 to 29,000 (38 sites) and from –20 to 1100 mg/mˆ2/d (35 sites) at Sousaki and Nisyros respectively. At Sousaki measurement sites covered almost all the degassing area and the diffuse methane output can be estimated in about 20 t/a from a surface of about 10,000 mˆ2. At Nisyros measurements covered the Stephanos and Kaminakia areas, which represent only a part of the entire degassing area. The two areas show very different methane degassing pattern with latter showing much higher flux values. Methane output can be estimated in about 0.25 t/a from an area of about 30,000 mˆ2 at Stephanos and about 1 t/a from an area of about 20,000 mˆ2 at Kaminakia. The total output from the entire geothermal system of Nisyros probably should not exceed 2 t/a.

Description: Published

Description: Vienna, Austria

Description: 4.5. Studi sul degassamento naturale e sui gas petroliferi

Description: open

Description: A biomonitoring survey, above tree line level, using two endemic species (Senecio aethnensis and Rumex aethnensis) was performed on Mt. Etna, in order to evaluate the dispersion and the impact of volcanic atmospheric emissions. Samples of leaves were collected in summer 2008 from 30 sites in the upper part of the volcano (1500- 3000 m a.s.l). Acid digestion of samples was carried out with a microwave oven, and 44 elements were analyzed by using plasma spectrometry (ICP-MS and ICP-OES). The highest concentrations of all investigated elements were found in the samples collected closest to the degassing craters, and in the downwind sector, confirming that the eastern flank of Mt. Etna is the most impacted by volcanic emissions. Leaves collected along two radial transects from the active vents on the eastern flank, highlight that the levels of metals decrease one or two orders of magnitude with increasing distance from the source. This variability is higher for volatile elements (As, Bi, Cd, Cs, Pb, Sb, Tl) than for more refractory elements (Al, Ba, Sc, Si, Sr, Th, U). The two different species of plants do not show significant differences in the bioaccumulation of most of the analyzed elements, except for lanthanides, which are systematically enriched in Rumex leaves. The high concentrations of many toxic elements in the leaves allow us to consider these plants as highly tolerant species to the volcanic emissions, and suitable for biomonitoring researches in the Mt. Etna area.

Description: Published

Description: Vienna, Austria

Description: 4.4. Scenari e mitigazione del rischio ambientale

Description: open

Description: Etna volcano, Italy, hosts one of the major groundwater systems of the island of Sicily. Waters circulate within highly permeable fractured, mainly hawaiitic, volcanic rocks. Aquifers are limited downwards by the underlying impermeable sedimentary terrains. Thickness of the volcanic rocks generally does not exceed some 300 m, preventing the waters to reach great depths. This is faced by short travel times (years to tens of years) and low thermalisation of the Etnean groundwaters. Measured temperatures are, in fact, generally lower than 25 °C. But the huge annual meteoric recharge (about 0.97 kmˆ3) with a high actual infiltration coefficient (0.75) implies a great underground circulation. During their travel from the summit area to the periphery of the volcano, waters acquire magmatic heat together with volcanic gases and solutes through water-rock interaction processes. In the last 20 years the Etnean aquifers has been extensively studied. Their waters were analysed for dissolved major, minor and trace element, O, H, C, S, B, Sr and He isotopes, and dissolved gas composition. These data have been published in several articles. Here, after a summary of the obtained results, the estimation of the magmatic heat flux through the aquifer will be discussed. To calculate heat uptake during subsurface circulation, for each sampling point (spring, well or drainage gallery) the following data have been considered: flow rate, water temperature, and oxygen isotopic composition. The latter was used to calculate the mean recharge altitude through the measured local isotopic lapse rate. Mean recharge temperatures, weighted for rain amount throughout the year, were obtained from the local weather station network. Calculations were made for a representative number of sampling points (216) including all major issues and corresponding to a total water flow of about 0.315 kmˆ3/a, which is 40% of the effective meteoric recharge. Results gave a total energy output of about 140 MW/a the half of which is ascribable to only 13 sampling points. These correspond to the highest flow drainage galleries with fluxes ranging from 50 to 1000 l/s and wells with pumping rates from 70 to 250 l/s. Geographical distribution indicates that, like magmatic gas leakage, heat flow is influenced by structural features of the volcanic edifice. The major heat discharge through groundwater are all tightly connected either to the major regional tectonic systems or to the major volcanic rift zones along which the most important flank eruptions take place. But rift zones are much more important for heat upraise due to the frequent dikes injection than for gas escape because generally when dikes have been emplaced the structure is no more permeable to gases because it becomes sealed by the cooling magma.

Description: Published

Description: Vienna, Austria

Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive

Description: open

Description: 〈b〉Intercultural interaction and "situational places": a perspective for urban cultural geography within and beyond the performative turn〈/b〉〈br〉 P. Dirksmeier and I. Helbrecht〈br〉 Soc. Geogr., 5, 39-48, doi:10.5194/sg-5-39-2010, 2010〈br〉 With the performative turn in social sciences and the humanities the concept of performance has arrived in human geography. Performance denotes an understanding of social actions and practices as constitutive for non-representational realities. This paper looks at the relationship between places and performance especially in urban geography and develops the new term "situational place" to grasp the increasing phenomenon of (intercultural) encounters in the cities of modern world society. "Situational places" are situated performances of these (intercultural) interactions between strangers in cities of the contemporary world society. With the aid of performance theory the influence of the omnipresent interactions between strangers in cities on urban space is conceptualized. Therewith, we hope to present some fruitful theoretical and empirical possibilities for a cultural urban geography within and beyond the performative turn.

Description: 〈b〉Déjà-vu: tourist practices of repeat visitors in the city of Paris〈/b〉〈br〉 T. Freytag〈br〉 Soc. Geogr., 5, 49-58, doi:10.5194/sg-5-49-2010, 2010〈br〉 In the context of sustained growth in European city tourism, competing travel destinations develop marketing strategies that include measures to attract an increasing number of repeat visitors. This paper explores the case of Paris in order to provide a better understanding of the specific motivations, interests and activities of leisure tourists who had previously stayed in the capital of France. Drawing on Pierre Bourdieu's concept of "distinction" it is argued that repeat visitors tend to differentiate themselves from other tourists. On the basis of substantive field work in Paris, a set of repeat visitor practices is presented that include strategies to avoid spatial concentrations of major tourist spots in order to participate in Parisian everyday life. Moreover, it is suggested to conceptualize the encounters between repeat visitors and tourism destinations as a lifelong relationship, which can be renewed and reproduced through further visits and virtual encounters. The distinct characteristics of repeat visitor practices have substantial implications for the organization of tourism in the city and the relationships between first-time tourists, repeat visitors and the local population.

Description: 〈b〉Intercultural interaction and "situational places": a perspective for urban cultural geography within and beyond the performative turn〈/b〉〈br〉 P. Dirksmeier and I. Helbrecht〈br〉 Soc. Geogr., 5, 39-48, doi:10.5194/sg-5-39-2010, 2010〈br〉 With the performative turn in social sciences and the humanities the concept of performance has arrived in human geography. Performance denotes an understanding of social actions and practices as constitutive for non-representational realities. This paper looks at the relationship between places and performance especially in urban geography and develops the new term "situational place" to grasp the increasing phenomenon of (intercultural) encounters in the cities of modern world society. "Situational places" are situated performances of these (intercultural) interactions between strangers in cities of the contemporary world society. With the aid of performance theory the influence of the omnipresent interactions between strangers in cities on urban space is conceptualized. Therewith, we hope to present some fruitful theoretical and empirical possibilities for a cultural urban geography within and beyond the performative turn.

Description: 〈b〉Plate tectonics conserves angular momentum〈/b〉〈br〉 C. Bowin〈br〉 eEarth, 5, 1-20, doi:10.5194/ee-5-1-2010, 2010〈br〉 A new combined understanding of plate tectonics, Earth internal structure, and the role of impulse in deformation of the Earth's crust is presented. Plate accelerations and decelerations have been revealed by iterative filtering of the quaternion history for the Euler poles that define absolute plate motion history for the past 68 million years, and provide an unprecedented precision for plate angular rotation variations with time at 2-million year intervals. Stage poles represent the angular rotation of a plate's motion between adjacent Euler poles, and from which the maximum velocity vector for a plate can be determined. The consistent maximum velocity variations, in turn, yield consistent estimates of plate accelerations and decelerations. The fact that the Pacific plate was shown to accelerate and decelerate, implied that conservation of plate tectonic angular momentum must be globally conserved, and that is confirmed by the results shown here (total angular momentum ~1.4〈sup〉+27〈/sup〉 kg m〈sup〉2〈/sup〉 s〈sup〉−1〈/sup〉). Accordingly, if a plate decelerates, other plates must increase their angular momentums to compensate. In addition, the azimuth of the maximum velocity vectors yields clues as to why the "bend" in the Emperor-Hawaiian seamount trend occurred near 46 Myr. This report summarizes processing results for 12 of the 14 major tectonic plates of the Earth (except for the Juan de Fuca and Philippine plates). 〈br〉〈br〉 Plate accelerations support the contention that plate tectonics is a product of torques that most likely are sustained by the sinking of positive density anomalies revealed by geoid anomalies of the degree 4–10 packet of the Earth's spherical harmonic coefficients. These linear positive geoid anomalies underlie plate subduction zones and are presumed due to phase changes in subducted gabbroic lithosphere at depth in the upper lower mantle (above 1200 km depth). The tectonic plates are pulled along by the sinking of these positive mass anomalies, rather than moving at near constant velocity on the crests of convection cells driven by rising heat. The magnitude of these sinking mass anomalies is inferred also to be sufficient to overcome basal plate and transform fault frictions. These results imply that spreading centers are primarily passive reactive features, and fracture zones (and wedge-shaped sites of seafloor spreading) are adjustment zones that accommodate strains in the lithosphere. Further, the interlocked pattern of the Australian and Pacific plates the past 42 Million years (with their absolute plate motions near 90° to each other) is taken as strong evidence that large thermally driven "roller" convection cells previously inferred as the driving mechanism in earlier interpretations of continental drift and plate tectonics, have not been active in the Earth's mantle the past 42 Million years, if ever. 〈br〉〈br〉 This report also presents estimates of the changes in location and magnitude of the Earth's axis of total plate tectonic angular momentum for the past 62 million years.

Description: 〈b〉Déjà-vu: tourist practices of repeat visitors in the city of Paris〈/b〉〈br〉 T. Freytag〈br〉 Soc. Geogr., 5, 49-58, doi:10.5194/sg-5-49-2010, 2010〈br〉 In the context of sustained growth in European city tourism, competing travel destinations develop marketing strategies that include measures to attract an increasing number of repeat visitors. This paper explores the case of Paris in order to provide a better understanding of the specific motivations, interests and activities of leisure tourists who had previously stayed in the capital of France. Drawing on Pierre Bourdieu's concept of "distinction" it is argued that repeat visitors tend to differentiate themselves from other tourists. On the basis of substantive field work in Paris, a set of repeat visitor practices is presented that include strategies to avoid spatial concentrations of major tourist spots in order to participate in Parisian everyday life. Moreover, it is suggested to conceptualize the encounters between repeat visitors and tourism destinations as a lifelong relationship, which can be renewed and reproduced through further visits and virtual encounters. The distinct characteristics of repeat visitor practices have substantial implications for the organization of tourism in the city and the relationships between first-time tourists, repeat visitors and the local population.

Description: 〈b〉Plate tectonics conserves angular momentum〈/b〉〈br〉 C. Bowin〈br〉 eEarth, 5, 1-20, doi:10.5194/ee-5-1-2010, 2010〈br〉 A new combined understanding of plate tectonics, Earth internal structure, and the role of impulse in deformation of the Earth's crust is presented. Plate accelerations and decelerations have been revealed by iterative filtering of the quaternion history for the Euler poles that define absolute plate motion history for the past 68 million years, and provide an unprecedented precision for plate angular rotation variations with time at 2-million year intervals. Stage poles represent the angular rotation of a plate's motion between adjacent Euler poles, and from which the maximum velocity vector for a plate can be determined. The consistent maximum velocity variations, in turn, yield consistent estimates of plate accelerations and decelerations. The fact that the Pacific plate was shown to accelerate and decelerate, implied that conservation of plate tectonic angular momentum must be globally conserved, and that is confirmed by the results shown here (total angular momentum ~1.4〈sup〉+27〈/sup〉 kg m〈sup〉2〈/sup〉 s〈sup〉−1〈/sup〉). Accordingly, if a plate decelerates, other plates must increase their angular momentums to compensate. In addition, the azimuth of the maximum velocity vectors yields clues as to why the "bend" in the Emperor-Hawaiian seamount trend occurred near 46 Myr. This report summarizes processing results for 12 of the 14 major tectonic plates of the Earth (except for the Juan de Fuca and Philippine plates). 〈br〉〈br〉 Plate accelerations support the contention that plate tectonics is a product of torques that most likely are sustained by the sinking of positive density anomalies revealed by geoid anomalies of the degree 4–10 packet of the Earth's spherical harmonic coefficients. These linear positive geoid anomalies underlie plate subduction zones and are presumed due to phase changes in subducted gabbroic lithosphere at depth in the upper lower mantle (above 1200 km depth). The tectonic plates are pulled along by the sinking of these positive mass anomalies, rather than moving at near constant velocity on the crests of convection cells driven by rising heat. The magnitude of these sinking mass anomalies is inferred also to be sufficient to overcome basal plate and transform fault frictions. These results imply that spreading centers are primarily passive reactive features, and fracture zones (and wedge-shaped sites of seafloor spreading) are adjustment zones that accommodate strains in the lithosphere. Further, the interlocked pattern of the Australian and Pacific plates the past 42 Million years (with their absolute plate motions near 90° to each other) is taken as strong evidence that large thermally driven "roller" convection cells previously inferred as the driving mechanism in earlier interpretations of continental drift and plate tectonics, have not been active in the Earth's mantle the past 42 Million years, if ever. 〈br〉〈br〉 This report also presents estimates of the changes in location and magnitude of the Earth's axis of total plate tectonic angular momentum for the past 62 million years.

Description: One year of multi-wavelength (3+2) Raman lidar measurements at Gual Pahari, close to Delhi, were analysed. The data was split into four seasons: spring (March–May), summer (June–August), autumn (September–November) and winter (December–February). The vertical profiles of backscatter, extinction, and lidar ratio and their variability during each season are presented. The measurements revealed that, on average, the aerosol layer was at its highest in spring (5.5 km). In summer, the vertically averaged (between 1–3 km) backscatter and extinction coefficients had the highest averages (3.3 Mm−1 sr−1 and 142 Mm−1 at 532 nm, respectively). Aerosol concentrations were slightly higher in summer compared with other seasons, and particles were larger in size. The autumn showed the highest lidar ratio and high extinction-related Ångström exponents (AEext), indicating the presence of smaller probably absorbing particles. The winter had the lowest backscatter and extinction coefficients, but AEext was the highest, suggesting still a large amount of small particles.

Description: The formation of organic nitrates and secondary organic aerosol (SOA) were monitored during the NO3 + limonene reaction in the atmosphere simulation chamber SAPHIR at Research Center Jülich. The 24-h run began in a purged, dry, particle-free chamber and comprised two injections of limonene and oxidants, such that the first experiment measured SOA yield in the absence of seed aerosol, and the second experiment yields in the presence of 10 μg m−3 seed organic aerosol. After each injection, two separate increases in aerosol mass were observed, corresponding to sequential oxidation of the two limonene double bonds. Analysis of the measured NO3, limonene, product nitrate concentrations, and aerosol properties provides mechanistic insight and constrains rate constants, branching ratios and vapor pressures of the products. The organic nitrate yield from NO3 + limonene is ≈30%. The SOA mass yield was observed to be 25–40%. The first injection is reproduced by a kinetic model. PMF analysis of the aerosol composition suggests that much of the aerosol mass results from combined oxidation by both O3 and NO3, e.g., oxidation of NO3 + limonene products by O3. Further, later aerosol nitrate mass seems to derive from heterogeneous uptake of NO3 onto unreacted aerosol alkene.

Description: The radiative forcing estimation of the polluted mineral dust is limited due to lack of morphological analysis, mixing state with the carbonaceous components and the hematite content in the pure dust. The accumulation mode mineral dust has been found to mix with anthropogenically produced black carbon, organic carbon and brown carbon during long range transport. The above features of the polluted dust are not well accounted in the optical models and lead the uncertainty in the numerical estimation of their radiative impact. The Semi-external mixing being a prominent mixing of dust and carbonaceous components has not been studied in details so for compared to core-shell, internal and external mixing studies. In present study, we consider the pure mineral dust composed of non-metallic components (such as Quartz, Feldspar, Mica and Calcite) and metalic component like hematite (Fe2O3). The hematite percentage in the pure mineral dust governs its absorbance. Based on this hematite variation, the hematite fraction in pure mineral dust has been constrained between 0–8%. The morphological and mineralogical characterization of the polluted dust led to consider the three sphere, two sphere and two spheroid model shapes for polluted dust particle system. The pollution gives rise to various light absorbing aerosol components like black carbon, brown carbon and organic carbon (comprising of HUmic-Like Substances, HULIS) in the atmosphere. The entire above discussed model shapes have been considered for the mineral dust getting polluted with (1) organic carbon (especially HULIS component) (2) Brown carbon and (3) black carbon by making a semi-external mixture with pure mineral dust. The optical properties (like Single Scattering Albedo, SSA; Asymmetry parameter, g and Extinction efficiency, Qext) of above model shapes for the polluted dust have been computed using Discrete Dipole Approximation, DDA code. For above model shapes, the SSA was found to vary depending on hematite content (0–8%) and model shape composition. For the two sphere BC-mineral dust cluster, hematite was found to be dominating absorber compared to that of black carbon as the RBC/Rdust decreases. (i.e. with increase of dust sphere size compared to black carbon sphere in the composite 2-sphere cluster). SSA was found to be very sensitivity for the hematite content when both of the spheres (i.e. mineral dust and BC) are nearly of same size. The two spheroid system composed of organic carbon and dust with 0% hematite (OCD'-0) showed the maximum deviation of SSA (i.e.~5%) compared to the two sphere system of same composition and hematite content (OCD-0 ). Increase in hematite from 0 to 8% caused maximum SSA deviation of ~20% for two sphere organic carbon-dust system (OCD) while the same has been observed to be ~18% for two spheroid organic carbon-dust system (OCD'). SSA was found to be more sensitive to hematite content than that of particle shape. Compared to SSA, Asymmetry parameter, g was found to be more sensitive towards particle shape. For three-sphere model shapes with 0% hematite composed of black carbon-dust-dust (BCDD-0), brown carbon-dust-dust (BrCDD-0 ) and organic carbon-dust-dust (OCDD-0), the deviation of SSA and g relative to conjugate black carbon (BC), brown carbon (BrC) and organic carbon (OC) spheres are ~68% and ~31%, ~83% and ~31% and ~70% and ~33%, respectively. Thus modeled polluted dust optics will provide a better basis for radiative forcing estimation and many sensitivity studies.

Description: A plume rise algorithm for wildfires was included in WRF-Chem, and applied to look at the impact of intense wildfires during the 2004 Alaska wildfire season on weather simulations using model resolutions of 10 km and 2 km. Biomass burning emissions were estimated using a biomass burning emissions model. In addition a 1-D time dependent cloud model was used online in WRF-Chem to estimate injection heights as well as the final emission rates. It was shown that with the inclusion of the intense wildfires of the 2004 fire season in the model simulations the interaction of the aerosols with the atmospheric radiation lead to significant modifications of vertical profiles of temperature and moisture in cloud-free areas. On the other hand, when clouds were present, the high concentrations of fine aerosol (PM2.5) and the resulting large numbers of Cloud Condensation Nuclei (CCN) had a strong impact on clouds and microphysics, with decreased precipitation coverage and precipitation amounts during the first 12 h of the integration, but significantly stronger storms during the afternoon hours.

Description: This study is based on 18 months (20 July 2006–5 February 2008) of continuous measurements of aerosol particle size distributions, air ion size distributions, trace gas concentrations and basic meteorology in a semi-clean savannah environment in Republic of South Africa. New particle formation and growth was observed on 69% of the days and bursts of non-growing ions/sub-10 nm particles on additional 14% of the days. The new particle formation and growth rates were among the highest reported in the literature for continental boundary layer locations; median 10 nm formation rate was 2.2 cm−3s−1 and median 10–30 nm growth rate 8.9 nm h−1. The median 2 nm ion formation rate was 0.5 cm−3s−1 and the median ion growth rates were 6.2, 8.0 and 8.1 nm h−1 for size ranges 1.5–3 nm, 3–7 nm and 7–20 nm, respectively. Three different approaches were used to study the origin of the formation and growth rates: seasonal variation, air mass history analysis and estimated sulphuric acid contribution to the growth. The growth rates had a clear seasonal dependency with minimum during winter and maxima in spring and late summer and the air mass history analysis indicated the highest formation and growth rates to be associated with the area of highest VOC (Volatile Organic Compounds) emissions rather than the highest estimated sulphuric acid concentrations. The relative contribution of estimated sulphuric acid to the growth rate was decreasing with increasing particle size and could explain more than 20% of the observed growth rate only for the 1.5–3 nm size range. The implication is that the sulphuric acid alone is not enough to explain the growth, but the highest growth rates seem to originate in VOC emissions following from biological activity. The frequency of new particle formation, however, increased nearly monotonously with the estimated sulphuric acid reaching 100% at H2SO4 concentration of 4×107cm−3, which suggests the formation and growth to be independent of each other.

Description: Nitrous acid (HONO) often plays an important role in tropospheric photochemistry as a major precursor of the hydroxyl radical (OH) in early morning hours and potentially during the day. However, the processes leading to formation of HONO and its vertical distribution at night, which can have a considerable impact on daytime ozone formation, are currently poorly characterized by observations and models. Long-path differential optical absorption spectroscopy (LP-DOAS) measurements of HONO during the 2006 TexAQS II Radical and Aerosol Measurement Project (TRAMP), near downtown Houston, TX, show nocturnal vertical profiles of HONO, with mixing ratios of up to 2.2 ppb near the surface and below 100 ppt aloft. Three nighttime periods of HONO, NO2 and O3 observations during TRAMP were used to perform model simulations of vertical mixing ratio profiles. By adjusting vertical mixing and NOx emissions the modeled NO2 and O3 mixing ratios showed very good agreement with the observations. Using a simple conversion of NO2 to HONO on the ground, direct HONO emissions, as well as HONO loss at the ground and on aerosol, the observed HONO profiles were reproduced well by the model. The unobserved increase of HONO to NO2 ratio (HONO/NO2) with altitude that was simulated by the initial model runs was found to be due to HONO uptake being too small on aerosol and too large on the ground. Refined model runs, with adjusted HONO uptake coefficients, showed much better agreement of HONO and HONO/NO2 for two typical nights, except during morning rush hour, when other HONO formation pathways are most likely active. One of the nights analyzed showed increase of HONO mixing ratios together with decreasing NO2 mixing ratios that the model was unable to reproduce, most likely due to the impact of weak precipitation during this night. HONO formation and removal rates averaged over the lowest 300 m of the atmosphere showed that NO2 to HONO conversion on the ground was the dominant source of HONO, followed by traffic emission. Aerosol did not play an important role in HONO formation. Although ground deposition was also a major removal pathway of HONO, net HONO production at the ground was the main source of HONO in our model studies. Sensitivity studies showed that in the stable NBL, net HONO production at the ground tends to increase with faster vertical mixing and stronger emission. Vertical transport was found to be the dominant source of HONO aloft.

Description: The quantification of sources of carbonaceous aerosol is important to understand their atmospheric concentrations and regulating processes and to study possible effects on climate and air quality, in addition to develop mitigation strategies. In the framework of the European Aerosol Cloud Climate Interaction (EUCAARI) project fine (Dp 〈 2.5 μm) and coarse (2.5 μm 〈 Dp 〈 10 μm) aerosol particles were sampled from February to June (wet season) and from August to September (dry season) 2008 in the Central Amazon Basin. The mass of fine particles averaged 2.4 μg m−3 during the wet season and 4.2 μg m−3 during the dry season. The average coarse aerosol mass concentration during wet and dry periods was 7.9 and 7.6 μg m−3, respectively. The overall chemical composition of fine and coarse mass did not show any seasonality with the largest fraction of fine and coarse aerosol mass explained by organic carbon (OC); the average OC to mass ratio was 0.4 and 0.6 in fine and coarse aerosol modes, respectively. The mass absorbing cross section of soot was determined by comparison of elemental carbon and light absorption coefficient measurements and it was equal to 4.7 m2 g−1 at 637 nm. Carbon aerosol sources were identified by Positive Matrix Factorization (PMF) analysis of thermograms: 43% of fine total carbon mass was assigned to biomass burning, 34% to secondary organic aerosol (SOA), and 23% to volatile species that are difficult to apportion. In the coarse mode, primary biogenic aerosol particles (PBAP) dominated the carbonaceous aerosol mass. The results confirmed the importance of PBAP in forested areas. The source apportionment results were employed to evaluate the ability of global chemistry transport models to simulate carbonaceous aerosol sources in a regional tropical background site. The comparison showed an overestimation of elemental carbon (EC) by the TM5 model during the dry season and OC both during the dry and wet periods. The overestimation was likely due to the overestimation of biomass burning emission inventories and SOA production over tropical areas.

Description: The frequency of occurrence of cirrus clouds and contrails, their life time, ice crystal size spectra and thus their radiative properties depend strongly on the ambient distribution of the relative humidity with respect to ice (RHice). Ice clouds do not form below a certain supersaturation and both cirrus and contrails need at least saturation conditions to persist over a longer period. Under subsaturated conditions, cirrus and contrails should dissipate. During the mid-latitude aircraft experiment CONCERT 2008 (CONtrail and Cirrus ExpeRimenT), RHice and ice crystals were measured in cirrus and contrails. Here, we present results from 2.3/1.7 h of observation in cirrus/contrails during 6 flights. Thin and subvisible cirrus with contrails embedded therein have been detected frequently in a subsaturated environment. Nevertheless, ice crystals up to radii of 50 μm and larger, but with low number densities were often observed inside the contrails as well as in the cirrus. Analysis of the meteorological situation indicates that the crystals in the contrails were entrained from the thin/subvisible cirrus clouds, which emerged in frontal systems with low updrafts. From model simulations of cirrus evaporation times it follows that such thin/subvisible cirrus can exist for time periods of a couple of hours and longer in a subsaturated environment and thus may represent a considerable part of the cirrus coverage.

Description: The atmospheric chemistry general circulation model ECHAM5/MESSy is used to simulate polar surface air temperature effects of geomagnetic activity variations. A transient model simulation was performed for the years 1960–2004 and is shown to develop polar surface air temperature patterns that depend on geomagnetic activity strength, similar to previous studies. In order to eliminate influencing factors such as sea surface temperatures (SST) or UV variations, two nine-year long simulations were carried out, with strong and weak geomagnetic activity, respectively, while all other boundary conditions were held to year 2000 levels. Statistically significant temperature effects that were observed in previous reanalysis and model results are also obtained from this set of simulations, suggesting that such patterns are indeed related to geomagnetic activity. In the model, strong geomagnetic activity and the associated NOx enhancements lead to polar stratospheric ozone loss. Compared with the simulation with weak geomagnetic activity, the ozone loss causes a decrease in ozone radiative cooling and thus a temperature increase in the polar winter mesosphere. Similar to previous studies, a cooling is found below the stratopause, which other authors have attributed to a decrease in the mean meridional circulation. In the polar stratosphere this leads to a more stable vortex. A strong (weak) Northern Hemisphere vortex is known to be associated with a positive (negative) Northern Annular Mode (NAM) index; our simulations exhibit a positive NAM index for strong geomagnetic activity, and a negative NAM for weak geomagnetic activity. Such NAM anomalies have been shown to propagate to the surface, and this is also seen in the model simulations. NAM anomalies are known to lead to specific surface temperature anomalies: a positive NAM is associated with warmer than average northern Eurasia and colder than average eastern North Atlantic. This is also the case in our simulation. Our simulations suggest a link between geomagnetic activity, ozone loss, stratospheric cooling, the NAM, and surface temperature variability.

Description: Sun-lit snow is increasingly recognized as a chemical reactor that plays an active role in uptake, transformation, and release of atmospheric trace gases. Snow is known to influence boundary layer air on a local scale, and given the large global surface coverage of snow may also be significant on regional and global scales. We present a new detailed one-dimensional snow chemistry module that has been coupled to the 1-D atmospheric boundary layer model MISTRA, we refer to the coupled model as MISTRA-SNOW. The new 1-D snow module, which is dynamically coupled to the overlaying atmospheric model, includes heat transport in the snowpack, molecular diffusion, and wind pumping of gases in the interstitial air. The model includes gas phase photochemistry and chemical reactions both in the interstitial air and the atmosphere. Heterogeneous and multiphase chemistry on atmospheric aerosol is considered explicitly. The chemical interaction of interstitial air with snow grains is simulated assuming chemistry in a liquid (aqueous) layer on the grain surface. The model was used to investigate snow as the source of nitrogen oxides (NOx) and gas phase reactive bromine in the atmospheric boundary layer in the remote snow covered Arctic (over the Greenland ice sheet) as well as to investigate the link between halogen cycling and ozone depletion that has been observed in interstitial air. The model is validated using data taken 10 June–13 June, 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). The model predicts that reactions involving bromide and nitrate impurities in the surface snow at Summit can sustain atmospheric NO and BrO mixing ratios measured at Summit during this period.

Description: This study reports laboratory measurements of cloud condensation nuclei (CCN) activity and droplet activation kinetics of aerosols dry-generated from clays, calcite, quartz, and desert soil samples from Northern Africa, East Asia/China, and Northern America. Based on the observed dependence of critical supersaturation, sc, with particle dry diameter, Ddry, we find that FHH adsorption activation theory is a far more suitable framework for describing fresh dust CCN activity than Köhler theory. One set of FHH parameters (AFFH ~ 2.25 ± 0.75, BFFH ~ 1.20 ± 0.10) can adequately reproduce the measured CCN activity for all species considered, and also explains the large range of hygroscopicities reported in the literature. Based on threshold droplet growth analysis, mineral dust aerosols were found to display retarded activation kinetics compared to ammonium sulfate. Comprehensive simulations of mineral dust activation and growth in the CCN instrument suggest that this retardation is equivalent to a reduction of the water vapor uptake coefficient (relative to that for calibration ammonium sulfate aerosol) by 30–80%. These results suggest that dust particles do not require deliquescent material to act as CCN in the atmosphere.

Description: European pollutants are known to affect the Eastern Mediterranean (EM). 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 EM. In the current study, spatially tagged carbon monoxide was used as a tracer for pollutant transport from Europe to the EM 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. 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 EM shore.

Description: Scattering and absorption were measured at the SMEAR II station in Hyytiälä, Finland, from October 2006 to May 2009. The average scattering coefficient σSP (λ=550 nm) 18 Mm−1 was about twice as much as at the Pallas GAW station in Finnish Lapland. The average absorption coefficient σAP (λ=550 nm) was 2.1 Mm−1. The seasonal cycles were analyzed from hourly-averaged data classified according to the measurement month. The ratio of the highest to the lowest average σSP and σAP was ~1.8 and ~2.8, respectively. The average single-scattering albedo (ω0) was 0.86 in winter and 0.91 in summer. σSP was highly correlated with the volume concentrations calculated from number size distributions in the size range 0.003–10 μm yielding PM10 mass scattering efficiency of 2.75 ± 0.01 g m−2 at λ=550 nm. Scattering coefficients were also calculated from the number size distributions by using a Mie code and the refractive index of ammonium sulfate. The linear regression yielded σSP(modelled)=1.04×σSP(measured) but there were also large deviations from the regression line: 10% of the σSP(modelled)-to-σSP(measured) ratios, calculated for each hour, were smaller than 0.9 and 10% of them were larger than 1.27. The scattering size distributions were bimodal, with a large submicrometer mode with geometric mean diameters Dg between ~300 and 400 nm and a smaller supermicrometer mode with Dg at ~1.5–1.9 μm. The contribution of submicrometer particles to scattering was ~90%. The Ångström exponent of scattering, αSP, was compared with the following weighted mean diameters: count mean diameter (CMD), surface mean diameter (SMD), scattering mean diameter (ScMD), condensation sink mean diameter (CsMD), and volume mean diameter (VMD). If αSP is to be used for estimating some measure of the size of particles, the best choice would be ScMD, then SMD, and then VMD. In all of these the qualitative relationship is similar: the larger the Ångström exponent, the smaller the weighted mean diameter. Contrary to these, CMD increased with increasing αSP and CsMD did not have any clear relationship with αSP. Source regions were estimated with backtrajectories and trajectory statistics. The geometric mean σSP and σAP associated with the grid cells in Eastern Europe were in the range 20–40 Mm−1 and 4–6 Mm−1, respectively. The respective geometric means of σSP and σAP in the grid cells over Norwegian Sea were in the range 5–10 Mm−1 and

Description: In the frame of the European project, entitled MULTI-ASSESS, specimens of structural metals, glass, stone and concrete materials were exposed to air pollution at a station, which was installed for this purpose on a building, located in the centre of Athens. The main purpose of this project was to determine the corrosion and soiling effects of air pollution on materials. A set of the specimens was exposed in a position that was sheltered from rain and partly from wind, and another set was exposed in unsheltered positions on the roof of the above said building. In addition, other specimens were exposed at different heights on the same building, in order to investigate for the first time the corrosion and soiling effects on various materials as a function of height. For the determination of these effects, chemical analysis of the specimens was performed and basic parameters as the weight change, the layer thickness and the optical properties were calculated. Finally, the results obtained are discussed and their plausible interpretation is attempted.

Description: The ash cloud of the Eyjafjallajökull1 volcano on Iceland caused closure of large parts of European airspace in April and May 2010. For the validation and improvement of the European volcanic ash forecast models several research flights were performed. Also the CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) flying laboratory, which routinely measures at cruise altitude (≈11 km) performed three dedicated measurements flights through sections of the ash plume. Although the focus of these flights was on the detection and quantification of the volcanic ash, we report here on sulphur dioxide (SO2) and bromine monoxide (BrO) measurements with the CARIBIC DOAS (Differential Optical Absorption Spectroscopy) instrument during the second of these special flights on 16 May 2010. As the BrO and the SO2 observations coincide, we assume the BrO to have been formed inside the volcanic plume. Both SO2 and BrO observations agree well with simultaneous satellite (GOME-2) observations. SO2 column densities retrieved from satellite observations are often used as an indicator for volcanic ash. For SO2 some additional information on the local distribution can be derived from a~comparison of forward and back scan GOME-2 data. More details on the local plume size and position are retrieved by combining CARIBIC and GOME-2 data. 1Also referred to as: Eyjafjalla (e.g. Schumann et al., 2010), Eyjafjöll or Eyjafjoll (e.g. Ansmann et al., 2010).

Description: This study explores the indirect effects of anthropogenic and biomass burning aerosols on Arctic clouds by co-locating a combination of MODIS and POLDER cloud products with output from the FLEXPART tracer transport model. During the activities of the International Polar Year for the Spring and Summer of 2008, we find a high sensitivity of Arctic cloud radiative properties to both anthropogenic and biomass burning pollution plumes, particularly at air temperatures near freezing or potential temperatures near 286 K. However, the sensitivity is much lower at both colder and warmer temperatures, likely due increases in the wet scavenging of cloud condensation nuclei: the pollution plumes remain but the component that influences clouds has been removed along transport pathways. The analysis shows that, independent of temperature, cloud optical depth is approximately four times more sensitive to changes in pollution levels than is cloud effective radius. This suggests that some form of feedback mechanism amplifies the radiative response of Arctic clouds to pollution through changes in cloud liquid water path.

Description: This paper presents an analysis of the recent tropospheric molecular hydrogen (H2) budget with a particular focus on soil uptake and surface emissions. A variational inversion scheme is combined with observations from the RAMCES and EUROHYDROS atmospheric networks, which include continuous measurements performed between mid-2006 and mid-2009. Net H2 surface flux, soil uptake distinct from surface emissions and finally, soil uptake, biomass burning, anthropogenic emissions and N2 fixation-related emissions separately were inverted in several scenarios. The various inversions generate an estimate for each term of the H2 budget. The net H2 flux per region (High Northern Hemisphere, Tropics and High Southern Hemisphere) varies between −8 and 8 Tg yr−1. The best inversion in terms of fit to the observations combines updated prior surface emissions and a soil deposition velocity map that is based on soil uptake measurements. Our estimate of global H2 soil uptake is −59 ± 4.0 Tg yr−1. Forty per cent of this uptake is located in the High Northern Hemisphere and 55% is located in the Tropics. In terms of surface emissions, seasonality is mainly driven by biomass burning emissions. The inferred European anthropogenic emissions are consistent with independent H2 emissions estimated using a H2/CO mass ratio of 0.034 and CO emissions considering their respective uncertainties. To constrain a more robust partition of H2 sources and sinks would need additional constraints, such as isotopic measurements.

Description: A major contribution to intensity changes of tropical cyclones (TCs) is believed to be associated with interaction with dry environmental air. However, the conditions under which pronounced TC-environment interaction takes place are not well understood. As a step towards improving our understanding of this problem we analyze the flow topology of a TC in vertical wind shear in an idealized, three-dimensional, convection-permitting numerical experiment. A set of distinct streamlines, the so-called separatrices, can be identified under the assumptions of steady and layer-wise horizontal flow. The separatrices are shown to divide the flow around the TC into distinct regions. The separatrix structure in our numerical experiment is more complex than the well-known flow topology of a non-divergent point vortex in uniform background flow. In particular, one separatrix spirals inwards and ends in a limit cycle, a meso-scale dividing streamline encompassing the eyewall above the inflow and below the outflow layer. Air with the highest values of moist entropy resides within this limit cycle supporting the notion that the eyewall is well protected from intrusion of dry environmental air despite the adverse impact of the vertical wind shear. This "moist envelope" is distorted considerably by the vertical wind shear, and the shape of the moist envelope is closely related to the shape of the limit cycle. A simple kinematic model based on a weakly divergent point vortex in background flow is presented. The model is shown to capture the essence of many salient features of the flow topology in the idealized experiment. A regime diagram representing realistic values of TC intensity and vertical wind shear can be constructed for this simple model. The results indicate distinct scenarios of environmental interaction depending on the ratio of storm intensity and shear magnitude. Further implications of the new results derived from the flow topology analysis for TCs in the real atmosphere are discussed.

Description: Three years (2006–2008) of ground-based observations of the Aerosol Optical Depth (AOD) in the urban environment of Athens, in the Eastern Mediterranean, are analysed in this work. Measurements were acquired with a Multi-Filter Rotating Shadowband Radiometer at five wavelengths. The daily average AOD at 500 nm is 0.23, and the mean Ångström coefficient calculated between 415 and 867 nm is 1.41. The annual variability of AOD has a spring maximum dominated by coarse dust particles from the Sahara (AOD 0.34–0.42), while the diurnal pattern is typical for urban sites, with AOD steadily increasing throughout the day. Secondary contributors of high aerosol loadings over Athens are identified, namely the Istanbul metropolitan area, the extended areas of biomass burning around the north coast of the Black Sea, power plants spread throughout the Balkans and the industrial area in the Po valley, with average daily AOD in the range of 0.25–0.35. The geographical distribution of the above sources in conjunction with the prevailing synoptic situation and contribution of local sources, lead to mixed types of aerosols over Athens with highly variable contribution of fine and coarse particles to AOD in the range 10%–90%. This is the first long-term, ground based data set available for Athens, and has also been used for the validation of satellite derived AOD by MODIS, showing good agreement on an annual basis, but with an overestimation of satellite AODs in the warm period.

Description: We have been conducting continuous measurements of CH4 and CO2 on a network of towers (JR-STATION: Japan–Russia Siberian Tall Tower Inland Observation Network) located in taiga, steppe, and wetland biomes of Siberia. Here we describe measurements from two forested bog sites, Karasevoe (KRS; 58°15′ N, 82°25′ E) and Demyanskoe (DEM; 59°47′ N, 70°52′ E), in West Siberia from 2005 to 2009. Although both CH4 and CO2 accumulation (ΔCH4 and ΔCO2) during nighttime (duration of 7 h beginning 21:30 LST) at KRS in July 2007 showed an anomalously high concentration, the higher ratios of ΔCH4/ΔCO2 compared with those in other years indicate that a considerably more CH4 flux occurred relative to the CO2 flux in response to large precipitation recorded in 2007 (~2.7 mm d−1 higher than the climatological 1979–1998 base). Estimated seasonal CH4 fluxes based on the ratio of ΔCH4/ΔCO2 and the CASA 3-hourly CO2 flux for the 2005–2009 period exhibited a seasonal variation with a maximum in July at both sites. Annual values of the CH4 emission from the forested bogs around KRS (approx. 7.8×104 km2) calculated from a process-based ecosystem model, Vegetation Integrative Simulator for Trace gases (VISIT), showed inter-annual variation of 0.54, 0.31, 0.94, 0.44, and 0.41 Tg CH4 yr−1 from 2005 to 2009, respectively, with the highest values in 2007. It was assumed in the model that the area flooded with water is proportional to the cumulative anomaly in monthly precipitation rate.

Description: We report simultaneous measurements of volatile organic compound (VOC) mixing ratios including C6 to C8 aromatics, isoprene, monoterpenes, acetone and organic aerosol mass loadings at a rural location in Southwestern Ontario, Canada by Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) and Aerosol Mass Spectrometry (AMS), respectively. During the three-week-long Border Air Quality and Meteorology Study in June–July 2007, air was sampled from a range of sources, including aged air from the polluted US Midwest, direct outflow from Detroit 50 km away, and clean air with higher biogenic input. After normalization to the diurnal profile of CO, a long-lived tracer, diurnal analyses show clear photochemical loss of reactive aromatics and production of oxygenated VOCs and secondary organic aerosol (SOA) during the daytime. Biogenic VOC mixing ratios increase during the daytime in accord with their light- and temperature-dependent sources. Long-lived species, such as hydrocarbon-like organic aerosol and benzene show little to no photochemical reactivity on this timescale. From the normalized diurnal profiles of VOCs, an estimate of OH concentrations during the daytime, measured O3 concentrations, and laboratory SOA yields, we calculate integrated organic aerosol production amounts associated with each measured SOA precursor. Depending on whether the SOA formation is occurring in a low- or high-NOx regime, we estimate that the biogenic gases contribute between 10 to 36 times as much SOA as do the aromatic precursors, making this a highly biogenically dominated region for SOA formation. The conclusion that biogenic SOA formation is of significance to air quality in this region is supported by detailed air quality modeling during this period (Stroud et al., 2010).

Description: Simultaneous measurements of atomic iodine (I), molecular iodine (I2) and ultrafine particles were made at O Grove, Galicia (42.50° N, 8.87° W), on the northwest coast of Spain. The observations show a strong tidal signature, and indicate that the most probable sources of reactive iodine species are the exposed macroalgae during low tide. For the first time, I2 and I were concurrently measured revealing a high average I2/I ratio of ~32, which is higher than previously inferred by modelling studies. A 1-dimensional photochemical model is employed to simulate the observations showing that the high I2/I ratio can be reproduced in the presence of fast vertical mixing close to the surface, or using an extra chemical loss for I atoms with an unknown species. There is a lack of strong correlation between the I2/I and ultrafine particles, indicating that although they both have macroalgal sources, these were not at the same location. The model simulations also suggest that the source of the observed ultrafine particles is likely not very close to the measurement site, in order for the particles to form and grow, but the source for I and I2 must be local. Finally, the effect of NOx levels on iodine oxides, and the conditions under which iodine particle bursts will be suppressed, are explored.

Description: The record–breaking major stratospheric warming of northern winter 2009 (January–February) is studied using BASCOE (Belgian Assimilation System for Chemical ObsErvation) stratospheric water vapour analyses and MLS (Microwave Limb Sounder) water vapour observations, together with meteorological data from the European Centre for Medium-Range Weather Forecasts (ECMWF) and potential vorticity derived from ECMWF meteorological data. We focus on the interaction between the cyclonic wintertime stratospheric polar vortex and subsidiary anticyclonic stratospheric circulations during the build-up, peak and aftermath of the major warming. We show dynamical consistency between the water vapour analysed fields, and the meteorological and PV fields. New results include the analysis of water vapour during the major warming and demonstration of the benefit of assimilating MLS satellite data into the BASCOE model.

Description: A quantum cascade laser based absorption spectrometer (QCLAS) is applied for the first time to perform in situ, continuous and high precision isotope ratio measurements of CO2 in the free troposphere. Time series of the three main CO2 isotopologue mixing ratios (12C16O2, 12C16O2 and 12C18O16O) have simultaneously been measured at one second time resolution over two years (from August 2008 to present) at the High Altitude Research Station Jungfraujoch (3580 m a.s.l., Switzerland). This work focuses on periods in February 2009 only, when sudden and pronounced enhancements in the tropospheric CO2 were observed. These short-term changes were closely correlated with variations in CO mixing ratios measured at the same site, indicating combustion related emissions as potential source. The analytical precision of 0.046‰ (at 50 s integration time) for both δ13C and δ18O and the high temporal resolution allowed the application of the Keeling plot method for source signature identification. The spatial origin of these CO2 emission sources was then determined by backward Lagrangian particle dispersion simulations.

Description: Businger and Delany (1990) presented an approach to estimate the sensor resolution required to limit the contribution of the uncertainty in the chemical concentration measurement to the flux measurement uncertainty to 10% for eddy covariance, gradient, and relaxed eddy accumulation flux measurement methods. We describe an improvement to their approach to estimate required resolution for the covariance method. In addition, we provide data to support selection of a form for the dimensionless scalar standard deviation similarity function based on observations of the variance of water vapor fluctuations from recent field experiments. We also redefine the atmospheric parameter of Businger and Delany in a more convenient, dimensionless form. To make the expression convenient for gas transfer applications, we introduce a "chemical parameter" based on the gas transfer (piston) velocity. Finally, we provide examples in which the approach is applied to measurement of carbon dioxide, dimethylsulfide, and hexachlorobenzene fluxes. The information provided here will be useful to plan field measurements of atmosphere-surface exchange fluxes of trace gases.

Description: Sea-salt aerosol mass, optical depth, and number concentration over the global oceans have significant implications for aerosol direct and indirect climate effects. We modeled sea-salt aerosol in a coupled climate and sectional microphysical model, CAM/CARMA, with aerosol dynamics including sea salt emission, gravitational sedimentation, dry deposition, wet scavenging, and particle swelling. We aimed at finding an integrated sea salt source function parameterization in the global climate model to simultaneously represent mass, optical depth, and number concentration. Each of these quantities is sensitive to a different part of the aerosol size distribution, which requires a size resolved microphysical model to treat properly. The CMS source function introduced in the research, based upon several earlier source functions, reproduced measurements of mass, optical depth and number concentration as well as the size distribution better than other source function choices we tried. However, as we note, it is also important to properly set the removal rate of the particles. The source function and removal rate are coupled in producing observed abundances. We find that sea-salt mass and optical depth peak in the winter, when winds are highest. However, surprisingly, particle numbers and CCN concentrations peak in summer when rainfall is lowest. The quadratic dependence of sea salt optical depth on wind speed, observed by some, is well represented in the model. We also found good agreement with the wind speed dependency of the number concentration at the measurement location and the regional scale. The work is the basis for further investigation of the effects of sea-salt aerosol on climate and atmospheric chemistry.

Description: This review is based on ca. 250 publications, from which 92 published data on the temporal and spatial variation of the concentration of small ions (

Description: Spaceborne lidar measurements from CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations) are used to provide a vortex-wide perspective of the 2009–2010 Arctic polar stratospheric cloud (PSC) season to complement more focused measurements from the European Union RECONCILE (reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interactions) field campaign. The 2009–2010 Arctic winter was unusually cold at stratospheric levels, especially from mid-December 2009 until the end of January 2010, and was one of only a few winters from the past 52 years with synoptic-scale regions of temperatures below the frost point. More PSCs were observed by CALIPSO during the 2009–2010 Arctic winter than in the previous three Arctic seasons combined. In particular, there were significantly more observations of high number density nitric acid trihydrate (NAT) mixtures (referred to as Mix 2-enh) and ice PSCs. We found that the 2009–2010 season could roughly be divided into four periods with distinctly different PSC optical characteristics. The early season (15–30 December 2009) was characterized by patchy, tenuous PSCs, primarily low number density liquid/NAT mixtures. The second phase of the season (31 December 2009–14 January 2010) was characterized by frequent mountain wave ice clouds that nucleated widespread NAT particles throughout the vortex, including Mix 2-enh. The third phase of the season (15–21 January 2010) was characterized by synoptic-scale temperatures below the frost point which led to a rare outbreak of widespread ice clouds. The fourth phase of the season (22–28 January) was characterized by a major stratospheric warming that distorted the vortex, displacing the cold pool from the vortex center. This final phase was dominated by supercooled ternary solution (STS) PSCs, although NAT particles may have been present in low number densities, but were masked by the more abundant STS droplets at colder temperatures. We also found distinct variations in the relative proportion of PSCs in each composition class with altitude over the course of the 2009–2010 Arctic season. Lower number density liquid/NAT mixtures were most frequently observed in the lower altitude regions of the clouds (below ∼18–20 km), which is consistent with CALIPSO observations in the Antarctic. Higher number density liquid/NAT mixtures, especially Mix 2-enh, were most frequently observed at altitudes above 18–20 km, primarily downstream of wave ice clouds. This pattern is consistent with the conceptual model whereby low number density, large NAT particles are precipitated from higher number density NAT clouds (i.e. mother clouds) that are nucleated downstream of mountain wave ice clouds.

Description: The UV Aerosol Indices (UVAI) form one of very few available tools in satellite remote sensing that provide information on aerosol absorption. The UVAI are also quite insensitive to surface type and are determined in the presence of clouds – situations where most aerosol retrieval algorithms do not work. The UVAI are most sensitive to elevated layers of absorbing aerosols, such as mineral dust and smoke from biomass burning, but they can also be used to study non-absorbing aerosols, such as sulphate and secondary organic aerosols. Although UVAI are determined for cloud-contaminated pixels, clouds do affect the value of UVAI in several ways. One way to correct for these effects is to remove clouded pixels using a cloud filter. However, this causes a large loss of data, biases the results towards clear skies, and removes all potentially very interesting pixels where aerosols and clouds co-exist. We here propose to correct the effects of clouds on UVAI in a more sophisticated way, namely by simulating the contribution of clouds to UVAI, and then subtracting it from the measured data. To this aim, we modelled UVAI from clouds by using measured cloud optical parameters – either with low spatial resolution from SCIAMACHY, or high resolution from MERIS – as input. The modelled UVAI were compared with UVAI measured by SCIAMACHY on different spatial (local, regional and global) and temporal scales (single measurement, daily means and seasonal means). The general dependencies of UVAI on cloud parameters were quite well reproduced, but several issues remain unclear: compared to the modelled UVAI, measured UVAI show a bias, in particular for large cloud fractions, and much larger scatter. Also, the viewing angle dependence differs for measured and modelled UVAI. The modelled UVAI from clouds will be used to correct measured UVAI for the effect of clouds, thus allowing a more quantitative analysis of UVAI and enabling investigations of aerosol-cloud interactions.

Description: Phase transitions of atmospheric water play a ubiquitous role in the Earth's climate system, but their direct impact on atmospheric dynamics has escaped wide attention. Here we examine and advance a theory as to how condensation influences atmospheric pressure through the mass removal of water from the gas phase with a simultaneous account of the latent heat release. Building from fundamental physical principles we show that condensation is associated with a decline in air pressure in the lower atmosphere. This decline occurs up to a certain height, which ranges from 3 to 4 km for surface temperatures from 10 to 30 °C. We then estimate the horizontal pressure differences associated with water vapor condensation and find that these are comparable in magnitude with the pressure differences driving observed circulation patterns. The water vapor delivered to the atmosphere via evaporation represents a store of potential energy available to accelerate air and thus drive winds. Our estimates suggest that the global mean power at which this potential energy is released by condensation is around one per cent of the global solar power – this is similar to the known stationary dissipative power of general atmospheric circulation. We conclude that condensation and evaporation merit attention as major, if previously overlooked, factors in driving atmospheric dynamics.

Description: Regional trans-boundary air pollution has become an important issue in the field of air pollution modeling. This paper presents the results of the implementation of the MM5-CMAQ modeling system in the Yangtze River Delta (YRD) for the months of January and July of 2004. The meteorological parameters are obtained by using the MM5 model. A new regional emission inventory with spatial and temporal allocations based on local statistical data has been developed to provide input emissions data to the MM5-CMAQ modeling system. The pollutant concentrations obtained from the MM5-CMAQ modeling system have been compared with observational data from the national air pollution monitoring network. It is found that air quality in winter in the YRD is generally worse than in summer, due mainly to unfavorable meteorological dispersion conditions. In winter the pollution transport from Northern China to the YRD reinforces the pollution caused by large local emissions. The monthly average concentration of SO2 in the YRD is 0.026 ± 0.011 mg m−3 in January and 0.017 ± 0.009 mg m−3 in July. Monthly average concentrations of NO2 in the YRD in January and July are 0.021 ± 0.009 mg m−3, and 0.014 ± 0.008 mg m−3 respectively. Visibility is also a problem, with average deciview values of 26.4 ± 2.95 dcv in winter and 17.6 ± 3.3 dcv in summer. The ozone concentration in the downtown area of a city like Zhoushan can be very high, with the highest simulated value reaching 107 ppb. Our results show that ozone and haze have become extremely important issues in the regional air quality. Thus, regional air pollution control is urgently needed to improve air quality in the YRD.

Description: Field experiments were performed to investigate the effects of photo-oxidation on fine particle emissions from an in-use CFM56-2B gas turbine engine mounted on a KC-135 Stratotanker airframe. Emissions were sampled into a portable smog chamber from a rake inlet installed one-meter downstream of the engine exit plane of a parked and chocked aircraft. The chamber was then exposed to sunlight and/or UV lights to initiate photo-oxidation. Separate tests were performed at different engine loads (4, 7, 30, 85%). Photo-oxidation created substantial secondary particulate matter (PM), greatly exceeding the direct PM emissions at each engine load after an hour or less of aging at typical summertime conditions. After several hours of photo-oxidation, the ratio of secondary-to-primary PM mass was on average 35 ± 4.1, 17 ± 2.5, 60 ± 2.2, and 2.7 ± 1.1 times the primary PM for the 4, 7, 30, and 85% load experiments, respectively. The composition of secondary PM formed strongly depended on load. At 4% load, secondary PM was dominated by secondary organic aerosol (SOA). At higher loads, the secondary PM was mainly secondary sulfate. Predictions of an SOA model are compared to the measured SOA formation. The SOA model predicts ~40% of the SOA produced during the 4% load experiment and ~60% for the 85% load experiment. Significant emissions of low-volatility compounds present in both the vapor- and particle-phase were measured in the exhaust and represent a significant pool of SOA precursors that appear to form SOA efficiently when oxidized. These results underscore the importance of accounting for atmospheric processing when assessing the influence of aircraft emissions on ambient PM levels.

Description: In this paper we present evidence that the observed increase in tropical upwelling after the year 2000 may be attributed to a change in the Brewer-Dobson circulation pattern. For this purpose, we use the concept of transit times derived from residual circulation trajectories and different in-situ measurements of ozone and nitrous dioxide. Observations from the Canadian midlatitude ozone profile record, probability density functions of in-situ N2O observations and a shift of the N2O-O3 correlation slopes, taken together, indicate that the increased upwelling in the tropics after the year 2000 appears to have triggered an intensification of tracer transport from the tropics into the extratropics in the lower stratosphere below about 500 K. This finding is corroborated by the fact that transit times along the shallow branch of the residual circulation into the LMS have decreased for the same time period (1993–2003). On a longer time scale (1979–2009), the transit time of the shallow residual circulation branch show a steady decrease of about −1 month/decade over the last 30 years, while the transit times of the deep branch remain unchanged. This highlights the fact that a change in the upwelling across the tropical tropopause is not a direct indicator for changes of the whole Brewer-Dobson circulation.

Description: Field observations and quantum chemical calculations have shown that organic amine compounds may be important in new particle formation processes involving H2SO4. Here, we report laboratory observations that investigate the effect of trimethylamine (TMA) on H2SO4-H2O nucleation made under aerosol precursor concentrations typically found in the lower troposphere ([H2SO4] of 106–107 cm−3; [TMA] of 180–1350 pptv). These results show that the threshold [H2SO4] needed to produce the unity nucleation rate ([H2SO4] of 106–107 cm−3) and the number of precursor molecules in the critical cluster (nH2SO4 = 4–6; nTMA = 1) are surprisingly similar to those found in the ammonia (NH3) ternary nucleation study (Benson et al., 2010a). At lower RH, however, enhancement in nucleation rates due to TMA was up to an order of magnitude greater than that due to NH3. These findings imply that both amines and NH3 are important nucleation species, but under dry atmospheric conditions, amines may have stronger effects on H2SO4 nucleation than NH3. Aerosol models should therefore take into account inorganic and organic bases together to fully understand the widespread new particle formation events in the lower troposphere.

Description: An ion chromatographic method is described for the quantification of the simple alkyl amines: methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA) and triethylamine (TEA), in the ambient atmosphere. Limits of detection (3σ) are in the tens of pmol range for all of these amines, and good resolution is achieved for all compounds except for TMA and DEA. The technique was applied to the analysis of time-integrated samples collected using a micro-orifice uniform deposition impactor (MOUDI) with ten stages for size resolution of particles with aerodynamic diameters between 56 nm and 18 μm. In eight samples from urban and rural continental airmasses, the mass loading of amines consistently maximized on the stage corresponding to particles with aerodynamic diameters between 320 and 560 nm. The molar ratio of amines to ammonium (R3NH+/NH4+) in fine aerosol ranged between 0.005 and 0.2, and maximized for the smallest particle sizes. The size-dependence of the R3NH+/NH4+ ratio indicates differences in the relative importance of the processes leading to the incorporation of amines and ammonia into secondary particles. The technique was also used to make simultaneous hourly online measurements of amines in the gas phase and in fine particulate matter using an Ambient Ion Monitor Ion Chromatograph (AIM-IC). During a ten day campaign in downtown Toronto, DMA, TMA+DEA, and TEA were observed to range from below detection limit to 2.7 ppt in the gas phase. In the particle phase, MAH+ and TMAH++DEAH+ were observed to range from below detection limit up to 15 ng m−3. The presence of detectable levels of amines in the particle phase corresponded to periods with higher relative humidity and higher mass loadings of nitrate. While the hourly measurements made using the AIM-IC provide data that can be used the evaluate the application of gas-particle partitioning models to amines, the strong size-dependence of the R3NH+/NH4+ ratio indicates that using bulk measurements and an assumption of internal mixing may not be appropriate.

Description: The supply of bioavailable iron to the high-nitrate low-chlorophyll (HNLC) waters of the Southern Ocean through atmospheric pathways could stimulate phytoplankton blooms and have major implications for the global carbon cycle. In this study, model results and remotely-sensed data are analyzed to examine the horizontal and vertical transport pathways of Patagonian dust and quantify the effect of iron-laden mineral dust deposition on marine biological productivity in the surface waters of the South Atlantic Ocean (SAO). Model simulations for the atmospheric transport and deposition of mineral dust and bioavailable iron are carried out for two large dust outbreaks originated at the source regions of Northern Patagonia during the austral summer of 2009. Model-simulated horizontal and vertical transport pathways of Patagonian dust plumes are in reasonable agreement with remotely-sensed data. Simulations indicate that the synoptic meteorological patterns of high and low pressure systems are largely accountable for dust transport trajectories over the SAO. According to model results and retrievals from the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO), synoptic flows caused by opposing pressure systems (a high pressure system located to the east or north-east of a low pressure system) elevate the South American dust plumes well above the marine boundary layer. Under such conditions, the bulk concentration of mineral dust can quickly be transported around the low pressure system in a clockwise manner, follow the southeasterly advection pathway, and reach the HNLC waters of the SAO and Antarctica in ~3–4 days after emission from the source regions of Northern Patagonia. Two different mechanisms for dust-iron mobilization into a bioavailable form are considered in this study. A global 3-D chemical transport model (GEOS-Chem), implemented with an iron dissolution scheme, is employed to estimate the atmospheric fluxes of soluble iron, while a dust/biota assessment tool (Boyd et al., 2010) is applied to evaluate the amount of bioavailable iron formed through the slow and sustained leaching of dust in the ocean mixed layer. The effect of iron-laden mineral dust supply on surface ocean biomass is investigated by comparing predicted surface chlorophyll-a concentration ([Chl-a]) to remotely-sensed data. As the dust transport episodes examined here represent large summertime outflows of mineral dust from South American continental sources, this study suggests that (1) atmospheric fluxes of mineral dust from Patagonia are not likely to be the major source of bioavailable iron to ocean regions characterized by high primary productivity; (2) even if Patagonian dust plumes may not cause visible algae blooms, they could still influence background [Chl-a] in the South Atlantic sector of the Southern Ocean.

Description: The radiative forcing of dust and its impact on precipitation over the West Africa monsoon (WAM) region is simulated using a coupled meteorology and aerosol/chemistry model (WRF-Chem). During the monsoon season, dust is a dominant contributor to aerosol optical depth (AOD) over West Africa. In the control simulation, on 24-h domain average, dust has a cooling effect (−6.11 W/m2) at the surface, a warming effect (6.94 W/m2) in the atmosphere, and a relatively small TOA forcing (0.83 W/m2). Dust modifies the surface energy budget and atmospheric diabatic heating and hence causes lower atmospheric cooling in the daytime but warming in the nighttime. As a result, atmospheric stability is increased in the daytime and reduced in the nighttime, leading to a reduction of late afternoon precipitation by up to 0.14 mm/h (25%) and an increase of nocturnal and early morning precipitation by up to 0.04 mm/h (45%) over the WAM region. Dust-induced reduction of diurnal precipitation variation improves the simulated diurnal cycle of precipitation when compared to measurements. However, daily precipitation is only changed by a relatively small amount (−0.17 mm/day or −4%). The dust-induced change of WAM precipitation is not sensitive to interannual monsoon variability. On the other hand, sensitivity simulations show that, from weaker to stronger absorbing dust representing the uncertainty in dust solar absorptivity, dust longwave warming effect in the nighttime surpasses its shortwave cooling effect in the daytime at the surface, leading to a less stable atmosphere associated with more convective precipitation in the nighttime. As a result, the dust-induced change of daily WAM precipitation varies from a significant reduction of −0.52 mm/day (−12%, weaker absorbing dust) to a small increase of 0.03 mm/day (1%, stronger absorbing dust). This variation originates from the competition between dust impact on daytime and nighttime precipitation, which depends on dust shortwave absorption. Dust reduces the diurnal variation of precipitation regardless of its absorptivity, but more reduction is associated with stronger absorbing dust.

Description: Recent research has shown that orographic precipitation and the water resources that depend on it in the Colorado Rocky Mountains are sensitive to the variability of the region's aerosols, whether emitted locally or from distant sources. However, observations of cloud-active aerosols in western Colorado, climatologically upwind of the Colorado Rocky Mountains, have been limited to a few studies at a single, northern site. To address this knowledge gap, atmospheric aerosols were sampled at a ground site in southwestern Colorado and in low-level north to south transects of the Colorado Western Slope as part of the Inhibition of Snowfall by Pollution Aerosols (ISPA-III) field campaign. Total particle and cloud condensation nuclei (CCN) number concentration were measured for a 24-day period in Mesa Verde National Park, climatologically upwind of the San Juan Mountains, in Sept. and Oct. 2009. Regression analysis showed a positive relationship between mid-troposphere atmospheric pressure to the west of the site and the total particle count at the ground site, but no similar statistically significant relationship for the observed CCN. These data were supplemented with particle and CCN number concentration, as well as particle size distribution measurements aboard the KingAir platform during December 2009. A CCN closure attempt was performed using the size distribution information and suggested that the sampled aerosol in general had low hygroscopicity that changed slightly with the large-scale wind direction. Together, the sampled aerosols from these field programs were characteristic of a rural continental environment with a cloud active portion that varied slowly in time, and little in space along the Western Slope.

Description: During the African Monsoon Multidisciplinary Analyses (AMMA) airborne measurements of ozone, CO and nitrogen oxides by the French and German falcon aircraft took place near three cities in West Africa (Cotonou, Niamey and Ouagadougou). Significant ozone production (O3 increase of 40–50 ppbv) took place during two specific events: one near Cotonou on the coast of the Guinea Gulf, and the other near Niamey in the Sahel region. In both cases a high level of NOx (〉3 ppbv) is related to the ozone production. The ozone production is mainly driven by the Lagos-Cotonou anthropogenic emissions in Cotonou. In Niamey the combined effect of advection of VOC emissions from the forest and stagnation over the city area and the poorly vegetated soils recently wetted by convected systems is needed to achieve a similar level of ozone precursors. In Ouagadougou no ozone plume is found because of the absence of a pause in the convective activity and of the larger vegetated area around the city which prevented ozone plume formation during the wet season. To discuss the ozone increase near Cotonou two different approaches have been implemented: a FLEXPART simulation to quantify the probability of transport from the SH compared to air mass stagnation over the emission area and a simulation of the BOLAM mesoscale model with two different tracers for the anthropogenic emission (RETRO inventory for 2000) and the biomass burning. The BOLAM model shows a good agreement with the meteorological observations of the aircraft and allows to identify the key influence of the anthropogenic emissions in the first 3 km while the biomass burning plume remains above this altitude. The day to day variability of the ozone and CO in Niamey and Ouagadougou is discussed using FLEXPART simulations of the air mass stagnation in the 12° N–14° N latitude band and northward advection of air masses from the vegetated areas influenced by the biogenic volatile organic compound (VOC) emissions. Both conditions need to be fulfilled to be able to detect ozone increase within the city plume. The first condition is necessary to obtain a significant increase of the NOx concentrations by combining the city emission and the soil emission. It also shows that, contrary to the Niamey conditions, the Ouagadougou air mass transport and its timing respective to the convective activity did not correspond to favourable conditions for O3 formation during the time period of the aircraft data. Finally to check the magnitude of the ozone production related to the observed CO and NOx observations, a 2-days stationary run of the CittyCAT Lagrangian model was conducted at Cotonou location. The initialisation of the chemical concentrations not measured is done by scaling to the NOx and CO concentrations observed in the polluted plume. The scaling factor is derived from the low altitude observations provided by the DF20 and the BAe-146 aircraft during the AMMA campaign. Under such conditions, the simulation show that 50 ppbv of ozone can be produced in a 2-days period.

Description: Anthropogenic emissions of air pollutants in China influence not only local and regional environments but also the global atmospheric environment; therefore, it is important to understand how China's air pollutant emissions will change and how they will affect regional air quality in the future. Emission scenarios in 2020 were projected using forecasts of energy consumption and emission control strategies based on emissions in 2005, and on recent development plans for key industries in China. We developed four emission scenarios: REF[0] (current control legislations and implementation status), PC[0] (improvement of energy efficiencies and current environmental legislation), PC[1] (improvement of energy efficiencies and better implementation of environmental legislation), and PC[2] (improvement of energy efficiencies and strict environmental legislation). Under the REF[0] scenario, the emission of SO2, NOx, VOC and NH3 will increase by 17%, 50%, 49% and 18% in 2020, while PM will be reduced by 10% over East China, compared to that in 2005. In PC[2], sustainable energy polices will reduce SO2, NOx and PM10 emissions by 4.1 Tg, 2.6 Tg and 1.8 Tg, respectively; better implementation of current control policies will reduce SO2, NOx and PM10 emission by 2.9 Tg, 1.8 Tg, and 1.4 Tg, respectively; strict emission standards will reduce SO2, NOx and PM10 emissions by 3.2 Tg, 3.9 Tg, and 1.7 Tg, respectively. Under the PC[2] scenario, SO2 and PM10 emissions will decrease by 18% and 38%, while NOx and VOC emissions will increase by 3% and 8%, compared to that in 2005. Future air quality in China was simulated using the Community Multi-scale Air Quality Model (CMAQ) with 2005 emissions and 2020 emission scenarios. Under REF[0] emissions, the concentrations of SO2, NO2, hourly maximum ozone in summer, PM2.5, total sulfur and nitrogen depositions will increase by 5~47%, 45~53%, 8~12%, 4~15%, 4~37% and 7~14%, respectively, over East China. Under the PC[2] emission scenario, the concentrations of SO2, NO2, hourly maximal ozone in summer, PM2.5, total sulfur and nitrogen depositions will change by −28%~16%, −1%~11%, 1%~2%, −24%~−12%, −24%~13%, and 0~3%, respectively. The individual impacts of SO2, NOx, NH3, NMVOC and primary PM emission changes on ozone and PM2.5 concentrations have been analyzed using sensitivity analysis. The results suggest that NOx emission control need to be enhanced during the summertime to obtain both ozone and PM2.5 reduction benefits. NH3 emission controls should also be considered in order to reduce total nitrogen deposition in the future.

Description: Past research has shown that the dominant influence on recent global climate changes is from anthropogenic greenhouse gas increases with implications for future increases in global temperatures. One mitigation proposal is to reduce black carbon aerosol emissions. How much warming can be offset by the aerosol's control is unclear, especially as its influence on past climate has not been previously unambiguously detected. In this study observations of near-surface warming over the last century are compared with simulations using a climate model, HadGEM1. In the simulations black carbon, from fossil fuel and bio-fuel sources (fBC), produces a positive radiative forcing of about + 0.25 Wm−2 over the 20th century, compared with a little under + 2.5 Wm−2 for well mixed greenhouse gases. A simulated warming of global mean near-surface temperatures over the twentieth century from fBC of 0.14 ± 0.1 K compares with 1.06 ± 0.07 K from greenhouse gases, -0.58 ± 0.10 K from anthropogenic aerosols, ozone and land use changes and 0.09 ± 0.09 K from natural influences. Using a detection and attribution methodology, the observed warming since 1900 has detectable influences from anthropogenic and natural factors. Fossil fuel and bio-fuel black carbon is found to have a detectable contribution to the warming over the last 50 years of the 20th century, although the results are sensitive to a number of analysis choices, and fBC is not detected for the later fifty year period ending in 2006. The attributed warming of fBC was found to be consistent with the warming from the unscaled simulation. This study suggests that there is a possible significant influence from fBC on global temperatures, but its influence is small compared to that from greenhouse gas emissions.

Description: Hydroperoxy radical (HO2) concentrations were measured during the formal blind intercomparison campaign HOxComp carried out in Jülich, Germany. Three instruments detected HO2 via chemical conversion to hydroxyl radicals (OH) and subsequent detection of the sum of OH and HO2 by laser induced fluorescence (LIF). Instruments sampled ambient air for three days and were attached to the atmosphere simulation chamber SAPHIR during the second part of the campaign. Six experiments of one day each were conducted in SAPHIR, where air masses were homogeneously mixed, in order to investigate the performance of instruments and to determine potential interferences of measurements under well-controlled conditions. Linear correlation coefficients between measurements of the LIF instruments are generally high and range from 0.82 to 0.98. However, the agreement between measurements is variable. The regression analysis of the entire data set of measurements in SAPHIR yields slopes between 0.69 to 1.26 and intercepts are smaller than typical atmospheric daytime concentrations (less than 1 pptv). The quality of fit parameters improves significantly, when data are grouped into data subsets of similar water vapor concentrations. Because measurements of LIF instruments were corrected for a well-characterized water dependence of their sensitivities, this indicates that an unknown factor related to water vapor affected measurements in SAPHIR. Measurements in ambient air are also well correlated, but regression parameters differ from results obtained from SAPHIR experiments. This is most likely caused by sampling different air masses at the slightly distant locations of instruments.

Description: Secondary aerosol produced from marine biogenic sources in algal-rich coastal locations will initially be composed of iodine oxide species, most likely I2O5, or its hydrated form HIO3, formed as a result of iodine gas-phase chemistry. At present, there is no quantitative hygroscopic data for these compounds and very little data available for iodate solutions (HIO3 and I2O5 share a common aqueous phase). With increased interest in the role of such aerosol in the marine atmosphere, we have conducted studies of (i) the deliquescence behaviour of crystalline HIO3 and I2O5 at 273–303 K, (ii) the efflorescence behaviour of aqueous iodate solution droplets, and (iii) properties (water activity, density, and viscosity) of subsaturated and saturated iodate solutions. The deliquescence of I2O5 crystals at 293 K was observed to occur at a relative humidity (DRH) of 80.8±1.0%, whereas for HIO3, a DRH of 85.0±1.0% was measured. These values are consistent with measured water activity values for saturated I2O5 and HIO3 solutions at 293 K of 0.80±0.01 and 0.84±0.01 respectively. At all temperatures, DRH values for HIO3 crystals were observed to be higher than for those of I2O5. The temperature-dependent DRH data, along with solubility and water activity data were used to evaluate the enthalpy of solution (ΔHsol) for HIO3 and I2O5. A (ΔHsol value of 8.3±0.7 kJ mol−1 was determined for HIO3 which is consistent with a literature value of 8.8 kJ mol−1. For I2O5, we report for the first time its solubility at various temperatures and (ΔHsol=12.4±.6 kJ mol−1. The measured water activity values confirm that aqueous iodate solutions are strongly non-ideal, consistent with previous reports of complex ion formation and molecular aggregation.

Description: The impact of two recent gas-phase chemical kinetic mechanisms (CB05 and RACM2) on the formation of secondary inorganic and organic aerosols is compared for simulations of PM2.5 over Europe between 15 July and 15 August 2001. The host chemistry transport model is Polair3D of the Polyphemus air-quality platform. Particulate matter is modeled with SIREAM, which is coupled to the thermodynamic model ISORROPIA and to the secondary organic aerosol module MAEC. Model performance is satisfactory with both mechanisms for speciated PM2.5. The monthly-mean difference of the concentration of PM2.5 is less than 1 μg/m3 (6%) over the entire domain. Secondary chemical components of PM2.5 include sulfate, nitrate, ammonium and organic aerosols, and the chemical composition of PM2.5 is not significantly different between the two mechanisms. Monthly-mean concentrations of inorganic aerosol are higher with RACM2 than with CB05 (+16% for sulfate, +11% for nitrate, and +12% for ammonium), whereas the concentrations of organic aerosols are slightly higher with CB05 than with RACM2 (+26% for anthropogenic SOA and +1% for biogenic SOA). Differences in the inorganic and organic aerosols result primarily from differences in oxidant concentrations (OH, O3 and NO3). Nitrate formation tends to be HNO3-limited over land and differences in the concentrations of nitrate are due to differences in concentration of HNO3. Differences in aerosols formed from aromatics SVOC are due to different aromatics oxidation between CB05 and RACM2. The aromatics oxidation in CB05 leads to more cresol formation, which then leads to more SOA. Differences in the aromatics aerosols would be significantly reduced with the recent CB05-TU mechanism for toluene oxidation. Differences in the biogenic aerosols are due to different oxidant concentrations (monoterpenes) and different particulate organic mass concentrations affecting the gas-particle partitioning of SOA (isoprene).

Description: The tropical transport processes of 14 different models or model versions were compared, within the framework of the SCOUT-O3 (Stratospheric-Climate Links with Emphasis on the Upper Troposphere and Lower Stratosphere) project. The tested models range from the regional to the global scale, and include numerical weather prediction (NWP), chemistry transport, and climate chemistry models. Idealised tracers were used in order to prevent the model's chemistry schemes from influencing the results substantially, so that the effects of modelled transport could be isolated. We find large differences in the vertical transport of very short lived tracers (with a lifetime of 6 hours) within the tropical troposphere. Peak convective outflow altitudes range from around 300 hPa to almost 100 hPa among the different models, and the upper tropospheric tracer mixing ratios differ by up to an order of magnitude. The timing of convective events is found to differ between the models, even among those which source their forcing data from the same NWP model (ECMWF). The differences are less pronounced for longer lived tracers, however they could have implications for the modelling of the halogen burden of the lowermost stratosphere through species such as bromoform, or for the transport of short lived hydrocarbons into the lowermost stratosphere. The modelled tracer profiles are found to be strongly influenced by the convective transport parameterisations, and boundary layer mixing parameterisations of the models. The location of rapid transport into the upper troposphere is similar among the models, and is mostly concentrated over the western Pacific, the Maritime Continent and the Indian Ocean. In contrast, none of the models indicates significant enhancement in upward transport over western Africa. The mean mixing ratios of an idealised CO like tracer in the upper tropical troposphere are found to be sensitive to the surface CO mixing ratios in the regions with the most active convection, revealing the importance of correctly modelling both the location of convective transport and the geographical pollutant emission patterns.

Description: The UK Met Office's Unified Model is used at a high global resolution (N216, ~0.83° × ~0.56°, ~60 km) to assess the impact of deep tropical convection on the structure of the tropical tropopause layer (TTL). We focus on the potential for rapid transport of short-lived ozone depleting species to the stratosphere by rapid convective uplift. The modelled horizontal structure of organised convection is shown to match closely with signatures found in the OLR satellite data. In the model, deep convective elevators rapidly lift air from 4–5 km up to 12–14 km. The influx of tropospheric air entering the TTL (11–12 km) is similar for all tropical regions with most convection stopping below ~14 km. The tropical tropopause is coldest and driest between November and February, coinciding with the greatest upwelling over the tropical warm pool. As this deep convection is co-located with bromine-rich biogenic coastal emissions, this period and location could potentially be the preferential gateway for stratospheric bromine.

Description: Regional and global chemical transport models underpredict NOx (NO+NO2) in the upper troposphere where it is a precursor to the greenhouse gas ozone. The NOx bias been shown in model evaluations using aircraft data (Singh et al., 2007) and total column NO2 (molecules cm−2) from satellite observations (Napelenok et al., 2008). The causes of NOx underpredictions have yet to be fully understood due to the interconnected nature of simulated emission, transport, and chemistry processes. Recent observation-based studies suggest that, in the upper troposphere, simulated chemistry overpredicts hydrogen radicals (OH• and HO2•) and would convert NOx to HNO3 too quickly (Olson et al., 2006; Bertram et al., 2007; Ren et al., 2008). Since typical chemistry evaluation techniques are not available for upper tropospheric conditions, this study develops an evaluation platform from in situ observations, stochastic convection, and deterministic chemistry. We derive a stochastic convection model and optimize it using two simulated datasets of time since convection, one based on meteorology and the other on chemistry. The chemistry surrogate for time since convection is calculated using seven different chemical mechanisms, all of which predict shorter time since convection than our meteorological analysis. We evaluate chemical simulations by inter-comparison and by pairing results with observations based on NOx:HNO3, a photochemical aging indicator. Inter-comparison reveals individual chemical mechanism biases and recommended updates. Evaluation against observations shows that all chemical mechanisms overpredict NOx removal relative to long-lived methanol and carbon monoxide. All chemical mechanisms underpredict observed NOx by at least 30%, and further evaluation is necessary to refine simulation sensitivities to initial conditions and chemical rate uncertainties.

Description: Mineral dust aerosols collected during the years 2008/2009 at the high-altitude research station Jungfraujoch (46°33´, 7°59´; 3580 m a.s.l.) were compared to windblown mineral dust deposited at the Colle Gnifetti glacier (45°55´ N, 7°52´ E; 4455 m a.s.l.) over the last millennium. Insoluble dust has been characterized in terms of mineralogy, Sr and Nd isotopic ratios, and trace element composition. Results demonstrate that the Saharan origin of the airborne dust did not change significantly throughout the past. Backward trajectories analysis of modern analogs furthermore confirms that major dust sources are situated in the north-central to north-western part of the Saharan desert. By contrast, less radiogenic Sr isotopic compositions are associated with lower abundances of crustal elements during low rates of dust deposition, suggesting intercontinental transport of background dust rather than activation of a secondary source. Saharan dust mobilization and meridional advection of air masses were relatively reduced during the second part of the Little Ice Age (ca. 1690–1870), except within the greatest Saharan dust event deposited around 1780–1790. Higher dust deposition with larger mean grain size and Saharan fingerprint began ca. 20 years after the industrial revolution of 1850, suggesting that increased mineral dust transport over the Alps during the last century was primarily due to drier winters in North Africa and stronger spring/summer North Atlantic southwesterlies, rather than to direct anthropogenic sources. Meanwhile, increasing carbonaceous particle emissions from fossil fuels combustion combined to higher lead enrichment factor during the last century, point to concomitant anthropogenic sources of particulate pollutants reaching high-altitude European glaciers.

Description: Vegetation commonly managed by prescribed burning was collected from five southeastern and southwestern US military bases and burned under controlled conditions at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The smoke emissions were measured with a large suite of state-of-the-art instrumentation including an open-path Fourier transform infrared (OP-FTIR) spectrometer for measurement of gas-phase species. The OP-FTIR detected and quantified 19 gas-phase species in these fires: CO2, CO, CH4, C2H2, C2H4, C3H6, HCHO, HCOOH, CH3OH, CH3COOH, furan, H2O, NO, NO2, HONO, NH3, HCN, HCl, and SO2. Emission factors for these species are presented for each vegetation type burned. Gas-phase nitrous acid (HONO), an important OH precursor, was detected in the smoke from all fires. The HONO emission factors ranged from 0.15 to 0.60 g kg−1 and were higher for the southeastern fuels. The fire-integrated molar emission ratios of HONO (relative to NOx) ranged from approximately 0.03 to 0.20, with higher values also observed for the southeastern fuels. The majority of non-methane organic compound (NMOC) emissions detected by OP-FTIR were oxygenated volatile organic compounds (OVOCs) with the total identified OVOC emissions constituting 61±12% of the total measured NMOC on a molar basis. These OVOC may undergo photolysis or further oxidation contributing to ozone formation. Elevated amounts of gas-phase HCl and SO2 were also detected during flaming combustion, with the amounts varying greatly depending on location and vegetation type. The fuels with the highest HCl emission factors were all located in the coastal regions, although HCl was also observed from fuels farther inland. Emission factors for HCl were generally higher for the southwestern fuels, particularly those found in the chaparral biome in the coastal regions of California.

Description: New burned area datasets and top-down constraints from atmospheric concentration measurements of pyrogenic gases have decreased the large uncertainty in fire emissions estimates. However, significant gaps remain in our understanding of the contribution of deforestation, savanna, forest, agricultural waste, and peat fires to total global fire emissions. Here we used a revised version of the Carnegie-Ames-Stanford-Approach (CASA) biogeochemical model and improved satellite-derived estimates of area burned, fire activity, and plant productivity to calculate fire emissions for the 1997–2009 period on a 0.5° spatial resolution with a monthly time step. For November 2000 onwards, estimates were based on burned area, active fire detections, and plant productivity from the Moderate Resolution Imaging Spectroradiometer (MODIS) sensor. For the partitioning we focused on the MODIS era. We used burned area estimates based on Tropical Rainfall Measuring Mission (TRMM) Visible and Infrared Scanner (VIRS) and Along-Track Scanning Radiometer (ATSR) active fire data prior to MODIS (1997–2000) and Advanced Very High Resolution Radiometer (AVHRR) derived estimates of plant productivity during the same period. Average global fire carbon emissions were 2.0 Pg yr−1 with significant interannual variability during 1997–2001 (2.8 Pg yr−1 in 1998 and 1.6 Pg yr−1 in 2001). Emissions during 2002–2007 were relatively constant (around 2.1 Pg yr−1) before declining in 2008 (1.7 Pg yr−1) and 2009 (1.5 Pg yr−1) partly due to lower deforestation fire emissions in South America and tropical Asia. During 2002–2007, emissions were highly variable from year-to-year in many regions, including in boreal Asia, South America, and Indonesia, but these regional differences cancelled out at a global level. During the MODIS era (2001–2009), most fire carbon emissions were from fires in grasslands and savannas (44%) with smaller contributions from tropical deforestation and degradation fires (20%), woodland fires (mostly confined to the tropics, 16%), forest fires (mostly in the extratropics, 15%), agricultural waste burning (3%), and tropical peat fires (3%). The contribution from agricultural waste fires was likely a lower bound because our approach for measuring burned area could not detect all of these relatively small fires. For reduced trace gases such as CO and CH4, deforestation, degradation, and peat fires were more important contributors because of higher emissions of reduced trace gases per unit carbon combusted compared to savanna fires. Carbon emissions from tropical deforestation, degradation, and peatland fires were on average 0.5 Pg C yr−1. The carbon emissions from these fires may not be balanced by regrowth following fire. Our results provide the first global assessment of the contribution of different sources to total global fire emissions for the past decade, and supply the community with an improved 13-year fire emissions time series.

Description: Emissions of CO2 from fossil fuel combustion are a critical quantity that must be accurately given in established flux inversion frameworks. Work with emerging satellite-based inversions requires spatiotemporally-detailed inventories that permit analysis of regional sources and sinks. Conventional approaches for disaggregating national emissions beyond the country and city levels based on population distribution have certain difficulties in their application. We developed a global 1 km×1 km fossil fuel CO2 emission inventory for the years 1980–2007 by combining a worldwide point source database and satellite observations of the global nightlight distribution. In addition to estimating the national emissions using global energy consumption statistics, emissions from point sources were estimated separately and were spatially allocated to exact locations indicated by the point source database. Emissions from other sources were distributed using a special nightlight dataset that had fewer saturated pixels compared with regular nightlight datasets. The resulting spatial distributions differed in several ways from those derived using conventional population-based approaches. Because of the inherent characteristics of the nightlight distribution, source regions corresponding to human settlements and land transportation were well articulated. Our distributions showed good agreement with a high-resolution inventory across the US at spatial resolutions that were adequate for regional flux inversions. The inventory will be incorporated into models for operational flux inversions that use observational data from the Japanese Greenhouse Gases Observing SATellite (GOSAT).

Description: Understanding the processes controlling black carbon (BC) in the Arctic is crucial for evaluating the impact of anthropogenic and natural sources of BC on Arctic climate. Vertical profiles of BC mass were observed from the surface to near 7-km altitude in April 2008 using a Single-Particle Soot Photometer (SP2) during flights on the NOAA WP-3D research aircraft from Fairbanks, Alaska. These measurements were conducted during the NOAA-sponsored Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC) project as part of POLARCAT, an International Polar Year (IPY) activity. In the free troposphere, the Arctic air mass was influenced by long-range transport from biomass-burning and anthropogenic source regions at lower latitudes especially during the latter part of the campaign. Maximum average BC mass loadings of 150 ng kg−1 were observed near 5.5-km altitude in the aged Arctic air mass. In biomass-burning plumes, BC was enhanced from near the top of the Arctic boundary layer (ABL) to 5.5 km compared to the aged Arctic air mass. At the bottom of some of the profiles, positive vertical gradients in BC were observed in the vicinity of open leads in the sea-ice. BC mass loadings increased by about a factor of two across the boundary layer transition in the ABL in these cases while carbon monoxide (CO) remained constant, evidence for depletion of BC in the ABL. BC mass loadings were positively correlated with O3 in ozone depletion events (ODEs) for all the observations in the ABL suggesting that BC was removed by dry deposition of BC on the snow or ice because molecular bromine, Br2, which photolyzes and catalytically destroys O3, is thought to be released near the open leads in regions of ice formation. We estimate the deposition flux of BC mass to the snow using a box model constrained by the vertical profiles of BC in the ABL. The open leads may increase vertical mixing in the ABL and entrainment of pollution from the free troposphere possibly enhancing the deposition of BC to the snow.

Description: Measurements of nitrous acid (HONO) were performed as part of the 2007 Border Air Quality and Meteorology Study (BAQS-Met) at the Harrow Ontario supersite between 20 June and 10 July 2007. Nitrous acid is an important precursor of the hydroxy radical and understanding its chemistry is important to understanding daytime oxidation chemistry. The HONO measurements were made using a custom built Long Path Absorption Photometer (LOPAP). The goal of this work was to shed light on sources of daytime HONO in the border region. During the course of the campaign HONO mixing ratios consistently exceeded expected daytime values by as much as a factor of 6. Mean daytime concentrations of 61 pptv were observed. While HONO decay began at sunrise, minimum HONO values were not measured until the late afternoon. There was little difference between the daytime (mean=1.5%) and night-time (mean=1.7%) ratios of HONO/NO2. Thus there was a very strong daytime source of HONO which is consistent with other recent studies. Correlations of daytime HONO production with a variety of chemical and meteorological parameters indicate that production is dependent on UV radiation, NO2 and water vapour but is not consistent with a simple gas phase process. Apparent rate constants for the production of HONO from photolyticly excited NO2 and water vapour vary from 2.8–7.8×10−3 molec−1 s−1, during the campaign.

Description: Volcanic emissions from the Eyjafjallajökull volcano on the Southern fringe of Iceland were detected at different places in Germany by means of in-situ measurements, ozone sondes and a dense network of ceilometers of the German Meteorological Service (DWD). In-situ measurements of sulphur dioxide and particulate matter were performed at the Global Atmosphere Watch (GAW) station Zugspitze/Hohenpeissenberg. At Hohenpeissenberg, a number of reactive gases, e.g. sulphuric acid, carbon monoxide and nitrogen oxides were additionally measured during the period of interest. Also ozone sondes were launched at Hohenpeissenberg in the pre-alpine area. A newly established network of ceilometers (Jenoptik CHM15K) at currently 36 meteorological stations in Germany provided the temporal evolution of emissions over Germany. The sensitivity of these instruments with respect to atmospheric aerosols further allowed the inversion of gathered backscatter profiles, and aerosol extinction coefficients and particle mass concentration were finally obtained.

Description: This paper reports on daytime total vertical column abundances of formic acid (HCOOH) above the Northern mid-latitude, high altitude Jungfraujoch station (Switzerland; 46.5° N, 8.0° E, 3580 m altitude). The columns were derived from the analysis of infrared solar observations regularly performed with high spectral resolution Fourier transform spectrometers during over 1537 days between September 1985 and September 2007. The investigation was based on the spectrometric fitting of five spectral intervals, one encompassing the HCOOH ν6 band Q branch at 1105 cm−1, and four additional ones allowing to optimally account for critical temperature-sensitive or timely changing interferences by other atmospheric gases, in particular HDO, CCl2F2 and CHClF2. The main results derived from the 22 yr long database indicate that the free tropospheric burden of HCOOH above the Jungfraujoch undergoes important short-term daytime variability, diurnal and seasonal modulations, inter-annual anomalies, but no statistically significant long-term background change at the 1-sigma level. A major progress in the remote determination of the atmospheric HCOOH columns reported here has resulted from the adoption of new, improved absolute spectral line intensities for the infrared ν6 band of trans-formic acid, resulting in retrieved free tropospheric loadings being about a factor two smaller than if derived with previous spectroscopic parameters. Implications of this significant change with regard to earlier remote measurements of atmospheric formic acid and comparison with relevant Northern mid-latitude in situ findings will be assessed critically. Sparse HCOOH model predictions will also be evoked.

Description: The reactive uptake of ozone to deliquesced potassium iodide aerosol particles coated with linear saturated fatty acids (C9, C12, C15, C18 and C20) as surfactants was studied. The experiments were performed in an aerosol flow tube at 293 K and atmospheric pressure. The uptake coefficient on pure deliquesced KI aerosol was γ=(1.10±0.20)×10−2 at 72–75% relative humidity. In presence of organic coatings, the uptake coefficient decreased significantly for long straight chain surfactants (〉C15), while it was only slightly reduced for the short ones (C9, C12). We linked the kinetic results to the monolayer properties of the surfactants, and specifically to the phase state of the monolayer formed (liquid expanded or liquid condensed state). We also investigated the effect of organic films to mixed deliquesced aerosol composed of a variable mixture of KI and NaCl, which allowed determining the resistance exerted to O3 at the aqueous surface by the two longer chained surfactants pentadecanoic acid (C15) and stearic acid (C18). Finally, the effect of two-component coatings, consisting of a mixture of long and short chained surfactants, was also studied.

Description: There is a growing understanding that secondary organic aerosol (SOA) can form through reactions in atmospheric waters (i.e., clouds, fogs, and aerosol water). In clouds and wet aerosols, water-soluble organic products of gas-phase photochemistry dissolve into the aqueous phase where they can react further (e.g. with OH radicals) to form low volatility products that are largely retained in the particle phase. Organic acids, oligomers and other products form via radical- and non-radical reactions, including hemiacetal formation during droplet evaporation, acid/base catalyzation, and reaction of organics with other constituents (e.g. NH4+). This paper uses kinetic modeling, experiments conducted with aqueous carbonyl solutions in the presence and absence of OH radicals, electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, and the literature to describe aqueous chemistry at cloud- and aerosol-relevant concentrations and during droplet evaporation. At least for aqueous reactions of glyoxal with OH radicals, chemical modeling can reproduce experiments conducted at cloud-relevant concentrations without including radical–radical reactions, whereas radical–radical reactions become dramatically more important at higher concentrations. We demonstrate that reactions with OH radicals tend to be faster and form more SOA than "non-radical" reactions (e.g., acid catalyzation).

Description: Ternary homogeneous nucleation (THN) of H2SO4, NH3 and H2O has been used to explain new particle formation in various atmospheric regions, yet laboratory measurements have failed to reproduce atmospheric observations. Here, we report laboratory observations of THN made under conditions relevant to the lower troposphere (H2SO4 of 106–107 cm−3, NH3 of 0.08–20 ppbv, and 288 K). Our observations show that NH3 can enhance atmospheric H2SO4 aerosol nucleation and the enhancement factor (EF) in nucleation rate due to NH3 increases linearly with increasing NH3 and increases exponentially with decreasing H2SO4 and RH. The critical clusters of ternary homogeneous nucleation contain 3–5 molecules of H2SO4, 1–4 molecules of H2O, and only 1 molecule of NH3. The composition of H2SO4 and H2O in critical clusters and the threshold of H2SO4 concentrations required for the unit nucleation rate both do not vary in the presence and absence of NH3. These observations can be directly used to improve aerosol nucleation models to correctly assess how man-made SO2 and NH3 affect aerosol formation and CCN production at the global scale.

Description: Since data from the Infrared Atmospheric Sounding Interferometer (IASI) became available in 2007, a number of papers have appeared in the literature which have reported relatively large discrepancies between IASI spectra and forward calculations in the centre of the CO2 Q-branch at 667 cm−1. In this paper we argue that these discrepancies are primarily due to errors in the temperature profiles used in the forward calculations. In particular, we have used temperature profiles from the European Centre for Medium-Range Weather Forecasts (ECMWF) analysis to demonstrate that for the case study considered in this paper, these profiles are affected by systematic errors of the order of 7–10 K at the level of the stratopause. To derive the magnitude and the spatial location of the systematic errors in the temperature profile, we have carried out forward/inverse calculations for a number of clear-sky, daytime, IASI tropical soundings over the sea. The forward calculations have been performed using atmospheric state vectors which have been obtained either from the direct inversion of the IASI radiances or from space-time co-located profiles derived from radiosonde observations and from the ECMWF analysis. To rule out any effect due to the accuracy of the forward model, we have performed the forward calculations using two independent models. The sensitivity of the temperature biases to the variability of the CO2 profile and to spectroscopy errors has also been studied.

Description: The presence of aerosols over highly reflective liquid water cloud tops poses a big challenge in simulating their radiative impacts. Particularly, absorbing aerosols, such as smoke, may have significant impact in such situations and even change the sign of net radiative forcing. Until now, it was not possible to obtain information on such overlap events realistically from the existing passive satellite sensors. However, the CALIOP instrument onboard NASA's CALIPSO satellite allows us to examine these events with an unprecedented accuracy. Using four years of collocated CALIPSO 5 km Aerosol and Cloud Layer Version 3 Products (June 2006–May 2010), we quantify, for the first time, the macrophysical characteristics of overlapping aerosol and water cloud layers globally. We investigate seasonal variability in these characteristics over six latitude bands to understand the hemispheric differences. We compute a) the percentage cases when such overlap is seen globally and seasonally when all aerosol types are included (AAO case) in the analysis, b) the joint histograms of aerosol layer base height and cloud layer top height, and c) the joint histograms of aerosol and cloud geometrical thicknesses in such overlap cases. We also investigate frequency of smoke aerosol-cloud overlap (SAO case). The results show a distinct seasonality in overlap frequency in both AAO and SAO cases. Globally, the frequency is highest during JJA months in AAO case, while for the SAO case, it is highest in SON months. The seasonal mean overlap frequency can regionally exceed 20% in AAO case and 10% in SAO case. There is a tendency that the vertical separation between aerosol and cloud layers increases from high to low latitude regions in the both hemispheres. In about 5–10% cases the vertical distance between aerosol and cloud layers is less than 100 m, while about in 45–60% cases it less than a kilometer in the annual means for different latitudinal bands. The frequency of occurrence of thicker aerosol layers gradually increases from poles to tropics. In about 70–80% cases, aerosol layers are less than a kilometer thick, while in about 18–22% cases they are 1–2 km thick. The frequency of aerosol layers 2–3 km thick is about 4–5% in the tropical belts during overlap events. The results further highlight spatial and temporal variations in aerosol-liquid water cloud overlap and suggest that the frequency of occurrence of such overlap events is far from being negligible globally.

Description: During the "African Monsoon Multidisciplinary Analysis" (AMMA) field phase in August 2006, a variety of measurements focusing on deep convection were performed over West Africa. The German research aircraft Falcon based in Ouagadougou (Burkina Faso) investigated the chemical composition in the outflow of large mesoscale convective systems (MCS). Here we analyse two different types of MCS originating north and south of the intertropical convergence zone (ITCZ, ~10° N), respectively. In addition to the airborne trace gas measurements, stroke measurements from the Lightning Location Network (LINET), set up in Northern Benin, are analysed. The main focus of the present study is 1) to analyse the trace gas composition (CO, O3, NO, NOx, NOy, and HCHO) in the convective outflow as a function of distance from the convective core, 2) to investigate how different trace gas compositions in the boundary layer (BL) and ambient air may influence the O3 concentration in the convective outflow, and 3) to estimate the rate of lightning-produced nitrogen oxides per flash in selected thunderstorms and compare it to our previous results for the tropics. The MCS outflow was probed at different altitudes (~10–12 km) and distances from the convective core (

Description: The Tibetan Plateau (TP), the highest and largest plateau in the world, has long been identified to be critical in regulating the Asian monsoon climate and hydrological cycle. The snowpack and glaciers over the TP provide fresh water to billions of people in Asian countries, but the TP glaciers have been retreating faster than those anywhere else in the world. In this modeling study a series of numerical experiments with a global climate model are designed to simulate radiative forcing of black carbon (BC) and dust in snow, and to assess the relative impacts of anthropogenic CO2 and carbonaceous particles in the atmosphere and snow on the snowpack over the TP and subsequent impacts on the Asian monsoon climate and hydrological cycle. Simulations results show a large BC content in snow over the TP, especially the southern slope, with concentration larger than 100 μg/kg. Because of the high aerosol content in snow and large incident solar radiation in the low latitude and high elevation, the TP exhibits the largest surface radiative forcing induced by aerosols (e.g. BC, Dust) in snow compared to other snow-covered regions in the world. Simulation results show that the aerosol-induced snow albedo perturbations generate surface radiative forcing of 5–25 W m−2 during spring, with a maximum in April or May. BC-in-snow increases the surface air temperature by around 1.0 °C averaged over the TP and reduces spring snowpack over the TP more than pre-industrial to present CO2 increase and carbonaceous particles in the atmosphere. As a result, runoff increases during late winter and early spring but decreases during late spring and early summer (i.e. a trend toward earlier melt dates). The snowmelt efficacy, defined as the snowpack reduction per unit degree of warming induced by the forcing agent, is 1–4 times larger for BC-in-snow than CO2 increase during April–July, indicating that BC-in-snow more efficiently accelerates snowmelt because the increased net solar radiation induced by reduced albedo melts the snow more efficiently than snow melt due to warming in the air. The TP also influences the South (SAM) and East (EAM) Asian monsoon through its dynamical and thermal forcing. Simulation results show that during boreal spring aerosols are transported by southwesterly, causing some particles to reach higher altitude and deposit to the snowpack over the TP. While BC and OM in the atmosphere directly absorb sunlight and warm the air, the darkened snow surface polluted by BC absorbs more solar radiation and increases the skin temperature, which warms the air above through sensible heat flux. Both effects enhance the upward motion of air and spur deep convection along the TP during the pre-monsoon season, resulting in earlier onset of the SAM and increase of moisture, cloudiness and convective precipitation over Northern India. BC-in-snow has a more significant impact on the EAM in July than CO2 increase and carbonaceous particles in the atmosphere. Contributed by the significant increase of both sensible heat flux associated with the warm skin temperature and latent heat flux associated with increased soil moisture with long memory, the role of the TP as a heat pump is elevated from spring through summer as the land-sea thermal contrast increases to strengthen the EAM. As a result, both Southern China and Northern China become wetter, but Central China (i.e. Yangtze River Basin) becomes drier – a near-zonal anomaly pattern that is consistent with the dominant mode of precipitation variability in East Asia.

Description: Diurnal variations in hydroxyl (OH) in the stratosphere and mesosphere are analyzed using measurements from the Aura Microwave Limb Sounder (MLS). The primary driver for OH diurnal variations is the ultraviolet actinic flux that initiates photochemical reactions which produce OH. The magnitude of this flux is governed largely by changes in solar zenith angle (SZA) throughout the day, and OH diurnal variations are well approximated by an exponential function of the secant of SZA. Measured OH concentrations are fit to a function of the form exp[−βsec(SZA)], where the parameter β is a function of altitude. We examine the magnitude of β and show that it is related to the optical depths of ultraviolet absorption by ozone and oxygen. Comparison of β values obtained from SLIMCAT model simulations with those derived from MLS observations shows very good agreement. The vertical profile of β from MLS can be represented by a simple analytic formulation involving the ozone and water vapor photodissociation rates. This formulation is used to infer the altitude dependence of the primary production mechanisms for OH: the reaction of excited-state atomic oxygen with water vapor versus the direct photodissociation of water vapor.

Description: Validation of cloud properties retrieved from passive spaceborne imagers is essential for cloud and climate applications but complicated due to the large differences in scale and observation geometry between the satellite footprint and the independent ground based or airborne observations. Here we illustrate and demonstrate an alternative approach: starting from the output of the COSMO-EU weather model of the German Weather Service realistic three-dimensional cloud structures at a spatial scale of 2.33 km are produced by statistical downscaling and microphysical properties are associated to them. The resulting data sets are used as input to the one-dimensional radiative transfer model libRadtran to simulate radiance observations for all eleven low resolution channels of MET-8/SEVIRI. At this point, both cloud properties and satellite radiances are known such that cloud property retrieval results can be tested and tuned against the objective input "truth". As an example, we validate a cloud property retrieval of the Institute of Atmospheric Physics of DLR and that of EUMETSAT's Climate Monitoring Science Application Facility CMSAF. Cloud detection and cloud phase assignment perform well. By both retrievals 88% of the pixels are correctly classified as clear or cloudy. The DLR algorithm assigns the correct thermodynamic phase to 95% of the cloudy pixels and the CMSAF retrieval to 79%. Cloud top temperature is slightly overestimated by the DLR code (+3.1 K mean difference with a standard deviation of 10.6 K) and underestimated by the CMSAF code (−16.4 K with a standard deviation of 37.3 K). Both retrievals account reasonably well for the distribution of optical thickness for both water and ice clouds, with a tendency to underestimation for the DLR and to overestimation for the CMSAF algorithm. Cloud effective radii are most difficult to evaluate and not always the algorithms are able to produce realistic values. The CMSAF cloud water path, which is a combination of the last two quantities, is particularly accurate for ice clouds, while water clouds are overestimated, mainly because of the effective radius overestimation for water clouds.

Description: Broadband cavity enhanced absorption spectroscopy (BBCEAS) has been used to measure the sum of concentrations of NO3 and N2O5 from the BT (telecommunications) Tower 160 m above street level in central London during the REPARTEE II campaign in October and November 2007. Substantial variability was observed in these night-time nitrogen compounds: peak NO3+N2O5 mixing ratios reached 800 pptv, whereas the mean night-time NO3+N2O5 was approximately 30 pptv. Additionally, [NO3+N2O5] showed negative correlations with [NO] and [NO2] and a positive correlation with [O3]. Co-measurements of temperature and NO2 from the BT Tower were used to calculate the equilibrium partitioning between NO3 and N2O5 which was always found to strongly favour N2O5 (NO3/N2O5=0.01 to 0.04). Two methods are used to calculate the lifetimes for NO3 and N2O5, the results being compared and discussed in terms of the implications for the night-time oxidation of nitrogen oxides and the night-time sinks for NOy.

Description: In this paper, we provide a detailed comparison between carbon monoxide (CO) data measured by the Infrared Atmospheric Sounding Interferometer (IASI)/METOP and aircraft measurements over the Arctic. The CO measurements were obtained during North American campaigns (NASA ARCTAS and NOAA ARCPAC) and European campaigns (POLARCAT-France, POLARCAT-GRACE and YAK-AEROSIB) as part of the International Polar Year (IPY) in spring and summer 2008. During the campaigns different air masses were sampled including clean air, polluted plumes originating from anthropogenic sources in Europe, Asia and North America, and forest fire plumes originating from Siberia and Canada. CO-rich plumes following different transport pathways were captured well by the IASI instrument, illustrated for example by a transport event over the North Pole from Asia on 9 July 2008. The comparison between the IASI CO profiles and aircraft data was achieved by first completing the latter for higher altitudes using a latitudinally dependent climatology of ACE-FTS satellite CO profiles (2004–2009) and by subsequently smoothing the resulting full profiles by the IASI averaging kernels. Proceeding this way, the IASI profiles were shown to be in good agreement with smoothed in situ profiles (with a difference of about 10 ppbv) in spring. In summer, the IASI profiles were higher than the smoothed in situ profiles below 8 km, for all polluted cases. Correlations between IASI and combination ACE-FTS/aircraft derived total columns varied from 0.15 to 0.74 in spring and 0.26 to 0.84 in summer, with better results over the sea in spring (0.73) and over the land in summer (0.69).

Description: The annual and seasonal variability of aerosol optical properties observed by means of an elastic-Raman lidar over Northeastern Spain has been assessed. The lidar representativeness has first been checked against sun-photometer measurements in terms of aerosol optical thickness. Then the annual cycle and the seasonal variability of the planetary boundary layer aerosol optical thickness and its fraction compared to the columnar optical thickness, the lidar ratio, the backscatter-related Ångström exponent and the planetary boundary layer height have been analyzed and discussed. Winter and summer mean profiles of extinction, backscatter and lidar ratio retrieved with the Raman algorithm have been presented. The analysis shows the impact of most of the natural events (Saharan dust intrusions, wildfires, etc.) and meteorological situations (summer anticyclonic situation, the formation of the Iberian thermal low, winter long-range transport from North Europe and/or North America, re-circulation flows, etc.) occurring in the Barcelona area. A detail study of a special event including a combined intrusion of Saharan dust and biomass-burning particles has proven the suitability of combining nighttime Raman- and daytime pure elastic-inversions to discriminate spatially different types of aerosols and to follow their spatial and temporal evolution.

Description: Size-resolved vertical aerosol number fluxes of particles in the diameter range 0.25–2.5 μm were measured with the eddy covariance method from a 53 m high tower over the Amazon rain forest, 60 km NNW of Manaus, Brazil. This study focuses on data measured during the relatively clean wet season, but a shorter measurement period from the more polluted dry season is used as a comparison. Size-resolved net particle fluxes of the five lowest size bins, representing 0.25–0.45 μm in diameter, pointed downward in more or less all wind sectors in the wet season. This is an indication that the source of primary biogenic aerosol particles may be small in this particle size range. In the diameter range 0.5–2.5 μm, vertical particle fluxes were highly dependent on wind direction. In wind sectors where anthropogenic influence was low, net emission fluxes dominated. However, in wind sectors associated with higher anthropogenic influence, net deposition fluxes dominated. The net emission fluxes were interpreted as primary biogenic aerosol emission, but deposition of anthropogenic particles seems to have masked this emission in wind sectors with higher anthropogenic influence. The emission fluxes were at maximum in the afternoon when the mixed layer is well developed, and these emissions were best correlated with horizontal wind speed by the equation log10F=0.47·U+2.26 where F is the emission number flux of 0.5–2.5 μm particles [m−2s−1] and U is the horizontal wind speed [ms−1] at the top of the tower.

Description: Retrievals of cloud top effective radius from MODIS (as derived by CERES) were combined with aerosol concentrations from the CCCma CanAM4 to examine relationships between aerosol and cloud that underlie the first aerosol indirect (cloud albedo) effect. Evidence of a strong negative relationship between sulphate, and organic aerosols, with cloud top effective radius was found for low clouds, indicating both aerosol types are contributing to the first indirect effect on a global scale. Furthermore, effects of aerosol on the cloud droplet effective radius are more pronounced for larger cloud liquid water paths. While CanAM4 broadly reproduces the observed relationship between sulphate aerosols and cloud droplets, it does not reproduce the dependency of cloud top droplet size on organic aerosol concentrations nor the dependency on cloud liquid water path. Simulations with a modified version of the model yield a more realistic dependency of cloud droplets on organic carbon. The robustness of the methods used in the study are investigated by repeating the analysis using aerosol simulated by the GOCART model and cloud top effective radii derived from the MODIS science team.

Description: Within the project EUCAARI (European Integrated project on Aerosol Cloud Climate and Air Quality interactions), atmospheric nucleation was studied by (i) developing and testing new air ion and cluster spectrometers, (ii) conducting homogeneous nucleation experiments for sulphate and organic systems in the laboratory, (iii) investigating atmospheric nucleation mechanism under field conditions, and (iv) applying new theoretical and modelling tools for data interpretation and development of parameterisations. The current paper provides a synthesis of the obtained results and identifies the remaining major knowledge gaps related to atmospheric nucleation. The most important technical achievement of the project was the development of new instruments for measuring sub-3 nm particle populations, along with the extensive application of these instruments in both the laboratory and the field. All the results obtained during EUCAARI indicate that sulphuric acid plays a central role in atmospheric nucleation, in addition to which other vapours, especially organic ones, are needed to explain the nucleation and the subsequent growth processes. Both our field and laboratory data demonstrate that the nucleation rate scales to the first or second power of the nucleating vapour concentration(s). This agrees with the few earlier field observations, but is in stark contrast with classical thermodynamic nucleation theories. The average formation rates of 2-nm particles were found to vary by almost two orders of magnitude between the different EUCAARI sites, whereas the formation rates of charged 2-nm particles varied very little between the sites. Overall, our observations are indicative of frequent, yet moderate, ion-induced nucleation usually outweighed by much stronger neutral nucleation events in the lower troposphere. The most concrete outcome of the EUCAARI nucleation studies are the new semi-empirical nucleation rate parameterizations based on field observations, along with updated aerosol formation parameterizations.

Description: We present trajectory-based estimates of Ozone Depletion Potentials (ODPs) for very short-lived halogenated source gases as a function of surface emission location. The ODPs are determined by the fraction of source gas and its degradation products which reach the stratosphere, depending primarily on tropospheric transport and chemistry, and the effect of the resulting reactive halogen in the stratosphere, which is determined by stratospheric transport and chemistry, in particular by stratospheric residence time. Reflecting the different timescales and physico-chemical processes in the troposphere and stratosphere, the estimates are based on calculation of separate ensembles of trajectories for the troposphere and stratosphere. A methodology is described by which information from the two ensembles can be combined to give the ODPs. The ODP estimates for a species with a 20 d lifetime, representing a compound like n-propyl bromide, are presented as an example. The estimated ODPs show strong geographical and season variation, particularly within the tropics. The values of the ODPs are sensitive to the inclusion of a convective parametrization in the trajectory calculations, but the relative spatial and seasonal variation is not. The results imply that ODPs are largest for emissions from South and South-East Asia during Northern Hemisphere summer and from the Western Pacific during Northern Hemisphere winter. Large ODPs are also estimated for emissions throughout the tropics with also non-negligible values extending into northern mid-latitudes particularly in the summer. These first estimates, which include some simplifying assumptions, show larger ODP values than previous studies, particularly over Southern Asia, suggesting that emissions of short-lived halogen source gases in certain geographical regions could have a significant impact on stratospheric ozone depletion.

Description: Soil biogenic NO emissions (SNOx) play important direct and indirect roles in chemical processes of the troposphere. The most widely applied algorithm to calculate SNOx in global models was published 15 years ago by Yienger and Levy (1995), was based on very few measurements. Since then numerous new measurements have been published, which we used to build up a atabase of field measurements conducted world wide covering the period from 1978 to 2009, including 108 publications with 560 measurements. Recently, several satellite based top-down approaches, which recalculated the different sources of NOx (fossil fuel, biomass burning, soil and lightning), have shown an underestimation of SNOx by the algorithm of Yienger and Levy (1995). Nevertheless, to our knowledge no general improvements of this algorithm have yet been published. Here we present major improvements to the algorithm, which should help to optimize the representation of SNOx in atmospheric-chemistry global climate models, without modifying the underlying principal or mathematical equations. The changes include: 1) Using a new up to date land cover map, with twice the number of land cover classes, and using annually varying fertilizer application rates; 2) Adopting the fraction of SNOx induced by fertilizer application based on our database; 3) Switching from soil water column to volumetric soil moisture, to distinguish between the wet and dry state; 4) Tuning the emission factors to reproduce the measured emissions in our database and calculate the emissions based on their mean value. These steps lead us to increased global yearly SNOx, and our total SNOx source ends up being close to one of the top-down approaches. In some geographical regions the new results agree better with the top-down approach, but there are also distinct differences in other regions. This suggests that a ombination of both top-down and bottom-up approaches could be combined in a future attempt to provide an even better calculation of SNOx.

Description: Ozone sondes launched from Trinidad Head, California provide a measure of background O3 transported ashore, and allow an evaluation of the impact of this transport on air quality in California's Northern Sacramento Valley. A strong summertime vertical O3 gradient and correlation analysis indicate that O3-rich air from above the marine boundary layer is transported to the surface. Surface O3 increases proportionally to the transported background. At the surface site experiencing the highest O3 concentrations, transported background O3 accounts for more than half (11 ppbv) of the 20 ppbv difference in the mean maximum 8-h average O3 between exceedance and non-exceedance days. This finding contrasts with model calculations that indicate the US policy relevant O3 background is generally 15–35 ppbv, and that it decreases during pollution episodes. The present work indicates that O3 transported on hemispheric scales substantially impacts air quality in some areas of the US.

Description: As part of Campaigns of Air Quality Research in Beijing and Surrounding Region–2008 (CAREBeijing-2008), an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed in urban Beijing to characterize submicron aerosol particles during the time of 2008 Beijing Olympic Games and Paralytic Games (24 July to 20 September 2008). The campaign mean PM1 mass concentration was 63.1±39.8 μg m−3; the mean composition consisted of organics (37.9%), sulfate (26.7%), ammonium (15.9%), nitrate (15.8%), black carbon (3.1%), and chloride (0.87%). The average size distributions of the species (except BC) were all dominated by an accumulation mode peaking at about 600 nm in vacuum aerodynamic diameter, and organics was characterized by an additional smaller mode extending below 100 nm. Positive Matrix Factorization (PMF) analysis of the high resolution organic mass spectral dataset differentiated the organic aerosol into four components, i.e., hydrocarbon-like (HOA), cooking-related (COA), and two oxygenated organic aerosols (OOA-1 and OOA-2), which on average accounted for 18.1, 24.4, 33.7 and 23.7% of the total organic mass, respectively. The HOA was identified to be closely associated with primary combustion sources, while the COA mass spectrum showed high similarity to that measured from cooking aerosol emissions. The OOA components correspond to aged secondary organic aerosol. Although the two OOA components have similar elemental (O/C, H/C) compositions, they display differences in mass spectra and time series which appear to correlate with the different source regions sampled during the campaign. Back trajectory clustering analysis indicated that the southerly air flows were associated with the highest PM1 pollution during the campaign. This result is similar to observations made in the summer of 2006, although the average PM1 concentration level for the southerly air flows is 31% lower than for the 2008 campaign. Aerosol particles in southern airmasses were especially rich in inorganic and oxidized organic species. Aerosol particles in northern airmasses contained a large fraction of primary HOA and COA species, probably due to stronger influences from local emissions. The lowest concentration levels for all major species were obtained during the Olympic game days (8–24 August 2008), possibly due to the effects of both strict emission controls and favorable meteorological conditions.

Description: As a contribution to the Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001) field campaign in the heart of the Amazon Basin, we analyzed the temporal and spatial dynamics of the urban plume of Manaus City during the wet-to-dry season transition period in July 2001. During the flights, we performed vertical stacks of crosswind transects in the urban outflow downwind of Manaus City, measuring a comprehensive set of trace constituents including O3, NO, NO2, CO, VOC, CO2, and H2O. Aerosol loads were characterized by total aerosol number concentration (CN) and cloud condensation nuclei (CCN) concentrations, and light scattering properties. Measurements over pristine rainforest areas during the campaign showed low levels of pollution from biomass burning or industrial emissions, representative of wet season background conditions. The urban plume of Manaus City was found to be joined by plumes from power plants south of the city, all showing evidence of very strong photochemical ozone formation. One episode is discussed in detail, where a threefold increase in ozone mixing ratios in the atmospheric boundary layer occurred within a 100 km travel distance downwind of Manaus. Observation-based estimates of the ozone production rates in the plume reached 15 ppb h−1. Within the plume core, aerosol concentrations were strongly enhanced, with ΔCN/ΔCO ratios about one order of magnitude higher than observed in Amazon biomass burning plumes. ΔCN/ΔCO ratios tended to decrease with increasing transport time, indicative of a significant reduction in particle number by coagulation, and without substantial new particle nucleation occurring within the time/space observed. While in the background atmosphere a large fraction of the total particle number served as CCN (about 60–80% at 0.6% supersaturation), the CCN/CN ratios within the plume indicated that only a small fraction (16 ± 12%) of the plume particles were CCN. The fresh plume aerosols showed relatively weak light scattering efficiency. The CO-normalized CCN concentrations and light scattering coefficients increased with plume age in most cases, suggesting particle growth by condensation of soluble organic or inorganic species. We used a Single Column Chemistry and Transport Model (SCM) to infer the urban pollution emission fluxes of Manaus City, implying observed mixing ratios of CO, NOx and VOC. The model can reproduce the temporal/spatial distribution of ozone enhancements in the Manaus plume, both with and without accounting for the distinct (high NOx) contribution by the power plants; this way examining the sensitivity of ozone production to changes in the emission rates of NOx. The VOC reactivity in the Manaus region was dominated by a high burden of biogenic isoprene from the background rainforest atmosphere, and therefore NOx control is assumed to be the most effective ozone abatement strategy. Both observations and models show that the agglomeration of NOx emission sources, like power plants, in a well-arranged area can decrease the ozone production efficiency in the near field of the urban populated cores. But on the other hand remote areas downwind of the city then bear the brunt, being exposed to increased ozone production and N-deposition. The simulated maximum stomatal ozone uptake fluxes were 4 nmol m−2 s−1 close to Manaus, and decreased only to about 2 nmol m−2 s−1 within a travel distance 〉1500 km downwind from Manaus, clearly exceeding the critical threshold level for broadleaf trees. Likewise, the simulated N deposition close to Manaus was ~70 kg N ha−1 a−1 decreasing only to about 30 kg N ha−1 a−1 after three days of simulation.

Description: We report results from our atmospheric flask sampling network for three European sites: Lutjewad in the Netherlands, Mace Head in Ireland and the North Sea F3 platform. The air samples from these stations are primarily being analyzed for their CO2 and O2 concentrations. In this paper we present the CO2 and O2 data series from these sites between 1998 and 2009, as well as the atmospheric potential oxygen (APO). The seasonal pattern and long term trends agree to a large extent between our three measurement locations. We however find an increasing gradient between Mace Head and Lutjewad, both for CO2 and O2. As Lutjewad is influenced by local fluctuations in the fossil fuel sources, we use an atmospheric transport model in combination with CO2 emission data and information on the fossil fuel mix per region and category in order to correct the tracer APO for a residual fossil fuel component. For Lutjewad this correction differs significantly from the global average. Using the APO trend from Mace Head we obtain an estimate for the global oceanic CO2 uptake of 1.8 ± 0.8 PgC/year.

Description: A large number of calculations of the absorptive partitioning of organic compounds have been made using a number of methods to predict the component vapour pressures, p0, and activity coefficients, γi, required in the calculations. The sensitivities of the predictions in terms of the condensed component masses, volatility, O:C ratio, molar mass and functionality distributions to the choice of p0 and γi models and to the number of components to represent the organic mixture have been systematically compared. The condensed component mass was found to be highly sensitive to the vapour pressure model, and less sensitive to both the activity coefficient model and the number of components used to represent the mixture although the sensitivity to the change in property estimation method increased substantially with increased simplification in the treatment of the organic mixture. This was a general finding and was also clearly evident in terms of the predicted component functionality, O:C ratio, molar mass and volatility distributions of the condensed organic components. Within the limitations of the study, this clearly demonstrates the requirement for more accurate representation of the p0 and γi of the semi-volatile organic proxy components used in simplified models as the degree of simplification increases. This presents an interesting paradox, since such reduction in complexity necessarily leads to divergence from the complex behaviour of real multicomponent atmospheric aerosol.

Description: We report measurements of bromoform made by gas chromatography during the OP3 campaign in 2008. Measurements were made simultaneously for a few days at the World Meteorological Organization (WMO) Global Atmospheric Watch (GAW) site in the Danum Valley, a rainforest location in Sabah, Borneo, and at a nearby coastal site at Kunak. Background values at Kunak were higher than those measured in the rainforest (2–5 ppt compared with 1 ppt) and excursions away from the background were very much higher, reaching 10s of ppt. Measurements of C2Cl4, an industrial tracer, showed no significant difference in background at the two sites. The data are consistent with a strong, local coastal source of bromoform in eastern Sabah. Modelling using two different models can reproduce many of the observed features. The bromoform data are consistent with a lower global source (190 Gg Br yr−1) than indicated by our recent measurements on Cape Verde (O'Brien et al., 2009) and point to the difficulty for short-lived species of extrapolating local measurements to a global source.

Description: The stratospheric ozone loss during the Arctic winters 2004/05–2009/10 is investigated by using high resolution simulations from the chemical transport model Mimosa-Chim and observations from Microwave Limb Sounder (MLS) on Aura by the passive tracer technique. The winter 2004/05 was the coldest of the series with strongest chlorine activation. The ozone loss diagnosed from both model and measurements inside the polar vortex at 475 K ranges from ~1–0.7 ppmv in the warm winter 2005/06 to 1.7 ppmv in the cold winter 2004/05. Halogenated (chlorine and bromine) catalytic cycles contribute to 75–90% of the accumulated ozone loss at this level. At 675 K the lowest loss of ~0.4 ppmv is computed in 2008/09 from both simulations and observations and, the highest loss is estimated in 2006/07 by the model (1.3 ppmv) and in 2004/05 by MLS (1.5 ppmv). Most of the ozone loss (60–75%) at this level results from cycles catalysed by nitrogen oxides (NO and NO2) rather than halogens. At both 475 and 675 K levels the simulated ozone evolution inside the polar vortex is in reasonably good agreement with the observations. The ozone total column loss deduced from the model calculations at the MLS sampling locations inside the vortex ranges between 40 DU in 2005/06 and 94 DU in 2004/05, while that derived from observations ranges between 37 DU and 111 DU in the same winters. These estimates from both Mimosa-Chim and MLS are in general good agreement with those from the ground-based UV-VIS (ultra violet–visible) ozone loss analyses for the respective winters.

Description: The atmospheric concentrations of gaseous ammonia have been measured during two field campaigns in the winter and in the summer of 2007 at Beijing (China). These measurements were carried out by means of diffusion annular denuders coated with phosphorous acid. The results were discussed from the standpoint of seasonal and diurnal variations and meteorological effects. The daily average NH3 concentrations were in the range of 0.20–44.38 μg/m3 and showed regular seasonal variations with higher concentrations during summer and with lower during winter. The seasonal trends seemed to be largely affected by air temperature because of agricultural sources. No diurnal variability was observed for gaseous NH3 levels in both winter and summer seasons. The highest ammonia value of 105.67 μg/m3 was measured in the early morning during the summer period when stable atmospheric conditions occurred. The diurnal winter and summer trends of ammonia were nearly independent on the air temperatures but they were affected by wind direction suggesting a strong local source influences. Ammonia was also correlated with the atmospheric mixing in the boundary layer, and, with NOx and CO air concentrations supporting the hypothesis that the traffic may be also an important source of ammonia in Beijing.

Description: Three recently-completed sets of simulations of multiple chemistry-climate models with greenhouse gases only, with all anthropogenic forcings, and with anthropogenic and natural forcings, allow the causes of observed stratospheric changes to be quantitatively assessed using detection and attribution techniques. The total column ozone response to halogenated ozone depleting substances and to natural forcings is detectable and consistent in models and observations. However, the total ozone response to greenhouse gases in the models and observations appears to be inconsistent, which may be due to the models' inability to properly simulate tropospheric ozone changes. In the middle and upper stratosphere, simulated and observed SBUV/SAGE ozone changes are broadly consistent, and separate anthropogenic and natural responses are detectable in observations. The influence of ozone depleting substances and natural forcings can also be detected separately in observed lower stratospheric temperature, and the magnitudes of the simulated and observed responses to these forcings and to greenhouse gas changes are found to be consistent. In the mid and upper stratosphere the simulated natural and combined anthropogenic responses are detectable and consistent with observations, but the influences of greenhouse gases and ozone-depleting substances could not be separately detected in our analysis.

Description: Oil sands comprise 30% of the world's oil reserves and the crude oil reserves in Canada's oil sands deposits are second only to Saudi Arabia. The extraction and processing of oil sands is much more challenging than for light sweet crude oils because of the high viscosity of the bitumen contained within the oil sands and because the bitumen is mixed with sand and contains chemical impurities such as sulphur. Despite these challenges, the importance of oil sands is increasing in the energy market. To our best knowledge this is the first peer-reviewed study to characterize volatile organic compounds (VOCs) emitted from Alberta's oil sands mining sites. We present high-precision gas chromatography measurements of 76 speciated C2–C10 VOCs (alkanes, alkenes, alkynes, cycloalkanes, aromatics, monoterpenes, oxygenates, halocarbons, and sulphur compounds) in 17 boundary layer air samples collected over surface mining operations in northeast Alberta on 10 July 2008, using the NASA DC-8 airborne laboratory as a research platform. In addition to the VOCs, we present simultaneous measurements of CO2, CH4, CO, NO, NO2, NOy, O3 and SO2, which were measured in situ aboard the DC-8. Methane, CO, CO2, NO, NO2, NOy, SO2 and 53 VOCs (e.g., halocarbons, sulphur species, NMHCs) showed clear statistical enhancements (up to 1.1–397×) over the oil sands compared to local background values and, with the exception of CO, were higher over the oil sands than at any other time during the flight. Twenty halocarbons (e.g., CFCs, HFCs, halons, brominated species) either were not enhanced or were minimally enhanced (〈 10%) over the oil sands. Ozone levels remained low because of titration by NO, and three VOCs (propyne, furan, MTBE) remained below their 3 pptv detection limit throughout the flight. Based on their mutual correlations, the compounds emitted by the oil sands industry fell into two groups: (1) evaporative emissions from the oil sands and its products and/or from the diluent used to lower the viscosity of the extracted bitumen (i.e., C4–C9 alkanes, C5–C6 cycloalkanes, C6–C8 aromatics), together with CO; and (2) emissions associated with the mining effort (i.e., CO2, CO, CH4, NO, NO2, NOy, SO2, C2–C4 alkanes, C2–C4 alkenes, C9 aromatics, short-lived solvents such as C2Cl4 and C2HCl3, and longer-lived species such as HCFC-22 and HCFC-142b). Prominent in the second group, SO2 and NO were remarkably enhanced over the oil sands, with maximum enhancements of 38.7 and 5.0 ppbv, or 383 and 319× the local background, respectively. The SO2 enhancements are comparable to maximum values measured in heavily polluted megacities such as Mexico City and are attributed to coke combustion. By contrast, relatively poor correlations between CH4 ethane and propane suggest low natural gas leakage despite its heavy use at the surface mining sites. In addition to the emission of many trace gases, the natural drawdown of OCS by vegetation was absent above the surface mining operations, presumably because of the widespread land disturbance. Unexpectedly, the mixing ratios of α- and β-pinene were much higher over the oil sands (up to 217 and 610 pptv, respectively) than over vegetation in the background boundary layer (20±7 and 84±24 pptv, respectively), and the pinenes correlated well with several industrial tracers that were elevated in the oil sands plumes. Because so few independent measurements from the oil sands mining industry exist, this study provides an important initial characterization of trace gas emissions from oil sands surface mining operations.

Description: A variable residence time thermodenuder (TD) was combined with an Aerodyne Aerosol Mass Spectrometer (AMS) and a Scanning Mobility Particle Sizer (SMPS) to measure the volatility distribution of aged organic aerosol in the Eastern Mediterranean during the Finokalia Aerosol Measurement Experiment in May of 2008 (FAME-2008). A new method for the quantification of the organic aerosol volatility distribution was developed combining measurements of all three instruments together with an aerosol dynamics model. Challenges in the interpretation of ambient thermodenuder-AMS measurements include the potential resistances to mass transfer during particle evaporation, the effects of particle size on the evaporated mass fraction, the changes in the AMS collection efficiency and particle density as the particles evaporate partially in the TD, and finally potential losses inside the TD. Our proposed measurement and data analysis method accounts for all of these problems combining the AMS and SMPS measurements. The AMS collection efficiency of the aerosol that passed through the TD was found to be approximately 10% lower than the collection efficiency of the aerosol that passed through the bypass. The organic aerosol measured at Finokalia is approximately 2 orders of magnitude less volatile than fresh laboratory-generated biogenic secondary organic aerosol. This low volatility is consistent with its highly oxygenated AMS mass spectrum. The results are found to be highly sensitive to the mass accommodation coefficient of the evaporating species.

Description: An inventory of anthropogenic primary aerosol emissions in China was developed for 1990–2005 using a technology-based approach. Taking into account changes in the technology penetration within industry sectors and improvements in emission controls driven by stricter emission standards, a dynamic methodology was derived and implemented to estimate inter-annual emission factors. Emission factors of PM2.5 decreased by 7%–69% from 1990 to 2005 in different industry sectors of China, and emission factors of TSP decreased by 18%–80% as well. Emissions of PM2.5, PM10 and TSP presented similar trends: increased in the first six years of 1990s and decreased until 2000, then increased again in the following years. Emissions of TSP reached a historical high (35.5 Tg) in 1996, while the peak of PM10 (18.8 Tg) and PM2.5 (12.7 Tg) emissions occurred in 2005. Although various emission trends were identified across sectors, the cement industry and biofuel combustion in the residential sector were consistently the largest sources of PM2.5 emissions, accounting for 53%–62% of emission over the study period. The non-metallic mineral product industry, including the cement, lime and brick industries, accounted for 54%–63% of national TSP emissions. There were no significant trends of BC and OC emissions until 2000, but the increase after 2000 brought the historical high of BC (1.51 Tg) and OC (3.19 Tg) emissions in 2005. Although significant improvements in the estimation of primary aerosols are presented, there still exist large uncertainties. More accurate and detailed activity information and emission factors based on local tests are essential to further improve emission estimates, this especially being so for the brick and coke industries, as well as for coal-burning stoves and biofuel usage in the residential sector.

Description: Thermal-optical evolved gas analysis (TOEGA) is a conventional method for classifying carbonaceous aerosols as organic carbon (OC) and elemental carbon (EC). Its main source of uncertainty arises from accounting for pyrolyzed OC (char), which has similar behavior to the EC originally present on the filter. Sample composition can also cause error, at least partly by complicating the charred carbon correction. In this study, lab generated metal salt particles, including alkali (NaCl, KCl, Na2SO4), alkaline-earth (MgCl2, CaCl2) and transition metal salts (CuCl2, FeCl2, FeCl3, CuCl, ZnCl2, MnCl2, CuSO4, Fe2(SO4)3), were deposited on a layer of diesel particles to investigate their effect on EC and OC quantification with TOEGA. Measurements show that metals reduce the oxidation temperature of EC and enhance the charring of OC. The split point used to determine classification of EC vs. OC is more dependent on changes in EC oxidation temperature than it was on charring. The resulting EC/OC ratio is reduced by 0–80% in the presence of most of the salts, although some metal salts increased reported EC/OC at low metal to carbon ratios. In general, transition metals are more active than alkali and alkaline-earth metals; copper is the most active. Copper and iron chlorides are more active than sulfates. The melting point of metal salts is strongly correlated with the increase of OC charring, but not with the reduction of EC oxidation temperature. Other chemistry, such as redox reactions, may affect the EC oxidation. A brief discussion of possible catalytic mechanisms for the metals is provided.