ALBERT

Description: Considering the Mediterranean as a region of high evaporation and low precipitation, evaluations of the moisture and precipitation sources and sinks in the Mediterranean basin have been carried out within the frame of the CIRCE project. In addition, residence time and stagnation/ventilation have been analysed to investigate transport to and from the Mediterranean basin and in the basin itself. A Lagrangian moisture diagnosis method calculating budgets of evaporation minus precipitation was applied to a 5.5 year (October 1999–April 2005) trajectory data set and evaluated for eight Mediterranean regions of interest. The Mediterranean basin has been identified as a major source of moisture and precipitation to the surrounding land area and to the basin itself. Regions of stagnation have been identified through the analysis of the average 24-hour and 5-day displacements for the four seasons, and the Po basin was identified as being strongly affected by stagnation. Evaluation of the transport to and from the basin shows that the Mediterranean is a crossroad of airstreams where air enters mainly from the northwest and continues in two separate airstreams: one turns towards southwest, passing over North Africa into the trade wind zone while the other one continues northeastwards through Central Asia.

Description: We estimate the effect of the Arctic sea ice on the absorbed (net) solar flux using a radiation transfer model. Ice and cloud input data to the model come from satellite observations, processed by the International Satellite Cloud Climatology Project (ISCCP) and span the period July 1983–June 2007. The sea-ice effect on the solar radiation fluctuates seasonally with the solar flux and decreases interannually in synchronisation with the decreasing sea-ice extent. A disappearance of the Arctic ice cap during the sunlit period of the year would radically reduce the local albedo and cause a 19.7 W m−2 increase in absorbed solar flux at the Arctic Ocean surface, or equivalently a 0.55 W m−2 increase on the planetary scale. In the clear-sky scenario these numbers increase to 34.9 and 0.97 W m−2, respectively. A meltdown only in September, with all other months unaffected, increases the Arctic annually averaged solar absorption by 0.32 W m−2. We examined the net solar flux trends for the Arctic Ocean and found that the areas absorbing the solar flux more rapidly are the North Chukchi and Kara Seas, Buffin and Hudson Bays, and Davis Strait. The sensitivity of the Arctic absorbed solar flux on sea-ice extent and cloud amount was assessed. Although sea ice and cloud affect jointly the solar flux, we found little evidence of strong non-linearities.

Description: Inverse modeling is widely employed to provide "top-down" emission estimates using atmospheric measurements. Here, we analyze the dependence of derived CH4 emissions on the sampling frequency and density of the observational surface network, using the TM5-4DVAR inverse modeling system and synthetic observations. This sensitivity study focuses on Europe. The synthetic observations are created by TM5 forward model simulations. The inversions of these synthetic observations are performed using virtually no knowledge on the a priori spatial and temporal distribution of emissions, i.e. the emissions are derived mainly from the atmospheric signal detected by the measurement network. Using the European network of stations for which continuous or weekly flask measurements are available for 2001, the synthetic experiments can retrieve the "true" annual total emissions for single countries such as France within 20%, and for all North West European countries together within ~5%. However, larger deviations are obtained for South and East European countries due to the scarcity of stations in the measurement network. Upgrading flask sites to stations with continuous measurements leads to an improvement for central Europe in emission estimates. For realistic emission estimates over the whole European domain, however, a major extension of the number of stations in the existing network is required. We demonstrate the potential of an extended network of a total of ~60 European stations to provide realistic emission estimates over the whole European domain.

Description: This paper reports the first record of extreme ozone measurement in Africa. As part of the AMMA program, the ozone vertical profile recorded on 20 December over Cotonou presents exceptionally high ozone concentrations with up to 295 ppbv at 1 km altitude. Retroplumes from the Flexpart model show that the air masses sampled at 1 km over Cotonou on this day come from the burning area situated north-east of Cotonou and pass over Lagos, Nigeria, which is highly impacted by urban pollution. We used the Master Mechanism box model to simulate the chemical composition of the plume during its transit. We find that neither the biomass burning emissions of ozone precursors nor additional urban emissions from Lagos are high enough to simulate more than 120–150 ppbv of ozone. The only way to reach almost 300 ppb of ozone within a few hours is to feed the air mass with large amounts of reactive VOCs as those recorded in the vicinity of petrochemical area. Sensitivity tests show that 250–600 ppbv of VOCs combined with 35–80 ppb of NOx allow the ozone concentrations to be higher than 250 ppb. Nigeria is the first African country with gas extraction and petrochemical industries, and petrochemical explosions frequently happen in the vicinity of Lagos. The hypothesis of a petrochemical explosion in this area is the most likely scenario which explains the 295 ppbv ozone maximum measured over Cotonou, downwind of Lagos.

Description: Heterogeneous ice nucleation on solid ammonium sulfate and solid amorphous glutaric acid particles was studied using optical microscopy and Raman spectroscopy. Optical microscopy was used to detect selective nucleation events as water vapor was slowly introduced into an environmental sample cell. Particles that nucleated ice were dried via sublimation and examined in detail using Raman spectroscopy. Depositional ice nucleation occurred preferentially on just a few ammonium sulfate and glutaric acid particles in each sample. For freezing temperatures between 214 K and 235 K average ice saturation ratios of S=1.10±0.07 for solid ammonium sulfate and S=1.39±0.16 for solid amorphous glutaric acid particles were determined. Experiments with externally mixed particles further show that ammonium sulfate is a more potent ice nucleus that glutaric acid. Our results suggest that heterogeneous nucleation on ammonium sulfate may be an important pathway for atmospheric ice nucleation and cirrus cloud formation when solid aerosol particles are available for ice formation. This pathway for ice formation may be particularly significant near the tropopause region where sulfates are abundant and other species known to be good ice nuclei are depleted.

Description: Sander et al. (2006) proposed that CaCO3 precipitation can be an important factor in triggering tropospheric ozone depletion events. Recently, Morin et al. (2008b) presented calculations with the FREZCHEM model and concluded that their results and interpretation cast doubt on the validity of this hypothesis. In this joint publication, we have re-analyzed the implications of the FREZCHEM results and show how they can be reconciled with the proposal of Sander et al. (2006). The chemical predictions of both approaches are consistent. Although an interpretation solely based on the alkalinity change in the brine does not support the conclusion of Sander et al. (2006), we show that the bromide/alkalinity ratio (which increases during the cooling of the brine) can be used as an indicator of the potential for triggering bromine explosions.

Description: Two proton-transfer-reaction mass spectrometry systems were deployed at the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen-Southern Rocky Mountain 2008 field campaign (BEACHON-SRM08; July to September 2008) at the Manitou Forest observatory in a Ponderosa pine woodland near Woodland Park, Colorado USA to simultaneously measure BVOC emissions and ambient distributions of their oxidation products. Here, we present mass spectral analysis in a wide range of masses (m/z=40+ to 210+) to assess our understanding of BVOC emissions and their photochemical process inside of the forest canopy. The biogenic terpenoids, 2-methyl-3-butene-2-ol (MBO, 50.2%) and several monoterpenes (MT, 33.5%) were identified as the dominant BVOC emissions from a transmission corrected mass spectrum, averaged over the daytime (11 am to 3 p.m., local time) of three days. To assess contributions of oxidation products of local BVOC, we calculate a oxidation product spectrum with the OH- and ozone-initiated oxidation product distribution mass spectra of two major BVOC at the ecosystem (MBO and β-pinene) that were observed from laboratory oxidation experiments. A majority (~73%) of the total signal could be explained by known compounds. The remainder are attributed to oxidation products of BVOC, emitted from nearby ecosystems and transported to the site, and oxidation products of unidentified BVOC emitted from the Ponderosa pine ecosystem.

Description: We use measurements by the 52 MHz wind-profiling radar ESRAD, situated near Kiruna in Arctic Sweden, and simulations using the Advanced Research and Weather Forecasting model, WRF, to study vertical winds and turbulence in the troposphere in mountain-wave conditions on 23 , 24 and 25 January 2003. We find that WRF can accurately match the vertical wind signatures at the radar site when the spatial resolution for the simulations is 1 km. The horizontal and vertical wavelengths of the dominating mountain-waves are ∼10–20 km and the amplitudes in vertical wind 1–2 m/s. Turbulence below 5500 m height, is seen by ESRAD about 40% of the time. This is a much higher rate than WRF predictions for conditions of Richardson number (Ri) 〉1 but similar to WRF predictions of Ri〉2. WRF predicts that air crossing the 100 km wide model domain centred on ESRAD has a ∼10% chance of encountering convective instabilities (Ri〉0.) somewhere along the path. The cause of low Ri is a combination of wind-shear at synoptic upper-level fronts and perturbations in static stability due to the mountain-waves. Comparison with radiosondes suggests that WRF underestimates wind-shear and the occurrence of thin layers with very low static stability, so that vertical mixing by turbulence associated with mountain waves may be significantly more than suggested by the model.

Description: An accurate but simple quantification of the fraction of aerosol particles that can act as cloud condensation nuclei (CCN) is needed for implementation in large-scale models. Data on aerosol size distribution, chemical composition, and CCN concentration from six different locations have been analyzed to explore the extent to which simple assumptions of composition and mixing state of the organic fraction can reproduce measured CCN number concentrations. Fresher pollution aerosol as encountered in Riverside, CA, and the ship channel in Houston, TX, cannot be represented without knowledge of more complex (size-resolved) composition. For aerosol that has experienced processing (Mexico City, Holme Moss (UK), Point Reyes (CA), and Chebogue Point (Canada)), CCN can be predicted within a factor of two assuming either externally or internally mixed soluble organics although these simplified compositions/mixing states might not represent the actual properties of ambient aerosol populations. Under typical conditions, a factor of two uncertainty in CCN concentration translates to an uncertainty of ~15% in cloud drop concentration, which might be adequate for large-scale models given the much larger uncertainty in cloudiness.

Description: A numerical evaluation of global oceanic emissions of α-pinene and isoprene based on both "bottom-up" and "top-down" methods is presented. As far as we know, this is the first quantification of global oceanic emission of α-pinene. We infer that the global "bottom-up" oceanic emissions of α-pinene and isoprene are 0.013 Tg C yr−1 and 0.32 Tg C yr−1, respectively. By constraining global chemistry model simulations with the shipboard measurement of Organics over the Ocean Modifying Particles in both Hemispheres summer cruise, we derived the global "top-down" oceanic α-pinene source of 35.1 Tg C yr−1 and isoprene source of 2.5 Tg C yr−1. The global oceanic α-pinene source and its impact on organic aerosol formation is significant based on "top-down" method, but is negligible based on "bottom-up" approach. Our research highlights the importance to carry out further research (especially measurements) to resolve the large offset in the derived oceanic organic emission based on two different approaches.

Description: Optical properties of cirrus ice clouds play an important role in regulating Earth's radiative balance. It has been hypothesized that the surfaces of cirrus ice crystals may be characterized by mesoscopic (micrometer-scale) texturing, or roughness, in order to explain discrepancies between theoretical and observed light-scattering properties. Here, we present the first clearly resolved observations of surfaces of hexagonal ice crystals, using variable-pressure scanning electron microscopy. During growth conditions, the ice surface develops trans-prismatic strands, separated from one another by distances of 5–10 μm. These strands become more pronounced during ablation, and exhibit a wider range of separations. Under re-growth conditions, faceting is re-established initially at prismatic edges. Molecular dynamics studies of a free-standing ice Ih nanocolumn showed no trans-prismatic strands at the atomistic level, suggesting that these strands originate at a spatial scale greater than 10 nm. The observed surface roughness could be used to construct more realistic representations of cirrus clouds in climate models, and constrain theories of ice crystal growth and ablation.

Description: This paper presents a complete characterization of a very deep stratospheric intrusion which occurred over the British Isles on 15 August 2007. The signature of this event is diagnosed using ozonesonde measurements over Lerwick, UK (60.14° N, 1.19° W) and is also well characterized using meteorological analyses from the global operational weather prediction model of Météo-France, ARPEGE. Modelled as well as assimilated fields of both ozone (O3) and carbon monoxide (CO) have been used in order to better document this event. The paper also presents a demonstration of the capability of O3 and CO assimilated fields to better describe a stratosphere-troposphere exchange (STE) event in comparison with the free run modelled O3 and CO fields. O3 and CO from Aura/MLS and Terra/MOPITT instruments, respectively, are assimilated into the three-dimensional chemical transport model MOCAGE of Météo-France using a variational 3-D-FGAT (First Guess at Appropriate Time) method within the MOCAGE-PALM assimilation system. The usefulness of assimilated MOPITT CO data in a STE study is demonstrated in this novel result. The study shows that the use of the model MOCAGE gives consistent 3-D fields capable of describing the synoptic evolution of the event. However, modelled O3 and CO vertical distributions do not provide a quantitative evaluation of the intrusion. Although the assimilation of MLS data improves the distribution of O3 above the tropopause compared to the free model run, it is not sufficient to reproduce the stratospheric intrusion event well. Conversely, assimilated MOPITT CO allows a better description of the stratospheric intrusion event. Indeed, the horizontal distribution of the CO assimilated field is consistent with meteorological analyses. Moreover, the vertical distribution of the CO assimilated field is in accordance with the potential vorticity distribution and reveals a deeper intrusion from the lower stratosphere downward to the mid-troposphere compared to the O3 assimilated field. This study clearly demonstrates the capability of the assimilation of MOPITT CO to improve the CO distribution in the upper troposphere and lower stratosphere region. In addition, the behaviour of CO assimilated field is consistent with the synoptic evolution of the meteorological conditions. Therefore, the results of this study open the perspectives for using MOPITT CO in the STE studies.

Description: We analyze a multi-year record of aerosol smoke plume heights derived from observations over North America made by the Multi-angle Imaging SpectroRadiometer (MISR) instrument on board the NASA Earth Observing System Terra satellite. We characterize the magnitude and variability of smoke plume heights for various biomes, and assess the contribution of local atmospheric and fire conditions to this variability. Plume heights are highly variable, ranging from a few hundred meters up to 5000 m above the terrain at the Terra overpass time (11:00–14:00 local time). The largest plumes are found over the boreal region (median values of ∼850 m height, 24 km length and 940 m thickness), whereas the smallest plumes are found over cropland and grassland fires in the contiguous US (median values of ∼530 m height, 12 km length and 550–640 m thickness). The analysis of plume heights in combination with assimilated meteorological observations from the NASA Goddard Earth Observing System indicates that a significant fraction (4–12%) of plumes from fires are injected above the boundary layer (BL), consistent with earlier results for Alaska and the Yukon Territories during summer 2004. Most of the plumes located above the BL (〉83%) are trapped within stable atmospheric layers. We find a correlation between plume height and the MODerate resolution Imaging Spectroradiometer (MODIS) fire radiative power (FRP) thermal anomalies associated with each plume. Smoke plumes located in the free troposphere (FT) exhibit larger FRP values (1620–1640 MW) than those remaining within the BL (174–465 MW). Plumes located in the FT without a stable layer reach higher altitudes and are more spread-out vertically than those associated with distinct stable layers (2490 m height and 2790 m thickness versus 1880 m height and 1800 thickness). The MISR plume climatology exhibits a well-defined seasonal cycle of plume heights in boreal and temperate biomes, with greater heights during June–July. MODIS FRP measurements indicate that larger summertime heights are the result of higher fire intensity, likely due to more severe fire weather during these months. This work demonstrates the significant effect of fire radiative heat and atmospheric structure on the ultimate rise of fire emissions, and underlines the importance of considering such physical processes in modeling smoke dispersion.

Description: Hydroxyl radicals are important oxidants in the atmosphere and in natural waters. They are also expected to be important in snow and ice, but their reactivity has not been widely studied in frozen aqueous solution. We have developed a spectroscopic probe to monitor the formation and reactions of hydroxyl radicals in situ. Hydroxyl radicals are produced in aqueous solution via the photolysis of nitrite, nitrate, and hydrogen peroxide, and react rapidly with benzene to form phenol. Similar phenol formation rates were observed in aqueous solution and bulk ice. However, no reaction was observed at the air-ice interface, or when bulk ice samples were crushed prior to photolysis to increase their surface area. We also monitored the heterogeneous reaction between benzene present at air-water and air-ice interfaces with gas-phase OH produced from HONO photolysis. Rapid phenol formation was observed on water surfaces, but no reaction was observed at the surface of ice. Under the same conditions, we observed rapid loss of the polycyclic aromatic hydrocarbon (PAH) anthracene at the air-water interface, but no loss was observed at the air-ice interface. Our results suggest that the reactivity of hydroxyl radicals toward aromatic organics is similar in bulk ice samples and in aqueous solution, but is significantly suppressed in the quasi-liquid layer (QLL) that exists at the air-ice interface.

Description: This study describes high-resolution numerical simulations of the evolution of an aircraft contrail and its transition into a contrail-cirrus. The contrail is modeled as a vortex pair descending in a stratified atmosphere where turbulent fluctuations are sustained in the late regime of diffusion. The focus of this study is laid on the three-dimensional vortex dynamics – including vortex instability and turbulence – and on the interaction between dynamics and microphysics and its role in determining the growth and the distribution of ice crystals. The results show the feasibility of three-dimensional simulations of the entire lifetime of a contrail until its transformation into a contrail-cirrus in supersaturated conditions. In particular, it is shown that the contrail-cirrus optical depth is maintained as the cloud expands, in agreement with available observations.

Description: Carbonaceous aerosols affect the radiative balance of the Earth by absorbing and scattering light. While BC is highly absorbing, some organic compounds also have significant absorption, which is greater at near-ultraviolet and blue wavelengths. To the extent that OC absorbs visible light, it may be a non-negligible contributor to direct aerosol radiative forcing. In this work, we examine absorption by primary OC emitted from solid fuel pyrolysis. We provide absorption spectra of this material, which can be related to the imaginary refractive index. This material has polar character but is not fully water-soluble: more than 92% was extractable by methanol or acetone, compared with 73% for water and 52% for hexane. Water-soluble organic carbon contributed to light absorption at both ultraviolet and visible wavelengths. However, a larger portion came from organic carbon that is extractable only by methanol. The spectra of water-soluble organic carbon are similar to others in the literature. We compared spectra for material generated with different wood type, wood size and pyrolysis temperature. Higher wood temperature is the main factor creating organic aerosol with higher absorption, causing about a factor of four increase in mass-normalized absorption at visible wavelengths. A simple model suggests that, despite the absorption, both high-temperature and low-temperature carbon have negative climate forcing over a surface with average albedo.

Description: Gaseous mercury in the marine boundary layer has been measured with a 15 min temporal resolution at the Global Atmosphere Watch station Cape Point since March 2007. The most prominent features of the data until July 2008 are the frequent occurrences of pollution (PEs) and depletion events (DEs). Both types of events originate mostly within a short transport distance (up to about 100 km), which are embedded in air masses ranging from marine background to continental. The Hg/CO emission ratios observed during the PEs are within the range reported for biomass burning and industrial/urban emissions. The depletion of gaseous mercury during the DEs is almost quantitative in many cases and suggests a lifetime of elemental mercury as short as a few dozens of hours, which is in contrast to the commonly used estimate of approximately 1 year. The characteristics of the DE occurrence at Cape Point is neither similar to the halogen driven atmospheric mercury depletion events (AMDEs) observed in Polar Regions nor to the DEs reported for plumes of urban air. Additional measurements are necessary to reveal the chemical mechanism of the observed DEs and to assess its importance on larger scales.

Description: NOx measurements were conducted at the Halley Research Station, Antarctica, during the austral summer period 1 January–10 February 2005. A clear NOx diurnal cycle was observed with minimum concentrations close to instrumental detection limit (5 pptv) measured between 04:00–05:00 GMT. NOx concentrations peaked (24 pptv) between 19:00–20:00 GMT, approximately 5 h after local solar noon. An optimised box model of NOx concentrations based on production from in-snow nitrate photolysis and chemical loss derives a mean noon emission rate of 3.48×108 molecules cm−2 s−1, assuming a 100 m boundary layer mixing height, and a relatively short NOx lifetime of ~6.4 h. This emission rate compares to directly measured values ranging from 1.7 to 3.4×108 molecules cm−2 s−1 made on 3 days at the end of the study period. Calculations of the maximum rate of NO2 loss via a variety of conventional HOx and halogen oxidation processes show that the lifetime of NOx is predominantly controlled by halogen processing, namely BrNO3 and INO3 gas-phase formation and their subsequent heterogeneous uptake, with a potential smaller contribution from HNO4 formation and uptake. Furthermore the presence of halogen oxides is shown to significantly perturb NOx concentrations by decreasing the NO/NO2 ratio. We conclude that in coastal Antarctica, the potential ozone production efficiency of NOx emitted from the snowpack is mitigated by the more rapid NOx loss due to halogen nitrate hydrolysis. These results suggest that the role of halogen oxides need to be considered when interpreting the isotopic signature of nitrate impurities held within snow and ice.

Description: Using the Swedish icebreaker Oden as a platform, continuous measurements of airborne mercury (gaseous elemental mercury (Hg0), divalent mercury HgII(g) (acronym RGM) and mercury attached to particles (PHg)) and some long-lived trace gases (carbon monoxide CO and ozone O3) were performed over the North Atlantic and the Arctic Ocean. The measurements were performed for nearly three months (July–September, 2005) during the Beringia 2005 expedition (from Göteborg, Sweden via the proper Northwest Passage to the Beringia region Alaska – Chukchi Penninsula – Wrangel Island and in-turn via a north-polar transect to Longyearbyen, Spitsbergen). The Beringia 2005 expedition was the first time that these species have been measured during summer over the Arctic Ocean going from 60° to 90° N. During the North Atlantic transect, concentration levels of Hg0, CO and O3 were measured comparable to typical levels for the ambient mid-hemispheric average. However, a rapid increase of Hg0 in air and surface water was observed when entering the ice-covered waters of the Canadian Arctic archipelago. Large parts of the measured waters were supersaturated with respect to Hg0, reflecting a strong disequilibrium. Heading through the sea ice of the Arctic Ocean, a fraction of the strong Hg0} pulse in the water was spilled with some time-delay into the air samples collected ~20 m a.s.l. Several episodes of elevated Hg0(g) were encountered along the sea ice route with higher mean concentration (1.81±0.43 ng m−3) compared to the marine boundary layer over ice-free oceanic waters (1.55±0.21 ng m−3). In addition, an overall majority of the variance in the temporal series of Hg0 concentrations was observed during July. Atmospheric boundary layer {O3} mixing ratios decreased when initially sailing northward. In the Arctic, an O3 minimum around 15–20 ppbv was observed during summer (July–August). Alongside the polar transect during the beginning of autumn, a steady trend of increasing O3 mixing ratios was measured returning to initial levels of the expedition (〉30 ppbv). Ambient CO was fairly stable (84±12 ppbv) during the expedition. However, from the Beaufort Sea and moving onwards steadily increasing CO mixing ratios were observed (0.3 ppbv day−1). On a comparison with coeval archived CO and O3 data from the Arctic coastal strip monitoring sites Barrow and Alert, the observations from Oden indicate these species to be homogeneously distributed over the Arctic Ocean. Neither correlated low ozone and GEM events nor elevated concentrations of RGM and PHg were at any extent sampled, suggesting that atmospheric mercury deposition to the Arctic basin is low during the Polar summer and autumn. Elevated levels of Hg0 and CO were episodically observed in air along the Chukchi Peninsula indicating transport of regional pollution.

Description: Organic matter frequently represents the single largest fraction of fine particulates in urban environments and yet the exact contributions from different sources and processes remain uncertain, owing in part to its substantial chemical complexity. Positive Matrix Factorisation (PMF) has recently proved to be a powerful tool for the purposes of source attribution and profiling when applied to ambient organic aerosol data from the Aerodyne Aerosol Mass Spectrometer (AMS). Here we present PMF analysis applied to AMS data from UK cities for the first time. Three datasets are analysed, with the focus on objectivity and consistency. The data were collected in London during the Regent's Park and Tower Environmental Experiment (REPARTEE) intensives and Manchester. These occurred during the autumn and wintertime, such that the primary fraction would be prominent. Ambiguities associated with rotationality within sets of potential solutions are explored and the most appropriate solution sets selected based on comparisons with external data. In addition to secondary organic aerosols, three candidate sources of primary organic aerosol (POA) were identified according to mass spectral and diurnal profiles; traffic emissions, cooking and solid fuel burning. Traffic represented, on average, 40% of POA during colder conditions and exhibited a hydrocarbon-like mass spectrum similar to those previously reported. Cooking aerosols represented 34% of POA and through laboratory work, their profile was matched with that sampled from the heating of seed oils, rather than previously-published spectra derived from charbroiling. This suggests that in these locations, oil from frying may have contributed more to the particulate than the meat itself. Solid fuel aerosols represented 26% of POA during cold weather conditions but were not discernable during the first REPARTEE experiment, when conditions were warmer than the other campaigns. This factor showed features associated with biomass burning and occurred mainly at night. Grid-scale emission factors of the combustion aerosols suitable for use in chemical transport models were derived relative to CO and NOx. The traffic aerosols were found to be 14.4 μg m−3 ppm−1 relative to CO for Manchester and 28 μg m−3 ppm−1 relative to NOx for London. Solid fuel emissions were derived as 17.3 μg m−3 ppm−1 relative to CO for Manchester. These correspond to mass emission ratios of 0.012, 0.021 (as NO) and 0.014 respectively and are of a similar order to previously published estimates, derived from other regions or using other approaches.

Description: Aerosol in the size range 0.8–20 μm was characterized according to optical equivalent diameter, DP, morphology and the presence of biological material, the latter determined by recording fluorescence excited by ultraviolet light pulses at two different wavelengths. Single-particle measurements were performed within and subsequently above a tropical rainforest in Borneo, Malaysia, in June and July 2008. In both locations the aerosol number size distribution exhibited a primary biological aerosol (PBA) mode sized 2 μm2 μm and possessed a wider morphological range than non-PBA. It also accounted for around 80% of the total number in the understory and 40% of the total number above canopy. Canopy transmission efficiencies for the total aerosol number and PBA are calculated to be 0.48±0.19 and 0.31±0.15 respectively, with the former appearing to peak during the daytime because of a lack of PBA emission below the canopy.

Description: A new methodology is developed to constrain Chinese anthropogenic emissions of nitrogen oxides (NOx) from four major sectors (industry, power plants, mobile and residential) in July 2008. It combines tropospheric NO2 column retrievals from GOME-2 and OMI, taking advantage of their different passing time over China (9:30 a.m. local time versus 1:30 p.m.), and explicitly accounts for diurnal variations in anthropogenic emissions of NOx as well as their tropospheric lifetime and column concentrations. The approach is based on the daytime variation of NOx (when its lifetime is relatively short) alone; and potential errors in inverse modeling by neglecting horizontal transport are minimized. Separation of anthropogenic sectors relies on the estimated diurnal profiles and budget uncertainties. Our best top-down estimate suggests a national budget of 6.8 Tg N/yr (5.5 Tg N/yr for East China), close to the a priori bottom-up emission estimate from the INTEX-B mission. The top-down emissions are lower than the a priori near Beijing, in the northeastern provinces and along the east coast; yet they exceed the a priori over many inland regions. Systematic errors in satellite retrievals are estimated to lead to underestimation of top-down emissions by at most 17% (most likely 10%). Effects of other factors on the top-down estimate are typically less than 15%, including lightning, soil emissions, mixing in planetary boundary layer, anthropogenic emissions of carbon monoxide and volatile organic compounds, assumptions on emission diurnal variations, and uncertainties in the four sectors. The a posteriori emission budget is 5.7 Tg N/yr for East China.

Description: We present net emission estimates of CH4 and N2O of The Netherlands based on measurements conducted during the period of May 2006 to April 2009 at station Lutjewad, The Netherlands (6° 21' E, 53° 24' N, 1 m a.s.l.). 222Radon mixing ratios were applied as an indicator for vertical mixing and long-range air mass transport and used to calculate the net surface fluxes from atmospheric mixing ratios of CH4 and N2O. Our study shows that our measurement site Lutjewad is well-suited to measure emissions from The Netherlands and validation of the national inventories using the 222Radon flux method. Since this study is purely observation-based it is independent from inventories or atmospheric models. Our results are compared to the national inventories as reported to the UNFCCC. We found net emissions of: (15.2±5.3) t km-2 a-1 for CH4 and (0.9±0.3) t km-2 a-1 for N2O. These values are lower than the inventory-based emissions (2006–2008 averages) of (18.3±3.3) t km-2 a-1 for CH4, and (1.3±0.6) t km-2 a-1 for N2O, but the differences are insignificant.

Description: A new path for hydroxyl radical formation via photo-excitation of nitrogen dioxide (NO2) and the reaction of photo-excited NO2 with water is evaluated using the UCI-CIT model for the South Coast Air Basin of California (SoCAB). Two separate studies predict different reaction rates, which differ by nearly an order of magnitude, for the reaction of photo-excited NO2 with water. Impacts of this new chemical mechanism on ozone and particulate matter formation, while utilizing both reaction rates, are quantified by simulating a two-day summer episode. In addition, sensitivity simulations are conducted to evaluate the uncertainty in the rate of reaction of photo-excited NO2 with water reported in the literature. Results indicate that the addition of photo-excited NO2 chemistry increases peak 1-h average ozone concentrations by up to 20.6%. Also, the new chemistry leads to moderate increases in particulate matter concentrations of up to 2.9%. The importance of this new chemistry is then evaluated in the context of pollution control strategies. A series of simulations are conducted to generate isopleths for ozone and particulate matter concentrations, varying baseline nitrogen oxides (NOx) and volatile organic compounds emissions. Results show that including NO2 photo-excitation increases the sensitivity of ozone concentration to changes in NOx emissions. Namely, increasing NOx when NO2 photo-excitation is included, while utilizing the higher reaction rate, leads to an increase in ozone concentration of up to 38.7% higher than a case without photo-excited NO2. Ozone and particulate matter control strategies rely heavily on the variation of NOx and VOC emissions and the addition of the new chemical mechanism increases peak ozone and 24-h average PM concentrations in all locations under all NOx and VOC scaling factors while utilizing both reaction rates. Therefore, three-dimensional air quality models should be modified to include this new OH production mechanism, especially if used to develop emission controls strategies.

Description: The Aerosol Optical Depth (AOD) and Angstrom Coefficient (AC) predictions in the GISS-TOMAS model of global aerosol microphysics are evaluated against remote sensing data from MODIS, MISR, and AERONET. The model AOD agrees well (within a factor of two) over polluted continental (or high sulfate), dusty, and moderate sea-salt regions but less well over the equatorial, high sea-salt, and biomass burning regions. Underprediction of sea-salt in the equatorial region is likely due to GCM meteorology (low wind speeds and high precipitation). For the Southern Ocean, overprediction of AOD is very likely due to high sea-salt emissions and perhaps aerosol water uptake in the model. However, uncertainties in cloud screening in high latitude make it difficult to evaluate the model AOD at high latitudes with the satellite-based AOD. AOD in biomass burning regions is underpredicted, a problem also seen in other global aerosol models but more severely in this work. Using measurements from the LBA-SMOCC 2002 campaign, the surface-level OC and EC concentrations in the model are found to be underpredicted severely during the dry season, suggesting the low AOD in the model is due to underpredictions in OM and EC mass. These, in turn, result from unrealistically short wet deposition lifetimes during the dry season in the GCM.

Description: Using the nadir-viewing Global Ozone Measuring Experiment (GOME) UV/VIS spectrometer on the ERS-2 satellite, we investigate short term variations in the vertical magnesium column densities in the atmosphere and any connection to possible enhanced mass deposition during a meteor shower. Time-dependent mass influx rates are derived for all the major meteor showers using published estimates of mass density and temporal profiles of meteor showers. An average daily sporadic background mass flux rate is also calculated and used as a baseline against which calculated shower mass flux rates are compared. These theoretical mass flux rates are then compared with GOME derived metal vertical column densities of Mg and Mg+ from the years 1996–2001. There is no correlation between theoretical mass flux rates and changes in the Mg and Mg+ metal column densities. A possible explanation for the lack of a shower related increase in metal concentrations may be differences in the mass regimes dominating the average background mass flux and shower mass flux.

Description: The Airborne Mobile Aerosol Lidar (AMALi) is an instrument developed at the Alfred Wegener Institute for Polar and Marine Research for a trouble-free operation under the challenging weather conditions at the Earth's polar regions. Since 2003 the AMALi has been successfully deployed for measurements in the ground-based installation and the zenith- or nadir-aiming airborne configurations during several scientific campaigns in the Arctic. The lidar provides profiles of the total backscatter at two wavelengths, from which aerosol and cloud properties are derived. It measures also the linear depolarization of the backscattered return, allowing for the discrimination of thermodynamic cloud phase and the identification of the presence of non-spherical aerosol particles. This paper presents the capability characteristics and performance of the past and present state of the AMALi system, as well as discusses the ground-based and airborne evaluation schemes applied to invert the data.

Description: Aerosol measurements at Barrow, AK during the past 30 years have identified the long range transport of pollution associated with Arctic Haze as well as ocean-derived aerosols of more local origin. Here, we focus on measurements of aerosol chemical composition to assess 1) trends in Arctic Haze aerosol and implications for source regions, 2) the interaction between pollution-derived and ocean-derived aerosols and the resulting impacts on the chemistry of the Arctic boundary layer, and 3) the response of aerosols to a changing climate. Aerosol chemical composition measured at Barrow, AK during the Arctic haze season is compared for the years 1976–1977 and 1997–2008. Based on these two data sets, concentrations of non-sea salt (nss) sulfate (SO4=) and non-crustal (nc) vanadium (V) have decreased by about 60% over this 30 year period. Consistency in the ratios of nss SO4=/ncV and nc manganese (Mn)/ncV between the two data sets indicates that, although emissions have decreased in the source regions, the source regions have remained the same over this time period. The measurements from 1997–2008 indicate that, during the haze season, the nss SO4= aerosol at Barrow is becoming less neutralized by ammonium (NH4+) yielding an increasing sea salt aerosol chloride (Cl−) deficit. The expected consequence is an increase in the release of Cl atoms to the atmosphere and a change in the lifetime of volatile organic compounds (VOCs) including methane. In addition, summertime concentrations of biogenically-derived methanesulfonate (MSA−) and nss SO4= are increasing at a rate of 12 and 8% per year, respectively. Further research is required to assess the environmental factors behind the increasing concentrations of biogenic aerosol.

Description: The transport of very short-lived substances into the tropical upper troposphere and lower stratosphere is investigated by a three-dimensional chemical transport model using archived convective updraft mass fluxes (or detrainment rates) from the European Centre for Medium-Range Weather Forecast's ERA-Interim reanalysis. Large-scale vertical velocities are calculated from diabatic heating rates. With this approach we explicitly model the large scale subsidence in the tropical troposphere with convection taking place in fast and isolated updraft events. The model calculations agree generally well with observations of bromoform and methyl iodide from aircraft campaigns and with ozone and water vapor from sonde and satellite observations. Using a simplified treatment of dehydration and bromine product gas washout we give a range of 1.6 to 3 ppt for the contribution of bromoform to stratospheric bromine, assuming a uniform source in the boundary layer of 1 ppt. We show that the most effective region for VSLS transport into the stratosphere is the West Pacific, accounting for about 55% of the bromine from bromoform transported into the stratosphere under the supposition of a uniformly distributed source.

Description: OH reactivity is one of key indicators which reflect impacts of photochemical reactions in the atmosphere. An observation campaign has been conducted in the summer of 2007 at the heart of Tokyo metropolitan area to measure OH reactivity. The total OH reactivity measured directly by the laser-induced pump and probe technique was higher than the sum of the OH reactivity calculated from concentrations and reaction rate coefficients of individual species measured in this campaign. And then, three-dimensional air quality simulation has been conducted to evaluate the simulation performance on the total OH reactivity including "missing sinks", which correspond to the difference between the measured and calculated total OH reactivity. The simulated OH reactivity is significantly underestimated because the OH reactivity of volatile organic compounds (VOCs) and missing sinks are underestimated. When scaling factors are applied to input emissions and boundary concentrations, a good agreement is observed between the simulated and measured concentrations of VOCs. However, the simulated OH reactivity of missing sinks is still underestimated. Therefore, impacts of unidentified missing sinks are investigated through sensitivity analyses. In the cases that unknown secondary products are assumed to account for unidentified missing sinks, they tend to suppress formation of secondary aerosol components and enhance formation of ozone. In the cases that unidentified primary emitted species are assumed to account for unidentified missing sinks, a variety of impacts may be observed, which could serve as precursors of secondary organic aerosols (SOA) and significantly increase SOA formation. Missing sinks are considered to play an important role in the atmosphere over Tokyo metropolitan area.

Description: Concentrations of peroxy radicals (HO2+ΣiRiO2) in addition to other trace gases were measured onboard the UK Meteorological Office/Natural Environment Research Council British Aerospace 146-300 atmospheric research aircraft during the Intercontinental Transport of Ozone and Precursors (ITOP) campaign based at Horta Airport, Faial, Azores (38.58° N, 28.72° W) in July/August 2004. The overall peroxy radical altitude profile displays an increase with altitude that is likely to have been impacted by the effects of long-range transport. The peroxy radical altitude profile for air classified as of marine origin shows no discernable altitude profile. A range of air-masses were intercepted with varying source signatures, including those with aged American and Asian signatures, air-masses of biomass burning origin, and those that originated from the east coast of the United States. Enhanced peroxy radical concentrations have been observed within this range of air-masses indicating that long-range transported air-masses traversing the Atlantic show significant photochemical activity. The net ozone production at clear sky limit is in general negative, and as such the summer mid-Atlantic troposphere is at limit net ozone destructive. However, there is clear evidence of positive ozone production even at clear sky limit within air masses undergoing long-range transport, and during ITOP especially between 5 and 5.5 km, which in the main corresponds to a flight that extensively sampled air with a biomass burning signature. Ozone production was NOx limited throughout ITOP, as evidenced by a good correlation (r2=0.72) between P(O3) and NO. Strong positive net ozone production has also been seen in varying source signature air-masses undergoing long-range transport, including but not limited to low-level export events, and export from the east coast of the United States.

Description: In this paper, we discuss scintillation time-spectra of the double star α Cru, which were measured by the GOMOS/Envisat photometer. The components of α Cru are not resolved by the angular field of view of the detector. The double structure of the light source reveals itself in the modulation of the observed scintillation spectra; this modulation is caused by anisotropic irregularities of stratospheric air density. We present qualitative and quantitative explanation of properties of the double-star scintillation spectra. Possibilities of using double star scintillations for studying atmospheric air density irregularities are also discussed in the paper.

Description: Data from research vessels and merchant ships are used to estimate ocean CO2 uptake via parameterizations of the gas transfer velocity (k) and measurements of the difference between the concentration of CO2 in the ocean (pCO2sw) and atmosphere (pCO2atm) and of wind speed. Gas transfer velocities estimated using wind speed dependent parameterisations may be in error due to air flow distortion by the ship's hull and superstructure introducing biases into the measured wind speed. The effect of airflow distortion on estimates of the transfer velocity was examined by modelling the airflow around the three-dimensional geometries of the research vessels Hakuho Maru and Mirai, using the Large Eddy Simulation code GERRIS. For airflows within ±45° of the bow the maximum bias was +16%. For wind speed of 10 m s−1 to 15 m s−1, a +16% bias in wind speed would cause an overestimate in the calculated value of k of 30% to 50%, depending on which k parameterisation is used. This is due to the propagation of errors when using quadratic or cubic parameterizations. Recommendations for suitable anemometer locations on research vessels are given. The errors in transfer velocity may be much larger for typical merchant ships, as the anemometers are generally not as well-exposed as those on research vessels. Flow distortion may also introduce biases in the wind speed dependent k parameterizations themselves, since these are obtained by relating measurements of the CO2 flux to measurements of the wind speed and the CO2 concentration difference. To investigate this, flow distortion effects were estimated for three different platforms from which wind speed dependent parameterizations are published. The estimates ranged from –4% to +14% and showed that flow distortion may have a significant impact on wind speed dependent parameterizations. However, the wind biases are not large enough to explain the differences at high wind speeds in parameterizations which are based on eddy covariance and deliberate tracer methods.

Description: A DUALER (dual-channel airborne peroxy radical chemical amplifier) instrument has been developed and optimised for the airborne measurement of the total sum of peroxy radicals during the AMMA (African Monsoon Multidisciplinary Analyses) measurement campaign which took place in Burkina Faso in August 2006. The innovative feature of the instrument is that both reactors are sampling simultaneously from a common pre-reactor nozzle while the whole system is kept at a constant pressure to ensure more signal stability and accuracy. Laboratory experiments were conducted to characterise the stability of the NO2 detector signal and the chain length with the pressure. The results show that airborne measurements using chemical amplification require constant pressure at the luminol detector. Wall losses of main peroxy radicals HO2 and CH3O2 were investigated. The chain length was experimentally determined for different ambient mixtures and compared with simulations performed by a chemical box model. The DUALER instrument was successfully mounted within the German DLR-Falcon. The analysis of AMMA data utilises a validation procedure based on the O3 mixing ratios simultaneously measured onboard. The validation and analysis procedure is illustrated by means of the data measured during the AMMA campaign. The detection limit and the accuracy of the ambient measurements are also discussed.

Description: Measurements of aerosol optical properties and aerosol number size distribution obtained during the period from December 2005 to November 2007 at Granada, an urban site in south-eastern Spain, are analyzed. Large variations of the measured variables have been found, and related to variations in emissions sources and meteorological conditions. High values of aerosol absorption and scattering coefficients are obtained during winter and low values are measured during summer. This seasonal pattern in the surface aerosol optical properties is opposite to the seasonal cycle showed by columnar aerosol optical depth. The differences in the seasonal features of the surface and column-integrated data are related to seasonal variations in the aerosol vertical distribution, aerosol sources and boundary layer height. In winter the number density of fine particles (0.5

Description: We measured the mobility equivalent critical dry diameter for CCN activation (dcme) and the particle mass of size-selected (NH4)2SO4 and NaCl particles to calibrate a CCN counter (CCNC) precisely. The CCNC was operated downstream of a differential mobility analyzer (DMA) for the measurement of dcme. The particle mass was measured using an aerosol particle mass analyzer (APM) operated downstream of the DMA. The measurement of particle mass was conducted for 50–150-nm particles. Effective densities (ρeff) of (NH4)2SO4 particles were 1.67–1.75 g cm−3, which correspond to the dynamic shape factors (χ) of 1.01–1.04. This shows that (NH4)2SO4 particles are not completely spherical. In the case of NaCl particles, ρeff was 1.75–1.99 g cm−3 and χ was 1.05–1.14, demonstrating that their particle shape was non-spherical. Using these experimental data, the volume equivalent critical dry diameter (dcve) was calculated, and it was used as an input parameter for calculations of critical supersaturation (S). Several thermodynamics models were used for the calculation of water activity. When the Pitzer model was employed for the calculations, the critical S calculated for (NH4)2SO4 and NaCl agreed to well within the uncertainty of 2% (relative). This result demonstrates that the use of the Pitzer model for the calibration of CCNCs gives the most probable value of S.

Description: In this study we compare the performance of conventional Lagrangian stochastic (LS) footprint models that use parameterised flow field characteristics with results of a Lagrangian trajectory model embedded in a large eddy simulation (LES) framework. The two conventional models follow the particles backward and forward in time while the trajectories in LES only evolve forward in time. We assess their performance in unstably and neutrally stratified boundary layers at observation levels covering the whole depth of the atmospheric boundary layer. We present a concept for footprint model comparison that can be applied for 2-D footprints and demonstrate that comparison of only cross wind integrated footprints is not sufficient for purposes facilitating two dimensional footprint information. Because the flow field description among the three models is most realistic in LES we use those results as the reference in the comparison. We found that the agreement of the two conventional models against the LES is generally better for intermediate measurement heights and for the convective case, whereas the two conventional flux footprint models agree best under near neutral conditions.

Description: We examine the dependence of the inferred isoprene surface emission flux from atmospheric concentration on the diurnal variability of the convective boundary layer (CBL). A series of systematic numerical experiments carried out using the mixed-layer technique enabled us to study the sensitivity of isoprene fluxes to the entrainment process, the partition of surface fluxes, the horizontal advection of warm/cold air masses and subsidence. Our findings demonstrate the key role played by the evolution of boundary layer height in modulating the retrieved isoprene flux. More specifically, inaccurate values of the potential temperature lapse rate lead to changes in the dilution capacity of the CBL and as a result the isoprene flux may be overestimated or underestimated by as much as 20%. The inferred emission flux estimated in the early morning hours is highly dependent on the accurate estimation of the discontinuity of the thermodynamic values between the residual layer and the rapidly forming CBL. Uncertainties associated with the partition of the sensible and latent heat flux also yield large deviations in the calculation of the isoprene surface flux. Similar results are obtained if we neglect the influence of warm or cold advection in the development of the CBL. We show that all the above-mentioned processes are non-linear, for which reason the dynamic and chemical evolutions of the CBL must be solved simultaneously. Based on the discussion of our results, we suggest the measurements needed to correctly apply the mixed-layer technique in order to minimize the uncertainties associated with the diurnal variability of the convective boundary layer.

Description: Detailed 3-D structures of Trans-Pacific Asian dust transport occurring during 5–15 May 2007 were investigated using the NASA/CALIOP vertical-resolved measurements and a three-dimensional aerosol model (SPRINTARS). Both CALIOP and SPRINTARS dust extinctions showed a good agreement along the way of the transport from the dust source regions across North Pacific into North America. A vertically two-layered dust distribution was observed over the northeastern Pacific and North America. The lower dust layer originated from a dust storm generated in the Gobi Desert on 5 May. It was transported at an altitude of around 4 km MSL and has mixed with Asian anthropogenic air pollutants during the course of transport. The upper dust layer mainly originated from a dust storm that occurred in the Taklimakan Desert 2–3 days after the Gobi dust storm generation. The upper dust cloud was transported in higher altitudes above the major clouds layer during the Trans-Pacific transport. It therefore has remained unmixed with the Asian air pollutants and almost unaffected by wet removal. The decay of its concentration level was small (only one-half after its long-distance transport crossing the Pacific). Our dust budget analysis revealed that the Asian dust flux passing through the longitude plane of 140° E was 2.1 Tg, and one third of that arrived North America. The cases analyzed in this study revealed that, while the Gobi Desert is an important source that can contribute to the long-range dust transport, the Taklimakan Desert appears to be another important source that can contribute to the dust transport occurring particularly at high altitudes.

Description: The factors that control the influence of deep convective detrainment on water vapor in the tropical upper troposphere are examined using observations from multiple satellites in conjunction with a trajectory model. Deep convection is confirmed to act primarily as a moisture source to the upper troposphere, modulated by the ambient relative humidity (RH). Convective detrainment provides strong moistening at low RH and offsets drying due to subsidence across a wide range of RH. Strong day-to-day moistening and drying takes place most frequently in relatively dry transition zones where the frequency of deep convective events is neither very high nor very low. Many of these strong moistening events can be directly attributed to detrainment from recent tropical convection. The temporal and spatial limits of the convective source are estimated to be about 36–48 h and 600–1500 km, respectively, consistent with the lifetimes of detrainment cirrus clouds. Larger amounts of detrained ice and smaller ice particle sizes are both associated with enhanced upper tropospheric moistening.

Description: In order to investigate the spatial distribution of air pollutants in the Inn valley (Tyrol, Austria) during wintertime, a joint field campaign of the three research projects ALPNAP (Monitoring and Minimisation of Traffic-Induced Noise and Air Pollution Along Major Alpine Transport Routes), INNAP (Boundary Layer Structure in the Inn Valley during high Air Pollution) and INNOX (NOx-structure in the Inn Valley during High Air Pollution) was carried out in January/February 2006. In addition to continuous ground based measurements, vertical profiles of various air pollutants and meteorological parameters were obtained on six selected days. For in-situ investigations, a tethered balloon was used to analyse the lowest atmospheric layers, 0–500 m above the valley bottom (a.v.b.), and a research aircraft sampled at 150–2200 m a.v.b. An aircraft equipped with an aerosol backscatter lidar performed nadir measurements at 3000 m a.v.b. Combined results from a typical day show a strongly polluted layer up to about 125 m a.v.b. in the morning. Around midday concentrations on the valley floor decrease indicating some vertical air exchange despite thermally stable conditions. Strong vertical and horizontal gradients with enhanced pollution levels along the sunny side of the valley up to 1300 m a.v.b. were observed in the afternoon. However, this vertical mixing due to thermally or dynamically driven slope and valley winds was not strong enough to renew the valley air volume.

Description: The heterogeneous reaction of OH radicals with sub-micron squalane particles, in the presence of O2, is used as a model system to explore the fundamental chemical mechanisms that control the oxidative aging of organic aerosols in the atmosphere. Detailed kinetic measurements combined with elemental mass spectrometric analysis reveal that the reaction proceeds sequentially by adding an average of one oxygenated functional group per reactive loss of squalane. The reactive uptake coefficient of OH with squalane particles is determined to be 0.3±0.07 at an average OH concentration of ~1×1010 molecules·cm−3. Based on a comparison between the measured particle mass and model predictions it appears that significant volatilization of a reduced organic particle would be extremely slow in the real atmosphere. However, as the aerosols become more oxygenated, volatilization becomes a significant loss channel for organic material in the particle phase. Together these results provide a chemical framework in which to understand how heterogeneous chemistry transforms the physiochemical properties of particle phase organic matter in the troposphere.

Description: Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. We have measured and characterized CCN at water vapor supersaturations in the range of S=0.10–0.82% in pristine tropical rainforest air during the AMAZE-08 campaign in central Amazonia. The effective hygroscopicity parameters describing the influence of chemical composition on the CCN activity of aerosol particles varied in the range of κ=0.05–0.45. The overall median value of κ≈0.15 was only half of the value typically observed for continental aerosols in other regions of the world. Aitken mode particles were less hygroscopic than accumulation mode particles (κ≈0.1 at D≈50 nm; κ≈0.2 at D≈200 nm). The CCN measurement results were fully consistent with aerosol mass spectrometry (AMS) data, which showed that the organic mass fraction (Xm,org) was on average as high as ~90% in the Aitken mode (D≤100 nm) and decreased with increasing particle diameter in the accumulation mode (~80% at D≈200 nm). The κ values exhibited a close linear correlation with Xm,org and extrapolation yielded the following effective hygroscopicity parameters for organic and inorganic particle components: κorg≈0.1 which is consistent with laboratory measurements of secondary organic aerosols and κinorg≈0.6 which is characteristic for ammonium sulfate and related salts. Both the size-dependence and the temporal variability of effective particle hygroscopicity could be parameterized as a function of AMS-based organic and inorganic mass fractions (κp=0.1 Xm,org+0.6 Xm,inorg), and the CCN number concentrations predicted with κp were in fair agreement with the measurement results. The median CCN number concentrations at S=0.1–0.82% ranged from NCCN,0.10≈30 cm−3 to NCCN,0.82≈150 cm−3, the median concentration of aerosol particles larger than 30 nm was NCN,30≈180 cm−3, and the corresponding integral CCN efficiencies were in the range of NCCN,0.10/NCN,30≈0.1 to NCCN,0.82/NCN,30≈0.8. Although the number concentrations and hygroscopicity parameters were much lower, the integral CCN efficiencies observed in pristine rainforest air were similar to those in highly polluted mega-city air. Moreover, model calculations of NCCN,S with a global average value of κ=0.3 led to systematic overpredictions, but the relative deviations exceeded ~50% only at low water vapor supersaturation (0.1%) and low particle number concentrations (≤100 cm−3). These findings confirm earlier studies suggesting that aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the information and parameterizations presented in this paper should enable efficient description of the CCN properties of pristine tropical rainforest aerosols in detailed process models as well as in large-scale atmospheric and climate models.

Description: A biennial dataset of ambient particle number size distributions (diameter range 4–800 nm) collected in urban air in Leipzig, Germany, was analysed with respect to the influence of traffic emissions. Size distributions were sampled continuously in 2005 and 2006 inside a street canyon trafficked by ca. 10 000 motor vehicles per day, and at a background reference site distant at 1.5 km. Auto-correlation analysis showed that the impact of fresh traffic emissions could be seen most intensely below particle sizes of 60 nm. The traffic-induced concentration increment at roadside was estimated by subtracting the urban background values from the street canyon measurement. To describe the variable dispersion conditions inside the street canyon, micro-meteorological dilution factors were calculated using the Operational Street Pollution Model (OSPM), driven by above-roof wind speed and wind direction observations. The roadside increment concentrations, dilution factor, and real-time traffic counts were used to calculate vehicle emission factors (aerosol source rates) that are representative of the prevailing driving conditions, i.e. stop-and-go traffic including episodes of fluent traffic flow at speeds up to 40 km h−1. The size spectrum of traffic-derived particles was essentially bimodal – with mode diameters around 12 and 100 nm, while statistical analysis suggested that the emitted number concentration varied with time of day, wind direction, particle size and fleet properties. Significantly, the particle number emissions depended on ambient temperature, ranging between 4.8 (±1.8) and 7.8 (±2.9).1014 p. veh−1 km−1 in summer and winter, respectively. A separation of vehicle types according to vehicle length suggested that lorry-like vehicles emit about 80 times more particle number than passenger car-like vehicles. Using nitrogen oxide (NOx) measurements, specific total particle number emissions of 338 p. (pg NOx)−1 were inferred. The calculated traffic emission factors, considering particle number and size, are anticipated to provide useful input for future air quality and particle exposure modelling in densely populated urban areas.

Description: Two 40-year meteorological datasets are used to drive the Model of Ozone and Related Tracers chemical transport model, version 2 (MOZART2) in hindcast simulations. One dataset is from the National Center for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) reanalysis, the second dataset uses meteorology from the Community Atmosphere Model (CAM3) forced with observed interannually varying sea surface temperatures. All emissions, except those from lightning are annually constant. Analysis of these simulations is from 1979–1999, due to meteorological discontinuities in the NCEP reanalysis during the 1970s. The meteorology using CAM3 captures observed trends in temperature, water vapor, precipitation and cloudiness; the simulation using NCEP meteorology does not. This paper examines the regional and global interannual variability of various chemical and meteorological fields: CO, OH, O3 and HNO3, the surface photolysis rate of NO2 (as a proxy for overhead cloudiness), lightning NO emissions, water vapor, planetary boundary layer height, and temperature. The variability due to changes in emissions is not considered in this analysis. In both the NCEP and CAM3 simulations the relative variability of CO, OH, O3 and HNO3 are qualitatively similar, with variability maxima both in the tropics and the high latitudes. Locally, relative variability generally ranges between 3 and 10%; globally the tropospheric variability generally ranges from half to one percent, but can be higher. For most fields the leading Empirical Orthogonal Function explains approximately 10% of the variability and correlates significantly with El Niño. In both simulations the first principal component of a multiple tracer, globally averaged analysis shows a strong coupling between surface temperature, measures of the hydrological cycle, CO and OH, but is not correlated with El Niño. In both simulations we examine the global response of the selected variables to changes in global surface temperature, and compare with a climate simulation over the 21st century.

Description: This study uses a combination of POAM III aerosol extinction measurements and CHAMP GPS/RO temperature measurements to examine the role of atmospheric gravity waves in Polar Stratospheric Cloud (PSC) formation in the Antarctic. POAM III aerosol extinction observations are used to identify Type I Polar Stratospheric Clouds using an unsupervised clustering algorithm. The seasonal and spatial distribution of PSCs observed by POAM III is examined to determine whether there is a bias towards regions of high wave activity early in the Antarctic winter which may enhance PSC formation. Examination of the probability of temperatures below the Type Ia formation temperature threshold based on UKMO analyses displays a good correspondence to the PSC occurrence derived from POAM III extinction data in general. However, in June the POAM III observations of PSC are more abundant than expected from temperature thresholds. In addition the PSC occurrence based on temperature thresholds in September and October is often significantly higher than the PSC occurrence observed by POAM III, this observation probably being due to dehydration and denitrification. Use of high resolution temperatures from CHAMP GPS/RO observations provide a slightly improved relationship to the POAM III derived values. Analysis of the CHAMP temperature observations indicates that temperature perturbations associated with gravity waves may explain the enhanced PSC incidence observed in June compared to the UKMO analyses. Comparison of the UKMO analyses temperatures relative to corresponding CHAMP observations also suggests a small warm bias in the UKMO analyses during June. Examination of the longitudinal structure PSC occurrence in June 2005 also shows that regions of enhancement are associated with data near the Antarctic peninsula a known Mountain wave "hotspot". The impact of temperature perturbations causing enhanced temperature threshold crossings is shown to be particularly important early in the Antarctic winter while later in the season temperature perturbations associated with gravity waves could contribute to about 15% of the PSC observed, a value which corresponds well to several previous studies.

Description: Comparisons of cloud liquid water path (LWP) retrievals are presented from the Moderate Resolution Imaging Spectroradiometer (MODIS) and the Advanced Microwave Scanning Radiometer (AMSR-E) located aboard the Aqua spacecraft. LWP differences as a function of cloud top height, cloud fraction, cloud top temperature, LWP, cloud effective radius and cloud optical thickness are quantified in most geophysical conditions. The assumption of vertically homogeneous distributions of cloud water content in the MODIS LWP retrieval yields a slightly poorer agreement than the assumption of stratified cloud liquid water. Furthermore, for a fixed cloud top pressure, the cloud top temperature can lead to sign changes in the LWP difference. In general, AMSR-E LWP is larger than MODIS for small cloud fractions, low values of LWP, and warmer cloud top temperatures. On the other hand, clouds with optical thicknesses above 20 lead to larger MODIS LWP. Using cloud optical thickness as a proxy for cloud type, deep convective clouds and stratus are shown to have the poorest agreement between AMSR-E and MODIS LWP. Particularly large differences are also found at latitudes poleward of 50°. The results of this work help characterize the scene- and cloud-dependent performance of microwave and visible/near infrared retrievals of LWP.

Description: Very dry high-ozone layers have been repeatedly observed with the ozone lidar in Garmisch-Partenkirchen (Germany) starting one or two days after the onset of high-pressure periods during the warm season. These episodes have been analysed by trajectory calculations and extended simulations with the FLEXPART particle dispersion model. Mixed contributions from the stratosphere over the Pacific Ocean and the boundary layers of East Asia and North America were found. The stratospheric influence is mostly dominating and caused by a rather shallow transfer from the stratosphere into these rapid upper- and mid-tropospheric air streams. The considerable vertical extent of these layers and peak ozone mixing ratios between 80 and 150 ppb suggest an important mechanism for stratosphere-to-troposphere transport.

Description: We present an original multi-spectrum fitting procedure to retrieve volume mixing ratio (VMR) profiles of carbonyl fluoride (COF2) from ground-based high resolution Fourier transform infrared (FTIR) solar spectra. The multi-spectrum approach consists of simultaneously combining, during the retrievals, all spectra recorded consecutively during the same day and with the same resolution. Solar observations analyzed in this study with the SFIT-2 v3.91 fitting algorithm correspond to more than 2900 spectra recorded between January 2000 and December 2007 at high zenith angles, with a Fourier Transform Spectrometer operated at the high-altitude International Scientific Station of the Jungfraujoch (ISSJ, 46.5° N latitude, 8.0° E longitude, 3580 m altitude), Switzerland. The goal of the retrieval strategy described here is to provide information about the vertical distribution of carbonyl fluoride. The microwindows used are located in the ν1 or in the ν4 COF2 infrared (IR) absorption bands. Averaging kernel and eigenvector analysis indicates that our FTIR retrieval is sensitive to COF2 inversion between 17 and 30 km, with the major contribution to the retrieved information always coming from the measurement. Moreover, there was no significant bias between COF2 partial columns, total columns or VMR profiles retrieved from the two bands. For each wavenumber region, a complete error budget including all identified sources has been carefully established. In addition, comparisons of FTIR COF2 17–30 km partial columns with KASIMA and SLIMCAT 3-D CTMs are also presented. If we do not notice any significant bias between FTIR and SLIMCAT time series, KASIMA COF2 17–30 km partial columns are lower of around 25%, probably due to incorrect lower boundary conditions. For each times series, linear trend estimation for the 2000–2007 time period as well as a seasonal variation study are also performed and critically discussed. We further demonstrate that all time series are able to reproduce the COF2 seasonal cycle, which main seasonal characteristics deduced from each data set agree quite well.

Description: The present work analyzes the effect of dust aerosols on the surface and top of atmosphere radiative budget, surface temperature, sensible heat fluxes, atmospheric heating rate and convective activity over West Africa. The study is focused on the regional impact of a major dust event over the period of 9–13 March. Numerical simulations have been performed with the MesoNH model in which full interactions between radiation and dynamics are introduced, through various components representing size-resolved aerosol and cloud microphysics, radiative properties of particles and clouds, dynamics, and a surface model. Due to its importance on radiative budgets, a specific attention has been paid to the representation of dust SSA in MesoNH by using AERONET inversions. The radiative impacts are estimated using two parallel simulations, one including radiative effects of dust and the other without them. The simulations of dust aerosol impacts on the radiative budget indicate remarkable instantaneous decrease of shortwave (SW) radiations, with regional (09°–17° N, 10° W–20° E) mean of −160 W/m2 during the 9 to 13 March period. The surface dimming resulting from the presence of dust is shown to cause important reduction of both surface temperature (up to 4°C over regions where high AODs occur) and sensible heat fluxes (up to 100 W/m2), which is consistent with experimental observations performed over the same region. At the top of the atmosphere, the SW cooling (regional mean of −13.5 W/m2) induced by mineral dust, although moderated by the longwave (LW) warming (regional mean of +5 W/m2), dominates the total net (shortwave + longwave) effect. The maximum SW heating occurs within the dusty layer with values comprised between 4 and 7°K by day and LW effect results in strong cooling (−6 to −16°K by day) below the dust layer. Finally, the simulations suggest the decrease of the convective available potential energy (CAPE) over the region in the presence of mineral dust.

Description: The global marine sources of organic carbon (OC) are estimated here using a physically-based parameterization for the emission of marine isoprene and primary organic matter. The model developed in this study allowed us, for the first time, to explore the relative contributions of sub- and super-micron organic matter and phytoplankton-produced secondary organic aerosol (SOA) to the total OC fraction of marine aerosol. New laboratory measurements of isoprene production by some of the main phytoplankton species under a range of environmental conditions was scaled up, with the help of satellite products, to infer the total annual mean ocean isoprene emissions of 0.92 Tg C yr−1. The sensitivity studies using different schemes for the euphotic zone depth and ocean phytoplankton speciation produced the upper and the lower range of marine-isoprene emissions of 0.31 to 1.09 Tg C yr−1, respectively. Empirical relationships between fluxes of water soluble (WSOM) and water insoluble (WIOM) organic matter (OM) and chlorophyll-a concentration was used to estimate the total primary sources of oceanic sub- and super-micron OC of 1.26 and 19.01 Tg C yr−1, respectively. Using a fixed 3% mass yield for the conversion of isoprene to SOA, our model simulations show minor (less than 0.2%) contribution of ocean produced isoprene to the total marine source of OC. However, our model calculations also indicate that over the tropical waters, marine isoprene-derived SOA could contribute over 40% of the total monthly-averaged sub-micron OC fraction of marine aerosol. The estimated contribution of ocean-isoprene SOA to hourly averaged sub-micron marine OC fluxes is even higher, reaching nearly 100% over the vast regions of the oceans during the midday hours. As it is widely believed that cloud condensation nuclei (CCN) is typically dominated by sub-micron sized particles, our findings suggest that marine sources of SOA could play a critical role in modulating properties of shallow marine clouds and influencing the climate.

Description: The role of isoprene as a precursor to secondary organic aerosol (SOA) over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr−1 and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of particulate organic matter (POM) during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC) emissions from vegetation. However, during winter, our model strongly underestimates POM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning) of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr−1). The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Tropospheric isoprene SOA production over Europe in summer more than doubles when, in addition to pre-existing carbonaceous aerosols, condensation of semi volatile vapours on ammonium and sulphate aerosols is considered. Consequently, smog chamber experiments on SOA formation should be performed with different types of seed aerosols and without seed aerosols in order to derive an improved treatment of the absorption of SOA in the models. Consideration of a number of recent insights in isoprene SOA formation mechanisms reduces the tropospheric production of isoprene derived SOA over Europe from 0.4 Tg yr−1 in our reference simulation to 0.1 Tg yr−1.

Description: By emission of volatile organic compounds (VOC) which on oxidation form secondary organic aerosols (SOA) the vegetation is coupled to atmosphere and climate. New particle formation from tree emissions was investigated in a new setup: a plant chamber coupled to a reaction chamber for oxidizing the plant emissions and for forming SOA. The boreal tree species birch, pine, and spruce were studied and α-pinene was used as reference compound. Under the experimental conditions OH radicals were essential for inducing new particle formation, although O3 (≤80 ppb) was always present and a part of the monoterpenes and the sesquiterpenes reacted already with ozone before OH was generated. Formation rates of 3 nm particles were linearly related to the carbon mixing ratios of the VOC, as were the maximum observed volume and the condensational growth rates. The threshold of new particle formation was lower for the tree emissions than for α-pinene. It was lowest for birch with the largest fraction of oxygenated VOC (OVOC) suggesting that OVOC may play a pivotal role in new particle formation. Incremental mass yields were ≈5% for pine, spruce and α-pinene, and ≈10% for birch. α-Pinene was a good model compound to describe the yield and the growth of SOA particles from coniferous emissions. The mass fractional yields agreed well with observations for boreal forests. Despite our somewhat enhanced VOC and OH concentrations our results may thus be up-scaled to eco-system level. Using the mass fractional yields observed for the tree emissions and weighting them with the abundance of the respective trees in boreal forests we calculate SOA mass concentrations which agree within 6% with field observations. For a future VOC increase of 50% we predict a particle mass increase due to SOA of 19% assuming today's mass contribution of pre-existing aerosol.

Description: We investigate the spatial and temporal distribution of hydrogen cyanide (HCN) in the upper troposphere through numerical simulations and comparison with observations from a space-based instrument. To perform the simulations, we used the Global Environmental Multiscale Air Quality model (GEM-AQ), which is based on the three-dimensional global multiscale model developed by the Meteorological Service of Canada for operational weather forecasting. The model was run for the period 2004–2006 on a 1.5°×1.5° global grid with 28 hybrid vertical levels from the surface up to 10 hPa. Objective analysis data from the Canadian Meteorological Centre were used to update the meteorological fields every 24 h. Fire emission fluxes of gas species were generated by using year-specific inventories of carbon emissions with 8-day temporal resolution from the Global Fire Emission Database (GFED) version 2. The model output is compared with HCN profiles measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) instrument onboard the Canadian SCISAT-1 satellite. High values of up to a few ppbv are observed in the tropics in the Southern Hemisphere; the enhancement in HCN volume mixing ratios in the upper troposphere is most prominent in October. Low upper-tropospheric mixing ratios of less than 100 pptv are mostly recorded at middle and high latitudes in the Southern Hemisphere in May–July. Mixing ratios in Northern Hemisphere peak in the boreal summer. The amplitude of the seasonal variation is less pronounced than in the Southern Hemisphere. Our model results show that in the upper troposphere GEM-AQ performs well globally for all seasons, except at Northern high and middle latitudes in summer, where the model has a large negative bias, and in the tropics in winter and spring, where it exhibits large positive bias. This may reflect inaccurate emissions or possible inaccuracies in the emission profile. The model is able to explain most of the observed variability in the upper troposphere HCN field, including the interannual variations in the observed mixing ratio. The estimated average global emission equals 1.3 Tg N yr−1. The average atmospheric burden is 0.53 Tg N, and the corresponding lifetime is 4.9 months.

Description: This paper presents first results of a comprehensive emission inventory of chemical species from anthropogenic activities (power generation, vehicles, ships and aircraft) in Antarctica, covering the 2004–2005 period. The inventory is based on estimated emission rates of fuel consumption provided by some of the Antarctic research stations. Since the emission sources have different modes of operation and use a variety of fuel, the emission flux rate of chemical species is calculated by multiplying the fuel consumption value with the density of fuel and appropriate emission factors. A separate inventory is prepared for each anthropogenic emission source in Antarctica. Depending on the type of operation, emission rates of SO2, and BC (Black Carbon, from shipping only) have been calculated using the above technique. However, only results of SO2 emissions from each source are presented here. Emission inventory maps of SO2 depicting the track/path taken by each mobile source are shown. The total annual SO2 is 158 Mg from power generation and vehicle operations, 3873 Mg from ships and 56 Mg from aircraft for 2004–2005 and these values undergo strong seasonality following the human activity in Antarctica. Though these figures are small when compared to the emissions at most other regions of the world, they are an indication that human presence in Antarctica leads to at least local pollution. The sources are mainly line and point sources and thus the local pollution potentially is relatively strong.

Description: Gas and particle-phase organic carbon compounds soluble in water (e.g., WSOC) were measured simultaneously in Atlanta throughout the summer of 2007 to investigate gas/particle partitioning of ambient secondary organic aerosol (SOA). Previous studies have established that, in the absence of biomass burning, particulate WSOC (WSOCp) is mainly from secondary organic aerosol (SOA) production. Comparisons between WSOCp, organic carbon (OC) and elemental carbon (EC) indicate that WSOCp was a nearly comprehensive measure of SOA in the Atlanta summertime. To study SOA formation mechanisms, WSOC gas-particle partitioning was investigated as a function of temperature, RH, NOx, O3, and organic aerosol mass concentration. Identifying a clear temperature effect on partitioning was confounded by other temperature-dependent processes, which likely included the emissions of biogenic SOA precursors and photochemical SOA formation. Relative humidity data indicated a linear dependence between partitioning and fine particle liquid water. Lower NOx concentrations were associated with greater partitioning to particles, but WSOC partitioning had no visible relation to O3 or fine particle OC mass concentration. There was, however, a relationship between WSOC partitioning and the WSOCp concentration, suggesting a compositional dependence between partitioning semi-volatile gases and the phase state of the aerosol. Combined, the overall results suggest that partitioning to liquid water, followed by heterogeneous reactions may represent the main process by which SOA is formed in urban Atlanta during summer.

Description: Measurements of cloud condensation nuclei (CCN) made over the remote North Pacific Ocean in July 2002 are analysed with concurrent measurements of aerosol number, mass and composition. Overall the CCN are controlled by the sulphate, including one case of particle nucleation and growth resulting from dimethyl sulphide oxidation that enhanced CCN concentrations. Hourly CCN concentrations are correlated with concentrations of sulphate plus methanesulphonic acid (MSA) over the entire study period (r2=0.43 and 0.52 for supersaturations of 0.34 and 0.19%, respectively), and are not well correlated with other organics (r2

Description: In this work, inorganic ammonium ions, NH4+, and carbonate ions, CO32−, are reported for the first time as catalysts for organic reactions in atmospheric aerosols and other natural environments at the Earth's surface. These reactions include the formation of C–C and C–O bonds by aldol condensation and acetal formation, and reveal a new aspect of the interactions between organic and inorganic materials in natural environments. The catalytic properties of inorganic ammonium ions, in particular, were not previously known in chemistry. The reactions were found to be as fast in tropospheric ammonium sulfate composition as in concentrated sulfuric acid. The ubiquitous presence and large concentrations of ammonium ions in tropospheric aerosols would make of ammonium catalysis a main consumption pathway for organic compounds in these aerosols, while acid catalysis would have a minor contribution. In particular, ammonium catalysis would account quantitatively for the aging of carbonyl compounds into secondary ''fulvic'' compounds in tropospheric aerosols, a transformation affecting the optical properties of these aerosols. In general, ammonium catalysis is likely to be responsible for many observations previously attributed to acid catalysis in the troposphere.

Description: Knowledge about temporal and spatial variations of the O3 and NOx relationship in the urban environment are necessary to assess the exceedance of air quality standards for NO2. Both reliable measurements and validated high-resolution air quality models are important to assess the effect of traffic emission on air quality. In this study, measurements of NO, NO2 and O3 concentrations were performed in Gothenburg, Sweden, during the Göte-2005 campaign in February 2005. The aim was to evaluate the variation of pollutant concentrations in the urban landscape in relation to urban air quality monitoring stations and wind speed. A brief description of the meteorological conditions and the air pollution situation during the Göte-2005 campaign was also given. Furthermore, the Air Pollution Model (TAPM) was used to simulate the NOx-regime close to an urban traffic route and the simulations were compared to the measurements. Important conclusions were that the pollutant concentrations varied substantially in the urban landscape and the permanent monitoring stations were not fully representative for the most polluted environments. As expected, wind speed strongly influenced measured pollutant concentrations and gradients. Higher wind speeds dilute NO2 due to stronger dispersion; while at the same time vertical transport of O3 is enhanced, which produces NO2 through oxidation of NO. The oxidation effect was predominant at the more polluted sites, while the dilution effect was more important at the less polluted sites. TAPM reproduced the temporal variability in pollutant concentrations satisfactorily, but was not able to resolve the situation at the most polluted site, due to the local scale site-specific conditions.

Description: The occurrence of and conditions favourable to nucleation were investigated at an industrial and commercial coastal location in Brisbane, Australia during five different campaigns covering a total period of 13 months. To identify potential nucleation events, the difference in number concentration in the size range 14–30 nm (N14−30) between consecutive observations was calculated using first-order differencing. The data showed that nucleation events were a rare occurrence, and that in the absence of nucleation the particle number was dominated by particles in the range 30–300 nm. In many instances, total particle concentration declined during nucleation. There was no clear pattern in change in NO and NO2 concentrations during the events. SO2 concentration, in the majority of cases, declined during nucleation but there were exceptions. Most events took place in summer, followed by winter and then spring, and no events were observed for the autumn campaigns. The events were associated with sea breeze and long-range transport. Roadside emissions, in contrast, did not contribute to nucleation, probably due to the predominance of particles in the range 50–100 nm associated with these emissions.

Description: A large SO2-rich pollution plume of Chinese origin was detected by aircraft based CIMS (Chemical Ionization Mass Spectrometry) measurements at 3–7.5 km altitude over the North Atlantic on 3 May 2006 during the INTEX (Intercontinental Chemical Transport Experiment) campaign. Additional trace gases (NO, NOy, CO, H2O) were measured and used for comparison and source identification. All measurements took place aboard the German research aircraft Falcon. The atmospheric SO2 mole fraction was markedly increased inside the plume and reached up to 900 pmol/mol. The measured ratio SO2/NOy of 1.4 suggests combustion of coal or fuel with a very high sulfur content as a source of the excess SO2. Accompanying FLEXPART particle dispersion model simulations indicate that the probed pollution plume originated at low altitudes over densely populated and industrialized areas in eastern China about 8–12 days prior to the measurements.

Description: The influence is investigated of the assumed ice particle microphysical and optical model on inferring ice cloud optical thickness (τ) from satellite measurements of the Earth's reflected shortwave radiance. Ice cloud τ are inferred, and subsequently compared, using products from MODIS (MODerate resolution Imaging Spectroradiometer) and POLDER (POLarization and Directionality of the Earth's Reflectances). POLDER τ values are found to be substantially smaller than those from collocated MODIS data. It is shown that this difference is caused primarily by the use of different ice particle bulk scattering models in the two retrievals, and more specifically, the scattering phase function. Furthermore, the influence of the ice particle model on the derivation of ice cloud radiative forcing (CRF) from satellite retrievals is studied. Three sets of shortwave CRF are calculated using different combinations of the retrieval and associated ice particle models. It is shown that the uncertainty associated with an ice particle model may lead to two types of errors in estimating CRF from satellite retrievals. One stems from the retrieval itself and the other is due to the optical properties, such as the asymmetry factor, used for CRF calculations. Although a comparison of the CRFs reveals that these two types of errors tend to cancel each other, significant differences are still found between the three CRFs, which indicates that the ice particle model affects not only optical thickness retrievals but also CRF calculations. In addition to CRF, the effect of the ice particle model on the derivation of seasonal variation of τ from satellite measurements is discussed. It is shown that optical thickness retrievals based on the same MODIS observations, but derived using different assumptions of the ice particle model, can be substantially different. These differences can be divided into two parts. The first-order difference is mainly caused by the differences in the asymmetry factor. The second-order difference is related to seasonal changes in the sampled scattering angles and therefore dependent on the sun-satellite viewing geometry. Because of this second-order difference, the use of different ice particle models may lead to a different understanding of the seasonal variation of τ.

Description: During the Arctic Study of Tropospheric Aerosol, Clouds and Radiation (ASTAR) campaign, which was conducted in March and April 2007, an optically thin ice cloud was observed at around 3 km altitude south of Svalbard. The microphysical and radiative properties of this particular subvisible midlevel cloud were investigated with complementary remote sensing and in-situ instruments. Collocated airborne lidar remote-sensing and spectral solar radiation measurements were performed at a flight altitude of 2300 m below the cloud base. Under almost stationary atmospheric conditions, the same subvisible midlevel cloud was probed with various in-situ sensors roughly 30 min later. From individual ice crystal samples detected with the Cloud Particle Imager and the ensemble of particles measured with the Polar Nephelometer, we retrieved the single-scattering albedo, the scattering phase function as well as the volume extinction coefficient and the effective diameter of the crystal population. Furthermore, a lidar ratio of 21 (±6) sr was deduced by two independent methods. These parameters in conjunction with the cloud optical thickness obtained from the lidar measurements were used to compute spectral and broadband radiances and irradiances with a radiative transfer code. The simulated results agreed with the observed spectral downwelling radiance within the range given by the measurement uncertainty. Furthermore, the broadband radiative simulations estimated a net (solar plus thermal infrared) radiative forcing of the subvisible midlevel ice cloud of −0.4 W m−2 (−3.2 W m−2 in the solar and +2.8 W m−2 in the thermal infrared wavelength range).

Description: We present results of experiments at the aerosol interactions and dynamics in the atmosphere (AIDA) chamber facility looking at the freezing of water by three different types of mineral particles at temperatures between −12°C and −33°C. The three different dusts are Asia Dust-1 (AD1), Sahara Dust-2 (SD2) and Arizona test Dust (ATD). The dust samples used had particle concentrations of sizes that were log-normally distributed with mode diameters between 0.3 and 0.5 μm and standard deviations, σg, of 1.6–1.9. The results from the freezing experiments are consistent with the singular hypothesis of ice nucleation. The dusts showed different nucleation abilities, with ATD showing a rather sharp increase in ice-active surface site density at temperatures less than −24°C. AD1 was the next most efficient freezing nuclei and showed a more gradual increase in activity than the ATD sample. SD2 was the least active freezing nuclei. We used data taken with particle counting probes to derive the ice-active surface site density forming on the dust as a function of temperature for each of the three samples and polynomial curves are fitted to this data. The curve fits are then used independently within a bin microphysical model to simulate the ice formation rates from the experiments in order to test the validity of parameterising the data with smooth curves. Good agreement is found between the measurements and the model for AD1 and SD2; however, the curve for ATD does not yield results that agree well with the observations. The reason for this is that more experiments between −20 and −24°C are needed to quantify the rather sharp increase in ice-active surface site density on ATD in this temperature regime. The curves presented can be used as parameterisations in atmospheric cloud models where cooling rates of approximately 1°C min−1 or more are present to predict the concentration of ice crystals forming by the condensation-freezing mode of ice nucleation. Finally a polynomial is fitted to all three samples together in order to have a parameterisation describing the average ice-active surface site density vs. temperature for an equal mixture of the three dust samples.

Description: In order to study particulate matter transport and transformation in the Megacity environment, fine particulate carbons were measured simultaneously at two supersites, suburban T1 and rural T2, downwind of Mexico City during the MILAGRO field campaign in March 2006. Organic carbon (OC), element carbon (EC), and total carbon (TC=OC+EC) were determined in near real-time using a Sunset semi-continuous OC/EC field analyzer. The semi-empirical EC tracer method was used to derive primary organic carbon (POC) and secondary organic carbon (SOC). Diurnal variations of primary and secondary carbons were observed at T1 and T2, which resulted from boundary layer inversion and impacted by local traffic patterns. The majority of organic carbon particles at T1 and T2 were secondary. The SOC% (SOC%=SOC/TC×100%) at T1 ranged from 1.2–100% with an average of 80.7±14.4%. The SOC% at T2 ranged from 12.8–100% with an average of 80.1±14.0%. The average EC to PM2.5 percentage (ECPM%=EC/PM2.5×100%) and OCPM% were 6.0% and 20.0% over the whole sampling time at T1. The POC to PM percentage (POCPM%) and SOCPM% were 3.7% and 16.3%, respectively at the same site. The maximum ECPM% was 21.2%, and the maximum OCPM% was 57.2% at T1. The maximum POCPM% was 12.9%, and the maximum SOCPM% was 49.7% at the suburban site. Comparison of SOC and POC at T1 and T2 showed similar characteristics under favorable meteorological conditions, which indicated that transport between the two supersites took place. Strong correlations between EC and carbon monoxide (CO) and odd nitrogen species (NO and NOx) were observed at T1. This indicated that EC had nearby sources, such as local traffic emissions. The EC/CO ratio derived by linear regression analysis, when parameters in μg C/m3 and μg/m3, respectively, was 0.0045 at T1. Correlations were also seen between OC and SOC vs. the sum of oxidants, such as O3 and NO2, suggesting the secondary nature of carbons observed at T1.

Description: A daytime climatological spatio-temporal distribution of high opaque ice cloud (HOIC) classes over the Indian subcontinent (0–40° N, 60° E–100° E) is presented using 25-year data from the Advanced Very High Resolution Radiometers (AVHRRs) for the summer monsoon months. The HOICs are important for regional radiative balance, precipitation and troposphere-stratosphere exchange. In this study, HOICs are sub-divided into three classes based on their cloud top brightness temperatures (BT). Class I represents very deep convection (BT

Description: We present a method for harmonized retrieval of integrated water vapor (IWV) trends from existing, long-term, measurement records at the ground-based mid-infrared solar FTIR spectrometry stations of the Network for the Detection of Atmospheric Composition Change (NDACC). Correlation of IWV from FTIR with radiosondes shows an ideal slope of 1.00(3). This optimum matching is achieved via tuning one FTIR retrieval parameter, i.e., the strength of a Tikhonov regularization constraining the derivative (with respect to height) of retrieved water profiles given in per cent difference relative to an a priori profile. All other FTIR-sonde correlation parameters (intercept =0.02(12) mm, bias =0.02(5) mm, standard deviation of coincident IWV differences (stdv)=0.27 mm, R=0.99) are comparable to or better than results for all other ground-based IWV sounding techniques given in the literature. An FTIR-FTIR side-by-side intercomparison reveals a strong exponential increase in stdv as a function of increasing temporal mismatch starting at Δt ~1 min. This is due to atmospheric water vapor variability. Based on this result we derive an upper limit for the precision of the FTIR IWV retrieval for the smallest Δt(=3.75 min) still giving a statistically sufficient sample (32 coincidences), i.e., precision (IWVFTIR)

Description: We investigate the aerosol mass apportionment and derive aerosol optical properties that characterize the aerosol over extratropical and tropical southern Africa during the biomass burning season. We find that 54% and 83% of the extratropical and tropical aerosol mass, respectively, is composed of carbonaceous species, consistent with the fact that the major source of particulate matter in southern Africa is biomass burning. This mass apportionment implies that carbonaceous species in the form of organic carbon (OC) and black carbon (BC) play a critical role in the aerosol optical properties. By combining the in situ measurements of aerosol mass concentrations with concurrent measurements of aerosol optical properties at a wavelength of 550 nm, we find that 80–90% of the aerosol scattering is due to carbonaceous aerosol, where our derived mass scattering cross sections (MSC) for OC and BC are 3.9±0.6 m2/g and 1.6±0.2 m2/g, respectively. Our derived values of mass absorption cross sections (MAC) for OC and BC are 0.7±0.6 m2/g and 8.2±1.1 m2/g, respectively. The values of MAC imply that 26–27% of the aerosol absorption in southern Africa is due to OC, with the remainder due to BC. Our results provide important constraints for aerosol properties in a region dominated by biomass burning and should be integrated into climate models to improve aerosol simulations.

Description: The world's forests produce atmospheric aerosol by emitting volatile organic compounds (VOC) which, after being oxidized in the atmosphere, readily condense on the omnipresent nanometer-sized nuclei and grow them to climatically relevant sizes. The cooling effect of aerosols is the greatest uncertainty in current climate models and estimates of radiative forcing. Therefore, identifying the environmental factors influencing the biogenic formation of aerosols is crucial. We show that, in addition to local meteorological factors in the forest, the magnitude of evaporation from oceans hundreds of kilometers upwind can effectively suppress or enhance new-particle formation. Our findings indicate that, unlike warm waters, the cold polar oceans provide excellent clean and dry background air that enhances aerosol formation above near-coastal forests in Fennoscandia and South-East Australia.

Description: Experiments are conducted to determine the photolysis quantum yields of nitrate, FeOH2+, and H2O2 in the bulk and at the surface layer of water. Results show that the quantum yields of nitrate and FeOH2+ are enhanced at the surface compared to the bulk due to a reduced water-cage surrounding the photo-fragments (•OH+•NO2 and Fe2++•OH, respectively). However, no evidence is found for an enhanced quantum yield for H2O2 at the surface. The photolysis rate constant distribution within nitrate, FeOH2+, and H2O2 aerosols is calculated by combining the quantum yield data with Mie theory calculations of light intensity. Values for the photolysis rate constant of nitrate and FeOH2+ are significantly higher at the surface than in the bulk due to enhanced quantum yields at the surface. The results concerning the rates of photolysis of these photoactive species are applied to the assessment of the reaction between benzene and •OH in the presence of •OH scavengers in an atmospherically relevant scenario. For a droplet of 1μm radius, a large fraction of the total •OH-benzene reaction (15% for H2O2, 20% for nitrate, and 35% for FeOH2+) occurs in the surface layer, which accounts for just 0.15% of the droplet volume. By neglecting the surface effects on photochemistry, the rate of the important reactions could be underestimated by a considerable amount.

Description: We present a photochemical model developed for the explicit calculation of triple oxygen isotopic compositions (Δ17O) of major atmospheric species. While we focus on the Δ17O of HNO3 and aerosol nitrate (NO−3) and its precursors such as NO, NO2 and N2O5, the general implementation given here also provides Δ17O predictions for other important atmospheric compounds such as OH, H2O2, and HO2. Through the use of a simple aerosol surface area model, we calculate the Δ17O composition of aerosol nitrate produced as a function of aerosol size and aerosol surface type. We explore the sensitivity of the Δ17O of atmospheric species through a series of sensitivity studies and show that the Δ17O of atmospheric compounds is affected to various degrees by environmental factors such as temperature, relative humidity, ozone concentration, NOx flux, and total ozone column density. In addition, we find that Δ17O of these species is sensitive to photochemical conditions such as cloud albedo, latitude, and time of year. We compare the Δ17O calculation outputs to previous methods and find significant differences in the Δ17O of NO2. We describe the origins of these and suggest studies that may help to resolve these differences.

Description: The origin of aerosol particles in the upper troposphere and lowermost stratosphere over the Eurasian continent was investigated by applying cluster analysis methods to in situ measured data. Number concentrations of submicrometer aerosol particles and trace gas mixing ratios derived by the CARIBIC (Civil Aircraft for Regular Investigation of the Atmosphere Based on an Instrument Container) measurement system on flights between Germany and South-East Asia were used for this analysis. Four cluster analysis methods were applied to a test data set and their capability of separating the data points into scientifically reasonable clusters was assessed. The best method was applied to seasonal data subsets for summer and winter resulting in five cluster or air mass types: stratosphere, tropopause, free troposphere, high clouds, and boundary layer influenced. Other source clusters, like aircraft emissions could not be resolved in the present data set with the used methods. While the cluster separation works satisfactory well for the summer data, in winter interpretation is more difficult, which is attributed to either different vertical transport pathways or different chemical lifetimes in the two seasons. The geographical distribution of the clusters together with histograms for nucleation and Aitken mode particles within each cluster are presented. Aitken mode particle number concentrations show a clear vertical gradient with the lowest values in the lowermost stratosphere (750–2820 particles/cm3 STP, minimum of the two 25%- and maximum of the two 75%-percentiles of both seasons) and the highest values for the boundary-layer-influenced air (4290–22 760 particles/cm3 STP). Nucleation mode particles are also highest in the boundary-layer-influenced air (1260–29 500 particles/cm3 STP, but are lowest in the free troposphere (0–450 particles/cm3 STP). The given submicrometer particle number concentrations represent the first statistically sound data set for the upper troposphere and lowermost stratosphere over the Eurasian continent.

Description: China implemented systematic air pollution control measures during the 2008 Beijing Summer Olympics and Paralympics to improve air quality. This study used an innovative mobile laboratory to conduct in situ monitoring of on-road air pollutants along Beijing's 4th Ring Road on 31 selected days before, during, and after the Olympics air pollution control period. A suite of instruments with response times of less than 30 s was used to measure temporal and spatial variations in traffic-related air pollutants, including NOx, CO, PM1.0 surface area (SPM1), black carbon (BC), and benzene, toluene, ethylbenzene, and m-, p-, and o-xylene (BTEX). During the Olympics (8–23 August 2008), on-road air pollutant concentrations decreased significantly by up to 54% for CO, 41% for NOx, 70% for SO2, 66% for BTEX, 12% for BC, and 18% for SPM1 compared to the pre-control period (before 20 July). Concentrations increased again after the control period ended (after 20 September), with average increases of 33% for CO, 42% for NOx, 60% for SO2, 40% for BTEX, 26% for BC, and 37% for SPM1. Variations in pollutants concentrations were correlated with changes in traffic speed and the number and types of vehicles on the road. Throughout the measurement periods, the concentrations of NOx, CO, and BTEX varied markedly with the numbers of light- and medium-duty vehicles (LDVs and MDVs, respectively) on the road. Only after 8 August was a noticeable relationship between BC and SPM1 and the number of heavy-duty vehicles (HDVs) found. Additionally, BC and SPM1 showed a strong correlation with SO2 before the Olympics, indicating possible industrial sources from local emissions as well as regional transport activities in the Beijing area. Such factors were identified in measurements conducted on 6 August in an area southwest of Beijing. The ratio of benzene to toluene, a good indicator of traffic emissions, shifted suddenly from about 0.26 before the Olympics to approximately 0.48 after the Olympics began. This finding suggests that regulations on traffic volume and restrictions on the use of painting solvents were effective after the Olympics began. This study demonstrated the effectiveness of air pollution control measures and identified local and regional pollution sources within and surrounding the city of Beijing. The findings will be invaluable for emission inventory evaluations and model verifications.

Description: Monoterpenes, primarily emitted by terrestrial vegetation, can influence atmospheric ozone chemistry, and can form precursors for secondary organic aerosol. The short-term emissions of monoterpenes have been well studied and understood, but their long-term variability, which is particularly important for atmospheric chemistry, has not. This understanding is crucial for the understanding of future changes. In this study, two algorithms of terrestrial biogenic monoterpene emissions, the first one based on the short-term volatilization of monoterpenes, as commonly used for temperature-dependent emissions, and the second one based on long-term production of monoterpenes (linked to photosynthesis) combined with emissions from storage, were compared and evaluated with measurements from a Ponderosa pine plantation (Blodgett Forest, California). The measurements were used to parameterize the long-term storage of monoterpenes, which takes place in specific storage organs and which determines the temporal distribution of the emissions over the year. The difference in assumptions between the first (emission-based) method and the second (production-based) method, which causes a difference in upscaling from instantaneous to daily emissions, requires roughly a doubling of emission capacities to bridge the gap to production capacities. The sensitivities to changes in temperature and light were tested for the new methods, the temperature sensitivity was slightly higher than that of the short-term temperature dependent algorithm. Applied on a global scale, the first algorithm resulted in annual total emissions of 29.6 Tg C a−1, the second algorithm resulted in 31.8 Tg C a−1 when applying the correction factor 2 between emission capacities and production capacities. However, the exact magnitude of such a correction is spatially varying and hard to determine as a global average.

Description: Following the launch of several satellite ultraviolet and visible spectrometers including the Ozone Monitoring Instrument (OMI), much has been learned about the global distribution of nitrogen dioxide (NO2). NO2, which is mostly anthropogenic in origin, absorbs solar radiation at ultraviolet and visible wavelengths. We parameterized NO2 absorption for fast radiative transfer calculations. Using this parameterization with cloud, surface, and NO2 information from different sensors in the NASA A-train constellation of satellites and NO2 profiles from the Global Modeling Initiative (GMI), we compute the global distribution of net atmospheric heating due to tropospheric NO2 for January and July 2005. We assess the impact of clouds and find that because most of N02 is contained in the boundary layer in polluted regions, the cloud shielding effect can significantly reduce the net atmospheric heating due to NO2. We examine the effect of diurnal variations in NO2 emissions and chemistry on net atmospheric heating and find only a small impact of these on the daily-averaged heating. While the impact of NO2 on the global radiative forcing is small, locally it can produce instantaneous net atmospheric heating of 2–4 W/m2 in heavily polluted areas. We also examine the sensitivity of NO2 absorption to various geophysical conditions. Effects of the vertical distributions of cloud optical depth and NO2 on net atmospheric heating and downwelling radiance are simulated in detail for various scenarios including vertically-inhomogeneous convective clouds observed by CloudSat. The maximum effect of NO2 on downwelling radiance occurs when the NO2 is located in the middle part of the cloud where the optical extinction peaks.

Description: The stellar light passed through the Earth atmosphere is affected by refractive effects, which should be taken into account in retrievals from stellar occultation measurements. Scintillation caused by air density irregularities is a nuisance for retrievals of atmospheric composition. In this paper, we consider the influence of scintillation on stellar occultation measurements and on quality of ozone retrievals from these measurements, based on experience of the GOMOS (Global Ozone Monitoring by Occultation of Stars) instrument on board the Envisat satellite. In the GOMOS retrievals, the scintillation effect is corrected using scintillation measurements by the fast photometer. We present quantitative estimates of the current scintillation correction quality and of the impact of scintillation on ozone retrievals by GOMOS. The analysis has shown that the present scintillation correction efficiently removes the distortion of transmission spectra caused by anisotropic scintillations. The impact of errors of dilution and anisotropic scintillation correction on quality of ozone retrievals is negligible. However, the current scintillation correction is not able to remove the wavelength-dependent distortion of transmission spectra caused by isotropic scintillations, which can be present in off-orbital-plane occultations. This distortion may result in error of ozone retrievals of 0.5–1.5% at altitudes 20–40 km. This contribution to the error budget is significant for bright stars. The advanced inversion methods that can minimize the influence of scintillation correction error are also discussed.

Description: In this study we present measurements of selected trace gases and aerosol made in a boreal forest during the BACCI-QUEST IV intensive field campaign in Hyytiälä, Finland in April 2005. Several clear aerosol "nucleation events" were observed and characterized. One type of "event" occurred synchronously with huge increases in monoterpenes, while a second event type correlated instead with sulphuric acid. Here we elucidate the origin of these two distinct forms of aerosol production at the Hyytiälä site using the measurement data, airmass back trajectories and the optical stereoisomery of monoterpenes.

Description: Cloud condensation nuclei (CCN) are derived from particles emitted directly into the atmosphere (primary emissions) or from the growth of nanometer-sized particles nucleated in the atmosphere. It is important to separate these two sources because they respond in different ways to gas and particle emission control strategies and environmental changes. Here, we use a global aerosol microphysics model to quantify the contribution of primary and nucleated particles to global CCN. The model considers primary emissions of sea spray, sulfate and carbonaceous particles, and nucleation processes appropriate for the free troposphere and boundary layer. We estimate that 45% of global low-level cloud CCN at 0.2% supersaturation are secondary aerosol derived from nucleation (ranging between 31–49% taking into account uncertainties primary emissions and nucleation rates), the remainder being directly emitted as primary aerosol. The model suggests that 35% of CCN (0.2%) in low-level clouds were created in the free and upper troposphere. In the marine boundary layer 55% of CCN (0.2%) are from nucleation, 45% being entrained from the free troposphere. Both in global and marine boundary layer 10% of CCN (0.2%) is nucleated in the boundary layer. Combinations of model runs show that primary and nucleated CCN are non-linearly coupled. In particular, boundary layer nucleated CCN are strongly suppressed by both primary emissions and entrainment of particles nucleated in the free troposphere. Elimination of all primary emissions reduces global CCN (0.2%) by only 20% and elimination of upper tropospheric nucleation reduces CCN (0.2%) by only 12% because of increased impact of boundary layer nucleation on CCN.

Description: The nitrogen (δ15N) and triple oxygen (δ17/18O) isotopic composition of nitrate (NO3−) was measured year-round in the atmosphere and snow pits at Dome C (DC, 75.1° S, 123.3° E), and in surface snow on a transect between DC and the coast. Snow pit profiles of δ15N (δ18O) in NO3− show significant enrichment (depletion) of 〉200 (

Description: The first study of the global atmospheric distribution of carbon tetrachloride (CCl4), as a function of altitude and latitude, was performed using solar occultation measurements obtained by the Atmospheric Chemistry Experiment (ACE) mission using Fourier transform spectroscopy. A total of 8703 profile measurements were used in the study taken between February 2004 and August 2007. The zonal distribution of carbon tetrachloride displays a slight hemispheric asymmetry and decreasing concentration with increasing altitude at all latitudes. Maximum carbon tetrachloride concentrations are situated below 10 km in altitude with VMR (Volume Mixing Ratio) values of 100–130 ppt (parts per trillion). The highest concentrations are located about the equator and at mid-latitudes, particularly for latitudes in heavily industrialised regions (20–45° N), with values declining towards the poles. Global distributions obtained from ACE were compared with predictions from three chemistry transport models. The ACE dataset gives unique global and temporal coverage of carbon tetrachloride and its transport through the atmosphere. An estimated lifetime for carbon tetrachloride of 34±5 years was determined through correlation with CFC-11.

Description: For the first time the long-term interannual and spatial variability of residence time (τ) is presented for the TTL between 360 K and 400 K theta (~14 to 18 km altitude). The analysis is based on a Lagrangian approach using offline calculated diabatic heating rates as vertical velocities, covering Northern Hemisphere (NH) winters from 1962–2004. The residence time varies spatially. τ, analysed for the Lagrangian Cold Point (LCP), displays a longer duration time of air parcels between LCP and 400 K over the maritime continent (〉50 days), as the LCP tropopause has a minimum over the maritime continent (

Description: Inverse modeling of CO2 satellite observations to better quantify carbon surface fluxes requires a forward model such as a chemical transport model (CTM) to relate the fluxes to the observed column concentrations. Model transport error is an important source of observational error. We investigate the potential of using CO satellite observations as additional constraints in a joint CO2–CO inversion to improve CO2 flux estimates, by exploiting the CTM transport error correlations between CO2 and CO. We estimate the error correlation globally and for different seasons by a paired-model method (comparing CTM simulations of CO2 and CO columns using different assimilated meteorological data sets for the same meteorological year) and a paired-forecast method (comparing 48- vs. 24-h CTM forecasts of CO2 and CO columns for the same forecast time). We find strong positive and negative error correlations (r2〉0.5) between CO2 and CO columns over much of the world throughout the year, and strong consistency between different methods to estimate the error correlation. Application of the averaging kernels used in the retrieval for thermal IR CO measurements weakens the correlation coefficients by 15% on average (mostly due to variability in the averaging kernels) but preserves the large-scale correlation structure. Results from a testbed inverse modeling application show that CO2–CO error correlations can indeed significantly reduce uncertainty on surface carbon fluxes in a joint CO2–CO inversion vs. a CO2–only inversion.

Description: A photochemical ship-plume model, which can consider the ship-plume dynamics and ship-plume chemistry, simultaneously, was developed to gain a better understanding of atmospheric impact of ship emissions. The model performance was then evaluated by a comparison with the observation data measured on a NOAA WP-3D flight during the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) airborne field campaign. The simulation conditions and parameters, such as meteorological conditions, emission rates, and background gas and particulate species concentrations, were obtained directly and/or inferred indirectly from the ITCT 2K2 observation data. The model-predicted concentrations showed good agreement with the observed concentrations of five ambient species (NOx, NOy, O3, HNO3, and H2SO4) at the eight plume transects by the WP-3D flight with strong correlations around the 1:1 line (0.66≤R≤0.85). In addition, a set of tests were carried out to approximate the magnitude of the reaction probability of HNO3 onto sea-salt particles in the model-observation comparison framework. These results suggest that the reaction probability of HNO3 onto sea-salt particles may be in the order of 10−3 or smaller. The equivalent NOx lifetime throughout the "entire" plume was also estimated from ship-plume chemistry modeling. The NOx lifetimes estimated throughout the "entire ship plume" was 3.36 h. The short NOx lifetime over the entire ship plume clearly shows that the ship-plume chemistry shortens the NOx lifetime considerably. Therefore, the ship-plume chemistry model should be used to model the changes in ship-plume chemical compositions and better evaluate the atmospheric impact of ocean-going ship emissions.

Description: A suite of diagnostics is applied to in-situ aircraft measurements and one Chemistry-Climate Model (CCM) data to characterize the vertical structure of the Tropical Tropopause Layer (TTL). The diagnostics are based on the vertical tracers profiles, relative vertical tracers gradients, and tracer-tracer relationships in the tropical Upper Troposphere/Lower Stratosphere (UT/LS), using tropopause coordinates. Observations come from the four tropical campaigns performed from 1998 to 2006 with the research aircraft Geophysica and have been directly compared to the output of the ECHAM5/MESSy CCM. The model vertical resolution in the TTL allows for appropriate comparison with high-resolution aircraft observations and the diagnostics used highlight common TTL features between the model and the observational data. The analysis of the vertical profiles of water vapour, ozone, and nitrous oxide, in both the observations and the model, shows that concentration mixing ratios exhibit a strong gradient change across the tropical tropopause, due to the role of this latter as a transport barrier and that transition between the tropospheric and stratospheric regimes occurs within a finite layer. The use of relative vertical ozone gradients, in addition to the vertical profiles, helps to highlight the region where this transition occurs and allows to give an estimate of its thickness. The analysis of the CO-O3 and H2O-O3 scatter plots and of the Probability Distribution Function (PDF) of the H2O-O3 pair completes this picture as it allows to better distinguish tropospheric and stratospheric regimes that can be identified, first, by their differing chemical composition. The joint analysis and comparison of observed and modelled data allows us to evaluate the capability of the model in reproducing the observed vertical structure of the TTL and its variability, and also to assess whether observations from particular regions on a monthly timescale can be representative of the fine scale mean structure of the Tropical Tropopause Layer.

Description: The 14-channel Ames Airborne Tracking Sunphotometer (AATS) was operated on a Jetstream 31 (J31) aircraft in March 2006 during MILAGRO/INTEX-B (Megacity Initiative-Local And Global Research Observations/Phase B of the Intercontinental Chemical Transport Experiment). We compare AATS retrievals of spectral aerosol optical depth (AOD) and related aerosol properties with corresponding spatially coincident and temporally near-coincident measurements acquired by the MODIS-Aqua and MODIS-Terra satellite sensors. These comparisons are carried out for the older MODIS Collection 4 (C4) and the new Collection 5 (C5) data set, the latter representing a reprocessing of the entire MODIS data set completed during 2006 with updated calibration and aerosol retrieval algorithm. Our analysis yields a direct, validated assessment of the differences between select MODIS C4 and C5 aerosol retrievals. Our analyses of 37 coincident observations by AATS and MODIS-Terra and 18 coincident observations between AATS and MODIS-Aqua indicate notable differences between MODIS C4 and C5 and between the two sensors. For MODIS-Terra, we find an average increase in AOD of 0.02 at 553 nm and 0.01 or less at the shortwave infrared (SWIR) wavelengths. The change from C4 to C5 results in less good agreement with the AATS derived spectral AOD, with average differences at 553 nm increasing from 0.03 to 0.05. For MODIS-Aqua, we find an average increase in AOD of 0.008 at 553 nm, but an increase of nearly 0.02 at the SWIR wavelengths. The change from C4 to C5 results in slightly less good agreement to the AATS derived visible AOD, with average differences at 553 nm increasing from 0.03 to 0.04. However, at SWIR wavelengths, the changes from C4 to C5 result in improved agreement between MODIS-Aqua and AATS, with the average differences at 2119 nm decreasing from -0.02 to -0.003. Comparing the Angstrom exponents calculated from AOD at 553 nm and 855 nm, we find an increased rms difference from AATS derived Angstrom exponents in going from C4 to C5 for MODIS-Terra, and a decrease in rms difference, hence an improvement, for the transition from C4 to C5 in MODIS-Aqua. Combining the AATS retrievals with in situ measurements of size-dependent aerosol extinction, we derive a suborbital measure of the aerosol submicron fraction (SMF) of AOD and compare it to MODIS retrievals of aerosol fine mode fraction (FMF). Our analysis shows a significant rms-difference between the MODIS-Terra FMF and suborbitally-derived SMF of 0.17 for both C4 and C5. For MODIS-Aqua, there is a slight improvement in the transition from C4 to C5, with the rms-difference from AATS dropping from 0.23 to 0.16. The differences in MODIS C4 and C5 AOD in this limited data set can be traced to changes in the reflectances input to the aerosol retrievals. An extension of the C4-C5 comparisons from the area along the J31 flight track to a larger study region between 18–23° N and 93–100° W on each of the J31 flight days supports the finding of significant differences between MODIS C4 and C5.

Description: This paper presents the first multi-year global set of observations of CO2 in the mesosphere and lower thermosphere (MLT) obtained by the ACE-FTS instrument on SCISAT-I, a small Canadian satellite launched in 2003. The observations use the solar occultation technique and document the fall-off in the mixing ratio of CO2 in the MLT region. The beginning of the fall-off of the CO2, or "knee" occurs at about 78 km and lies higher than in the CRISTA measurements (~70 km) but lower than in the SABER 1.06 (~82 km) and much lower than in rocket measurements. We also present the measurements of CO obtained concurrently which provide important constraints for analysis. We have compared the ACE measurements with simulations of the CO2 and CO distributions in the vertically extended version of the Canadian Middle Atmosphere Model (CMAM). Applying standard chemistry we find that we cannot get agreement between the model and ACE CO2 observations although the CO observations are adequately reproduced. There appears to be about a 10 km offset compared to the observed ACE CO2, with the model knee occurring too high. In analysing the disagreement, we have investigated the variation of several parameters of interest, photolysis rates, formation rate for CO2, and the impact of uncertainty in eddy diffusion, in order to explore parameter space for this problem. Our conclusions are that there must be a loss process for CO2, about 2–4 times faster than photolysis that will sequester the carbon in some form other than CO and we have speculated on the role of meteoritic dust as a possible candidate. In addition, from this study we have highlighted a possible important role for vertical eddy diffusion in 3-D models in determining the distribution of candidate species in the mesosphere which requires further study.

Description: Eddy-covariance and Sodar/RASS experimental measurement data of the COPS (Convective and Orographically-induced Precipitation Study) field campaign 2007 are used to investigate the generation of near-ground free convection events in the Kinzig valley, Black Forest, Southwest Germany. The measured high-quality turbulent flux data revealed free convection to be induced in situations where high buoyancy fluxes and a simultaneously occurring wind speed collapse were present. The minimum in wind speed – observable by the Sodar measurements through the whole vertical extension of the valley atmosphere – is the consequence of a thermally-induced valley wind system, which changes its wind direction from down to up-valley winds in the morning hours. Buoyant forces then dominate over shear forces within turbulence production. These situations are detected by the stability parameter (ratio of the measurement height to the Obukhov length) calculated from directly measured turbulent fluxes. An analysis of the scales of turbulent motions during the free convection event using wavelet transform confirms the large-eddy scale character of the detected plume-like coherent structures. Regarding the entire COPS measurement period, free convection events (FCEs) in the morning hours occur on about 50% of all days.

Description: The natural environment is a major source of atmospheric aerosols, including dust, secondary organic material from terrestrial biogenic emissions, carbonaceous particles from wildfires, and sulphate from marine phytoplankton dimethyl sulphide emissions. These aerosols also have a significant effect on many components of the Earth system such as the atmospheric radiative balance and photosynthetically available radiation entering the biosphere, the supply of nutrients to the ocean, and the albedo of snow and ice. The physical and biological systems that produce these aerosols can be highly susceptible to modification due to climate change so there is the potential for important climate feedbacks. We review the impact of these natural systems on atmospheric aerosol based on observations and models, including the potential for long term changes in emissions and the feedbacks on climate. The number of drivers of change is very large and the various systems are strongly coupled. There have therefore been very few studies that integrate the various effects to estimate climate feedback factors. Nevertheless, available observations and model studies suggest that the regional radiative forcings are potentially several Watts per square metre due to changes in these natural aerosol emissions in a future climate. The level of scientific understanding of the climate drivers, interactions and impacts is very low.

Description: A newly developed ice nucleation experimental set up was used to investigate the heterogeneous ice nucleation properties of three Saharan and one Spanish dust particle samples. It was observed that the spread in the onset relative humidities with respect to ice (RHi) for Saharan dust particles varied from 104% to 110%, whereas for the Spanish dust from 106% to 110%. The elemental composition analysis shows a prominent Ca feature in the Spanish dust sample which could potentially explain the differences in nucleation threshold. Although the spread in the onset RHi) for the Saharan dust samples were in agreement, the active fractions and nucleation time-lags calculated at various temperature and RHi) conditions were found to differ. This could be due to the subtle variation in the elemental composition of the dust samples, and surface irregularities like steps, cracks, cavities etc. A combination of classical nucleation theory and active site theory is used to understand the importance of these surface irregularities on the nucleability parameter contact angle that is widely used in the ice cloud modeling. These calculations show that the surface irregularities can reduce the contact angle by approximately 10°.

Description: A feedback loop between regional scale deforestation and climate change was investigated in an experiment using novel, small size airborne platforms and instrument setups. Experiments were performed in a worldwide unique natural laboratory in Western Australia, characterized by two adjacent homogeneous observation areas with distinctly different land use characteristics. Conversion of several ten thousand square km of forests into agricultural land began more than a century ago. Changes in albedo and surface roughness and the water budget of soil and the planetary boundary layer evolved over decades. Besides different meteorology we found a significant up to now overseen source of aerosol over the agriculture. The enhanced number of cloud condensation nuclei is coupled through the hydrological groundwater cycle with deforestation. Modification of surface properties and aerosol number concentrations are key factors for the observed reduction of precipitation. The results document the importance of aerosol indirect effects on climate due to nanometer size biogenic aerosol and human impact on aerosol sources.

Description: Emission inventories of sixty-nine speciated non-methane volatile organic compounds (NMVOC) from on-road vehicles in China were estimated for the period of 1980–2005, using seven NMVOC emission profiles, which were summarized based on local and international measurements from published literatures dealing with specific vehicle categories running under particular modes. Results show an exponential growth trend of China's historical emissions of alkanes, alkenes, alkines, aromatics and carbonyls during the period of 1980–2005, increasing from 63.9, 39.3, 6.9, 36.8 and 24.1 thousand tons, respectively, in 1980 to 2781.4, 1244.9, 178.5, 1350.7 and 403.3 thousand tons, respectively, in 2005, which coincided well with China's economic growth. Emission inventories of alkenes, aromatics and carbonyls were gridded at a high resolution of 40 km×40 km for air quality simulation and health risk evaluation, using the geographic information system (GIS) methodology. Spatial distribution of speciated NMVOC emissions shows a clear difference in emission densities between developed eastern and relatively underdeveloped western and inland China. Besides, the appearance and expansion of high-emission areas was another notable characteristic of spatial distribution of speciated NMVOC emissions during the period. Emission contributions of vehicle categories to speciated NMVOC groups showed annual variation, due to the variance in the provincial emissions and in the relative fractions of the seven emission profiles adopted at the provincial level. Highly reactive and toxic compounds accounted for high proportions of emissions of speciated NMVOC groups. The most abundant compounds were isopentane, pentane and butane from alkanes; ethene, propene, 2-methyl-2-butene and ethyne from alkenes and alkines; benzene, toluene, ethylbenzene, o-xylene, and m,p-xylene (BTEX) and 1,2,4-trimethylbenzene from aromatics and formaldehyde, acetaldehyde, benzaldehyde, acetone and acrolein from carbonyls.

Description: We derive an analytic solution to the spectral growth/sublimation equation for ice crystals and apply it to idealised cases. The results are used to test parameterisations of the ice sublimation process in two-moment bulk microphysics models. Although it turns out that the relation between number loss fraction and mass loss fraction is not a function since it is not unique, it seems that a functional parameterisation is the best that one can do in a bulk model. Testing a more realistic case with humidity oscillations shows that artificial crystal loss can occur in simulations of mature cirrus clouds with relative humidity fluctuating about ice saturation.

Description: A weekly cycle in aerosol pollution and meteorological quantities is observed over Europe. In the present study we exploit this effect to analyse aerosol-cloud-radiation interactions. A weekly cycle is imposed on anthropogenic emissions in two general circulation models that include parameterizations of aerosol cycles and cloud microphysics. It is found that the simulated weekly cycles in sulfur dioxide, sulfate, and aerosol optical depth in both models agree reasonably well with the observed ones indicating model skill in simulating the aerosol cycle. A distinct weekly cycle in cloud droplet number concentration is demonstrated in both observations and models. For other variables, such as cloud liquid water path, cloud cover, top-of-the-atmosphere radiation fluxes, precipitation, and surface temperature, large variability and contradictory results between observations, model simulations, and model control simulations without a weekly cycle in emissions prevent us from reaching any firm conclusions about the potential aerosol impact on meteorology or the realism of the modeled second aerosol indirect effects.

Description: We have performed simulations using a 3-D global chemistry-transport model to investigate the influence that biogenic emissions from the African continent exert on the composition of the tropopause in the tropical region. For this purpose we have applied two recently developed biogenic emission inventories provided for use in large-scale global models (Granier et al., 2005; Lathiére et al., 2006) whose seasonality and temporal distribution for isoprene, biogenic NO and biogenic volatile organic compounds is markedly different. The use of the climatological values for biogenic emissions provided by Lathiére et al. (2006) results in an increase in the amount of nitrogen sequestrated into longer lived reservoir compounds which contributes to the reduction in tropospheric ozone burden in the tropics. The associated re-partitioning of nitrogen between PAN, HNO3 and organic nitrates also results in a ~5% increase in the loss of nitrogen by wet deposition. At a global scale there is a reduction in the oxidizing capacity of the model atmosphere which increases the atmospheric lifetimes of CH4 and CO by ~1.5% and ~4%, respectively. By the use of sensitivity studies we show that the release of NO from soils in Africa accounts for between ~5–45% of tropospheric ozone in the African troposphere, ~10% in the upper troposphere and between ~5–20% of the tropical tropospheric ozone column over the tropical Atlantic Ocean. The subsequent reduction in OH over the source regions allows enhanced transport of CO out of the region. For biogenic volatile organic C1 to C3 species released from Africa the effects on tropical tropospheric ozone are rather limited, although this source contributes to the global burden of VOC by between ~2–4% and has a large influence on the organic composition of the troposphere over the tropical Atlantic Ocean. Comparisons against a range of different measurements indicate that applying the climatology of Lathiére et al. (2006) improves the performance of TM4 for 2006 in the tropics.

Description: We use the GEOS-Chem global 3-D chemistry transport model to investigate the relative importance of chemical and physical processes that determine observed variability of hydrogen cyanide (HCN) in the troposphere and lower stratosphere. Consequently, we reconcile ground-based FTIR column measurements of HCN, which show annual and semi-annual variations, with recent space-borne measurements of HCN mixing ratio in the tropical lower stratosphere, which show a large two-year variation. We find that the observed column variability over the ground-based stations is determined by a superposition of HCN from several regional burning sources, with GEOS-Chem reproducing these column data with a positive bias of 5%. GEOS-Chem reproduces the observed tropical HCN variability from the Microwave Limb Sounder and the Atmospheric Chemistry Experiment satellite instruments with a negative bias of 7%. We show the tropical biomass burning emissions explain mostly the observed HCN variations in the upper troposphere and lower stratosphere (UTLS), with the remainder due to atmospheric transport and HCN chemistry. In the mid and upper stratosphere, atmospheric dynamics progressively exerts more influences on HCN variations. The extent of temporal overlap between African and other continental burning seasons is key in establishing the apparent bienniel cycle in the UTLS. Similar analysis of other, shorter-lived trace gases have not observed the transition between annual and bienniel cycles in the UTLS probably because the signal of inter-annual variations from surface emission has vanished before arriving at the lower stratosphere (LS), due to shorter atmospheric lifetimes.