ALBERT

Description: Volcanoes represent an important natural source of several trace elements to the atmosphere. For some species (e.g., As, Cd, Pb and Se) they may be the main natural source and thereby strongly influencing geochemical cycles from the local to the global scale. Mount Etna is one of the most actively degassing volcanoes in the world, and it is considered to be, on the long-term average, the major atmospheric point source of many environmental harmful compounds. Their emission occurs either through continuous passive degassing from open-conduit activity or through sporadic paroxysmal eruptive activity, in the form of gases, aerosols or particulate. To estimate the environmental impact of magma-derived trace metals and their depositions processes, rainwater and snow samples were collected at Mount Etna area. Five bulk collectors have been deployed at various altitudes on the upper flanks around the summit craters of the volcano; samples were collected every two week for a period of one year and analyzed for the main chemical-physical parameters (electric conductivity and pH) and for major and trace elements concentrations. Chemical analysis of rainwater clearly shows that the volcanic contribution is always prevailing in the sampling site closest to the summit crater (about 1.5 km). In the distal sites (5.5-10 km from the summit) and downwind of the summit craters, the volcanic contribution is also detectable but often overwhelmed by anthropogenic or other natural (seawater spray, geogenic dust) contributions. Volcanic contribution may derive from both dry and wet deposition of gases and aerosols from the volcanic plume, but sometimes also from leaching of freshly emitted volcanic ashes. In fact, in our background site (7.5 km in the upwind direction) volcanic contribution has been detected only following an ash deposition event. About 30 samples of fresh snow were collected in the upper part of the volcano, during the winters 2006 and 2007 to estimate deposition processes at high altitude during cold periods. Some of the samples were collected immediately after a major explosive event from the summit craters to understand the interaction between snow and fresh erupted ash. Sulphur, Chlorine and Fluorine, are the major elements that prevailingly characterize the volcanic contribution in atmospheric precipitation on Mount Etna, but high concentrations of many trace elements are also detected in the studied samples. In particular, bulk deposition samples display high concentration of Al, Fe, Ti, Cu, As, Rb, Pb, Tl, Cd, Cr, U and Ag, in the site most exposed to the volcanic emissions: median concentration values are about two orders of magnitude higher than those measured in our background site. Also in the snow samples the volcanic signature is clearly detectable and decreases with distance from the summit craters. Some of the analysed elements display very high enrichment values with respect to the average crust and, in the closest site to the summit craters, also deposition values higher than those measured in polluted urban or industrial sites.

Description: Published

Description: Vienna, Austria

Description: 4.5. Degassamento naturale

Description: open

Description: 〈b〉Foraminiferal response to environmental changes in Kiel Fjord, SW Baltic Sea〈/b〉〈br〉 A. Nikulina, I. Polovodova, and J. Schönfeld〈br〉 eEarth, 3, 37-49, doi:10.5194/ee-3-37-2008, 2008〈br〉 The living benthic foraminiferal assemblages in Kiel Fjord (SW Baltic Sea) were investigated in the years 2005 and 2006. The faunal studies were accomplished by geochemical analyses of surface sediments. In general, sediment pollution by copper, zinc, tin and lead is assessed as moderate in comparison with levels reported from other areas of the Baltic Sea. However, the inner Kiel Fjord is still exposed to a high load of metals and organic matter due to enhanced accumulation of fine-grained sediments in conjunction with potential pollution sources as shipyards, harbours and intensive traffic. The results of our survey show that the dominant environmental forcing of benthic foraminifera is nutrients availability coupled with human impact. A comparison with faunal data from the 1960s reveals apparent changes in species composition and population densities. The stress-tolerant species 〈i〉Ammonia beccarii〈/i〉 invaded Kiel Fjord. 〈i〉Ammotium cassis〈/i〉 had disappeared that reflects apparently the changes in salinity over the last 10 years. These changes in foraminiferal community and a significant increase of test abnormalities indicate an intensified environmental stress since the 1960s.

Description: 〈b〉Foraminiferal response to environmental changes in Kiel Fjord, SW Baltic Sea〈/b〉〈br〉 A. Nikulina, I. Polovodova, and J. Schönfeld〈br〉 eEarth, 3, 37-49, doi:10.5194/ee-3-37-2008, 2008〈br〉 The living benthic foraminiferal assemblages in Kiel Fjord (SW Baltic Sea) were investigated in the years 2005 and 2006. The faunal studies were accomplished by geochemical analyses of surface sediments. In general, sediment pollution by copper, zinc, tin and lead is assessed as moderate in comparison with levels reported from other areas of the Baltic Sea. However, the inner Kiel Fjord is still exposed to a high load of metals and organic matter due to enhanced accumulation of fine-grained sediments in conjunction with potential pollution sources as shipyards, harbours and intensive traffic. The results of our survey show that the dominant environmental forcing of benthic foraminifera is nutrients availability coupled with human impact. A comparison with faunal data from the 1960s reveals apparent changes in species composition and population densities. The stress-tolerant species 〈i〉Ammonia beccarii〈/i〉 invaded Kiel Fjord. 〈i〉Ammotium cassis〈/i〉 had disappeared that reflects apparently the changes in salinity over the last 10 years. These changes in foraminiferal community and a significant increase of test abnormalities indicate an intensified environmental stress since the 1960s.

Description: 〈b〉Decline of coral reefs during late Paleocene to early Eocene global warming〈/b〉〈br〉 C. Scheibner and R. P. Speijer〈br〉 eEarth, 3, 19-26, doi:10.5194/ee-3-19-2008, 2008〈br〉 Since the 1980s the frequency of warming events has intensified and simultaneously widespread coral bleaching, and enhanced coral mortality have been observed. Yet, it remains unpredictable how tropical coral reef communities will react to prolonged adverse conditions. Possibly, coral reef systems are sufficiently robust to withstand continued environmental pressures. But if coral mortality increases, what will platform communities of the future look like? The co-evolution of early Paleogene carbonate platforms and palaeoclimate may provide insight. Here we document the impact of early Paleogene global warming on shallow-water carbonate platforms in the Tethys. Between 59 and 55 Ma, three discrete stages in platform development can be identified Tethys-wide: during the first stage carbonate platforms mainly consisted of coralgal reefs; during the second – transitional – stage coralgal reefs thrived only at middle latitudes and gave way to larger foraminifera as dominant carbonate producer in low latitudes; finally, during the third stage, newly developing larger foraminifera lineages completely took over the role as main carbonate-producing organisms in low to middle latitudes. We postulate that rising temperatures led to a stepwise demise of Paleocene coral reefs, giving way to an unprecedented expansion of larger foraminifera, dominating Tethyan platforms during the early Eocene.

Description: 〈b〉Palaeomagnetic investigations of sediments cores from Axios zone (N. Greece): implications of low inclinations in the Aegean〈/b〉〈br〉 E. Aidona, D. Kondopoulou, R. Scholger, A. Georgakopoulos, and A. Vafeidis〈br〉 eEarth, 3, 7-18, doi:10.5194/ee-3-7-2008, 2008〈br〉 Sediment cores from 13 deep boreholes (1–4.1 km) distributed within Axios zone in Northern Greece have been studied by means of palaeomagnetism. Both low field magnetic susceptibility and intensity of the natural remanent magnetization (NRM) indicate rather weakly magnetised materials. A set of 390 samples have been subjected to thermal and alternative field demagnetization. Isothermal remanent magnetization (IRM) acquisition curves and thermomagnetic analysis suggest the dominance of magnetite. Thin sections from 30 selected samples were studied in order to more precisely characterise their magnetic mineralogy. This investigation also reveals the presence of magnetite and pyrite in framboidal form. An attempt to re-orient some of the samples was partially successful by using the viscous component and the anisotropy method. These techniques were applied in order to correct the palaeomagnetic directions due to the orientation ambiguity of the core samples. The corrected mean direction converges towards an eastward value, in agreement with the overall pattern of the onshore results from previous investigations in the study area. 〈br〉〈br〉 Finally, the observed inclinations of characteristic remanences in these rocks are much lower than the expected ones but converge with those obtained from formations on land.

Description: 〈b〉Zoogeography of the bottom Foraminifera of the West-African coast〈/b〉〈br〉 V. Mikhalevich〈br〉 eEarth Discuss., 3, 1-9, doi:10.5194/eed-3-1-2008, 2008〈br〉 〈b〉Revised manuscript has not been submitted〈/b〉 (discussion: closed, 8 comments)〈br〉 The sediment samples from the continental shelf of West-Equatorial Africa (from the Strait of Gibraltar to the Niger estuary), depths ranging from 0 to 69 m were found to contain 176 bottom foraminiferal species. For the majority of them (126 species), their areas of occurrences were mapped and the peculiar features of the geographical range and distribution were studied. The species natural habitats were established based on the taxonomical revision of the species in study all over the World Ocean based on the collections of the Zoological Institute RAS and wide literary data. The method of perforated cards was used to mark the geographical locations of all of the species studied. In order to establish the species geographic zonal distribution (together with their depth habitat) the five characteristic groups of the species were separated: 1. pan-oceanic (cosmopolitan), 2. widely spread tropical-boreal, 3. tropical-law boreal, 4. tropical-subtropical, 5. tropical. The percent of the species of each group among the species composition was established for the fauna of each station and for the whole region.

Description: 〈b〉Zoogeography of the bottom Foraminifera of the West-African coast〈/b〉〈br〉 V. Mikhalevich〈br〉 eEarth Discuss., 3, 1-9, doi:10.5194/eed-3-1-2008, 2008〈br〉 〈b〉Revised manuscript has not been submitted〈/b〉 (discussion: closed, 8 comments)〈br〉 The sediment samples from the continental shelf of West-Equatorial Africa (from the Strait of Gibraltar to the Niger estuary), depths ranging from 0 to 69 m were found to contain 176 bottom foraminiferal species. For the majority of them (126 species), their areas of occurrences were mapped and the peculiar features of the geographical range and distribution were studied. The species natural habitats were established based on the taxonomical revision of the species in study all over the World Ocean based on the collections of the Zoological Institute RAS and wide literary data. The method of perforated cards was used to mark the geographical locations of all of the species studied. In order to establish the species geographic zonal distribution (together with their depth habitat) the five characteristic groups of the species were separated: 1. pan-oceanic (cosmopolitan), 2. widely spread tropical-boreal, 3. tropical-law boreal, 4. tropical-subtropical, 5. tropical. The percent of the species of each group among the species composition was established for the fauna of each station and for the whole region.

Description: 〈b〉Use of remote sensing and GIS in mapping the environmental sensitivity areas for desertification of Egyptian territory〈/b〉〈br〉 A. Gad and I. Lotfy〈br〉 eEarth Discuss., 3, 41-85, doi:10.5194/eed-3-41-2008, 2008〈br〉 〈b〉Revised manuscript has not been submitted〈/b〉 (discussion: closed, 3 comments)〈br〉 Desertification is defined in the first art of the convention to combat desertification as 〈i〉"land degradation in arid, semiarid and dry sub-humid areas resulting from climatic variations and human activities".〈/i〉 Its consequence include a set of important processes which are active in arid and semi arid environment, where water is the main limiting factor of land use performance in such ecosystem . Desertification indicators or the groups of associated indicators should be focused on a single process. They should be based on available reliable information sources, including remotely sensed images, topographic data (maps or DEM'S), climate, soils and geological data. The current work aims to map the Environmental Sensitivity Areas (ESA's) to desertification in whole territory of Egypt at a scale of 1:1 000 000. 〈br〉〈br〉 ETM satellite images, geologic and soil maps were used as main sources for calculating the index of Environmental Sensitivity Areas (ESAI) for desertification. The algorism is adopted from MEDALLUS methodology as follows; 〈br〉〈br〉 ESAI = (SQI * CQI * VQI)〈sup〉1/3〈/sup〉 〈br〉〈br〉 Where SQI is the soil quality index, CQI is the climate quality index and VQI is the vegetation quality index. The SQI is based on rating the parent material, slope, soil texture, and soil depth. The VQI is computed on bases of rating three categories (i.e. erosion protection, drought resistance and plant cover). The CQI is based on the aridity index, derived from values of annual rainfall and potential evapotranspiration. Arc-GIS 9 software was used for the computation and sensitivity maps production. 〈br〉〈br〉 The results show that the soil of the Nile Valley are characterized by a moderate SQI, however the those in the interference zone are low soil quality indexed. The dense vegetation of the valley has raised its VQI to be good, however coastal areas are average and interference zones are low. The maps of ESA's for desertification show that 86.1% of Egyptian territory is classified as very sensitive areas, while 4.3% as Moderately sensitive, and 9.6% as sensitive. 〈br〉〈br〉 It can be concluded that implementing the maps of sensitivity to desertification is rather useful in the arid and semi arid areas as they give more likely quantitative trend for frequency of sensitive areas. The integration of different factors contributing to desertification sensitivity may lead to plan a successful combating. The usage of space data and GIS proved to be suitable tools to rely estimation and to fulfill the needed large computational requirements. They are also useful in visualizing the sensitivity situation of different desertification parameters.

Description: 〈b〉Palaeomagnetic investigations of sediments cores from Axios zone (N. Greece): implications of low inclinations in the Aegean〈/b〉〈br〉 E. Aidona, D. Kondopoulou, R. Scholger, A. Georgakopoulos, and A. Vafeidis〈br〉 eEarth, 3, 7-18, doi:10.5194/ee-3-7-2008, 2008〈br〉 Sediment cores from 13 deep boreholes (1–4.1 km) distributed within Axios zone in Northern Greece have been studied by means of palaeomagnetism. Both low field magnetic susceptibility and intensity of the natural remanent magnetization (NRM) indicate rather weakly magnetised materials. A set of 390 samples have been subjected to thermal and alternative field demagnetization. Isothermal remanent magnetization (IRM) acquisition curves and thermomagnetic analysis suggest the dominance of magnetite. Thin sections from 30 selected samples were studied in order to more precisely characterise their magnetic mineralogy. This investigation also reveals the presence of magnetite and pyrite in framboidal form. An attempt to re-orient some of the samples was partially successful by using the viscous component and the anisotropy method. These techniques were applied in order to correct the palaeomagnetic directions due to the orientation ambiguity of the core samples. The corrected mean direction converges towards an eastward value, in agreement with the overall pattern of the onshore results from previous investigations in the study area. 〈br〉〈br〉 Finally, the observed inclinations of characteristic remanences in these rocks are much lower than the expected ones but converge with those obtained from formations on land.

Description: 〈b〉Geometry of the Turkey-Arabia and Africa-Arabia plate boundaries in the latest Miocene to Mid-Pliocene: the role of the Malatya-Ovacık Fault Zone in eastern Turkey〈/b〉〈br〉 R. Westaway, T. Demir, and A. Seyrek〈br〉 eEarth, 3, 27-35, doi:10.5194/ee-3-27-2008, 2008〈br〉 We suggest a working hypothesis for the geometry of the strike-slip faults that formed the boundaries between the Turkish, African and Arabian plates in the latest Miocene to Mid-Pliocene (LMMP), between ~7–6 Ma and ~3.5 Ma. This geometry differed significantly from the modern geometry; the northern Dead Sea Fault Zone (DSFZ) was located east of its present line and the TR-AR boundary was formed by the Malatya-Ovacık Fault Zone (MOFZ), located well north of the modern East Anatolian Fault Zone (EAFZ). The MOFZ is potentially the most problematic aspect of such a scheme, given the dramatically different interpretations of it that have been proposed. However, the presently-available evidence, albeit limited, is consistent with our proposed interpretation. Significant differences between the proposed LMMP fault geometry and the modern geometry include, first, the transtensional geometry of the MOFZ, the modern EAFZ being typically a left-lateral transform fault zone but with localized transpression. Second, the MOFZ slip rate was much lower than the ~9–10 mm a〈sup〉−1〈/sup〉 EAFZ slip rate; it is estimated as ~2–3 mm a〈sup〉−1〈/sup〉, having produced no more than ~8 km of slip during its approximately three million year long activity. The Euler vector is tentatively inferred to have involved relative rotation between the Turkish and Arabian Plates at ~0.85±0.15° Ma〈sup〉−1〈/sup〉 about a pole at ~37.75±0.15° N, ~38.8±0.3° E. Third, unlike at present, there was no throughgoing linkage of left-lateral faulting between the LMMP DSFZ and the MOFZ; instead, the DSFZ terminated northward, and the MOFZ terminated southward, in a zone of localised crustal shortening adjoining the suture of the former Neotethys Ocean in the Kahramanmaraş-Pazarcık region of SE Turkey. The different motion of the Turkish plate relative to Arabia, and, thus, relative to Eurasia, means that senses and rates of crustal deformation can be expected to have been different during the LMMP phase from at present, throughout the eastern Mediterranean region.

Description: 〈b〉Decline of coral reefs during late Paleocene to early Eocene global warming〈/b〉〈br〉 C. Scheibner and R. P. Speijer〈br〉 eEarth, 3, 19-26, doi:10.5194/ee-3-19-2008, 2008〈br〉 Since the 1980s the frequency of warming events has intensified and simultaneously widespread coral bleaching, and enhanced coral mortality have been observed. Yet, it remains unpredictable how tropical coral reef communities will react to prolonged adverse conditions. Possibly, coral reef systems are sufficiently robust to withstand continued environmental pressures. But if coral mortality increases, what will platform communities of the future look like? The co-evolution of early Paleogene carbonate platforms and palaeoclimate may provide insight. Here we document the impact of early Paleogene global warming on shallow-water carbonate platforms in the Tethys. Between 59 and 55 Ma, three discrete stages in platform development can be identified Tethys-wide: during the first stage carbonate platforms mainly consisted of coralgal reefs; during the second – transitional – stage coralgal reefs thrived only at middle latitudes and gave way to larger foraminifera as dominant carbonate producer in low latitudes; finally, during the third stage, newly developing larger foraminifera lineages completely took over the role as main carbonate-producing organisms in low to middle latitudes. We postulate that rising temperatures led to a stepwise demise of Paleocene coral reefs, giving way to an unprecedented expansion of larger foraminifera, dominating Tethyan platforms during the early Eocene.

Description: 〈b〉Characteristics of chlorites in seismogenic fault zones: the Taiwan Chelungpu Fault Drilling Project (TCDP) core sample〈/b〉〈br〉 Y. Hashimoto, O. Tadai, M. Tanimizu, W. Tanikawa, T. Hirono, W. Lin, T. Mishima, M. Sakaguchi, W. Soh, S. R. Song, K. Aoike, T. Ishikawa, M. Murayama, K. Fujimoto, T. Fukuchi, M. Ikehara, H. Ito, H. Kikuta, M. Kinoshita, K. Masuda, T. Matsubara, O. Matsubayashi, K. Mizoguchi, N. Nakamura, K. Otsuki, T. Shimamoto, H. Sone, and M. Takahashi〈br〉 eEarth, 3, 1-6, doi:10.5194/ee-3-1-2008, 2008〈br〉 The iron content and the asymmetry of iron and magnesium ions in chlorites are examined for the Chelungpu Fault in Taiwan, which is a seismogenic fault. The samples are collected from the cores drilled for the Taiwan Chelungpu Fault Drilling Project (TCDP, borehole B). Three fault zones are recognized as candidates for the source of seismogenic materials. The fault zones are composed of fractured-damaged rocks, breccia, gray gouge, black gouge, and black material. Chlorite from each type of rock was analyzed by using X-ray diffraction (XRD). The iron content and asymmetry of the iron and magnesium ions in the chlorites were estimated from the XRD peak ratios. The hydroxide and silicate layers of chlorite in the black gouge and black material have low iron contents. Many studies have suggested that a temperature rise occurred at the fault zones. In addition, the temperature rise can result in the production of iron oxides such as magnetite or maghemite, as reported by other studies. However, the temperature rise cannot explain the low value of iron content in the chlorites. Another reason for the low value of iron content is the variation in the pH of the fluid, which can be controlled by radical reactions. Therefore, on the basis of chlorite characteristics, the reactions at the seismogenic fault are due not only to the thermal decomposition resulting from the temperature rise and but also to rock-fluid interactions.

Description: 〈b〉Characteristics of chlorites in seismogenic fault zones: the Taiwan Chelungpu Fault Drilling Project (TCDP) core sample〈/b〉〈br〉 Y. Hashimoto, O. Tadai, M. Tanimizu, W. Tanikawa, T. Hirono, W. Lin, T. Mishima, M. Sakaguchi, W. Soh, S. R. Song, K. Aoike, T. Ishikawa, M. Murayama, K. Fujimoto, T. Fukuchi, M. Ikehara, H. Ito, H. Kikuta, M. Kinoshita, K. Masuda, T. Matsubara, O. Matsubayashi, K. Mizoguchi, N. Nakamura, K. Otsuki, T. Shimamoto, H. Sone, and M. Takahashi〈br〉 eEarth, 3, 1-6, doi:10.5194/ee-3-1-2008, 2008〈br〉 The iron content and the asymmetry of iron and magnesium ions in chlorites are examined for the Chelungpu Fault in Taiwan, which is a seismogenic fault. The samples are collected from the cores drilled for the Taiwan Chelungpu Fault Drilling Project (TCDP, borehole B). Three fault zones are recognized as candidates for the source of seismogenic materials. The fault zones are composed of fractured-damaged rocks, breccia, gray gouge, black gouge, and black material. Chlorite from each type of rock was analyzed by using X-ray diffraction (XRD). The iron content and asymmetry of the iron and magnesium ions in the chlorites were estimated from the XRD peak ratios. The hydroxide and silicate layers of chlorite in the black gouge and black material have low iron contents. Many studies have suggested that a temperature rise occurred at the fault zones. In addition, the temperature rise can result in the production of iron oxides such as magnetite or maghemite, as reported by other studies. However, the temperature rise cannot explain the low value of iron content in the chlorites. Another reason for the low value of iron content is the variation in the pH of the fluid, which can be controlled by radical reactions. Therefore, on the basis of chlorite characteristics, the reactions at the seismogenic fault are due not only to the thermal decomposition resulting from the temperature rise and but also to rock-fluid interactions.

Description: 〈b〉Geometry of the Turkey-Arabia and Africa-Arabia plate boundaries in the latest Miocene to Mid-Pliocene: the role of the Malatya-Ovacık Fault Zone in eastern Turkey〈/b〉〈br〉 R. Westaway, T. Demir, and A. Seyrek〈br〉 eEarth, 3, 27-35, doi:10.5194/ee-3-27-2008, 2008〈br〉 We suggest a working hypothesis for the geometry of the strike-slip faults that formed the boundaries between the Turkish, African and Arabian plates in the latest Miocene to Mid-Pliocene (LMMP), between ~7–6 Ma and ~3.5 Ma. This geometry differed significantly from the modern geometry; the northern Dead Sea Fault Zone (DSFZ) was located east of its present line and the TR-AR boundary was formed by the Malatya-Ovacık Fault Zone (MOFZ), located well north of the modern East Anatolian Fault Zone (EAFZ). The MOFZ is potentially the most problematic aspect of such a scheme, given the dramatically different interpretations of it that have been proposed. However, the presently-available evidence, albeit limited, is consistent with our proposed interpretation. Significant differences between the proposed LMMP fault geometry and the modern geometry include, first, the transtensional geometry of the MOFZ, the modern EAFZ being typically a left-lateral transform fault zone but with localized transpression. Second, the MOFZ slip rate was much lower than the ~9–10 mm a〈sup〉−1〈/sup〉 EAFZ slip rate; it is estimated as ~2–3 mm a〈sup〉−1〈/sup〉, having produced no more than ~8 km of slip during its approximately three million year long activity. The Euler vector is tentatively inferred to have involved relative rotation between the Turkish and Arabian Plates at ~0.85±0.15° Ma〈sup〉−1〈/sup〉 about a pole at ~37.75±0.15° N, ~38.8±0.3° E. Third, unlike at present, there was no throughgoing linkage of left-lateral faulting between the LMMP DSFZ and the MOFZ; instead, the DSFZ terminated northward, and the MOFZ terminated southward, in a zone of localised crustal shortening adjoining the suture of the former Neotethys Ocean in the Kahramanmaraş-Pazarcık region of SE Turkey. The different motion of the Turkish plate relative to Arabia, and, thus, relative to Eurasia, means that senses and rates of crustal deformation can be expected to have been different during the LMMP phase from at present, throughout the eastern Mediterranean region.

Description: 〈b〉Use of remote sensing and GIS in mapping the environmental sensitivity areas for desertification of Egyptian territory〈/b〉〈br〉 A. Gad and I. Lotfy〈br〉 eEarth Discuss., 3, 41-85, doi:10.5194/eed-3-41-2008, 2008〈br〉 〈b〉Revised manuscript has not been submitted〈/b〉 (discussion: closed, 3 comments)〈br〉 Desertification is defined in the first art of the convention to combat desertification as 〈i〉"land degradation in arid, semiarid and dry sub-humid areas resulting from climatic variations and human activities".〈/i〉 Its consequence include a set of important processes which are active in arid and semi arid environment, where water is the main limiting factor of land use performance in such ecosystem . Desertification indicators or the groups of associated indicators should be focused on a single process. They should be based on available reliable information sources, including remotely sensed images, topographic data (maps or DEM'S), climate, soils and geological data. The current work aims to map the Environmental Sensitivity Areas (ESA's) to desertification in whole territory of Egypt at a scale of 1:1 000 000. 〈br〉〈br〉 ETM satellite images, geologic and soil maps were used as main sources for calculating the index of Environmental Sensitivity Areas (ESAI) for desertification. The algorism is adopted from MEDALLUS methodology as follows; 〈br〉〈br〉 ESAI = (SQI * CQI * VQI)〈sup〉1/3〈/sup〉 〈br〉〈br〉 Where SQI is the soil quality index, CQI is the climate quality index and VQI is the vegetation quality index. The SQI is based on rating the parent material, slope, soil texture, and soil depth. The VQI is computed on bases of rating three categories (i.e. erosion protection, drought resistance and plant cover). The CQI is based on the aridity index, derived from values of annual rainfall and potential evapotranspiration. Arc-GIS 9 software was used for the computation and sensitivity maps production. 〈br〉〈br〉 The results show that the soil of the Nile Valley are characterized by a moderate SQI, however the those in the interference zone are low soil quality indexed. The dense vegetation of the valley has raised its VQI to be good, however coastal areas are average and interference zones are low. The maps of ESA's for desertification show that 86.1% of Egyptian territory is classified as very sensitive areas, while 4.3% as Moderately sensitive, and 9.6% as sensitive. 〈br〉〈br〉 It can be concluded that implementing the maps of sensitivity to desertification is rather useful in the arid and semi arid areas as they give more likely quantitative trend for frequency of sensitive areas. The integration of different factors contributing to desertification sensitivity may lead to plan a successful combating. The usage of space data and GIS proved to be suitable tools to rely estimation and to fulfill the needed large computational requirements. They are also useful in visualizing the sensitivity situation of different desertification parameters.

Description: The atmospheric chemistry general circulation model ECHAM5/MESSy1 has been extended by processes that parameterize particle precipitation. Several types of particle precipitation that directly affect NOy and HOx concentrations in the middle atmosphere are accounted for and discussed in a series of papers. In the companion paper, the ECHAM5/MESSy1 solar proton event parameterization is discussed, while in the current paper we focus on low energy electrons (LEE) that produce NOx in the upper atmosphere. For the flux of LEE NOx into the top of the model domain a novel technique which can be applied to most atmospheric chemistry general circulation models has been developed and is presented here. The technique is particularly useful for models with an upper boundary between the stratopause and mesopause and therefore cannot directly incorporate upper atmospheric NOx production. The additional NOx source parametrization is based on a measure of geomagnetic activity, the Ap index, which has been shown to be a good proxy for LEE NOx interannual variations. HALOE measurements of LEE NOx that has been transported into the stratosphere are used to develop a scaling function which yields a flux of NOx that is applied to the model top. We describe the implementation of the parameterization as the submodel SPACENOX in ECHAM5/MESSy1 and discuss the results from test simulations. The NOx enhancements and associated effects on ozone are shown to be in good agreement with independent measurements. Ap index data is available for almost one century, thus the parameterization is suitable for simulations of the recent climate.

Description: Water vapor is an important constituent of the atmosphere. Because of its abundance it plays an important role for the radiation budget of the atmosphere and has major influence on weather and climate. In this work the integrated water vapor (IWV) measurements derived from the measurements of two satellite sensors, SCIAMACHY and AMSU-B, and two ground-based sensors, a Fourier-transform spectrometer (FTIR) and an O3 microwave ozone sensor (RAM), are compared to radio-sonde measurements in Ny Ålesund, 79° N. All four remote sensors exploit different principles and work in different wavelength regions. Combined they deliver a comprehensive picture of the IWV above Ny Ålesund. The ground-based FTIR reproduces the radio-sonde measurements very well and also shows a high correlation and very little scatter of about 10%. The other remote sensing instruments show a good correlation with the coincident radio-sonde measurements but show high scatter of about 20% (standard deviation). The ground-based RAM performs similar to the satellite instruments, which is somewhat surprising, because measuring IWV is only a by-product for this sensor. The RAM sensor records a measurement every hour and is therefore suited to observe the diurnal variation. As measured by the RAM and FTIR the variance within 4 h is often in excess of 50% (minimum – maximum of the measured IWV). This large variance in the integrated water vapor renders the comparison of different sensors a difficult task. The derived variance of the instruments when compared to radio-sonde measurements can be explained by the high natural variability of IWV.

Description: This paper analyses a stratospheric injection by deep convection of biomass fire emissions over North America (Alaska, Yukon and Northwest Territories) on 24 June 2004 and its long-range transport over the eastern coast of the United States and the eastern Atlantic. The case study is done using MOZAIC observations of ozone, carbon monoxide, nitrogen oxides (NOx+PAN) and water vapour during the crossing of the southernmost tip of an upper level trough over the Eastern Atlantic on 30 June 03:00 UTC and 10:00 UTC and in a vertical profile over Washington DC on 30 June 17:00 UTC, and by lidar observations of aerosol backscattering at Madison (University of Wisconsin) on 28 June. Attribution of the plumes to the boreal fires is achieved by backward simulations with a Lagrangian particle dispersion model (FLEXPART). A simulation with the Meso-NH model for the source region shows that a boundary layer tracer, mimicking the boreal forest fire smoke, is lofted into the lowermost stratosphere (2–5 pvu layer) during the diurnal convective cycle. The isentropic levels (above 335 K) correspond to those of the downstream MOZAIC observations. The parameterized convective detrainment flux is intense enough to fill the volume of a model mesh (20 km horizontal, 500 m vertical) above the tropopause with pure boundary layer air in a time period compatible with the convective diurnal cycle, i.e. about 5 h. The maximum instantaneous detrainment fluxes deposited about 15–20% of the initial boundary layer tracer concentration at 335 K, which according to the 275-ppbv carbon monoxide maximum mixing ratio observed by MOZAIC over eastern Atlantic, would be associated with a 1.4–1.8 ppmv carbon monoxide mixing ratio in the boundary layer over the source region.

Description: Chamber studies of glyoxal uptake onto neutral ammonium sulphate aerosol were performed under dark and irradiated conditions to gain further insight into processes controlling glyoxal uptake onto ambient aerosol. Organic fragments from glyoxal dimers and trimers were observed within the aerosol under dark and irradiated conditions; glyoxal oligomer formation and overall organic growth were found to be reversible under dark conditions. Analysis of high-resolution time-of-flight aerosol mass spectra provides evidence for irreversible formation of carbon-nitrogen (C-N) compounds in the aerosol. These compounds are likely to be imidazoles formed by reaction of glyoxal with the ammonium sulphate seed. To the authors' knowledge, this is the first time C-N compounds resulting from condensed phase reactions with ammonium sulphate seed have been detected in aerosol. Organosulphates were not detected under dark conditions. However, active oxidative photochemistry, similar to that found in cloud processing, was found to occur within aerosol during irradiated experiments. Organosulphates, carboxylic acids, and organic esters were identified within the aerosol. Our study suggests that both C-N compound formation and photochemical processes should be considered in models of secondary organic aerosol formation via glyoxal.

Description: We present the first single particle results obtained using an Aerodyne time-of-flight aerosol mass spectrometer coupled with a light scattering module (LS-ToF-AMS). The instrument was deployed at the T1 ground site approximately 40 km northeast of the Mexico City Metropolitan Area (MCMA) as part of the MILAGRO field study in March of 2006. The instrument was operated as a standard AMS from 12–30 March, acquiring average chemical composition and size distributions for the ambient aerosol, and in single particle mode from 27–30 March. Over a 75-h sampling period, 12 853 single particle mass spectra were optically triggered, saved, and analyzed. The correlated optical and chemical detection allowed detailed examination of single particle collection and quantification within the LS-ToF-AMS. The single particle data enabled the mixing states of the ambient aerosol to be characterized within the context of the size-resolved ensemble chemical information. The particulate mixing states were examined as a function of sampling time and most of the particles were found to be internal mixtures containing many of the organic and inorganic species identified in the ensemble analysis. The single particle mass spectra were deconvolved, using techniques developed for ensemble AMS data analysis, into HOA, OOA, NH4NO3, (NH4)2SO4, and NH4Cl fractions. Average single particle mass and chemistry measurements are shown to be in agreement with ensemble MS and PTOF measurements. While a significant fraction of ambient particles were internal mixtures of varying degrees, single particle measurements of chemical composition allowed the identification of time periods during which the ambient ensemble was externally mixed. In some cases the chemical composition of the particles suggested a likely source. Throughout the full sampling period, the ambient ensemble was an external mixture of combustion-generated HOA particles from local sources (e.g. traffic), with number concentrations peaking during morning rush hour (04:00–08:00 LT) each day, and more processed particles of mixed composition from nonspecific sources. From 09:00–12:00 LT all particles within the ambient ensemble, including the locally produced HOA particles, became coated with NH4NO3 due to photochemical production of HNO3. The number concentration of externally mixed HOA particles remained low during daylight hours. Throughout the afternoon the OOA component dominated the organic fraction of the single particles, likely due to secondary organic aerosol formation and condensation. Single particle mass fractions of (NH4)2SO4 were lowest during the day and highest during the night. In one instance, gas-to-particle condensation of (NH4)2SO4 was observed on all measured particles within a strong SO2 plume arriving at T1 from the northwest. Particles with high NH4Cl mass fractions were identified during early morning periods. A limited number of particles (~5% of the total number) with mass spectral features characteristic of biomass burning were also identified.

Description: The seasonality of transport and mixing of air into the lowermost stratosphere (LMS) is studied using distributions of mean age of air and a~mass balance approach, based on in-situ observations of SF6 and CO2 during the SPURT (Spurenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region) aircraft campaigns. Combining the information of the mean age of air and the water vapour distributions we demonstrate that the tropospheric air transported into the LMS above the extratropical tropopause layer (ExTL) originates predominantly from the tropical tropopause layer (TTL). The concept of our mass balance is based on simultaneous measurements of the two passive tracers and the assumption that transport into the LMS can be described by age spectra which are superposition of two different modes. Based on this concept we conclude that the stratospheric influence on LMS composition is strongest in April with tropospheric fractions (α1) below 20% and that the strongest tropospheric signatures are found in October with (α1 greater than 80%. Beyond the fractions, our mass balance concept allows to calculate the associated transit times for transport of tropospheric air from the tropics into the LMS. The shortest transit times (

Description: Field and lab measurements suggest that low-molecular weight (MW) organic acids and bases exist in accumulation and nucleation mode particles, despite their relatively high pure-liquid vapor pressures. The mechanism(s) by which such compounds contribute to the mass growth of existing aerosol particles and newly formed particles has not been thoroughly explored. One mechanism by which low-MW compounds may contribute to new particle growth is through the formation of organic salts. In this paper we use thermodynamic modeling to explore the potential for organic salt formation by atmospherically relevant organic acids and bases for two system types: one in which the relative contribution of ammonia vs. amines in forming organic salts was evaluated, the other in which the decrease in volatility of organic acids and bases due to organic salt formation was assessed. The modeling approach employed relied heavily on group contribution and other estimation methods for necessary physical and chemical parameters. The results of this work suggest that amines may be an important contributor to organic salt formation, and that experimental data are greatly needed to improve our understanding of organic salt formation in atmospherically relevant systems and to accurately predict the potential contribution of such salts to new particle growth.

Description: An Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed at the peak of Whistler Mountain (elevation 2182 m-MSL), British Columbia, from 19 April to 16 May 2006, as part of the Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign. The mass concentrations and size distributions of non-refractory submicron particle (NR-PM1) species (i.e., sulfate, nitrate, ammonium, chloride, and organics) were measured in situ every 5 min. The HR-ToF-AMS results agreed well with collocated measurements. The average concentration of non-refractory submicron particulate matter (NR-PM1; 1.9 μg m−3) is similar to those observed at other remote, high elevation sites in North America. Episodes of enhanced aerosol loadings were observed, due to influences of regional and trans-Pacific transport of air pollution. Organics and sulfate were the dominant species, on average accounting for 55% and 30%, respectively, of the NR-PM1 mass. The average size distributions of sulfate and ammonium both showed a~large accumulation mode peaking around 500–600 nm in Dva while those of organic aerosol (OA) and nitrate peaked at ~300 nm. The size differences suggest that sulfate and OA were mostly present in external mixtures from different source origins. We also quantitatively determined the elemental composition of OA using the high resolution mass spectra. Overall, OA at Whistler Peak was highly oxygenated, with an average organic-mass-to-organic-carbon ratio (OM/OC) of 2.28±0.23 and an atomic ratio of oxygen-to-carbon (O/C) of 0.83±0.17. The nominal formula for OA was C1H1.66N0.03O0.83 for the entire study. Two significant trans-Pacific dust events originated from Asia were observed at Whistler Peak during this study. While both events were characterized with significant enhancements of coarse mode particles and mineral contents, the composition and characteristics of NR-PM1 were significantly different between them. One trans-Pacific event occurred on 15 May 2006, during which ammonium sulfate contributed 〉90% of the total NR-PM1 mass. This event was followed by a~high OA episode likely associated with regional emissions. The trans-Pacific OA were more oxidized and aged than the regional OA.

Description: We examine the hygroscopic properties of secondary organic aerosol particles generated through the reaction of alpha-pinene and ozone using a continuous flow reaction chamber. The water activity versus composition relationship is calculated from measurements of growth factors at relative humidities up to 99.6% and from measurements of cloud condensation nuclei activity. The observed relationships are complex, suggesting highly non-ideal behavior for aerosol water contents at relative humidities less than 98%. We present two models that may explain the observed water activity-composition relationship equally well. The first model assumes that the aerosol is a pseudo binary mixture of infinitely water soluble compounds and sparingly soluble compounds that gradually enter the solution as dilution increases. The second model is used to compute the Gibbs free energy of the aerosol-water mixture and shows that the aerosol behaves similarly to what can be expected for single compounds that contain a certain fraction of oxygenated and non-polar functional groups.

Description: In spite of the strict EU regulations, concentrations of surface ozone and PM10 often exceed the pollution standards for The Netherlands and Europe. Their concentrations are controlled by (precursor) emissions, social and economic developments and a complex combination of meteorological actors. This study tackles the latter, and provides insight in the meteorological processes that play a role in O3 and PM10 levels in Cabauw (The Netherlands). The relations between meteorological actors and air quality are studied on a~local scale based on observations from Cabauw and are determined by a comprehensive correlation analysis and a multiple regression (MLR) analysis in 2 modes, with and without air quality variables as predictors. Furthermore, the objective Lamb Weather Type (WT) approach based on ECMWF (European Center for Medium-range Weather Forecasting) operational data is used to assess the influence of the large-scale circulation on air quality. Keeping in mind its future use in downscaling future climate scenarios for air quality purposes, special emphasis is given to an appropriate selection of the regressor variables readily available from operational meteorological forecasts or OAGCMs (Ocean-Atmosphere coupled General Circulation Models). The regression models perform satisfactory for both O3 and PM10, with an increased performance when including previous days air quality information. The lamb weather types show a seasonal distinct pattern for high (low) episodes of average O3 and PM10 concentrations, and these are clear related with the meteorology-air quality correlation analysis. Although using a circulation type approach can bring some interesting physical relations forward, our analysis reveals the circulation method is limited in terms of short-term air quality forecast for both O3 and PM10. In summary, it is concluded that the use of a regression model is more promising for short-term downscaling from climate scenarios than the use of a weather type classification approach.

Description: We present global distributions of carbon monoxide (CO) from the upper troposphere to the mesosphere observed by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat. Vertically resolved volume mixing ratio profiles have been retrieved from 4.7 μm limb emission spectra under consideration of non-local thermodynamic equilibrium. The precision of individual CO profiles is typically 5–30 ppbv (15–40%). Estimated systematic errors are in the order of 8–15%. Below 60 km, the vertical resolution is 4–7 km. The data set which covers 54 days from September 2003 to March 2004 has been derived with an improved retrieval version including (i) the retrieval of log(vmr), (ii) the consideration of illumination-dependent vibrational population gradients along the instrument's line of sight, and (iii) joint-fitted vmr horizontal gradients in latitudinal and longitudinal directions. A detailed analysis of spatially resolved CO distributions during the 2003/2004 Northern Hemisphere major warming event demonstrate the potential of MIPAS CO observations to obtain new information on transport processes during dynamical active episodes, particularly on those acting in the vertical. From the temporal evolution of zonally averaged CO abundances, we derived extraordinary polar winter descent velocities of 1200 m per day inside the recovered polar vortex in January 2004. Middle stratospheric CO abundances show a well established correlation with the chemical source CH4, particularly in the tropics. In the upper troposphere, a~moderate CO decrease from September 2003 to March 2004 was observed. Upper tropospheric CO observations provide a detailed picture of long-range transport of polluted air masses and uplift events. MIPAS observations taken on 9–11 September 2003 confirm the trapping of convective outflow of polluted CO-rich air from Southeast Asia into the Asian monsoon anticyclone, which has been described in previous studies. Upper tropospheric CO plumes, observed by MIPAS on this day, were predominantly located in the Northern Hemisphere. Most of these plumes could be related to Southeast Asian pollution by means of backward trajectory calculations. During 20–22 October, southern hemispheric biomass burning was the most likely source of the major CO plumes observed over the Southern Atlantic and Indian Ocean.

Description: We undertook three-dimensional numerical studies of a marine stratus deck under a strong inversion using an interactive shortwave- and longwave-radiation module. A suite of sensitivity tests were conducted to address the effects of model resolution on entrainment (inversion heights), cloud-radiation interactions, and cloud radiative-forcings by varying model horizontal resolution only, varying vertical resolution only, and varying horizontal- and vertical-resolution simultaneously but with a fixed aspect ratio of 2.5. Our results showed that entrainment (inversion height) is more sensitive to vertical- than to horizontal-resolution. A vertical resolution finer than 40 m can simulate spatial- and temporal-variations in the inversion height well. The inversion height decreases with increasing vertical resolution, but tends to increase with increasing horizontal resolution. Cloud liquid water path doubles after refining both the vertical- and horizontal-resolution by a factor of four. This doubling is associated with a positive feedback between cloud water and cloud top radiative cooling, which amplifies small differences initiated by changes in the model resolution. The magnitude of the cloud radiative-forcing tends to increase with increasing model resolution, mainly attributable to the increase in the cloud liquid water path. Shortwave radiative forcing is dominant, and more sensitive to model resolution than the longwave counterpart.

Description: Since aerosols act as cloud condensation nuclei (CCN) for cloud water droplets, changes in aerosol concentrations having significant impacts on the corresponding cloud properties. An increase in aerosol concentration leads to an increase in CCN, with an associated decrease in cloud droplet size for a given cloud liquid water content. Smaller droplet sizes may then lead to a reduction in precipitation efficiency and an increase in cloud lifetimes, which induces more reflection of solar radiation back into space, cooling the atmosphere below the cloud layer. In reality, this relationship is much more complex and is interrelated between aerosol, cloud, and atmospheric conditions present at any one time. MODIS aerosol and cloud properties are combined with NCEP Reanalysis data for eight different regions around the globe between March 2000 and December 2005 to study the effects of different aerosol, cloud, and atmospheric conditions on the aerosol indirect effect (AIE). The first AIE for both anthropogenic and dust aerosols is calculated so that the importance of each can be compared. The unique aspect of this research is that it combines multiple satellite data sets over a six year period to provide a comprehensive analysis of indirect effects for different aerosol regimes around the globe. Results show that in most regions, AIE has a distinct seasonal cycle, though the cycle varies in significance and period from region to region. In the Arabian Sea, the six-year mean anthropogenic + dust AIE is −0.4 Wm−2 and is greatest during the summer months (

Description: Mechanisms controlling surface ozone (O3) over East Asia are examined using the regional Community Multiscale Air Quality (CMAQ) model at two horizontal scales: 81 km and 27 km. Through sensitivity studies and comparison with recently available satellite data and surface measurements in China and Japan, we find that the O3 budget over East Asia shows complex interactions among photochemical production, regional transport, meteorological conditions, burning of agricultural residues, and global inflows. For example, wintertime surface O3 over northern domain is sensitive to boundary conditions derived from the MOZART (Model for Ozone and Related Tracers) global model, whereas summertime O3 budget is controlled by the competitive processes between photochemical production and monsoonal intrusion of low-O3 marine air masses from tropical Pacific. We find that simulated surface O3 for 2001 does not exhibit the same sharp drop in July and August concentrations that is observed at two mountaintop sites (Tai and Hua) for 2004 and Beijing for 1995–2005. CMAQ sensitivity tests with two widely used photochemical schemes demonstrate that over the industrial areas in East Asia north of 30° N, SAPRC99 produces higher values of mean summertime O3 than CBIV, amounting to a difference of 10 ppb. In addition, analysis of NCEP winds and geopotential heights suggests that southwesterly monsoonal intrusion in central east China is weakened in August 2001 as compared with the climatologically mean for 1980–2005. Further examination of the O3 diurnal cycle at nine Japanese sites shows that boundary layer evolution has an important effect on the vertical mixing of ground-level O3, and error in near surface meteorology might contribute to overprediction of nighttime O3 in urban and rural areas. In conclusion, the uncertainties in simulating cloud activities and convection mixing, Asian monsoon circulation, photochemical production, and nighttime cooling explain why CMAQ with 81 km horizontal scale overpredicts the observed surface O3 in July and August over central east China and central Japan by 5–15 ppb (CBIV) and 15–25 ppb (SAPRC99). The results suggest clear benefits in evaluating atmospheric chemistry over Asia with high resolution regional model.

Description: A new technique is described for the analysis of cloud-resolving model simulations, which allows one to investigate the statistics of the lifecycles of cumulus clouds. Clouds are tracked from timestep-to-timestep within the model run. This allows for a very simple method of tracking, but one which is both comprehensive and robust. An approach for handling cloud splits and mergers is described which allows clouds with simple and complicated time histories to be compared within a single framework. This is found to be important for the analysis of an idealized simulation of radiative-convective equilibrium, in which the moist, buoyant, updrafts (i.e., the convective cores) were tracked. Around half of all such cores were subject to splits and mergers during their lifecycles. For cores without any such events, the average lifetime is 30 min, but events can lengthen the typical lifetime considerably.

Description: We measured the size distribution of atmospheric neutral and charged clusters and particles down to mobility diameter around 1.5 nm by applying pulse-height CPC technique at SMEAR II station in Hyytiälä, southern Finland during spring 2007 and May 2008. The concentration of molecular clusters smaller than 3 nm seems to be highly variable in boreal forest environment. The concentration varied typically between 500–50 000 cm−3, the medians being 8060 cm−3 in year 2007 and 3380 cm−3 in 2008. By comparing to concentrations measured with ion spectrometers, we conclude that ion clusters and neutral clusters produced by ion-ion recombination are usually not sufficient to explain all of the observed clusters; the median fraction of recombination products from all neutral clusters was 4.9%. Before and during most new particle formation events the cluster formation rate rose only slightly, or remained close to stable. Nocturnal formation of clusters was also frequently observed.

Description: Simulations of future tropospheric composition often include substantial increases in biogenic isoprene emissions arising from the Arrhenius-like leaf emission response and warmer surface temperatures, and from enhanced vegetation productivity in response to temperature and atmospheric CO2 concentration. However, a number of recent laboratory and field data have suggested a direct inhibition of leaf isoprene production by increasing atmospheric CO2 concentration, notwithstanding isoprene being produced from precursor molecules that include some of the primary products of carbon assimilation. The cellular mechanism that underlies the decoupling of leaf photosynthesis and isoprene production still awaits a full explanation but accounting for this observation in a dynamic vegetation model that contains a semi-mechanistic treatment of isoprene emissions has been shown to change future global isoprene emission estimates notably. Here we use these estimates in conjunction with a chemistry-climate model to compare the effects of isoprene simulations without and with a direct CO2-inhibition on late 21st century O3 and OH levels. The impact on surface O3 was significant. Including the CO2-inhibition of isoprene resulted in opposing responses in polluted (O3 decreases of up to 10 ppbv) vs. less polluted (O3 increases of up to 10 ppbv) source regions, due to isoprene nitrate and peroxy acetyl nitrate (PAN) chemistry. OH concentration increased with relatively lower future isoprene emissions, decreasing methane lifetime by ~7 months. Our simulations underline the large uncertainties in future chemistry and climate studies due to biogenic emission patterns and emphasize the problems of using globally averaged climate metrics to quantify the atmospheric impact of reactive, heterogeneously distributed substances.

Description: The first measurements of stratospheric bromine nitrate (BrONO2) are reported. Bromine nitrate has been clearly identified in atmospheric infrared emission spectra recorded with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the European Envisat satellite, and stratospheric concentration profiles have been determined for different conditions (day and night, different latitudes). The BrONO2 concentrations show strong day/night variations, with much lower concentrations during the day. Maximum volume mixing ratios observed during night are 20 to 25 pptv. The observed concentration profiles are in agreement with estimations from photochemical models and show that the current understanding of stratospheric bromine chemistry is generally correct.

Description: Boreal spring climate is uniquely susceptible to solar warming mechanisms because it has expansive snow cover and receives relatively strong insolation. Carbonaceous particles can influence snow coverage by warming the atmosphere, reducing surface-incident solar energy (dimming), and reducing snow reflectance after deposition (darkening). We apply a range of models and observations to explore impacts of these processes on springtime climate, drawing several conclusions: 1) Nearly all atmospheric particles (those with visible-band single-scatter albedo less than 0.999), including all mixtures of black carbon (BC) and organic matter (OM), increase net solar heating of the atmosphere-snow column. 2) Darkening caused by small concentrations of particles within snow exceeds the loss of absorbed energy from concurrent dimming, thus increasing solar heating of snowpack as well (positive net surface forcing). Over global snow, we estimate 6-fold greater surface forcing from darkening than dimming, caused by BC+OM. 3) Equilibrium climate experiments suggest that fossil fuel and biofuel emissions of BC+OM induce 95% as much springtime snow cover loss over Eurasia as anthropogenic carbon dioxide, a consequence of strong snow-albedo feedback and large BC+OM emissions from Asia. 4) Of 22 climate models contributing to the IPCC Fourth Assessment Report, 21 underpredict the rapid warming (0.64°C decade−1) observed over springtime Eurasia since 1979. Darkening from natural and anthropogenic sources of BC and mineral dust exerts 3-fold greater forcing on springtime snow over Eurasia (3.9 W m−2) than North America (1.2 W m−2). Inclusion of this forcing significantly improves simulated continental warming trends, but does not reconcile the low bias in rate of Eurasian spring snow cover decline exhibited by all models.

Description: We have developed an ensemble Kalman Filter (EnKF) to estimate 8-day regional surface fluxes of CO2 from space-borne CO2 dry-air mole fraction observations (XCO2

Description: There is currently a need of reliable experimental procedure to follow the heterogeneous processing simulating the atmospheric conditions. This work offers a new experimental approach to study the reactivity and the behaviour of SVOC associated with atmospheric particles. The heterogeneous ozonolysis of naphthalene adsorbed on silica and XAD-4 particles is investigated in specially designed flow tube reactors. The experimental procedure consists in adsorbing gaseous naphthalene on particles before exposing it to ozone. By this novel approach the kinetics is determined following the consumption of naphthalene. Using this procedure, the rate constant kO3 of naphthalene is equal to (2.26±0.09)×10−17cm3.molec−1.s−1 and (4.31±1.07)×10−19cm3.molec−1.s−1 at 25°C for silica and XAD-4, respectively. The results show both that nature of the particles significantly affects the kinetics and that heterogeneous ozonolysis of naphthalene is faster than in the gaseous phase.

Description: Formaldehyde (HCHO) is an important intermediate compound in the degradation of volatile organic compounds (VOCs) in the troposphere. Sources of HCHO are largely dominated by its secondary production from VOC oxidation, methane and isoprene being the main precursors in unpolluted areas. As a result of the moderate lifetime of HCHO, its spatial distribution is determined by reactive hydrocarbon emissions. We focus here on Europe, never studied before, and investigate the influence of the different emissions on HCHO tropospheric columns with the CHIMERE chemical transport model in order to interpret the comparisons between SCIAMACHY and simulated HCHO columns. Observed columns present a bias less than 20% on average. The differences are discussed according to the errors on the model and the observations and the remaining discrepancies are attributed to a misrepresentation of biogenic emissions. This study requires the characterisation of: (1) the model errors and performances concerning formaldehyde. The errors on the HCHO columns, mainly related to chemistry and mixed emission types, are evaluated to 2×1015 molecule/cm2 and the model performances evaluated using surface measurements are satisfactory (~13%); (2) the observation errors that define the needs in spatial and temporal averaging for meaningful comparisons. Perspectives of using SCIAMACHY observations as constraint for biogenic isoprene emissions with an adapted averaging are approached: this new constraint should help to reduce their uncertainties more than 50% in region of intense emissions.

Description: For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (13C and 18O) abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the δ18O signature of CO2 from combustion processes, which are widely present both naturally (wild fires), and human induced (fossil fuel combustion, biomass burning) in the carbon cycle. All these combustion processes use atmospheric oxygen, of which the isotopic signature is assumed to be constant with time throughout the whole atmosphere. The combustion is generally presumed to take place at high temperatures, thus minimizing isotopic fractionation. Therefore it is generally supposed that the 18O signature of the produced CO2 is equal to that of the atmospheric oxygen. This study, however, reveals that the situation is much more complicated and that important fractionation effects do occur. From laboratory studies fractionation effects in the order of about 26‰ became obvious, a clear differentiation of about 7‰ was also found in car exhausts which were sampled directly under ambient atmospheric conditions. We investigated a wide range of materials (both different raw materials and similar materials with different inherent 18O signature), sample geometries (e.g. texture and surface-volume ratios) and combustion circumstances. We found that the main factor influencing the specific isotopic signatures of the combustion-derived CO2 and of the concomitantly released oxygen-containing side products, is the case-specific rate of combustion. This points firmly into the direction of (diffusive) transport of oxygen to the reaction zone as the cause of the isotope fractionation. The original 18O signature of the material appeared to have little or no influence.

Description: We present vertical profiles of the aerosol extinction coefficient retrieved from ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements at Tsukuba, Japan (36.1° N, 140.1° E), from November 2006 to March 2007. Retrievals utilizing absorption by the oxygen collision complex O4 are first made at two wavelengths, 354 and 476 nm. A robust assessment of the MAX-DOAS aerosol data is made using coincident lidar measurements throughout the period. Agreement between aerosol extinction coefficients measured by MAX-DOAS and the lidar tends to be better at the longer wavelength and at lower altitudes. At 476 nm, the best agreement, to within 30%, is found at altitudes of 0–1 km, confirming results from a literature assessment for a two-month measurement period. These findings are supported by comparisons of the aerosol optical depth by MAX-DOAS and sky radiometer measurements and are further explained by differences in the O4 absorption and the air mass factor profile between 354 and 476 nm. Thus, uncertainty in MAX-DOAS aerosol measurements is well quantified and characterized, providing a basis for quantitative studies using MAX-DOAS measurements.

Description: The pre-industrial and present day distributions and burdens of Secondary Organic Aerosol (SOA) have been calculated using the off-line aerosol chemistry transport model Oslo CTM2. The production of SOA was found to have increased from about 43 Tg yr−1 to 69 Tg yr−1 since pre-industrial times, leading to an increase in the global annual mean SOA burden from 0.44 Tg to 0.70 Tg, or about 59%. The increases are greatest over industrialised areas, as well as over regions with high biogenic precursor emissions. The contribution of emissions from different sources to the larger SOA burdens has been calculated. The results suggest that the majority of the increase is caused by emissions of primary organic aerosols (POA), from fossil fuel and bio fuel combustion. When SOA partitioning to ammonium sulphate aerosol was not accounted for, the increase in SOA burden between pre-industrial times and the present was found to be lower (51%), with a production increase of 55%. As yet, very few radiative forcing estimates of SOA exist, and no such estimates were provided in the latest IPCC report. In this study, we find that the change in SOA burden caused a radiative forcing of −0.09 W m−2, when SOA was allowed to partition to both organic and sulphate aerosols, and −0.06 W m−2 when only partitioning to organic aerosols was assumed. Therefore, the radiative forcing of SOA is found to be substantially stronger than the best estimate for POA in the latest IPCC assessment.

Description: An inverse model using atmospheric CO2 observations from a European network of stations to reconstruct daily CO2 fluxes and their uncertainties over Europe at 50 km resolution has been developed within a Bayesian framework. We use the pseudo-data or identical twin approach in which we try to recover known fluxes using a range of perturbations to the input. In this second part, the focus is put on the sensitivity of flux accuracy to the inverse setup, varying the prior flux errors, the pseudo-data errors and the network of stations. We show that, under a range of assumptions about prior error and data error we can recover fluxes reliably at the scale of 1000 km and 10 days. At smaller scales the performance is highly sensitive to details of the inverse set-up. The use of temporal correlations in the flux domain appears to be of the same importance as the spatial correlations. We also note that the use of simple, isotropic correlations on the prior flux errors is more reliable than the use of apparently physically-based errors. Finally, increasing the European atmospheric network density improves the area with significant error reduction in the flux retrieval.

Description: A mineral dust module is developed and implemented into the global aerosol microphysics model, GISS-TOMAS. The model is evaluated against long-term measurements of dust surface mass concentrations and deposition fluxes. Predicted mass concentrations and deposition fluxes are in error on average by a factor of 3 and 5, respectively. The comparison shows that the model performs better near the dust source regions but underestimates surface concentrations and deposition fluxes in more remote regions. For example, including only sites with measured dust concentrations of at least 0.5 μg m−3, the model prediction agrees with observations to within a factor of 2. It was hypothesized that the lifetime of dust, 2.6 days in our base case, is too short and causes the underestimation in remote areas. However, a sensitivity simulation with smaller dust particles and increased lifetime, 3.7 days, does not significantly improve the comparison. We conclude that the underestimation of mineral dust in remote areas results from local factors and sources not well described by the dust source function and/or the GCM meteorology. The effect of dust aerosols on CCN(0.2%) concentrations is negligible in most regions of the globe; however, CCN(0.2%) concentrations decrease by 10–20% in dusty regions as a result of coagulational scavenging of CCN particles by dust and a decrease in H2SO4 condensation to CCN particles due to the additional surface area of dust.

Description: Multi-platform and multi-sensor observations are employed to investigate the impact of mineral dust on cloud microphysical and precipitation processes in mesoscale convective systems. It is clearly evident that for a given convection strength,small hydrometeors were more prevalent in the stratiform rain regions with dust than in those regions that were dust free. Evidence of abundant cloud ice particles in the dust sector, particularly at altitudes where heterogeneous nucleation process of mineral dust prevails, further supports the observed changes of precipitation. The consequences of the microphysical effects of the dust aerosols were to shift the precipitation size spectrum from heavy precipitation to light precipitation and ultimately suppressing precipitation.

Description: Night-time ozone deposition for a Scots pine forest in Southern Finland was studied at the SMEAR II measurement station by evaluating the turbulent eddy covariance (EC), storage change and vertical advection fluxes. Similarly to night-time carbon dioxide flux, the eddy-covariance flux of ozone was decreasing with turbulence intensity (friction velocity), and storage change of the compound did not compensate the reduction (well-known night-time measurement problem). Accounting for vertical advection resulted in invariance of ozone deposition rate on turbulence intensity. This was also demonstrated for carbon dioxide, verified by independent measurements of NEE by chamber systems. The result highlights the importance of advection when considering the exchange measurements of any scalar. Analysis of aerodynamic and laminar boundary layer resistances by the model approach indicated that the surface resistance and/or chemical sink strength was limiting ozone deposition. The possible aerial ozone sink by known fast chemical reactions with sesquiterpenes and NO explain only a minor fraction of ozone sink. Thus the deposition is controlled either by stomatal uptake or surface reactions or both of them, the mechanisms not affected by turbulence intensity. Therefore invariance of deposition flux on turbulence intensity is expected also from resistance and chemical sink analysis.

Description: To estimate the impact of emissions by road, aircraft and ship traffic on ozone and OH of the present-day atmosphere seven different atmospheric chemistry models simulated the atmospheric composition of the year 2003. Based on newly developed global emission inventories for road, maritime and aircraft emission data sets each model performed a series of five simulations: A base scenario using the full set of emissions, three sensitivity studies with each individual sector of transport reduced by 5% and one simulation with all traffic related emissions reduced by 5%. The approach minimizes non-linearities in atmospheric chemical effects and are later scaled to 100%. The global annual mean impact of ship emissions on ozone in the boundary layer leads to an increase of ozone of 1.2%, followed by road (0.87%) and aircraft emissions (0.3%). In the upper troposphere between 200–300 hPa both road and ship traffic affect ozone by 1.1%, whereas aircraft emissions contribute 0.9%. However, the sensitivity of ozone formation per NOx molecule emitted is highest for aircraft exhausts. The local maximum effect of the summed traffic emissions on the ozone column predicted by the models is 4.0 DU and occurs over the northern subtropical Atlantic. The impact of traffic emissions on total ozone in the Southern Hemisphere is approximately half of the northern hemispheric perturbation. Below 800 hPa both ozone and OH respond most sensitively to ship emissions in the marine boundary layer over the Atlantic, where the effect can exceed 10% (zonal mean) which is 80% of the total traffic induced ozone perturbation. In the Southern Hemisphere ship emissions contribute relatively strongly to the total ozone perturbation by 60%–80% throughout the year (equivalent to 1–1.5 ppbv). Road emissions have the strongest impact on ozone in the continental boundary layer and the free troposphere in summer. They also affect the upper troposphere particularly during northern summer associated with strong convection in mid latitudes. Ozone perturbations due to road traffic show the strongest seasonal cycle in the northern troposphere, and can even change sign in the continental boundary layer during winter. The OH concentration in the boundary layer is most strongly affected by ship emissions, which has a significant influence on the lifetime of many trace gases including methane. Methane lifetime changes due to ship emissions amount to 4.1%, followed by road (1.6%) and air traffic (1.0%).

Description: An inverse model using atmospheric CO2 observations from a European network of stations to reconstruct daily CO2 fluxes and their uncertainties over Europe at 50 km resolution has been developed within a Bayesian framework. In this first part, a pseudo-data experiment is performed to assess the potential of continuous measurements over Europe using a network of 10 stations such as in 2001. Under the assumptions of a small observation noise and a perfect atmospheric transport model, the reconstruction of daily CO2 fluxes and in particular of their synoptic variability is best over Western Europe where the network is the densest. At least a 10 days temporal and a 1000 km spatial averaging of the inverted daily/50 km fluxes is required in order to obtain a good agreement between the estimated and the "true" fluxes in terms of correlation and variability. The performances of the inversion system rapidly degrade when fluxes are sought for a smaller temporal or spatial averaging.

Description: Binary heterogeneous nucleation of water-succinic/glutaric/malonic/adipic acid on nanometer-sized particles is investigated within the frame of classical heterogeneous nucleation theory. Homogeneous nucleation is also included for comparison. It is found that the nucleation probabilities depend on the contact angle and on the size of the seed particles. New thermodynamical properties, such as saturation vapor pressure, density and surface tension for all the dicarboxylic acid aqueous solutions are included in the calculations. While the new surface tension and density formulations do not bring any significant difference in the computed nucleation rate for homogeneous nucleation for succinic and glutaric acids, the use of the newly derived equations for the vapor pressure decrease the acid concentrations in gas phase with 3 orders of magnitude. According to our calculations, the binary heterogeneous nucleation of succinic acid-water and glutaric acid-water – although it requires a 3–4 orders of magnitude lower vapor concentrations than the homogeneous nucleation – cannot take place in atmospheric conditions. On the other hand binary homogeneous nucleation of adipic acid-water systems might be possible in conditions occuring in upper boundary layer. However, a more detailed characterization of the interaction between the surface and the molecules of the nucleating vapor should be considered in the future.

Description: Detrended fluctuation analysis is applied to the time series of the global tropopause height derived from the 1980–2004 daily radiosonde data, in order to detect long-range correlations in its time evolution. Global tropopause height fluctuations in small time-intervals are found to be positively correlated to those in larger time intervals in a power-law fashion. The exponent of this dependence is larger in the tropics than in the middle and high latitudes in both hemispheres. Greater persistence is observed in the tropopause of the Northern than in the Southern Hemisphere. This finding for the tropopause height variability should reduce the existing uncertainties in assessing the climatic characteristics.

Description: We conducted measurements of Hg° and RGM at two inland sites, Thompson Farm (TF) and Pac Monadnock (PM), and a marine site (Appledore Island – AI) from the UNH AIRMAP observing network in New Hampshire in 2007. Measurements of other important trace gases and meteorological variables were used to help understand influences on the atmospheric Hg budget in New England. Seasonal variation in both species observed at TF and PM is attributable to such factors as seasonal variation in deposition strength, meteorological conditions and biogenic emissions. Hg° and RGM varied diurnally at TF, particularly in spring, following the trend in air temperature and jNO2 and suggesting photochemical production of RGM. The diurnal patterns of Hg° and RGM at AI during summer were nearly opposite in phase, with Hg° decreasing through late afternoon, suggesting more significant photochemical oxidation of Hg° to RGM in the marine environment, likely due to the presence of marine halogen compounds. A strong relationship of RGM with SO2 at TF suggests a strong contribution of RGM from anthropogenic sources. Significant levels of halogen compounds measured at TF in previous studies, as well as similar Hg° levels and Hg°-CO ratios at TF and AI may suggest that similar air masses are prevalent at these sites.

Description: In this study, we analyse the sensitivity of nadir viewing satellite observations in the visible range to freshly produced lightning NOx, i.e. for meteorological and (photo-) chemical conditions found in and around cumulonimbus clouds. For the first time, such a study is performed accounting for photo-chemistry, dynamics, and radiative transfer in a consistent way: A one week episode in the TOGA COARE/CEPEX region (Pacific) in December 1992 is simulated with a 3-D cloud resolving chemistry model. The simulated hydrometeor mixing ratios are fed into a Monte Carlo radiative transfer model to calculate box-Air Mass Factors (box-AMFs) for NO2. From these box-AMFs, together with model NOx profiles, slant columns of NO2 (SNO2), i.e. synthetic satellite measurements, are calculated and set in relation to the actual model NOx vertical column (VNOx), yielding the "sensitivity" SNO2/VNOx. From this study, we find a mean sensitivity of 0.46. NOx below the cloud bottom is mostly present as NO2, but shielded from the satellites' view, whereas NOx at the cloud top or above is shifted to NO due to high photolysis and low temperature, and hence not detectable from space. But a significant fraction of the lightning produced NOx in the middle part of the cloud is present as NO2 and has a good visibility from space. Due to the resulting total sensitivity being quite high, nadir viewing satellites provide a valuable additional platform to quantify NOx production by lightning; strong lightning events over "clean" regions should be clearly detectable in satellite observations. Since the observed enhancement of NO2 column densities over mesoscale convective systems are lower than expected for current estimates of NOx production per flash, satellite measurements can in particular constrain the upper bound of lightning NOx production estimates.

Description: The yields of organic nitrates and of secondary organic aerosol (SOA) particle formation were measured for the reaction NO3+β-pinene under dry and humid conditions in the atmosphere simulation chamber SAPHIR at Research Center Jülich. These experiments were conducted at low concentrations of NO3 (NO3+N2O5

Description: Ice crystals, also known as diamond dust, are suspended in the boundary layer air under clear sky conditions during most of the Arctic winter in Northern Canada. Occasionally ice crystal events can produce significantly thick layers with optical depths in excess of 2.0 even in the absence of liquid water clouds. Four case studies of high optical depth ice crystal events at Eureka in the Nunavut Territory of Canada during the winter of 2006–2007 are presented. They show that the measured ice crystal surface infrared downward radiative forcing ranged from 8 to 36 W m−2 in the wavelength band from 5.6 to 20 μm for visible optical depths ranging from 0.2 to 1.7. MODIS infrared and visible images and the operational radiosonde wind profile were used to show that these high optical depth events were caused by surface snow being blown off 600 to 800 m high mountain ridges about 20 to 30 km North-West of Eureka and advected by the winds towards Eureka as they settled towards the ground within the highly stable boundary layer. This work presents the first study that demonstrates the important role that surrounding topography plays in determining the occurrence of high optical depth ice crystal events and points to a new source of boundary layer ice crystal events distinct from the classical diamond dust phenomenon.

Description: Recently it was discovered that over the Middle East during summer ozone mixing ratios can reach a pronounced maximum in the middle troposphere. Here we extend the analysis to the surface and show that especially in the Persian Gulf region conditions are highly favorable for ozone air pollution. Model results indicate that the region is a hot spot of photo-smog where air quality standards are violated throughout the year. Long-distance transports of air pollution from Europe, the Middle East, natural emissions and stratospheric ozone conspire to bring about high background ozone mixing ratios. This provides a hotbed to indigenous air pollution in the dry local weather conditions, which are likely to get worse in future.

Description: This study examined the estimation accuracy of NOx emissions over East Asia with particular focus on North China and South Korea due to their strong source (North China)-receptor (South Korea) relationship. In order to determine contributions of North China emissions to South Korean air quality accurately, it is important to examine the accuracy of the emission inventories of both regions. In this study, NO2 columns from the US EPA Models-3/CMAQ model simulations carried out using the 2001 ACE-ASIA (Asia Pacific Regional Aerosol Characterization Experiment) emission inventory over East Asia were compared with the GOME-derived NO2 columns. There were large discrepancies between the CMAQ-predicted and GOME-derived NO2 columns in the fall and winter seasons. In particular, while the CMAQ-predicted NO2 columns produced larger values than the GOME-derived NO2 columns over South Korea (receptor region) for all four seasons, the CMAQ-predicted NO2 columns produced smaller values than the GOME-derived NO2 columns over North China (source region) for all seasons with the exception of summer. It is believed that there might be some estimation error in the NOx emissions as well as large uncertainty in NOx loss rates over North China and South Korea. Regarding the latter, this study further focused on the biogenic VOC emissions that were strongly coupled with NOx chemistry in East Asia. It was found that the rates of NOx loss determined by CMAQ modeling studies might be significantly low due to the possible overestimation of biogenic isoprene emissions during summer, particularly in China. In addition, due to the possible overestimation of isoprene emissions, the CMAQ-modeled NO2/NOx ratios might show an incorrectly high level, compared with the actual NO2/NOx ratios. In addition to the retarded NOx chemical loss rates and overestimated NO2/NOx ratios, the omission of soil NOx emissions over North China during summer can lead to an underestimation of NOx emissions over North China during summer. Overall, it is estimated that the NOx emissions in North China are underestimated possibly by ~50% over an entire year. In order to confirm the uncertainty in NOx emissions, the NOx emission over South Korea was further investigated using the ACE-ASIA inventory, REAS (Regional Emission inventory in ASia) and CAPSS (Clean Air Policy Support System) by NIER (National Institute of Environmental Research) in Korea. The NOx emissions from ACE-ASIA and the REAS inventories appear to be approximately 2 times larger for mega-cities in Korea than that from the CAPSS inventory. In contrast, the NOx emissions of ACE-ASIA and REAS inventories are only 10% smaller for North China than the recently-estimated "date-back" ANL (Argonne National Laboratory) inventory. A comparison between the CMAQ-predicted and GOME-derived NO2 columns indicated that both the ACE-ASIA and REAS inventories have some uncertainty in NOx emissions over North China (A) and South Korea (C), which can lead to some error in modeling the formation of ozone and secondary aerosols in South Korea and North China.

Description: A new one-decade dataset of formaldehyde (HCHO) columns retrieved from GOME and SCIAMACHY is compared with HCHO columns simulated by an updated version of the IMAGES global chemical transport model. This model version includes an optimized chemical scheme with respect to HCHO production, where the short-term and final HCHO yields from pyrogenically emitted non-methane volatile organic compounds (NMVOCs) are estimated from the Master Chemical Mechanism (MCM) and an explicit speciation profile of pyrogenic emissions. The model is driven by the Global Fire Emissions Database (GFED) version 1 or 2 for biomass burning, whereas biogenic emissions are provided either by the Global Emissions Inventory Activity (GEIA), or by a newly developed inventory based on the Model of Emissions of Gases and Aerosols from Nature (MEGAN) algorithms driven by meteorological fields from the European Centre for Medium-Range Weather Forecasts (ECMWF). The comparisons focus on tropical ecosystems, North America and China, which experience strong biogenic and biomass burning NMVOC emissions reflected in the enhanced measured HCHO columns. These comparisons aim at testing the ability of the model to reproduce the observed features of the HCHO distribution on the global scale and at providing a first assessment of the performance of the current emission inventories. The high correlation coefficients (r〉0.8) between the observed and simulated columns over most regions indicate a very good consistency between the model, the implemented inventories and the HCHO dataset. The use of the MEGAN-ECMWF inventory improves the model/data agreement in almost all regions, but biases persist over parts of Africa and the Northern Australia. Although neither GFED version is consistent with the data over all regions, a better match is achieved over Indonesia and Southern Africa when GFEDv2 is used, but GFEDv1 succeeds better in getting the correct seasonal patterns and intensities of the fire episodes over the Amazon basin, as reflected by the higher correlations calculated in this region.

Description: A photoacoustic spectrometer, a nephelometer, an aetholemeter, and an aerosol mass spectrometer were used to measure at ground level real-time aerosol light absorption, scattering, and chemistry at an urban site located in north east Mexico City (Instituto Mexicano del Petroleo, Mexican Petroleum Institute, denoted by IMP), as part of the Megacity Impact on Regional and Global Environments field experiment, MILAGRO, in March 2006. Photoacoustic and reciprocal nephelometer measurements at 532 nm accomplished with a single instrument compare favorably with conventional measurements made with an aethelometer and a TSI nephelometer. The diurnally averaged single scattering albedo at 532 nm was found to vary from 0.60 to 0.85 with the peak value at midday and the minimum value at 7 a.m. local time, indicating that the Mexico City plume is likely to have a net warming effect on local climate. The peak value is associated with strong photochemical generation of secondary aerosol. It is estimated that the same-day photochemical production of secondary aerosol (inorganic and organic) is approximately 40 percent of the aerosol mass concentration and light scattering in association with the peak single scattering albedo. A strong correlation of aerosol scattering at 532 nm and total aerosol mass concentration was found, and an average mass scattering efficiency factor of 3.8 m2/g was determined. Comparisons of photoacoustic and aethalometer light absorption with oxygenated organic aerosol concentration (OOA) indicate a very small systematic bias of the filter based measurement associated with OOA and the peak aerosol single scattering albedo.

Description: We report on satellite observations of atmospheric Sulfur Dioxide (SO2) emitted from metal smelting industries in Peru, South America and Siberia, Russia. Most of the non-ferrous metal ores are sulfidic and during the smelting process the sulfur is emitted as SO2. In addition to Norilsk, Russia, Peruvian copper smelters are among the most polluting point sources in the world. We retrieve SO2 column amounts from spectra of the Global Ozone Monitoring Experiment (GOME) on the Earth Research Satellite 2 (ERS-2) for the years 1996 to 2002 using an algorithm based on differential Optical Absorption Spectroscopy (DOAS). Areas of enhanced SO2 column amounts are clearly identified on a 7-years mean map of GOME observations over the regions with La Oroya and Ilo copper smelters of Peru and Norilsk smelters of Russia. Since the instrument sensitivity is highly dependent on surface albedo, SO2 vertical profile, solar zenith angle (SZA), wavelength, clouds, and aerosol, radiative transfer modelling is used to convert the analysed slant column densities into vertical column densities. In this study, the full spherical Monte-Carlo radiative transport model TRACY-II is used for SO2 AMF calculation. GOME data is analysed in further detail by calculating time series over these regions. For the different locations, the results demonstrate both, increasing and decreasing trends in the SO2 column amounts over the time period of 1996–2002. The decreasing trend for the Ilo copper smelter is in good agreement with implemented measures for emission reductions. However, even for the cases with decreasing trends, these point sources are still a dominant source of anthropogenic SO2 emissions in their region. For the smelters in Peru, the potential influence due to SO2 emission by the nearby volcanoes is investigated and found to be negligible.

Description: Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) in dilute wood smoke by exposing emissions from soft- and hard-wood fires to UV light in a smog chamber. This paper focuses on changes in OA composition measured using a unit mass resolution quadrupole Aerosol Mass Spectrometer (AMS). The results highlight how photochemical processing can lead to considerable evolution of the mass, the volatility and the level of oxygenation of biomass-burning OA. Photochemical oxidation produced substantial new OA, more than doubling the primary contribution after a few hours of aging under typical summertime conditions. Aging decreased the OA volatility of the total OA as measured with a thermodenuder; it also made the OA progressively more oxygenated in every experiment. With explicit knowledge of the condensed-phase mass spectrum (MS) of the primary emissions from each fire, each MS can be decomposed into primary and residual spectra throughout the experiment. The residual spectra provide an estimate of the composition of the photochemically produced OA. These spectra are also very similar to those of the oxygenated OA that dominates ambient AMS datasets. In addition, aged wood smoke spectra are shown to be similar to those from OA created by photo-oxidized dilute diesel exhaust and aged biomass-burning OA measured in urban and remote locations. This demonstrates that the oxygenated OA observed in the atmosphere can be produced by photochemical aging of dilute emissions from combustion of fuels containing both modern and fossil carbon.

Description: In this paper we demonstrate the potential of the infrared Fourier transform spectrometer IASI in analysing volcanic eruptions, using the September 2007 eruption at Jebel at Tair as an illustrative example. Detailed radiative transfer calculations are presented, simulating IASI-like transmittance spectra for a variety of volcanic plumes. We analyse the sensitivity of IASI to SO2 at different altitudes and demonstrate that IASI is in principle capable of sensing SO2 down to the surface. Using the brightness temperature difference of well chosen SO2 channels as a filter, we are able to track the plume of the Jebel at Tair eruption for 12 days, on a par with state of the art UV sounders. A method is presented for quickly estimating the altitude of a volcanic plume based on the relative intensities of the SO2 absorption lines. Despite recent advances, it is still very challenging to retrieve vertical profiles of SO2 from nadir viewing satellites. Currently the most accurate profiles in nadir are retrieved using backtracking of the plume with atmospheric transport models. Via full inverse retrievals using the optimal estimation method, we show the possibility of extracting medium coarse vertical profiles from IASI data. The retrieval allows us to present an evolution of the total mass of SO2 in the plume for the Jebel at Tair eruption. An analytical relation is derived between brightness temperature differences and concentrations, which fits the experimental data very well. The spectral range of IASI also allows retrieval of volcanic aerosols. In the initial plume of the Jebel at Tair eruption, volcanic aerosols were found in the form of ice particles, for which we derived particle sizes.

Description: The second generation Collection 005 (C005) MODIS operational algorithm for retrieval of aerosol properties was evaluated and validated for the greater Mediterranean basin (29.5° N–46.5° N and 10.5° W–38.5° E), a region with an atmosphere under siege by air pollution and diminishing water resources that are exacerbated by high aerosol loads and climatic change. The present study aims to quantify the differences between the C005 and the previous (C004) MODIS collections, and re-assess the results of previous studies that have been performed for the region using MODIS C004 aerosol optical depth (AOD) products. Daily data of AOD from EOS-Terra covering the 6-year period 2000–2006 were taken from both C005 and C004 Level-3 datasets, and were inter-compared and validated against ground-based measurements from 29 AERONET stations. The C005 data were found to significantly better agree with the AERONET data than those of C004. The correlation coefficient between MODIS and AERONET was found to increase from 0.66 to 0.76 and the slope of linear regression MODIS/AERONET from 0.79 to 0.85. The MODIS C005 data still overestimate/underestimate the AERONET AOD values smaller/larger than 0.25, but to a much smaller extent than C004 data. The better agreement of C005 with AERONET data arises from the generally lower C005 values, with regional mean AOD values equal to 0.27 and 0.22 for C004 and C005, respectively. This decrease, however, is not uniform over the region and involves a significant decrease over land and a small increase over the ocean for AOD values greater than 0.1 (opposite changes were found under aerosol-clean conditions). Both data sets indicate a decrease in the regional mean AOD over the period 2000–2006, equal to 20% based on C005 and 17% based on C004 datasets, though the intra-annual and inter-annual variation did not change significantly, thus indicating a systematic correction to C004 values.

Description: 10Be concentrations measured in ice cores exhibit larger temporal variability than expected based on theoretical production calculations. To investigate whether this is due to atmospheric transport a general circulation model study is performed with the 10Be production divided into stratospheric, tropospheric tropical, tropospheric subtropical and tropospheric polar sources. A control run with present day 10Be production rate is compared with a run during a geomagnetic minimum. The present 10Be production rate is 4–5 times higher at high latitudes than in the tropics whereas during a period of no geomagnetic dipole field it is constant at all latitudes. The 10Be deposition fluxes, however, show a very similar latitudinal distribution in both the present day and the geomagnetic minimum run indicating that 10Be is well mixed in the atmosphere before its deposition. This is also confirmed by the fact that the contribution of 10Be produced in the stratosphere is dominant (55%–70%) and relatively constant at all latitudes. The contribution of stratospheric 10Be is approximately 70% in Greenland and 60% in Antarctica reflecting the weaker stratosphere-troposphere air exchange in the Southern Hemisphere.

Description: Dust and black carbon aerosol have long been known to have potentially important and diverse impacts on cloud droplet formation. Most studies to date focus on the soluble fraction of such particles, and ignore interactions of the insoluble fraction with water vapor (even if known to be hydrophilic). To address this gap, we develop a new parameterization framework that considers cloud droplet formation within an ascending air parcel containing insoluble (but wettable) particles mixed with aerosol containing an appreciable soluble fraction. Activation of particles with a soluble fraction is described through well-established Köhler Theory, while the activation of hydrophilic insoluble particles is treated by "adsorption-activation" theory. In the latter, water vapor is adsorbed onto insoluble particles, the activity of which is described by a multilayer Frankel-Halsey-Hill (FHH) adsorption isotherm modified to account for particle curvature. We further develop FHH activation theory, and i) find combinations of the adsorption parameters AFHH, BFHH for which activation into cloud droplets is not possible, and, ii) express activation properties (critical supersaturation) that follow a simple power law with respect to dry particle diameter. Parameterization formulations are developed for sectional and lognormal aerosol size distribution functions. The new parameterization is tested by comparing the parameterized cloud droplet number concentration against predictions with a detailed numerical cloud model, considering a wide range of particle populations, cloud updraft conditions, water vapor condensation coefficient and FHH adsorption isotherm characteristics. The agreement between parameterization and parcel model is excellent, with an average error of 10% and R2 ~0.98.

Description: Zenith-sky scattered sunlight observations using differential optical absorption spectroscopy (DOAS) technique were carried out in Shanghai, China (31.3° N, 121.5° E) since December 2006. At this polluted urban site, the measurement provided NO2 total columns in the daytime. Here, we present a new method to extract time series of tropospheric vertical column densities (VCD) of NO2 from these observations. The derived tropospheric NO2 VCD is an important quantity for the estimation of emissions and for the validation of satellite observations. Our method makes use of assumptions on the relative NO2 height profiles and on the diurnal variation of the stratospheric NO2 VCD. The influence of these parameters on the retrieved tropospheric NO2 VCD is discussed; for a polluted site like Shanghai, the accuracy of our method is estimated to be

Description: In this study, we present carbonyl sulfide (COS) measurements from an ice core drilled near South Pole, East Antarctica (SPRESSO). The samples are from 135–291 m, with estimated mean COS ages ranging from 278 to 2155 years before present (defined as 2000 C.E.). When combined with the previous records of COS from Antarctic ice cores and firn air, the current data provide a continuous record of COS extending beyond the last two millennia. The general agreement between ice cores, firn air, and modern air measurements supports the idea that polar ice is a valid archive for paleoatmospheric COS. The average COS mixing ratio of the SPRESSO data set is (331±18) ppt (parts per trillion as mol/mol, ±1σ, n=100), excluding 6 outliers. These data confirm earlier firn air and ice core measurements indicating that the late 20th century COS levels of 500 ppt are greatly increased over preindustrial levels and represent the highest atmospheric levels over the past 2000 years. The data also provide evidence of climate-related variability on centennial time-scales, with relative maxima at the peaks of Medieval Climate Anomaly and Little Ice Age. There is evidence for a long-term increasing trend in COS of 1.8 ppt per 100 years. Further ice core studies will be needed to determine whether this trend reflects secular variability in atmospheric COS, or a slow post-depositional chemical loss of COS in the ice core.

Description: Observations of the Arctic winter lower stratosphere over the past four decades suggest that the thermodynamic conditions required for the formation of polar stratospheric clouds (PSCs) have become increasingly widespread in the Northern Hemisphere. The trend is apparent only in the coldest winters during which the Arctic stratosphere is minimally disturbed by upwelling wave activity from the troposphere. The mechanism responsible for this increase remains unclear. In an effort to evaluate possible mechanisms, we analyze here the polar stratospheric temperatures in an ensemble of three 150-year integrations of the Canadian Middle Atmosphere Model (CMAM), an interactive chemistry-climate model which simulates ozone depletion and recovery, as well as climate change. We find that in the Antarctic winter lower stratosphere, the low temperature extremes required for PSC formation increase in the model as ozone is depleted, but remain steady through the twenty-first century as the warming from ozone recovery roughly balances the cooling from climate change. Thus, ozone depletion itself plays a major role in the Antarctic response. The model trend in low temperature extremes in the Arctic through the latter half of the twentieth century is weaker and less statistically robust than the observed trend. It is not projected to continue into the future. Ozone depletion in the Arctic is weaker in the CMAM than in observations, which may account for the weak past trend in low temperature extremes. In the future, radiative cooling in the Arctic winter due to climate change is more than compensated by an increase in dynamically driven downwelling over the pole.

Description: We describe an instrument for simultaneous measurements of glyoxal (CHOCHO) and nitrogen dioxide (NO2) using cavity enhanced absorption spectroscopy with a broadband light source. The output of a Xenon arc lamp is coupled into a 1 m optical cavity, and the spectrum of light exiting the cavity is recorded by a grating spectrometer with a charge-coupled device (CCD) array detector. The mirror reflectivity and effective path lengths are determined from the known Rayleigh scattering of He and dry zero air (N2+O2). Least-squares fitting, using published reference spectra, allow the simultaneous retrieval of CHOCHO, NO2, O4, and H2O in the 441 to 469 nm spectral range. For a 1-min sampling time, the minimum detectable absorption is 4×10−10 cm−1, and the precision (±1σ) on signal for measurements of CHOCHO and NO2 is 29 pptv and 20 pptv, respectively. We directly compare the incoherent broadband cavity enhanced absorption spectrometer to 404 and 532 nm cavity ringdown instruments for CHOCHO and NO2 detection, and find linear agreement over a wide range of concentrations. The instrument has been tested in the laboratory with both synthetic and real air samples, and the demonstrated sensitivity and specificity suggest a strong potential for field measurements of both CHOCHO and NO2.

Description: The production of splashing-generated balloelectric intermediate ions was studied by means of mobility spectrometry in the atmosphere during the rain and in a laboratory experiment simulating the heavy rain. The partial neutralization of intermediate ions with cluster ions generated by beta rays suppressed the space charge of intermediate ions but preserved the shape of the mobility distribution. The balloelectric ions produced from the waterworks water of high TDS (Total Dissolved Solids) had about the same mobilities as the ions produced from the rainwater of low TDS. This suggests that the balloelectric ions can be considered as singly charged water nanodroplets. By different measurements, the diameter mode of these droplets was 2.2–2.7 nm, which is close to the diameter of 2.5 nm of the Chaplin's 280-molecule magic icosahedron superclusters. The measurements can be explained by a hypothesis that the pressure of saturated vapor over the nanodroplet surface is suppressed by a number of magnitudes due to the internal structure of the droplets near the size of 2.5 nm. The records of the concentration bursts of balloelectric ions in the atmosphere are formally similar to the records of the nucleation bursts but they cannot be qualified as nucleation bursts because the particles are not growing but shrinking.

Description: This paper describes a modelling study of several HOx and NOx species (OH, HO2, organic peroxy radicals, NO3 and N2O5) in the marine boundary layer. A model based upon the Master Chemical Mechanism (MCM) was constrained to observations of chemical and physical parameters made onboard the NOAA ship R/V Brown as part of the New England Air Quality Study (NEAQS) in the summer of 2004. The model was used to calculate [OH] and to determine the composition of the peroxy radical pool. Modelled [NO3] and [N2O5] were compared to in-situ measurements by Cavity Ring-Down Spectroscopy. The comparison showed that the model generally overestimated the measurements by 30–50%, on average. The model results were analyzed with respect to several chemical and physical parameters, including uptake of NO3 and N2O5 on fog droplets and on aerosol, dry deposition of NO3 and N2O5, gas-phase hydrolysis of N2O5 and reactions of NO3 with NMHCs and peroxy radicals. The results suggest that fog, when present, is an important sink for N2O5 via rapid heterogeneous uptake. The comparison between the model and the measurements were consistent with values of the heterogeneous uptake coefficient of N2O5 (γN2O5)〉1×10−2, independent of aerosol composition in this marine environment. The analysis of the different loss processes of the nitrate radical showed the important role of the organic peroxy radicals, which accounted for a significant fraction (median: 15%) of NO3 gas-phase removal, particularly in the presence of high concentrations of dimethyl sulphide (DMS).

Description: By applying four-dimensional variational data-assimilation (4D-Var) to a combined ozone and dynamics Numerical Weather Prediction model (NWP), ozone observations generate wind increments through the ozone-dynamics coupling. The dynamical impact of Aura/MLS satellite ozone profiles is investigated using Météo–France operational ARPEGE NWP 4D-Var assimilation system for a period of 3 months. A data-assimilation procedure has been designed and run on 6-h windows. The procedure includes: (1) 4D-Var assimilating both ozone and operational NWP standard observations, (2) ARPEGE transporting ozone as a passive-tracer, (3) MOCAGE, the Météo–France chemistry and transport model re-initializing the ARPEGE ozone background at the beginning time of the assimilation window. The Degrees of Freedom for Signal diagnostics show that the MLS data covering the 68.1–31.6 hPa vertical pressure range are the most informative and their information content is nearly of the same order as tropospheric humidity-sensitive radiances. Furthermore, with the help of error variance reduction diagnostics, the ozone contribution to the reduction of the horizontal divergence background-error variance is shown to be better than tropospheric humidity-sensitive radiances. Moreover, by using observation minus forecast statistics, it is found that the ozone assimilation reduces the wind bias in the lower stratosphere.

Description: We have conducted the first closure study to couple high-resolution aerosol mass spectrometer (AMS) composition data with size-resolved, multiple-RH, high-time-resolution hygroscopic growth factor (GF) measurements from the differential aerosol sizing and hygroscopicity spectrometer probe (DASH-SP). These data were collected off the coast of Central California during seven of the 16 flights carried out during the MASE-II field campaign in July 2007. Two of the seven flights were conducted in airmasses that originated over the continental United States. These flights exhibited elevated organic volume fractions (VForganic=0.46±0.22, as opposed to 0.24±0.18 for all other flights), corresponding to significantly suppressed GFs at high RH (1.61±0.14 at 92% RH, as compared with 1.91±0.07 for all other flights), more moderate GF suppression at intermediate RH (1.53±0.10 at 85%, compared with 1.58±0.08 for all other flights, and no measurable GF suppression at low RH (1.31±0.06 at 74%, compared with 1.31±0.07 for all other flights). Organic loadings were slightly elevated in above-cloud aerosols, as compared with below-cloud aerosols, and corresponded to a similar trend of significantly suppressed GF at high RH, but more moderate impacts at lower values of RH. A hygroscopic closure based on a volume-weighted mixing rule provided excellent agreement with DASH-SP measurements (R2=0.79). Minimization of root mean square error between observations and predictions indicated mission-averaged organic GFs of 1.20, 1.43, and 1.46 at 74, 85, and 92% RH, respectively. These values agree with previously reported values for water-soluble organics such as dicarboxylic and multifunctional acids, and correspond to a highly oxidized, presumably water-soluble, organic fraction (O:C=0.92±0.33). Finally, a backward stepwise linear regression revealed that, other than RH, the most important predictor for GF is VForganic, indicating that a simple emperical model relating GF, RH, and the relative abundance of organic material can provide accurate predictions of hygroscopic growth in the marine atmosphere.

Description: We present the first in situ detection of molecular iodine emitted from the brown macroalga Laminaria digitata under natural stress conditions. We show that the release of I2 occurs in short, strong bursts with a complex time signature. The new data indicate that algal control of I2 release in the form of an oscillatory time-dependence may be based on a nonlinear autocatalytic reaction scheme which is closely linked to the production of H2O2.

Description: The indirect effect of aerosols on climate is highly uncertain and limits our ability to assess anthropogenic climate change. The foundation of this uncertainty is uncertainty in the number of cloud condensation nuclei (CCN), which itself stems from uncertainty in aerosol nucleation, primary emission and growth rates. In this paper, we use a global general circulation model with aerosol microphysics to assess how the uncertainties in aerosol nucleation, emission and growth rates affect our prediction of CCN(0.2%) concentrations. Using two nucleation rate parameterizations that differ in globally averaged nucleation rate by 106, the tropospheric average CCN(0.2%) concentrations vary by 17% and the boundary layer average vary by 12%. This sensitivity of tropospheric average CCN(0.2%) to the nucleation parameterizations increases to 33% and 20% when the total primary emissions are reduced by a factor of 3 and the SOA condensation rates are increased by a factor of 3.5, respectively. These results show that it is necessary to understand better global nucleation rates when determining CCN concentrations. When primary emissions rates are varied by a factor of 3 while using the slower nucleation rate parameterization, tropospheric average CCN(0.2%) concentrations also vary by 17%, but boundary layer average vary by 40%. Using the faster nucleation rate parameterization, these changes drop to 3% and 22%, respectively. These results show the importance of reducing uncertainties in primary emissions, which appear from these results to be somewhat more important for CCN than the much larger uncertainties in nucleation. These results also show that uncertainties in nucleation and primary emissions are more important when sufficient condensable material is available to grow them to CCN sizes. The percent change in CCN(0.2%) concentration between pre-industrial times and present day does not depend greatly on the nucleation rate parameterization used for our base case scenarios; however, because other factors, such as primary emissions and SOA, are uncertain in both time periods, this may be a coincidence.

Description: Interannual variations in background tropospheric trace gases (such as carbon monoxide, CO) are largely driven by variations in emissions (especially wildfires), transport pathways and tropospheric oxidizing capacity. Understanding this variability is essential to quantify the intercontinental contribution to US air quality. We investigate the interannual variability of long-range transport of Asian pollutants to the Northeast Pacific via measurements from the Mt. Bachelor Observatory (MBO: 43.98° N, 121.69° W; 2.7 km above sea level) and GEOS-Chem chemical transport model simulations in spring 2005 vs. the INTEX-B campaign during spring 2006. Measurements of CO at MBO were significantly enhanced during spring 2005 relative to the same time in 2006 (the INTEX-B study period); a monthly mean decline in CO of 41 ppbv was observed between April 2005 and April 2006. Meteorological indices show that long-range transport of CO from the heavily industrialized region of East Asia was significantly greater in 2005 than in 2006. In addition, spring 2005 was an anomalously strong biomass burning season in Southeast Asia. Data presented by Yurganov et al. (2008) using MOPITT satellite retrievals from this area reveal an average CO burden anomaly (referenced to March 2000–February 2002 mean values) between October 2004 through April 2005 of 2.6 Tg CO vs. 0.6 Tg CO for the same period a year later. The Naval Research Laboratory's global aerosol transport model shows that emissions from these fires were efficiently transported to MBO throughout April 2005. Asian dust transport, however, was substantially greater in 2006 than 2005, particularly in May. Monthly mean aerosol light scattering coefficient at 532 nm (σsp) at MBO more than doubled from 2.7 Mm−1 in May 2005 to 6.2 Mm−1 in May 2006. We also evaluate CO interannual variability throughout the western US via Earth System Research Laboratory ground site data and throughout the Northern Hemisphere via MOPITT and TES satellite observations. Both in the Northeast Pacific and on larger scales, we reveal a significant decrease (from 2–21%) in springtime maximum CO between 2005 and 2006, evident in all platforms and the GEOS-Chem model. We attribute this to (a) anomalously strong biomass burning in Southeast Asia during winter 2004 through spring 2005, and (b) the transport pattern in 2006 which limited the inflow of Asian pollution to the lower free troposphere over western North America.

Description: We have combined the first satellite maps of the global distribution of phytoplankton functional type and new measurements of phytoplankton-specific isoprene productivities, with available remote marine isoprene observations and a global model, to evaluate our understanding of the marine isoprene source and its impacts on organic aerosol abundances. Using satellite products to scale up data on phytoplankton-specific isoprene productivity to the global oceans, we infer a mean "bottom-up" oceanic isoprene emission of 0.31±0.08 (1 σ) Tg/yr. By minimising the mean bias between the model and isoprene observations in the marine atmosphere remote from the continents, we produce a "top-down" oceanic isoprene source estimate of 1.9 Tg/yr. We suggest our reliance on limited atmospheric isoprene data, and limited knowledge of isoprene productivity across the broad range of phytoplankton communities in the oceans as contributors to this difference between the two estimates. Inclusion of secondary organic aerosol (SOA) production from oceanic isoprene in the model with a 2% yield produces small contributions (0.01–1.6%) to observed organic carbon (OC) aerosol mass at three remote marine sites in the Northern and Southern Hemispheres. In addition, we find the seasonal cycle of the isoprene SOA source is out of phase with the observed cycle in OC in the remote Southern Ocean. Based on these findings we suggest an insignificant role for isoprene in modulating remote marine aerosol abundances, giving further support to a recently postulated primary OC source in the remote marine atmosphere.

Description: It is not practical to measure air-sea gas fluxes in the open ocean for all conditions and areas of interest. Therefore, in many cases fluxes are estimated from measurements of air-phase and water-phase gas concentrations, a measured environmental forcing function such as wind speed, and a parameterization of the air-sea transfer velocity in terms of the environmental forcing function. One problem with this approach is that when direct measurements of the transfer velocity are plotted versus the most commonly used forcing function, wind speed, there is considerable scatter, leading to a relatively large uncertainty in the flux. Because it is known that multiple processes can affect gas transfer, it is commonly assumed that this scatter is caused by single-forcing function parameterizations being incomplete in a physical sense. However, scatter in the experimental data can also result from experimental uncertainty (i.e., measurement error). Here, results from field and laboratory results are used to estimate how experimental uncertainty contributes to the observed scatter in the measured fluxes and transfer velocities as a function of environmental forcing. The results show that experimental uncertainty could explain a major portion of the observed scatter in field and laboratory measurements of the air-sea gas transfer velocity.

Description: Secondary organic aerosol formation from the reaction of tertiary amines with nitrate radical was investigated in an indoor environmental chamber. Particle chemistry was monitored using a high resolution aerosol mass spectrometer while gas-phase species were detected using a proton transfer reaction mass spectrometer. Trimethylamine, triethylamine and tributylamine were studied. Results indicate that tributylamine forms the most aerosol mass followed by trimethylamine and triethylamine respectively. Spectra from the aerosol mass spectrometer indicate the formation of complex non-salt aerosol products. We propose a reaction mechanism that proceeds via abstraction of a proton by nitrate radical followed by RO2 chemistry. Rearrangement of the aminyl alkoxy radical through hydrogen shift leads to the formation of hydroxylated amides, which explain most of the higher mass ions in the mass spectra. These experiments show that oxidation of tertiary amines by nitrate radical may be an important night-time source of secondary organic aerosol.

Description: Remote sensing data provide area integrated information of surface properties in different spatial or temporal resolutions according to different sensor features. Landsat ETM+, Terra MODIS and NOAA-AVHRR surface temperature and spectral reflectance were used to infer further surface parameters and radiant- and energy flux densities for LITFASS-area, a 20×20 km2 heterogeneous area in Eastern Germany, mainly characterized by the land use types forest, crop, grass and water. Based on the Penman-Monteith-approach the actual latent heat flux (L.E), as key quantity of the hydrological cycle, is determined for each sensor in the accordant spatial resolution with an improved parametrization. However, using three sensors, significant discrepancies between the inferred parameters can cause flux distinctions resultant from differences of the sensor filter response functions or atmospheric correction methods. The approximation of MODIS- and AVHRR- derived surface parameters to the reference parameters of ETM (via regression lines and histogram stretching, respectively), further the use of accurate land use classifications (CORINE and a new Landsat-classification), and a consistent parametrization for the three sensors were realized to obtain a uniform base for investigations of the spatial variability. For the target area the spatial heterogeneity is analysed investigating frequency distribution functions (PDF) for surface parameters and energy fluxes. PDF is the most promising way to describe subgrid heterogeneity due to the given data in different spatial resolution. Aim of this study is to find typical distribution pattern of parameters (albedo, NDVI) for the determination of L.E determined from the highly resolved ETM data within pixel on coarser scale (MODIS, AVHRR). The analyses for 4 scenes in 2002 and 2003 showed that clear distribution-pattern for forest for NDVI and albedo are found. Grass and crop distributions show higher variability and differ significantly to each other in NDVI but only marginal in albedo. Regarding NDVI-distribution functions NDVI was found to be the key variable for L.E-determination.

Description: During the period of scientific campaign "Arctic Study of Tropospheric Aerosols, Clouds and Radiation 2004" (ASTAR2004), precipitation samples were collected in late spring at Ny-Alesund, Svalbard and their ionic components were analyzed in parallel with the measurement of properties of atmospheric aerosol particles at the same place. Backward trajectory analyses indicated that the air mass above the observatory initially dominated by air masses from the Arctic Ocean, then those from western Siberia and later those from Greenland and the Arctic Ocean. In the measurement period, six precipitation samples were obtained and five of them were analyzed their ionic components by ionchromatography. The concentrations of nss-sulphate in precipitations were between 1.8 and 24.6 ppm from which the scavenging ratio and scavenging coefficients were calculated using the data such as the concentrations of nss-sulphate in aerosol particles, amounts of precipitations, and the heights of precipitations obtained from radar echo data. The scavenging ratio ranged from 1.0×106 to 17×106 which are comparable values reported in other areas. A detailed comparison between precipitation events and the number concentration of aerosol particles obtained from optical particle counters suggests that the type of precipitations, i.e. rain or snow, significantly affects the number concentrations of aerosol particles.

Description: In order to quantitatively analyse the chemical and dynamical evolution of the polar vortex it has proven extremely useful to work with coordinate systems that follow the vortex flow. We propose here a two-dimensional quasi-Lagrangian coordinate system {χi, Δχi}, based on the mixing ratio of a long-lived stratospheric trace gas i, and its systematic use with i = N2O, in order to describe the structure of a well-developed Antarctic polar vortex. In the coordinate system {χi, Δχi} the mixing ratio χi is the vertical coordinate and Δχi = χi(Θ)−χivort(Θ) is the meridional coordinate (χivort(Θ) being a vertical reference profile in the vortex core). The quasi-Lagrangian coordinates {χi, Δχi} persist for much longer time than standard isentropic coordinates, potential temperature Θ and equivalent latitude φe, do not require explicit reference to geographic space, and can be derived directly from high-resolution in situ measurements. They are therefore well-suited for studying the evolution of the Antarctic polar vortex throughout the polar winter with respect to the relevant chemical and microphysical processes. By using the introduced coordinate system {χN2O, ΔχN2O} we analyze the well-developed Antarctic vortex investigated during the APE-GAIA (Airborne Polar Experiment – Geophysica Aircraft in Antarctica – 1999) campaign (Carli et al., 2000). A criterion, which uses the local in-situ measurements of χi=χi(Θ) and attributes the inner vortex edge to a rapid change (δ-step) in the meridional profile of the mixing ratio χi, is developed to determine the (Antarctic) inner vortex edge. In turn, we suggest that the outer vortex edge of a well-developed Antarctic vortex can be attributed to the position of a local minimum of the χH2O gradient in the polar vortex area. For a well-developed Antarctic vortex, the ΔχN2O-parametrization of tracer-tracer relationships allows to distinguish the tracer inter-relationships in the vortex core, vortex boundary region and surf zone and to examine their meridional variation throughout these regions. This is illustrated by analyzing the tracer-tracer relationships χi : χN2O obtained from the in-situ data of the APE-GAIA campaign for i = CFC-11, CFC-12, H-1211 and SF6. A number of solitary anomalous points in the CFC-11 : N2O correlation, observed in the Antarctic vortex core, are interpreted in terms of small-scale cross-isentropic dispersion.

Description: The global structure and propagation of large-scale (periods 〉5 days) waves in the Southern Hemisphere summer (December 2006–February 2007) at 60° S–75° S latitude are examined using temperature data from GPS radio occultation measurements by COSMIC/FORMOSAT 3 satellite constellation from 10 to 40 km altitude. Spectral analysis has revealed eastward propagating planetary scale perturbations with wavenumbers 1 and 2 and periods of 10-, 16- and 23 days, zonally symmetric waves with the same periods and stationary waves with wavenumber 1 and 2. The presence of the zonally symmetric waves is interpreted as an indication of the coupling of the stationary and traveling waves. The results obtained show a very dynamically active Antarctic summer stratosphere. The novel aspect of the work is in the use of the GPS COSMIC data providing multiple local times each day, thus allowing large-scale wave analysis at high Southern latitudes and revealing planetary wave activity not normally observed in summer, but more consistent with late winter and spring conditions in the stratosphere.

Description: Particulate matter was collected at an urban site in Göteborg (Sweden) in February/March 2005 and in June/July 2006. Additional samples were collected at a rural site for the winter period. Elemental carbon (EC), organic carbon (OC), water-insoluble OC (WINSOC), and water-soluble OC (WSOC) were analyzed for 14C in order to distinguish fossil from non-fossil emissions. As wood burning is the single major source of non-fossil EC, its contribution can be quantified directly. For non-fossil OC, the wood burning fraction was determined independently by levoglucosan and 14C analysis and combined using Latin-hypercube sampling (LHS). For the winter period, the relative contribution of EC from wood burning to the total EC was 〉3 times higher at the rural site compared to the urban site, whereas the absolute concentrations of EC from wood burning were comparable at both sites. Thus, the urban site is substantially more influenced by fossil EC emissions. For summer, biogenic emissions dominated OC concentrations most likely due to secondary organic aerosol (SOA) formation. During both seasons, a more pronounced fossil signal was observed for Göteborg than has previously been reported for Zurich, Switzerland. Analysis of air mass origin using back trajectories suggests that the fossil impact was larger when local sources dominated, whereas long-range transport caused an enhanced non-fossil signal. In comparison to other European locations, concentrations of levoglucosan and other monosaccharide anhydrides were low for the urban and the rural site in the area of Göteborg during winter. The comparison of summer and winter results provides insight into the annual cycle of anthropogenic vs. biogenic contributions to the atmospheric aerosol.

Description: An inventory of NOx emission from international shipping has been evaluated by comparing NO2 tropospheric columns derived from the satellite instruments SCIAMACHY (January 2003 to February 2008), GOME (January 1996 to June 2003), and GOME-2 (March 2007 to February 2008) to NO2 columns calculated with the atmospheric chemistry general circulation model ECHAM5/MESSy1 (January 2000 to October 2005). The data set from SCIAMACHY yields the first monthly analysis of ship induced NO2 enhancements in the Indian Ocean. For both data and model consistently the tropospheric excess method was used to obtain mean NO2 columns over the shipping lane from India to Indonesia, and over two ship free regions, the Bay of Bengal and the central Indian Ocean. In general, the model simulates the differences between the regions affected by ship pollution and ship free regions reasonably well. Minor discrepancies between model results and satellite data were identified during biomass burning seasons in March to May over India and the Indochinese Peninsula and August to October over Indonesia. We conclude that the NOx ship emission inventory used in this study is a good approximation of NOx ship emissions in the Indian Ocean for the years 2002 to 2007. It assumes that around 6 Tg(N) yr−1 are emitted by international shipping globally, resulting in 90 Gg(N) yr−1 in the region of interest when using Automated Mutual Assistance Vessel Rescue System (AMVER) or 72 Gg(N) yr−1 when using the International Comprehensive Ocean-Atmosphere Data Set (ICOADS) as spatial proxy. The results do not support some previously published lower ship emissions estimates of 3–4 Tg(N) yr−1 globally, making this study the first that evaluates atmospheric response to NOx ship emission estimates from space.

Description: We have developed a new technique for estimating ozone mixing ratio inside deep convective clouds. The technique uses the concept of an optical centroid cloud pressure that is indicative of the photon path inside clouds. Radiative transfer calculations based on realistic cloud vertical structure as provided by CloudSat radar data show that because deep convective clouds are optically thin near the top, photons can penetrate significantly inside the cloud. This photon penetration coupled with in-cloud scattering produces optical centroid pressures that are hundreds of hPa inside the cloud. We use the measured column ozone and the optical centroid cloud pressure derived using the effects of rotational-Raman scattering to estimate O3 mixing ratio in the upper regions of deep convective clouds. The data are obtained from the Ozone Monitoring Instrument (OMI) aboard NASA's Aura satellite. Our results show that low O3 concentrations in these clouds are a common occurrence throughout much of the tropical Pacific. Ozonesonde measurements in the tropics following convective activity also show very low concentrations of O3 in the upper troposphere. These low amounts are attributed to vertical injection of ozone poor oceanic boundary layer air during convection into the upper troposphere followed by convective outflow. Over South America and Africa, O3 mixing ratio inside deep convective clouds often exceeds 50 ppbv which is comparable to mean background (cloud-free) concentrations. These areas contain higher amounts of ozone precursors due to biomass burning and lightning. Assuming that O3 is well mixed (i.e. constant mixing ratio with height) up to the tropopause, we can estimate the stratospheric column O3 over clouds. Stratospheric column ozone derived in this manner agrees well with that retrieved independently with the Aura Microwave Limb Sounder (MLS) instrument and thus provides a consistency check of our method.

Description: Temperature soundings are performed by lidar at the mid-latitude station of Kühlungsborn (Germany, 54° N, 12° E). The profiles cover the complete range from the lower troposphere (~1 km) to the lower thermosphere (~105 km) by simultaneous and co-located operation of a Rayleigh-Mie-Raman lidar and a potassium resonance lidar. Observations have been done during 266 nights between June 2002 and July 2007, each of 3–15 h length. This large and unique data set provides comprehensive information on the altitudinal and seasonal variation of temperatures from the troposphere to the lower thermosphere. The remaining day-to-day-variability is strongly reduced by harmonic fits at constant altitude levels and a representative data set is achieved. This data set reveals a two-level mesopause structure with an altitude of about 86–87 km (~144 K) in summer and ~102 km (~170 K) during the rest of the year. The average stratopause altitude is ~48 km throughout the whole year, with temperatures varying between 258 and 276 K. From the fit parameters amplitudes and phases of annual, semi-annual, and quarter-annual variations are derived. The amplitude of the annual component is largest with amplitudes of up to 30 K in 85 km, while the quarter-annual variation is smallest and less than 3 K at all altitudes. The lidar data set is compared with ECMWF temperatures below about 70 km altitude and reference data from the NRLMSISE-00 model above. Apart from the temperature soundings the aerosol backscatter ratio is measured between 20 and 35 km. The seasonal variation of these values is presented here for the first time.

Description: We present a study of Saharan dust export towards the tropical North Atlantic using the regional dust emission, transport and deposition model LM-MUSCAT. Horizontal and vertical distribution of dust optical thickness, concentration, and dry and wet deposition rates are used to describe seasonality of dust export and deposition towards the eastern Atlantic for three exemplary months in different seasons. Deposition rates strongly depend on the vertical dust distribution, which differs with seasons. Furthermore the contribution of dust originating from the Bodélé Depression to Saharan dust over the Atlantic is investigated. A maximum contribution of Bodélé dust transported towards the Cape Verde Islands is evident in winter when the Bodélé source area is most active and dominant with regard activation frequency and dust emission. Limitations of using satellite retrievals to estimate dust deposition are highlighted.

Description: Among the numerous atmospheric constituents, aerosols play a unique role on climate, due to their scattering and absorbing capabilities, visibility degradation and their effect on incoming and outgoing radiation. The most important optical properties are the aerosol optical depth (AOD), the asymmetry parameter (g) and the single scattering albedo (SSA). Uncertainties in aerosol microphysics in global models, which in turn affect their optical properties, propagate to uncertainties on the effect of aerosols on climate. This study aims to estimate the uncertainty of AOD, g and SSA attributable to the aerosol representation in models, namely mixing state, aerosol size and aerosol associated water. As a reference, the monthly mean output of the general circulation model LMDz-INCA from the international comparison exercise AEROCOM B was used. For the optical properties calculations, aerosols were considered either externally mixed, homogeneously internally mixed or coated spheres. The radius was allowed to vary by ±20% (with 2% intervals) and the aerosol water content by ±50% (with 5% intervals) with respect to the reference model output. All of these possible combinations were assumed to be equally likely and the optical properties were calculated for each one of them. A probability density function (PDF) was constructed at each model grid point for AOD, g and SSA. From this PDF, the 1σ and 2σ uncertainties of the AOD, g and SSA were calculated and are available as global maps for each month. For the range of the cases studied, we derive a maximum 2σ uncertainty range in AOD of 70%, while for g and SSA the maxima reach 18% and 28% respectively. The mixing state was calculated to be important, with the aerosol absorption and SSA being the most affected properties when absorbing aerosols are present.

Description: During the wet season of the African Monsoon Multidisciplinary Analyses (AMMA) campaign, airborne measurements of several chemical species were made onboard the French Falcon-20 (FF20) aircraft. The scientific flights were planned in order to document, on one hand the regional distribution of trace gas species related to the oxidizing capacity of the troposphere, and on the other hand their spatial variability in the outflow of mesoscale convective systems (MCSs). The main objectives of this paper are the analysis of the main transport processes responsible for the observed variability, and the discussion of differences and similarities related to the convective transport by 4 different MCSs. This work is needed before using this data set for future studies of the convective transport of chemical species or for modeling work in the frame of the AMMA project. Regarding the regional distribution, five air masses types have been identified using the Lagrangian particle dispersion model FLEXPART, and by considering relationship between the measured trace gas concentrations (O3, CO, NOx, H2O, and hydroperoxides). This paper specifically discusses the advantage of hydroperoxide measurements in order to document the impact of recent or aged convection. The highest values of O3 are found to be related to transport from the subtropical tropopause region into the mid-troposphere at latitudes as low as 10° N. The lowest ozone values have been always explained by recent uplifting from the monsoon layer where O3 is photochemically destroyed. Regarding the analysis of the MCS outflow, the CO and H2O2 enhancements are related to the age and the southernmost position of the MCS. The analysis of the long range transport of the air masses where convection occurred, shows a connection with the Persian Gulf emissions for the largest CO concentrations in MCS outflow. However for our observations, Lagrangian particle dispersion modelling shows that this possible source is always modified by the convective transport of CO from the African lower troposphere when the air masses encounter a convective system at latitudes below 10° N.

Description: The effect of diurnal variations in sea surface temperature (SST) on the air-sea flux of CO2 over the central Atlantic ocean and Mediterranean Sea is evaluated for 2005–2006. We use high resolution hourly satellite SST data to determine the diurnal warming (ΔSST). The CO2 flux is then computed using three different temperature fields – a foundation temperature (Tf, measured at a depth where there is no diurnal variation), Tf plus the hourly ΔSST and Tf plus monthly-averaged ΔSST. This is done in conjunction with a physically-based parameterisation for the gas transfer velocity (NOAA-COARE). The differences between the fluxes evaluated for these three different temperature fields quantifies the effects of both diurnal warming and diurnal covariations. We find that including diurnal warming increases the CO2 flux out of the Atlantic for 2005–2006 from 9.6 Tg C a−1 to 30.4 Tg C a−1 (hourly ΔSST) and 31.2 Tg C a−1 (monthly ΔSST). Diurnal warming, therefore, has a large impact on the annual net CO2 flux but diurnal covariations in variables are negligible implying that CO2 fluxes may be adequately computed using monthly averaged ΔSSTs along with a suitable foundation temperature.

Description: Collocated measurements of spectral aerosol optical depths (AODs), total and BC mass concentrations, and number size distributions of near surface aerosols, along with sea surface winds, made onboard a scientific cruise over southeastern Arabian Sea, are used to delineate the effects of changes in the wind speed on aerosol properties and its implication on the shortwave and longwave radiative forcing. The results indicated that an increase in the sea-surface wind speed from calm to moderate (

Description: Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) in wood smoke by exposing diluted emissions from soft- and hard-wood fires to UV light in a smog chamber. Particle- and gas-phase concentrations were monitored with a suite of instruments including a Proton Transfer Reaction Mass Spectrometer (PTR-MS), an Aerosol Mass Spectrometer (AMS) and a thermodenuder to measure aerosol volatility. The measurements highlight how in-plume processing can lead to considerable evolution of the mass and volatility of biomass burning OA. Photochemical oxidation produced substantial new OA, increasing concentrations by a factor of 1.5 to 2.8 after several hours of exposure to typical summertime hydroxyl radical (OH) concentrations. Less than 20% of this new OA could be explained using the measured decay of traditional secondary organic aerosol (SOA) precursors and a state-of-the-art SOA model. Aging also created less volatile OA; at 50°C between 50 and 80% of the fresh primary OA evaporated but only 20 to 40% of aged OA. Therefore, the data provide additional evidence that primary OA is semivolatile. They also raise questions about the current approach used to simulate OA in chemical transport models, which assume that primary OA are non-volatile but that SOA is semivolatile. Predictions of a volatility basis-set model that explicitly tracks the partitioning and aging of low-volatile organics are compared to the chamber data. This model demonstrates that the OA production observed in these experiments can be explained by oxidation of low volatility organic vapors. The basis-set model can also simulate observed changes in OA volatility and composition, predicting the OA production and the increased oxygenation and decreased volatility of the OA.

Description: Boundary layer clouds were investigated with a complementary set of remote sensing and in situ instruments during the Arctic Study of Tropospheric Aerosol, Clouds and Radiation (ASTAR) campaign in March and April 2007. The clouds that formed in a cold air outbreak over the open Greenland sea showed a variety in their thermodynamic state. Beside the predominant mixed-phase clouds pure liquid and ice clouds were observed. Utilizing the measurements of solar radiation reflected by the clouds three methods to retrieve the thermodynamic phase of the cloud were defined and compared. Two ice indices IS and IP were obtained by analyzing the spectral pattern of the cloud top reflectance in the near infrared (1500–1800 nm wavelength) characterized by ice and water absorption. A third ice index IA is based on the different side scattering of spherical liquid water particles and nonspherical ice crystals which was recorded in simultaneous measurements of cloud albedo and reflectance. Radiative transfer simulations showed that IS, IP and IA range between 5 to 80, 0 to 20 and 1 to 1.25, respectively, with lowest values indicating pure liquid water clouds and highest values pure ice clouds. IS and IP were found to be strongly sensitive to the effective diameter of the ice crystals present in the cloud. Therefore the identification of mixed-phase clouds requires a priori knowledge of the ice crystal dimension. IA has the disadvantage that this index is mainly dominated by the uppermost cloud layer (τ

Description: Particle number concentration and size distribution are amongst the most important variables needed to constrain the role of the atmospheric particles in the Earth radiative budget. They are also linked to regulated variables such as particle mass (PM) and therefore of interest to air quality studies. However, data on their long-term variability are scarce, in particular at high altitudes where the occurrence of aerosol in elevated layers cannot be resolved from most instruments in space. Therefore it is crucial to provide ground based measurements of suited aerosol variables to obtain closure between all independent information sources. In this paper, we investigate diurnal and seasonal variability of aerosol number concentration and size distribution at the Puy de Dôme research station (France, 1465 m a.s.l.). We report variability of aerosol particle total number concentration measured over a five years (2003–2007) period and aerosol size distributions over a one year period (January to December 2006). Concentrations show a strong seasonality with maxima during summer and minima during winter. A diurnal variation is also observed with maxima between 12:00 and 18:00 UTC. At night (00:00–06:00 UTC), the median hourly total concentration varies from 600 to 800 cm−3 during winter and from 1700 to 2200 cm−3 during summer. During the day (08:00–18:00 UTC), the concentration is in the range of 700 to 1400 cm−3 during winter and from 2500 to 3500 cm−3 during summer. An averaged size distribution of particles (10–500 nm) was calculated for each season. A variability in the size of aerosols sampled at the Puy de Dôme is also observed on the seasonal and diurnal basis. Because the site lies in the free troposphere only a fraction of the time, in particular at night and during the winter season, we have subsequently analyzed the variability for free tropospheric conditions only. We show that the variability is due to both seasonal changes in air mass origin from winter to summer and enhanced concentration of the free troposphere in summer. The later observation can be explained by higher emission intensity in the boundary layer, stronger exchange between the boundary layer and the free troposphere as well as enhanced photochemical processes. Finally, aerosol mean size distributions are calculated for a given air mass type (marine/continental/regional) according to the season, for the specific conditions of the free troposphere. These results are of regional relevance and can be used to constrain chemical-transport models over Western Europe.

Description: Atmospheric particle number size distributions of airborne particles (diameter range 10–500 nm) were measured over ten weeks at three sites in the vicinity of the A100 urban motorway in Berlin, Germany. The A100 carries about 180 000 vehicles on a weekday, and roadside particle size distributions showed a number maximum between 20 and 60 nm clearly related to the motorway emissions. The average total number concentration at roadside was 28 000 cm−3 with a total range between 1200 and 168 000 cm−3. At distances of 80 and 400 m from the motorway the concentrations decreased to mean levels of 11 000 and 9 000 cm−3, respectively. An obstacle-resolving dispersion model was applied to simulate the 3-D flow field and traffic tracer transport in the urban environment around the motorway. By inverse modelling, vehicle emission factors were derived, representative of a relative share of 6% lorry-like vehicles, and a driving speed of about 80 km h−1. Three different calculation approaches were compared, which differ in the choice of the experimental winds driving the flow simulation. The average emission factor per vehicle was 2.1(±0.2) · 1014 km−1 for particle number and 0.077(±0.01) · 1014 cm3 km−1 for particle volume. Regression analysis suggested that lorry-like vehicles emit 116 (± 21) times more particulate number than passenger car-like vehicles, and that lorry-like vehicles account for about 91% of particulate number emissions on weekdays. Our work highlights the increasing applicability of 3-D flow models in urban microscale environments and their usefulness in determining traffic emission factors.

Description: Observations at a mountain-top site within the Mexico City basin are used to characterize ozone production and destruction, the nitrogen oxide budget, and the radical budget during the MILAGRO campaign. An ozone production rate of ~50 ppbv/h was observed in a stagnant air mass during the afternoon of 12 March 2006, which is among the highest observed anywhere in the world. Approximately half of the ozone destruction was due to the oxidation of NO2. During this time period ozone production was VOC-limited, deduced by a comparison of the radical production rates and the formation rate of NOx oxidation products (NOz) For [NOx]/[NOy] values between 0.2 and 0.8, gas-phase HNO3 typically accounted for less than 10% of NOz and accumulation-mode particulate nitrate (NO3−(PM)) accounted for 20%–70% of NOz, consistent with high ambient NH3 concentrations. The fraction of NOz accounted for by the sum of HNO3(g) and NO3−(PM) decreased with photochemical processing. This decrease is apparent even when dry deposition of HNO3 is accounted for, and indicates that HNO3 formation decreased relative to other NOx "sink" processes during the first 12 h of photochemistry and/or a significant fraction of the nitrate was associated with the coarse aerosol size mode. The ozone production efficiency of NOx on 11 and 12 March 2006 was approximately 7 on a time scale of one day. A new metric for ozone production efficiency that relates the dilution-adjusted ozone mixing ratio to cumulative OH exposure is proposed.

Description: Direct measurements of OH and HO2 over a tropical rainforest were made for the first time during the GABRIEL campaign in October 2005, deploying the custom-built HORUS instrument (HydrOxyl Radical measurement Unit based on fluorescence Spectroscopy), adapted to fly in a Learjet wingpod. Biogenic hydrocarbon emissions were expected to strongly reduce the OH and HO2 mixing ratios as the air is transported from the ocean over the forest. However, surprisingly high mixing ratios of both OH and HO2 were encountered in the boundary layer over the rainforest. The HORUS instrumentation and calibration methods are described in detail and the measurement results obtained are discussed. The extensive dataset collected during GABRIEL, including measurements of many other trace gases and photolysis frequencies, has been used to quantify the main sources and sinks of OH. Comparison of these measurement-derived formation and loss rates of OH indicates strong previously overlooked recycling of OH in the boundary layer over the tropical rainforest, occurring in chorus with isoprene emission.

Description: Secondary organic aerosol (SOA) formation has been investigated as a function of temperature and humidity for the ozone-initiated reaction of the two monoterpenes α-pinene (243–313 K) and limonene (253–313 K) using the 84.5 m3 aerosol chamber AIDA. This paper gives an overview of the measurements done and presents parameters specifically useful for aerosol yield calculations. The ozonolysis reaction, selected oxidation products and subsequent aerosol formation were followed using several analytical techniques for both gas and condensed phase characterisation. The effective densities of the SOA were determined by comparing mass and volume size distributions to (1.25±0.10) g cm−3 for α-pinene and (1.3±0.2) g cm−3 for limonene. The detailed aerosol dynamics code COSIMA-SOA proved to be essential for a comprehensive evaluation of the experimental results and for providing parameterisations directly applicable within atmospheric models. The COSIMA-assisted analysis succeeded to reproduce the observed time evolutions of SOA total mass, number and size distributions by adjusting the following properties of two oxidation product proxies: individual yield parameters (αi), partitioning coefficients (Ki), vapour pressures (pi) and effective accommodation coefficients (γi). For these properties temperature dependences were derived and parameterised. Vapour pressures and partitioning coefficients followed classical Clausius-Clapeyron temperature dependences. From this relationship enthalpies of vaporisation were derived for the two more and less volatile product proxies of α-pinene: (59±8) kJ mol−1 and (24±9) kJ mol−1, and limonene: (55±14) kJ mol−1 and (25±12) kJ mol−1. The more volatile proxy components had a notably low enthalpy of vaporisation while the less volatile proxy components gave enthalpies of vaporisation comparable with those of typical products from α-pinene oxidation, e.g. pinonaldehyde and pinonic acid.

Description: We present a parameterization of cirrus cloud formation that computes the ice crystal number and size distribution under the presence of homogeneous and heterogeneous freezing. The parameterization is very simple to apply and is derived from the analytical solution of the cloud parcel equations, assuming that the ice nuclei population is monodisperse and chemically homogeneous. In addition to the ice distribution, an analytical expression is provided for the limiting ice nuclei number concentration that suppresses ice formation from homogeneous freezing. The parameterization is evaluated against a detailed numerical parcel model, and reproduces numerical simulations over a wide range of conditions with an average error of 6±33%.