bluuebunny/crossref_metadata_2025 huggingface dataset:
Consistency between parameterisations of aerosol hygroscopicity and CCN activity during the RHaMBLe discovery cruise
Authors: Good N. , Topping D. O. , Allan J. D. , Flynn M. , Fuentes E. , Irwin M. , Williams P. I. , Coe H. , McFiggans G.
Published: April 2010

Abstract. Results from a measurement study performed in the Tropical Atlantic on board the RHaMBLe Discovery Cruise D319 are presented. Measurements of aerosol composition, hygroscopicity and CCN activity were used to test the ability of a single parameter model to describe water uptake in sub- and supersaturated conditions. It was found that the magnitude and temporal variability of the sub-saturated water uptake could be well represented using the non-refractory composition to derive the model input for 2 periods when the large majority of the aerosol mass was non-refractory. As may be expected, when a significant fraction of the aerosol volume is refractory the sub-saturated water uptake is not well predicted by the non-refractory composition. When predicting the cloud activation potential from the composition and the hygroscopicity there is a consistent under-prediction of the CCN activity. The prediction of CCN activity from the sub-saturated water uptake gives a better prediction of the CCN activity than the composition when the non-refractory components are not fully representative of the aerosol composition. Based on these observations it appears that a single parameter cannot always capture the behavior fully across the sub- and supersaturated regimes. Measurements made at relative humidities (RHs) up to 94% showed that the water activity appears satisfactorily represented by a single parameter derived at 90% RH. It therefore appears that the change in the observed hygroscopicity take place between 94% RH and the point of activation. This change may be due in part to a change solution non-ideality, surface tension effects or the presence of sparingly soluble compounds for example, but cannot be reconciled without measurements at higher RHs.
Fluorescent biological aerosol particle concentrations and size distributions measured with an Ultraviolet Aerodynamic Particle Sizer (UV-APS) in Central Europe
Authors: Huffman J. A. , Treutlein B. , Pöschl U.
Published: April 2010

Abstract. Primary Biological Aerosol Particles (PBAPs), including bacteria, spores and pollen, are essential for the spread of organisms and disease in the biosphere, and numerous studies have suggested that they may be important for atmospheric processes, including the formation of clouds and precipitation. The atmospheric abundance and size distribution of PBAPs, however, are largely unknown. At a semi-urban site in Mainz, Germany we used an Ultraviolet Aerodynamic Particle Sizer (UV-APS) to measure Fluorescent Biological Aerosol Particles (FBAPs), which provide an estimate of viable bioaerosol particles and can be regarded as an approximate lower limit for the actual abundance of PBAPs. Fluorescence of non-biological aerosol components are likely to influence the measurement results obtained for fine particles (<1 μm), but not for coarse particles (1–20 μm). Averaged over the four-month measurement period (August–December 2006), the mean number concentration of coarse FBAPs was ~3×10−2 cm−3, corresponding to ~4% of total coarse particle number. The mean mass concentration of FBAPs was ~1μg m−3, corresponding to ~20% of total coarse particle mass. The FBAP number size distributions exhibited alternating patterns with peaks at various diameters. A pronounced peak at ~3 μm was essentially always observed and can be described by the following campaign-average lognormal fit parameters: geometric mean diameter 3.2 μm, geometric standard deviation 1.3, number concentration 1.6×10−2 cm−3. This peak is likely due to fungal spores or agglomerated bacteria, and it exhibited a pronounced diel cycle (24-h) with maximum intensity during early/mid-morning. FBAP peaks around ~1.5 μm, ~5 μm, and ~13 μm were also observed, but less pronounced and less frequent. These may be single bacterial cells, larger fungal spores, and pollen grains, respectively. The observed number concentrations and characteristic sizes of FBAPs are consistent with microscopic, biological and chemical analyses of PBAPs in aerosol filter samples. To our knowledge, however, this is the first exploratory study reporting continuous online measurements of bioaerosol particles over several months and a range of characteristic size distribution patterns with a persistent bioaerosol peak at ~3 μm. The measurement results confirm that PBAPs account for a substantial proportion of coarse aerosol particle number and mass in continental boundary layer air. Moreover, they suggest that the number concentration of viable bioparticles is dominated by fungal spores or agglomerated bacteria with aerodynamic diameters around 3 μm rather than single bacterial cells with diameters around 1 μm.
The net climate impact of coal-fired power plant emissions
Authors: Shindell D. , Faluvegi G.
Published: April 2010

Abstract. Coal-fired power plants influence climate via both the emission of long-lived carbon dioxide (CO2) and short-lived ozone and aerosol precursors. Using a climate model, we perform the first study of the spatial and temporal pattern of radiative forcing specifically for coal plant emissions. Without substantial pollution controls, we find that near-term net global mean climate forcing is negative due to the well-known aerosol masking of the effects of CO2. Imposition of pollution controls on sulfur dioxide and nitrogen oxides leads to a rapid realization of the full positive forcing from CO2, however. Long-term global mean forcing from stable (constant) emissions is positive regardless of pollution controls. Emissions from coal-fired power plants until ~1970, including roughly 1/3 of total anthropogenic CO2 emissions, likely contributed little net global mean climate forcing during that period though they may have induce weak Northern Hemisphere mid-latitude (NHml) cooling. After that time many areas imposed pollution controls or switched to low-sulfur coal. Hence forcing due to emissions from 1970 to 2000 and CO2 emitted previously was strongly positive and contributed to rapid global and especially NHml warming. Most recently, new construction in China and India has increased rapidly with minimal application of pollution controls. Continuation of this trend would add negative near-term global mean climate forcing but severely degrade air quality. Conversely, following the Western and Japanese pattern of imposing air quality pollution controls at a later time could accelerate future warming rates, especially at NHmls. More broadly, our results indicate that due to spatial and temporal inhomogenaities in forcing, climate impacts of multi-pollutant emissions can vary strongly from region to region and can include substantial effects on maximum rate-of-change, neither of which are captured by commonly used global metrics. The method we introduce here to estimate regional temperature responses may provide additional insight.
Parametric studies of contrail ice particle formation in jet regime using microphysical parcel modeling
Authors: Wong H.-W. , Miake-Lye R. C.
Published: April 2010

Abstract. Condensation trails (contrails) formed from water vapor emissions behind aircraft engines are the most uncertain components of the aviation impacts on climate change. To gain improved knowledge of contrail and contrail-induced cirrus cloud formation, understanding of contrail ice particle formation immediately after aircraft engines is needed. Despite many efforts spent in modeling the microphysics of ice crystal formation in jet regime (with a plume age <5 s), systematic understanding of parametric effects of variables affecting contrail ice particle formation is still limited. In this work, we apply a microphysical parcel modeling approach to study contrail ice particle formation in near-field aircraft plumes up to 1000 m downstream of an aircraft engine in the soot-rich regime (soot number emission index >1×1015 (kg-fuel)−1) at cruise. The effects of dilution history, ion-mediated nucleation, ambient relative humidity, fuel sulfur contents, and initial soot emissions were investigated. Our simulation results suggest that ice particles are mainly formed by water condensation on emitted soot particles. The growth of ice coated soot particles is driven by water vapor emissions in the first 1000 m and by ambient relative humidity afterwards. The presence of chemi-ions does not significantly contribute to the formation of ice particles in the soot-rich regime, and the effect of fuel sulfur contents is small over the range typical of standard jet fuels. The initial properties of soot emissions play the most critical role, and our calculations suggest that higher number concentration and smaller size of contrail particle nuclei may be able to effectively suppress the formation of contrail ice particles. Further modeling and experimental studies are needed to verify if our findings can provide a possible approach for contrail mitigation.
Trans-Pacific transport of Asian dust and CO: accumulation of biomass burning CO in the subtropics and dipole structure of transport
Authors: Nam J. , Wang Y. , Luo C. , Chu D. A.
Published: April 2010

Abstract. In May 2003, both MODIS aerosol optical depth (AOD) and carbon monoxide (CO) measurements from MOPITT show significant trans-Pacific transport to North America. We apply the global chemical transport model, GEOS-Chem, to analyze the main features of the long-range transport events. Enhancements of MOPITT CO over the tropical Pacific are much broader than MODIS AOD enhancements. We find in model simulations that a major fraction of the CO enhancements in the subtropics in May is due to biomass burning in Southeast Asia in April. Biomass burning CO was recirculated into the subtropical high-pressure system and lingered for a much longer period than aerosols transported at higher latitudes. Simulated AOD enhancements are due to a combination of dust, sulfate, and organic and elemental carbons. Dust contribution dominates the AOD enhancements in early May. Model results indicate that dust transport takes place at higher altitude than the other aerosols. MODIS observations indicate a bias in model simulated pathway of dust transport in one out of the three cases analyzed. Sensitivities of dust transport pathways are analyzed in the model. The dipole structure of transport, consisting of the Aleutian Low to the north and the Pacific High to the south, over the Pacific is found to be a key factor. The placement of the dipole structure relative to model parameters such as up-stream wind field and source location may lead to the high sensitivity of simulated transport pathways.
Pressure dependence of the deuterium isotope effect in the photolysis of formaldehyde by ultraviolet light
Authors: Nilsson E. J. K. , Andersen V. F. , Skov H. , Johnson M. S.
Published: April 2010

Abstract. The pressure dependence of the relative photolysis rate of HCHO vs. HCDO has been investigated for the first time, using a photochemical reactor at the University of Copenhagen. The dissociation of HCHO vs. HCDO using a UVA lamp was measured at total bath gas pressures of 50, 200, 400, 600 and 1030 mbar. The products of formaldehyde photodissociation are either H2 + CO (molecular channel) or HCO + H (radical channel), and a photolysis lamp was chosen to emit light at wavelengths that greatly favor the molecular channel. The isotope effect in the dissociation, kHCHO/kHCDO, was found to depend strongly on pressure, varying from 1.1 + 0.15/−0.1 at 50 mbar to 1.75±0.10 at 1030 mbar. The results can be corrected for radical channel contribution to yield the kinetic isotope effect for the molecular channel; i.e. the KIE in the production of molecular hydrogen. This is done and the results at 1030 mbar are discussed in relation to previous studies at ambient pressure. In the atmosphere the relative importance of the two product channels changes with altitude as a result of changes in pressure and actinic flux. The study demonstrates that the δD of photochemical hydrogen produced from formaldehyde will increase substantially as pressure decreases.
Numerical simulation of tropospheric injection of biomass burning products by pyro-thermal plumes
Authors: Rio C. , Hourdin F. , Chédin A.
Published: April 2010

Abstract. The thermal plume model, a mass-flux scheme originally developed to represent the vertical transport by convective structures within the boundary layer, is adapted to the representation of plumes generated by fires, with the aim of estimating the height at which fire emissions are actually injected in the atmosphere. The parameterization, which takes into account the excess of near surface temperature induced by fires and the mixing between convective plumes and environmental air, is first evaluated on two well-documented fires. Simulations over Southern Africa performed with the general circulation model LMDZ over one month show that the CO2 can be injected far above the boundary layer height, leading to a daily excess of CO2 in the mid-troposphere of an order of 2 ppmv. These results agree with satellite retrievals of a diurnal cycle of CO2 in the free troposphere over regions affected by biomass burning in the Tropics.
Amine exchange into ammonium bisulfate and ammonium nitrate nuclei
Authors: Bzdek B. R. , Ridge D. P. , Johnston M. V.
Published: April 2010

Abstract. The exchange kinetics and thermodynamics of amines for ammonia in small (1–2 nm diameter) ammonium bisulfate and ammonium nitrate clusters were investigated using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Ammonium salt clusters were reacted with amine gas at constant pressure to determine the kinetics of exchange. The reverse reactions, where aminium salt clusters reacted with ammonia gas, were also studied, and no substitution of ammonia for amine was observed. Gibbs free energy changes for these substitutions were determined to be highly exothermic, −7 kJ/mol or more negative in all cases. Uptake coefficients (reaction probabilities) were found to be near unity, implying that complete exchange of ammonia in small clusters by amine would be expected to occur within several seconds to minutes in the ambient atmosphere. These results suggest that if salt clusters are a component of the sub-3 nm cluster pool, they are likely to be aminium salts rather than ammonium salts, even if they were initially formed as ammonium salts.
OMI and MODIS observations of the anomalous 2008–2009 Southern Hemisphere biomass burning seasons
Authors: Torres O. , Chen Z. , Jethva H. , Ahn C. , Freitas S. R. , Bhartia P. K.
Published: April 2010

Abstract. Significant inter-annual variability of biomass burning was observed in South America over the 2007–2009 period. The 2007 number of fires detected from space in South America, as well as the magnitude of the atmospheric aerosol load resulting from fire activity, was the largest over the last ten years. The huge 2007 increase in fire activity was followed by large reductions in the 2008 and 2009 burning seasons. Large drops of the atmospheric load of carbonaceous aerosols over the subcontinent, relative to previous years, was registered in 2008 and 2009 by the OMI sensor onboard the Aura platform, and the MODIS sensors on the Terra and Aqua satellites. The 2009 fire season in South America was the least active of the last ten years. Satellite observations of fire statistics, precipitation, and aerosol optical depth data were used to analyze the fire season over South America and Central Africa during the last ten years to understand the factors that led to the 2007 and 2009 extremes. An analysis of precipitation anomaly data shows that the largest 6-month (May–October) precipitation deficit of the last ten years in South America occurred during 2007. The same analysis indicates that in 2009, this region experienced the largest excess precipitation of the decade. Since precipitation is the most important meteorological factor controlling biomass burning activity, it can be concluded that the 2007 maximum and 2009 minimum in fire activity and aerosol load were driven by the observed levels of precipitation. Analysis of the precipitation record, however, does not explain the extremely low 2008 biomass burning activity. Although the 2008 precipitation deficit was similar in magnitude to the one that in 2005 contributed to the second most intense biomass burning season in the last ten years, the 2008 fire season was surprisingly weak. The combined analysis of satellite data on atmospheric aerosol load, fire counts and precipitation strongly suggests that the observed 2008 decline in aerosol load and fire activity in South America was heavily influenced by conditions other than meteorological factors.
Heterogeneous freezing of droplets with immersed mineral dust particles – measurements and parameterization
Authors: Niedermeier D. , Hartmann S. , Shaw R. A. , Covert D. , Mentel T. F. , Schneider J. , Poulain L. , Reitz P. , Spindler C. , Clauss T. , Kiselev A. , Hallbauer E. , Wex H. , Mildenberger K. , Stratmann F.
Published: April 2010

Abstract. During the measurement campaign FROST (FReezing Of duST), LACIS (Leipzig Aerosol Cloud Interaction Simulator) was used to investigate the immersion freezing behavior of size selected, coated and uncoated Arizona Test Dust (ATD) particles with a mobility diameter of 300 nm. Particles were coated with succinic acid (C4H6O4), sulfuric acid (H2SO4) and ammonium sulfate ((NH4)2SO4). Ice fractions at mixed-phase cloud temperatures ranging from 233.15 K to 239.15 K (±0.60 K) were determined for all types of particles. In this temperature range, pure ATD particles and those coated with C4H6O4 or small amounts of H2SO4 were found to be the most efficient ice nuclei (IN). ATD particles coated with (NH4)2SO4 were the most inefficient IN. Since the supercooled droplets were highly diluted before freezing occurred, a freezing point suppression due to the soluble material on the particles (and therefore in the droplets) cannot explain this observation. Therefore, it is reasonable to assume that the coatings lead to particle surface alterations which cause the differences in the IN abilities. Two different theoretical approaches based on the stochastic and the singular hypotheses were applied to clarify and parameterize the freezing behavior of the particles investigated. Both approaches describe the experimentally determined results, yielding parameters that can subsequently be used to compare our results to those from other studies. However, we cannot clarify at the current state which of the two approaches correctly describes the investigated immersion freezing process. But both approaches confirm the assumption that the coatings lead to particle surface modifications lowering the nucleation efficiency. The stochastic approach interprets the reduction in nucleation rate from coating as primarily due to an increase in the thermodynamic barrier for ice formation (i.e., changes in interfacial free energies). The singular approach interprets the reduction as resulting from a reduced surface density of active sites.
Mercury emission from crematories in Japan
Authors: Takaoka M. , Oshita K. , Takeda N. , Morisawa S.
Published: April 2010

Abstract. Anthropogenic sources of mercury emissions have a significant impact on global pollution. Therefore, finding uncharacterised sources and assessing the emissions from these sources are important. However, limited data are available worldwide on mercury emissions from crematories. In Japan, 99.9% of dead bodies are cremated, which is the highest percentage in the world, and more than 1600 crematories are in operation. We thus focused on emissions from crematories in Japan. The number of targeted facilities was seven, and we used continuous emission monitoring to measure the mercury concentrations and investigate mercury behaviour. The total mercury concentrations in stack gases were a few μg/Nm3 (normal cubic meters). Considering the time profile of mercury and its species in cremations, the findings confirmed that the mercury in stack gas originated from dental amalgam. The amount of mercury emissions was calculated using the total concentration and gas flow rate. Furthermore, the annual amount of mercury emission from crematories in Japan was estimated by using the total number of corpses. The emission amount was considerably lower than that estimated in the United Kingdom. From statistical analyses on population demographics and measurements, future total emissions from crematories were also predicted. As a result, the amount of mercury emitted by crematories will likely increase by 2.6-fold from 2007 to 2037.
Winter- and summertime continental influences on tropospheric O3 and CO observed by TES over the western North Atlantic Ocean
Authors: Hegarty J. , Mao H. , Talbot R.
Published: April 2010

Abstract. The distributions of tropospheric ozone (O3) and carbon monoxide (CO), and the synoptic factors regulating these distributions over the western North Atlantic Ocean during winter and summer were investigated using profile retrievals from the Tropospheric Emission Spectrometer (TES) for 2004–2006. Seasonal composites of TES retrievals, reprocessed to remove the influence of the a priori on geographical and seasonal structure, exhibited strong seasonal differences. At the 681 hPa level during winter months of December, January and February (DJF) the composite O3 mixing ratios were uniformly low (~45 ppbv), but continental export was evident in a channel of enhanced CO (100–110 ppbv) flowing eastward from the US coast. In summer months June, July, and August (JJA) O3 mixing ratios were variable (45–65 ppbv) and generally higher due to increased photochemical production. The summer distribution also featured a channel of enhanced CO (95–105 ppbv) flowing northeastward around an anticyclone and exiting the continent over the Canadian Maritimes around 50° N. Offshore O3-CO slopes were generally 0.15–0.20 mol mol−1 in JJA, indicative of photochemical O3 production. Composites for 4 predominant synoptic patterns or map types in DJF suggested that export to the lower free troposphere (681 hPa level) was enhanced by the warm conveyor belt airstream of mid-latitude cyclones while stratospheric intrusions increased TES O3 levels at 316 hPa. A major finding in the DJF data was that offshore 681 hPa CO mixing ratios behind cold fronts could be enhanced up to >150 ppbv likely by lofting from the surface via shallow convection resulting from rapid destabilization of cold air flowing over much warmer ocean waters. In JJA composites for 3 map types showed that the general export pattern of the seasonal composites was associated with a synoptic pattern featuring the Bermuda High. However, weak cyclones and frontal troughs could enhance offshore 681 hPa CO mixing ratios to >110 ppbv with O3-CO slopes >0.50 mol mol−1 south of 45° N. Intense cyclones, which were not as common in the summer, enhanced export by lofting of boundary layer pollutants from over the US and also provided a possible mechanism for transporting pollutants from boreal fire outflow southward to the US east coast. Overall, for winter and summer the TES retrievals showed substantial evidence of air pollution export to the western North Atlantic Ocean with the most distinct differences in distribution patterns related to strong influences of mid-latitude cyclones in winter and the Bermuda High anticyclone in summer.
Ozone response to emission changes: a modeling study during the MCMA-2006/MILAGRO Campaign
Authors: Song J. , Lei W. , Bei N. , Zavala M. , de Foy B. , Volkamer R. , Cardenas B. , Zheng J. , Zhang R. , Molina L. T.
Published: April 2010

Abstract. The sensitivity of ozone production to precursor emissions was investigated under five different meteorological conditions in the Mexico City Metropolitan Area (MCMA) during the MCMA-2006/MILAGRO field campaign using the gridded photochemical model CAMx driven by observation-nudged WRF meteorology. Precursor emissions were constrained by the comprehensive data from the field campaign and the routine ambient air quality monitoring network. Simulated plume mixing and transport were examined by comparing with measurements from the G-1 aircraft during the campaign. The observed concentrations of ozone precursors and ozone were reasonably well reproduced by the model. The effects of reducing precursor emissions on urban ozone production were performed for three representative emission control scenarios. A 50% reduction in VOC emissions led to 7 to 22 ppb decrease in daily maximum ozone concentrations, while a 50% reduction in NOx emissions leads to 4 to 21 ppb increase, and 50% reductions in both NOx and VOC emission decrease the daily maximum ozone concentrations up to 10 ppb. These results along with a chemical indicator analysis using the chemical production ratios of H2O2 to HNO3 demonstrate that the MCMA urban core region is VOC-limited for all meteorological episodes, which is consistent with the results from MCMA-2003 field campaign; however the degree of the VOC-sensitivity is higher during MCMA-2006 due to lower VOCs, lower VOC reactivity and moderately higher NOx emissions. Ozone formation in the surrounding mountain/rural area is mostly NOx-limited, but can be VOC-limited, and the range of the NOx-limited or VOC-limited areas depends on meteorology.
The impact of aerosols on polarized sky radiance: model development, validation, and applications
Authors: Emde C. , Buras R. , Mayer B. , Blumthaler M.
Published: April 2010

Abstract. Although solar radiation initially is unpolarized when entering the Earth's atmosphere, it is polarized by scattering processes with molecules, water droplets, ice crystals, and aerosols. Hence, measurements of the polarization state of radiation can be used to improve remote sensing of aerosols and clouds. The analysis of polarized radiance measurements requires an accurate radiative transfer model. To this end, a new efficient and flexible three-dimensional Monte Carlo code to compute polarized radiances has been developed and implemented into MYSTIC (Monte Carlo code for the phYSically correct Tracing of photons In Cloudy atmospheres). The code has been extensively validated against published benchmark results. The polarized downwelling radiation field is calculated for various aerosol types showing the high sensitivity of polarized ultraviolet radiances to the particle microphysics. Model simulations are compared to ground based measurements and found to be qualitatively in good agreement. Quantitative differences can be attributed to the assumed aerosol models based on the OPAC aerosol database, which does not include exactly the types of aerosols that have been observed. This comparison to the measurements shows that there is a high potential to retrieve information about the aerosol type from polarized radiance measurements.
Temperature effect on physical and chemical properties of secondary organic aerosol from m-xylene photooxidation
Authors: Qi L. , Nakao S. , Tang P. , Cocker D. R.
Published: April 2010

Abstract. The chemical and physical differences of secondary organic aerosol (SOA) formed at select isothermal temperatures (278 K, 300 K, and 313 K) are explored with respect to density, particle volatility, particle hygroscopicity, and elemental chemical composition. A transition point in SOA density, volatility, hygroscopicity and elemental composition is observed near 290–292 K as SOA within an environmental chamber is heated from 278 K to 313 K, indicating the presence of a thermally labile compound. No such transition points are observed for SOA produced at 313 K or 300 K and subsequently cooled to 278 K. The SOA formed at the lowest temperatures (278 K) is more than double the SOA formed at 313 K. SOA formed at 278 K is less hydrophilic and oxygenated while more volatile and dense than SOA formed at 300 K or 313 K. The properties of SOA formed at 300 K and 313 K when reduced to 278 K did not match the properties of SOA initially formed at 278 K. This study demonstrates that it is insufficient to utilize the enthalpy of vaporization when predicting SOA temperature dependence.
Cloud droplet activation of mixed organic-sulfate particles produced by the photooxidation of isoprene
Authors: King S. M. , Rosenoern T. , Shilling J. E. , Chen Q. , Wang Z. , Biskos G. , McKinney K. A. , Pöschl U. , Martin S. T.
Published: April 2010

Abstract. The cloud condensation nuclei (CCN) properties of ammonium sulfate particles mixed with organic material condensed during the hydroxyl-radical-initiated photooxidation of isoprene (C5H8) were investigated in the continuous-flow Harvard Environmental Chamber. CCN activation curves were measured for organic particle mass concentrations of 0.5 to 10.0 μg m−3, NOx concentrations from under 0.4 ppbv up to 38 ppbv, particle mobility diameters from 70 to 150 nm, and thermodenuder temperatures from 25 to 100 °C. At 25 °C, the observed CCN activation curves were accurately described by a Köhler model having two internally mixed components, namely ammonium sulfate and secondary organic material. The modeled physicochemical parameters of the organic material were equivalent to an effective hygroscopicity parameter κORG of 0.10±0.03, regardless of the C5H8:NOx concentration ratio for the span of >200:0.4 to 50:38 (ppbv:ppbv). The volatilization curves (i.e., plots of the residual organic volume fraction against temperature) were also similar for the span of investigated C5H8:NOx ratios, suggesting a broad similarity of particle chemical composition. This suggestion was supported by limited variance at 25 °C among the particle mass spectra. For example, the signal intensity at m/z 44 (which can result from the fragmentation of oxidized molecules believed to affect hygroscopicity and CCN properties) varied weakly from 6 to 9% across the range of investigated conditions. In contradistinction to the results for 25 °C, conditioning up to 100 °C in the thermodenuder significantly reduced CCN activity. The altered CCN activity might be explained by chemical reactions (e.g., decomposition or oligomerization) of the secondary organic material at elevated temperatures. The study's results at 25 °C, in conjunction with the results of other chamber and field studies for a diverse range of conditions, suggest that a value of 0.10±0.05 for κORG is representative of both anthropogenic and biogenic secondary organic material. This finding supports the use of κORG as a simplified yet accurate general parameter to represent the CCN activation of secondary organic material in large-scale atmospheric and climate models.
Greenhouse gas relationships in the Indian summer monsoon plume measured by the CARIBIC passenger aircraft
Authors: Schuck T. J. , Brenninkmeijer C. A. M. , Baker A. K. , Slemr F. , von Velthoven P. F. J. , Zahn A.
Published: April 2010

Abstract. During the Indian summer monsoon period 2008, regular measurement flights were performed by the CARIBIC aircraft between Germany and India. Measurements included whole air sampling and subsequent analysis for greenhouse gases (CH4, CO2, N2O, SF6) and in-situ measurements of CO, O3, and H2O. For all these tracers a distinct monsoon signature was observed in the longitude range 50–80° E south of 40° N at flight altitudes 8–12.5 km. The formation of a monsoon plume with enhanced mixing ratios was observed for CH4, N2O, SF6, CO and H2O. The plume began to develop in May and persisted through September, and maximum mixing ratios and maximum spatial extension of the plume were observed in August. For CO2 and O3 a minimum was observed. The amplitude of the CO2 seasonal cycle was larger than at comparable latitudes outside the monsoon region, and the CO2 spring maximum was observed with a delay of one month. Different tracer relationships show strong spatial variations across the plume. The comparison with NOAA ground station data shows a clear enhancement for CH4, N2O, SF6 and CO and a decrease in CO2 mixing ratios. Assuming seasonally invariant SF6 emissions based on the EDGAR 4.0 inventory, monthly emissions were estimated for the period June–September for CH4, N2O, and CO, and the CO2 uptake was estimated. While for N2O an emission decrease during the monsoon period was derived, emissions of CH4 were highest in September indicating a different seasonal cycle of emissions. Net CO2 uptake by the vegetation was largest in September.
A detailed aerosol mixing state model for investigating interactions between mixing state, semivolatile partitioning, and coagulation
Authors: Lu J. , Bowman F. M.
Published: April 2010

Abstract. A new method for describing externally mixed particles, the Detailed Aerosol Mixing State (DAMS) representation, is presented in this study. This novel method classifies aerosols by both composition and size, using a user-specified mixing criterion to define boundaries between compositional populations. Interactions between aerosol mixing state, semivolatile partitioning, and coagulation are investigated with a Lagrangian box model that incorporates the DAMS approach. Model results predict that mixing state affects the amount and types of semivolatile organics that partition to available aerosol phases, causing external mixtures to produce a more size-varying composition than internal mixtures. Both coagulation and condensation contribute to the mixing of emitted particles, producing a collection of multiple compositionally distinct aerosol populations that exists somewhere between the extremes of a strictly external or internal mixture. The selection of mixing criteria has a significant impact on the size and type of individual populations that compose the modeled aerosol mixture. Computational demands for external mixture modeling are significant and can be controlled by limiting the number of aerosol populations used in the model.
Airborne measurements of the spatial distribution of aerosol chemical composition across Europe and evolution of the organic fraction
Authors: Morgan W. T. , Allan J. D. , Bower K. N. , Highwood E. J. , Liu D. , McMeeking G. R. , Northway M. J. , Williams P. I. , Krejci R. , Coe H.
Published: April 2010

Abstract. The spatial distribution of aerosol chemical composition and the evolution of the Organic Aerosol (OA) fraction is investigated based upon airborne measurements of aerosol chemical composition in the planetary boundary layer across Europe. Sub-micron aerosol chemical composition was measured using a compact Time-of-Flight Aerosol Mass Spectrometer (cToF-AMS). A range of sampling conditions were evaluated, including relatively clean background conditions, polluted conditions in North-Western Europe and the near-field to far-field outflow from such conditions. Ammonium nitrate and OA were found to be the dominant chemical components of the sub-micron aerosol burden, with mass fractions ranging from 20–50% each. Ammonium nitrate was found to dominate in North-Western Europe during episodes of high pollution, reflecting the enhanced NOx and ammonia sources in this region. OA was ubiquitous across Europe and concentrations generally exceeded sulphate by 30–160%. A factor analysis of the OA burden was performed in order to probe the evolution across this large range of spatial and temporal scales. Two separate Oxygenated Organic Aerosol (OOA) components were identified; one representing an aged-OOA, termed Low Volatility-OOA and another representing fresher-OOA, termed Semi Volatile-OOA on the basis of their mass spectral similarity to previous studies. The factors derived from different flights were not chemically the same but rather reflect the range of OA composition sampled during a particular flight. Significant chemical processing of the OA was observed downwind of major sources in North-Western Europe, with the LV-OOA component becoming increasingly dominant as the distance from source and photochemical processing increased. The measurements suggest that the aging of OA can be viewed as a continuum, with a progression from a less oxidised, semi-volatile component to a highly oxidised, less-volatile component. Substantial amounts of pollution were observed far downwind of continental Europe, with OA and ammonium nitrate being the major constituents of the sub-micron aerosol burden. Such anthropogenically perturbed air masses can significantly perturb regional climate far downwind of major source regions.
IASI spectral radiance validation inter-comparisons: case study assessment from the JAIVEx field campaign
Authors: Larar A. M. , Smith W. L. , Zhou D. K. , Liu X. , Revercomb H. , Taylor J. P. , Newman S. M. , Schlüssel P.
Published: April 2010

Abstract. Advanced satellite sensors are tasked with improving global-scale measurements of the Earth's atmosphere, clouds, and surface to enable enhancements in weather prediction, climate monitoring, and environmental change detection. Measurement system validation is crucial to achieving this goal and maximizing research and operational utility of resultant data. Field campaigns employing satellite under-flights with well-calibrated Fourier Transform Spectrometer (FTS) sensors aboard high-altitude aircraft are an essential part of this validation task. The National Polar-orbiting Operational Environmental Satellite System (NPOESS) Airborne Sounder Testbed-Interferometer (NAST-I) has been a fundamental contributor in this area by providing coincident high spectral and spatial resolution observations of infrared spectral radiances along with independently-retrieved geophysical products for comparison with like products from satellite sensors being validated. This manuscript focuses on validating infrared spectral radiance from the Infrared Atmospheric Sounding Interferometer (IASI) through a case study analysis using data obtained during the recent Joint Airborne IASI Validation Experiment (JAIVEx) field campaign. Emphasis is placed upon the benefits achievable from employing airborne interferometers such as the NAST-I since, in addition to IASI radiance calibration performance assessments, cross-validation with other advanced sounders such as the AQUA Atmospheric InfraRed Sounder (AIRS) is enabled.
Contributions from transport, solid fuel burning and cooking to primary organic aerosols in two UK cities
Authors: Allan J. D. , Williams P. I. , Morgan W. T. , Martin C. L. , Flynn M. J. , Lee J. , Nemitz E. , Phillips G. J. , Gallagher M. W. , Coe H.
Published: April 2010

Abstract. Organic matter frequently represents the single largest fraction of fine particulates in urban environments and yet the exact contributions from different sources and processes remain uncertain, owing in part to its substantial chemical complexity. Positive Matrix Factorisation (PMF) has recently proved to be a powerful tool for the purposes of source attribution and profiling when applied to ambient organic aerosol data from the Aerodyne Aerosol Mass Spectrometer (AMS). Here we present PMF analysis applied to AMS data from UK cities for the first time. Three datasets are analysed, with the focus on objectivity and consistency. The data were collected in London during the Regent's Park and Tower Environmental Experiment (REPARTEE) intensives and Manchester. These occurred during the autumn and wintertime, such that the primary fraction would be prominent. Ambiguities associated with rotationality within sets of potential solutions are explored and the most appropriate solution sets selected based on comparisons with external data. In addition to secondary organic aerosols, three candidate sources of primary organic aerosol (POA) were identified according to mass spectral and diurnal profiles; traffic emissions, cooking and solid fuel burning (for space heating). Traffic represented, on average, 40% of POA during colder conditions and exhibited a hydrocarbon-like mass spectrum similar to those previously reported. Cooking aerosols represented 34% of POA and through laboratory work, their profile was matched with that sampled from the heating of seed oils, rather than previously-published spectra derived from charbroiling. This suggests that in these locations, oil from frying may have contributed more to the particulate than the meat itself. Solid fuel aerosols represented 26% of POA during cold weather conditions but were not discernable during the first REPARTEE campaign, when conditions were warmer than the other campaigns. This factor showed features associated with biomass burning and occurred mainly at night. Grid-scale emission factors of the combustion aerosols suitable for use in chemical transport models were derived relative to CO and NOx. The traffic aerosols were found to be 20.5 μg m−3 ppm−1 relative to CO for Manchester and 31.6 μg m−3 ppm−1 relative to NOx for London. Solid fuel emissions were derived as 24.7 μg m−3 ppm−1 relative to CO for Manchester. These correspond to mass emission ratios of 0.018, 0.026 (as NO) and 0.021 respectively and are of a similar order to previously published estimates, derived from other regions or using other approaches.
The critical assessment of vapour pressure estimation methods for use in modelling the formation of atmospheric organic aerosol
Authors: Barley M. H. , McFiggans G.
Published: April 2010

Abstract. A selection of models for estimating vapour pressures have been tested against experimental data for a set of compounds selected for their particular relevance to the formation of atmospheric aerosol by gas-liquid partitioning. The experimental vapour pressure data (all <100 Pa) of 45 multifunctional compounds provide a stringent test of the estimation techniques, with a recent complex group contribution method providing the best overall results. The effect of errors in vapour pressures upon the formation of organic aerosol by gas-liquid partitioning in an atmospherically relevant example is also investigated. The mass of organic aerosol formed under typical atmospheric conditions was found to be very sensitive to the variation in vapour pressure values typically present when comparing estimation methods.
High resolution modeling of CO2 over Europe: implications for representation errors of satellite retrievals
Authors: Pillai D. , Gerbig C. , Marshall J. , Ahmadov R. , Kretschmer R. , Koch T. , Karstens U.
Published: April 2010

Abstract. Satellite retrievals for column CO2 with better spatial and temporal sampling are expected to improve the current surface flux estimates of CO2 via inverse techniques. However, the spatial scale mismatch between remotely sensed CO2 and current generation inverse models can induce representation errors, which can cause systematic biases in flux estimates. This study is focused on estimating these representation errors associated with utilization of satellite measurements in global models with a horizontal resolution of about 1 degree or less. For this we used simulated CO2 from the high resolution modeling framework WRF-VPRM, which links CO2 fluxes from a diagnostic biosphere model to a weather forecasting model at 10×10 km2 horizontal resolution. Sub-grid variability of column averaged CO2, i.e. the variability not resolved by global models, reached up to 1.2 ppm with a median value of 0.4 ppm. Statistical analysis of the simulation results indicate that orography plays an important role. Using sub-grid variability of orography and CO2 fluxes as well as resolved mixing ratio of CO2, a linear model can be formulated that could explain about 50% of the spatial patterns in the systematic (bias or correlated error) component of representation error in column and near-surface CO2 during day- and night-times. These findings give hints for a parameterization of representation error which would allow for the representation error to taken into account in inverse models or data assimilation systems.
Cluster analysis of the impact of air back-trajectories on aerosol optical properties at Hornsund, Spitsbergen
Authors: Rozwadowska A. , Zieliński T. , Petelski T. , Sobolewski P.
Published: April 2010

Abstract. In this paper, spectra of aerosol optical thickness from the AERONET (AErosol RObotic NETwork) station at Hornsund in the southern part of Spitsbergen were employed to study the impact of air mass history on aerosol optical thickness for wavelength λ=500 nm – AOT(500) – and the Ångström exponent. Backward trajectories computed, using the NOAA HYSPLIT model, were used to trace air history. It was found that in spring, the changes in AOT values over the Hornsund station were strongly influenced by air mass trajectories 8 days or longer in duration, arriving both in the free troposphere and at an altitude of 1 km above sea level. Nevertheless, free tropospheric advection was dominant. AOT variability in summer was best explained by the local direction and speed of advection (1-day trajectories) and was dominated by the effectiveness of cleansing processes. During the ASTAR 2007 campaign, the aerosols near Hornsund displayed low AOT values ranging from 0.06 to 0.09, which is lower than the mean AOT(500) for spring seasons from 2005 to 2007 (0.110±0.007; mean ± standard deviation of mean). 9 April 2007 with AOT(500)=0.147 was exceptional. The back-trajectories belonged to clusters with low and average cluster mean AOT. Apart from the maximum AOT of 9 April 2007, the observed AOT values were close to or lower than the means for the clusters to which they belonged.
A comprehensive evaluation of seasonal simulations of ozone in the northeastern US during summers of 2001–2005
Authors: Mao H. , Chen M. , Hegarty J. D. , Talbot R. W. , Koermer J. P. , Thompson A. M. , Avery M. A.
Published: April 2010

Abstract. Regional air quality simulations were conducted for summers 2001–2005 in the eastern US and subjected to extensive evaluation using various ground and airborne measurements. A brief climate evaluation focused on transport by comparing modeled dominant map types with ones from reanalysis. Reasonable agreement was found for their frequency of occurrence and distinctness of circulation patterns. The two most frequent map types from reanalysis were the Bermuda High (22%) and passage of a Canadian cold frontal over the northeastern US (20%). The model captured their frequency of occurrence at 25% and 18% respectively. The simulated five average distributions of 1-h ozone (O3) daily maxima using the Community Multiscale Air Quality (CMAQ) modeling system reproduced salient features in observations. This suggests that the ability of the regional climate model to depict transport processes accurately is critical for reasonable simulations of surface O3. Comparison of mean bias, root mean square error, and index of agreement for CMAQ summer surface 8-h O3 daily maxima and observations showed –0.6±14 nmol/mol, 14 nmol/mol, and 71% respectively. CMAQ performed best in moderately polluted conditions and less satisfactorily in highly polluted ones. This highlights the common problem of overestimating/underestimating lower/higher modeled O3 levels. Diagnostic analysis suggested that significant overestimation of inland nighttime low O3 mixing ratios may be attributed to underestimates of nitric oxide (NO) emissions at night. The absence of the second daily peak in simulations for the Appledore Island marine site possibly resulted from coarse grid resolution misrepresentation of land surface type. Comparison with shipboard measurements suggested that CMAQ has an inherent problem of underpredicting O3 levels in continental outflow. Modeled O3 vertical profiles exhibited a lack of structure indicating that key processes missing from CMAQ, such as lightning produced NO and stratospheric intrusions, are important for accurate upper tropospheric representations.