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Atmospheric Chemistry and Physics - Current Research Articles



Current research articles: Atmospheric Chemistry

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Atmospheric Chemistry and Physics - published by Copernicus Publications

ACP is an international scientific open access journal dedicated to the publication and public discussion of high quality studies investigating the Earth's atmosphere and the underlying chemical and physical processes. It covers the altitude range from the land and ocean surface up to the turbopause, including the troposphere, stratosphere and mesosphere.




Current articles of the journal:



Aerosol processing and CCN formation of an intense Saharan dust plume during the EUCAARI 2008 campaign

Aerosol processing and CCN formation of an intense Saharan dust plume during the EUCAARI 2008 campaign

Atmospheric Chemistry and Physics, 15, 3497-3516, 2015

Author(s): N. Bègue, P. Tulet, J. Pelon, B. Aouizerats, A. Berger, and A. Schwarzenboeck

Atmospheric processing and CCN formation of Saharan dust is illustrated through the analysis of a case of dust transport over northern Europe. This spread of dust is investigated by combining satellite, airborne and ground-based observations and the non-hydrostatic meso-scale model Meso-NH. The altitude of the dust plume during its transport to northwestern Europe was assessed using the CALIPSO observations and our model results. The major dust plume was transported toward Mediterranean and European regions between 2 and 5 km above sea level (a.s.l.). This is confirmed by an average particle depolarization ratio equal to 30%. Due to transport, this layer split into two layers over northern Europe, and we analyzed in this paper possible mixing of the European pollution aerosol with dust particles in the lower layer. The simulations have shown that the lower dust layer has interacted with the anthropogenic aerosol mainly over Belgium and the Netherlands. The analyses of numerical simulation results show that mineral dust particles accumulated soluble material through internal mixing over the Netherlands. The value of the CCN0.2 / CN ratio obtained over the Netherlands (~ 70%) is much greater than those observed over the Saharan region. In addition over the Netherlands, the CCN measurement reached 14 000 particles cm?3 at 0.63% supersaturation level on 30 May. Our model results reveal that more than 70% of the CCN concentration observed on 30 May can be explained by the presence of Saharan aged dust. The study reveals that heterogeneous reactions with inorganic salts converted this Saharan mineral dust into compounds that were sufficiently soluble to impact hygroscopic growth and cloud droplet activation over the Netherlands.

Posted on 31 March 2015 | 12:00 am


Step changes in persistent organic pollutants over the Arctic and their implications

Step changes in persistent organic pollutants over the Arctic and their implications

Atmospheric Chemistry and Physics, 15, 3479-3495, 2015

Author(s): Y. Zhao, T. Huang, L. Wang, H. Gao, and J. Ma

While some persistent organic pollutants (POPs) have been declining globally due to their worldwide ban since the 1980s, the declining trends of many of these toxic chemicals become less significant and in some cases their ambient air concentrations, e.g., polychlorinated biphenyls (PCBs), showed observable increase during the 2000s, disagreeing with their declining global emissions and environmental degradation. As part of the efforts to assess the influences of environmental factors on the long-term trend of POPs in the Arctic, step change points in the time series of ambient POP atmospheric concentrations collected from four arctic monitoring sites were examined using various statistical techniques. Results showed that the step change points of these POP data varied in different years and at different sites. Most step change points were found in 2001–2002 and 2007–2008. In particular, the step change points of many PCBs for 2007–2008 were coincident with the lowest arctic sea ice concentration occurring during the 2000s. The perturbations of air concentration and water–air exchange fluxes of several selected POPs averaged over the Arctic, simulated by a POP mass balance perturbation model, switched from negative to positive during the early 2000s, indicating a tendency for reversal of POPs from deposition to volatilization which coincides with a positive to negative reversal of arctic sea ice extent anomalies from 2001. Perturbed ice–air exchange flux of PCB 28 and 153 showed an increasing trend and a negative to positive reversal in 2007, the year with the lowest arctic sea ice concentration. On the other hand, perturbed ice–air exchange flux of ?-hexachlorocyclohexane decreased over the period of 1995 to 2012, likely owing to its lower Henry's law constant which indicates its relatively lower tendency for volatilization from ice to air.

Posted on 31 March 2015 | 12:00 am


Estimated desert-dust ice nuclei profiles from polarization lidar: methodology and case studies

Estimated desert-dust ice nuclei profiles from polarization lidar: methodology and case studies

Atmospheric Chemistry and Physics, 15, 3463-3477, 2015

Author(s): R. E. Mamouri and A. Ansmann

A lidar method is presented that permits the estimation of height profiles of ice nuclei concentrations (INC) in desert dust layers. The polarization lidar technique is applied to separate dust and non-dust backscatter and extinction coefficients. The desert dust extinction coefficients σd are then converted to aerosol particle number concentrations APC280 which consider particles with radius > 280 nm only. By using profiles of APC280 and ambient temperature T along the laser beam, the profile of INC can be estimated within a factor of 3 by means of APC-T-INC parameterizations from the literature. The observed close relationship between σd at 500 nm and APC280 is of key importance for a successful INC retrieval. We studied this link by means of AERONET (Aerosol Robotic Network) sun/sky photometer observations at Morocco, Cabo Verde, Barbados, and Cyprus during desert dust outbreaks. The new INC retrieval method is applied to lidar observations of dust layers with the spaceborne lidar CALIOP (Cloud Aerosol Lidar with Orthogonal Polarization) during two overpasses over the EARLINET (European Aerosol Research Lidar Network) lidar site of the Cyprus University of Technology (CUT), Limassol (34.7° N, 33° E), Cyprus. The good agreement between the CALIOP and CUT lidar retrievals of σd, APC280, and INC profiles corroborates the potential of CALIOP to provide 3-D global desert dust APC280 and INC data sets.

Posted on 30 March 2015 | 12:00 am


Long-term particulate matter modeling for health effect studies in California – Part 1: Model performance on temporal and spatial variations

Long-term particulate matter modeling for health effect studies in California – Part 1: Model performance on temporal and spatial variations

Atmospheric Chemistry and Physics, 15, 3445-3461, 2015

Author(s): J. Hu, H. Zhang, Q. Ying, S.-H. Chen, F. Vandenberghe, and M. J. Kleeman

For the first time, a ~ decadal (9 years from 2000 to 2008) air quality model simulation with 4 km horizontal resolution over populated regions and daily time resolution has been conducted for California to provide air quality data for health effect studies. Model predictions are compared to measurements to evaluate the accuracy of the simulation with an emphasis on spatial and temporal variations that could be used in epidemiology studies. Better model performance is found at longer averaging times, suggesting that model results with averaging times ≥ 1 month should be the first to be considered in epidemiological studies. The UCD/CIT model predicts spatial and temporal variations in the concentrations of O3, PM2.5, elemental carbon (EC), organic carbon (OC), nitrate, and ammonium that meet standard modeling performance criteria when compared to monthly-averaged measurements. Predicted sulfate concentrations do not meet target performance metrics due to missing sulfur sources in the emissions. Predicted seasonal and annual variations of PM2.5, EC, OC, nitrate, and ammonium have mean fractional biases that meet the model performance criteria in 95, 100, 71, 73, and 92% of the simulated months, respectively. The base data set provides an improvement for predicted population exposure to PM concentrations in California compared to exposures estimated by central site monitors operated 1 day out of every 3 days at a few urban locations.

Uncertainties in the model predictions arise from several issues. Incomplete understanding of secondary organic aerosol formation mechanisms leads to OC bias in the model results in summertime but does not affect OC predictions in winter when concentrations are typically highest. The CO and NO (species dominated by mobile emissions) results reveal temporal and spatial uncertainties associated with the mobile emissions generated by the EMFAC 2007 model. The WRF model tends to overpredict wind speed during stagnation events, leading to underpredictions of high PM concentrations, usually in winter months. The WRF model also generally underpredicts relative humidity, resulting in less particulate nitrate formation, especially during winter months. These limitations must be recognized when using data in health studies. All model results included in the current manuscript can be downloaded free of charge at http://faculty.engineering.ucdavis.edu/kleeman/ .

Posted on 30 March 2015 | 12:00 am


Total sulfate vs. sulfuric acid monomer concenterations in nucleation studies

Total sulfate vs. sulfuric acid monomer concenterations in nucleation studies

Atmospheric Chemistry and Physics, 15, 3429-3443, 2015

Author(s): K. Neitola, D. Brus, U. Makkonen, M. Sipilä, R. L. Mauldin III, N. Sarnela, T. Jokinen, H. Lihavainen, and M. Kulmala

Sulfuric acid is known to be a key component for atmospheric nucleation. Precise determination of sulfuric-acid concentration is a crucial factor for prediction of nucleation rates and subsequent growth. In our study, we have noticed a substantial discrepancy between sulfuric-acid monomer concentrations and total-sulfate concentrations measured from the same source of sulfuric-acid vapor. The discrepancy of about 1–2 orders of magnitude was found with similar particle-formation rates. To investigate this discrepancy, and its effect on nucleation, a method of thermally controlled saturator filled with pure sulfuric acid (97% wt.) for production of sulfuric-acid vapor is applied and rigorously tested. The saturator provided an independent vapor-production method, compared to our previous method of the furnace (Brus et al., 2010, 2011), to find out if the discrepancy is caused by the production method itself. The saturator was used in a H2SO4–H2O nucleation experiment, using a laminar flow tube to check reproducibility of the nucleation results with the saturator method, compared to the furnace. Two independent methods of mass spectrometry and online ion chromatography were used for detecting sulfuric-acid or sulfate concentrations. Measured sulfuric-acid or total-sulfate concentrations are compared to theoretical predictions calculated using vapor pressure and a mixing law. The calculated prediction of sulfuric-acid concentrations agrees very well with the measured values when total sulfate is considered. Sulfuric-acid monomer concentration was found to be about 2 orders of magnitude lower than theoretical predictions, but with a temperature dependency similar to the predictions and the results obtained with the ion-chromatograph method. Formation rates are reproducible when compared to our previous results with both sulfuric-acid or total-sulfate detection and sulfuric-acid production methods separately, removing any doubts that the vapor-production method would cause the discrepancy. Possible reasons for the discrepancy are discussed and some suggestions include that the missing sulfuric acid is in clusters, formed with contaminants found in most laboratory experiments. One-to-two-order-of-magnitude higher sulfuric-acid concentrations (measured as total sulfate in this study) would contribute to a higher fraction of particle growth rate than assumed from the measurements by mass spectrometers (i.e. sulfuric-acid monomer). However, the observed growth rates by sulfate-containing vapor in this study does not directly imply a similar situation in the field, where sources of sulfate are much more diverse.

Posted on 28 March 2015 | 12:00 am


Major contribution of neutral clusters to new particle formation at the interface between the boundary layer and the free troposphere

Major contribution of neutral clusters to new particle formation at the interface between the boundary layer and the free troposphere

Atmospheric Chemistry and Physics, 15, 3413-3428, 2015

Author(s): C. Rose, K. Sellegri, E. Asmi, M. Hervo, E. Freney, A. Colomb, H. Junninen, J. Duplissy, M. Sipilä, J. Kontkanen, K. Lehtipalo, and M. Kulmala

The formation of new aerosol particles in the atmosphere is a key process influencing the aerosol number concentration as well as the climate, in particular at high altitude, where the newly formed particles directly influence cloud formation. However, free tropospheric new particle formation (NPF) is poorly documented due to logistic limitations and complex atmospheric dynamics around high-altitude stations that make the observation of this day-time process challenging. Recent improvements in measurement techniques make now possible the detection of neutral clusters down to ~ 1 nm sizes, which opens new horizons in our understanding of the nucleation process. Indeed, only the charged fraction of clusters has been reported in the upper troposphere up to now. Here we report day-time concentrations of charged and neutral clusters (1 to 2.5 nm mobility diameter) recorded at the interface between the boundary layer (BL) and the FT as well as in the FT at the altitude site of Puy de Dôme (1465 m a.s.l.), central France, between 10 and 29 February 2012. Our findings demonstrate that in the FT, and especially at the interface between the BL and the FT, the formation of 1.5 nm neutral clusters significantly exceeds the one of ionic clusters during NPF events, clearly indicating that they dominate in the nucleation process. We also observe that the total cluster concentration significantly increases during NPF events compared to the other days, which was not clearly observed for the charged cluster population in the past. During the studied period, the nucleation process does not seem to be sulfuric acid-limited and could be promoted by the transport of pollutants to the upper troposphere, coupled with low temperatures.

Posted on 27 March 2015 | 12:00 am


Using the chemical equilibrium partitioning space to explore factors influencing the phase distribution of compounds involved in secondary organic aerosol formation

Using the chemical equilibrium partitioning space to explore factors influencing the phase distribution of compounds involved in secondary organic aerosol formation

Atmospheric Chemistry and Physics, 15, 3395-3412, 2015

Author(s): F. Wania, Y. D. Lei, C. Wang, J. P. D. Abbatt, and K.-U. Goss

Many atmospheric and chemical variables influence the partitioning equilibrium between gas phase and condensed phases of compounds implicated in the formation of secondary organic aerosol (SOA). The large number of factors and their interaction makes it often difficult to assess their relative importance and concerted impact. Here we introduce a two-dimensional space which maps regions of dominant atmospheric phase distribution within a coordinate system defined by equilibrium partition coefficients between the gas phase, an aqueous phase and a water-insoluble organic matter (WIOM) phase. Placing compounds formed from the oxidation of n-alkanes, terpenes and mono-aromatic hydrocarbons on the maps based on their predicted partitioning properties allows for a simple graphical assessment of their equilibrium phase distribution behaviour. Specifically, it allows for the simultaneous visualisation and quantitative comparison of the impact on phase distribution of changes in atmospheric parameters (such as temperature, salinity, WIOM-phase polarity, organic aerosol load, and liquid water content) and chemical properties (such as oxidation state, molecular size, functionalisation, and dimerisation). The graphical analysis reveals that the addition of hydroxyl, carbonyl and carboxyl groups increases the affinity of aliphatic, alicyclic and aromatic hydrocarbons for the aqueous phase more rapidly than their affinity for WIOM, suggesting that the aqueous phase may often be relevant even for substances that are considerably larger than the C2 and C3 compounds that are typically believed to be associated with aqueous SOA. In particular, the maps identify some compounds that contribute to SOA formation if partitioning to both WIOM and aqueous phase is considered but would remain in the gas phase if either condensed phase were neglected. For example, many semi-volatile ?-pinene oxidation products will contribute to aqueous SOA under the conditions of high liquid water content encountered in clouds but would remain vapours in wet aerosol. It is conceivable to develop parameterisations of "partitioning basis sets" that group compounds with comparable partitioning properties, which – when combined with data on the abundance of those groups of compounds – could serve in the simulation of SOA formation.

Posted on 27 March 2015 | 12:00 am


Hygroscopic properties of NaCl and NaNO3 mixture particles as reacted inorganic sea-salt aerosol surrogates

Hygroscopic properties of NaCl and NaNO3 mixture particles as reacted inorganic sea-salt aerosol surrogates

Atmospheric Chemistry and Physics, 15, 3379-3393, 2015

Author(s): D. Gupta, H. Kim, G. Park, X. Li, H.-J. Eom, and C.-U. Ro

NaCl in fresh sea-salt aerosol (SSA) particles can partially or fully react with atmospheric NOx/HNO3, so internally mixed NaCl and NaNO3 aerosol particles can co-exist over a wide range of mixing ratios. Laboratory-generated, micrometer-sized NaCl and NaNO3 mixture particles at 10 mixing ratios (mole fractions of NaCl (XNaCl) = 0.1 to 0.9) were examined systematically to observe their hygroscopic behavior, derive experimental phase diagrams for deliquescence and efflorescence, and understand the efflorescence mechanism. During the humidifying process, aerosol particles with the eutonic composition (XNaCl = 0.38) showed only one phase transition at their mutual deliquescence relative humidity (MDRH) of 67.9 (±0.5)% On the other hand, particles with other mixing ratios showed two distinct deliquescence transitions; i.e., the eutonic component dissolved at MDRH, and the remainder in the solid phase dissolved completely at their DRHs depending on the mixing ratios, resulting in a phase diagram composed of four different phases, as predicted thermodynamically. During the dehydration process, NaCl-rich particles (XNaCl > 0.38) showed a two stage efflorescence transition: the first stage was purely driven by the homogeneous nucleation of NaCl and the second stage at the mutual efflorescence RH (MERH) of the eutonic components, with values in the range of 30.0–35.5%. Interestingly, aerosol particles with the eutonic composition (XNaCl = 0.38) also showed two-stage efflorescence, with NaCl crystallizing first followed by heterogeneous nucleation of the remaining NaNO3 on the NaCl seeds. NaNO3-rich particles (XNaCl ≤ 0.3) underwent single-stage efflorescence transitions at ERHs progressively lower than the MERH because of the homogeneous nucleation of NaCl and the almost simultaneous heterogeneous nucleation of NaNO3 on the NaCl seeds. SEM/EDX elemental mapping indicated that the effloresced NaCl–NaNO3 particles at all mixing ratios were composed of a homogeneously crystallized NaCl moiety in the center, surrounded either by the eutonic component (for XNaCl > 0.38) or NaNO3 (for XNaCl ≤ 0.38). During the humidifying or dehydration process, the amount of eutonic composed part drives particle/droplet growth or shrinkage at the MDRH or MERH (second ERH), respectively, and the amount of pure salts (NaCl or NaNO3 in NaCl- or NaNO3-rich particles, respectively) drives the second DRHs or first ERHs, respectively. Therefore, their behavior can be a precursor to the optical properties and direct radiative forcing for these atmospherically relevant mixture particles representing the coarse, reacted inorganic SSAs. In addition, the NaCl–NaNO3 mixture aerosol particles can maintain an aqueous phase over a wider RH range than pure NaCl particles as SSA surrogate, making their heterogeneous chemistry more probable.

Posted on 26 March 2015 | 12:00 am


Diel and seasonal changes of biogenic volatile organic compounds within and above an Amazonian rainforest

Diel and seasonal changes of biogenic volatile organic compounds within and above an Amazonian rainforest

Atmospheric Chemistry and Physics, 15, 3359-3378, 2015

Author(s): A. M. Yáñez-Serrano, A. C. Nölscher, J. Williams, S. Wolff, E. Alves, G. A. Martins, E. Bourtsoukidis, J. Brito, K. Jardine, P. Artaxo, and J. Kesselmeier

The Amazonian rainforest is a large tropical ecosystem, which is one of the last pristine continental terrains. This ecosystem is ideally located for the study of diel and seasonal behaviour of biogenic volatile organic compounds (BVOCs) in the absence of local human interference. In this study, we report the first atmospheric BVOC measurements at the Amazonian Tall Tower Observatory (ATTO) site, located in central Amazonia. A quadrupole proton-transfer-reaction mass spectrometer (PTR-MS), with seven ambient air inlets, positioned from near ground to about 80 m (0.05, 0.5, 4, 24, 38, 53 and 79 m above the forest floor), was deployed for BVOC monitoring. We report diel and seasonal (February–March 2013 as wet season and September 2013 as dry season) ambient mixing ratios for isoprene, monoterpenes, isoprene oxidation products, acetaldehyde, acetone, methyl ethyl ketone (MEK), methanol and acetonitrile. Clear diel and seasonal patterns were observed for all compounds. In general, lower mixing ratios were observed during night, while maximum mixing ratios were observed during the wet season (February–March 2013), with the peak in solar irradiation at 12:00 LT (local time) and during the dry season (September 2013) with the peak in temperature at 16:00 LT. Isoprene and monoterpene mixing ratios were the highest within the canopy with a median of 7.6 and 1 ppb, respectively (interquartile range (IQR) of 6.1 and 0.38 ppb) during the dry season (at 24 m, from 12:00 to 15:00 LT). The increased contribution of oxygenated volatile organic compounds (OVOCs) above the canopy indicated a transition from dominating forest emissions during the wet season (when mixing ratios were higher than within the canopy), to a blend of biogenic emission, photochemical production and advection during the dry season when mixing ratios were higher above the canopy. Our observations suggest strong seasonal interactions between environmental (insolation, temperature) and biological (phenology) drivers of leaf BVOC emissions and atmospheric chemistry. Considerable differences in the magnitude of BVOC mixing ratios, as compared to other reports of Amazonian BVOC, demonstrate the need for long-term observations at different sites and more standardized measurement procedures, in order to better characterize the natural exchange of BVOCs between the Amazonian rainforest and the atmosphere.

Posted on 25 March 2015 | 12:00 am


Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of ?-pinene

Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of ?-pinene

Atmospheric Chemistry and Physics, 15, 3339-3358, 2015

Author(s): C. Denjean, P. Formenti, B. Picquet-Varrault, E. Pangui, P. Zapf, Y. Katrib, C. Giorio, A. Tapparo, A. Monod, B. Temime-Roussel, P. Decorse, C. Mangeney, and J. F. Doussin

Secondary organic aerosol (SOA) were generated from the ozonolysis of ?-pinene in the CESAM (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) simulation chamber. The SOA formation and aging were studied by following their optical, hygroscopic and chemical properties. The optical properties were investigated by determining the particle complex refractive index (CRI). The hygroscopicity was quantified by measuring the effect of relative humidity (RH) on the particle size (size growth factor, GF) and on the scattering coefficient (scattering growth factor, f(RH)). The oxygen to carbon atomic ratios (O : C) of the particle surface and bulk were used as a sensitive parameter to correlate the changes in hygroscopic and optical properties of the SOA composition during their formation and aging in CESAM.

The real CRI at 525 nm wavelength decreased from 1.43–1.60 (±0.02) to 1.32–1.38 (±0.02) during the SOA formation. The decrease in the real CRI correlated to the O : C decrease from 0.68 (±0.20) to 0.55 (±0.16). In contrast, the GF remained roughly constant over the reaction time, with values of 1.02–1.07 (±0.02) at 90% (±4.2%) RH. Simultaneous measurements of O : C of the particle surface revealed that the SOA was not composed of a homogeneous mixture, but contained less oxidised species at the surface which may limit water absorption. In addition, an apparent change in both mobility diameter and scattering coefficient with increasing RH from 0 to 30% was observed for SOA after 14 h of reaction. We postulate that this change could be due to a change in the viscosity of the SOA from a predominantly glassy state to a predominantly liquid state.

Posted on 25 March 2015 | 12:00 am


Energetic particle induced intra-seasonal variability of ozone inside the Antarctic polar vortex observed in satellite data

Energetic particle induced intra-seasonal variability of ozone inside the Antarctic polar vortex observed in satellite data

Atmospheric Chemistry and Physics, 15, 3327-3338, 2015

Author(s): T. Fytterer, M. G. Mlynczak, H. Nieder, K. Pérot, M. Sinnhuber, G. Stiller, and J. Urban

Measurements from 2002 to 2011 by three independent satellite instruments, namely MIPAS, SABER, and SMR on board the ENVISAT, TIMED, and Odin satellites are used to investigate the intra-seasonal variability of stratospheric and mesospheric O3 volume mixing ratio (vmr) inside the Antarctic polar vortex due to solar and geomagnetic activity. In this study, we individually analysed the relative O3 vmr variations between maximum and minimum conditions of a number of solar and geomagnetic indices (F10.7 cm solar radio flux, Ap index, ≥ 2 MeV electron flux). The indices are 26-day averages centred at 1 April, 1 May, and 1 June while O3 is based on 26-day running means from 1 April to 1 November at altitudes from 20 to 70 km. During solar quiet time from 2005 to 2010, the composite of all three instruments reveals an apparent negative O3 signal associated to the geomagnetic activity (Ap index) around 1 April, on average reaching amplitudes between ?5 and ?10% of the respective O3 background. The O3 response exceeds the significance level of 95% and propagates downwards throughout the polar winter from the stratopause down to ~ 25 km. These observed results are in good qualitative agreement with the O3 vmr pattern simulated with a three-dimensional chemistry-transport model, which includes particle impact ionisation.

Posted on 24 March 2015 | 12:00 am


Dust aerosol radiative effects during summer 2012 simulated with a coupled regional aerosol–atmosphere–ocean model over the Mediterranean

Dust aerosol radiative effects during summer 2012 simulated with a coupled regional aerosol–atmosphere–ocean model over the Mediterranean

Atmospheric Chemistry and Physics, 15, 3303-3326, 2015

Author(s): P. Nabat, S. Somot, M. Mallet, M. Michou, F. Sevault, F. Driouech, D. Meloni, A. di Sarra, C. Di Biagio, P. Formenti, M. Sicard, J.-F. Léon, and M.-N. Bouin

The present study investigates the radiative effects of dust aerosols in the Mediterranean region during summer 2012 using a coupled regional aerosol–atmosphere–ocean model (CNRM-RCSM5). A prognostic aerosol scheme, including desert dust, sea salt, organic, black-carbon and sulphate particles, has been integrated to CNRM-RCSM5 in addition to the atmosphere, land surface and ocean components. An evaluation of this aerosol scheme of CNRM-RCSM5, and especially of the dust aerosols, has been performed against in situ and satellite measurements, showing its ability to reproduce the spatial and temporal variability of aerosol optical depth (AOD) over the Mediterranean region in summer 2012. The dust vertical and size distributions have also been evaluated against observations from the TRAQA/ChArMEx campaign. Three simulations have been carried out for summer 2012 with CNRM-RCSM5, including the full prognostic aerosol scheme, only monthly-averaged AOD means from the aerosol scheme or no aerosols at all, in order to focus on the radiative effects of dust particles and the role of the prognostic scheme. Surface short-wave aerosol radiative forcing variability is found to be more than twice as high over regions affected by dust aerosols, when using a prognostic aerosol scheme instead of monthly AOD means. In this case downward surface solar radiation is also found to be better reproduced according to a comparison with several stations across the Mediterranean. A composite study over 14 stations across the Mediterranean, designed to identify days with high dust AOD, also reveals the improvement of the representation of surface temperature brought by the use of the prognostic aerosol scheme. Indeed the surface receives less radiation during dusty days, but only the simulation using the prognostic aerosol scheme is found to reproduce the observed intensity of the dimming and warming on dusty days. Moreover, the radiation and temperature averages over summer 2012 are also modified by the use of prognostic aerosols, mainly because of the differences brought in short-wave aerosol radiative forcing variability. Therefore this first comparison over summer 2012 highlights the importance of the choice of the representation of aerosols in climate models.

Posted on 24 March 2015 | 12:00 am


Mesoscale modelling study of the interactions between aerosols and PBL meteorology during a haze episode in China Jing–Jin–Ji and its near surrounding region – Part 2: Aerosols' radiative feedback effects

Mesoscale modelling study of the interactions between aerosols and PBL meteorology during a haze episode in China Jing–Jin–Ji and its near surrounding region – Part 2: Aerosols' radiative feedback effects

Atmospheric Chemistry and Physics, 15, 3277-3287, 2015

Author(s): H. Wang, G. Y. Shi, X. Y. Zhang, S. L. Gong, S. C. Tan, B. Chen, H. Z. Che, and T. Li

Two model experiments, namely a control (CTL) experiment without aerosol–radiation feedbacks and a experiment with online aerosol–radiation (RAD) interactions, were designed to study the radiative feedback on regional radiation budgets, planetary boundary layer (PBL) meteorology and haze formation due to aerosols during haze episodes over Jing–Jin–Ji, China, and its near surroundings (3JNS region of China: Beijing, Tianjin, Hebei, East Shanxi, West Shandong and North Henan) with a two-way atmospheric chemical transport model. The impact of aerosols on solar radiation reaching Earth's surface, outgoing long-wave emission at the top of the atmosphere, air temperature, PBL turbulence diffusion, PBL height, wind speeds, air pressure pattern and PM2.5 has been studied focusing on a haze episode during the period from 7 to 11 July 2008. The results show that the mean solar radiation flux that reaches the ground decreases by about 15% in 3JNS and 20 to 25%in the region with the highest aerosol optical depth during the haze episode. The fact that aerosol cools the PBL atmosphere but warms the atmosphere above it leads to a more stable atmospheric stratification over the region, which causes a decrease in turbulence diffusion of about 52% and a decrease in the PBL height of about 33%. This consequently forms a positive feedback on the particle concentration within the PBL and the surface as well as the haze formation. Additionally, aerosol direct radiative forcing (DRF) increases PBL wind speed by about 9% and weakens the subtropical high by about 14 hPa, which aids the collapse of haze pollution and results in a negative feedback to the haze episode. The synthetic impacts from the two opposite feedbacks result in about a 14% increase in surface PM2.5. However, the persistence time of both high PM2.5 and haze pollution is not affected by the aerosol DRF. On the contrary over offshore China, aerosols heat the PBL atmosphere and cause unstable atmospheric stratification, but the impact and its feedback on the planetary boundary layer height, turbulence diffusion and wind is weak, with the exception of the evident impacts on the subtropical high.

Posted on 23 March 2015 | 12:00 am


Mesoscale modeling study of the interactions between aerosols and PBL meteorology during a haze episode in Jing–Jin–Ji (China) and its nearby surrounding region – Part 1: Aerosol distributions and meteorological features

Mesoscale modeling study of the interactions between aerosols and PBL meteorology during a haze episode in Jing–Jin–Ji (China) and its nearby surrounding region – Part 1: Aerosol distributions and meteorological features

Atmospheric Chemistry and Physics, 15, 3257-3275, 2015

Author(s): H. Wang, M. Xue, X. Y. Zhang, H. L. Liu, C. H. Zhou, S. C. Tan, H. Z. Che, B. Chen, and T. Li

The urbanized region ofJing(Beijing)-Jin(Tianjin)-Ji (alias of Hebei province) and its nearby surrounding region (3JNS) is becoming China's most polluted area by haze, exceeding even the Yangtze and Pearl river deltas. Aside from pollutant emission, the meteorology of the planetary boundary layer (PBL) is the most important factor affecting haze pollution. Focusing on July 2008, the aerosol optical properties and PBL meteorology features closely related to haze formation were simulated in the 3JNS region using an online atmospheric chemical transport model. The relationship between regional PBL meteorology, PM2.5, and haze is discussed. Model results accurately simulated the aerosol optical depth (AOD), single scattering albedo (SSA) and asymmetry parameter (ASY), validated by comparison with observations from the MODerate Resolution Imaging Spectroradiometer (MODIS), the China Aerosol Remote Sensing NETwork (CARSNET) and the Aerosol Robotic NETwork (AERONET). Modeled PBL wind speeds showed reasonable agreement with those from the National Centers for Environmental Prediction (NCEP) Reanalysis 2. A monthly mean AOD value as high as 1.2 was found from both model and observations, with a daily mean larger than 2.0 during haze episodes in the 3JNS region. Modeled and observed SSA values of 0.90–0.96 and ASY values of 0.72–0.74 demonstrated the high scattering characteristic of summer aerosols in this region. PBL wind speeds from modeled and NCEP data both showed a reversing trend of PM2.5 variation, illustrating the importance of the "PBL window shadow" in haze formation. Turbulence diffusion and PBL height had opposite phases to surface PM2.5, indicating that lower PBL height and weaker PBL turbulence diffusion are essential to haze formation. It is noted that homogeneous air pressure does not occur at the surface, but at an 850–950 hPa height during the haze episode. The momentum transmitting downward of the cold air from above the PBL to the low PBL and surface lead to an increase in surface wind speeds and haze dispersal.

Posted on 23 March 2015 | 12:00 am


Spaceborne observations of the lidar ratio of marine aerosols

Spaceborne observations of the lidar ratio of marine aerosols

Atmospheric Chemistry and Physics, 15, 3241-3255, 2015

Author(s): K. W. Dawson, N. Meskhidze, D. Josset, and S. Gassó

Retrievals of aerosol optical depth (AOD) from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) satellite sensor require the assumption of the extinction-to-backscatter ratio, also known as the lidar ratio. This paper evaluates a new method to calculate the lidar ratio of marine aerosols using two independent sources: the AOD from the Synergized Optical Depth of Aerosols (SODA) project and the integrated attenuated backscatter from CALIOP. With this method, the particulate lidar ratio can be derived for individual CALIOP retrievals in single aerosol layer, cloud-free columns over the ocean. Global analyses are carried out using CALIOP level 2, 5 km marine aerosol layer products and the collocated SODA nighttime data from December 2007 to November 2010. The global mean lidar ratio for marine aerosols was found to be 26 sr, roughly 30% higher than the current value prescribed by the CALIOP standard retrieval algorithm. Data analysis also showed considerable spatiotemporal variability in the calculated lidar ratio over the remote oceans. The calculated marine aerosol lidar ratio is found to vary with the mean ocean surface wind speed (U10). An increase in U10 reduces the mean lidar ratio for marine regions from 32 ± 17 sr (for 0 < U10 < 4 m s−1) to 22 ± 7 sr (for U10 > 15 m s−1). Such changes in the lidar ratio are expected to have a corresponding effect on the marine AOD from CALIOP. The outcomes of this study are relevant for future improvements of the SODA and CALIOP operational product and could lead to more accurate retrievals of marine AOD.

Posted on 23 March 2015 | 12:00 am


Aerosol physicochemical properties and implications for visibility during an intense haze episode during winter in Beijing

Aerosol physicochemical properties and implications for visibility during an intense haze episode during winter in Beijing

Atmospheric Chemistry and Physics, 15, 3205-3215, 2015

Author(s): Y. H. Wang, Z. R. Liu, J. K. Zhang, B. Hu, D. S. Ji, Y. C. Yu, and Y. S. Wang

The evolution of physical, chemical and optical properties of urban aerosol particles was characterized during an extreme haze episode in Beijing, PRC, from 24 through 31 January 2013 based on in situ measurements. The average mass concentrations of PM1, PM2.5 and PM10 were 99 ± 67 ?g m−3 (average ± SD), 188 ± 128 ?g m−3 and 265 ± 157 ?g m−3, respectively. A significant increase in PM1-2.5 fraction was observed during the most heavily polluted period. The average scattering coefficient at 550 nm was 877 ± 624 Mm−1. An increasing relative amount of coarse particles can be deduced from the variations of backscattering ratios, asymmetry parameter and scattering Ångström exponent. Particle number-size distributions between 14 and 2500 nm diameter showed high number concentrations, particularly in the nucleation mode and accumulation mode. Size-resolved chemical composition of submicron aerosol from a high-resolution time-of-flight aerosol mass spectrometer showed that the mass concentrations of organic, sulfate, nitrate, ammonium and chlorine mainly resided on particles between 500 and 800 nm (vacuum diameter), and nitrate and ammonium contributed greatly to particle growth during the heavily polluted day (28 January). Increasing relative humidity and stable synoptic conditions on 28 January combined with heavy pollution on 28 January, leading to enhanced water uptake by the hygroscopic submicron particles and formation of secondary aerosol, which might be the main reasons for the severity of the haze episode. Light-scattering apportionment showed that organic, sulfate, ammonium nitrate and ammonium chloride compounds contributed to light-scattering fractions of 54, 24, 12 and 10%, respectively. This study indicated that the organic component in submicron aerosol played an important role in visibility degradation during the haze episode in Beijing.

Posted on 23 March 2015 | 12:00 am


Seasonal changes in the tropospheric carbon monoxide profile over the remote Southern Hemisphere evaluated using multi-model simulations and aircraft observations

Seasonal changes in the tropospheric carbon monoxide profile over the remote Southern Hemisphere evaluated using multi-model simulations and aircraft observations

Atmospheric Chemistry and Physics, 15, 3217-3239, 2015

Author(s): J. A. Fisher, S. R. Wilson, G. Zeng, J. E. Williams, L. K. Emmons, R. L. Langenfelds, P. B. Krummel, and L. P. Steele

The combination of low anthropogenic emissions and large biogenic sources that characterizes the Southern Hemisphere (SH) leads to significant differences in atmospheric composition relative to the better studied Northern Hemisphere. This unique balance of sources poses significant challenges for global models. Carbon monoxide (CO) in particular is difficult to simulate in the SH due to the increased importance of secondary chemical production associated with the much more limited primary emissions. Here, we use aircraft observations from the 1991–2000 Cape Grim Overflight Program (CGOP) and the 2009–2011 HIAPER (High-performance Instrumented Airborne Platform for Environmental Research) Pole-to-Pole Observations (HIPPO), together with model output from the SH Model Intercomparison Project, to elucidate the drivers of CO vertical structure in the remote SH. Observed CO vertical profiles from Cape Grim are remarkably consistent with those observed over the southern mid-latitudes Pacific 10–20 years later, despite major differences in time periods, flight locations, and sampling strategies between the two data sets. These similarities suggest the processes driving observed vertical gradients are coherent across much of the remote SH and have not changed significantly over the past 2 decades. Model ability to simulate CO profiles reflects the interplay between biogenic emission sources, the chemical mechanisms that drive CO production from these sources, and the transport that redistributes this CO throughout the SH. The four chemistry-climate and chemical transport models included in the intercomparison show large variability in their abilities to reproduce the observed CO profiles. In particular, two of the four models significantly underestimate vertical gradients in austral summer and autumn, which we find are driven by long-range transport of CO produced from oxidation of biogenic compounds. Comparisons between the models show that more complex chemical mechanisms do not necessarily provide more accurate simulation of CO vertical gradients due to the convolved impacts of emissions, chemistry, and transport. Our results imply a large sensitivity of the remote SH troposphere to biogenic emissions and chemistry, both of which remain key uncertainties in global modeling. We suggest that the CO vertical gradient can be used as a metric for future model evaluation as it provides a sensitive test of the processes that define the chemical state of the background atmosphere.

Posted on 23 March 2015 | 12:00 am


The influence of clouds on radical concentrations: observations and modelling studies of HOx during the Hill Cap Cloud Thuringia (HCCT) campaign in 2010

The influence of clouds on radical concentrations: observations and modelling studies of HOx during the Hill Cap Cloud Thuringia (HCCT) campaign in 2010

Atmospheric Chemistry and Physics, 15, 3289-3301, 2015

Author(s): L. K. Whalley, D. Stone, I. J. George, S. Mertes, D. van Pinxteren, A. Tilgner, H. Herrmann, M. J. Evans, and D. E. Heard

The potential for chemistry occurring in cloud droplets to impact atmospheric composition has been known for some time. However, the lack of direct observations and uncertainty in the magnitude of these reactions led to this area being overlooked in most chemistry transport models. Here we present observations from Mt Schmücke, Germany, of the HO2 radical made alongside a suite of cloud measurements. HO2 concentrations were depleted in-cloud by up to 90% with the rate of heterogeneous loss of HO2 to clouds necessary to bring model and measurements into agreement, demonstrating a dependence on droplet surface area and pH. This provides the first observationally derived assessment for the uptake coefficient of HO2 to cloud droplets and was found to be in good agreement with theoretically derived parameterisations. Global model simulations, including this cloud uptake, showed impacts on the oxidising capacity of the troposphere that depended critically on whether the HO2 uptake leads to production of H2O2 or H2O.

Posted on 23 March 2015 | 12:00 am


Interannual variability of isotopic composition in water vapor over western Africa and its relationship to ENSO

Interannual variability of isotopic composition in water vapor over western Africa and its relationship to ENSO

Atmospheric Chemistry and Physics, 15, 3193-3204, 2015

Author(s): A. Okazaki, Y. Satoh, G. Tremoy, F. Vimeux, R. Scheepmaker, and K. Yoshimura

This study was performed to examine the relationship between isotopic composition in near-surface vapor (?18Ov) over western Africa during the monsoon season and El Niño–Southern Oscillation (ENSO) activity using the Isotope-incorporated Global Spectral Model. The model was evaluated using a satellite and in situ observations at daily to interannual timescales. The model provided an accurate simulation of the spatial pattern and seasonal and interannual variations of isotopic composition in column and surface vapor and precipitation over western Africa. Encouraged by this result, we conducted a simulation stretching 34 years (1979–2012) to investigate the relationship between atmospheric environment and isotopic signature on an interannual timescale. The simulation indicated that the depletion in the monsoon season does not appear every year at Niamey. The major difference between the composite fields with and without depletion was in the amount of precipitation in the upstream area of Niamey. As the interannual variation of the precipitation amount is influenced by the ENSO, we regressed the monsoon season averaged ?18Ov from the model and annually averaged NINO3 index and found a statistically significant correlation (R = 0.56, P < 0.01) at Niamey. This relationship suggests that there is a possibility of reconstructing past western African monsoon activity and ENSO using climate proxies.

Posted on 20 March 2015 | 12:00 am


Explaining variance in black carbon's aging timescale

Explaining variance in black carbon's aging timescale

Atmospheric Chemistry and Physics, 15, 3173-3191, 2015

Author(s): L. Fierce, N. Riemer, and T. C. Bond

The size and composition of particles containing black carbon (BC) are modified soon after emission by condensation of semivolatile substances and coagulation with other particles, known collectively as "aging" processes. Although this change in particle properties is widely recognized, the timescale for transformation is not well constrained. In this work, we simulated aerosol aging with the particle-resolved model PartMC-MOSAIC (Particle Monte Carlo – Model for Simulating Aerosol Interactions and Chemistry) and extracted aging timescales based on changes in particle cloud condensation nuclei (CCN). We simulated nearly 300 scenarios and, through a regression analysis, identified the key parameters driving the value of the aging timescale. We show that BC's aging timescale spans from hours to weeks, depending on the local environmental conditions and the characteristics of the fresh BC-containing particles. Although the simulations presented in this study included many processes and particle interactions, we show that 80% of the variance in the aging timescale is explained by only a few key parameters. The condensation aging timescale decreased with the flux of condensing aerosol and was shortest for the largest fresh particles, while the coagulation aging timescale decreased with the total number concentration of large (D >100 nm), CCN-active particles and was shortest for the smallest fresh particles. Therefore, both condensation and coagulation play important roles in aging, and their relative impact depends on the particle size range.

Posted on 20 March 2015 | 12:00 am


Sources and contributions of wood smoke during winter in London: assessing local and regional influences

Sources and contributions of wood smoke during winter in London: assessing local and regional influences

Atmospheric Chemistry and Physics, 15, 3149-3171, 2015

Author(s): L. R. Crilley, W. J. Bloss, J. Yin, D. C. S. Beddows, R. M. Harrison, J. D. Allan, D. E. Young, M. Flynn, P. Williams, P. Zotter, A. S. H. Prevot, M. R. Heal, J. F. Barlow, C. H. Halios, J. D. Lee, S. Szidat, and C. Mohr

Determining the contribution of wood smoke to air pollution in large cities such as London is becoming increasingly important due to the changing nature of domestic heating in urban areas. During winter, biomass burning emissions have been identified as a major cause of exceedances of European air quality limits. The aim of this work was to quantify the contribution of biomass burning in London to concentrations of PM2.5 and determine whether local emissions or regional contributions were the main source of biomass smoke. To achieve this, a number of biomass burning chemical tracers were analysed at a site within central London and two sites in surrounding rural areas. Concentrations of levoglucosan, elemental carbon (EC), organic carbon (OC) and K+ were generally well correlated across the three sites. At all the sites, biomass burning was found to be a source of OC and EC, with the largest contribution of EC from traffic emissions, while for OC the dominant fraction included contributions from secondary organic aerosols, primary biogenic and cooking sources. Source apportionment of the EC and OC was found to give reasonable estimation of the total carbon from non-fossil and fossil fuel sources based upon comparison with estimates derived from 14C analysis. Aethalometer-derived black carbon data were also apportioned into the contributions from biomass burning and traffic and showed trends similar to those observed for EC. Mean wood smoke mass at the sites was estimated to range from 0.78 to 1.0 ?g m?3 during the campaign in January–February 2012. Measurements on a 160 m tower in London suggested a similar ratio of brown to black carbon (reflecting wood burning and traffic respectively) in regional and London air. Peaks in the levoglucosan and K+ concentrations were observed to coincide with low ambient temperature, consistent with domestic heating as a major contributing local source in London. Overall, the source of biomass smoke in London was concluded to be a background regional source overlaid by contributions from local domestic burning emissions. This could have implications when considering future emission control strategies during winter and may be the focus of future work in order to better determine the contributing local sources.

Posted on 20 March 2015 | 12:00 am


Dicarboxylic acids, ketocarboxylic acids, ?-dicarbonyls, fatty acids and benzoic acid in PM2.5 aerosol collected during CAREBeijing-2007: an effect of traffic restriction on air quality

Dicarboxylic acids, ketocarboxylic acids, ?-dicarbonyls, fatty acids and benzoic acid in PM2.5 aerosol collected during CAREBeijing-2007: an effect of traffic restriction on air quality

Atmospheric Chemistry and Physics, 15, 3111-3123, 2015

Author(s): K. F. Ho, R.-J. Huang, K. Kawamura, E. Tachibana, S. C. Lee, S. S. H. Ho, T. Zhu, and L. Tian

Thirty water-soluble organic species, including dicarboxylic acids, ketocarboxylic acids, ?-dicarbonyls, fatty acids and benzoic acid were determined as well as organic carbon (OC), elemental carbon (EC) and water-soluble organic carbon (WSOC) in PM2.5 samples collected during the Campaign of Air Quality Research in Beijing 2007 (CAREBeijing-2007) in the urban and suburban areas of Beijing. The objective of this study is to identify the influence of traffic emissions and regional transport to the atmosphere in Beijing during summer. PM2.5 samples collected with or without traffic restriction in Beijing are selected to evaluate the effectiveness of local traffic restriction measures on air pollution reduction. The average concentrations of the total quantified bifunctional organic compounds (TQBOCs), total fatty acids and benzoic acid during the entire sampling period were 1184±241, 597±159 and 1496±511 ng m?3 in Peking University (PKU), and 1050±303, 475±114 and 1278±372 ng m?3 in Yufa, Beijing. Oxalic acid (C2) was found as the most abundant dicarboxylic acid at PKU and Yufa followed by phthalic acid (Ph). A strong even carbon number predominance with the highest level at stearic acid (C18:0), followed by palmitic acid (C16:0) was found for fatty acids. According to the back trajectories modeling results, the air masses were found to originate mainly from the northeast, passing over the southeast or south of Beijing (heavily populated, urbanized and industrialized areas), during heavier pollution events, whereas they are mainly from the north or northwest sector (mountain areas without serious anthropogenic pollution sources) during less pollution events. The data with wind only from the same sector (minimizing the difference from regional contribution) but with and without traffic restriction in Beijing were analyzed to evaluate the effectiveness of local traffic restriction measures on the reduction of local air pollution in Beijing. The results suggested that the traffic restriction measures can reduce the air pollutants, but the decrease of pollutants is generally smaller in Yufa compared to that in PKU. Moreover, an enhancement of EC value indicates more elevated primary emissions in Yufa during restriction periods than in non-restriction periods. This study demonstrates that even when primary exhaust was controlled by traffic restriction, the contribution of secondary organic species formed from photochemical processes was critical with long-range atmospheric transport of pollutants.

Posted on 19 March 2015 | 12:00 am


Spatiotemporal variability of water vapor investigated using lidar and FTIR vertical soundings above the Zugspitze

Spatiotemporal variability of water vapor investigated using lidar and FTIR vertical soundings above the Zugspitze

Atmospheric Chemistry and Physics, 15, 3135-3148, 2015

Author(s): H. Vogelmann, R. Sussmann, T. Trickl, and A. Reichert

Water vapor is the most important greenhouse gas and its spatiotemporal variability strongly exceeds that of all other greenhouse gases. However, this variability has hardly been studied quantitatively so far. We present an analysis of a 5-year period of water vapor measurements in the free troposphere above the Zugspitze (2962 m a.s.l., Germany). Our results are obtained from a combination of measurements of vertically integrated water vapor (IWV), recorded with a solar Fourier transform infrared (FTIR) spectrometer on the summit of the Zugspitze and of water vapor profiles recorded with the nearby differential absorption lidar (DIAL) at the Schneefernerhaus research station. The special geometrical arrangement of one zenith-viewing and one sun-pointing instrument and the temporal resolution of both instruments allow for an investigation of the spatiotemporal variability of IWV on a spatial scale of less than 1 km and on a timescale of less than 1 h. The standard deviation of differences between both instruments σIWV calculated for varied subsets of data serves as a measure of variability. The different subsets are based on various spatial and temporal matching criteria. Within a time interval of 20 min, the spatial variability becomes significant for horizontal distances above 2 km, but only in the warm season (σIWV =0.35 mm). However, it is not sensitive to the horizontal distance during the winter season. The variability of IWV within a time interval of 30 min peaks in July and August (σIWV > 0.55 mm, mean horizontal distance = 2.5 km) and has its minimum around midwinter (σIWV < 0.2 mm, mean distance > 5 km). The temporal variability of IWV is derived by selecting subsets of data from both instruments with optimal volume matching. For a short time interval of 5 min, the variability is 0.05 mm and increases to more than 0.5 mm for a time interval of 15 h. The profile variability of water vapor is determined by analyzing subsets of water vapor profiles recorded by the DIAL within time intervals from 1 to 5 h. For all altitudes, the variability increases with widened time intervals. The lowest relative variability is observed in the lower free troposphere around an altitude of 4.5 km. Above 5 km, the relative variability increases continuously up to the tropopause by about a factor of 3. Analysis of the covariance of the vertical variability reveals an enhanced variability of water vapor in the upper troposphere above 6 km. It is attributed to a more coherent flow of heterogeneous air masses, while the variability at lower altitudes is also driven by local atmospheric dynamics. By studying the short-term variability of vertical water vapor profiles recorded within a day, we come to the conclusion that the contribution of long-range transport and the advection of heterogeneous layer structures may exceed the impact of local convection by 1 order of magnitude even in the altitude range between 3 and 5 km.

Posted on 19 March 2015 | 12:00 am


Comparison of mercury concentrations measured at several sites in the Southern Hemisphere

Comparison of mercury concentrations measured at several sites in the Southern Hemisphere

Atmospheric Chemistry and Physics, 15, 3125-3133, 2015

Author(s): F. Slemr, H. Angot, A. Dommergue, O. Magand, M. Barret, A. Weigelt, R. Ebinghaus, E.-G. Brunke, K. A. Pfaffhuber, G. Edwards, D. Howard, J. Powell, M. Keywood, and F. Wang

Our knowledge of the distribution of mercury concentrations in air of the Southern Hemisphere was until recently based mostly on intermittent measurements made during ship cruises. In the last few years continuous mercury monitoring has commenced at several sites in the Southern Hemisphere, providing new and more refined information. In this paper we compare mercury measurements at several remote sites in the Southern Hemisphere made over a period of at least 1 year at each location. Averages of monthly medians show similar although small seasonal variations at both Cape Point and Amsterdam Island. A pronounced seasonal variation at Troll research station in Antarctica is due to frequent mercury depletion events in the austral spring. Due to large scatter and large standard deviations of monthly average median mercury concentrations at Cape Grim, no systematic seasonal variation could be found there. Nevertheless, the annual average mercury concentrations at all sites during the 2007–2013 period varied only between 0.85 and 1.05 ng m?3. Part of this variability is likely due to systematic measurement uncertainties which we propose can be further reduced by improved calibration procedures. We conclude that mercury is much more uniformly distributed throughout the Southern Hemisphere than the distributions suggested by measurements made onboard ships. This finding implies that smaller trends can be detected in shorter time periods. We also report a change in the trend sign at Cape Point from decreasing mercury concentrations in 1996–2004 to increasing concentrations since 2007.

Posted on 19 March 2015 | 12:00 am


Properties and evolution of biomass burning organic aerosol from Canadian boreal forest fires

Properties and evolution of biomass burning organic aerosol from Canadian boreal forest fires

Atmospheric Chemistry and Physics, 15, 3077-3095, 2015

Author(s): M. D. Jolleys, H. Coe, G. McFiggans, J. W. Taylor, S. J. O'Shea, M. Le Breton, S. J.-B. Bauguitte, S. Moller, P. Di Carlo, E. Aruffo, P. I. Palmer, J. D. Lee, C. J. Percival, and M. W. Gallagher

Airborne measurements of biomass burning organic aerosol (BBOA) from boreal forest fires reveal highly contrasting properties for plumes of different ages. These measurements, performed using an Aerodyne Research Inc. compact time-of-flight aerosol mass spectrometer (C-ToF-AMS) during the BORTAS (quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) experiment in the summer of 2011, have been used to derive normalised excess organic aerosol (OA) mass concentrations (?OA / ?CO), with higher average ratios observed closer to source (0.190±0.010) than in the far-field (0.097±0.002). The difference in ?OA / ?CO between fresh and aged plumes is influenced by a change in dominant combustion conditions throughout the campaign. Measurements at source comprised 3 plume interceptions during a single research flight and sampled largely smouldering fires. Twenty-three interceptions were made across four flights in the far-field, with plumes originating from fires occurring earlier in the campaign when fire activity had been more intense, creating an underlying contrast in emissions prior to any transformations associated with aging. Changing combustion conditions also affect the vertical distribution of biomass burning emissions, as aged plumes from more flaming-dominated fires are injected to higher altitudes of up to 6000 m. Proportional contributions of the mass-to-charge ratio (m/z) 60 and 44 peaks in the AMS mass spectra to the total OA mass (denoted f60 and f44) are used as tracers for primary and oxidised BBOA, respectively. f44 is lower on average in near-field plumes than those sampled in the far-field, in accordance with longer aging times as plumes are transported a greater distance from source. However, high levels of ?O3 / ?CO and ?log(NOx / NOy) close to source indicate that emissions can be subject to very rapid oxidation over short timescales. Conversely, the lofting of plumes into the upper troposphere can lead to the retention of source profiles after transportation over extensive temporal and spatial scales, with f60 also higher on average in aged plumes. Evolution of OA composition with aging is comparable to observations of BB tracers in previous studies, revealing a consistent progression from f60 to f44. The elevated levels of oxygenation in aged plumes, and their association with lower average ?OA / ?CO, are consistent with OA loss through evaporation during aging due to a combination of dilution and chemical processing, while differences in combustion conditions throughout the campaign also have a significant influence on BBOA production and composition.

Posted on 18 March 2015 | 12:00 am


Chemical and stable carbon isotopic composition of PM2.5 from on-road vehicle emissions in the PRD region and implications for vehicle emission control policy

Chemical and stable carbon isotopic composition of PM2.5 from on-road vehicle emissions in the PRD region and implications for vehicle emission control policy

Atmospheric Chemistry and Physics, 15, 3097-3108, 2015

Author(s): S. Dai, X. Bi, L. Y. Chan, J. He, B. Wang, X. Wang, P. Peng, G. Sheng, and J. Fu

Vehicle emissions are a major source of urban air pollution. In recent decade, the Chinese government has introduced a range of policies to reduce vehicle emissions. In order to understand the chemical characteristics of PM2.5 from on-road vehicle emissions in the Pearl River Delta (PRD) region and to evaluate the effectiveness of control policies on vehicle emissions, the emission factors of PM2.5 mass, elemental carbon (EC), organic carbon (OC), water-soluble organic carbon (WSOC), water-soluble inorganic ions (WSII), metal elements, organic compounds and stable carbon isotopic composition were measured in the Zhujiang tunnel of Guangzhou, in the PRD region of China in 2013. Emission factors of PM2.5 mass, OC, EC and WSOC were 92.4, 16.7, 16.4 and 1.31 mg vehicle?1 km?1 respectively. Emission factors of WSII were 0.016 (F-) ~ 4.17 (Cl) mg vehicle?1 km?1, contributing about 9.8% to the PM2.5 emissions. The sum of 27 measured metal elements accounted for 15.2% of PM2.5 emissions. Fe was the most abundant metal element, with an emission factor of 3.91 mg vehicle?1 km?1. Emission factors of organic compounds including n-alkanes, polycyclic aromatic hydrocarbons, hopanes and steranes were 91.9, 5.02, 32.0 and 7.59 ?g vehicle?1 km?1, respectively. Stable carbon isotopic composition ?13C value was ?25.0‰ on average. An isotopic fractionation of 3.2‰ was found during fuel combustion. Compared to a previous study in Zhujiang tunnel in 2004, emission factors of PM2.5mass, EC, OC, WSII except Cl- and organic compounds decreased by 16.0 ~ 93.4%, which could be attributed to emission control policy from 2004 to 2013. However, emission factors of most of the metal elements increased significantly, which could be partially attributed to the changes in motor oil additives and vehicle conditions. There are no mandatory national standards to limit metal content from vehicle emissions, which should be a concern of the government. A snapshot of the 2013 characteristic emissions of PM2.5 and its constituents from the on-road vehicular fleet in the PRD region retrieved from our study would be helpful for the assessment of past and future implementations of vehicle emission control policy.

Posted on 18 March 2015 | 12:00 am


Effect of oxidant concentration, exposure time, and seed particles on secondary organic aerosol chemical composition and yield

Effect of oxidant concentration, exposure time, and seed particles on secondary organic aerosol chemical composition and yield

Atmospheric Chemistry and Physics, 15, 3063-3075, 2015

Author(s): A. T. Lambe, P. S. Chhabra, T. B. Onasch, W. H. Brune, J. F. Hunter, J. H. Kroll, M. J. Cummings, J. F. Brogan, Y. Parmar, D. R. Worsnop, C. E. Kolb, and P. Davidovits

We performed a systematic intercomparison study of the chemistry and yields of secondary organic aerosol (SOA) generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0 × 108 to 2.2 × 1010 molec cm?3 over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2 × 106 to 2 × 107 molec cm?3 over exposure times of several hours. The OH concentration in the chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. In most cases, for a specific SOA type the most-oxidized chamber SOA and the least-oxidized flow reactor SOA have similar mass spectra, oxygen-to-carbon and hydrogen-to-carbon ratios, and carbon oxidation states at integrated OH exposures between approximately 1 × 1011 and 2 × 1011 molec cm?3 s, or about 1–2 days of equivalent atmospheric oxidation. This observation suggests that in the range of available OH exposure overlap for the flow reactor and chambers, SOA elemental composition as measured by an aerosol mass spectrometer is similar whether the precursor is exposed to low OH concentrations over long exposure times or high OH concentrations over short exposure times. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed particles are routinely used.

Posted on 18 March 2015 | 12:00 am


Comment on "Observation and modelling of HOx radicals in a boreal forest" by Hens et al. (2014)

Comment on "Observation and modelling of HOx radicals in a boreal forest" by Hens et al. (2014)

Atmospheric Chemistry and Physics, 15, 3109-3110, 2015

Author(s): D. Mogensen and M. Boy

No abstract available.

Posted on 18 March 2015 | 12:00 am


Impact of pollution controls in Beijing on atmospheric oxygenated volatile organic compounds (OVOCs) during the 2008 Olympic Games: observation and modeling implications

Impact of pollution controls in Beijing on atmospheric oxygenated volatile organic compounds (OVOCs) during the 2008 Olympic Games: observation and modeling implications

Atmospheric Chemistry and Physics, 15, 3045-3062, 2015

Author(s): Y. Liu, B. Yuan, X. Li, M. Shao, S. Lu, Y. Li, C.-C. Chang, Z. Wang, W. Hu, X. Huang, L. He, L. Zeng, M. Hu, and T. Zhu

Oxygenated volatile organic compounds (OVOCs) are important products of the photo-oxidation of hydrocarbons. They influence the oxidizing capacity and the ozone-forming potential of the atmosphere. In the summer of 2008, 2 months of emission restrictions were enforced in Beijing to improve air quality during the Olympic Games. Observational evidence reported in related studies that these control measures were efficient in reducing the concentrations of primary anthropogenic pollutants (CO, NOx and non-methane hydrocarbons, i.e., NMHCs) by 30–40%. In this study, the influence of the emission restrictions on ambient levels of OVOCs was explored using a neural network analysis with consideration of meteorological conditions. Statistically significant reductions in formaldehyde (HCHO), acetaldehyde (CH3CHO), methyl ethyl ketone (MEK) and methanol were found to be 12.9, 15.8, 17.1 and 19.6%, respectively, when the restrictions were in place. The effect of emission controls on acetone was not detected in neural network simulations, probably due to pollution transport from surrounding areas outside Beijing. Although the ambient levels of most NMHCs were reduced by ~35% during the full control period, the emission ratios of reactive alkenes and aromatics closely related to automobile sources did not present much difference (< 30%). A zero-dimensional box model based on the Master Chemical Mechanism version 3.2 (MCM3.2) was applied to evaluate how OVOC production responds to the reduced precursors during the emissions control period. On average, secondary HCHO was produced from the oxidation of anthropogenic alkenes (54%), isoprene (30%) and aromatics (15%). The importance of biogenic sources for the total HCHO formation was almost on par with that of anthropogenic alkenes during the daytime. Anthropogenic alkenes and alkanes dominated the photochemical production of other OVOCs such as acetaldehyde, acetone and MEK. The relative changes of modeled HCHO, CH3CHO, methyl vinyl ketone and methacrolein (MVK + MACR) before and during the pollution controlled period were comparable to the estimated reductions in the neural network, reflecting that current mechanisms can largely explain secondary production of those species under urban conditions. However, it is worth noting that the box model overestimated the measured concentrations of aldehydes by a factor of 1.4–1.7 without consideration of loss of aldehydes on aerosols, and simulated MEK was in good agreement with the measurements when primary sources were taken into consideration. These results suggest that the understanding of the OVOCs budget in the box model remains incomplete, and that there is still considerable uncertainty in particular missing sinks (unknown chemical and physical processes) for aldehydes and absence of direct emissions for ketones.

Posted on 18 March 2015 | 12:00 am


Gauss–Seidel limb scattering (GSLS) radiative transfer model development in support of the Ozone Mapping and Profiler Suite (OMPS) limb profiler mission

Gauss–Seidel limb scattering (GSLS) radiative transfer model development in support of the Ozone Mapping and Profiler Suite (OMPS) limb profiler mission

Atmospheric Chemistry and Physics, 15, 3007-3020, 2015

Author(s): R. Loughman, D. Flittner, E. Nyaku, and P. K. Bhartia

The Gauss–Seidel limb scattering (GSLS) radiative transfer (RT) model simulates the transfer of solar radiation through the atmosphere and is imbedded in the retrieval algorithm used to process data from the Ozone Mapping and Profiler Suite (OMPS) limb profiler (LP), which was launched on the Suomi NPP satellite in October 2011. A previous version of this model has been compared with several other limb scattering RT models in previous studies, including Siro, MCC++, CDIPI, LIMBTRAN, SASKTRAN, VECTOR, and McSCIA. To address deficiencies in the GSLS radiance calculations revealed in earlier comparisons, several recent changes have been added that improve the accuracy and flexibility of the GSLS model, including

1. improved treatment of the variation of the extinction coefficient with altitude, both within atmospheric layers and above the nominal top of the atmosphere;

2. addition of multiple-scattering source function calculations at multiple solar zenith angles along the line of sight (LOS);

3. introduction of variable surface properties along the limb LOS, with minimal effort required to add variable atmospheric properties along the LOS as well;

4. addition of the ability to model multiple aerosol types within the model atmosphere.

The model improvements 1 and 2 are verified by comparison to previously published results (using standard radiance tables whenever possible), demonstrating significant improvement in cases for which previous versions of the GSLS model performed poorly. The single-scattered radiance errors that were as high as 4% in earlier studies are now generally reduced to 0.3%, while total radiance errors generally decline from 10% to 1–3%. In all cases, the tangent height dependence of the GSLS radiance error is greatly reduced.

Posted on 17 March 2015 | 12:00 am


Intercomparison of vertically resolved merged satellite ozone data sets: interannual variability and long-term trends

Intercomparison of vertically resolved merged satellite ozone data sets: interannual variability and long-term trends

Atmospheric Chemistry and Physics, 15, 3021-3043, 2015

Author(s): F. Tummon, B. Hassler, N. R. P. Harris, J. Staehelin, W. Steinbrecht, J. Anderson, G. E. Bodeker, A. Bourassa, S. M. Davis, D. Degenstein, S. M. Frith, L. Froidevaux, E. Kyrölä, M. Laine, C. Long, A. A. Penckwitt, C. E. Sioris, K. H. Rosenlof, C. Roth, H.-J. Wang, and J. Wild

In the framework of the SI2N (SPARC (Stratosphere-troposphere Processes And their Role in Climate)/IO3C (International Ozone Commission)/IGACO-O3 (Integrated Global Atmospheric Chemistry Observations – Ozone)/NDACC (Network for the Detection of Atmospheric Composition Change)) initiative, several long-term vertically resolved merged ozone data sets produced from satellite measurements have been analysed and compared. This paper presents an overview of the methods, assumptions, and challenges involved in constructing such merged data sets, as well as the first thorough intercomparison of seven new long-term satellite data sets. The analysis focuses on the representation of the annual cycle, interannual variability, and long-term trends for the period 1984–2011, which is common to all data sets. Overall, the best agreement amongst data sets is seen in the mid-latitude lower and middle stratosphere, with larger differences in the equatorial lower stratosphere and the upper stratosphere globally. In most cases, differences in the choice of underlying instrument records that were merged produced larger differences between data sets than the use of different merging techniques. Long-term ozone trends were calculated for the period 1984–2011 using a piecewise linear regression with a change in trend prescribed at the end of 1997. For the 1984–1997 period, trends tend to be most similar between data sets (with largest negative trends ranging from ?4 to ?8% decade?1 in the mid-latitude upper stratosphere), in large part due to the fact that most data sets are predominantly (or only) based on the SAGE-II record. Trends in the middle and lower stratosphere are much smaller, and, particularly for the lower stratosphere, large uncertainties remain. For the later period (1998–2011), trends vary to a greater extent, ranging from approximately ?1 to +5% decade?1 in the upper stratosphere. Again, middle and lower stratospheric trends are smaller and for most data sets not significantly different from zero. Overall, however, there is a clear shift from mostly negative to mostly positive trends between the two periods over much of the profile.

Posted on 17 March 2015 | 12:00 am


Gaseous products and secondary organic aerosol formation during long term oxidation of isoprene and methacrolein

Gaseous products and secondary organic aerosol formation during long term oxidation of isoprene and methacrolein

Atmospheric Chemistry and Physics, 15, 2953-2968, 2015

Author(s): L. Brégonzio-Rozier, F. Siekmann, C. Giorio, E. Pangui, S. B. Morales, B. Temime-Roussel, A. Gratien, V. Michoud, S. Ravier, M. Cazaunau, A. Tapparo, A. Monod, and J.-F. Doussin

First- and higher order-generation products formed from the oxidation of isoprene and methacrolein with OH radicals in the presence of NOx have been studied in a simulation chamber. Significant oxidation rates have been maintained for up to 7 h, allowing the study of highly oxidized products. Gas-phase product distribution and yields were obtained, and show good agreement with previous studies. Secondary organic aerosol (SOA) formation has also been investigated. SOA mass yields from previous studies show large discrepancies. The mass yields obtained here were consistent with the lowest values found in the literature, and more specifically in agreement with studies carried out with natural light or artificial lamps with emission similar to the solar spectrum. Differences in light source are therefore proposed to explain partially the discrepancies observed between different studies in the literature for both isoprene- and methacrolein-SOA mass yields. There is a high degree of similarity between the SOA mass spectra from isoprene and methacrolein photooxidation, thus strengthening the importance of the role of methacrolein in SOA formation from isoprene photooxidation under our experimental conditions (i.e., presence of NOx and long term oxidation). According to our results, SOA mass yields from both isoprene and methacrolein in the atmosphere could be lower than suggested by most of the current chamber studies.

Posted on 17 March 2015 | 12:00 am


Exploring the severe winter haze in Beijing: the impact of synoptic weather, regional transport and heterogeneous reactions

Exploring the severe winter haze in Beijing: the impact of synoptic weather, regional transport and heterogeneous reactions

Atmospheric Chemistry and Physics, 15, 2969-2983, 2015

Author(s): G. J. Zheng, F. K. Duan, H. Su, Y. L. Ma, Y. Cheng, B. Zheng, Q. Zhang, T. Huang, T. Kimoto, D. Chang, U. Pöschl, Y. F. Cheng, and K. B. He

Extreme haze episodes repeatedly shrouded Beijing during the winter of 2012–2013, causing major environmental and health problems. To better understand these extreme events, we performed a model-assisted analysis of the hourly observation data of PM2.5 and its major chemical compositions. The synthetic analysis shows that (1) the severe winter haze was driven by stable synoptic meteorological conditions over northeastern China, and not by an abrupt increase in anthropogenic emissions. (2) Secondary species, including organics, sulfate, nitrate, and ammonium, were the major constituents of PM2.5 during this period. (3) Due to the dimming effect of high loading of aerosol particles, gaseous oxidant concentrations decreased significantly, suggesting a reduced production of secondary aerosols through gas-phase reactions. Surprisingly, the observational data reveals an enhanced production rate of secondary aerosols, suggesting an important contribution from other formation pathways, most likely heterogeneous reactions. These reactions appeared to be more efficient in producing secondary inorganics aerosols than organic aerosols resulting in a strongly elevated fraction of inorganics during heavily polluted periods. (4) Moreover, we found that high aerosol concentration was a regional phenomenon. The accumulation process of aerosol particles occurred successively from cities southeast of Beijing. The apparent sharp increase in PM2.5 concentration of up to several hundred ?g m?3 per hour recorded in Beijing represented rapid recovery from an interruption to the continuous pollution accumulation over the region, rather than purely local chemical production. This suggests that regional transport of pollutants played an important role during these severe pollution events.

Posted on 17 March 2015 | 12:00 am


Two years of near real-time chemical composition of submicron aerosols in the region of Paris using an Aerosol Chemical Speciation Monitor (ACSM) and a multi-wavelength Aethalometer

Two years of near real-time chemical composition of submicron aerosols in the region of Paris using an Aerosol Chemical Speciation Monitor (ACSM) and a multi-wavelength Aethalometer

Atmospheric Chemistry and Physics, 15, 2985-3005, 2015

Author(s): J.-E. Petit, O. Favez, J. Sciare, V. Crenn, R. Sarda-Estève, N. Bonnaire, G. Mo?nik, J.-C. Dupont, M. Haeffelin, and E. Leoz-Garziandia

Aerosol mass spectrometer (AMS) measurements have been successfully used towards a better understanding of non-refractory submicron (PM1) aerosol chemical properties based on short-term campaigns. The recently developed Aerosol Chemical Speciation Monitor (ACSM) has been designed to deliver quite similar artifact-free chemical information but for low cost, and to perform robust monitoring over long-term periods. When deployed in parallel with real-time black carbon (BC) measurements, the combined data set allows for a quasi-comprehensive description of the whole PM1 fraction in near real time. Here we present 2-year long ACSM and BC data sets, between mid-2011 and mid-2013, obtained at the French atmospheric SIRTA supersite that is representative of background PM levels of the region of Paris. This large data set shows intense and time-limited (a few hours) pollution events observed during wintertime in the region of Paris, pointing to local carbonaceous emissions (mainly combustion sources). A non-parametric wind regression analysis was performed on this 2-year data set for the major PM1 constituents (organic matter, nitrate, sulfate and source apportioned BC) and ammonia in order to better refine their geographical origins and assess local/regional/advected contributions whose information is mandatory for efficient mitigation strategies. While ammonium sulfate typically shows a clear advected pattern, ammonium nitrate partially displays a similar feature, but, less expectedly, it also exhibits a significant contribution of regional and local emissions. The contribution of regional background organic aerosols (OA) is significant in spring and summer, while a more pronounced local origin is evidenced during wintertime, whose pattern is also observed for BC originating from domestic wood burning. Using time-resolved ACSM and BC information, seasonally differentiated weekly diurnal profiles of these constituents were investigated and helped to identify the main parameters controlling their temporal variations (sources, meteorological parameters). Finally, a careful investigation of all the major pollution episodes observed over the region of Paris between 2011 and 2013 was performed and classified in terms of chemical composition and the BC-to-sulfate ratio used here as a proxy of the local/regional/advected contribution of PM. In conclusion, these first 2-year quality-controlled measurements of ACSM clearly demonstrate their great potential to monitor on a long-term basis aerosol sources and their geographical origin and provide strategic information in near real time during pollution episodes. They also support the capacity of the ACSM to be proposed as a robust and credible alternative to filter-based sampling techniques for long-term monitoring strategies.

Posted on 17 March 2015 | 12:00 am


Long-term real-time chemical characterization of submicron aerosols at Montsec (southern Pyrenees, 1570 m a.s.l.)

Long-term real-time chemical characterization of submicron aerosols at Montsec (southern Pyrenees, 1570 m a.s.l.)

Atmospheric Chemistry and Physics, 15, 2935-2951, 2015

Author(s): A. Ripoll, M. C. Minguillón, J. Pey, J. L. Jimenez, D. A. Day, Y. Sosedova, F. Canonaco, A. S. H. Prévôt, X. Querol, and A. Alastuey

Real-time measurements of inorganic (sulfate, nitrate, ammonium, chloride and black carbon (BC)) and organic submicron aerosols (particles with an aerodynamic diameter of less than 1 ?m) from a continental background site (Montsec, MSC, 1570 m a.s.l.) in the western Mediterranean Basin (WMB) were conducted for 10 months (July 2011–April 2012). An aerosol chemical speciation monitor (ACSM) was co-located with other online and offline PM1 measurements. Analyses of the hourly, diurnal, and seasonal variations are presented here, for the first time, for this region.

Seasonal trends in PM1 components are attributed to variations in evolution of the planetary boundary layer (PBL) height, air mass origin, and meteorological conditions. In summer, the higher temperature and solar radiation increases convection, enhancing the growth of the PBL and the transport of anthropogenic pollutants towards high altitude sites. Furthermore, the regional recirculation of air masses over the WMB creates a continuous increase in the background concentrations of PM1 components and causes the formation of reservoir layers at relatively high altitudes. The combination of all these atmospheric processes results in a high variability of PM1 components, with poorly defined daily patterns, except for the organic aerosols (OA). OA was mostly composed (up to 90%) of oxygenated organic aerosol (OOA), split in two types: semivolatile (SV-OOA) and low-volatility (LV-OOA), the rest being hydrocarbon-like OA (HOA). The marked diurnal cycles of OA components regardless of the air mass origin indicates that they are not only associated with anthropogenic and long-range-transported secondary OA (SOA) but also with recently produced biogenic SOA.

Very different conditions drive the aerosol phenomenology in winter at MSC. The thermal inversions and the lower vertical development of the PBL leave MSC in the free troposphere most of the day, being affected by PBL air masses only after midday, when the mountain breezes transport emissions from the adjacent valleys and plains to the top of the mountain. This results in clear diurnal patterns of both organic and inorganic concentrations. OA was also mainly composed (71%) of OOA, with contributions from HOA (5%) and biomass burning OA (BBOA; 24%). Moreover, in winter sporadic long-range transport from mainland Europe is observed.

The results obtained in the present study highlight the importance of SOA formation processes at a remote site such as MSC, especially in summer. Additional research is needed to characterize the sources and processes of SOA formation at remote sites.

Posted on 16 March 2015 | 12:00 am


Trends of ozone total columns and vertical distribution from FTIR observations at eight NDACC stations around the globe

Trends of ozone total columns and vertical distribution from FTIR observations at eight NDACC stations around the globe

Atmospheric Chemistry and Physics, 15, 2915-2933, 2015

Author(s): C. Vigouroux, T. Blumenstock, M. Coffey, Q. Errera, O. García, N. B. Jones, J. W. Hannigan, F. Hase, B. Liley, E. Mahieu, J. Mellqvist, J. Notholt, M. Palm, G. Persson, M. Schneider, C. Servais, D. Smale, L. Thölix, and M. De Mazière

Ground-based Fourier transform infrared (FTIR) measurements of solar absorption spectra can provide ozone total columns with a precision of 2% but also independent partial column amounts in about four vertical layers, one in the troposphere and three in the stratosphere up to about 45km, with a precision of 5–6%. We use eight of the Network for the Detection of Atmospheric Composition Change (NDACC) stations having a long-term time series of FTIR ozone measurements to study the total and vertical ozone trends and variability, namely, Ny-Ålesund (79° N), Thule (77° N), Kiruna (68° N), Harestua (60° N), Jungfraujoch (47° N), Izaña (28° N), Wollongong (34° S) and Lauder (45° S). The length of the FTIR time series varies by station but is typically from about 1995 to present. We applied to the monthly means of the ozone total and four partial columns a stepwise multiple regression model including the following proxies: solar cycle, quasi-biennial oscillation (QBO), El Niño–Southern Oscillation (ENSO), Arctic and Antarctic Oscillation (AO/AAO), tropopause pressure (TP), equivalent latitude (EL), Eliassen–Palm flux (EPF), and volume of polar stratospheric clouds (VPSC).

At the Arctic stations, the trends are found mostly negative in the troposphere and lower stratosphere, very mixed in the middle stratosphere, positive in the upper stratosphere due to a large increase in the 1995–2003 period, and non-significant when considering the total columns. The trends for mid-latitude and subtropical stations are all non-significant, except at Lauder in the troposphere and upper stratosphere and at Wollongong for the total columns and the lower and middle stratospheric columns where they are found positive. At Jungfraujoch, the upper stratospheric trend is close to significance (+0.9 ± 1.0% decade−1). Therefore, some signs of the onset of ozone mid-latitude recovery are observed only in the Southern Hemisphere, while a few more years seem to be needed to observe it at the northern mid-latitude station.

Posted on 16 March 2015 | 12:00 am


Biases in atmospheric CO2 estimates from correlated meteorology modeling errors

Biases in atmospheric CO2 estimates from correlated meteorology modeling errors

Atmospheric Chemistry and Physics, 15, 2903-2914, 2015

Author(s): S. M. Miller, M. N. Hayek, A. E. Andrews, I. Fung, and J. Liu

Estimates of CO2 fluxes that are based on atmospheric measurements rely upon a meteorology model to simulate atmospheric transport. These models provide a quantitative link between the surface fluxes and CO2 measurements taken downwind. Errors in the meteorology can therefore cause errors in the estimated CO2 fluxes. Meteorology errors that correlate or covary across time and/or space are particularly worrisome; they can cause biases in modeled atmospheric CO2 that are easily confused with the CO2 signal from surface fluxes, and they are difficult to characterize. In this paper, we leverage an ensemble of global meteorology model outputs combined with a data assimilation system to estimate these biases in modeled atmospheric CO2. In one case study, we estimate the magnitude of month-long CO2 biases relative to CO2 boundary layer enhancements and quantify how that answer changes if we either include or remove error correlations or covariances. In a second case study, we investigate which meteorological conditions are associated with these CO2 biases.

In the first case study, we estimate uncertainties of 0.5–7 ppm in monthly-averaged CO2 concentrations, depending upon location (95% confidence interval). These uncertainties correspond to 13–150% of the mean afternoon CO2 boundary layer enhancement at individual observation sites. When we remove error covariances, however, this range drops to 2–22%. Top-down studies that ignore these covariances could therefore underestimate the uncertainties and/or propagate transport errors into the flux estimate.

In the second case study, we find that these month-long errors in atmospheric transport are anti-correlated with temperature and planetary boundary layer (PBL) height over terrestrial regions. In marine environments, by contrast, these errors are more strongly associated with weak zonal winds. Many errors, however, are not correlated with a single meteorological parameter, suggesting that a single meteorological proxy is not sufficient to characterize uncertainties in atmospheric CO2. Together, these two case studies provide information to improve the setup of future top-down inverse modeling studies, preventing unforeseen biases in estimated CO2 fluxes.

Posted on 13 March 2015 | 12:00 am


Stratospheric and mesospheric HO2 observations from the Aura Microwave Limb Sounder

Stratospheric and mesospheric HO2 observations from the Aura Microwave Limb Sounder

Atmospheric Chemistry and Physics, 15, 2889-2902, 2015

Author(s): L. Millán, S. Wang, N. Livesey, D. Kinnison, H. Sagawa, and Y. Kasai

This study introduces stratospheric and mesospheric hydroperoxyl radical (HO2) estimates from the Aura Microwave Limb Sounder (MLS) using an offline retrieval (i.e. run separately from the standard MLS algorithm). This new data set provides two daily zonal averages, one during daytime from 10 to 0.0032 hPa (using day-minus-night differences between 10 and 1 hPa to ameliorate systematic biases) and one during nighttime from 1 to 0.0032 hPa. The vertical resolution of this new data set varies from about 4 km at 10 hPa to around 14 km at 0.0032 hPa. A description of the methodology and an error analysis are presented. Comparisons against the Whole Atmosphere Community Climate Model (WACCM), the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) and the Far Infrared Spectrometer (FIRS-2) measurements, as well as photochemical simulations, demonstrate the robustness of the retrieval and indicate that the retrieval is sensitive enough to detect mesospheric HO2 layers during both day and night. This new data set is the first long-term HO2 stratospheric and mesospheric satellite record and it provides needed constraints to help resolve the O3 deficit problem and the "HOx dilemma".

Posted on 13 March 2015 | 12:00 am


Standard climate models radiation codes underestimate black carbon radiative forcing

Standard climate models radiation codes underestimate black carbon radiative forcing

Atmospheric Chemistry and Physics, 15, 2883-2888, 2015

Author(s): G. Myhre and B. H. Samset

Radiative forcing (RF) of black carbon (BC) in the atmosphere is estimated using radiative transfer codes of various complexities. Here we show that the two-stream radiative transfer codes used most in climate models give too strong forward scattering, leading to enhanced absorption at the surface and too weak absorption by BC in the atmosphere. Such calculations are found to underestimate the positive RF of BC by 10% for global mean, all sky conditions, relative to the more sophisticated multi-stream models. The underestimation occurs primarily for low surface albedo, even though BC is more efficient for absorption of solar radiation over high surface albedo.

Posted on 13 March 2015 | 12:00 am


Characterization of primary and secondary wood combustion products generated under different burner loads

Characterization of primary and secondary wood combustion products generated under different burner loads

Atmospheric Chemistry and Physics, 15, 2825-2841, 2015

Author(s): E. A. Bruns, M. Krapf, J. Orasche, Y. Huang, R. Zimmermann, L. Drinovec, G. Mo?nik, I. El-Haddad, J. G. Slowik, J. Dommen, U. Baltensperger, and A. S. H. Prévôt

Residential wood burning contributes to the total atmospheric aerosol burden; however, large uncertainties remain in the magnitude and characteristics of wood burning products. Primary emissions are influenced by a variety of parameters, including appliance type, burner wood load and wood type. In addition to directly emitted particles, previous laboratory studies have shown that oxidation of gas-phase emissions produces compounds with sufficiently low volatility to readily partition to the particles, forming considerable quantities of secondary organic aerosol (SOA). However, relatively little is known about wood burning SOA, and the effects of burn parameters on SOA formation and composition are yet to be determined. There is clearly a need for further study of primary and secondary wood combustion aerosols to advance our knowledge of atmospheric aerosols and their impacts on health, air quality and climate.

For the first time, smog chamber experiments were conducted to investigate the effects of wood loading on both primary and secondary wood combustion products. Products were characterized using a range of particle- and gas-phase instrumentation, including an aerosol mass spectrometer (AMS). A novel approach for polycyclic aromatic hydrocarbon (PAH) quantification from AMS data was developed and results were compared to those from GC-MS analysis of filter samples.

Similar total particle mass emission factors were observed under high and average wood loadings; however, high fuel loadings were found to generate significantly higher contributions of PAHs to the total organic aerosol (OA) mass compared to average loadings. PAHs contributed 15 ± 4% (mean ±2 sample standard deviations) to the total OA mass in high-load experiments, compared to 4 ± 1% in average-load experiments. With aging, total OA concentrations increased by a factor of 3 ± 1 for high load experiments compared to 1.6 ± 0.4 for average-load experiments. In the AMS, an increase in PAH and aromatic signature ions at lower m / z values, likely fragments from larger functionalized PAHs, was observed with aging. Filter samples also showed an increase in functionalized PAHs in the particles with aging, particularly oxidized naphthalene species. As PAHs and their oxidation products are known to have deleterious effects on health, this is a noteworthy finding to aid in the mitigation of negative wood burning impacts by improving burner operation protocols.

Posted on 12 March 2015 | 12:00 am


Temperature profiling of the atmospheric boundary layer with rotational Raman lidar during the HD(CP)2 Observational Prototype Experiment

Temperature profiling of the atmospheric boundary layer with rotational Raman lidar during the HD(CP)2 Observational Prototype Experiment

Atmospheric Chemistry and Physics, 15, 2867-2881, 2015

Author(s): E. Hammann, A. Behrendt, F. Le Mounier, and V. Wulfmeyer

The temperature measurements of the rotational Raman lidar of the University of Hohenheim (UHOH RRL) during the High Definition of Clouds and Precipitation for advancing Climate Prediction (HD(CP)2) Observation Prototype Experiment (HOPE) in April and May 2013 are discussed. The lidar consists of a frequency-tripled Nd:YAG laser at 355 nm with 10 W average power at 50 Hz, a two-mirror scanner, a 40 cm receiving telescope, and a highly efficient polychromator with cascading interference filters for separating four signals: the elastic backscatter signal, two rotational Raman signals with different temperature dependence, and the vibrational Raman signal of water vapor. The main measurement variable of the UHOH RRL is temperature. For the HOPE campaign, the lidar receiver was optimized for high and low background levels, with a novel switch for the passband of the second rotational Raman channel. The instrument delivers atmospheric profiles of water vapor mixing ratio as well as particle backscatter coefficient and particle extinction coefficient as further products. As examples for the measurement performance, measurements of the temperature gradient and water vapor mixing ratio revealing the development of the atmospheric boundary layer within 25 h are presented. As expected from simulations, a reduction of the measurement uncertainty of 70% during nighttime was achieved with the new low-background setting. A two-mirror scanner allows for measurements in different directions. When pointing the scanner to low elevation, measurements close to the ground become possible which are otherwise impossible due to the non-total overlap of laser beam and receiving telescope field of view in the near range. An example of a low-level temperature measurement is presented which resolves the temperature gradient at the top of the stable nighttime boundary layer 100 m above the ground.

Posted on 12 March 2015 | 12:00 am


Uplifting of carbon monoxide from biomass burning and anthropogenic sources to the free troposphere in East Asia

Uplifting of carbon monoxide from biomass burning and anthropogenic sources to the free troposphere in East Asia

Atmospheric Chemistry and Physics, 15, 2843-2866, 2015

Author(s): K. Ding, J. Liu, A. Ding, Q. Liu, T. L. Zhao, J. Shi, Y. Han, H. Wang, and F. Jiang

East Asia has experienced rapid development with increasing carbon monoxide (CO) emission in the past decades. Therefore, uplifting CO from the boundary layer to the free troposphere in East Asia can have great implications on regional air quality around the world. It can also influence global climate due to the longer lifetime of CO at higher altitudes. In this study, three cases of high CO episodes in the East China Sea and the Sea of Japan from 2003 to 2005 are examined with spaceborne Measurements of Pollution in the Troposphere (MOPITT) data, in combination with aircraft measurements from the Measurement of Ozone and Water Vapor by Airbus In-Service Aircraft (MOZAIC) program. High CO abundances of 300–550 ppbv are observed in MOZAIC data in the free troposphere during these episodes. These are among the highest CO abundances documented at these altitudes. On average, such episodes with CO over 400 ppbv (in the 2003 and 2004 cases) and between 200 and 300 ppbv (in the 2005 case) may occur 2–5 and 10–20% in time, respectively, in the respective altitudes over the region. Correspondingly, elevated CO is shown in MOPITT daytime data in the middle to upper troposphere in the 2003 case, in the lower to middle troposphere in the 2004 case, and in the upper troposphere in the 2005 case. Through analyses of the simulations from a chemical transport model GEOS-Chem and a trajectory dispersion model FLEXPART, we found different CO signatures in the elevated CO and distinct transport pathways and mechanisms for these cases. In the 2003 case, emissions from large forest fires near Lake Baikal dominated the elevated CO, which had been rapidly transported upward by a frontal system from the fire plumes. In the 2004 case, anthropogenic CO from the North China Plain experienced frontal lifting and mostly reached ~ 700 hPa near the East China Sea, while CO from biomass burning over Indochina experienced orographic lifting, lee-side-trough-induced convection, and frontal lifting through two separate transport pathways, leading to two distinct CO enhancements around 700 and 300 hPa. In the 2005 case, the observed CO of ~ 300 ppbv around 300 hPa originated from anthropogenic sources over the Sichuan Basin and the North China Plain and from forest fires over Indochina. The high CO was transported to such altitudes through strong frontal lifting, interacting with convection and orographic lifting. These cases show that topography affects vertical transport of CO in East Asia via different ways, including orographic uplifting over the Hengduan Mountains, assisting frontal lifting in the North China Plain, and facilitating convection in the Sichuan Basin. In particular, topography-induced lee-side troughs over Indochina led to strong convection that assisted CO uplifting to the upper troposphere. This study shows that the new daytime MOPITT near-infrared (NIR) and thermal-infrared (TIR) data (version 5 or above) have enhanced vertical sensitivity in the free troposphere and may help qualitative diagnosis of vertical transport processes in East Asia.

Posted on 12 March 2015 | 12:00 am


How emissions, climate, and land use change will impact mid-century air quality over the United States: a focus on effects at national parks

How emissions, climate, and land use change will impact mid-century air quality over the United States: a focus on effects at national parks

Atmospheric Chemistry and Physics, 15, 2805-2823, 2015

Author(s): M. Val Martin, C. L. Heald, J.-F. Lamarque, S. Tilmes, L. K. Emmons, and B. A. Schichtel

We use a global coupled chemistry–climate–land model (CESM) to assess the integrated effect of climate, emissions and land use changes on annual surface O3 and PM2.5 in the United States with a focus on national parks (NPs) and wilderness areas, using the RCP4.5 and RCP8.5 projections. We show that, when stringent domestic emission controls are applied, air quality is predicted to improve across the US, except surface O3 over the western and central US under RCP8.5 conditions, where rising background ozone counteracts domestic emission reductions. Under the RCP4.5 scenario, surface O3 is substantially reduced (about 5 ppb), with daily maximum 8 h averages below the primary US Environmental Protection Agency (EPA) National Ambient Air Quality Standards (NAAQS) of 75 ppb (and even 65 ppb) in all the NPs. PM2.5 is significantly reduced in both scenarios (4 ?g m?3; ~50%), with levels below the annual US EPA NAAQS of 12 ?g m?3 across all the NPs; visibility is also improved (10–15 dv; >75 km in visibility range), although some western US parks with Class I status (40–74 % of total sites in the US) are still above the 2050 planned target level to reach the goal of natural visibility conditions by 2064. We estimate that climate-driven increases in fire activity may dominate summertime PM2.5 over the western US, potentially offsetting the large PM2.5 reductions from domestic emission controls, and keeping visibility at present-day levels in many parks. Our study indicates that anthropogenic emission patterns will be important for air quality in 2050. However, climate and land use changes alone may lead to a substantial increase in surface O3 (2–3 ppb) with important consequences for O3 air quality and ecosystem degradation at the US NPs. Our study illustrates the need to consider the effects of changes in climate, vegetation, and fires in future air quality management and planning and emission policy making.

Posted on 10 March 2015 | 12:00 am


Competition between core and periphery-based processes in warm convective clouds – from invigoration to suppression

Competition between core and periphery-based processes in warm convective clouds – from invigoration to suppression

Atmospheric Chemistry and Physics, 15, 2749-2760, 2015

Author(s): G. Dagan, I. Koren, and O. Altaratz

How do changes in the amount and properties of aerosol affect warm clouds? Recent studies suggest that they have opposing effects. Some suggest that an increase in aerosol loading leads to enhanced evaporation and therefore smaller clouds, whereas other studies suggest clouds' invigoration. In this study, using an axisymmetric bin-microphysics cloud model, we propose a theoretical scheme that analyzes the evolution of key processes in warm clouds, under different aerosol loading and environmental conditions, to explain this contradiction.

Such an analysis of the key processes reveals a robust reversal in the trend of the clouds' response to an increase in aerosol loading. When aerosol conditions are shifted from superpristine to slightly polluted, the clouds formed are deeper and have larger water mass. Such a trend continues up to an optimal concentration (Nop) that allows the cloud to achieve a maximal water mass. Hence, for any concentration below Nop the cloud formed contains less mass and therefore can be considered as aerosol-limited, whereas for concentrations greater thanNop cloud periphery processes, such as enhanced entrainment and evaporation, take over leading to cloud suppression. We show that Nop is a function of the thermodynamic conditions (temperature and humidity profiles). Thus, profiles that favor deeper clouds would dictate larger values of Nop, whereas for profiles of shallow convective clouds, Nop corresponds to the pristine range of the aerosol loading.

Such a view of a trend reversal, marked by the optimal concentration, Nop, helps one to bridge the gap between the contradictory results of numerical models and observations. Satellite studies are biased in favor of larger clouds that are characterized by larger Nop values and therefore invigoration is observed. On the other hand, modeling studies of cloud fields are biased in favor of small, mostly trade-like convective clouds, which are characterized by low Nop values (in the pristine range) and, therefore, cloud suppression is mostly reported as a response to an increase in aerosol loading.

Posted on 10 March 2015 | 12:00 am


A critical evaluation of proxy methods used to estimate the acidity of atmospheric particles

A critical evaluation of proxy methods used to estimate the acidity of atmospheric particles

Atmospheric Chemistry and Physics, 15, 2775-2790, 2015

Author(s): C. J. Hennigan, J. Izumi, A. P. Sullivan, R. J. Weber, and A. Nenes

Given significant challenges with available measurements of aerosol acidity, proxy methods are frequently used to estimate the acidity of atmospheric particles. In this study, four of the most common aerosol acidity proxies are evaluated and compared: (1) the ion balance method, (2) the molar ratio method, (3) thermodynamic equilibrium models, and (4) the phase partitioning of ammonia. All methods are evaluated against predictions of thermodynamic models and against direct observations of aerosol–gas equilibrium partitioning acquired in Mexico City during the Megacity Initiative: Local and Global Research Objectives (MILAGRO) study. The ion balance and molar ratio methods assume that any deficit in inorganic cations relative to anions is due to the presence of H+ and that a higher H+ loading and lower cation / anion ratio both correspond to increasingly acidic particles (i.e., lower pH). Based on the MILAGRO measurements, no correlation is observed between H+ levels inferred with the ion balance and aerosol pH predicted by the thermodynamic models and NH3–NH4+ partitioning. Similarly, no relationship is observed between the cation / anion molar ratio and predicted aerosol pH. Using only measured aerosol chemical composition as inputs without any constraint for the gas phase, the E-AIM (Extended Aerosol Inorganics Model) and ISORROPIA-II thermodynamic equilibrium models tend to predict aerosol pH levels that are inconsistent with the observed NH3–NH4+ partitioning. The modeled pH values from both E-AIM and ISORROPIA-II run with gas + aerosol inputs agreed well with the aerosol pH predicted by the phase partitioning of ammonia. It appears that (1) thermodynamic models constrained by gas + aerosol measurements and (2) the phase partitioning of ammonia provide the best available predictions of aerosol pH. Furthermore, neither the ion balance nor the molar ratio can be used as surrogates for aerosol pH, and previously published studies with conclusions based on such acidity proxies may need to be reevaluated. Given the significance of acidity for chemical processes in the atmosphere, the implications of this study are important and far reaching.

Posted on 10 March 2015 | 12:00 am


Sources and fluxes of organic nitrogen in precipitation over the southern East Sea/Sea of Japan

Sources and fluxes of organic nitrogen in precipitation over the southern East Sea/Sea of Japan

Atmospheric Chemistry and Physics, 15, 2761-2774, 2015

Author(s): G. Yan and G. Kim

We measured total dissolved reactive nitrogen in precipitation samples collected at Uljin, a Korean coastal site upwind of the southern East Sea/Sea of Japan (EJS), selected as a representative study site of atmospheric deposition over the northwestern Pacific margin. NO3- was found to be the most abundant nitrogen species, followed by NH4+ and dissolved organic nitrogen (DON). Air-mass back-trajectory (AMBT) analysis revealed that a significant fraction of the inorganic nitrogen (NO3- and NH4+) originated from mainland Asia, whereas the DON was primarily derived from Korea. Using varimax-rotated factor analysis in combination with major ions as tracers, agricultural activities in Korea were identified as the primary sources of DON in these samples. In addition, a positive correlation was found at Uljin between the size of organic fraction in total reactive nitrogen and nitrogen to carbon atomic ratio in organic matter. This correlation has also been observed at other locations worldwide, implying the utilization potential of atmospheric organic nitrogen might increase with its proportion in total nitrogen. Combining wet deposition measurements in this study with literature values for dry deposition observed at a remote island in the EJS, the total atmospheric depositional flux of reactive nitrogen was estimated to be 115 mmol N m?2 yr?1 over the southern EJS. Our study sheds new light on the potentially significant contribution to primary productivity of the northwestern Pacific Ocean by atmospheric deposition of nitrogen, especially the organic fraction.

Posted on 10 March 2015 | 12:00 am


Evidence for tropospheric wind shear excitation of high-phase-speed gravity waves reaching the mesosphere using the ray-tracing technique

Evidence for tropospheric wind shear excitation of high-phase-speed gravity waves reaching the mesosphere using the ray-tracing technique

Atmospheric Chemistry and Physics, 15, 2709-2721, 2015

Author(s): M. Pramitha, M. Venkat Ratnam, A. Taori, B. V. Krishna Murthy, D. Pallamraju, and S. Vijaya Bhaskar Rao

Sources and propagation characteristics of high-frequency gravity waves observed in the mesosphere using airglow emissions from Gadanki (13.5° N, 79.2° E) and Hyderabad (17.5° N, 78.5° E) are investigated using reverse ray tracing. Wave amplitudes are also traced back, including both radiative and diffusive damping. The ray tracing is performed using background temperature and wind data obtained from the MSISE-90 and HWM-07 models, respectively. For the Gadanki region, the suitability of these models is tested. Further, a climatological model of the background atmosphere for the Gadanki region has been developed using nearly 30 years of observations available from a variety of ground-based (MST radar, radiosondes, MF radar) and rocket- and satellite-borne measurements. ERA-Interim products are utilized for constructing background parameters corresponding to the meteorological conditions of the observations. With the reverse ray-tracing method, the source locations for nine wave events could be identified to be in the upper troposphere, whereas for five other events the waves terminated in the mesosphere itself. Uncertainty in locating the terminal points of wave events in the horizontal direction is estimated to be within 50–100 km and 150–300 km for Gadanki and Hyderabad wave events, respectively. This uncertainty arises mainly due to non-consideration of the day-to-day variability in the tidal amplitudes. Prevailing conditions at the terminal points for each of the 14 events are provided. As no convection in and around the terminal points is noticed, convection is unlikely to be the source. Interestingly, large (~9 m s−1km−1) vertical shears in the horizontal wind are noticed near the ray terminal points (at 10–12 km altitude) and are thus identified to be the source for generating the observed high-phase-speed, high-frequency gravity waves.

Posted on 10 March 2015 | 12:00 am


Observations and modeling of air quality trends over 1990–2010 across the Northern Hemisphere: China, the United States and Europe

Observations and modeling of air quality trends over 1990–2010 across the Northern Hemisphere: China, the United States and Europe

Atmospheric Chemistry and Physics, 15, 2723-2747, 2015

Author(s): J. Xing, R. Mathur, J. Pleim, C. Hogrefe, C.-M. Gan, D. C. Wong, C. Wei, R. Gilliam, and G. Pouliot

Trends in air quality across the Northern Hemisphere over a 21-year period (1990–2010) were simulated using the Community Multiscale Air Quality (CMAQ) multiscale chemical transport model driven by meteorology from Weather Research and Forecasting (WRF) simulations and internally consistent historical emission inventories obtained from EDGAR. Thorough comparison with several ground observation networks mostly over Europe and North America was conducted to evaluate the model performance as well as the ability of CMAQ to reproduce the observed trends in air quality over the past 2 decades in three regions: eastern China, the continental United States and Europe.

The model successfully reproduced the observed decreasing trends in SO2, NO2, 8 h O3 maxima, SO42− and elemental carbon (EC) in the US and Europe. However, the model fails to reproduce the decreasing trends in NO3 in the US, potentially pointing to uncertainties of NH3 emissions. The model failed to capture the 6-year trends of SO2 and NO2 in CN-API (China – Air Pollution Index) from 2005 to 2010, but reproduced the observed pattern of O3 trends shown in three World Data Centre for Greenhouse Gases (WDCGG) sites over eastern Asia. Due to the coarse spatial resolution employed in these calculations, predicted SO2 and NO2 concentrations are underestimated relative to all urban networks, i.e., US-AQS (US – Air Quality System; normalized mean bias (NMB) = ?38% and ?48%), EU-AIRBASE (European Air quality data Base; NMB = ?18 and ?54%) and CN-API (NMB = ?36 and ?68%). Conversely, at the rural network EU-EMEP (European Monitoring and Evaluation Programme), SO2 is overestimated (NMB from 4 to 150%) while NO2 is simulated well (NMB within ±15%) in all seasons. Correlations between simulated and observed O3 wintertime daily 8 h maxima (DM8) are poor compared to other seasons for all networks. Better correlation between simulated and observed SO42− was found compared to that for SO2. Underestimation of summer SO42− in the US may be associated with the uncertainty in precipitation and associated wet scavenging representation in the model. The model exhibits worse performance for NO3 predictions, particularly in summer, due to high uncertainties in the gas/particle partitioning of NO3 as well as seasonal variations of NH3 emissions. There are high correlations (R > 0.5) between observed and simulated EC, although the model underestimates the EC concentration by 65% due to the coarse grid resolution as well as uncertainties in the PM speciation profile associated with EC emissions.

The almost linear response seen in the trajectory of modeled O3 changes in eastern China over the past 2 decades suggests that control strategies that focus on combined control of NOx and volatile organic compound (VOC) emissions with a ratio of 0.46 may provide the most effective means for O3 reductions for the region devoid of nonlinear response potentially associated with NOx or VOC limitation resulting from alternate strategies. The response of O3 is more sensitive to changes in NOx emissions in the eastern US because the relative abundance of biogenic VOC emissions tends to reduce the effectiveness of VOC controls. Increasing NH3 levels offset the relative effectiveness of NOx controls in reducing the relative fraction of aerosol NO3 formed from declining NOx emissions in the eastern US, while the control effectiveness was assured by the simultaneous control of NH3 emission in Europe.

Posted on 10 March 2015 | 12:00 am


Biomass burning related ozone damage on vegetation over the Amazon forest: a model sensitivity study

Biomass burning related ozone damage on vegetation over the Amazon forest: a model sensitivity study

Atmospheric Chemistry and Physics, 15, 2791-2804, 2015

Author(s): F. Pacifico, G. A. Folberth, S. Sitch, J. M. Haywood, L. V. Rizzo, F. F. Malavelle, and P. Artaxo

The HadGEM2 earth system climate model was used to assess the impact of biomass burning on surface ozone concentrations over the Amazon forest and its impact on vegetation, under present-day climate conditions. Here we consider biomass burning emissions from wildfires, deforestation fires, agricultural forest burning, and residential and commercial combustion. Simulated surface ozone concentration is evaluated against observations taken at two sites in the Brazilian Amazon forest for years 2010 to 2012. The model is able to reproduce the observed diurnal cycle of surface ozone mixing ratio at the two sites, but overestimates the magnitude of the monthly averaged hourly measurements by 5–15 ppb for each available month at one of the sites. We vary biomass burning emissions over South America by ±20, 40, 60, 80 and 100% to quantify the modelled impact of biomass burning on surface ozone concentrations and ozone damage on vegetation productivity over the Amazon forest. We used the ozone damage scheme in the "high" sensitivity mode to give an upper limit for this effect. Decreasing South American biomass burning emissions by 100% (i.e. to zero) reduces surface ozone concentrations (by about 15 ppb during the biomass burning season) and suggests a 15% increase in monthly mean net primary productivity averaged over the Amazon forest, with local increases up to 60%. The simulated impact of ozone damage from present-day biomass burning on vegetation productivity is about 230 TgC yr?1. Taking into account that uncertainty in these estimates is substantial, this ozone damage impact over the Amazon forest is of the same order of magnitude as the release of carbon dioxide due to fire in South America; in effect it potentially doubles the impact of biomass burning on the carbon cycle.

Posted on 10 March 2015 | 12:00 am


Analysis of the ozone profile specifications in the WRF-ARW model and their impact on the simulation of direct solar radiation

Analysis of the ozone profile specifications in the WRF-ARW model and their impact on the simulation of direct solar radiation

Atmospheric Chemistry and Physics, 15, 2693-2707, 2015

Author(s): A. Montornès, B. Codina, and J. W. Zack

Although ozone is an atmospheric gas with high spatial and temporal variability, mesoscale numerical weather prediction (NWP) models simplify the specification of ozone concentrations used in their shortwave schemes by using a few ozone profiles. In this paper, a two-part study is presented: (i) an evaluation of the quality of the ozone profiles provided for use with the shortwave schemes in the Advanced Research version of the Weather Research and Forecasting (WRF-ARW) model and (ii) an assessment of the impact of deficiencies in those profiles on the performance of model simulations of direct solar radiation. The first part compares simplified data sets used to specify the total ozone column in six schemes (i.e., Goddard, New Goddard, RRTMG, CAM, GFDL and Fu–Liou–Gu) with the Multi-Sensor Reanalysis data set during the period 1979–2008 examining the latitudinal, longitudinal and seasonal limitations in the ozone profile specifications of each parameterization. The results indicate that the maximum deviations are over the poles and show prominent longitudinal patterns in the departures due to the lack of representation of the patterns associated with the Brewer–Dobson circulation and the quasi-stationary features forced by the land–sea distribution, respectively. In the second part, the bias in the simulated direct solar radiation due to these deviations from the simplified spatial and temporal representation of the ozone distribution is analyzed for the New Goddard and CAM schemes using the Beer–Lambert–Bouguer law and for the GFDL using empirical equations. For radiative applications those simplifications introduce spatial and temporal biases with near-zero departures over the tropics throughout the year and increasing poleward with a maximum in the high middle latitudes during the winter of each hemisphere.

Posted on 10 March 2015 | 12:00 am


Air quality monitoring in communities of the Canadian Arctic during the high shipping season with a focus on local and marine pollution

Air quality monitoring in communities of the Canadian Arctic during the high shipping season with a focus on local and marine pollution

Atmospheric Chemistry and Physics, 15, 2651-2673, 2015

Author(s): A. A. Aliabadi, R. M. Staebler, and S. Sharma

The Canadian Arctic has experienced decreasing sea ice extent and increasing shipping activity in recent decades. While there are economic incentives to develop resources in the north, there are environmental concerns that increasing marine traffic will contribute to declining air quality in northern communities. In an effort to characterize the relative impact of shipping on air quality in the north, two monitoring stations have been installed in Cape Dorset and Resolute, Nunavut, and have been operational since 1 June 2013. The impact of shipping and other sources of emissions on NOx, O3, SO2, BC, and PM2.5 pollution have been characterized for the 2013 shipping season from 1 June to 1 November. In addition, a high-resolution Air Quality Health Index (AQHI) for both sites was computed. Shipping consistently increased O3 mixing ratio and PM2.5 concentration. The 90% confidence interval for mean difference in O3 mixing ratio between ship- and no ship-influenced air masses were up to 4.6–4.7 ppb and 2.5–2.7 ppb for Cape Dorset and Resolute, respectively. The same intervals for PM2.5 concentrations were up to 1.8–1.9 ?g m?3 and 0.5–0.6 ?g m?3. Ship-influenced air masses consistently exhibited an increase of 0.1 to 0.3 in the high-resolution AQHI compared to no ship-influenced air masses. Trajectory cluster analysis in combination with ship traffic tracking provided an estimated range for percent ship contribution to NOx, O3, SO2, and PM2.5 that were 12.9–17.5 %, 16.2–18.1 %, 16.9–18.3 %, and 19.5–31.7 % for Cape Dorset and 1.0–7.2 %, 2.9–4.8 %, 5.5–10.0 %, and 6.5–7.2 % for Resolute during the 2013 shipping season. Additional measurements in Resolute suggested that percent ship contribution to black carbon was 4.3–9.8 % and that black carbon constituted 1.3–9.7 % of total PM2.5 mass in ship plumes. Continued air quality monitoring in the above sites for future shipping seasons will improve the statistics in our analysis and characterize repeating seasonal patterns in air quality due to shipping, local pollution, and long-range transport.

Posted on 9 March 2015 | 12:00 am


Assessment of small-scale integrated water vapour variability during HOPE

Assessment of small-scale integrated water vapour variability during HOPE

Atmospheric Chemistry and Physics, 15, 2675-2692, 2015

Author(s): S. Steinke, S. Eikenberg, U. Löhnert, G. Dick, D. Klocke, P. Di Girolamo, and S. Crewell

The spatio-temporal variability of integrated water vapour (IWV) on small scales of less than 10 km and hours is assessed with data from the 2 months of the High Definition Clouds and Precipitation for advancing Climate Prediction (HD(CP)2) Observational Prototype Experiment (HOPE). The statistical intercomparison of the unique set of observations during HOPE (microwave radiometer (MWR), Global Positioning System (GPS), sun photometer, radiosondes, Raman lidar, infrared and near-infrared Moderate Resolution Imaging Spectroradiometer (MODIS) on the satellites Aqua and Terra) measuring close together reveals a good agreement in terms of random differences (standard deviation ≤1 kg m−2) and correlation coefficient (≥ 0.98). The exception is MODIS, which appears to suffer from insufficient cloud filtering.

For a case study during HOPE featuring a typical boundary layer development, the IWV variability in time and space on scales of less than 10 km and less than 1 h is investigated in detail. For this purpose, the measurements are complemented by simulations with the novel ICOsahedral Nonhydrostatic modelling framework (ICON), which for this study has a horizontal resolution of 156 m. These runs show that differences in space of 3–4 km or time of 10–15 min induce IWV variabilities on the order of 0.4 kg m−2. This model finding is confirmed by observed time series from two MWRs approximately 3 km apart with a comparable temporal resolution of a few seconds.

Standard deviations of IWV derived from MWR measurements reveal a high variability (> 1 kg m?2) even at very short time scales of a few minutes. These cannot be captured by the temporally lower-resolved instruments and by operational numerical weather prediction models such as COSMO-DE (an application of the Consortium for Small-scale Modelling covering Germany) of Deutscher Wetterdienst, which is included in the comparison. However, for time scales larger than 1 h, a sampling resolution of 15 min is sufficient to capture the mean standard deviation of IWV. The present study shows that instrument sampling plays a major role when climatological information, in particular the mean diurnal cycle of IWV, is determined.

Posted on 9 March 2015 | 12:00 am


How much is particulate matter near the ground influenced by upper-level processes within and above the PBL? A summertime case study in Milan (Italy) evidences the distinctive role of nitrate

How much is particulate matter near the ground influenced by upper-level processes within and above the PBL? A summertime case study in Milan (Italy) evidences the distinctive role of nitrate

Atmospheric Chemistry and Physics, 15, 2629-2649, 2015

Author(s): G. Curci, L. Ferrero, P. Tuccella, F. Barnaba, F. Angelini, E. Bolzacchini, C. Carbone, H. A. C. Denier van der Gon, M. C. Facchini, G. P. Gobbi, J. P. P. Kuenen, T. C. Landi, C. Perrino, M. G. Perrone, G. Sangiorgi, and P. Stocchi

Chemical and dynamical processes lead to the formation of aerosol layers in the upper planetary boundary layer (PBL) and above it. Through vertical mixing and entrainment into the PBL these layers may contribute to the ground-level particulate matter (PM); however, to date a quantitative assessment of such a contribution has not been carried out. This study investigates this aspect by combining chemical and physical aerosol measurements with WRF/Chem (Weather Research and Forecasting with Chemistry) model simulations. The observations were collected in the Milan urban area (northern Italy) during the summer of 2007. The period coincided with the passage of a meteorological perturbation that cleansed the lower atmosphere, followed by a high-pressure period favouring pollutant accumulation. Lidar observations revealed the formation of elevated aerosol layers and evidence of their entrainment into the PBL. We analysed the budget of ground-level PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 ?m) with the help of the online meteorology–chemistry WRF/Chem model, focusing in particular on the contribution of upper-level processes. Our findings show that an important player in determining the upper-PBL aerosol layer is particulate nitrate, which may reach higher values in the upper PBL (up to 30% of the aerosol mass) than in the lower PBL. The nitrate formation process is predicted to be largely driven by the relative-humidity vertical profile, which may trigger efficient aqueous nitrate formation when exceeding the ammonium nitrate deliquescence point. Secondary PM2.5 produced in the upper half of the PBL may contribute up to 7–8 ?g m?3 (or 25%) to ground-level concentrations on an hourly basis. The residual aerosol layer above the PBL is also found to potentially play a large role, which may occasionally contribute up to 10–12 ?g m?3 (or 40%) to hourly ground-level PM2.5 concentrations during the morning hours. Although the results presented here refer to one relatively short period in one location, this study highlights the importance of considering the interplay between chemical and dynamical processes occurring within and above the PBL when interpreting ground-level aerosol observations.

Posted on 9 March 2015 | 12:00 am


Theory of the norm-induced metric in atmospheric dynamics

Theory of the norm-induced metric in atmospheric dynamics

Atmospheric Chemistry and Physics, 15, 2571-2594, 2015

Author(s): T.-Y. Koh and F. Wan

We suggest that some metrics for quantifying distances in phase space are based on linearized flows about unrealistic reference states and hence may not be applicable to atmospheric flows. A new approach of defining a norm-induced metric based on the total energy norm is proposed. The approach is based on the rigorous mathematics of normed vector spaces and the law of energy conservation in physics. It involves the innovative construction of the phase space so that energy (or a certain physical invariant) takes the form of a Euclidean norm. The metric can be applied to both linear and nonlinear flows and for small and large separations in phase space. The new metric is derived for models of various levels of sophistication: the 2-D barotropic model, the shallow-water model and the 3-D dry, compressible atmosphere in different vertical coordinates. Numerical calculations of the new metric are illustrated with analytic dynamical systems as well as with global reanalysis data. The differences from a commonly used metric and the potential for application in ensemble prediction, error growth analysis and predictability studies are discussed.

Posted on 9 March 2015 | 12:00 am


Variations in global methane sources and sinks during 1910–2010

Variations in global methane sources and sinks during 1910–2010

Atmospheric Chemistry and Physics, 15, 2595-2612, 2015

Author(s): A. Ghosh, P. K. Patra, K. Ishijima, T. Umezawa, A. Ito, D. M. Etheridge, S. Sugawara, K. Kawamura, J. B. Miller, E. J. Dlugokencky, P. B. Krummel, P. J. Fraser, L. P. Steele, R. L. Langenfelds, C. M. Trudinger, J. W. C. White, B. Vaughn, T. Saeki, S. Aoki, and T. Nakazawa

Atmospheric methane (CH4) increased from ~900 ppb (parts per billion, or nanomoles per mole of dry air) in 1900 to ~1800 ppb in 2010 at a rate unprecedented in any observational records. However, the contributions of the various methane sources and sinks to the CH4 increase are poorly understood. Here we use initial emissions from bottom-up inventories for anthropogenic sources, emissions from wetlands and rice paddies simulated by a~terrestrial biogeochemical model, and an atmospheric general circulation model (AGCM)-based chemistry-transport model (i.e. ACTM) to simulate atmospheric CH4 concentrations for 1910–2010. The ACTM simulations are compared with the CH4 concentration records reconstructed from Antarctic and Arctic ice cores and firn air samples, and from direct measurements since the 1980s at multiple sites around the globe. The differences between ACTM simulations and observed CH4 concentrations are minimized to optimize the global total emissions using a mass balance calculation. During 1910–2010, the global total CH4 emission doubled from ~290 to ~580 Tg yr?1. Compared to optimized emission, the bottom-up emission data set underestimates the rate of change of global total CH4 emissions by ~30% during the high growth period of 1940–1990, while it overestimates by ~380% during the low growth period of 1990–2010. Further, using the CH4 stable carbon isotopic data (?13C), we attribute the emission increase during 1940–1990 primarily to enhancement of biomass burning. The total lifetime of CH4 shortened from 9.4 yr during 1910–1919 to 9 yr during 2000–2009 by the combined effect of the increasing abundance of atomic chlorine radicals (Cl) and increases in average air temperature. We show that changes of CH4 loss rate due to increased tropospheric air temperature and CH4 loss due to Cl in the stratosphere are important sources of uncertainty to more accurately estimate the global CH4 budget from ?13C observations.

Posted on 9 March 2015 | 12:00 am


Quantification of the depletion of ozone in the plume of Mount Etna

Quantification of the depletion of ozone in the plume of Mount Etna

Atmospheric Chemistry and Physics, 15, 2613-2628, 2015

Author(s): L. Surl, D. Donohoue, A. Aiuppa, N. Bobrowski, and R. von Glasow

Volcanoes are an important source of inorganic halogen species into the atmosphere. Chemical processing of these species generates oxidised, highly reactive, halogen species which catalyse considerable O3 destruction within volcanic plumes. A campaign of ground-based in situ O3, SO2 and meteorology measurements was undertaken at the summit of Mount Etna volcano in July/August 2012. At the same time, spectroscopic measurements were made of BrO and SO2 columns in the plume downwind.

Depletions of ozone were seen at all in-plume measurement locations, with average O3 depletions ranging from 11–35 nmol mol?1 (15–45%). Atmospheric processing times of the plume were estimated to be between 1 and 4 min. A 1-D numerical model of early plume evolution was also used. It was found that in the early plume O3 was destroyed at an approximately constant rate relative to an inert plume tracer. This is ascribed to reactive halogen chemistry, and the data suggests the majority of the reactive halogen that destroys O3 in the early plume is generated within the crater, including a substantial proportion generated in a high-temperature "effective source region" immediately after emission. The model could approximately reproduce the main measured features of the ozone chemistry. Model results show a strong dependence of the near-vent bromine chemistry on the presence or absence of volcanic NOx emissions and suggest that near-vent ozone measurements can be used as a qualitative indicator of NOx emission.

Posted on 9 March 2015 | 12:00 am


Corrigendum to "SO2 photolysis as a source for sulfur mass-independent isotope signatures in stratospheric aerosols" published in Atmos. Chem. Phys., 15, 1843–1864, 2015

Corrigendum to "SO2 photolysis as a source for sulfur mass-independent isotope signatures in stratospheric aerosols" published in Atmos. Chem. Phys., 15, 1843–1864, 2015

Atmospheric Chemistry and Physics, 15, 2569-2569, 2015

Author(s): A. R. Whitehill, B. Jiang, H. Guo, and S. Ono

No abstract available.

Posted on 6 March 2015 | 12:00 am


A comprehensive laboratory study on the immersion freezing behavior of illite NX particles: a comparison of 17 ice nucleation measurement techniques

A comprehensive laboratory study on the immersion freezing behavior of illite NX particles: a comparison of 17 ice nucleation measurement techniques

Atmospheric Chemistry and Physics, 15, 2489-2518, 2015

Author(s): N. Hiranuma, S. Augustin-Bauditz, H. Bingemer, C. Budke, J. Curtius, A. Danielczok, K. Diehl, K. Dreischmeier, M. Ebert, F. Frank, N. Hoffmann, K. Kandler, A. Kiselev, T. Koop, T. Leisner, O. Möhler, B. Nillius, A. Peckhaus, D. Rose, S. Weinbruch, H. Wex, Y. Boose, P. J. DeMott, J. D. Hader, T. C. J. Hill, Z. A. Kanji, G. Kulkarni, E. J. T. Levin, C. S. McCluskey, M. Murakami, B. J. Murray, D. Niedermeier, M. D. Petters, D. O'Sullivan, A. Saito, G. P. Schill, T. Tajiri, M. A. Tolbert, A. Welti, T. F. Whale, T. P. Wright, and K. Yamashita

Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice-nucleating particles. However, an intercomparison of these laboratory results is a difficult task because investigators have used different ice nucleation (IN) measurement methods to produce these results. A remaining challenge is to explore the sensitivity and accuracy of these techniques and to understand how the IN results are potentially influenced or biased by experimental parameters associated with these techniques.

Within the framework of INUIT (Ice Nuclei Research Unit), we distributed an illite-rich sample (illite NX) as a representative surrogate for atmospheric mineral dust particles to investigators to perform immersion freezing experiments using different IN measurement methods and to obtain IN data as a function of particle concentration, temperature (T), cooling rate and nucleation time. A total of 17 measurement methods were involved in the data intercomparison. Experiments with seven instruments started with the test sample pre-suspended in water before cooling, while 10 other instruments employed water vapor condensation onto dry-dispersed particles followed by immersion freezing. The resulting comprehensive immersion freezing data set was evaluated using the ice nucleation active surface-site density, ns, to develop a representative ns(T) spectrum that spans a wide temperature range (?37 °C < T < ?11 °C) and covers 9 orders of magnitude in ns.

In general, the 17 immersion freezing measurement techniques deviate, within a range of about 8 °C in terms of temperature, by 3 orders of magnitude with respect to ns. In addition, we show evidence that the immersion freezing efficiency expressed in ns of illite NX particles is relatively independent of droplet size, particle mass in suspension, particle size and cooling rate during freezing. A strong temperature dependence and weak time and size dependence of the immersion freezing efficiency of illite-rich clay mineral particles enabled the ns parameterization solely as a function of temperature. We also characterized the ns(T) spectra and identified a section with a steep slope between ?20 and ?27 °C, where a large fraction of active sites of our test dust may trigger immersion freezing. This slope was followed by a region with a gentler slope at temperatures below ?27 °C. While the agreement between different instruments was reasonable below ~ ?27 °C, there seemed to be a different trend in the temperature-dependent ice nucleation activity from the suspension and dry-dispersed particle measurements for this mineral dust, in particular at higher temperatures. For instance, the ice nucleation activity expressed in ns was smaller for the average of the wet suspended samples and higher for the average of the dry-dispersed aerosol samples between about ?27 and ?18 °C. Only instruments making measurements with wet suspended samples were able to measure ice nucleation above ?18 °C. A possible explanation for the deviation between ?27 and ?18 °C is discussed. Multiple exponential distribution fits in both linear and log space for both specific surface area-based ns(T) and geometric surface area-based ns(T) are provided. These new fits, constrained by using identical reference samples, will help to compare IN measurement methods that are not included in the present study and IN data from future IN instruments.

Posted on 6 March 2015 | 12:00 am


A new method for measuring the imaginary part of the atmospheric refractive index structure parameter in the urban surface layer

A new method for measuring the imaginary part of the atmospheric refractive index structure parameter in the urban surface layer

Atmospheric Chemistry and Physics, 15, 2521-2531, 2015

Author(s): R. Yuan, T. Luo, J. Sun, Z. Zeng, C. Ge, and Y. Fu

The atmospheric refractive index consists of both real and imaginary parts. The intensity of refractive index fluctuations is generally expressed as the refractive index structure parameter, with the real part reflecting the strength of atmospheric turbulence and the imaginary part reflecting absorption in the light path. A large aperture scintillometer (LAS) is often used to measure the structure parameter of the real part of the atmospheric refractive index, from which the sensible and latent heat fluxes can further be obtained, whereas the influence of the imaginary part is ignored or considered noise. In this theoretical analysis study, the relationship between logarithmic light intensity variance and the atmospheric refractive index structure parameter (ARISP), as well as that between the logarithmic light intensity structure function and the ARISP, is derived. Additionally, a simple expression for the imaginary part of the ARISP is obtained which can be conveniently used to determine the imaginary part of the ARISP from LAS measurements. Moreover, these relationships provide a new method for estimating the outer scale of turbulence. Light propagation experiments were performed in the urban surface layer, from which the imaginary part of the ARISP was calculated. The experimental results showed good agreement with the presented theory. The results also suggest that the imaginary part of the ARISP exhibits a different diurnal variation from that of the real part. For the wavelength of light used (0.62 ?m), the variation of the imaginary part of the ARISP is related to both the turbulent transport process and the spatial distribution characteristics of aerosols.

Posted on 6 March 2015 | 12:00 am


Corrigendum to "Development towards a global operational aerosol consensus: basic climatological characteristics of the International Cooperative for Aerosol Prediction Multi-Model Ensemble (ICAP-MME)" published in Atmos. Chem. Phys., 15, 335–362, 2015

Corrigendum to "Development towards a global operational aerosol consensus: basic climatological characteristics of the International Cooperative for Aerosol Prediction Multi-Model Ensemble (ICAP-MME)" published in Atmos. Chem. Phys., 15, 335–362, 2015

Atmospheric Chemistry and Physics, 15, 2533-2534, 2015

Author(s): W. R. Sessions, J. S. Reid, A. Benedetti, P. R. Colarco, A. da Silva, S. Lu, T. Sekiyama, T. Y. Tanaka, J. M. Baldasano, S. Basart, M. E. Brooks, T. F. Eck, M. Iredell, J. A. Hansen, O. C. Jorba, H.-M. H. Juang, P. Lynch, J.-J. Morcrette, S. Moorthi, J. Mulcahy, Y. Pradhan, M. Razinger, C. B. Sampson, J. Wang, and D. L. Westphal

No abstract available.

Posted on 6 March 2015 | 12:00 am


A science-based use of ensembles of opportunities for assessment and scenario studies

A science-based use of ensembles of opportunities for assessment and scenario studies

Atmospheric Chemistry and Physics, 15, 2535-2544, 2015

Author(s): E. Solazzo and S. Galmarini

The multimodel ensemble exercise performed within the HTAP project context (Fiore et al., 2009) is used here as an example of how a pre-inspection, diagnosis and selection of an ensemble, can produce more reliable results. The procedure is contrasted with the often-used practice of simply averaging model simulations, assuming different models produce independent results, and using the diversity of simulation as an illusory estimate of model uncertainty. It is further and more importantly demonstrated how conclusions can drastically change when future emission scenarios are analysed using an un-inspected ensemble. The HTAP multimodel ensemble analysis is only taken as an example of a widespread and common practice in air quality modelling.

Posted on 6 March 2015 | 12:00 am


Corrigendum to "High-resolution mapping of vehicle emissions in China in 2008" published in Atmos. Chem. Phys., 14, 9787–9805, 2014

Corrigendum to "High-resolution mapping of vehicle emissions in China in 2008" published in Atmos. Chem. Phys., 14, 9787–9805, 2014

Atmospheric Chemistry and Physics, 15, 2519-2519, 2015

Author(s): B. Zheng, H. Huo, Q. Zhang, Z. L. Yao, X. T. Wang, X. F. Yang, H. Liu, and K. B. He

No abstract available.

Posted on 6 March 2015 | 12:00 am


Importance of aerosol composition and mixing state for cloud droplet activation over the Arctic pack ice in summer

Importance of aerosol composition and mixing state for cloud droplet activation over the Arctic pack ice in summer

Atmospheric Chemistry and Physics, 15, 2545-2568, 2015

Author(s): C. Leck and E. Svensson

Concentrations of cloud condensation nuclei (CCN) were measured throughout an expedition by icebreaker around the central Arctic Ocean, including a 3 week ice drift operation at 87° N, from 3 August to 9 September 2008. In agreement with previous observations in the area and season, median daily CCN concentrations at 0.2% water vapour supersaturation (SS) were typically in the range of 15 to 30 cm?3, but concentrations varied by 2 to 3 orders of magnitude over the expedition and were occasionally below 1 cm?3. The CCN concentrations were highest near the ice edge and fell by a factor of 3 in the first 48 h of transport from the open sea into the pack ice region. For longer transport times they increased again, indicating a local source over the pack ice, suggested to be polymer gels, via drops injected into the air by bubbles bursting on open leads. We inferred the properties of the unexplained non-water soluble aerosol fraction that was necessary for reproducing the observed concentrations of CCN. This was made possible by assuming Köhler theory and simulating the cloud nucleation process using a Lagrangian adiabatic air parcel model that solves the kinetic formulation for condensation of water on size resolved aerosol particles. We propose that the portion of the internally/externally mixed water insoluble particles was larger in the corresponding smaller aerosol size ranges. These particles were physically and chemically behaving as polymer gels: the interaction of the hydrophilic and hydrophobic entities on the structures of polymer gels during cloud droplet activation would at first only show a partial wetting character and only weak hygroscopic growth. Given time, a high CCN activation efficiency is achieved, which is promoted by the hydrophilicity or surface-active properties of the gels. Thus the result in this study argues that the behaviour of the high Arctic aerosol in CCN-counters operating at water vapour SSs > 0.4% (high relative humidities) may not be properly explained by conventional Köhler theory.

Posted on 6 March 2015 | 12:00 am


Investigating a two-component model of solid fuel organic aerosol in London: processes, PM1 contributions, and seasonality

Investigating a two-component model of solid fuel organic aerosol in London: processes, PM1 contributions, and seasonality

Atmospheric Chemistry and Physics, 15, 2429-2443, 2015

Author(s): D. E. Young, J. D. Allan, P. I. Williams, D. C. Green, R. M. Harrison, J. Yin, M. J. Flynn, M. W. Gallagher, and H. Coe

Solid fuel emissions, including those from biomass burning, are increasing in urban areas across the European Union due to rising energy costs and government incentives to use renewable energy sources for heating. In order to help protect human health as well as to improve air quality and pollution abatement strategies, the sources of combustion aerosols, their contributions, and the processes they undergo need to be better understood. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was therefore deployed at an urban background site between January and February 2012 to investigate solid fuel organic aerosols (SFOA) in London. The variability of SFOA was examined and the factors governing the split between the two SFOA factors derived from Positive Matrix Factorisation (PMF) were assessed. The concentrations of both factors were found to increase during the night and during cold periods, consistent with domestic space heating activities. The split between the two factors is likely governed predominantly by differences in burn conditions where SFOA1 best represents more efficient burns and SFOA2 best represents less efficient burns. The differences in efficiency may be due to burner types or burn phase, for example. Different fuel types and levels of atmospheric processing also likely contribute to the two factors. As the mass spectral profile of SFOA is highly variable, the findings from this study may have implications for improving future source apportionment and factorisation analyses.

During the winter, SFOA was found to contribute 38% to the total non-refractory submicron organic aerosol (OA) mass, with similar contributions from both SFOA factors (20% from SFOA1 and 18% from SFOA2). A similar contribution of SFOA was derived for the same period from a compact time-of-flight AMS (cToF-AMS), which measured for a full calendar year at the same site. The seasonality of SFOA was investigated using the year-long data set where concentrations were greatest in the autumn and winter. During the summer, SFOA contributed 11% to the organic fraction, where emissions resulted from different anthropogenic activities such as barbecues and domestic garden wood burning. The significant contribution of SFOA to total organic mass throughout the year suggests that the negative effects on health and air quality, as well as climate, are not just confined to winter as exposure to these aerosols and the associated black carbon can also occur during the summer, which may have significant implications for air-quality policies and mitigation strategies.

Posted on 5 March 2015 | 12:00 am


Aerosol properties over the western Mediterranean basin: temporal and spatial variability

Aerosol properties over the western Mediterranean basin: temporal and spatial variability

Atmospheric Chemistry and Physics, 15, 2473-2486, 2015

Author(s): H. Lyamani, A. Valenzuela, D. Perez-Ramirez, C. Toledano, M. J. Granados-Muñoz, F. J. Olmo, and L. Alados-Arboledas

This study focuses on the analysis of Aerosol Robotic Network (AERONET) aerosol data obtained over Alborán Island (35.90° N, 3.03° W, 15 m a.s.l.) in the western Mediterranean from July 2011 to January 2012. Additional aerosol data from the three nearest AERONET stations (Málaga, Oujda and Palma de Mallorca) and the Maritime Aerosol Network (MAN) were also analyzed in order to investigate the temporal and spatial variations of aerosol over this scarcely explored region. High aerosol loads over Alborán were mainly associated with desert dust transport from North Africa and occasional advection of anthropogenic fine particles from central European urban-industrial areas. The fine particle load observed over Alborán was surprisingly similar to that obtained over the other three nearest AERONET stations, suggesting homogeneous spatial distribution of fine particle loads over the four studied sites in spite of the large differences in local sources. The results from MAN acquired over the Mediterranean Sea, Black Sea and Atlantic Ocean from July to November 2011 revealed a pronounced predominance of fine particles during the cruise period.

Posted on 5 March 2015 | 12:00 am


First quasi-Lagrangian in situ measurements of Antarctic Polar springtime ozone: observed ozone loss rates from the Concordiasi long-duration balloon campaign

First quasi-Lagrangian in situ measurements of Antarctic Polar springtime ozone: observed ozone loss rates from the Concordiasi long-duration balloon campaign

Atmospheric Chemistry and Physics, 15, 2463-2472, 2015

Author(s): R. Schofield, L. M. Avallone, L. E. Kalnajs, A. Hertzog, I. Wohltmann, and M. Rex

We present ozone measurements made using state-of-the-art ultraviolet photometers onboard three long-duration stratospheric balloons launched as part of the Concordiasi campaign in austral spring 2010. Ozone loss rates calculated by matching air parcels sampled at different times and places during the polar spring are in agreement with rates previously derived from ozonesonde measurements, for the vortex average, ranging between 2 and 7 ppbv per sunlit hour or between 25 and 110 ppbv per day. However, the geographical coverage of these long-duration stratospheric balloon platforms provides new insights into the temporal and spatial patterns of ozone loss over Antarctica. Very large ozone loss rates of up to 230 ppbv per day (16 ppbv per sunlit hour) are observed for air masses that are downwind of the Antarctic Peninsula and/or over the East Antarctic region. The ozone loss rate maximum downstream of the Antarctic Peninsula region is consistent with high PSC occurrence from CALIPSO and large ClO abundances from MLS satellite observations for 12–22 September 2010, and with a chemical box model simulation using JPL 2011 kinetics with full chlorine activation.

Posted on 5 March 2015 | 12:00 am


Corrigendum to "Seasonal and interannual variations of HCN amounts in the upper troposphere and lower stratosphere observed by MIPAS" published in Atmos. Chem. Phys., 15, 563–582, 2015

Corrigendum to "Seasonal and interannual variations of HCN amounts in the upper troposphere and lower stratosphere observed by MIPAS" published in Atmos. Chem. Phys., 15, 563–582, 2015

Atmospheric Chemistry and Physics, 15, 2487-2488, 2015

Author(s): N. Glatthor, M. Höpfner, G. P. Stiller, T. von Clarmann, B. Funke, S. Lossow, E. Eckert, U. Grabowski, S. Kellmann, A. Linden, K. A. Walker, and A. Wiegele

No abstract available.

Posted on 5 March 2015 | 12:00 am


Variability of mixed-phase clouds in the Arctic with a focus on the Svalbard region: a study based on spaceborne active remote sensing

Variability of mixed-phase clouds in the Arctic with a focus on the Svalbard region: a study based on spaceborne active remote sensing

Atmospheric Chemistry and Physics, 15, 2445-2461, 2015

Author(s): G. Mioche, O. Jourdan, M. Ceccaldi, and J. Delanoë

The Arctic region is known to be very sensitive to climate change. Clouds and in particular mixed-phase clouds (MPCs) remain one of the greatest sources of uncertainties in the modelling of the Arctic response to climate change due to an inaccurate representation of their variability and their quantification. In this study, we present a characterisation of the vertical, spatial and seasonal variability of Arctic clouds and MPCs over the entire Arctic region based on satellite active remote sensing observations. MPC properties in the region of the Svalbard archipelago (78° N, 15° E) are also investigated. The occurrence frequency of clouds and MPCs are determined from CALIPSO/CLOUDSAT measurements processed with the DARDAR retrieval algorithm, which allow for a reliable cloud thermodynamic phase classification (warm liquid, supercooled liquid, ice, mixing of ice and supercooled liquid). Significant differences are observed between MPC properties over the entire Arctic region and over the Svalbard region. Results show that MPCs are encountered all year long, with a minimum occurrence of 30% in winter and 50% during the rest of the year on average over the entire Arctic. Over the Svalbard region, MPC occurrence is more constant with time with larger values (55%) compared to the average observed in the Arctic. MPCs are especially located at low altitudes, below 3000 m, where their frequency of occurrence reaches 90%, particularly during winter, spring and autumn. Moreover, results highlight that MPCs are statistically more frequent above open sea than land or sea ice. The temporal and spatial distribution of MPCs over the Svalbard region seems to be linked to the supply of moister air and warmer water from the North Atlantic Ocean, which contribute to the initiation of the liquid water phase. Over the whole Arctic, and particularly in western regions, the increase of MPC occurrence from spring to autumn could be connected to the sea ice melting. During this period, the open water transports some of the warm water from the North Atlantic Ocean to the rest of the Arctic region. This facilitates the vertical transfer of moisture and thus the persistence of the liquid phase. Particular attention is also paid to the measurement uncertainties and how they could affect our conclusions.

Posted on 5 March 2015 | 12:00 am


Estimating sources of elemental and organic carbon and their temporal emission patterns using a least squares inverse model and hourly measurements from the St. Louis–Midwest supersite

Estimating sources of elemental and organic carbon and their temporal emission patterns using a least squares inverse model and hourly measurements from the St. Louis–Midwest supersite

Atmospheric Chemistry and Physics, 15, 2405-2427, 2015

Author(s): B. de Foy, Y. Y. Cui, J. J. Schauer, M. Janssen, J. R. Turner, and C. Wiedinmyer

Emission inventories of elemental carbon (EC) and organic carbon (OC) contain large uncertainties both in their spatial and temporal distributions for different source types. An inverse model was used to evaluate EC and OC emissions based on 1 year of hourly measurements from the St. Louis–Midwest supersite. The input to the model consisted of continuous measurements of EC and OC obtained for 2002 using two semicontinuous analyzers. High resolution meteorological simulations were performed for the entire time period using the Weather Research and Forecasting Model (WRF). These were used to simulate hourly back trajectories at the measurement site using a Lagrangian model (FLEXPART-WRF). In combination, an Eulerian model (CAMx: The Comprehensive Air Quality Model with Extensions ) was used to simulate the impacts at the measurement site using known emissions inventories for point and area sources from the Lake Michigan Directors Consortium (LADCO) as well as for open burning from the Fire Inventory from NCAR (FINN). By considering only passive transport of pollutants, the Bayesian inversion simplifies to a single least squares inversion. The inverse model combines forward Eulerian simulations with backward Lagrangian simulations to yield estimates of emissions from sources in current inventories as well as from emissions that might be missing in the inventories. The CAMx impacts were disaggregated into separate time chunks in order to determine improved diurnal, weekday and monthly temporal patterns of emissions. Because EC is a primary species, the inverse model estimates can be interpreted directly as emissions. In contrast, OC is both a primary and a secondary species. As the inverse model does not differentiate between direct emissions and formation in the plume of those direct emissions, the estimates need to be interpreted as contributions to measured concentrations. Emissions of EC and OC in the St. Louis region from on-road, non-road, marine/aircraft/railroad (MAR), "other" and point sources were revised slightly downwards on average. In particular, both MAR and point sources had a more pronounced diurnal variation than in the inventory. The winter peak in "other" emissions was not corroborated by the inverse model. On-road emissions have a larger difference between weekday and weekends in the inverse estimates than in the inventory, and appear to be poorly simulated or characterized in the winter months. The model suggests that open burning emissions are significantly underestimated in the inventory. Finally, contributions of unknown sources seems to be from areas to the south of St. Louis and from afternoon and nighttime emissions.

Posted on 5 March 2015 | 12:00 am


Kerb and urban increment of highly time-resolved trace elements in PM10, PM2.5 and PM1.0 winter aerosol in London during ClearfLo 2012

Kerb and urban increment of highly time-resolved trace elements in PM10, PM2.5 and PM1.0 winter aerosol in London during ClearfLo 2012

Atmospheric Chemistry and Physics, 15, 2367-2386, 2015

Author(s): S. Visser, J. G. Slowik, M. Furger, P. Zotter, N. Bukowiecki, R. Dressler, U. Flechsig, K. Appel, D. C. Green, A. H. Tremper, D. E. Young, P. I. Williams, J. D. Allan, S. C. Herndon, L. R. Williams, C. Mohr, L. Xu, N. L. Ng, A. Detournay, J. F. Barlow, C. H. Halios, Z. L. Fleming, U. Baltensperger, and A. S. H. Prévôt

Ambient concentrations of trace elements with 2 h time resolution were measured in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 size ranges at kerbside, urban background and rural sites in London during winter 2012. Samples were collected using rotating drum impactors (RDIs) and subsequently analysed with synchrotron radiation-induced X-ray fluorescence spectrometry (SR-XRF). Quantification of kerb and urban increments (defined as kerb-to-urban and urban-to-rural concentration ratios, respectively), and assessment of diurnal and weekly variability provided insight into sources governing urban air quality and the effects of urban micro-environments on human exposure. Traffic-related elements yielded the highest kerb increments, with values in the range of 10.4 to 16.6 for SW winds (3.3–6.9 for NE) observed for elements influenced by brake wear (e.g. Cu, Sb, Ba) and 5.7 to 8.2 for SW (2.6–3.0 for NE) for other traffic-related processes (e.g. Cr, Fe, Zn). Kerb increments for these elements were highest in the PM10–2.5 mass fraction, roughly twice that of the PM1.0–0.3 fraction. These elements also showed the highest urban increments (~ 3.0), although no difference was observed between brake wear and other traffic-related elements. All elements influenced by traffic exhibited higher concentrations during morning and evening rush hours, and on weekdays compared to weekends, with the strongest trends observed at the kerbside site, and additionally enhanced by winds coming directly from the road, consistent with street canyon effects. Elements related to mineral dust (e.g. Al, Si, Ca, Sr) showed significant influences from traffic-induced resuspension, as evidenced by moderate kerb (3.4–5.4 for SW, 1.7–2.3 for NE) and urban (~ 2) increments and increased concentrations during peak traffic flow. Elements related to regional transport showed no significant enhancement at kerb or urban sites, with the exception of PM10–2.5 sea salt (factor of up to 2), which may be influenced by traffic-induced resuspension of sea and/or road salt. Heavy-duty vehicles appeared to have a larger effect than passenger vehicles on the concentrations of all elements influenced by resuspension (including sea salt) and wearing processes. Trace element concentrations in London were influenced by both local and regional sources, with coarse and intermediate fractions dominated by traffic-induced resuspension and wearing processes and fine particles influenced by regional transport.

Posted on 4 March 2015 | 12:00 am


Oxidant production from source-oriented particulate matter – Part 1: Oxidative potential using the dithiothreitol (DTT) assay

Oxidant production from source-oriented particulate matter – Part 1: Oxidative potential using the dithiothreitol (DTT) assay

Atmospheric Chemistry and Physics, 15, 2327-2340, 2015

Author(s): J. G. Charrier, N. K. Richards-Henderson, K. J. Bein, A. S. McFall, A. S. Wexler, and C. Anastasio

Recent epidemiological evidence supports the hypothesis that health effects from inhalation of ambient particulate matter (PM) are governed by more than just the mass of PM inhaled. Both specific chemical components and sources have been identified as important contributors to mortality and hospital admissions, even when these end points are unrelated to PM mass. Sources may cause adverse health effects via their ability to produce reactive oxygen species in the body, possibly due to the transition metal content of the PM. Our goal is to quantify the oxidative potential of ambient particle sources collected during two seasons in Fresno, CA, using the dithiothreitol (DTT) assay. We collected PM from different sources or source combinations into different ChemVol (CV) samplers in real time using a novel source-oriented sampling technique based on single-particle mass spectrometry. We segregated the particles from each source-oriented mixture into two size fractions – ultrafine Dp ≤ 0.17 ?m) and submicron fine (0.17 ?m ≤ Dp ≤ 1.0 ?m) – and measured metals and the rate of DTT loss in each PM extract. We find that the mass-normalized oxidative potential of different sources varies by up to a factor of 8 and that submicron fine PM typically has a larger mass-normalized oxidative potential than ultrafine PM from the same source. Vehicular emissions, regional source mix, commute hours, daytime mixed layer, and nighttime inversion sources exhibit the highest mass-normalized oxidative potential. When we apportion DTT activity for total PM sampled to specific chemical compounds, soluble copper accounts for roughly 50% of total air-volume-normalized oxidative potential, soluble manganese accounts for 20%, and other unknown species, likely including quinones and other organics, account for 30%. During nighttime, soluble copper and manganese largely explain the oxidative potential of PM, while daytime has a larger contribution from unknown (likely organic) species.

Posted on 4 March 2015 | 12:00 am


Ensemble simulations of the role of the stratosphere in the attribution of northern extratropical tropospheric ozone variability

Ensemble simulations of the role of the stratosphere in the attribution of northern extratropical tropospheric ozone variability

Atmospheric Chemistry and Physics, 15, 2341-2365, 2015

Author(s): P. Hess, D. Kinnison, and Q. Tang

Despite the need to understand the impact of changes in emissions and climate on tropospheric ozone, the attribution of tropospheric interannual ozone variability to specific processes has proven difficult. Here, we analyze the stratospheric contribution to tropospheric ozone variability and trends from 1953 to 2005 in the Northern Hemisphere (NH) mid-latitudes using four ensemble simulations of the free running (FR) Whole Atmosphere Community Climate Model (WACCM). The simulations are externally forced with observed time-varying (1) sea-surface temperatures (SSTs), (2) greenhouse gases (GHGs), (3) ozone depleting substances (ODS), (4) quasi-biennial oscillation (QBO), (5) solar variability (SV) and (6) stratospheric sulfate surface area density (SAD). A detailed representation of stratospheric chemistry is simulated, including the ozone loss due to volcanic eruptions and polar stratospheric clouds. In the troposphere, ozone production is represented by CH4–NOx smog chemistry, where surface chemical emissions remain interannually constant. Despite the simplicity of its tropospheric chemistry, at many NH measurement locations, the interannual ozone variability in the FR WACCM simulations is significantly correlated with the measured interannual variability. This suggests the importance of the external forcing applied in these simulations in driving interannual ozone variability. The variability and trend in the simulated 1953–2005 tropospheric ozone from 30 to 90° N at background surface measurement sites, 500 hPa measurement sites and in the area average are largely explained on interannual timescales by changes in the 30–90° N area averaged flux of ozone across the 100 hPa surface and changes in tropospheric methane concentrations. The average sensitivity of tropospheric ozone to methane (percent change in ozone to a percent change in methane) from 30 to 90° N is 0.17 at 500 hPa and 0.21 at the surface; the average sensitivity of tropospheric ozone to the 100 hPa ozone flux (percent change in ozone to a percent change in the ozone flux) from 30 to 90° N is 0.19 at 500 hPa and 0.11 at the surface. The 30–90° N simulated downward residual velocity at 100 hPa increased by 15% between 1953 and 2005. However, the impact of this on the 30–90° N 100 hPa ozone flux is modulated by the long-term changes in stratospheric ozone. The ozone flux decreases from 1965 to 1990 due to stratospheric ozone depletion, but increases again by approximately 7% from 1990 to 2005. The first empirical orthogonal function of interannual ozone variability explains from 40% (at the surface) to over 80% (at 150 hPa) of the simulated ozone interannual variability from 30 to 90° N. This identified mode of ozone variability shows strong stratosphere–troposphere coupling, demonstrating the importance of the stratosphere in an attribution of tropospheric ozone variability. The simulations, with no change in emissions, capture almost 50% of the measured ozone change during the 1990s at a variety of locations. This suggests that a large portion of the measured change is not due to changes in emissions, but can be traced to changes in large-scale modes of ozone variability. This emphasizes the difficulty in the attribution of ozone changes, and the importance of natural variability in understanding the trends and variability of ozone. We find little relation between the El Niño–Southern Oscillation (ENSO) index and large-scale tropospheric ozone variability over the long-term record.

Posted on 4 March 2015 | 12:00 am


Simulating aerosol–radiation–cloud feedbacks on meteorology and air quality over eastern China under severe haze conditionsin winter

Simulating aerosol–radiation–cloud feedbacks on meteorology and air quality over eastern China under severe haze conditionsin winter

Atmospheric Chemistry and Physics, 15, 2387-2404, 2015

Author(s): B. Zhang, Y. Wang, and J. Hao

The aerosol-radiation-cloud feedbacks on meteorology and air quality over eastern China under severe winter haze conditions in January 2013 are simulated using the fully coupled online Weather Research and Forecasting/Chemistry (WRF-Chem) model. Three simulation scenarios including different aerosol configurations are undertaken to distinguish the aerosol's radiative (direct and semi-direct) and indirect effects. Simulated spatial and temporal variations of PM2.5 are generally consistent with surface observations, with a mean bias of −18.9 ?g m?3 (−15.0%) averaged over 71 big cities in China. Comparisons between different scenarios reveal that aerosol radiative effects (direct effect and semi-direct effects) result in reductions of downward shortwave flux at the surface, 2 m temperature, 10 m wind speed and planetary boundary layer (PBL) height by up to 84.0 W m?2, 3.2°C, 0.8 m s?1, and 268 m, respectively. The simulated impact of the aerosol indirect effects is comparatively smaller. Through reducing the PBL height and stabilizing lower atmosphere, the aerosol effects lead to increases in surface concentrations of primary pollutants (CO and SO2). Surface O3 mixing ratio is reduced by up to 6.9 ppb (parts per billion) due to reduced incoming solar radiation and lower temperature, while the aerosol feedbacks on PM2.5 mass concentrations show some spatial variations. Comparisons of model results with observations show that inclusion of aerosol feedbacks in the model significantly improves model performance in simulating meteorological variables and improves simulations of PM2.5 temporal distributions over the North China Plain, the Yangtze River delta, the Pearl River delta, and central China. Although the aerosol–radiation–cloud feedbacks on aerosol mass concentrations are subject to uncertainties, this work demonstrates the significance of aerosol–radiation–cloud feedbacks for real-time air quality forecasting under haze conditions.

Posted on 4 March 2015 | 12:00 am


Persistent after-effects of heavy rain on concentrations of ice nuclei and rainfall suggest a biological cause

Persistent after-effects of heavy rain on concentrations of ice nuclei and rainfall suggest a biological cause

Atmospheric Chemistry and Physics, 15, 2313-2326, 2015

Author(s): E. K. Bigg, S. Soubeyrand, and C. E. Morris

Rainfall is one of the most important aspects of climate, but the extent to which atmospheric ice nuclei (IN) influence its formation, quantity, frequency, and location is not clear. Microorganisms and other biological particles are released following rainfall and have been shown to serve as efficient IN, in turn impacting cloud and precipitation formation. Here we investigated potential long-term effects of IN on rainfall frequency and quantity. Differences in IN concentrations and rainfall after and before days of large rainfall accumulation (i.e., key days) were calculated for measurements made over the past century in southeastern and southwestern Australia. Cumulative differences in IN concentrations and daily rainfall quantity and frequency as a function of days from a key day demonstrated statistically significant increasing logarithmic trends (R2 > 0.97). Based on observations that cumulative effects of rainfall persisted for about 20 days, we calculated cumulative differences for the entire sequence of key days at each site to create a historical record of how the differences changed with time. Comparison of pre-1960 and post-1960 sequences most commonly showed smaller rainfall totals in the post-1960 sequences, particularly in regions downwind from coal-fired power stations. This led us to explore the hypothesis that the increased leaf surface populations of IN-active bacteria due to rain led to a sustained but slowly diminishing increase in atmospheric concentrations of IN that could potentially initiate or augment rainfall. This hypothesis is supported by previous research showing that leaf surface populations of the ice-nucleating bacterium Pseudomonas syringae increased by orders of magnitude after heavy rain and that microorganisms become airborne during and after rain in a forest ecosystem. At the sites studied in this work, aerosols that could have initiated rain from sources unrelated to previous rainfall events (such as power stations) would automatically have reduced the influences on rainfall of those whose concentrations were related to previous rain, thereby leading to inhibition of feedback. The analytical methods described here provide means to map and delimit regions where rainfall feedback mediated by microorganisms is suspected to occur or has occurred historically, thereby providing rational means to establish experimental set-ups for verification.

Posted on 3 March 2015 | 12:00 am


A new model for the global biogeochemical cycle of carbonyl sulfide – Part 1: Assessment of direct marine emissions with an oceanic general circulation and biogeochemistry model

A new model for the global biogeochemical cycle of carbonyl sulfide – Part 1: Assessment of direct marine emissions with an oceanic general circulation and biogeochemistry model

Atmospheric Chemistry and Physics, 15, 2295-2312, 2015

Author(s): T. Launois, S. Belviso, L. Bopp, C. G. Fichot, and P. Peylin

The global budget of tropospheric carbonyl sulfide (OCS) is believed to be at equilibrium because background air concentrations have remained roughly stable over at least the last decade. Since the uptake of OCS by leaves (associated with photosynthesis) and soils have been revised significantly upwards recently, an equilibrated budget can only be obtained with a compensatory source of OCS. It has been assumed that the missing source of OCS comes from the low-latitude ocean, following the incident solar flux. The present work uses parameterizations of major production and removal processes of organic compounds in the NEMO-PISCES (Nucleus for European Modelling of the Ocean, Pelagic Interaction Scheme for Carbon and Ecosystem Studies) ocean general circulation and biogeochemistry model to assess the marine source of OCS. In addition, the OCS photo-production rates computed with the NEMO-PISCES model~were evaluated independently using the UV absorption coefficient of chromophoric dissolved organic matter (derived from satellite ocean color data) and apparent quantum yields available in the literature. Our simulations show global direct marine emissions of OCS in the range of 573–3997 GgS yr?1, depending mostly on the quantification of the absorption rate of chromophoric dissolved organic matter. The high estimates of that range are unlikely, as they correspond to a formulation that most likely overestimate photo-production process. Low and medium (813 GgS yr?1) estimates derived from the NEMO-PISCES model are however consistent spatially and temporally~with the suggested missing source of Berry et al. (2013), allowing us thus to close the global budget of OCS given the recent estimates of leaf and soil OCS uptake.

Posted on 3 March 2015 | 12:00 am


Copernicus stratospheric ozone service, 2009–2012: validation, system intercomparison and roles of input data sets

Copernicus stratospheric ozone service, 2009–2012: validation, system intercomparison and roles of input data sets

Atmospheric Chemistry and Physics, 15, 2269-2293, 2015

Author(s): K. Lefever, R. van der A, F. Baier, Y. Christophe, Q. Errera, H. Eskes, J. Flemming, A. Inness, L. Jones, J.-C. Lambert, B. Langerock, M. G. Schultz, O. Stein, A. Wagner, and S. Chabrillat

This paper evaluates and discusses the quality of the stratospheric ozone analyses delivered in near real time by the MACC (Monitoring Atmospheric Composition and Climate) project during the 3-year period between September 2009 and September 2012. Ozone analyses produced by four different chemical data assimilation (CDA) systems are examined and compared: the Integrated Forecast System coupled to the Model for OZone And Related chemical Tracers (IFS-MOZART); the Belgian Assimilation System for Chemical ObsErvations (BASCOE); the Synoptic Analysis of Chemical Constituents by Advanced Data Assimilation (SACADA); and the Data Assimilation Model based on Transport Model version 3 (TM3DAM). The assimilated satellite ozone retrievals differed for each system; SACADA and TM3DAM assimilated only total ozone observations, BASCOE assimilated profiles for ozone and some related species, while IFS-MOZART assimilated both types of ozone observations.

All analyses deliver total column values that agree well with ground-based observations (biases < 5%) and have a realistic seasonal cycle, except for BASCOE analyses, which underestimate total ozone in the tropics all year long by 7 to 10%, and SACADA analyses, which overestimate total ozone in polar night regions by up to 30%. The validation of the vertical distribution is based on independent observations from ozonesondes and the ACE-FTS (Atmospheric Chemistry Experiment – Fourier Transform Spectrometer) satellite instrument. It cannot be performed with TM3DAM, which is designed only to deliver analyses of total ozone columns. Vertically alternating positive and negative biases are found in the IFS-MOZART analyses as well as an overestimation of 30 to 60% in the polar lower stratosphere during polar ozone depletion events. SACADA underestimates lower stratospheric ozone by up to 50% during these events above the South Pole and overestimates it by approximately the same amount in the tropics. The three-dimensional (3-D) analyses delivered by BASCOE are found to have the best quality among the three systems resolving the vertical dimension, with biases not exceeding 10% all year long, at all stratospheric levels and in all latitude bands, except in the tropical lowermost stratosphere.

The northern spring 2011 period is studied in more detail to evaluate the ability of the analyses to represent the exceptional ozone depletion event, which happened above the Arctic in March 2011. Offline sensitivity tests are performed during this month and indicate that the differences between the forward models or the assimilation algorithms are much less important than the characteristics of the assimilated data sets. They also show that IFS-MOZART is able to deliver realistic analyses of ozone both in the troposphere and in the stratosphere, but this requires the assimilation of observations from nadir-looking instruments as well as the assimilation of profiles, which are well resolved vertically and extend into the lowermost stratosphere.

Posted on 3 March 2015 | 12:00 am


Aerosol size distribution and radiative forcing response to anthropogenically driven historical changes in biogenic secondary organic aerosol formation

Aerosol size distribution and radiative forcing response to anthropogenically driven historical changes in biogenic secondary organic aerosol formation

Atmospheric Chemistry and Physics, 15, 2247-2268, 2015

Author(s): S. D. D'Andrea, J. C. Acosta Navarro, S. C. Farina, C. E. Scott, A. Rap, D. K. Farmer, D. V. Spracklen, I. Riipinen, and J. R. Pierce

Emissions of biogenic volatile organic compounds (BVOCs) have changed in the past millennium due to changes in land use, temperature, and CO2 concentrations. Recent reconstructions of BVOC emissions have predicted that global isoprene emissions have decreased, while monoterpene and sesquiterpene emissions have increased; however, all three show regional variability due to competition between the various influencing factors.

In this work, we use two modeled estimates of BVOC emissions from the years 1000 to 2000 to test the effect of anthropogenic changes to BVOC emissions on secondary organic aerosol (SOA) formation, global aerosol size distributions, and radiative effects using the GEOS-Chem-TOMAS (Goddard Earth Observing System; TwO-Moment Aerosol Sectional) global aerosol microphysics model. With anthropogenic emissions (e.g., SO2, NOx, primary aerosols) turned off and BVOC emissions changed from year 1000 to year 2000 values, decreases in the number concentration of particles of size Dp > 80 nm (N80) of > 25% in year 2000 relative to year 1000 were predicted in regions with extensive land-use changes since year 1000 which led to regional increases in the combined aerosol radiative effect (direct and indirect) of > 0.5 W m?2 in these regions. We test the sensitivity of our results to BVOC emissions inventory, SOA yields, and the presence of anthropogenic emissions; however, the qualitative response of the model to historic BVOC changes remains the same in all cases. Accounting for these uncertainties, we estimate millennial changes in BVOC emissions cause a global mean direct effect of between +0.022 and +0.163 W m?2 and the global mean cloud-albedo aerosol indirect effect of between ?0.008 and ?0.056 W m?2. This change in aerosols, and the associated radiative forcing, could be a largely overlooked and important anthropogenic aerosol effect on regional climates.

Posted on 2 March 2015 | 12:00 am


Identifying fire plumes in the Arctic with tropospheric FTIR measurements and transport models

Identifying fire plumes in the Arctic with tropospheric FTIR measurements and transport models

Atmospheric Chemistry and Physics, 15, 2227-2246, 2015

Author(s): C. Viatte, K. Strong, J. Hannigan, E. Nussbaumer, L. K. Emmons, S. Conway, C. Paton-Walsh, J. Hartley, J. Benmergui, and J. Lin

We investigate Arctic tropospheric composition using ground-based Fourier transform infrared (FTIR) solar absorption spectra, recorded at the Polar Environment Atmospheric Research Laboratory (PEARL, Eureka, Nunavut, Canada, 80°05' N, 86°42' W) and at Thule (Greenland, 76°53' N, ?68°74' W) from 2008 to 2012. The target species, carbon monoxide (CO), hydrogen cyanide (HCN), ethane (C2H6), acetylene (C2H2), formic acid (HCOOH), and formaldehyde (H2CO) are emitted by biomass burning and can be transported from mid-latitudes to the Arctic.

By detecting simultaneous enhancements of three biomass burning tracers (HCN, CO, and C2H6), ten and eight fire events are identified at Eureka and Thule, respectively, within the 5-year FTIR time series. Analyses of Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model back-trajectories coupled with Moderate Resolution Imaging Spectroradiometer (MODIS) fire hotspot data, Stochastic Time-Inverted Lagrangian Transport (STILT) model footprints, and Ozone Monitoring Instrument (OMI) UV aerosol index maps, are used to attribute burning source regions and travel time durations of the plumes. By taking into account the effect of aging of the smoke plumes, measured FTIR enhancement ratios were corrected to obtain emission ratios and equivalent emission factors. The means of emission factors for extratropical forest estimated with the two FTIR data sets are 0.40 ± 0.21 g kg?1 for HCN, 1.24 ± 0.71 g kg?1 for C2H6, 0.34 ± 0.21 g kg?1 for C2H2, and 2.92 ± 1.30 g kg?1 for HCOOH. The emission factor for CH3OH estimated at Eureka is 3.44 ± 1.68 g kg?1.

To improve our knowledge concerning the dynamical and chemical processes associated with Arctic pollution from fires, the two sets of FTIR measurements were compared to the Model for OZone And Related chemical Tracers, version 4 (MOZART-4). Seasonal cycles and day-to-day variabilities were compared to assess the ability of the model to reproduce emissions from fires and their transport. Good agreement in winter confirms that transport is well implemented in the model. For C2H6, however, the lower wintertime concentration estimated by the model as compared to the FTIR observations highlights an underestimation of its emission. Results show that modeled and measured total columns are correlated (linear correlation coefficient r > 0.6 for all gases except for H2CO at Eureka and HCOOH at Thule), but suggest a general underestimation of the concentrations in the model for all seven tropospheric species in the high Arctic.

Posted on 2 March 2015 | 12:00 am





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