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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:



Impact of the Asian monsoon anticyclone on the variability of mid-to-upper tropospheric methane above the Mediterranean Basin

Impact of the Asian monsoon anticyclone on the variability of mid-to-upper tropospheric methane above the Mediterranean Basin

Atmospheric Chemistry and Physics, 14, 11427-11446, 2014

Author(s): P. Ricaud, B. Si?, L. El Amraoui, J.-L. Attié, R. Zbinden, P. Huszar, S. Szopa, J. Parmentier, N. Jaidan, M. Michou, R. Abida, F. Carminati, D. Hauglustaine, T. August, J. Warner, R. Imasu, N. Saitoh, and V.-H. Peuch

The space and time variabilities of methane (CH4) total column and upper tropospheric mixing ratios are analysed above the Mediterranean Basin (MB) as part of the Chemical and Aerosol Mediterranean Experiment (ChArMEx) programme. Since the analysis of the mid-to-upper tropospheric CH4 distribution from spaceborne sensors and model outputs is challenging, we have adopted a climatological approach and have used a wide variety of data sets. We have combined spaceborne measurements from the Thermal And Near infrared Sensor for carbon Observations – Fourier Transform Spectrometer (TANSO-FTS) instrument on the Greenhouse gases Observing SATellite (GOSAT) satellite, the Atmospheric InfraRed Spectrometer (AIRS) on the AURA platform and the Infrared Atmospheric Sounder Interferometer (IASI) instrument aboard the MetOp-A platform with model results from the Chemical Transport Model (CTM) MOCAGE, and the Chemical Climate Models (CCMs) CNRM-AOCCM and LMDz-OR-INCA (according to different emission scenarios). In order to minimize systematic errors in the spaceborne measurements, we have only considered maritime pixels over the MB. The period of interest spans from 2008 to 2011 considering satellite and MOCAGE data and, regarding the CCMs, from 2001 to 2010. Although CH4 is a long-lived tracer with lifetime of ~12 years and is supposed to be well mixed in the troposphere, an east–west gradient in CH4 is observed and modelled in the mid-to-upper troposphere with a maximum in the Western MB in all seasons except in summer when CH4 accumulates above the Eastern MB. The peak-to-peak amplitude of the east–west seasonal variation in CH4 above the MB in the upper troposphere (300 hPa) is weak but almost twice as great in the satellite measurements (~25 ppbv) as in the model data (~15 ppbv). The maximum of CH4 in summer above the eastern MB can be explained by a series of dynamical processes only occurring in summer. The Asian monsoon traps and uplifts high amounts of CH4 to the upper troposphere where they build up. The Asian Monsoon Anticyclone redistributes these elevated CH4 amounts towards North Africa and the Middle East to finally reach and descend in the eastern MB. In the lower troposphere, the CH4 variability is mainly driven by the local sources of emission in the vicinity of the MB.

Posted on 29 October 2014 | 12:00 am


The effect of low solubility organic acids on the hygroscopicity of sodium halide aerosols

The effect of low solubility organic acids on the hygroscopicity of sodium halide aerosols

Atmospheric Chemistry and Physics, 14, 11409-11425, 2014

Author(s): L. Miñambres, E. Méndez, M. N. Sánchez, F. Castaño, and F. J. Basterretxea

In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be investigated in this study. The hygroscopic properties of sodium halide sub-micrometre particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were generated by flowing atomized sodium halide particles (either dry or aqueous) through a heated oven containing the gaseous acid. The obtained results indicate that gaseous organic acids easily nucleate onto dry and aqueous sodium halide particles. On the other hand, scanning electron microscopy (SEM) images indicate that lauric acid coating on NaCl particles makes them to aggregate in small clusters. The hygroscopic behaviour of covered sodium halide particles in deliquescence mode shows different features with the exchange of the halide ion, whereas the organic surfactant has little effect in NaBr particles, NaCl and NaI covered particles experience appreciable shifts in their deliquescence relative humidities, with different trends observed for each of the acids studied. In efflorescence mode, the overall effect of the organic covering is to retard the loss of water in the particles. It has been observed that the presence of gaseous water in heterogeneously nucleated particles tends to displace the cover of hexanoic acid to energetically stabilize the system.

Posted on 29 October 2014 | 12:00 am


Constraining mass–diameter relations from hydrometeor images and cloud radar reflectivities in tropical continental and oceanic convective anvils

Constraining mass–diameter relations from hydrometeor images and cloud radar reflectivities in tropical continental and oceanic convective anvils

Atmospheric Chemistry and Physics, 14, 11367-11392, 2014

Author(s): E. Fontaine, A. Schwarzenboeck, J. Delanoë, W. Wobrock, D. Leroy, R. Dupuy, C. Gourbeyre, and A. Protat

In this study the density of ice hydrometeors in tropical clouds is derived from a combined analysis of particle images from 2-D-array probes and associated reflectivities measured with a Doppler cloud radar on the same research aircraft. Usually, the mass–diameter m(D) relationship is formulated as a power law with two unknown coefficients (pre-factor, exponent) that need to be constrained from complementary information on hydrometeors, where absolute ice density measurement methods do not apply. Here, at first an extended theoretical study of numerous hydrometeor shapes simulated in 3-D and arbitrarily projected on a 2-D plan allowed to constrain the exponent ?of the m(D) relationship from the exponent σ of the surface–diameterS(D)relationship, which is likewise written as a power law. Since S(D) always can be determined for real data from 2-D optical array probes or other particle imagers, the evolution of the m(D) exponent can be calculated. After that, the pre-factor ? of m(D) is constrained from theoretical simulations of the radar reflectivities matching the measured reflectivities along the aircraft trajectory.

The study was performed as part of the Megha-Tropiques satellite project, where two types of mesoscale convective systems (MCS) were investigated: (i) above the African continent and (ii) above the Indian Ocean. For the two data sets, two parameterizations are derived to calculate the vertical variability of m(D) coefficients ? and ? as a function of the temperature. Originally calculated (with T-matrix) and also subsequently parameterized m(D) relationships from this study are compared to other methods (from literature) of calculating m(D) in tropical convection. The significant benefit of using variable m(D) relations instead of a single m(D) relationship is demonstrated from the impact of all these m(D) relations on Z-CWC (Condensed Water Content) and Z-CWC-T-fitted parameterizations.

Posted on 29 October 2014 | 12:00 am


New emission factors for Australian vegetation fires measured using open-path Fourier transform infrared spectroscopy – Part 2: Australian tropical savanna fires

New emission factors for Australian vegetation fires measured using open-path Fourier transform infrared spectroscopy – Part 2: Australian tropical savanna fires

Atmospheric Chemistry and Physics, 14, 11335-11352, 2014

Author(s): T. E. L. Smith, C. Paton-Walsh, C. P. Meyer, G. D. Cook, S. W. Maier, J. Russell-Smith, M. J. Wooster, and C. P. Yates

Savanna fires contribute approximately 40–50% of total global annual biomass burning carbon emissions. Recent comparisons of emission factors from different savanna regions have highlighted the need for a regional approach to emission factor development, and better assessment of the drivers of the temporal and spatial variation in emission factors. This paper describes the results of open-path Fourier transform infrared (OP-FTIR) spectroscopic field measurements at 21 fires occurring in the tropical savannas of the Northern~Territory, Australia, within different vegetation assemblages and at different stages of the dry season. Spectra of infrared light passing through a long (22–70 m) open-path through ground-level smoke released from these fires were collected using an infrared lamp and a field-portable FTIR system. The IR spectra were used to retrieve the mole fractions of 14 different gases present within the smoke, and these measurements used to calculate the emission ratios and emission factors of the various gases emitted by the burning. Only a handful of previous emission factor measures are available specifically for the tropical savannas of Australia and here we present the first reported emission factors for methanol, acetic acid, and formic acid for this biome. Given the relatively large sample size, it was possible to study the potential causes of the within-biome variation of the derived emission factors. We find that the emission factors vary substantially between different savanna vegetation assemblages; with a majority of this variation being mirrored by variations in the modified combustion efficiency (MCE) of different vegetation classes. We conclude that a significant majority of the variation in the emission factor for trace gases can be explained by MCE, irrespective of vegetation class, as illustrated by variations in the calculated methane emission factor for different vegetation classes using data sub-set by different combustion efficiencies. Therefore, the selection of emission factors for emissions modelling purposes need not necessarily require detailed fuel type information, if data on MCE (e.g. from future spaceborne total column measurements) or a correlated variable were available.

From measurements at 21 fires, we recommend the following emission factors for Australian tropical savanna fires (in grams of gas emitted per kilogram of dry fuel burned), which are our mean measured values: 1674 ± 56 g kg?1 of carbon dioxide; 87 ± 33 g kg?1 of carbon monoxide; 2.1 ± 1.2 g kg?1 of methane; 0.11 ± 0.04 g kg?1 of acetylene; 0.49 ± 0.22 g kg?1 of ethylene; 0.08 ± 0.05 g kg?1 of ethane; 1.57 ± 0.44 g kg?1 of formaldehyde; 1.06 ± 0.87 g kg?1 of methanol; 1.54 ± 0.64 g kg?1 of acetic acid; 0.16 ± 0.07 g kg?1 of formic acid; 0.53 ± 0.31 g kg?1 of hydrogen cyanide; and 0.70 ± 0.36 g kg?1 of ammonia. In a companion paper, similar techniques are used to characterise the emissions from Australian temperate forest fires.

Posted on 29 October 2014 | 12:00 am


Impacts of new particle formation on aerosol cloud condensation nuclei (CCN) activity in Shanghai: case study

Impacts of new particle formation on aerosol cloud condensation nuclei (CCN) activity in Shanghai: case study

Atmospheric Chemistry and Physics, 14, 11353-11365, 2014

Author(s): C. Leng, Q. Zhang, J. Tao, H. Zhang, D. Zhang, C. Xu, X. Li, L. Kong, T. Cheng, R. Zhang, X. Yang, J. Chen, L. Qiao, S. Lou, H. Wang, and C. Chen

New particle formation (NPF) events and their impacts on cloud condensation nuclei (CCN) were investigated using continuous measurements collected in urban Shanghai from 1 to 30 April 2012. During the campaign, NPF occurred in 8 out of the 30 days and enhanced CCN number concentration (NCCN) by a factor of 1.2–1.8, depending on supersaturation (SS). The NPF event on 3 April 2012 was chosen as an example to investigate the NPF influence on CCN activity. In this NPF event, secondary aerosols were produced continuously and increased PM2.5 mass concentration at a rate of 4.33 μg cm−3 h−1, and the growth rate (GR) and formation rate (FR) were on average 5 nm h?1 and 0.36 cm?3 s?1, respectively. The newly formed particles grew quickly from nucleation mode (10–20 nm) into CCN size range. NCCN increased rapidly at SS of 0.4–1.0% but weakly at SS of 0.2%. Correspondingly, aerosol CCN activities (fractions of activated aerosol particles in total aerosols, NCCN/NCN) were significantly enhanced from 0.24–0.60 to 0.30–0.91 at SS of 0.2–1.0% due to the NPF. On the basis of the κ-Köhler theory, aerosol size distributions and chemical composition measured simultaneously were used to predict NCCN. There was a good agreement between the predicted and measured NCCN (R2=0.96, Npredicted/Nmeasured=1.04). This study reveals that NPF exerts large impacts on aerosol particle abundance and size spectra; thus, it significantly promotes NCCN and aerosol CCN activity in this urban environment. The GR of NPF is the key factor controlling the newly formed particles to become CCN at all SS levels, whereas the FR is an effective factor only under high SS (e.g., 1.0%) conditions.

Posted on 29 October 2014 | 12:00 am


Airborne observations of IEPOX-derived isoprene SOA in the Amazon during SAMBBA

Airborne observations of IEPOX-derived isoprene SOA in the Amazon during SAMBBA

Atmospheric Chemistry and Physics, 14, 11393-11407, 2014

Author(s): J. D. Allan, W. T. Morgan, E. Darbyshire, M. J. Flynn, P. I. Williams, D. E. Oram, P. Artaxo, J. Brito, J. D. Lee, and H. Coe

Isoprene is a potentially highly significant but currently poorly quantified source of secondary organic aerosols (SOA). This is especially important in the tropics, where large rainforests act as significant sources of isoprene. Methylfuran, produced through thermal decomposition during analysis, has recently been suggested as a marker for isoprene SOA formation through the isoprene epoxydiol (IEPOX) route, which mostly occurs under low NOx conditions. This is manifested as a peak at m/z=82 in Aerodyne Aerosol Mass Spectrometer (AMS) data. Here we present a study of this marker measured during five flights over the Amazon rainforest on board the UK Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft during the South American Biomass Burning Analysis (SAMBBA) campaign. Cases where this marker is and is not present are contrasted and linked to the presence of acidic seed particles, lower NOx concentrations and higher humidities. There are also data to suggest a role of organic nitrogen in the particulate composition. Furthermore, an inspection of the vertical trends of the marker indicates that concentrations are highest at the top of the boundary layer (possibly due to semivolatile repartitioning) and that upwards through the free troposphere, the mass spectral profile evolves towards that of low volatility oxygenated aerosol. These observations offer insights into the behaviour of IEPOX-derived SOA formation above the Amazon rainforest and the suitability of methylfuran as a marker for this process.

Posted on 29 October 2014 | 12:00 am


New emission factors for Australian vegetation fires measured using open-path Fourier transform infrared spectroscopy – Part 1: Methods and Australian temperate forest fires

New emission factors for Australian vegetation fires measured using open-path Fourier transform infrared spectroscopy – Part 1: Methods and Australian temperate forest fires

Atmospheric Chemistry and Physics, 14, 11313-11333, 2014

Author(s): C. Paton-Walsh, T. E. L. Smith, E. L. Young, D. W. T. Griffith, and É.-A. Guérette

Biomass burning releases trace gases and aerosol particles that significantly affect the composition and chemistry of the atmosphere. Australia contributes approximately 8% of gross global carbon emissions from biomass burning, yet there are few previous measurements of emissions from Australian forest fires available in the literature. This paper describes the results of field measurements of trace gases emitted during hazard reduction burns in Australian temperate forests using open-path Fourier transform infrared spectroscopy. In a companion paper, similar techniques are used to characterise the emissions from hazard reduction burns in the savanna regions of the Northern Territory. Details of the experimental methods are explained, including both the measurement set-up and the analysis techniques employed. The advantages and disadvantages of different ways to estimate whole-fire emission factors are discussed and a measurement uncertainty budget is developed.

Emission factors for Australian temperate forest fires are measured locally for the first time for many trace gases. Where ecosystem-relevant data are required, we recommend the following emission factors for Australian temperate forest fires (in grams of gas emitted per kilogram of dry fuel burned) which are our mean measured values: 1620 ± 160 g kg?1 of carbon dioxide; 120 ± 20 g kg?1 of carbon monoxide; 3.6 ± 1.1 g kg?1 of methane; 1.3 ± 0.3 g kg?1 of ethylene; 1.7 ± 0.4 g kg?1 of formaldehyde; 2.4 ± 1.2 g kg?1 of methanol; 3.8 ± 1.3 g kg?1 of acetic acid; 0.4 ± 0.2 g kg?1 of formic acid; 1.6 ± 0.6 g kg?1 of ammonia; 0.15 ± 0.09 g kg?1 of nitrous oxide and 0.5 ± 0.2 g kg?1 of ethane.

Posted on 29 October 2014 | 12:00 am


Natural or anthropogenic? On the origin of atmospheric sulfate deposition in the Andes of southeastern Ecuador

Natural or anthropogenic? On the origin of atmospheric sulfate deposition in the Andes of southeastern Ecuador

Atmospheric Chemistry and Physics, 14, 11297-11312, 2014

Author(s): S. Makowski Giannoni, R. Rollenbeck, K. Trachte, and J. Bendix

Atmospheric sulfur deposition above certain limits can represent a threat to tropical forests, causing nutrient imbalances and mobilizing toxic elements that impact biodiversity and forest productivity. Atmospheric sources of sulfur deposited by precipitation have been roughly identified in only a few lowland tropical forests. Even scarcer are studies of this type in tropical mountain forests, many of them mega-diversity hotspots and especially vulnerable to acidic deposition. In these places, the topographic complexity and related streamflow conditions affect the origin, type, and intensity of deposition. Furthermore, in regions with a variety of natural and anthropogenic sulfur sources, like active volcanoes and biomass burning, no source emission data has been used for determining the contribution of each source to the deposition. The main goal of the current study is to evaluate sulfate (SO4- deposition by rain and occult precipitation at two topographic locations in a tropical mountain forest of southern Ecuador, and to trace back the deposition to possible emission sources applying back-trajectory modeling. To link upwind natural (volcanic) and anthropogenic (urban/industrial and biomass-burning) sulfur emissions and observed sulfate deposition, we employed state-of-the-art inventory and satellite data, including volcanic passive degassing as well. We conclude that biomass-burning sources generally dominate sulfate deposition at the evaluated sites. Minor sulfate transport occurs during the shifting of the predominant winds to the north and west. Occult precipitation sulfate deposition and likely rain sulfate deposition are mainly linked to biomass-burning emissions from the Amazon lowlands. Volcanic and anthropogenic emissions from the north and west contribute to occult precipitation sulfate deposition at the mountain crest Cerro del Consuelo meteorological station and to rain-deposited sulfate at the upriver mountain pass El Tiro meteorological station.

Posted on 28 October 2014 | 12:00 am


An important mechanism sustaining the atmospheric "water tower" over the Tibetan Plateau

An important mechanism sustaining the atmospheric "water tower" over the Tibetan Plateau

Atmospheric Chemistry and Physics, 14, 11287-11295, 2014

Author(s): X. Xu, T. Zhao, C. Lu, Y. Guo, B. Chen, R. Liu, Y. Li, and X. Shi

The Tibetan Plateau (TP), referred to as the "roof of the world", is also known as the "world water tower" because it contains a large amount of water resources and ceaselessly transports these waters to its surrounding areas. However, it is not clear how these waters are being supplied and replenished. In particular, how plausible hydrological cycles can be realized between tropical oceans and the TP. In order to explore the mechanism sustaining the atmospheric "water tower" over the TP, the relationship of a "heat source column" over the plateau and moist flows in the Asian summer monsoon circulation is investigated. Here we show that the plateau's thermal structure leads to dynamic processes with an integration of two couplings of lower convergence zones and upper divergences, respectively, over the plateau's southern slopes and main platform, which relay moist air in two ladders up to the plateau. Similarly to the CISK (conditional instability of the second kind) mechanism of tropical cyclones, the elevated warm–moist air, in turn, forces convective weather systems, hence building a water cycle over the plateau. An integration of mechanical and thermal TP forcing is revealed in relation to the Asian summer monsoon circulation knitting a close tie of vapor transport from tropical oceans to the atmospheric "water tower" over the TP.

Posted on 27 October 2014 | 12:00 am


Aerosol indirect effect on the grid-scale clouds in the two-way coupled WRF–CMAQ: model description, development, evaluation and regional analysis

Aerosol indirect effect on the grid-scale clouds in the two-way coupled WRF–CMAQ: model description, development, evaluation and regional analysis

Atmospheric Chemistry and Physics, 14, 11247-11285, 2014

Author(s): S. Yu, R. Mathur, J. Pleim, D. Wong, R. Gilliam, K. Alapaty, C. Zhao, and X. Liu

This study implemented first, second and glaciation aerosol indirect effects (AIE) on resolved clouds in the two-way coupled Weather Research and Forecasting Community Multiscale Air Quality (WRF–CMAQ) modeling system by including parameterizations for both cloud drop and ice number concentrations on the basis of CMAQ-predicted aerosol distributions and WRF meteorological conditions. The performance of the newly developed WRF–CMAQ model, with alternate Community Atmospheric Model (CAM) and Rapid Radiative Transfer Model for GCMs (RRTMG) radiation schemes, was evaluated with observations from the Clouds and the See http://ceres.larc.nasa.gov/. Earth's Radiant Energy System (CERES) satellite and surface monitoring networks (AQS, IMPROVE, CASTNET, STN, and PRISM) over the continental US (CONUS) (12 km resolution) and eastern Texas (4 km resolution) during August and September of 2006. The results at the Air Quality System (AQS) surface sites show that in August, the normalized mean bias (NMB) values for PM2.5 over the eastern US (EUS) and the western US (WUS) are 5.3% (?0.1%) and 0.4% (?5.2%) for WRF–CMAQ/CAM (WRF–CMAQ/RRTMG), respectively. The evaluation of PM2.5 chemical composition reveals that in August, WRF–CMAQ/CAM (WRF–CMAQ/RRTMG) consistently underestimated the observed SO42- by ?23.0% (?27.7%), ?12.5% (?18.9%) and ?7.9% (?14.8%) over the EUS at the Clean Air Status Trends Network (CASTNET), Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciated Trends Network (STN) sites, respectively. Both configurations (WRF–CMAQ/CAM, WRF–CMAQ/RRTMG) overestimated the observed mean organic carbon (OC), elemental carbon (EC) and and total carbon (TC) concentrations over the EUS in August at the IMPROVE sites. Both configurations generally underestimated the cloud field (shortwave cloud forcing, SWCF) over the CONUS in August due to the fact that the AIE on the subgrid convective clouds was not considered when the model simulations were run at the 12 km resolution. This is in agreement with the fact that both configurations captured SWCF and longwave cloud forcing (LWCF) very well for the 4 km simulation over eastern Texas, when all clouds were resolved by the finer resolution domain. The simulations of WRF–CMAQ/CAM and WRF–CMAQ/RRTMG show dramatic improvements for SWCF, LWCF, cloud optical depth (COD), cloud fractions and precipitation over the ocean relative to those of WRF default cases in August. The model performance in September is similar to that in August, except for a greater overestimation of PM2.5 due to the overestimations of SO42-, NH4+, NO3-, and TC over the EUS, less underestimation of clouds (SWCF) over the land areas due to the lower SWCF values, and fewer convective clouds in September. This work shows that inclusion of indirect aerosol effect treatments in WRF–CMAQ represents a significant advancement and milestone in air quality modeling and the development of integrated emissions control strategies for air quality management and climate change mitigation.

Posted on 24 October 2014 | 12:00 am


Aerosol microphysics simulations of the Mt.~Pinatubo eruption with the UM-UKCA composition-climate model

Aerosol microphysics simulations of the Mt.~Pinatubo eruption with the UM-UKCA composition-climate model

Atmospheric Chemistry and Physics, 14, 11221-11246, 2014

Author(s): S. S. Dhomse, K. M. Emmerson, G. W. Mann, N. Bellouin, K. S. Carslaw, M. P. Chipperfield, R. Hommel, N. L. Abraham, P. Telford, P. Braesicke, M. Dalvi, C. E. Johnson, F. O'Connor, O. Morgenstern, J. A. Pyle, T. Deshler, J. M. Zawodny, and L. W. Thomason

We use a stratosphere–troposphere composition–climate model with interactive sulfur chemistry and aerosol microphysics, to investigate the effect of the 1991 Mount Pinatubo eruption on stratospheric aerosol properties. Satellite measurements indicate that shortly after the eruption, between 14 and 23 Tg of SO2 (7 to 11.5 Tg of sulfur) was present in the tropical stratosphere. Best estimates of the peak global stratospheric aerosol burden are in the range 19 to 26 Tg, or 3.7 to 6.7 Tg of sulfur assuming a composition of between 59 and 77 % H2SO4. In light of this large uncertainty range, we performed two main simulations with 10 and 20 Tg of SO2 injected into the tropical lower stratosphere. Simulated stratospheric aerosol properties through the 1991 to 1995 period are compared against a range of available satellite and in situ measurements. Stratospheric aerosol optical depth (sAOD) and effective radius from both simulations show good qualitative agreement with the observations, with the timing of peak sAOD and decay timescale matching well with the observations in the tropics and mid-latitudes. However, injecting 20 Tg gives a factor of 2 too high stratospheric aerosol mass burden compared to the satellite data, with consequent strong high biases in simulated sAOD and surface area density, with the 10 Tg injection in much better agreement. Our model cannot explain the large fraction of the injected sulfur that the satellite-derived SO2 and aerosol burdens indicate was removed within the first few months after the eruption. We suggest that either there is an additional alternative loss pathway for the SO2 not included in our model (e.g. via accommodation into ash or ice in the volcanic cloud) or that a larger proportion of the injected sulfur was removed via cross-tropopause transport than in our simulations.

We also critically evaluate the simulated evolution of the particle size distribution, comparing in detail to balloon-borne optical particle counter (OPC) measurements from Laramie, Wyoming, USA (41° N). Overall, the model captures remarkably well the complex variations in particle concentration profiles across the different OPC size channels. However, for the 19 to 27 km injection height-range used here, both runs have a modest high bias in the lowermost stratosphere for the finest particles (radii less than 250 nm), and the decay timescale is longer in the model for these particles, with a much later return to background conditions. Also, whereas the 10 Tg run compared best to the satellite measurements, a significant low bias is apparent in the coarser size channels in the volcanically perturbed lower stratosphere. Overall, our results suggest that, with appropriate calibration, aerosol microphysics models are capable of capturing the observed variation in particle size distribution in the stratosphere across both volcanically perturbed and quiescent conditions. Furthermore, additional sensitivity simulations suggest that predictions with the models are robust to uncertainties in sub-grid particle formation and nucleation rates in the stratosphere.

Posted on 24 October 2014 | 12:00 am


Reactive bromine chemistry in Mount Etna's volcanic plume: the influence of total Br, high-temperature processing, aerosol loading and plume–air mixing

Reactive bromine chemistry in Mount Etna's volcanic plume: the influence of total Br, high-temperature processing, aerosol loading and plume–air mixing

Atmospheric Chemistry and Physics, 14, 11201-11219, 2014

Author(s): T. J. Roberts, R. S. Martin, and L. Jourdain

Volcanic emissions present a source of reactive halogens to the troposphere, through rapid plume chemistry that converts the emitted HBr to more reactive forms such as BrO. The nature of this process is poorly quantified, yet is of interest in order to understand volcanic impacts on the troposphere, and infer volcanic activity from volcanic gas measurements (i.e. BrO / SO2 ratios). Recent observations from Etna report an initial increase and subsequent plateau or decline in BrO / SO2 ratios with distance downwind.

We present daytime PlumeChem model simulations that reproduce and explain the reported trend in BrO / SO2 at Etna including the initial rise and subsequent plateau. Suites of model simulations also investigate the influences of volcanic aerosol loading, bromine emission, and plume–air mixing rate on the downwind plume chemistry. Emitted volcanic HBr is converted into reactive bromine by autocatalytic bromine chemistry cycles whose onset is accelerated by the model high-temperature initialisation. These rapid chemistry cycles also impact the reactive bromine speciation through inter-conversion of Br, Br2, BrO, BrONO2, BrCl, HOBr.

We predict a new evolution of Br speciation in the plume. BrO, Br2, Br and HBr are the main plume species near downwind whilst BrO and HOBr are present further downwind (where BrONO2 and BrCl also make up a minor fraction). BrNO2 is predicted to be only a relatively minor plume component.

The initial rise in BrO / SO2 occurs as ozone is entrained into the plume whose reaction with Br promotes net formation of BrO. Aerosol has a modest impact on BrO / SO2 near-downwind (< ~6 km, ~10 min) at the relatively high loadings considered. The subsequent decline in BrO / SO2 occurs as entrainment of oxidants HO2 and NO2 promotes net formation of HOBr and BrONO2, whilst the plume dispersion dilutes volcanic aerosol so slows the heterogeneous loss rates of these species. A higher volcanic aerosol loading enhances BrO / SO2 in the (> 6 km) downwind plume.

Simulations assuming low/medium and high Etna bromine emissions scenarios show that the bromine emission has a greater influence on BrO / SO2 further downwind and a modest impact near downwind, and show either complete or partial conversion of HBr into reactive bromine, respectively, yielding BrO contents that reach up to ~50 or ~20% of total bromine (over a timescale of a few 10 s of minutes).

Plume–air mixing non-linearly impacts the downwind BrO / SO2, as shown by simulations with varying plume dispersion, wind speed and volcanic emission flux. Greater volcanic emission flux leads to lower BrO / SO2 ratios near downwind, but also delays the subsequent decline in BrO / SO2, and thus yields higher BrO / SO2 ratios further downwind. We highlight the important role of plume chemistry models for the interpretation of observed changes in BrO / SO2 during/prior to volcanic eruptions, as well as for quantifying volcanic plume impacts on atmospheric chemistry. Simulated plume impacts include ozone, HOx and NOx depletion, the latter converted into HNO3. Partial recovery of ozone occurs with distance downwind, although cumulative ozone loss is ongoing over the 3 h simulations.

Posted on 23 October 2014 | 12:00 am


Re-evaluating the reactive uptake of HOBr in the troposphere with implications for the marine boundary layer and volcanic plumes

Re-evaluating the reactive uptake of HOBr in the troposphere with implications for the marine boundary layer and volcanic plumes

Atmospheric Chemistry and Physics, 14, 11185-11199, 2014

Author(s): T. J. Roberts, L. Jourdain, P. T. Griffiths, and M. Pirre

The reactive uptake of HOBr onto halogen-rich aerosols promotes conversion of Br(aq) into gaseous reactive bromine (incl. BrO) with impacts on tropospheric oxidants and mercury deposition. However, experimental data quantifying HOBr reactive uptake on tropospheric aerosols is limited, and reported values vary in magnitude. This study introduces a new evaluation of HOBr reactive uptake coefficients in the context of the general acid-assisted mechanism. We emphasise that the termolecular kinetic approach assumed in numerical model studies of tropospheric reactive bromine chemistry to date is strictly only valid for a specific pH range and, according to the general acid-assisted mechanism for HOBr, the reaction kinetics becomes bimolecular and independent of pH at high acidity.

This study reconciles for the first time the different reactive uptake coefficients reported from laboratory experiments. The re-evaluation confirms HOBr reactive uptake is rapid on moderately acidified sea-salt aerosol (and slow on alkaline aerosol), but predicts very low reactive uptake coefficients on highly acidified submicron particles. This is due to acid-saturated kinetics combined with low halide concentrations induced by both acid-displacement reactions and the dilution effects of H2SO4(aq). A mechanism is thereby proposed for reported Br enhancement (relative to Na) in H2SO4-rich submicron particles in the marine environment. Further, the fact that HOBr reactive uptake on H2SO4-acidified supra-micron particles is driven by HOBr+Br (rather than HOBr+Cl) indicates self-limitation via decreasing γHOBr once aerosol Br- is converted into reactive bromine.

First predictions of HOBr reactive uptake on sulfate particles in halogen-rich volcanic plumes are also presented. High (accommodation limited) HOBr+Br- uptake coefficient in concentrated (> 1 ?mol mol?1 SO2) plume environments supports potential for rapid BrO formation in plumes throughout the troposphere. However, reduced HOBr reactive uptake may reduce the rate of BrO cycling in dilute plumes in the lower troposphere.

In summary, our re-evaluation of HOBr kinetics provides a new framework for the interpretation of experimental data and suggests that the reactive uptake of HOBr on H2SO4-acidified particles is substantially overestimated in current numerical models of BrO chemistry in the troposphere.

Posted on 23 October 2014 | 12:00 am


Hygroscopicity of organic compounds from biomass burning and their influence on the water uptake of mixed organic ammonium sulfate aerosols

Hygroscopicity of organic compounds from biomass burning and their influence on the water uptake of mixed organic ammonium sulfate aerosols

Atmospheric Chemistry and Physics, 14, 11165-11183, 2014

Author(s): T. Lei, A. Zuend, W. G. Wang, Y. H. Zhang, and M. F. Ge

Hygroscopic behavior of organic compounds, including levoglucosan, 4-hydroxybenzoic acid, and humic acid, as well as their effects on the hygroscopic properties of ammonium sulfate (AS) in internally mixed particles are studied by a hygroscopicity tandem differential mobility analyzer (HTDMA). The organic compounds used represent pyrolysis products of wood that are emitted from biomass burning sources. It is found that humic acid aerosol particles only slightly take up water, starting at RH (relative humidity) above ~70%. This is contrasted by the continuous water absorption of levoglucosan aerosol particles in the range 5–90% RH. However, no hygroscopic growth is observed for 4-hydroxybenzoic acid aerosol particles. Predicted water uptake using the ideal solution theory, the AIOMFAC model and the E-AIM (with UNIFAC) model are consistent with measured hygroscopic growth factors of levoglucosan. However, the use of these models without consideration of crystalline organic phases is not appropriate to describe the hygroscopicity of organics that do not exhibit continuous water uptake, such as 4-hydroxybenzoic acid and humic acid. Mixed aerosol particles consisting of ammonium sulfate and levoglucosan, 4-hydroxybenzoic acid, or humic acid with different organic mass fractions, take up a reduced amount of water above 80% RH (above AS deliquescence) relative to pure ammonium sulfate aerosol particles of the same mass. Hygroscopic growth of mixtures of ammonium sulfate and levoglucosan with different organic mass fractions agree well with the predictions of the thermodynamic models. Use of the Zdanovskii–Stokes–Robinson (ZSR) relation and AIOMFAC model lead to good agreement with measured growth factors of mixtures of ammonium sulfate with 4-hydroxybenzoic acid assuming an insoluble organic phase. Deviations of model predictions from the HTDMA measurement are mainly due to the occurrence of a microscopical solid phase restructuring at increased humidity (morphology effects), which are not considered in the models. Hygroscopic growth factors of mixed particles containing humic acid are well reproduced by the ZSR relation. Lastly, the organic surrogate compounds represent a selection of some of the most abundant pyrolysis products of biomass burning. The hygroscopic growths of mixtures of the organic surrogate compounds with ammonium sulfate with increasing organics mass fraction representing ambient conditions from the wet to the dry seasonal period in the Amazon basin, exhibit significant water uptake prior to the deliquescence of ammonium sulfate. The measured water absorptions of mixtures of several organic surrogate compounds (including levoglucosan) with ammonium sulfate are close to those of binary mixtures of levoglucosan with ammonium sulfate, indicating that levoglucosan constitutes a major contribution to the aerosol water uptake prior to (and beyond) the deliquescence of ammonium sulfate. Hence, certain hygroscopic organic surrogate compounds can substantially affect the deliquescence point of ammonium sulfate and overall particle water uptake.

Posted on 23 October 2014 | 12:00 am


Evaluation of tropospheric SO2 retrieved from MAX-DOAS measurements in Xianghe, China

Evaluation of tropospheric SO2 retrieved from MAX-DOAS measurements in Xianghe, China

Atmospheric Chemistry and Physics, 14, 11149-11164, 2014

Author(s): T. Wang, F. Hendrick, P. Wang, G. Tang, K. Clémer, H. Yu, C. Fayt, C. Hermans, C. Gielen, J.-F. Müller, G. Pinardi, N. Theys, H. Brenot, and M. Van Roozendael

Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of sulfur dioxide (SO2) have been performed at the Xianghe station (39.8° N, 117.0° E) located at ~ 50 km southeast of Beijing from March 2010 to February 2013. Tropospheric SO2 vertical profiles and corresponding vertical column densities (VCDs), retrieved by applying the optimal estimation method to the MAX-DOAS observations, have been used to study the seasonal and diurnal cycles of SO2, in combination with correlative measurements from in situ instruments, as well as meteorological data. A marked seasonality was observed in both SO2 VCD and surface concentration, with a maximum in winter (February) and a minimum in summer (July). This can be explained by the larger emissions in winter due to the domestic heating and, in case of surface concentration, by more favorable meteorological conditions for the accumulation of SO2 close to the ground during this period. Wind speed and direction are also found to be two key factors in controlling the level of the SO2-related pollution at Xianghe. In the case of east or southwest wind, the SO2 concentration does not change significantly with the wind speed, since the city of Tangshan and heavy polluting industries are located to the east and southwest of the station, respectively. In contrast, when wind comes from other directions, the stronger the wind, the less SO2 is observed due to a more effective dispersion. Regarding the diurnal cycle, the SO2 amount is larger in the early morning and late evening and lower at noon, in line with the diurnal variation of pollutant emissions and atmospheric stability. A strong correlation with correlation coefficients between 0.6 and 0.9 is also found between SO2 and aerosols in winter, suggesting that anthropogenic SO2, through the formation of sulfate aerosols, contributes significantly to the total aerosol content during this season. The observed diurnal cycles of MAX-DOAS SO2 surface concentration are also in very good agreement (correlation coefficient close to 0.9) with those from collocated in situ data, indicating the good reliability and robustness of our retrieval.

Posted on 23 October 2014 | 12:00 am


Climatology of free-tropospheric humidity: extension into the SEVIRI era, evaluation and exemplary analysis

Climatology of free-tropospheric humidity: extension into the SEVIRI era, evaluation and exemplary analysis

Atmospheric Chemistry and Physics, 14, 11129-11148, 2014

Author(s): M. Schröder, R. Roca, L. Picon, A. Kniffka, and H. Brogniez

A new free-tropospheric humidity (FTH) data record is presented. It is based on observations from the Meteosat Visible and Infrared Imager (MVIRI) onboard Meteosat-2–Meteosat-5, as well as Meteosat-7, and the Spinning Enhanced Visible and Infrared Imager (SEVIRI) onboard Meteosat-8 and Meteosat-9 at the water absorption band near 6.3 ?m. The data set is available under clear-sky and low-level cloud conditions. With the extension to SEVIRI observations, the data record covers the period 1983–2009 with a spatial resolution of 0.625° × 0.625° and a temporal resolution of 3 h.

The FTH is the mean relative humidity (RH) in a broad layer in the free troposphere. The relation between the observed brightness temperature (BT) and the FTH is well established. Previous retrievals are refined by taking into account the relative humidity Jacobians in the training process of the statistical retrieval. The temporal coverage is extended into the SEVIRI period, the homogenization of the BT record is improved, and the full archive is reprocessed using updated regression coefficients.

The FTH estimated from the Meteosat observations is compared to the FTH computed from the RH profiles of the Analyzed RadioSoundings Archive (ARSA). An average relative bias of ?3.2% and a relative root-mean-square difference (RMSD) of 16.8% are observed. This relative RMSD agrees with the outcome of an analysis of the total uncertainty of the FTH product. The decadal stability of the FTH data record is 0.5 ± 0.45% per decade.

As exemplary applications, the interannual standard deviation, the differences on decadal scales, and the linear trend in the FTH data record and in the frequency of occurrence of FTH < 10% (FTHp10) are analyzed per season. Interannual standard deviation maxima and maxima in absolute decadal differences are featured in gradient areas between dry and wet regions, as well as in areas where FTH reaches minima and FTHp10 reaches maxima. An analysis of the FTH linear trends and of the associated uncertainty estimates is achieved to identify possible problems with the data record. Positive trends in FTHp10 are featured in gradient areas between wet and dry regions, in regions where the FTH is minimum, in regions where FTHp10 is maximum, and in regions where differences between FTHp10 averaged over the 2000s and 1990s are negative. However, these positive trends in FTHp10 are associated with maximum standard deviation and are thus hardly significant. This analysis and intercomparisons with other humidity data records are part of the Global Energy and Water Cycle Experiment (GEWEX) Water Vapor Assessment (G-VAP).

Posted on 23 October 2014 | 12:00 am


The decreasing albedo of the Zhadang glacier on western Nyainqentanglha and the role of light-absorbing impurities

The decreasing albedo of the Zhadang glacier on western Nyainqentanglha and the role of light-absorbing impurities

Atmospheric Chemistry and Physics, 14, 11117-11128, 2014

Author(s): B. Qu, J. Ming, S.-C. Kang, G.-S. Zhang, Y.-W. Li, C.-D. Li, S.-Y. Zhao, Z.-M. Ji, and J.-J. Cao

A large change in albedo has a significant effect on glacier ablation. Atmospheric aerosols – e.g. black carbon (BC) and dust – can reduce the albedo of glaciers and thus contribute to their melting. In this study, two main themes were explored: (1) the decrease in albedo of the Zhadang glacier on Mt. Nyainqentanglha between 2001 and 2012, as observed by the Moderate Resolution Imaging Spectroradiometer (MODIS) on-board the Terra satellite, and the correlation of this albedo with mass balance; and (2) the concentrations of BC and dust in the glacier measured during 2012, and the associated impacts of these impurities on albedo and radiative forcings (RF). The average albedo of the Zhadang glacier from the MODIS increased with the altitude and fluctuated but had a decreasing trend (?0.003 a?1) during the period 2001–2012, with the highest (0.722) in 2003 and the lowest (0.597) in 2009 and 2010. The mass balance of the glacier has a positively significant correlation with its surface albedo derived from MODIS. Snow samples were collected on the Zhadang glacier to measure the BC and dust in the summer of 2012. The impacts of BC and dust on albedo reduction in different melting conditions were identified with the SNow ICe Aerosol Radiative (SNICAR) model initiated by in situ observation data. The sensitivity analysis showed that BC was a major factor in albedo reduction when the glacier was covered by newly fallen snow. Nevertheless, the contribution of dust to albedo reduction can reach as high as 56%, much exceeding that of BC (28%), when the glacier experiences strong surficial melting and its surface is almost bare ice. The average RF caused by dust could increase from 1.1 to 8.6 W m?2, exceeding the RF caused by BC after snow was deposited and surface melting occurred in the Zhadang glacier. This implies that it may be dust that primarily dominates the melting of some glaciers in the inner Tibetan Plateau during melting seasons, rather than BC.

Posted on 22 October 2014 | 12:00 am


Variability of the infrared complex refractive index of African mineral dust: experimental estimation and implications for radiative transfer and satellite remote sensing

Variability of the infrared complex refractive index of African mineral dust: experimental estimation and implications for radiative transfer and satellite remote sensing

Atmospheric Chemistry and Physics, 14, 11093-11116, 2014

Author(s): C. Di Biagio, H. Boucher, S. Caquineau, S. Chevaillier, J. Cuesta, and P. Formenti

Experimental estimations of the infrared refractive index of African mineral dust have been retrieved from laboratory measurements of particle transmission spectra in the wavelength range 2.5–25 ?m. Five dust samples collected at Banizoumbou (Niger) and Tamanrasset (Algeria) during dust events originated from different Western Saharan and Sahelian areas have been investigated. The real (n) and imaginary (k) parts of the refractive index obtained for the different dust samples vary in the range 1.1–2.7 and 0.05–1.0, respectively, and are strongly sensitive to the mineralogical composition of the particles, especially in the 8–12 and 17–25 ?m spectral intervals. Dust absorption is controlled mainly by clays (kaolinite, illite, smectite) and, to a lesser extent, by quartz and calcium-rich minerals (e.g. calcite, gypsum). Significant differences are obtained when comparing our results with existing experimental estimations available in the literature, and with the values of the OPAC (Optical Properties of Aerosols and Clouds) database. The different data sets appear comparable in magnitude, with our values of n and k falling within the range of variability of past studies. However, literature data fail in accurately reproducing the spectral signatures of the main minerals, in particular clays, and they significantly overestimate the contribution of quartz. Furthermore, the real and the imaginary parts of the refractive index from some literature studies are found not to verify the Kramers–Kronig relations, thus being theoretically incorrect. The comparison between our results, from western Africa, and literature data, from different locations in Europe, Africa, and the Caribbean, nonetheless, confirms the expected large variability of the dust infrared refractive index. This highlights the necessity for an extended systematic investigation of dust properties at infrared wavelengths.

For the five analysed dust samples, aerosol intensive optical properties relevant to radiative transfer (mass extinction efficiency, kext, single scattering albedo, ?, and asymmetry factor, g) have been calculated, by using the Mie theory, based on the estimated refractive index and measured particle size distribution. The optical properties show a large sample-to-sample variability, with kext, ?, and g varying in the range 0.05–0.35, 0.25–1.0, and 0.05–0.75. This variability is expected to significantly impact satellite retrievals of atmospheric and surface parameters (e.g. from the Infrared Atmospheric Sounding Interferometer, IASI) and estimates of the dust radiative forcing.

Posted on 22 October 2014 | 12:00 am


Modeling and sensitivity analysis of transport and deposition of radionuclides from the Fukushima Dai-ichi accident

Modeling and sensitivity analysis of transport and deposition of radionuclides from the Fukushima Dai-ichi accident

Atmospheric Chemistry and Physics, 14, 11065-11092, 2014

Author(s): X. Hu, D. Li, H. Huang, S. Shen, and E. Bou-Zeid

The atmospheric transport and ground deposition of radioactive isotopes 131I and 137Cs during and after the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident (March 2011) are investigated using the Weather Research and Forecasting-Chemistry (WRF-Chem) model. The aim is to assess the skill of WRF in simulating these processes and the sensitivity of the model's performance to various parameterizations of unresolved physics. The WRF-Chem model is first upgraded by implementing a radioactive decay term into the advection–diffusion solver and adding three parameterizations for dry deposition and two parameterizations for wet deposition. Different microphysics and horizontal turbulent diffusion schemes are then tested for their ability to reproduce observed meteorological conditions. Subsequently, the influence of emission characteristics (including the emission rate, the gas partitioning of 131I and the size distribution of 137Cs) on the simulated transport and deposition is examined. The results show that the model can predict the wind fields and rainfall realistically and that the ground deposition of the radionuclides can also be captured reasonably well. The modeled precipitation is largely influenced by the microphysics schemes, while the influence of the horizontal diffusion schemes on the wind fields is subtle. However, the ground deposition of radionuclides is sensitive to both horizontal diffusion schemes and microphysical schemes. Wet deposition dominated over dry deposition at most of the observation stations, but not at all locations in the simulated domain. To assess the sensitivity of the total daily deposition to all of the model physics and inputs, the averaged absolute value of the difference (AAD) is proposed. Based on AAD, the total deposition is mainly influenced by the emission rate for both 131I and 137Cs; while it is not sensitive to the dry deposition parameterizations since the dry deposition is just a minor fraction of the total deposition. Moreover, for 131I, the deposition is moderately sensitive (AAD between 10 and 40% between different runs) to the microphysics schemes, the horizontal diffusion schemes, gas-partitioning and wet deposition parameterizations. For 137Cs, the deposition is very sensitive (AAD exceeding 40% between different runs) to the microphysics schemes and wet deposition parameterizations, but moderately sensitive to the horizontal diffusion schemes and the size distribution.

Posted on 22 October 2014 | 12:00 am


A global model simulation of present and future nitrate aerosols and their direct radiative forcing of climate

A global model simulation of present and future nitrate aerosols and their direct radiative forcing of climate

Atmospheric Chemistry and Physics, 14, 11031-11063, 2014

Author(s): D. A. Hauglustaine, Y. Balkanski, and M. Schulz

The ammonia cycle and nitrate particle formation are introduced into the LMDz-INCA (Laboratoire de Météorologie Dynamique, version 4 – INteraction with Chemistry and Aerosols, version 3) global model. An important aspect of this new model is that both fine nitrate particle formation in the accumulation mode and coarse nitrate forming on existing dust and sea-salt particles are considered. The model simulates distributions of nitrates and related species in agreement with previous studies and observations. The calculated present-day total nitrate direct radiative forcing since the pre-industrial is ?0.056 W m?2. This forcing corresponds to 18% of the sulfate forcing. Fine particles largely dominate the nitrate forcing, representing close to 90% of this value. The model has been used to investigate the future changes in nitrates and direct radiative forcing of climate based on snapshot simulations for the four representative concentration pathway (RCP) scenarios and for the 2030, 2050, and 2100 time horizons. Due to a decrease in fossil fuel emissions in the future, the concentration of most of the species involved in the nitrate–ammonium–sulfate system drop by 2100 except for ammonia, which originates from agricultural practices and for which emissions significantly increase in the future. Despite the decrease of nitrate surface levels in Europe and North America, the global burden of accumulation mode nitrates increases by up to a factor of 2.6 in 2100. This increase in ammonium nitrate in the future arises despite decreasing NOx emissions due to increased availability of ammonia to form ammonium nitrate. The total aerosol direct forcing decreases from its present-day value of ?0.234 W m?2 to a range of ?0.070 to ?0.130 W m?2 in 2100 based on the considered scenario. The direct forcing decreases for all aerosols except for nitrates, for which the direct negative forcing increases to a range of ?0.060 to ?0.115 W m?2 in 2100. Including nitrates in the radiative forcing calculations increases the total direct forcing of aerosols by a factor of 1.3 in 2000, by a factor of 1.7–2.6 in 2030, by 1.9–4.8 in 2050, and by 6.4–8.6 in 2100. These results show that the agricultural emissions of ammonia will play a key role in the future mitigation of climate change, with nitrates becoming the dominant contributor to the anthropogenic aerosol optical depth during the second half of the 21st century and significantly increasing the calculated aerosol direct forcing. This significant increase in the influence that nitrate exerts on climate in the future will at the same time affect regional air quality and nitrogen deposition to the ecosystem.

Posted on 21 October 2014 | 12:00 am


Modeling ultrafine particle growth at a pine forest site influenced by anthropogenic pollution during BEACHON-RoMBAS 2011

Modeling ultrafine particle growth at a pine forest site influenced by anthropogenic pollution during BEACHON-RoMBAS 2011

Atmospheric Chemistry and Physics, 14, 11011-11029, 2014

Author(s): Y. Y. Cui, A. Hodzic, J. N. Smith, J. Ortega, J. Brioude, H. Matsui, E. J. T. Levin, A. Turnipseed, P. Winkler, and B. de Foy

Formation and growth of ultrafine particles is crudely represented in chemistry-climate models, contributing to uncertainties in aerosol composition, size distribution, and aerosol effects on cloud condensation nuclei (CCN) concentrations. Measurements of ultrafine particles, their precursor gases, and meteorological parameters were performed in a ponderosa pine forest in the Colorado Front Range in July–August 2011, and were analyzed to study processes leading to small particle burst events (PBEs) which were characterized by an increase in the number concentrations of ultrafine 4–30 nm diameter size particles. These measurements suggest that PBEs were associated with the arrival at the site of anthropogenic pollution plumes midday to early afternoon. During PBEs, number concentrations of 4–30 nm diameter particles typically exceeded 104 cm?3, and these elevated concentrations coincided with increased SO2 and monoterpene concentrations, and led to a factor-of-2 increase in CCN concentrations at 0.5% supersaturation. The PBEs were simulated using the regional WRF-Chem model, which was extended to account for ultrafine particle sizes starting at 1 nm in diameter, to include an empirical activation nucleation scheme in the planetary boundary layer, and to explicitly simulate the subsequent growth of Aitken particles (10–100 nm) by condensation of organic and inorganic vapors. The updated model reasonably captured measured aerosol number concentrations and size distribution during PBEs, as well as ground-level CCN concentrations. Model results suggest that sulfuric acid originating from anthropogenic SO2 triggered PBEs, and that the condensation of monoterpene oxidation products onto freshly nucleated particles contributes to their growth. The simulated growth rate of ~ 3.4 nm h?1 for 4–40 nm diameter particles was comparable to the measured average value of 2.3 nm h?1. Results also suggest that the presence of PBEs tends to modify the composition of sub-20 nm diameter particles, leading to a higher mass fraction of sulfate aerosols. Sensitivity simulations suggest that the representation of nucleation processes in the model largely influences the predicted number concentrations and thus CCN concentrations. We estimate that nucleation contributes 67% of surface CCN at 0.5% supersaturation in this pine forest environment.

Posted on 20 October 2014 | 12:00 am


Exploiting simultaneous observational constraints on mass and absorption to estimate the global direct radiative forcing of black carbon and brown carbon

Exploiting simultaneous observational constraints on mass and absorption to estimate the global direct radiative forcing of black carbon and brown carbon

Atmospheric Chemistry and Physics, 14, 10989-11010, 2014

Author(s): X. Wang, C. L. Heald, D. A. Ridley, J. P. Schwarz, J. R. Spackman, A. E. Perring, H. Coe, D. Liu, and A. D. Clarke

Atmospheric black carbon (BC) is a leading climate warming agent, yet uncertainties on the global direct radiative forcing (DRF) remain large. Here we expand a global model simulation (GEOS-Chem) of BC to include the absorption enhancement associated with BC coating and separately treat both the aging and physical properties of fossil-fuel and biomass-burning BC. In addition we develop a global simulation of brown carbon (BrC) from both secondary (aromatic) and primary (biomass burning and biofuel) sources. The global mean lifetime of BC in this simulation (4.4 days) is substantially lower compared to the AeroCom I model means (7.3 days), and as a result, this model captures both the mass concentrations measured in near-source airborne field campaigns (ARCTAS, EUCAARI) and surface sites within 30%, and in remote regions (HIPPO) within a factor of 2. We show that the new BC optical properties together with the inclusion of BrC reduces the model bias in absorption aerosol optical depth (AAOD) at multiple wavelengths by more than 50% at AERONET sites worldwide. However our improved model still underestimates AAOD by a factor of 1.4 to 2.8 regionally, with the largest underestimates in regions influenced by fire. Using the RRTMG model integrated with GEOS-Chem we estimate that the all-sky top-of-atmosphere DRF of BC is +0.13 Wm?2 (0.08 Wm?2 from anthropogenic sources and 0.05 Wm?2 from biomass burning). If we scale our model to match AERONET AAOD observations we estimate the DRF of BC is +0.21 Wm?2, with an additional +0.11 Wm?2 of warming from BrC. Uncertainties in size, optical properties, observations, and emissions suggest an overall uncertainty in BC DRF of ?80%/+140%. Our estimates are at the lower end of the 0.2–1.0 Wm?2 range from previous studies, and substantially less than the +0.6 Wm?2 DRF estimated in the IPCC 5th Assessment Report. We suggest that the DRF of BC has previously been overestimated due to the overestimation of the BC lifetime (including the effect on the vertical profile) and the incorrect attribution of BrC absorption to BC.

Posted on 20 October 2014 | 12:00 am


Volatile organic compound emissions from the oil and natural gas industry in the Uintah Basin, Utah: oil and gas well pad emissions compared to ambient air composition

Volatile organic compound emissions from the oil and natural gas industry in the Uintah Basin, Utah: oil and gas well pad emissions compared to ambient air composition

Atmospheric Chemistry and Physics, 14, 10977-10988, 2014

Author(s): C. Warneke, F. Geiger, P. M. Edwards, W. Dube, G. Pétron, J. Kofler, A. Zahn, S. S. Brown, M. Graus, J. B. Gilman, B. M. Lerner, J. Peischl, T. B. Ryerson, J. A. de Gouw, and J. M. Roberts

Emissions of volatile organic compounds (VOCs) associated with oil and natural gas production in the Uintah Basin, Utah were measured at a ground site in Horse Pool and from a NOAA mobile laboratory with PTR-MS instruments. The VOC compositions in the vicinity of individual gas and oil wells and other point sources such as evaporation ponds, compressor stations and injection wells are compared to the measurements at Horse Pool. High mixing ratios of aromatics, alkanes, cycloalkanes and methanol were observed for extended periods of time and for short-term spikes caused by local point sources. The mixing ratios during the time the mobile laboratory spent on the well pads were averaged. High mixing ratios were found close to all point sources, but gas well pads with collection and dehydration on the well pad were clearly associated with higher mixing ratios than other wells. The comparison of the VOC composition of the emissions from the oil and natural gas well pads showed that gas well pads without dehydration on the well pad compared well with the majority of the data at Horse Pool, and that oil well pads compared well with the rest of the ground site data. Oil well pads on average emit heavier compounds than gas well pads. The mobile laboratory measurements confirm the results from an emissions inventory: the main VOC source categories from individual point sources are dehydrators, oil and condensate tank flashing and pneumatic devices and pumps. Raw natural gas is emitted from the pneumatic devices and pumps and heavier VOC mixes from the tank flashings.

Posted on 17 October 2014 | 12:00 am


TNO-MACC_II emission inventory; a multi-year (2003–2009) consistent high-resolution European emission inventory for air quality modelling

TNO-MACC_II emission inventory; a multi-year (2003–2009) consistent high-resolution European emission inventory for air quality modelling

Atmospheric Chemistry and Physics, 14, 10963-10976, 2014

Author(s): J. J. P. Kuenen, A. J. H. Visschedijk, M. Jozwicka, and H. A. C. Denier van der Gon

Emissions to air are reported by countries to EMEP. The emissions data are used for country compliance checking with EU emission ceilings and associated emission reductions. The emissions data are also necessary as input for air quality modelling. The quality of these "official" emissions varies across Europe.

As alternative to these official emissions, a spatially explicit high-resolution emission inventory (7 × 7 km) for UNECE-Europe for all years between 2003 and 2009 for the main air pollutants was made. The primary goal was to supply air quality modellers with the input they need. The inventory was constructed by using the reported emission national totals by sector where the quality is sufficient. The reported data were analysed by sector in detail, and completed with alternative emission estimates as needed. This resulted in a complete emission inventory for all countries.

For particulate matter, for each source emissions have been split in coarse and fine particulate matter, and further disaggregated to EC, OC, SO4, Na and other minerals using fractions based on the literature. Doing this at the most detailed sectoral level in the database implies that a consistent set was obtained across Europe. This allows better comparisons with observational data which can, through feedback, help to further identify uncertain sources and/or support emission inventory improvements for this highly uncertain pollutant.

The resulting emission data set was spatially distributed consistently across all countries by using proxy parameters. Point sources were spatially distributed using the specific location of the point source. The spatial distribution for the point sources was made year-specific.

The TNO-MACC_II is an update of the TNO-MACC emission data set. Major updates included the time extension towards 2009, use of the latest available reported data (including updates and corrections made until early 2012) and updates in distribution maps.

Posted on 17 October 2014 | 12:00 am


Trends in particle-phase liquid water during the Southern Oxidant and Aerosol Study

Trends in particle-phase liquid water during the Southern Oxidant and Aerosol Study

Atmospheric Chemistry and Physics, 14, 10911-10930, 2014

Author(s): T. K. V. Nguyen, M. D. Petters, S. R. Suda, H. Guo, R. J. Weber, and A. G. Carlton

We present in situ measurements of particle-phase liquid water. Measurements were conducted from 3 June to 15 July 2013 during the Southern Oxidant and Aerosol Study (SOAS) in the southeastern US. The region is photochemically active, humid, dominated by biogenic emissions, impacted by anthropogenic pollution, and known to contain high concentrations of organic aerosol mass. Measurements characterized mobility number size distributions of ambient atmospheric aerosols in three states: unperturbed, dry, and dry-humidified. Unperturbed measurements describe the aerosol distribution at ambient temperature and relative humidity. For the dry state, the sample was routed through a cold trap upstream of the inlet then reheated, while for the dry-humidified state the sample was rehumidified after drying. The total volume of water and semi-volatile compounds lost during drying was quantified by differencing dry and unperturbed volumes from the integrated size spectra, while semi-volatile volumes lost during drying were quantified differencing unperturbed and dry-humidified volumes. Results indicate that particle-phase liquid water was always present. Throughout the SOAS campaign, median water mass concentrations at the relative humidity (RH) encountered in the instrument typically ranged from 1 to 5 ?g m?3 but were as high as 73 ?g m?3. On non-raining days, morning time (06:00–09:00) median mass concentrations exceeded 15 ?g m?3. Hygroscopic growth factors followed a diel cycle and exceed 2 from 07:00 to 09:00 local time. The hygroscopicity parameter kappa ranged from 0.14 to 0.46 and hygroscopicity increased with increasing particle size. An observed diel cycle in kappa is consistent with changes in aerosol inorganic content and a dependency of the hygroscopicity parameter on water content. Unperturbed and dry-humidified aerosol volumes did not result in statistically discernible differences, demonstrating that drying did not lead to large losses in dry particle volume. We anticipate that our results will help improve the representation of aerosol water content and aqueous-phase-mediated partitioning of atmospheric water-soluble gases in photochemical models.

Posted on 16 October 2014 | 12:00 am


Corrigendum to "A multi-year methane inversion using SCIAMACHY, accounting for systematic errors using TCCON measurements" published in Atmos. Chem. Phys., 14, 3991–4012, 2014

Corrigendum to "A multi-year methane inversion using SCIAMACHY, accounting for systematic errors using TCCON measurements" published in Atmos. Chem. Phys., 14, 3991–4012, 2014

Atmospheric Chemistry and Physics, 14, 10961-10962, 2014

Author(s): S. Houweling, M. Krol, P. Bergamaschi, C. Frankenberg, E. J. Dlugokencky, I. Morino, J. Notholt, V. Sherlock, D. Wunch, V. Beck, C. Gerbig, H. Chen, E. A. Kort, T. Röckmann, and I. Aben

No abstract available.

Posted on 16 October 2014 | 12:00 am


The BLLAST field experiment: Boundary-Layer Late Afternoon and Sunset Turbulence

The BLLAST field experiment: Boundary-Layer Late Afternoon and Sunset Turbulence

Atmospheric Chemistry and Physics, 14, 10931-10960, 2014

Author(s): M. Lothon, F. Lohou, D. Pino, F. Couvreux, E. R. Pardyjak, J. Reuder, J. Vilà-Guerau de Arellano, P Durand, O. Hartogensis, D. Legain, P. Augustin, B. Gioli, D. H. Lenschow, I. Faloona, C. Yagüe, D. C. Alexander, W. M. Angevine, E Bargain, J. Barrié, E. Bazile, Y. Bezombes, E. Blay-Carreras, A. van de Boer, J. L. Boichard, A. Bourdon, A. Butet, B. Campistron, O. de Coster, J. Cuxart, A. Dabas, C. Darbieu, K. Deboudt, H. Delbarre, S. Derrien, P. Flament, M. Fourmentin, A. Garai, F. Gibert, A. Graf, J. Groebner, F. Guichard, M. A. Jiménez, M. Jonassen, A. van den Kroonenberg, V. Magliulo, S. Martin, D. Martinez, L. Mastrorillo, A. F. Moene, F. Molinos, E. Moulin, H. P. Pietersen, B. Piguet, E. Pique, C. Román-Cascón, C. Rufin-Soler, F. Saïd, M. Sastre-Marugán, Y. Seity, G. J. Steeneveld, P. Toscano, O. Traullé, D. Tzanos, S. Wacker, N. Wildmann, and A. Zaldei

Due to the major role of the sun in heating the earth's surface, the atmospheric planetary boundary layer over land is inherently marked by a diurnal cycle. The afternoon transition, the period of the day that connects the daytime dry convective boundary layer to the night-time stable boundary layer, still has a number of unanswered scientific questions. This phase of the diurnal cycle is challenging from both modelling and observational perspectives: it is transitory, most of the forcings are small or null and the turbulence regime changes from fully convective, close to homogeneous and isotropic, toward a more heterogeneous and intermittent state.

These issues motivated the BLLAST (Boundary-Layer Late Afternoon and Sunset Turbulence) field campaign that was conducted from 14 June to 8 July 2011 in southern France, in an area of complex and heterogeneous terrain. A wide range of instrumented platforms including full-size aircraft, remotely piloted aircraft systems, remote-sensing instruments, radiosoundings, tethered balloons, surface flux stations and various meteorological towers were deployed over different surface types. The boundary layer, from the earth's surface to the free troposphere, was probed during the entire day, with a focus and intense observation periods that were conducted from midday until sunset. The BLLAST field campaign also provided an opportunity to test innovative measurement systems, such as new miniaturized sensors, and a new technique for frequent radiosoundings of the low troposphere.

Twelve fair weather days displaying various meteorological conditions were extensively documented during the field experiment. The boundary-layer growth varied from one day to another depending on many contributions including stability, advection, subsidence, the state of the previous day's residual layer, as well as local, meso- or synoptic scale conditions.

Ground-based measurements combined with tethered-balloon and airborne observations captured the turbulence decay from the surface throughout the whole boundary layer and documented the evolution of the turbulence characteristic length scales during the transition period.

Closely integrated with the field experiment, numerical studies are now underway with a complete hierarchy of models to support the data interpretation and improve the model representations.

Posted on 16 October 2014 | 12:00 am


Characteristics of the raindrop distributions in RICO shallow cumulus

Characteristics of the raindrop distributions in RICO shallow cumulus

Atmospheric Chemistry and Physics, 14, 10897-10909, 2014

Author(s): O. Geoffroy, A. P. Siebesma, and F. Burnet

The physical properties of rain spectra are generally modeled using an analytical distribution. It is common for the gamma distribution and, to a lesser extent, the lognormal distribution to be used. The majority of studies in the literature focusing on the characterization of raindrop distribution are based on deep convective cloud observations, mostly at ground level. This study focuses on shallow-cumulus rain distributions throughout the depth of the cloud layer and subcloud layer using airborne in situ measurements made with both the Particle Measuring Systems (PMS) Optical Array Probe 260X (OAP-260-X) and the PMS two-Dimensional Precipitation (2DP) instruments during the Rain in Cumulus over the Ocean (RICO) field experiment. Sampled spectra analyzed on the scale of large-eddy simulation resolution (100 m) are found to be relatively broad, with values of the shape parameter – υ for the gamma law and σg for the lognormal law – on the order of 1–3 and 1.5–2, respectively. The dependence of the shape parameters on the main rain variables (number concentration, water content, mean volume diameter, sedimentation fluxes and radar reflectivity) is examined, and a parameterization of the shape parameters υ and σg as a function of a power law of the rainwater content and raindrop number concentration is proposed.

Posted on 15 October 2014 | 12:00 am


The AeroCom evaluation and intercomparison of organic aerosol in global models

The AeroCom evaluation and intercomparison of organic aerosol in global models

Atmospheric Chemistry and Physics, 14, 10845-10895, 2014

Author(s): K. Tsigaridis, N. Daskalakis, M. Kanakidou, P. J. Adams, P. Artaxo, R. Bahadur, Y. Balkanski, S. E. Bauer, N. Bellouin, A. Benedetti, T. Bergman, T. K. Berntsen, J. P. Beukes, H. Bian, K. S. Carslaw, M. Chin, G. Curci, T. Diehl, R. C. Easter, S. J. Ghan, S. L. Gong, A. Hodzic, C. R. Hoyle, T. Iversen, S. Jathar, J. L. Jimenez, J. W. Kaiser, A. Kirkevåg, D. Koch, H. Kokkola, Y. H Lee, G. Lin, X. Liu, G. Luo, X. Ma, G. W. Mann, N. Mihalopoulos, J.-J. Morcrette, J.-F. Müller, G. Myhre, S. Myriokefalitakis, N. L. Ng, D. O'Donnell, J. E. Penner, L. Pozzoli, K. J. Pringle, L. M. Russell, M. Schulz, J. Sciare, Ø. Seland, D. T. Shindell, S. Sillman, R. B. Skeie, D. Spracklen, T. Stavrakou, S. D. Steenrod, T. Takemura, P. Tiitta, S. Tilmes, H. Tost, T. van Noije, P. G. van Zyl, K. von Salzen, F. Yu, Z. Wang, Z. Wang, R. A. Zaveri, H. Zhang, K. Zhang, Q. Zhang, and X. Zhang

This paper evaluates the current status of global modeling of the organic aerosol (OA) in the troposphere and analyzes the differences between models as well as between models and observations. Thirty-one global chemistry transport models (CTMs) and general circulation models (GCMs) have participated in this intercomparison, in the framework of AeroCom phase II. The simulation of OA varies greatly between models in terms of the magnitude of primary emissions, secondary OA (SOA) formation, the number of OA species used (2 to 62), the complexity of OA parameterizations (gas-particle partitioning, chemical aging, multiphase chemistry, aerosol microphysics), and the OA physical, chemical and optical properties. The diversity of the global OA simulation results has increased since earlier AeroCom experiments, mainly due to the increasing complexity of the SOA parameterization in models, and the implementation of new, highly uncertain, OA sources. Diversity of over one order of magnitude exists in the modeled vertical distribution of OA concentrations that deserves a dedicated future study. Furthermore, although the OA / OC ratio depends on OA sources and atmospheric processing, and is important for model evaluation against OA and OC observations, it is resolved only by a few global models.

The median global primary OA (POA) source strength is 56 Tg a?1 (range 34–144 Tg a−1) and the median SOA source strength (natural and anthropogenic) is 19 Tg a?1 (range 13–121 Tg a−1). Among the models that take into account the semi-volatile SOA nature, the median source is calculated to be 51 Tg a?1 (range 16–121 Tg a−1), much larger than the median value of the models that calculate SOA in a more simplistic way (19 Tg a?1; range 13–20 Tg a?1, with one model at 37 Tg a−1). The median atmospheric burden of OA is 1.4 Tg (24 models in the range of 0.6–2.0 Tg and 4 between 2.0 and 3.8 Tg), with a median OA lifetime of 5.4 days (range 3.8–9.6 days). In models that reported both OA and sulfate burdens, the median value of the OA/sulfate burden ratio is calculated to be 0.77; 13 models calculate a ratio lower than 1, and 9 models higher than 1. For 26 models that reported OA deposition fluxes, the median wet removal is 70 Tg a?1 (range 28–209 Tg a−1), which is on average 85% of the total OA deposition.

Fine aerosol organic carbon (OC) and OA observations from continuous monitoring networks and individual field campaigns have been used for model evaluation. At urban locations, the model–observation comparison indicates missing knowledge on anthropogenic OA sources, both strength and seasonality. The combined model–measurements analysis suggests the existence of increased OA levels during summer due to biogenic SOA formation over large areas of the USA that can be of the same order of magnitude as the POA, even at urban locations, and contribute to the measured urban seasonal pattern.

Global models are able to simulate the high secondary character of OA observed in the atmosphere as a result of SOA formation and POA aging, although the amount of OA present in the atmosphere remains largely underestimated, with a mean normalized bias (MNB) equal to ?0.62 (?0.51) based on the comparison against OC (OA) urban data of all models at the surface, ?0.15 (+0.51) when compared with remote measurements, and ?0.30 for marine locations with OC data. The mean temporal correlations across all stations are low when compared with OC (OA) measurements: 0.47 (0.52) for urban stations, 0.39 (0.37) for remote stations, and 0.25 for marine stations with OC data. The combination of high (negative) MNB and higher correlation at urban stations when compared with the low MNB and lower correlation at remote sites suggests that knowledge about the processes that govern aerosol processing, transport and removal, on top of their sources, is important at the remote stations. There is no clear change in model skill with increasing model complexity with regard to OC or OA mass concentration. However, the complexity is needed in models in order to distinguish between anthropogenic and natural OA as needed for climate mitigation, and to calculate the impact of OA on climate accurately.

Posted on 15 October 2014 | 12:00 am


The link between atmospheric radicals and newly formed particles at a spruce forest site in Germany

The link between atmospheric radicals and newly formed particles at a spruce forest site in Germany

Atmospheric Chemistry and Physics, 14, 10823-10843, 2014

Author(s): B. Bonn, E. Bourtsoukidis, T. S. Sun, H. Bingemer, L. Rondo, U. Javed, J. Li, R. Axinte, X. Li, T. Brauers, H. Sonderfeld, R. Koppmann, A. Sogachev, S. Jacobi, and D. V. Spracklen

It has been claimed for more than a century that atmospheric new particle formation is primarily influenced by the presence of sulfuric acid. However, the activation process of sulfuric acid related clusters into detectable particles is still an unresolved topic. In this study we focus on the PARADE campaign measurements conducted during August/September 2011 at Mt Kleiner Feldberg in central Germany. During this campaign a set of radicals, organic and inorganic compounds and oxidants and aerosol properties were measured or calculated. We compared a range of organic and inorganic nucleation theories, evaluating their ability to simulate measured particle formation rates at 3 nm in diameter (J3) for a variety of different conditions. Nucleation mechanisms involving only sulfuric acid tentatively captured the observed noon-time daily maximum in J3, but displayed an increasing difference to J3 measurements during the rest of the diurnal cycle. Including large organic radicals, i.e. organic peroxy radicals (RO2) deriving from monoterpenes and their oxidation products, in the nucleation mechanism improved the correlation between observed and simulated J3. This supports a recently proposed empirical relationship for new particle formation that has been used in global models. However, the best match between theory and measurements for the site of interest was found for an activation process based on large organic peroxy radicals and stabilised Criegee intermediates (sCI). This novel laboratory-derived algorithm simulated the daily pattern and intensity of J3 observed in the ambient data. In this algorithm organic derived radicals are involved in activation and growth and link the formation rate of smallest aerosol particles with OH during daytime and NO3 during night-time. Because the RO2 lifetime is controlled by HO2 and NO we conclude that peroxy radicals and NO seem to play an important role for ambient radical chemistry not only with respect to oxidation capacity but also for the activation process of new particle formation. This is supposed to have significant impact of atmospheric radical species on aerosol chemistry and should be taken into account when studying the impact of new particles in climate feedback cycles.

Posted on 15 October 2014 | 12:00 am


Comparison of Fast In situ Stratospheric Hygrometer (FISH) measurements of water vapor in the upper troposphere and lower stratosphere (UTLS) with ECMWF (re)analysis data

Comparison of Fast In situ Stratospheric Hygrometer (FISH) measurements of water vapor in the upper troposphere and lower stratosphere (UTLS) with ECMWF (re)analysis data

Atmospheric Chemistry and Physics, 14, 10803-10822, 2014

Author(s): A. Kunz, N. Spelten, P. Konopka, R. Müller, R. M. Forbes, and H. Wernli

An evaluation of water vapor in the upper troposphere and lower stratosphere (UTLS) of the ERA-Interim, the global atmospheric reanalysis produced by the European Centre for Medium-Range Weather Forecasts (ECMWF), is presented. Water vapor measurements are derived from the Fast In situ Stratospheric Hygrometer (FISH) during a large set of airborne measurement campaigns from 2001 to 2011 in the tropics, midlatitudes and polar regions, covering isentropic layers from 300 to 400K (5–18km).

The comparison shows around 87% of the reanalysis data are within a factor of 2 of the FISH water vapor measurements and around 30% have a nearly perfect agreement with an over- and underestimation lower than 10%. Nevertheless, strong over- and underestimations can occur both in the UT and LS, in particularly in the extratropical LS and in the tropical UT, where severe over- and underestimations up to 10 times can occur.

The analysis data from the evolving ECMWF operational system is also evaluated, and the FISH measurements are divided into time periods representing different cycles of the Integrated Forecast System (IFS). The agreement with FISH improves over the time, in particular when comparing water vapor fields for time periods before 2004 and after 2010. It appears that influences of tropical tropospheric and extratropical UTLS processes, e.g., convective and quasi-isentropic exchange processes, are particularly challenging for the simulation of the UTLS water vapor distribution. Both the reanalysis and operational analysis data show the tendency of an overestimation of low water vapor mixing ratio (⪅10ppmv) in the LS and underestimation of high water vapor mixing ratio (⪆300ppmv) in the UT.

Posted on 14 October 2014 | 12:00 am


Microphysical properties of synoptic-scale polar stratospheric clouds: in situ measurements of unexpectedly large HNO3-containing particles in the Arctic vortex

Microphysical properties of synoptic-scale polar stratospheric clouds: in situ measurements of unexpectedly large HNO3-containing particles in the Arctic vortex

Atmospheric Chemistry and Physics, 14, 10785-10801, 2014

Author(s): S. Molleker, S. Borrmann, H. Schlager, B. Luo, W. Frey, M. Klingebiel, R. Weigel, M. Ebert, V. Mitev, R. Matthey, W. Woiwode, H. Oelhaf, A. Dörnbrack, G. Stratmann, J.-U. Grooß, G. Günther, B. Vogel, R. Müller, M. Krämer, J. Meyer, and F. Cairo

In January 2010 and December 2011, synoptic-scale polar stratospheric cloud (PSC) fields were probed during seven flights of the high-altitude research aircraft M-55 Geophysica within the RECONCILE (Reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interaction) and the ESSenCe (ESSenCe: ESA Sounder Campaign) projects. Particle size distributions in a diameter range between 0.46 and 40?m were recorded by four different optical in situ instruments. Three of these particle instruments are based on the detection of forward-scattered light by single particles. The fourth instrument is a grayscale optical array imaging probe. Optical particle diameters of up to 35?m were detected with particle number densities and total particle volumes exceeding previous Arctic measurements. Also, gas-phase and particle-bound NOy was measured, as well as water vapor concentrations. The optical characteristics of the clouds were measured by the remote sensing lidar MAL (Miniature Aerosol Lidar) and by the in situ backscatter sonde MAS (Multiwavelength Aerosol Scatterometer), showing the synoptic scale of the encountered PSCs. The particle mode below 2?m in size diameter has been identified as supercooled ternary solution (STS) droplets. The PSC particles in the size range above 2?m in diameter are considered to consist of nitric acid hydrates, and the particles' high HNO3 content was confirmed by the NOy instrument. Assuming a particle composition of nitric acid trihydrate (NAT), the optically measured size distributions result in particle-phase HNO3 mixing ratios exceeding available stratospheric values. Therefore the measurement uncertainties concerning probable overestimations of measured particle sizes and volumes are discussed in detail. We hypothesize that either a strong asphericity or an alternate particle composition (e.g., water ice coated with NAT) could explain our observations. In particular, with respect to the denitrification by sedimentation of large HNO3-containing particles, generally considered to be NAT, our new measurements raise questions concerning composition, shape and nucleation pathways. Answering these would improve the numerical simulation of PSC microphysical processes like cloud particle formation, growth and denitrification, which is necessary for better predictions of future polar ozone losses, especially under changing global climate conditions. Generally, it seems that the occurrence of large NAT particles – sometimes termed "NAT rocks" – are a regular feature of synoptic-scale PSCs in the Arctic.

Posted on 14 October 2014 | 12:00 am


Laboratory studies of the aqueous-phase oxidation of polyols: submicron particles vs. bulk aqueous solution

Laboratory studies of the aqueous-phase oxidation of polyols: submicron particles vs. bulk aqueous solution

Atmospheric Chemistry and Physics, 14, 10773-10784, 2014

Author(s): K. E. Daumit, A. J. Carrasquillo, J. F. Hunter, and J. H. Kroll

Oxidation in the atmospheric aqueous phase (cloud droplets and deliquesced particles) has received recent attention as a potential pathway for the formation of highly oxidized organic aerosol. Most laboratory studies of aqueous-phase oxidation, however, are carried out in bulk solutions rather than aqueous droplets. Here we describe experiments in which aqueous oxidation of polyols (water-soluble species with chemical formula CnH2n+2On) is carried out within submicron particles in an environmental chamber, allowing for significant gas–particle partitioning of reactants, intermediates, and products. Dark Fenton chemistry is used as a source of hydroxyl radicals, and oxidation is monitored using a high-resolution aerosol mass spectrometer (AMS). Aqueous oxidation is rapid, and results in the formation of particulate oxalate; this is accompanied by substantial loss of carbon to the gas phase, indicating the formation of volatile products. Results are compared to those from analogous oxidation reactions carried out in bulk solution. The bulk-phase chemistry is similar to that in the particles, but with substantially less carbon loss. This is likely due to differences in partitioning of early-generation products, which evaporate out of the aqueous phase under chamber conditions (in which liquid water content is low), but remain in solution for further aqueous processing in the bulk phase. This work suggests that the product distributions from oxidation in aqueous aerosol may be substantially different from those in bulk oxidation experiments. This highlights the need for aqueous oxidation studies to be carried out under atmospherically relevant partitioning conditions, with liquid water contents mimicking those of cloud droplets or aqueous aerosol.

Posted on 14 October 2014 | 12:00 am


The influence of physical state on shikimic acid ozonolysis: a case for in situ microspectroscopy

The influence of physical state on shikimic acid ozonolysis: a case for in situ microspectroscopy

Atmospheric Chemistry and Physics, 14, 10761-10772, 2014

Author(s): S. S. Steimer, M. Lampimäki, E. Coz, G. Grzinic, and M. Ammann

Atmospheric soluble organic aerosol material can become solid or semi-solid. Due to increasing viscosity and decreasing diffusivity, this can impact important processes such as gas uptake and reactivity within aerosols containing such substances. This work explores the dependence of shikimic acid ozonolysis on humidity and thereby viscosity. Shikimic acid, a proxy for oxygenated reactive organic material, reacts with O3 in a Criegee-type reaction. We used an environmental microreactor embedded in a scanning transmission X-ray microscope (STXM) to probe this oxidation process. This technique facilitates in situ measurements with single micron-sized particles and allows to obtain near-edge X-ray absorption fine structure (NEXAFS) spectra with high spatial resolution. Thus, the chemical evolution of the interior of the particles can be followed under reaction conditions. The experiments show that the overall degradation rate of shikimic acid is depending on the relative humidity in a way that is controlled by the decreasing diffusivity of ozone with decreasing humidity. This decreasing diffusivity is most likely linked to the increasing viscosity of the shikimic acid–water mixture. The degradation rate was also depending on particle size, most congruent with a reacto-diffusion limited kinetic case where the reaction progresses only in a shallow layer within the bulk. No gradient in the shikimic acid concentration was observed within the bulk material at any humidity indicating that the diffusivity of shikimic acid is still high enough to allow its equilibration throughout the particles on the timescale of hours at higher humidity and that the thickness of the oxidized layer under dry conditions, where the particles are solid, is beyond the resolution of STXM.

Posted on 13 October 2014 | 12:00 am


Comparison of the diurnal variations of warm-season precipitation for East Asia vs. North America downstream of the Tibetan Plateau vs. the Rocky Mountains

Comparison of the diurnal variations of warm-season precipitation for East Asia vs. North America downstream of the Tibetan Plateau vs. the Rocky Mountains

Atmospheric Chemistry and Physics, 14, 10741-10759, 2014

Author(s): Yuanchun Zhang, Fuqing Zhang, and Jianhua Sun

A wave-number-frequency spectral decomposition technique is used to analyze the high-resolution NOAA/Climate Prediction Center morphing technique (CMORPH) precipitation data set and to explore the differences and similarities of the diurnal variation of warm-season precipitation in the East Asia and North America downstream of big topography. The predominant phase speed of precipitation at different time scales for North America, averaged over all warm-season months (May–August) for 2003–2010, is ~20 ms?1, which is faster than the speed of ~14 ms?1 calculated for East Asia. Consistent with the recent studies of the precipitation diurnal cycles for these two regions, the difference in the diurnal phase propagation is likely due to the difference in the mean steering level wind speed for these two regions. The wave-number-frequency spectral analysis further reveals the complex, multi-scale, multi-modal nature of the warm-season precipitation variation embedded within the diurnal cycle over both continents, with phase speeds varying from 10 to 30 ms?1 and wave periods varying from diurnal to a few hours. At the diurnal frequency regulated by the thermodynamically driven mountains–plains solenoids (MPSs), increased precipitation for both continents first originates in the afternoon from the eastern edge of big topography and subsequently moves downslope in the evening and reaches the broad plains area at night. More complex diurnal evolutions are observed in East Asia due to the more complex, multistep terrains east of the Tibetan Plateau and the associated localized MPS circulations. Nevertheless, increased variation of precipitation at smaller spatial and temporal scales is evident in the active phase of the dominant diurnal cycle for both continents.

Posted on 13 October 2014 | 12:00 am


Climate-relevant physical properties of molecular constituents for isoprene-derived secondary organic aerosol material

Climate-relevant physical properties of molecular constituents for isoprene-derived secondary organic aerosol material

Atmospheric Chemistry and Physics, 14, 10731-10740, 2014

Author(s): M. A. Upshur, B. F. Strick, V. F. McNeill, R. J. Thomson, and F. M. Geiger

Secondary organic aerosol (SOA) particles, formed from gas-phase biogenic volatile organic compounds (BVOCs), contribute large uncertainties to the radiative forcing that is associated with aerosols in the climate system. Reactive uptake of surface-active organic oxidation products of BVOCs at the gas–aerosol interface can potentially decrease the overall aerosol surface tension and therefore influence their propensity to act as cloud condensation nuclei (CCN). Here, we synthesize and measure some climate-relevant physical properties of SOA particle constituents consisting of the isoprene oxidation products ?-, ?-, and cis- and trans-?-IEPOX (isoprene epoxide), as well as syn- and anti-2-methyltetraol. Following viscosity measurements, we use octanol–water partition coefficients to quantify the relative hydrophobicity of the oxidation products while dynamic surface tension measurements indicate that aqueous solutions of ?- and trans-?-IEPOX exhibit significant surface tension depression. We hypothesize that the surface activity of these compounds may enhance aerosol CCN activity, and that trans-?-IEPOX may be highly relevant for surface chemistry of aerosol particles relative to other IEPOX isomers.

Posted on 10 October 2014 | 12:00 am


Mapping the physico-chemical properties of mineral dust in western Africa: mineralogical composition

Mapping the physico-chemical properties of mineral dust in western Africa: mineralogical composition

Atmospheric Chemistry and Physics, 14, 10663-10686, 2014

Author(s): P. Formenti, S. Caquineau, K. Desboeufs, A. Klaver, S. Chevaillier, E. Journet, and J. L. Rajot

In the last few years, several ground-based and airborne field campaigns have allowed the exploration of the properties and impacts of mineral dust in western Africa, one of the major emission and transport areas worldwide. In this paper, we explore the synthesis of these observations to provide a large-scale quantitative view of the mineralogical composition and its variability according to source region and time after transport. This work reveals that mineral dust in western Africa is a mixture of clays, quartz, iron and titanium oxides, representing at least 92% of the dust mass. Calcite ranged between 0.3 and 8.4% of the dust mass, depending on the origin. Our data do not show a systematic dependence of the dust mineralogical composition on origin; this is to be the case as, in most of the instances, the data represent the composition of the atmospheric burden after 1–2 days after emission, when air masses mix and give rise to a more uniform dust load. This has implications for the representation of the mineral dust composition in regional and global circulation models and in satellite retrievals. Iron oxides account for 58 ± 7% of the mass of elemental Fe and for between 2 and 5% of the dust mass. Most of them are composed of goethite, representing between 52 and 78% of the iron oxide mass. We estimate that titanium oxides account for 1–2% of the dust mass, depending on whether the dust is of Saharan or Sahelian origin. The mineralogical composition is a critical parameter for estimating the radiative and biogeochemical impact of mineral dust. The results regarding dust composition have been used to estimate the optical properties as well as the iron fractional solubility of Saharan and Sahelian dust. Data presented in this paper are provided in numerical form upon email request while they are being turned into a public database, the Dust-Mapped Archived Properties (DUST-MAP), which is an open repository for compositional data from other source regions in Africa and worldwide.

Posted on 10 October 2014 | 12:00 am


Estimating regional greenhouse gas fluxes: an uncertainty analysis of planetary boundary layer techniques and bottom-up inventories

Estimating regional greenhouse gas fluxes: an uncertainty analysis of planetary boundary layer techniques and bottom-up inventories

Atmospheric Chemistry and Physics, 14, 10705-10719, 2014

Author(s): X. Zhang, X. Lee, T. J. Griffis, J. M. Baker, and W. Xiao

Quantification of regional greenhouse gas (GHG) fluxes is essential for establishing mitigation strategies and evaluating their effectiveness. Here, we used multiple top-down approaches and multiple trace gas observations at a tall tower to estimate regional-scale GHG fluxes and evaluate the GHG fluxes derived from bottom-up approaches. We first applied the eddy covariance, equilibrium, inverse modeling (CarbonTracker), and flux aggregation methods using 3 years of carbon dioxide (CO2) measurements on a 244 m tall tower in the upper Midwest, USA. We then applied the equilibrium method for estimating CH4 and N2O fluxes with 1-month high-frequency CH4 and N2O gradient measurements on the tall tower and 1-year concentration measurements on a nearby tall tower, and evaluated the uncertainties of this application. The results indicate that (1) the flux aggregation, eddy covariance, the equilibrium method, and the CarbonTracker product all gave similar seasonal patterns of the regional CO2 flux (105−106 km2, but that the equilibrium method underestimated the July CO2 flux by 52–69%. (2) The annual budget varied among these methods from ?54 to ?131 g C–CO2 m?2 yr?1, indicating a large uncertainty in the annual CO2 flux estimation. (3) The regional CH4 and N2O emissions according to a top-down method were at least 6 and 2 times higher than the emissions from a bottom-up inventory (Emission Database for Global Atmospheric Research), respectively. (4) The global warming potentials of the CH4 and N2O emissions were equal in magnitude to the cooling benefit of the regional CO2 uptake. The regional GHG budget, including both biological and anthropogenic origins, is estimated at 7 ± 160 g CO2 equivalent m?2 yr?1.

Posted on 10 October 2014 | 12:00 am


Do anthropogenic, continental or coastal aerosol sources impact on a marine aerosol signature at Mace Head?

Do anthropogenic, continental or coastal aerosol sources impact on a marine aerosol signature at Mace Head?

Atmospheric Chemistry and Physics, 14, 10687-10704, 2014

Author(s): C. O'Dowd, D. Ceburnis, J. Ovadnevaite, A. Vaishya, M. Rinaldi, and M. C. Facchini

Atmospheric aerosols have been sampled and characterised at the Mace Head north-east (NE) Atlantic atmospheric research station since 1958, with many interesting phenomena being discovered. However, with the range of new discoveries and scientific advances, there has been a range of concomitant criticisms challenging the representativeness of aerosol sampled at the station compared to that of aerosol over the pristine open-ocean. Two recurring criticisms relate to the lack of representativeness due to potentially enhanced coastal sources, possibly leading to artificially high values of aerosol concentrations, and to the influence of long-range transport of anthropogenic or continental aerosol and its potential dominance over, or perturbation of, a natural marine aerosol signal. Here, we review the results of previous experimental studies on marine aerosols over the NE Atlantic and at Mace Head with the aim of evaluating their representativeness relative to that of a pristine open-ocean aerosol, i.e. with negligible anthropogenic/continental influence. Particular focus is given to submicron organic matter (OM) aerosol. In summary, no correlation was found between OM and black carbon (BC) in marine air conforming to clean-air sampling criteria, either at BC levels of 0–15 or 15–50 ng m?3, suggesting that OM concentrations, up to observed peak values of 3.8 ?g m?3, are predominantly natural in origin. Sophisticated carbon isotope analysis and aerosol mass spectral finger printing techniques corroborate the conclusion that there is a predominant natural source of OM, with 80% biogenic source apportionment being observed for general clean-air conditions, rising to ∼98% during specific primary marine organic plumes when peak OM mass concentrations > 3 ?g m?3 are observed. Similarly, a maximum contribution of 20% OM mass coming from non-marine sources was established by dual carbon isotope analysis. Further, analysis of a series of experiments conducted at Mace Head conclude that negligible coastal, surf zone, or tidal effects are discernible in the secondary or primary aerosol mass residing in the submicron size range for sampling heights of 7 m and above. The Mace Head marine-air criteria ensure anthropogenic and coastal effects are sufficiently minimised so as to guarantee a predominant, and sometimes overwhelming, natural marine aerosol contribution to the total aerosol population when the criteria are adhered to.

Posted on 10 October 2014 | 12:00 am


Airborne flux measurements of biogenic isoprene over California

Airborne flux measurements of biogenic isoprene over California

Atmospheric Chemistry and Physics, 14, 10631-10647, 2014

Author(s): P. K. Misztal, T. Karl, R. Weber, H. H. Jonsson, A. B. Guenther, and A. H. Goldstein

Biogenic isoprene fluxes were measured onboard the CIRPAS Twin Otter aircraft as part of the California Airborne Biogenic volatile organic compound (BVOC) Emission Research in Natural Ecosystem Transects (CABERNET) campaign during June 2011. The airborne virtual disjunct eddy covariance (AvDEC) approach used measurements from a proton transfer reaction mass spectrometer (PTR–MS) and a wind radome probe to directly determine fluxes of isoprene over 7400 km of flight paths focusing on areas of California predicted to have the largest emissions. The fast Fourier transform (FFT) approach was used to calculate fluxes of isoprene over long transects of more than 15 km, most commonly between 50 and 150 km. The continuous wavelet transformation (CWT) approach was used over the same transects to also calculate instantaneous isoprene fluxes with localization of both frequency and time independent of non-stationarities. Fluxes were generally measured by flying consistently at 400 m ± 50 m (a.g.l.) altitude, and extrapolated to the surface according to the determined flux divergence determined in the racetrack-stacked profiles. The wavelet-derived surface fluxes of isoprene averaged to 2 km spatial resolution showed good correspondence to basal emission factor (BEF) land-cover data sets used to drive BVOC emission models. The surface flux of isoprene was close to zero over Central Valley crops and desert shrublands, but was very high (up to 15 mg m?2 h−1) above oak woodlands, with clear dependence of emissions on temperature and oak density. Isoprene concentrations of up to 8 ppb were observed at aircraft height on the hottest days and over the dominant source regions.

Even though the isoprene emissions from agricultural crop regions, shrublands, and coniferous forests were extremely low, observations at the Walnut Grove tower south of Sacramento demonstrate that isoprene oxidation products from the high emitting regions in the surrounding oak woodlands accumulate at night in the residual layer above the valley and mix down into the valley in the morning. Thus, the isoprene emissions surrounding the valley have relevance for the regional photochemistry that is not immediately apparent solely from the direct emission flux distribution.

This paper reports the first regional observations of fluxes from specific sources by eddy covariance from an aircraft which can finally constrain statewide isoprene emission inventories used for ozone simulations by state agencies. While previously there was no available means to constrain the biogenic models, our results provide a good understanding of what the major sources of isoprene are in California, their magnitude, and how they are distributed.

This data set on isoprene fluxes will be particularly useful for evaluating potential model alternatives which will be dealt with in a separate paper to assess isoprene emission models and their driving variable data sets.

Posted on 10 October 2014 | 12:00 am


Optical, microphysical and compositional properties of the Eyjafjallajökull volcanic ash

Optical, microphysical and compositional properties of the Eyjafjallajökull volcanic ash

Atmospheric Chemistry and Physics, 14, 10649-10661, 2014

Author(s): A. Rocha-Lima, J. V. Martins, L. A. Remer, N. A. Krotkov, M. H. Tabacniks, Y. Ben-Ami, and P. Artaxo

Better characterization of the optical properties of aerosol particles are an essential step to improve atmospheric models and satellite remote sensing, reduce uncertainties in predicting particulate transport, and estimate aerosol forcing and climate change. Even natural aerosols such as mineral dust or particles from volcanic eruptions require better characterization in order to define the background conditions from which anthropogenic perturbations emerge. We present a detailed laboratorial study where the spectral optical properties of the ash from the April–May (2010) Eyjafjallajökull volcanic eruption were derived over a broad spectral range, from ultra-violet (UV) to near-infrared (NIR) wavelengths. Samples of the volcanic ash taken on the ground in the vicinity of the volcano were sieved, re-suspended, and collected on filters to separate particle sizes into fine and mixed (coarse and fine) modes. We derived the spectral mass absorption efficiency αabs [m2g−1] for fine and mixed modes particles in the wavelength range from 300 to 2500 nm from measurements of optical reflectance. We retrieved the imaginary part of the complex refractive index Im(m) from αabs, using Mie–Lorenz and T-matrix theories and considering the size distribution of particles obtained by scanning electron microscopy (SEM), and the grain density of the volcanic ash measured as ρ = 2.16 ± 0.13 g cm−3. Im(m) was found to vary from 0.001 to 0.005 in the measured wavelength range. The dependence of the retrieval on the shape considered for the particles were found to be small and within the uncertainties estimated in our calculation. Fine and mixed modes were also analyzed by X-ray fluorescence, exhibiting distinct elemental composition supporting the optical differences we found between the modes. This is a comprehensive and consistent characterization of spectral absorption and imaginary refractive index, density, size, shape and elemental composition of volcanic ash, which will help constrain assumptions of ash particles in models and remote sensing, thereby narrowing uncertainties in representing these particles both for short-term regional forecasts and long-term climate change.

Posted on 10 October 2014 | 12:00 am


Surface gas pollutants in Lhasa, a highland city of Tibet – current levels and pollution implications

Surface gas pollutants in Lhasa, a highland city of Tibet – current levels and pollution implications

Atmospheric Chemistry and Physics, 14, 10721-10730, 2014

Author(s): L. Ran, W. L. Lin, Y. Z. Deji, B. La, P. M. Tsering, X. B. Xu, and W. Wang

Through several years of development, the city of Lhasa has become one of the most populated and urbanized areas on the highest plateau in the world. In the process of urbanization, current and potential air quality issues have been gradually concerned. To investigate the current status of air pollution in Lhasa, various gas pollutants including NOx, CO, SO2, and O3, were continuously measured from June 2012 to May 2013 at an urban site (29.40° N, 91.08° E, 3650 m a.s.l.). The seasonal variations of primary gas pollutants exhibited a peak from November to January with a large variability. High mixing ratios of primary trace gases almost exclusively occurred under low wind speed and showed no distinct dependence on wind direction, implying local urban emissions to be predominant. A comparison of NO2, CO, and SO2 mixing ratios in summer between 1998 and 2012 indicated a significant increase in emissions of these gas pollutants and a change in their intercorrelations, as a result of a substantial growth in the demand of energy consumption using fossil fuels instead of previously widely used biomass. The pronounced diurnal double peaks of primary trace gases in all seasons suggested automobile exhaust to be a major emission source in Lhasa. The secondary gas pollutant O3 displayed an average diurnal cycle of a shallow flat peak for about 4–5 h in the afternoon and a minimum in the early morning. Nighttime O3 was sometimes completely consumed by the high level of NOx. Seasonally, the variations of O3 mixing ratios displayed a low valley in winter and a peak in spring. In autumn and winter, transport largely contributed to the observed O3 mixing ratios, given its dependence on wind speed and wind direction, while in spring and summer photochemistry played an important role. A more efficient buildup of O3 mixing ratios in the morning and a higher peak in the afternoon was found in summer 2012 than in 1998. An enhancement in O3 mixing ratios would be expected in the future and more attention should be given to O3 photochemistry in response to increasing precursor emissions in this area.

Posted on 10 October 2014 | 12:00 am


Summertime tropospheric-ozone variability over the Mediterranean basin observed with IASI

Summertime tropospheric-ozone variability over the Mediterranean basin observed with IASI

Atmospheric Chemistry and Physics, 14, 10589-10600, 2014

Author(s): C. Doche, G. Dufour, G. Foret, M. Eremenko, J. Cuesta, M. Beekmann, and P. Kalabokas

The Mediterranean basin is one of the most sensitive regions in the world regarding climate change and air quality. This is partly due to the singular dynamical situation of the Mediterranean basin that leads to tropospheric-ozone concentrations that are among the highest over the Northern Hemisphere. Six years of summertime tropospheric ozone observed by the Infrared Atmospheric Sounding Interferometer (IASI) instrument from 2007 to 2012 have been analysed to document the variability of ozone over this region. The satellite observations have been examined together with meteorological analyses (from ECMWF) to understand the processes driving this variability. Our work confirmed the presence of a steep west–east ozone gradient in the lower troposphere with the highest concentrations observed over the eastern part of the Mediterranean basin. This gradient is mainly explained by diabatic convection over the Persian Gulf during the Indian monsoon season, which induces an important subsidence of ozone-rich air masses from the upper to the lower troposphere over the central and the eastern Mediterranean basin. IASI observations of ozone concentrations at a 3 km height show a clear summertime maximum in July that is well correlated to the maximum of downward transport of ozone-rich air masses from the upper troposphere. Even if this feature is robust over the six analysed years, we have also investigated monthly ozone anomalies – one positive (June 2008) and one negative (June and July 2009) – using daily IASI observations. We show that the relative position and the strength of the meteorological systems (Azores anticyclone and Middle Eastern depression) present over the Mediterranean are key factors in explaining both the variability and the anomalies of ozone in the lower troposphere in this region.

Posted on 9 October 2014 | 12:00 am


Systematic satellite observations of the impact of aerosols from passive volcanic degassing on local cloud properties

Systematic satellite observations of the impact of aerosols from passive volcanic degassing on local cloud properties

Atmospheric Chemistry and Physics, 14, 10601-10618, 2014

Author(s): S. K. Ebmeier, A. M. Sayer, R. G. Grainger, T. A. Mather, and E. Carboni

The impact of volcanic emissions, especially from passive degassing and minor explosions, is a source of uncertainty in estimations of aerosol indirect effects. Observations of the impact of volcanic aerosol on clouds contribute to our understanding of both present-day atmospheric properties and of the pre-industrial baseline necessary to assess aerosol radiative forcing. We present systematic measurements over several years at multiple active and inactive volcanic islands in regions of low present-day aerosol burden. The time-averaged indirect aerosol effects within 200 km downwind of island volcanoes are observed using Moderate Resolution Imaging Spectroradiometer (MODIS, 2002–2013) and Advanced Along-Track Scanning Radiometer (AATSR, 2002–2008) data. Retrievals of aerosol and cloud properties at K?lauea (Hawai'i), Yasur (Vanuatu) and Piton de la Fournaise (la Réunion) are rotated about the volcanic vent to be parallel to wind direction, so that upwind and downwind retrievals can be compared. The emissions from all three volcanoes – including those from passive degassing, Strombolian activity and minor explosions – lead to measurably increased aerosol optical depth downwind of the active vent. Average cloud droplet effective radius is lower downwind of the volcano in all cases, with the peak difference ranging from 2–8 ?m at the different volcanoes in different seasons. Estimations of the difference in Top of Atmosphere upward Short Wave flux upwind and downwind of the active volcanoes from NASA's Clouds and the Earth's Radiant Energy System (CERES) suggest a downwind elevation of between 10 and 45 Wm?2 at distances of 150–400 km from the volcano, with much greater local (< 80 km) effects. Comparison of these observations with cloud properties at isolated islands without degassing or erupting volcanoes suggests that these patterns are not purely orographic in origin. Our observations of unpolluted, isolated marine settings may capture processes similar to those in the pre-industrial marine atmosphere.

Posted on 9 October 2014 | 12:00 am


First estimates of global free-tropospheric NO2 abundances derived using a cloud-slicing technique applied to satellite observations from the Aura Ozone Monitoring Instrument (OMI)

First estimates of global free-tropospheric NO2 abundances derived using a cloud-slicing technique applied to satellite observations from the Aura Ozone Monitoring Instrument (OMI)

Atmospheric Chemistry and Physics, 14, 10565-10588, 2014

Author(s): S. Choi, J. Joiner, Y. Choi, B. N. Duncan, A. Vasilkov, N. Krotkov, and E. Bucsela

We derive free-tropospheric NO2 volume mixing ratios (VMRs) by applying a cloud-slicing technique to data from the Ozone Monitoring Instrument (OMI) on the Aura satellite. In the cloud-slicing approach, the slope of the above-cloud NO2 column versus the cloud scene pressure is proportional to the NO2 VMR. In this work, we use a sample of nearby OMI pixel data from a single orbit for the linear fit. The OMI data include cloud scene pressures from the rotational-Raman algorithm and above-cloud NO2 vertical column density (VCD) (defined as the NO2 column from the cloud scene pressure to the top of the atmosphere) from a differential optical absorption spectroscopy (DOAS) algorithm. We compare OMI-derived NO2 VMRs with in situ aircraft profiles measured during the NASA Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign in 2006. The agreement is generally within the estimated uncertainties when appropriate data screening is applied. We then derive a global seasonal climatology of free-tropospheric NO2 VMR in cloudy conditions. Enhanced NO2 in the free troposphere commonly appears near polluted urban locations where NO2 produced in the boundary layer may be transported vertically out of the boundary layer and then horizontally away from the source. Signatures of lightning NO2 are also shown throughout low and middle latitude regions in summer months. A profile analysis of our cloud-slicing data indicates signatures of lightning-generated NO2 in the upper troposphere. Comparison of the climatology with simulations from the global modeling initiative (GMI) for cloudy conditions (cloud optical depth > 10) shows similarities in the spatial patterns of continental pollution outflow. However, there are also some differences in the seasonal variation of free-tropospheric NO2 VMRs near highly populated regions and in areas affected by lightning-generated NOx.

Posted on 9 October 2014 | 12:00 am


Air quality in Delhi during the Commonwealth Games

Air quality in Delhi during the Commonwealth Games

Atmospheric Chemistry and Physics, 14, 10619-10630, 2014

Author(s): P. Marrapu, Y. Cheng, G. Beig, S. Sahu, R. Srinivas, and G. R. Carmichael

Air quality during the Commonwealth Games (CWG, held in Delhi in October 2010) is analyzed using a new air quality forecasting system established for the games. The CWG stimulated enhanced efforts to monitor and model air quality in the region. The air quality of Delhi during the CWG had high levels of particles with mean values of PM2.5 and PM10 at the venues of 111 and 238 ?g m?3, respectively. Black carbon (BC) accounted for ~ 10% of the PM2.5 mass. It is shown that BC, PM2.5 and PM10 concentrations are well predicted, but with positive biases of ~ 25%. The diurnal variations are also well captured, with both the observations and the modeled values showing nighttime maxima and daytime minima. A new emissions inventory, developed as part of this air quality forecasting initiative, is evaluated by comparing the observed and predicted species-species correlations (i.e., BC : CO; BC : PM2.5; PM2.5 : PM10). Assuming that the observations at these sites are representative and that all the model errors are associated with the emissions, then the modeled concentrations and slopes can be made consistent by scaling the emissions by 0.6 for NOx, 2 for CO, and 0.7 for BC, PM2.5, and PM10. The emission estimates for particles are remarkably good considering the uncertainty in the estimates due to the diverse spread of activities and technologies that take place in Delhi and the rapid rates of change.

The contribution of various emission sectors including transportation, power, domestic and industry to surface concentrations are also estimated. Transport, domestic and industrial sectors all make significant contributions to PM levels in Delhi, and the sectoral contributions vary spatially within the city. Ozone levels in Delhi are elevated, with hourly values sometimes exceeding 100 ppb. The continued growth of the transport sector is expected to make ozone pollution a more pressing air pollution problem in Delhi. The sector analysis provides useful inputs into the design of strategies to reduce air pollution levels in Delhi. The contribution for sources outside of Delhi on Delhi air quality range from ~ 25% for BC and PM to ~ 60% for day time ozone. The significant contributions from non-Delhi sources indicates that in Delhi (as has been show elsewhere) these strategies will also need a more regional perspective.

Posted on 9 October 2014 | 12:00 am


Ion – particle interactions during particle formation and growth at a coniferous forest site in central Europe

Ion – particle interactions during particle formation and growth at a coniferous forest site in central Europe

Atmospheric Chemistry and Physics, 14, 10547-10563, 2014

Author(s): S. G. Gonser, F. Klein, W. Birmili, J. Größ, M. Kulmala, H. E. Manninen, A. Wiedensohler, and A. Held

In this work, we examined the interaction of ions and neutral particles during atmospheric new particle formation (NPF) events. The analysis is based on simultaneous field measurements of atmospheric ions and total particles using a neutral cluster and air ion spectrometer (NAIS) across the diameter range 2–25 nm. The Waldstein research site is located in a spruce forest in NE Bavaria, Southern Germany, known for enhanced radon concentrations, presumably leading to elevated ionization rates. Our observations show that the occurrence of the ion nucleation mode preceded that of the total particle nucleation mode during all analyzed NPF events. The time difference between the appearance of 2 nm ions and 2 nm total particles was typically about 20 to 30 min. A cross correlation analysis showed a rapid decrease of the time difference between the ion and total modes during the growth process. Eventually, this time delay vanished when both ions and total particles did grow to larger diameters. Considering the growth rates of ions and total particles separately, total particles exhibited enhanced growth rates at diameters below 15 nm. This observation cannot be explained by condensation or coagulation, because these processes would act more efficiently on charged particles compared to neutral particles. To explain our observations, we propose a mechanism including recombination and attachment of continuously present cluster ions with the ion nucleation mode and the neutral nucleation mode, respectively.

Posted on 9 October 2014 | 12:00 am


Airborne characterization of smoke marker ratios from prescribed burning

Airborne characterization of smoke marker ratios from prescribed burning

Atmospheric Chemistry and Physics, 14, 10535-10545, 2014

Author(s): A. P. Sullivan, A. A. May, T. Lee, G. R. McMeeking, S. M. Kreidenweis, S. K. Akagi, R. J. Yokelson, S. P. Urbanski, and J. L. Collett Jr.

A Particle-Into-Liquid Sampler – Total Organic Carbon (PILS-TOC) and fraction collector system was flown aboard a Twin Otter aircraft sampling prescribed burning emissions in South Carolina in November 2011 to obtain smoke marker measurements. The fraction collector provided 2 min time-integrated offline samples for carbohydrate (i.e., smoke markers levoglucosan, mannosan, and galactosan) analysis by high-performance anion-exchange chromatography with pulsed amperometric detection. Each fire location appeared to have a unique ?levoglucosan/?water-soluble organic carbon (WSOC) ratio (RF01/RF02/RF03/RF05 = 0.163 ± 0.007 ?g C ?g?1 C, RF08 = 0.115 ± 0.011 ?g C ?g?1 C, RF09A = 0.072 ± 0.028 ?g C ?g?1 C, and RF09B = 0.042 ± 0.008 ?g C ?g?1 C, where RF means research flight). These ratios were comparable to those obtained from controlled laboratory burns and suggested that the emissions sampled during RF01/F02/RF03/RF05 were dominated by the burning of grasses, RF08 by leaves, RF09A by needles, and RF09B by marsh grasses. These findings were further supported by the ?galactosan/?levoglucosan ratios (RF01/RF02/RF03/RF05 = 0.067 ± 0.004 ?g ?g?1, RF08 = 0.085 ± 0.009 ?g ?g?1, and RF09A = 0.101 ± 0.029 ?g ?g?1) obtained as well as by the ground-based fuel and filter sample analyses during RF01/RF02/RF03/RF05. Differences between ?potassium/?levoglucosan ratios obtained for these prescribed fires vs. laboratory-scale measurements suggest that some laboratory burns may not accurately represent potassium emissions from prescribed burns. The ?levoglucosan/?WSOC ratio had no clear dependence on smoke age or fire dynamics suggesting that this ratio is more dependent on the type of fuel being burned. Levoglucosan was stable over a timescale of at least 1.5 h and could be useful to help estimate the air quality impacts of biomass burning.

Posted on 9 October 2014 | 12:00 am


Size-dependent particle activation properties in fog during the ParisFog 2012/13 field campaign

Size-dependent particle activation properties in fog during the ParisFog 2012/13 field campaign

Atmospheric Chemistry and Physics, 14, 10517-10533, 2014

Author(s): E. Hammer, M. Gysel, G. C. Roberts, T. Elias, J. Hofer, C. R. Hoyle, N. Bukowiecki, J.-C. Dupont, F. Burnet, U. Baltensperger, and E. Weingartner

Fog-induced visibility reduction is responsible for a variety of hazards in the transport sector. Therefore there is a large demand for an improved understanding of fog formation and thus improved forecasts. Improved fog forecasts require a better understanding of the numerous complex mechanisms during the fog life cycle. During winter 2012/13 a field campaign called ParisFog aiming at fog research took place at SIRTA (Instrumented Site for Atmospheric Remote Sensing Research). SIRTA is located about 20 km southwest of the Paris city center, France, in a semi-urban environment. In situ activation properties of the prevailing fog were investigated by measuring (1) total and interstitial (non-activated) dry particle number size distributions behind two different inlet systems; (2) interstitial hydrated aerosol and fog droplet size distributions at ambient conditions; and (3) cloud condensation nuclei (CCN) number concentration at different supersaturations (SS) with a CCN counter. The aerosol particles were characterized regarding their hygroscopic properties, fog droplet activation behavior and contribution to light scattering for 17 developed fog events. Low particle hygroscopicity with an overall median of the hygroscopicity parameter, κ, of 0.14 was found, likely caused by substantial influence from local traffic and wood burning emissions. Measurements of the aerosol size distribution at ambient RH revealed that the critical wet diameter, above which the hydrated aerosols activate to fog droplets, is rather large (with a median value of 2.6μm) and is highly variable (ranging from 1 to 5μm) between the different fog events. Thus, the number of activated fog droplets was very small and the non-activated hydrated particles were found to contribute significantly to the observed light scattering and thus to the reduction in visibility. Combining all experimental data, the effective peak supersaturation, SSpeak, a measure of the peak supersaturation during the fog formation, was determined. The median SSpeak value was estimated to be in the range from 0.031 to 0.046% (upper and lower limit estimations), which is in good agreement with previous experimental and modeling studies of fog.

Posted on 7 October 2014 | 12:00 am


Temporal variations in rainwater methanol

Temporal variations in rainwater methanol

Atmospheric Chemistry and Physics, 14, 10509-10516, 2014

Author(s): J. D. Felix, S. B. Jones, G. B. Avery, J. D. Willey, R. N. Mead, and R. J. Kieber

This work reports the first comprehensive analysis of methanol concentrations in rainwater. Methanol concentrations measured in 49 rain events collected between 28 August 2007 and 10 July 2008 in Wilmington, NC, USA, ranged from below the detection limit of 6 nM to 9.3 ?M with a volume-weighted average concentration of 1 ± 0.2 ?M. Methanol concentrations in rainwater were up to ~200 times greater than concentrations reported previously in marine waters, indicating wet deposition as a potentially significant source of methanol to marine waters. Assuming that these methanol concentrations are an appropriate proxy for global methanol rainwater concentrations, the global methanol wet deposition sink is estimated as 20 Tg yr?1, which implies that previous methanol budgets underestimate removal by precipitation. Methanol concentrations in rainwater did not correlate significantly with H+, NO3, and NSS, which suggests that the dominant source of the alcohol to rainwater is not anthropogenic. However, methanol concentrations were strongly correlated with acetaldehyde, which has a primarily biogenic input. The methanol volume-weighted concentration during the summer (2.7 ± 0.9 ?M) was ~3 times that of the winter (0.9 ± 0.2 ?M), further promoting biogenic emissions as the primary cause of temporal variations of methanol concentrations. Methanol concentrations peaked in rainwater collected during the time period 12 p.m.–6 p.m. Peaking during this period of optimal sunlight implies a possible relationship with photochemical methanol production, but there are also increases in biogenic activity during this time period. Rain events with terrestrial origin had greater concentrations than those of marine origin, demonstrating the significance of the continental source of methanol in rainwater.

Posted on 7 October 2014 | 12:00 am


Characteristics of gravity waves resolved by ECMWF

Characteristics of gravity waves resolved by ECMWF

Atmospheric Chemistry and Physics, 14, 10483-10508, 2014

Author(s): P. Preusse, M. Ern, P. Bechtold, S. D. Eckermann, S. Kalisch, Q. T. Trinh, and M. Riese

Global model data from the European Centre for Medium-Range Weather Forecasts (ECMWF) are analyzed for resolved gravity waves (GWs). Based on fitted 3-D wave vectors of individual waves and using the ECMWF global scale background fields, backward ray tracing from 25 km altitude is performed. Different sources such as orography, convection and winter storms are identified. It is found that due to oblique propagation waves spread widely from narrow source regions. Gravity waves which originate from regions of strong convection are frequently excited around the tropopause and have in the ECMWF model low phase and group velocities as well as very long horizontal wavelengths compared to other models and to measurements. While the total amount of momentum flux for convective GWs changes little over season, GWs generated by storms and mountain waves show large day-to-day variability, which has a strong influence also on total hemispheric fluxes; from one day to the next the total hemispheric flux may increase by a factor of 3. Implications of these results for using the ECMWF model in predicting, analyzing and interpreting global GW distributions as well as implications for seamless climate prediction are discussed.

Posted on 2 October 2014 | 12:00 am


Different contact angle distributions for heterogeneous ice nucleation in the Community Atmospheric Model version 5

Different contact angle distributions for heterogeneous ice nucleation in the Community Atmospheric Model version 5

Atmospheric Chemistry and Physics, 14, 10411-10430, 2014

Author(s): Y. Wang, X. Liu, C. Hoose, and B. Wang

In order to investigate the impact of different treatments for the contact angle (α) in heterogeneous ice nucleating properties of natural dust and black carbon (BC) particles, we implement the classical-nucleation-theory-based parameterization of heterogeneous ice nucleation (Hoose et al., 2010) in the Community Atmospheric Model version 5 (CAM5) and then improve it by replacing the original single-contact-angle model with the probability-density-function-of-? (?-PDF) model to better represent the ice nucleation behavior of natural dust found in observations. We refit the classical nucleation theory (CNT) to constrain the uncertain parameters (i.e., onset ? and activation energy in the single-? model; mean contact angle and standard deviation in the ?-PDF model) using recent observation data sets for Saharan natural dust and BC (soot). We investigate the impact of the time dependence of droplet freezing on mixed-phase clouds and climate in CAM5 as well as the roles of natural dust and soot in different nucleation mechanisms. Our results show that, when compared with observations, the potential ice nuclei (IN) calculated by the ?-PDF model show better agreement than those calculated by the single-? model at warm temperatures (T; T > −20 °C). More ice crystals can form at low altitudes (with warm temperatures) simulated by the ?-PDF model than compared to the single-? model in CAM5. All of these can be attributed to different ice nucleation efficiencies among aerosol particles, with some particles having smaller contact angles (higher efficiencies) in the ?-PDF model. In the sensitivity tests with the ?-PDF model, we find that the change in mean contact angle has a larger impact on the active fraction at a given temperature than a change in standard deviation, even though the change in standard deviation can lead to a change in freezing behavior. Both the single-? and the ?-PDF model indicate that the immersion freezing of natural dust plays a more important role in the heterogeneous nucleation than that of soot in mixed-phase clouds. The new parameterizations implemented in CAM5 induce more significant aerosol indirect effects than the default parameterization.

Posted on 1 October 2014 | 12:00 am


Volatile and intermediate volatility organic compounds in suburban Paris: variability, origin and importance for SOA formation

Volatile and intermediate volatility organic compounds in suburban Paris: variability, origin and importance for SOA formation

Atmospheric Chemistry and Physics, 14, 10439-10464, 2014

Author(s): W. Ait-Helal, A. Borbon, S. Sauvage, J. A. de Gouw, A. Colomb, V. Gros, F. Freutel, M. Crippa, C. Afif, U. Baltensperger, M. Beekmann, J.-F. Doussin, R. Durand-Jolibois, I. Fronval, N. Grand, T. Leonardis, M. Lopez, V. Michoud, K. Miet, S. Perrier, A. S. H. Prévôt, J. Schneider, G. Siour, P. Zapf, and N. Locoge

Measurements of gaseous and particulate organic carbon were performed during the MEGAPOLI experiments, in July 2009 and January–February 2010, at the SIRTA observatory in suburban Paris. Measurements comprise primary and secondary volatile organic compounds (VOCs), of both anthropogenic and biogenic origins, including C12–C16 n-alkanes of intermediate volatility (IVOCs), suspected to be efficient precursors of secondary organic aerosol (SOA). The time series of gaseous carbon are generally consistent with times series of particulate organic carbon at regional scale, and are clearly affected by meteorology and air mass origin. Concentration levels of anthropogenic VOCs in urban and suburban Paris were surprisingly low (2–963 ppt) compared to other megacities worldwide and to rural continental sites. Urban enhancement ratios of anthropogenic VOC pairs agree well between the urban and suburban Paris sites, showing the regional extent of anthropogenic sources of similar composition. Contrary to other primary anthropogenic VOCs (aromatics and alkanes), IVOCs showed lower concentrations in winter (< 5 ppt) compared to summer (13–27 ppt), which cannot be explained by the gas-particle partitioning theory. Higher concentrations of most oxygenated VOCs in winter (18–5984 ppt) suggest their dominant primary anthropogenic origin. The respective role of primary anthropogenic gaseous compounds in regional SOA formation was investigated by estimating the SOA mass concentration expected from the anthropogenic VOCs and IVOCs (I / VOCs) measured at SIRTA. From an integrated approach based on emission ratios and SOA yields, 38 % of the SOA measured at SIRTA is explained by the measured concentrations of I / VOCs, with a 2% contribution by C12–C16 n-alkane IVOCs. From the results of an alternative time-resolved approach, the average IVOC contribution to SOA formation is estimated to be 7%, which is half of the average contribution of the traditional aromatic compounds (15%). Both approaches, which are based on in situ observations of particular I / VOCs, emphasize the importance of the intermediate volatility compounds in the SOA formation, and support previous results from chamber experiments and modeling studies. They also support the need to make systematic the IVOCs' speciated measurement during field campaigns.

Posted on 1 October 2014 | 12:00 am


How sensitive is the recovery of stratospheric ozone to changes in concentrations of very short-lived bromocarbons?

How sensitive is the recovery of stratospheric ozone to changes in concentrations of very short-lived bromocarbons?

Atmospheric Chemistry and Physics, 14, 10431-10438, 2014

Author(s): X. Yang, N. L. Abraham, A. T. Archibald, P. Braesicke, J. Keeble, P. J. Telford, N. J. Warwick, and J. A. Pyle

Naturally produced very short-lived substances (VSLS) account for almost a quarter of the current stratospheric inorganic bromine, Bry. Following VSLS oxidation, bromine radicals (Br and BrO) can catalytically destroy ozone. The extent to which possible increases in surface emissions or transport of these VSLS bromocarbons to the stratosphere could counteract the effect of halogen reductions under the Montreal Protocol is an important policy question. Here, by using a chemistry–climate model, UM-UKCA, we investigate the impact of a hypothetical doubling (an increase of 5 ppt Bry) of VSLS bromocarbons on ozone and how the resulting ozone changes depend on the background concentrations of chlorine and bromine. Our model experiments indicate that for the 5 ppt increase in Bry from VSLS, the ozone decrease in the lowermost stratosphere of the Southern Hemisphere (SH) may reach up to 10% in the annual mean; the ozone decrease in the Northern Hemisphere (NH) is smaller (4–6%). The largest impact on the ozone column is found in the Antarctic spring. There is a significantly larger ozone decrease following the doubling of the VSLS burden under a high stratospheric chlorine background than under a low chlorine background, indicating the importance of the inter-halogen reactions. For example, the decline in the high-latitude, lower-stratospheric ozone concentration as a function of Bry is higher by about 30–40% when stratospheric Cly is ~ 3 ppb (present day), compared with Cly of ~ 0.8 ppb (a pre-industrial or projected future situation). Bromine will play an important role in the future ozone layer. However, even if bromine levels from natural VSLS were to increase significantly later this century, changes in the concentration of ozone will likely be dominated by the decrease in anthropogenic chlorine. Our calculation suggests that for a 5 ppt increase in Bry from VSLS, the Antarctic ozone hole recovery date could be delayed by approximately 6–8 years, depending on Cly levels.

Posted on 1 October 2014 | 12:00 am


Constraining CO2 emissions from open biomass burning by satellite observations of co-emitted species: a method and its application to wildfires in Siberia

Constraining CO2 emissions from open biomass burning by satellite observations of co-emitted species: a method and its application to wildfires in Siberia

Atmospheric Chemistry and Physics, 14, 10383-10410, 2014

Author(s): I. B. Konovalov, E. V. Berezin, P. Ciais, G. Broquet, M. Beekmann, J. Hadji-Lazaro, C. Clerbaux, M. O. Andreae, J. W. Kaiser, and E.-D. Schulze

A method to constrain carbon dioxide (CO2) emissions from open biomass burning by using satellite observations of co-emitted species and a chemistry-transport model (CTM) is proposed and applied to the case of wildfires in Siberia. CO2 emissions are assessed by means of an emission model assuming a direct relationship between the biomass burning rate (BBR) and the fire radiative power (FRP) derived from MODIS measurements. The key features of the method are (1) estimating the FRP-to-BBR conversion factors (?) for different vegetative land cover types by assimilating the satellite observations of co-emitted species into the CTM, (2) optimal combination of the estimates of ? derived independently from satellite observations of different species (CO and aerosol in this study), and (3) estimation of the diurnal cycle of the fire emissions directly from the FRP measurements. Values of ? for forest and grassland fires in Siberia and their uncertainties are estimated using the Infrared Atmospheric Sounding Interferometer (IASI) carbon monoxide (CO) retrievals and MODIS aerosol optical depth (AOD) measurements combined with outputs from the CHIMERE mesoscale chemistry-transport model. The constrained CO emissions are validated through comparison of the respective simulations with independent data of ground-based CO measurements at the ZOTTO site. Using our optimal regional-scale estimates of the conversion factors (which are found to be in agreement with earlier published estimates obtained from local measurements of experimental fires), the total CO2 emissions from wildfires in Siberia in 2012 are estimated to be in the range from 280 to 550 Tg C, with the optimal (maximum likelihood) value of 392 Tg C. Sensitivity test cases featuring different assumptions regarding the injection height and diurnal variations of emissions indicate that the derived estimates of the total CO2 emissions in Siberia are robust with respect to the modeling options (the different estimates vary within less than 15% of their magnitude). The CO2 emission estimates obtained for several years are compared with independent estimates provided by the GFED3.1 and GFASv1.0 global emission inventories. It is found that our "top-down" estimates for the total annual biomass burning CO2 emissions in the period from 2007 to 2011 in Siberia are by factors of 2.5 and 1.8 larger than the respective bottom-up estimates; these discrepancies cannot be fully explained by uncertainties in our estimates. There are also considerable differences in the spatial distribution of the different emission estimates; some of those differences have a systematic character and require further analysis.

Posted on 1 October 2014 | 12:00 am


Model-simulated trend of surface carbon monoxide for the 2001–2010 decade

Model-simulated trend of surface carbon monoxide for the 2001–2010 decade

Atmospheric Chemistry and Physics, 14, 10465-10482, 2014

Author(s): J. Yoon and A. Pozzer

We present decadal trend estimates of surface carbon monoxide (CO) simulated using the atmospheric chemistry general circulation model ECHAM5/MESSy (EMAC; ECHAM5 and MESSy stand for fifth-generation European Centre Hamburg general circulation model and Modular Earth Submodel System, respectively) based on the emission scenarios Representative Concentration Pathways (RCP) 8.5 for anthropogenic activity and Global Fire Emissions Database (GFED) v3.1 for biomass burning from 2001 through 2010. The spatial distribution of the modeled surface CO is evaluated with monthly data from the Measurements Of Pollution In The Troposphere (MOPITT) thermal infrared product. The global means of correlation coefficient and relative bias for the decade 2001–2010 are 0.95 and ?4.29%, respectively. We also find a reasonable correlation (R = 0.78) between the trends of EMAC surface CO and full 10-year monthly records from ground-based observation (World Data Centre for Greenhouse Gases, WDCGG). Over western Europe, eastern USA, and northern Australia, the significant decreases in EMAC surface CO are estimated at ?35.5 ± 5.8, ?59.6 ± 9.1, and ?13.7 ± 9.5 ppbv decade?1, respectively. In contrast, the surface CO increases by +8.9 ± 4.8 ppbv decade?1 over southern Asia. A high correlation (R = 0.92) between the changes in EMAC-simulated surface CO and total emission flux shows that the significant regional trends are attributed to the changes in primary and direct emissions from both anthropogenic activity and biomass burning.

Posted on 1 October 2014 | 12:00 am


Development of an aerosol microphysical module: Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS)

Development of an aerosol microphysical module: Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS)

Atmospheric Chemistry and Physics, 14, 10315-10331, 2014

Author(s): H. Matsui, M. Koike, Y. Kondo, J. D. Fast, and M. Takigawa

Number concentrations, size distributions, and mixing states of aerosols are essential parameters for accurate estimations of aerosol direct and indirect effects. In this study, we develop an aerosol module, designated the Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS), that can explicitly represent these parameters by considering new particle formation (NPF), black carbon (BC) aging, and secondary organic aerosol (SOA) processes. A two-dimensional bin representation is used for particles with dry diameters from 40 nm to 10 ?m to resolve both aerosol sizes (12 bins) and BC mixing states (10 bins) for a total of 120 bins. The particles with diameters between 1 and 40 nm are resolved using additional eight size bins to calculate NPF. The ATRAS module is implemented in the WRF-Chem model and applied to examine the sensitivity of simulated mass, number, size distributions, and optical and radiative parameters of aerosols to NPF, BC aging, and SOA processes over East Asia during the spring of 2009. The BC absorption enhancement by coating materials is about 50% over East Asia during the spring, and the contribution of SOA processes to the absorption enhancement is estimated to be 10–20% over northern East Asia and 20–35% over southern East Asia. A clear north–south contrast is also found between the impacts of NPF and SOA processes on cloud condensation nuclei (CCN) concentrations: NPF increases CCN concentrations at higher supersaturations (smaller particles) over northern East Asia, whereas SOA increases CCN concentrations at lower supersaturations (larger particles) over southern East Asia. The application of ATRAS in East Asia also shows that the impact of each process on each optical and radiative parameter depends strongly on the process and the parameter in question. The module can be used in the future as a benchmark model to evaluate the accuracy of simpler aerosol models and examine interactions between NPF, BC aging, and SOA processes under different meteorological conditions and emissions.

Posted on 30 September 2014 | 12:00 am


The balances of mixing ratios and segregation intensity: a case study from the field (ECHO 2003)

The balances of mixing ratios and segregation intensity: a case study from the field (ECHO 2003)

Atmospheric Chemistry and Physics, 14, 10333-10362, 2014

Author(s): R. Dlugi, M. Berger, M. Zelger, A. Hofzumahaus, F. Rohrer, F. Holland, K. Lu, and G. Kramm

An inhomogeneous mixing of reactants causes a reduction of their chemical removal compared to the homogeneously mixed case in turbulent atmospheric flows. This can be described by the intensity of segregation IS being the covariance of the mixing ratios of two species divided by the product of their means. Both terms appear in the balance equation of the mixing ratio and are discussed for the reaction between isoprene and OH for data of the field study ECHO 2003 above a deciduous forest. For most of these data, IS is negatively correlated with the fraction of mean OH mixing ratio reacting with isoprene. IS is also negatively correlated with the isoprene standard deviation. Both findings agree with model results discussed by Patton et al. (2001) and others. The correlation coefficient between OH and isoprene and, therefore, IS increases with increasing mean reaction rate. In addition, the balance equation of the covariance between isoprene and OH is applied as the theoretical framework for the analysis of the same field data. The storage term is small, and, therefore, a diagnostic equation for this covariance can be derived. The chemical reaction term Rij is dominated by the variance of isoprene times the quotient of mixing ratios of OH and isoprene. Based on these findings a new diagnostic equation for IS is formulated. Comparing different terms of this equation, IS and Rij show a relation also to the normalised isoprene standard deviation. It is shown that not only chemistry but also turbulent and convective mixing and advection – considered in a residual term – influence IS. Despite this finding, a detection of the influence of coherent eddy transport above the forest according to Katul et al. (1997) on IS fails, but a relation to the turbulent and advective transport of isoprene variance is determined. The largest values of IS are found for most unstable conditions with increasing buoyant production, confirming qualitatively model predictions by Ouwersloot et al. (2011).

Posted on 30 September 2014 | 12:00 am


A molecular-level approach for characterizing water-insoluble components of ambient organic aerosol particulates using ultrahigh-resolution mass spectrometry

A molecular-level approach for characterizing water-insoluble components of ambient organic aerosol particulates using ultrahigh-resolution mass spectrometry

Atmospheric Chemistry and Physics, 14, 10299-10314, 2014

Author(s): A. S. Willoughby, A. S. Wozniak, and P. G. Hatcher

The chemical composition of organic aerosols in the atmosphere is strongly influenced by human emissions. The effect these have on the environment, human health, and climate change is determined by the molecular nature of these chemical species. The complexity of organic aerosol samples limits the ability to study the chemical composition, and therefore the associated properties and the impacts they have. Many studies have addressed the water-soluble fraction of organic aerosols and have had much success in identifying specific molecular formulas for thousands of compounds present. However, little attention is given to the water-insoluble portion, which can contain most of the fossil material that is emitted through human activity. Here we compare the organic aerosols present in water extracts and organic solvent extracts (pyridine and acetonitrile) of an ambient aerosol sample collected in a rural location that is impacted by natural and anthropogenic emission sources. A semiquantitative method was developed using proton nuclear magnetic resonance spectroscopy to determine that the amount of organic matter extracted by pyridine is comparable to that of water. Electrospray ionization Fourier transform ion cyclotron resonance mass spectra show that pyridine extracts a molecularly unique fraction of organic matter compared to water or acetonitrile, which extract chemically similar organic matter components. The molecular formulas unique to pyridine were less polar, more aliphatic, and reveal formulas containing sulfur to be an important component of insoluble aerosol organic matter.

Posted on 30 September 2014 | 12:00 am


Worldwide biogenic soil NOx emissions inferred from OMI NO2 observations

Worldwide biogenic soil NOx emissions inferred from OMI NO2 observations

Atmospheric Chemistry and Physics, 14, 10363-10381, 2014

Author(s): G. C. M. Vinken, K. F. Boersma, J. D. Maasakkers, M. Adon, and R. V. Martin

Biogenic NOx emissions from soils are a large natural source with substantial uncertainties in global bottom-up estimates (ranging from 4 to 15 Tg N yr?1). We reduce this range in emission estimates, and present a top-down soil NOx emission inventory for 2005 based on retrieved tropospheric NO2 columns from the Ozone Monitoring Instrument (OMI). We use a state-of-science soil NOx emission inventory (Hudman et al., 2012) as a priori in the GEOS-Chem chemistry transport model to identify 11 regions where tropospheric NO2 columns are dominated by soil NOx emissions. Strong correlations between soil NOx emissions and simulated NO2 columns indicate that spatial patterns in simulated NO2 columns in these regions indeed reflect the underlying soil NOx emissions. Subsequently, we use a mass-balance approach to constrain emissions for these 11 regions on all major continents using OMI observed and GEOS-Chem simulated tropospheric NO2 columns. We find that responses of simulated NO2 columns to changing NOx emissions are suppressed over low NOx regions, and account for these non-linearities in our inversion approach. In general, our approach suggests that emissions need to be increased in most regions. Our OMI top-down soil NOx inventory amounts to 10.0 Tg N for 2005 when only constraining the 11 regions, and 12.9 Tg N when extrapolating the constraints globally. Substantial regional differences exist (ranging from ?40% to +90%), and globally our top-down inventory is 4–35% higher than the GEOS-Chem a priori (9.6 Tg N yr?1). We evaluate NO2 concentrations simulated with our new OMI top-down inventory against surface NO2 measurements from monitoring stations in Africa, the USA and Europe. Although this comparison is complicated by several factors, we find an encouraging improved agreement when using the OMI top-down inventory compared to using the a priori inventory. To our knowledge, this study provides, for the first time, specific constraints on soil NOx emissions on all major continents using OMI NO2 columns. Our results rule out the low end of reported soil NOx emission estimates, and suggest that global emissions are most likely around 12.9 ± 3.9 Tg N yr?1.

Posted on 30 September 2014 | 12:00 am


Linking climate and air quality over Europe: effects of meteorology on PM2.5 concentrations

Linking climate and air quality over Europe: effects of meteorology on PM2.5 concentrations

Atmospheric Chemistry and Physics, 14, 10283-10298, 2014

Author(s): A. G. Megaritis, C. Fountoukis, P. E. Charalampidis, H. A. C. Denier van der Gon, C. Pilinis, and S. N. Pandis

The effects of various meteorological parameters such as temperature, wind speed, absolute humidity, precipitation and mixing height on PM2.5 concentrations over Europe were examined using a three-dimensional chemical transport model, PMCAMx-2008. Our simulations covered three periods, representative of different seasons (summer, winter, and fall). PM2.5 appears to be more sensitive to temperature changes compared to the other meteorological parameters in all seasons.

PM2.5 generally decreases as temperature increases, although the predicted changes vary significantly in space and time, ranging from ?700 ng m?3 K?1 (?8% K?1) to 300 ng m?3 K?1 (7% K?1). The predicted decreases of PM2.5 are mainly due to evaporation of ammonium nitrate, while the higher biogenic emissions and the accelerated gas-phase reaction rates increase the production of organic aerosol (OA) and sulfate, having the opposite effect on PM2.5. The predicted responses of PM2.5 to absolute humidity are also quite variable, ranging from ?130 ng m?3 %?1 (?1.6% %?1) to 160 ng m?3 %?1 (1.6% %?1) dominated mainly by changes in inorganic PM2.5 species. An increase in absolute humidity favors the partitioning of nitrate to the aerosol phase and increases the average PM2.5 during summer and fall. Decreases in sulfate and sea salt levels govern the average PM2.5 response to humidity during winter. A decrease of wind speed (keeping the emissions constant) increases all PM2.5 species (on average 40 ng m?3 %?1) due to changes in dispersion and dry deposition. The wind speed effects on sea salt emissions are significant for PM2.5 concentrations over water and in coastal areas. Increases in precipitation have a negative effect on PM2.5 (decreases up to 110 ng m?3 %?1) in all periods due to increases in wet deposition of PM2.5 species and their gas precursors. Changes in mixing height have the smallest effects (up to 35 ng m?3 %?1) on PM2.5 .

Regarding the relative importance of each of the meteorological parameters in a changed future climate, the projected changes in precipitation are expected to have the largest impact on PM2.5 levels during all periods (changes up to 2 ?g m?3 in the fall). The expected effects in future PM2.5 levels due to wind speed changes are similar in all seasons and quite close to those resulting from future precipitation changes (up to 1.4 ?g m?3). The expected increases in absolute humidity in the future can lead to large changes in PM2.5 levels (increases up to 2 ?g m?3) mainly in the fall due to changes in particulate nitrate levels. Despite the high sensitivity of PM2.5 levels to temperature, the small expected increases of temperature in the future will lead to modest PM2.5 changes and will not dominate the overall change.

Posted on 29 September 2014 | 12:00 am





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