scholarly journals Formaldehyde over the eastern Mediterranean during MINOS: Comparison of airborne in-situ measurements with 3D-model results

2003 ◽  
Vol 3 (3) ◽  
pp. 851-861 ◽  
Author(s):  
R. Kormann ◽  
H. Fischer ◽  
M. de Reus ◽  
M. Lawrence ◽  
Ch. Brühl ◽  
...  
Keyword(s):  
Boundary Layer ◽  
3D Model ◽  
Transport Model ◽  
Eastern Mediterranean ◽  
Lower Atmosphere ◽  
Photochemical Degradation ◽  
Chemical Transport Model ◽  
Acetone Concentration ◽  
Volatile Organic ◽  
The Mediterranean

Abstract. Formaldehyde (HCHO) is an important intermediate product in the photochemical degradation of methane and non-methane volatile organic compounds. In August 2001, airborne formaldehyde measurements based on the Hantzsch reaction technique were performed during the Mediterranean INtensive Oxidant Study, MINOS. The detection limit of the instrument was 42 pptv (1s) at a time resolution of 180 s (10-90%). The overall uncertainty of the HCHO measurements was 30% at a mixing ratio of 300 pptv. In the marine boundary layer over the eastern Mediterranean Sea average HCHO concentrations were of the order of 1500 pptv, in reasonable agreement with results from a three-dimensional global chemical transport model of the lower atmosphere including non-methane volatile organic compound (NMVOC) chemistry. Above the boundary layer HCHO mixing ratios decreased with increasing altitude to a minimum level of 250 pptv at about 7 km. At higher altitudes (above 7 km) HCHO levels showed a strong dependency on the airmass origin. In airmasses from the North Atlantic/North American area HCHO levels were of the order of 300 pptv, a factor of 6 higher than values predicted by the model. Even higher HCHO levels, increasing to values of the order of 600 pptv at 11 km altitude, were observed in easterlies transporting air affected by the Indian monsoon outflow towards the Mediterranean basin. Only a small part (~30 pptv) of the large discrepancy between the model results and the measurements of HCHO in the free troposphere could be explained by a strong underestimation of the upper tropospheric acetone concentration by up to a factor of ten by the 3D-model. Therefore, the measurement-model difference in the upper troposphere remains unresolved, while the observed dependency of HCHO on airmass origin might indicate that unknown, relatively long-lived NMVOCs - or their reaction intermediates - associated with biomass burning are at least partially responsible for the observed discrepancies.

scholarly journals Formaldehyde over the eastern Mediterranean during MINOS: Comparison of airborne in-situ measurements with 3D-model results

2003 ◽  
Vol 3 (2) ◽  
pp. 1303-1331 ◽  
Author(s):  
R. Kormann ◽  
H. Fischer ◽  
M. de Reus ◽  
M. Lawrence ◽  
C. Brühl ◽  
...  
Keyword(s):  
Boundary Layer ◽  
3D Model ◽  
Transport Model ◽  
Eastern Mediterranean ◽  
Lower Atmosphere ◽  
Photochemical Degradation ◽  
Chemical Transport Model ◽  
Acetone Concentration ◽  
Volatile Organic ◽  
The Mediterranean

Abstract. Formaldehyde (HCHO) is an important intermediate product in the photochemical degradation of methane and non-methane volatile organic compounds. In August 2001, airborne formaldehyde measurements based on the Hantzsch reaction technique were performed during the Mediterranean INtensive Oxidant Study, MINOS. The detection limit of the instrument was 42 pptv at a time resolution of 180 s (10–90%). The overall uncertainty of the HCHO measurements was 30% at a mixing ratio of 300 pptv. In the marine boundary layer over the eastern Mediterranean Sea average HCHO concentrations were of the order of 1500 pptv, in reasonable agreement with results from a three-dimensional global chemical transport model of the lower atmosphere including non-methane volatile organic compound (NMVOC) chemistry. Above the boundary layer HCHO mixing ratios decreased with increasing altitude to a minimum level of 250 pptv at about 7 km. At higher altitudes (above 7 km) HCHO levels showed a strong dependency on the airmass origin. In airmasses from the North Atlantic/North American area HCHO levels were of the order of 300 pptv, a factor of 6 higher than values predicted by the model. Even higher HCHO levels, increasing to values of the order of 600 pptv at 11 km altitude, were observed in easterlies transporting air affected by the Indian monsoon outflow towards the Mediterranean basin. Only a small part (~30 pptv) of the large discrepancy between the model results and the measurements of HCHO in the free troposphere could be explained by a strong underestimation of the upper tropospheric acetone concentration by up to a factor of ten by the 3D-model. Therefore, the measurement-model difference in the upper troposphere remains unresolved, while the observed dependency of HCHO on airmass origin might indicate that unknown, relatively long-lived NMVOCs &ndash or their reaction intermediates – associated with biomass burning are at least partially responsible for the observed discrepancies.

scholarly journals Carbon monoxide (CO) and ethane (C<sub>2</sub>H<sub>6</sub>) trends from ground-based solar FTIR measurements at six European stations, comparison and sensitivity analysis with the EMEP model

2011 ◽  
Vol 11 (17) ◽  
pp. 9253-9269 ◽  
Author(s):  
J. Angelbratt ◽  
J. Mellqvist ◽  
D. Simpson ◽  
J. E. Jonson ◽  
T. Blumenstock ◽  
...  
Keyword(s):  
Transport Model ◽  
Global Scale ◽  
Global Model ◽  
Scale Model ◽  
Chemical Transport Model ◽  
Suitable Alternative ◽  
European Model ◽  
Time Period ◽  
Volatile Organic ◽  
Made In

Abstract. Trends in the CO andC2H6 partial columns ~0–15 km) have been estimated from four European ground-based solar FTIR (Fourier Transform InfraRed) stations for the 1996–2006 time period. The CO trends from the four stations Jungfraujoch, Zugspitze, Harestua and Kiruna have been estimated to −0.45 ± 0.16% yr−1, −1.00 ± 0.24% yr−1, −0.62 ± 0.19 % yr−1 and −0.61 ± 0.16% yr−1, respectively. The corresponding trends for C2H6 are −1.51 ± 0.23% yr−1, −2.11 ± 0.30% yr−1, −1.09 ± 0.25% yr−1 and −1.14 ± 0.18% yr−1. All trends are presented with their 2-σ confidence intervals. To find possible reasons for the CO trends, the global-scale EMEP MSC-W chemical transport model has been used in a series of sensitivity scenarios. It is shown that the trends are consistent with the combination of a 20% decrease in the anthropogenic CO emissions seen in Europe and North America during the 1996–2006 period and a 20% increase in the anthropogenic CO emissions in East Asia, during the same time period. The possible impacts of CH4 and biogenic volatile organic compounds (BVOCs) are also considered. The European and global-scale EMEP models have been evaluated against the measured CO and C2H6 partial columns from Jungfraujoch, Zugspitze, Bremen, Harestua, Kiruna and Ny-Ålesund. The European model reproduces, on average the measurements at the different sites fairly well and within 10–22% deviation for CO and 14–31% deviation for C2H6. Their seasonal amplitude is captured within 6–35% and 9–124% for CO and C2H6, respectively. However, 61–98% of the CO and C2H6 partial columns in the European model are shown to arise from the boundary conditions, making the global-scale model a more suitable alternative when modeling these two species. In the evaluation of the global model the average partial columns for 2006 are shown to be within 1–9% and 37–50% of the measurements for CO and C2H6, respectively. The global model sensitivity for assumptions made in this paper is also analyzed.

scholarly journals A global off-line model of size-resolved aerosol microphysics: I. Model development and prediction of aerosol properties

2005 ◽  
Vol 5 (8) ◽  
pp. 2227-2252 ◽  
Author(s):  
D. V. Spracklen ◽  
K. J. Pringle ◽  
K. S. Carslaw ◽  
M. P. Chipperfield ◽  
G. W. Mann
Keyword(s):  
Boundary Layer ◽  
Sulfuric Acid ◽  
Size Distribution ◽  
Marine Boundary Layer ◽  
Transport Model ◽  
Model Development ◽  
Aerosol Size Distribution ◽  
Chemical Transport Model ◽  
Cloud Processing ◽  
Nucleation Mechanisms

Abstract. A GLObal Model of Aerosol Processes (GLOMAP) has been developed as an extension to the TOMCAT 3-D Eulerian off-line chemical transport model. GLOMAP simulates the evolution of the global aerosol size distribution using a sectional two-moment scheme and includes the processes of aerosol nucleation, condensation, growth, coagulation, wet and dry deposition and cloud processing. We describe the results of a global simulation of sulfuric acid and sea spray aerosol. The model captures features of the aerosol size distribution that are well established from observations in the marine boundary layer and free troposphere. Modelled condensation nuclei (CN>3nm) vary between about 250–500 cm-3 in remote marine boundary layer regions and are generally in good agreement with observations. Modelled continental CN concentrations are lower than observed, which may be due to lack of some primary aerosol sources or the neglect of nucleation mechanisms other than binary homogeneous nucleation of sulfuric acid-water particles. Remote marine CN concentrations increase to around 2000–10 000 cm

scholarly journals Observing atmospheric formaldehyde (HCHO) from space: validation and intercomparison of six retrievals from four satellites (OMI, GOME2A, GOME2B, OMPS) with SEAC<sup>4</sup>RS aircraft observations over the Southeast US

2016 ◽  
Author(s):  
Lei Zhu ◽  
Daniel J. Jacob ◽  
Patrick S. Kim ◽  
Jenny A. Fisher ◽  
Karen Yu ◽  
...  
Keyword(s):  
Transport Model ◽  
Research Groups ◽  
Chemical Transport Model ◽  
Shape Factors ◽  
Aircraft Observations ◽  
Volatile Organic ◽  
Satellite Retrievals ◽  
Mass Factor ◽  
The Mean ◽  
Southeast Us

Abstract. Formaldehyde (HCHO) column data from satellites are widely used as a proxy for emissions of volatile organic compounds (VOCs), but validation of the data has been extremely limited. Here we use highly accurate HCHO aircraft observations from the NASA SEAC4RS campaign over the Southeast US in August–September 2013 to validate and intercompare six operational and research retrievals of HCHO columns from four different satellite instruments (OMI, GOME2A, GOME2B and OMPS) and three different research groups. The GEOS-Chem chemical transport model provides a common intercomparison platform. We find that all retrievals capture the HCHO maximum over Arkansas and Louisiana, reflecting high emissions of biogenic isoprene, and are consistent in their spatial variability over the Southeast US (r = 0.4–0.8 on a 0.5° × 0.5° grid) as well as their day-to-day variability (r = 0.5–0.8). However, all satellite retrievals are biased low in the mean by 20–51 %, which would lead to corresponding bias in estimates of isoprene emissions from the satellite data. The smallest bias is for OMI-BIRA, which has the highest corrected slant columns and the lowest scattering weights in its air mass factor (AMF) calculation. Correcting the assumed HCHO vertical profiles (shape factors) used in the AMF calculation would further reduce the bias in the OMI-BIRA data. We conclude that current satellite HCHO data provide a reliable proxy for isoprene emission variability but with a low mean bias due both to the corrected slant columns and the scattering weights used in the retrievals.

scholarly journals Ammonia in the summertime Arctic marine boundary layer: sources, sinks, and implications

2016 ◽  
Vol 16 (4) ◽  
pp. 1937-1953 ◽  
Author(s):  
Gregory R. Wentworth ◽  
Jennifer G. Murphy ◽  
Betty Croft ◽  
Randall V. Martin ◽  
Jeffrey R. Pierce ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Transport Model ◽  
Canadian Arctic ◽  
Atmospheric Composition ◽  
Chemical Transport Model ◽  
Data Set ◽  
Baffin Bay ◽  
Melt Ponds ◽  
Ambient Nh3 ◽  
The Impact

Abstract. Continuous hourly measurements of gas-phase ammonia (NH3(g)) were taken from 13 July to 7 August 2014 on a research cruise throughout Baffin Bay and the eastern Canadian Arctic Archipelago. Concentrations ranged from 30 to 650 ng m−3 (40–870 pptv) with the highest values recorded in Lancaster Sound (74°13′ N, 84°00′ W). Simultaneous measurements of total ammonium ([NHx]), pH and temperature in the ocean and in melt ponds were used to compute the compensation point (χ), which is the ambient NH3(g) concentration at which surface–air fluxes change direction. Ambient NH3(g) was usually several orders of magnitude larger than both χocean and χMP (< 0.4–10 ng m3) indicating these surface pools are net sinks of NH3. Flux calculations estimate average net downward fluxes of 1.4 and 1.1 ng m−2 s−1 for the open ocean and melt ponds, respectively. Sufficient NH3(g) was present to neutralize non-sea-salt sulfate (nss-SO42−) in the boundary layer during most of the study. This finding was corroborated with a historical data set of PM2.5 composition from Alert, Nunavut (82°30′ N, 62°20′ W) wherein the median ratio of NH4+/nss-SO42− equivalents was greater than 0.75 in June, July and August. The GEOS-Chem chemical transport model was employed to examine the impact of NH3(g) emissions from seabird guano on boundary-layer composition and nss-SO42− neutralization. A GEOS-Chem simulation without seabird emissions underestimated boundary layer NH3(g) by several orders of magnitude and yielded highly acidic aerosol. A simulation that included seabird NH3 emissions was in better agreement with observations for both NH3(g) concentrations and nss-SO42− neutralization. This is strong evidence that seabird colonies are significant sources of NH3 in the summertime Arctic, and are ubiquitous enough to impact atmospheric composition across the entire Baffin Bay region. Large wildfires in the Northwest Territories were likely an important source of NH3, but their influence was probably limited to the Central Canadian Arctic. Implications of seabird-derived N-deposition to terrestrial and aquatic ecosystems are also discussed.

scholarly journals Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC<sup>4</sup>RS) and ground-based (SOAS) observations in the Southeast US

2016 ◽  
Vol 16 (9) ◽  
pp. 5969-5991 ◽  
Author(s):  
Jenny A. Fisher ◽  
Daniel J. Jacob ◽  
Katherine R. Travis ◽  
Patrick S. Kim ◽  
Eloise A. Marais ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Gas Phase ◽  
Transport Model ◽  
Oxidation Mechanism ◽  
Organic Nitrate ◽  
Organic Nitrates ◽  
Nox Emissions ◽  
Particle Phase ◽  
Chemical Transport Model ◽  
Southeast Us

Abstract. Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with  ∼  25  ×  25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25–50 % of observed RONO2 in surface air, and we find that another 10 % is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 % of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60 % of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20 % by photolysis to recycle NOx and 15 % by dry deposition. RONO2 production accounts for 20 % of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline.

scholarly journals A large and ubiquitous source of atmospheric formic acid

2015 ◽  
Vol 15 (11) ◽  
pp. 6283-6304 ◽  
Author(s):  
D. B. Millet ◽  
M. Baasandorj ◽  
D. K. Farmer ◽  
J. A. Thornton ◽  
K. Baumann ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Formic Acid ◽  
Transport Model ◽  
Model Simulation ◽  
Vertical Gradient ◽  
Precipitation Chemistry ◽  
Chemical Production ◽  
Chemical Transport Model ◽  
Criegee Intermediates ◽  
Isoprene Oxidation

Abstract. Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem CTM) to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2–3× larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based (i) solely on isoprene oxidation would require a 3× increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25× increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx : CH3OOH. Developing better constraints on SCI and RO2 + OH chemistry is a high priority for future work. The model neither captures the large diurnal amplitude in HCOOH seen in surface air, nor its inverted vertical gradient at night. This implies a substantial bias in our current representation of deposition as modulated by boundary layer dynamics, and may indicate an HCOOH sink underestimate and thus an even larger missing source. A more robust treatment of surface deposition is a key need for improving simulations of HCOOH and related trace gases, and our understanding of their budgets.

scholarly journals Simulating ultrafine particle formation in Europe using a regional CTM: contribution of primary emissions versus secondary formation to aerosol number concentrations

2012 ◽  
Vol 12 (18) ◽  
pp. 8663-8677 ◽  
Author(s):  
C. Fountoukis ◽  
I. Riipinen ◽  
H. A. C. Denier van der Gon ◽  
P. E. Charalampidis ◽  
C. Pilinis ◽  
...  
Keyword(s):  
Particle Number ◽  
Transport Model ◽  
Eastern Mediterranean ◽  
Lower Troposphere ◽  
Southeast Europe ◽  
Chemical Transport Model ◽  
The Balkans ◽  
Total Particle Number ◽  
Secondary Formation ◽  
Total Particle

Abstract. A three-dimensional regional chemical transport model (CTM) with detailed aerosol microphysics, PMCAMx-UF, was applied to the European domain to simulate the contribution of direct emissions and secondary formation to total particle number concentrations during May 2008. PMCAMx-UF uses the Dynamic Model for Aerosol Nucleation and the Two-Moment Aerosol Sectional (TOMAS) algorithm to track both aerosol number and mass concentration using a sectional approach. The model predicts nucleation events that occur over scales of hundreds up to thousands of kilometers especially over the Balkans and Southeast Europe. The model predictions were compared against measurements from 7 sites across Europe. The model reproduces more than 70% of the hourly concentrations of particles larger than 10 nm (N10) within a factor of 2. About half of these particles are predicted to originate from nucleation in the lower troposphere. Regional nucleation is predicted to increase the total particle number concentration by approximately a factor of 3. For particles larger than 100 nm the effect varies from an increase of 20% in the eastern Mediterranean to a decrease of 20% in southern Spain and Portugal resulting in a small average increase of around 1% over the whole domain. Nucleation has a significant effect in the predicted N50 levels (up to a factor of 2 increase) mainly in areas where there are condensable vapors to grow the particles to larger sizes. A semi-empirical ternary sulfuric acid-ammonia-water parameterization performs better than the activation or the kinetic parameterizations in reproducing the observations. Reducing emissions of ammonia and sulfur dioxide affects certain parts of the number size distribution.

scholarly journals Composite study of aerosol export events from East Asia and North America

2012 ◽  
Vol 12 (8) ◽  
pp. 21977-22022 ◽  
Author(s):  
Y. Luan ◽  
L. Jaeglé
Keyword(s):  
Boundary Layer ◽  
North America ◽  
East Asia ◽  
Transport Model ◽  
Lower Troposphere ◽  
Temporal Variations ◽  
The Arctic ◽  
Chemical Transport Model ◽  
Mean Values ◽  
Warm Conveyor Belts

Abstract. We use satellite observations of aerosol optical depth (AOD) from the Moderate Resolution Imaging Spectrometer (MODIS) together with the GEOS-Chem global chemical transport model to contrast export of aerosols from East Asia and North America during 2004–2010. The GEOS-Chem model reproduces the spatial distribution and temporal variations of Asian aerosol outflow generally well, although a low bias (−30%) is found in the model fine mode AOD. We use the model to identify 244 aerosol pollution export events from E. Asia and 251 export events from N. America over our 7-yr study period. When these events are composited by season, we find that the AOD in the outflow is enhanced by 50–100% relative to seasonal mean values. The composite Asian plume splits into one branch going poleward towards the Arctic, with the other crossing the Pacific in 6–8 days. A fraction of the aerosols is trapped in the subtropical Pacific High. The N. American plume travels to the northeast Atlantic, reaching Europe after 4–5 days. Part of the composite plume turns anticyclonically in the Azores High, where it slowly decays. Both the Asian and N. American export events are favored by a dipole structure in sea-level pressure anomalies, associated with mid-latitude cyclone activity over the respective source regions. The observed AOD in the E. Asian outflow exhibits stronger seasonality, with a spring maximum, than the N. American outflow, with a weak summer maximum. The large spring AOD in the Asian outflow is the result of enhanced sulfate and dust aerosol concentrations, but is also due to a larger export efficiency of sulfate and SO2 from the Asian boundary layer relative to the N. American boundary layer. While the N. American sulfate outflow is mostly found in the lower troposphere (1–3 km altitude), the Asian sulfate outflow occurs at higher altitudes (2–6 km). In the Asian outflow 42–59% of the sulfate column is present above 2 km altitude, with only 24–35% in the N. American outflow. We link this to the factor of 2–5 lower precipitation in the warm conveyor belts (WCB) of midlatitude cyclones over E. Asia compared to N. America. This relative lack of precipitation makes Asian WCB very efficient for injecting aerosols in the middle troposphere.

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