-
We assimilate stratospheric ozone profiles from MLS (Microwave Limb Sounder) into the MOCAGE Chemistry Transport Model (CTM) to study Stratosphere-Troposphere Exchange (STE). This study uses two horizontal grid resolutions of 2° and 0.2°. The combined impacts of MLS ozone assimilation and high horizontal resolution are illustrated in two case studies where STE events occurred (23 June 2009 and 17 July 2009). At high resolution the filamentary structures of stratospheric air which characterise STE events are captured by the model. To test the impact of the assimilation and the resolution, we compare model outputs from different experiments (high resolution and low resolution; MLS assimilation run and free run) with independent data (MOZAIC aircraft ozone data; WOUDC ozone sonde network data). MLS ozone analyses show a better description of the Upper Troposphere Lower Stratosphere (UTLS) region and the stratospheric intrusions than the free model run. In particular, at high horizontal resolution the MLS ozone analyses present realistic filamentary ozone structures in the UTLS and laminae structures in the ozone profile. Despite a low aspect ratio between horizontal resolution and vertical resolution in the UTLS at high horizontal resolution, MLS ozone analyses improve the vertical structures of the ozone fields. Results from backward trajectories and ozone forecasts show that assimilation at high horizontal resolution of MLS ozone profiles between 10 hPa and 215 hPa has an impact on tropospheric ozone.
-
We have developed a new nested-grid mercury (Hg) simulation over North America with a 1/2° latitude by 2/3° longitude horizontal resolution employing the GEOS-Chem global chemical transport model. Emissions, chemistry, deposition, and meteorology are self-consistent between the global and nested domains. Compared to the global model (4° latitude by 5° longitude), the nested model shows improved skill at capturing the high spatial and temporal variability of Hg wet deposition over North America observed by the Mercury Deposition Network (MDN) in 2008–2009. The nested simulation resolves features such as higher deposition due to orographic precipitation, land/ocean contrast and and predicts more efficient convective rain scavenging of Hg over the southeast United States. However, the nested model overestimates Hg wet deposition over the Ohio River Valley region (ORV) by 27%. We modify anthropogenic emission speciation profiles in the US EPA National Emission Inventory (NEI) to account for the rapid in-plume reduction of reactive to elemental Hg (IPR simulation). This leads to a decrease in the model bias to −2.3% over the ORV region. Over the contiguous US, the correlation coefficient (<i>r</i>) between MDN observations and our IPR simulation increases from 0.60 to 0.78. The IPR nested simulation generally reproduces the seasonal cycle in surface concentrations of speciated Hg from the Atmospheric Mercury Network (AMNet) and Canadian Atmospheric Mercury Network (CAMNet). In the IPR simulation, annual mean gaseous and particulate-bound Hg(II) are within 140% and 11% of observations, respectively. In contrast, the simulation with unmodified anthropogenic Hg speciation profiles overestimates these observations by factors of 4 and 2 for gaseous and particulate-bound Hg(II), respectively. The nested model shows improved skill at capturing the horizontal variability of Hg observed over California during the ARCTAS aircraft campaign. The nested model suggests that North American anthropogenic emissions account for 10–22% of Hg wet deposition flux over the US, depending on the anthropogenic emissions speciation profile assumed. The modeled percent contribution can be as high as 60% near large point sources in ORV. Our results indicate that the North American anthropogenic contribution to dry deposition is 13–20%.
-
A spectroscopic analysis of 115 wintertime particulate matter samples collected in rural California shows that wood smoke absorbs solar radiation with a strong spectral selectivity. This is consistent with prior work that has demonstrated that organic carbon (OC), in addition to black carbon (BC), appreciably absorbs solar radiation in the visible and ultraviolet spectral regions. We apportion light absorption to OC and BC and find that the absorption Ångström exponent of the light-absorbing OC in these samples ranges from 3.0 to 7.4 and averages 5.0. Further, we calculate that OC would account for 14% and BC would account for 86% of solar radiation absorbed by the wood smoke in the atmosphere (integrated over the solar spectrum from 300 to 2500 nm). OC would contribute 49% of the wood smoke particulate matter absorption of ultraviolet solar radiation at wavelengths below 400 nm and, therefore, may affect tropospheric photochemistry. These results illustrate that BC is the dominant light-absorbing particulate matter species in atmospheres burdened with residential wood smoke and OC absorption is secondary but not insignificant. Further, these results add to the growing body of evidence that light-absorbing OC is ubiquitous in atmospheres influenced by biomass burning and may be important to include when considering particulate matter effects on climate.
-
The impact of wood combustion on ambient aerosols was investigated in Augsburg, Germany during a winter measurement campaign of a six-week period. Special attention was paid to the high time resolution observations of wood combustion with different mass spectrometric methods. Here we present and compare the results from an Aerodyne aerosol mass spectrometer (AMS) and gas chromatographic – mass spectrometric (GC-MS) analysed PM<sub>1</sub> filters on an hourly basis. This includes source apportionment of the AMS derived organic matter (OM) using positive matrix factorisation (PMF) and analysis of levoglucosan as wood combustion marker, respectively. <br><br> During the measurement period nitrate and OM mass are the main contributors to the defined submicron particle mass of AMS and Aethalometer with 28% and 35%, respectively. Wood combustion organic aerosol (WCOA) contributes to OM with 23% on average and 27% in the evening and night time. Conclusively, wood combustion has a strong influence on the organic matter and overall aerosol composition. Levoglucosan accounts for 14% of WCOA mass with a higher percentage in comparison to other studies. The ratio between the mass of levoglucosan and organic carbon amounts to 0.06. <br><br> This study is unique in that it provides a one-hour time resolution comparison between the wood combustion results of the AMS and the GC-MS analysed filter method at a PM<sub>1</sub> particle size range. The comparison of the concentration variation with time of the PMF WCOA factor, levoglucosan estimated by the AMS data and the levoglucosan measured by GC-MS is highly correlated (<i>R</i><sup>2</sup> = 0.84), and a detailed discussion on the contributors to the wood combustion marker ion at mass-to-charge ratio 60 is given. At the end, both estimations, the WCOA factor and the levoglucosan concentration estimated by AMS data, allow to observe the variation with time of wood combustion emissions (gradient correlation with GC-MS levoglucosan of <i>R</i><sup>2</sup> = 0.84). In the case of WCOA, it provides the estimated magnitude of wood combustion emission. Quantitative estimation of the levoglucosan concentration from the AMS data is problematic due to its overestimation in comparison to the levoglucosan measured by the GC-MS.
-
We present a case study of Aitken and accumulation mode aerosol observed downwind of the anvil of a deep tropical thunderstorm. The measurements were made by condensation nuclei counters flown on the Egrett high-altitude aircraft from Darwin during the ACTIVE campaign, in monsoon conditions producing widespread convection over land and ocean. Maximum measured concentrations of aerosol with diameter greater than 10 nm were 25 000 cm<sup>−3</sup> (STP). By calculating back-trajectories from the observations, and projecting onto infrared satellite images, the time since the air exited cloud was estimated. In this way a time scale of about 3 hours was derived for the Aitken aerosol concentration to reach its peak. We examine the hypothesis that the growth in aerosol concentrations can be explained by production of sulphuric acid from SO<sub>2</sub> followed by particle nucleation and coagulation. Estimates of the sulphuric acid production rate show that the observations are only consistent with this hypothesis if the particles coagulate to sizes >10 nm much more quickly than is suggested by current theory. Alternatively, other condensible gases (possibly organic) drive the growth of aerosol particles in the TTL.
-
The Mass Absorption Cross section (MAC) and Absorption Ångström Exponent (AAE) have been commonly estimated for ambient aerosols but rarely for black carbon (BC) or organic aerosol (OA) alone in the ambient conditions. Here, we provide estimates of BC (and OA) MAC and AAE in East Asian outflow, by analyzing field data collected at the Gosan ABC super site. At this site, EC (and OC) carbon mass, the aerosol absorption coefficient at 7 wavelengths and PM mass density were continuously measured from October 2009 to June 2010. <br><br> We remove the absorption data with significant dust influence using the mass ratio of PM<sub>10</sub> to PM<sub>2.5</sub>. The remaining data shows an AAE of about 1.27, which we suggest represent the average carbonaceous aerosol (CA) AAE at Gosan. <br><br> We find a positive correlation between the mass ratio of OC to EC and CA AAE, and successfully increase the correlation by filtering out data associated with weak absorption signal. After the filtering, absorption coefficient is regressed on OC and EC mass densities. BC and OA MACs are found to be 5.1 (3.8–6.1) and 1.4 (0.8–2.0) m<sup>2</sup> g<sup>−1</sup> at 520 nm respectively. From the estimated BC and OA MAC, we find that OA contributes about 45% to CA absorption at 520 nm. BC AAE is found to be 0.7–1.0, and is probably even lower considering the instrument bias. OA AAE is found to be 1.6–1.8. Compared with a previous estimate of OA MAC and AAE near biomass burning, our estimates at Gosan strongly suggest that the strongly-absorbing so-called brown carbon spheres are either unrelated to biomass burning or absent near the emission source.
-
We use 2005–2009 satellite observations of formaldehyde (HCHO) columns from the OMI instrument to infer biogenic isoprene emissions at monthly 1 × 1° resolution over the African continent. Our work includes new approaches to remove biomass burning influences using OMI absorbing aerosol optical depth data (to account for transport of fire plumes) and anthropogenic influences using AATSR satellite data for persistent small-flame fires (gas flaring). The resulting biogenic HCHO columns (Ω<sub>HCHO</sub>) from OMI follow closely the distribution of vegetation patterns in Africa. We infer isoprene emission (<i>E</i><sub>ISOP</sub>) from the local sensitivity <i>S</i> = ΔΩ<sub>HCHO</sub> / Δ<i>E</i><sub>ISOP</sub> derived with the GEOS-Chem chemical transport model using two alternate isoprene oxidation mechanisms, and verify the validity of this approach using AMMA aircraft observations over West Africa and a longitudinal transect across central Africa. Displacement error (smearing) is diagnosed by anomalously high values of <i>S</i> and the corresponding data are removed. We find significant sensitivity of <i>S</i> to NO<sub>x</sub> under low-NO<sub>x</sub> conditions that we fit to a linear function of tropospheric column NO<sub>2</sub>. We estimate a 40% error in our inferred isoprene emissions under high-NO<sub>x</sub> conditions and 40–90% under low-NO<sub>x</sub> conditions. Our results suggest that isoprene emission from the central African rainforest is much lower than estimated by the state-of-the-science MEGAN inventory.
-
The legacy of long-term mining activities in Wanshan mercury (Hg) mining area (WMMA), Guizhou, China including a series of environmental issues related to Hg pollution. The spatial distribution of gaseous elemental mercury (Hg<sup>0</sup>) concentrations in ambient air were monitored using a mobile RA-915<sup>+</sup> Zeeman Mercury Analyzer during daytime and night time in May 2010. The data imply that calcines and mine wastes piles located at Dashuixi and on-going artisanal Hg mining activities at Supeng were major sources of atmospheric mercury in WMMA. For a full year (May 2010 to May 2011), sampling of precipitation and throughfall were conducted on a weekly basis at three sites (Shenchong, Dashuixi, and Supeng) within WMMA. Hg in deposition was characterized by analysis of total Hg (THg) and dissolved Hg (DHg) concentrations. The corresponding data exhibit a high degree of variability, both temporarily and spatially. The volume-weighted mean THg concentrations in precipitation and throughfall samples were 502.6 ng l<sup>−1</sup> and 977.8 ng l<sup>−1</sup> at Shenchong, 814.1 ng l<sup>−1</sup>and 3392.1 ng l<sup>−1</sup> at Dashuixi, 7490.1 ng l<sup>−1</sup>and 9641.5 ng l<sup>−1</sup> at Supeng, respectively. THg was enhanced in throughfall compared to wet deposition samples by up to a factor of 7. The annual wet Hg deposition fluxes were 29.1, 68.8 and 593.1 μg m<sup>−2</sup> yr<sup>−1</sup> at Shenchong, Dashuixi and Supeng, respectively, while the annual dry Hg deposition fluxes were estimated to be 378.9, 2613.6 and 6178 μg m<sup>−2</sup> yr<sup>−1</sup> at these sites, respectively. Dry deposition played a dominant role in total atmospheric Hg deposition in WMMA since the dry deposition fluxes were 10.4–37.9 times higher than the wet deposition fluxes during the whole sample period. Our data showed that air deposition was still an important pathway of Hg contamination to the local environment in WMMA.
-
The sulphate aerosols mass and number concentration during the Indian Ocean Experiment (INDOEX) Intensive Field Phase-1999 (INDOEX-IFP) has been simulated using an interactive chemistry GCM. The model considers an interactive scheme for feedback from chemistry to meteorology with internally resolving microphysical properties of aerosols. In particular, the interactive scheme has the ability to predict both particle mass and number concentration for the Aitken and accumulation modes as prognostic variables. <br><br> On the basis of size distribution retrieved from the observations made along the cruise route during IFP-1999, the model successfully simulates the order of magnitude of aerosol number concentration. The results show the southward migration of minimum concentrations, which follows ITCZ (Inter Tropical Convergence Zone) migration. Sulphate surface concentration during INDOEX-IFP at Kaashidhoo (73.46° E, 4.96° N) gives an agreement within a factor of 2 to 3. The measured aerosol optical depth (AOD) from all aerosol species at KCO was 0.37 ± 0.11 while the model simulated sulphate AOD ranged from 0.05 to 0.11. As sulphate constitutes 29% of the observed AOD, the model predicted values of sulphate AOD are hence fairly close to the measured values. The model thus has capability to predict the vertically integrated column sulphate burden. Furthermore, the model results indicate that Indian contribution to the estimated sulphate burden over India is more than 60% with values upto 40% over the Arabian Sea.
-
