Items

Advanced search

The role of semi-volatile organic compounds in the mesoscale evolution of biomass burning aerosol: a modeling case study of the 2010 mega-fire event in Russia

Chemistry transport models (CTMs) are an indispensable tool for studying and predicting atmospheric and climate effects associated with carbonaceous aerosol from open biomass burning (BB); this type of aerosol is known to contribute significantly to both global radiative forcing and to episodes of air pollution in regions affected by wildfires. Improving model performance requires systematic comparison of simulation results with measurements of BB aerosol and elucidation of possible reasons for discrepancies between them, which, by default, are frequently attributed in the literature to uncertainties in emission data. Based on published laboratory data on the atmospheric evolution of BB aerosol and using the volatility basis set (VBS) framework for organic aerosol modeling, we examined the importance of taking gas-particle partitioning and oxidation of semi-volatile organic compounds (SVOCs) into account in simulations of the mesoscale evolution of smoke plumes from intense wildfires that occurred in western Russia in 2010. Biomass burning emissions of primary aerosol components were constrained with PM10 and CO data from the air pollution monitoring network in the Moscow region. The results of the simulations performed with the CHIMERE CTM were evaluated by considering, in particular, the ratio of smoke-related enhancements in PM10 and CO concentrations (ΔPM10 and ΔCO) measured in Finland (in the city of Kuopio), nearly 1000 km downstream of the fire emission sources. It is found that while the simulations based on a "conventional" approach to BB aerosol modeling (disregarding oxidation of SVOCs and assuming organic aerosol material to be non-volatile) strongly underestimated values of ΔPM10/ΔCO observed in Kuopio (by a factor of 2), employing the "advanced" representation of atmospheric processing of organic aerosol material resulted in bringing the simulations to a much closer agreement with the ground measurements. Furthermore, taking gas-particle partitioning and oxidation of SVOCs into account is found to result in a major improvement of the agreement of simulations and satellite measurements of aerosol optical depth, as well as in considerable changes in predicted aerosol composition and top-down BB aerosol emission estimates derived from AOD measurements.
Boundary layer new particle formation over East Antarctic sea ice – possible Hg-driven nucleation?

Aerosol observations above the Southern Ocean and Antarctic sea ice are scarce. Measurements of aerosols and atmospheric composition were made in East Antarctic pack ice on board the Australian icebreaker Aurora Australis during the spring of 2012. One particle formation event was observed during the 32 days of observations. This event occurred on the only day to exhibit extended periods of global irradiance in excess of 600 W m−2. Within the single air mass influencing the measurements, number concentrations of particles larger than 3 nm (CN3) reached almost 7700 cm−3 within a few hours of clouds clearing, and grew at rates of 5.6 nm h−1. Formation rates of 3 nm particles were in the range of those measured at other Antarctic locations at 0.2–1.1 ± 0.1 cm−3 s−1. Our investigations into the nucleation chemistry found that there were insufficient precursor concentrations for known halogen or organic chemistry to explain the nucleation event. Modelling studies utilising known sulfuric acid nucleation schemes could not simultaneously reproduce both particle formation or growth rates. Surprising correlations with total gaseous mercury (TGM) were found that, together with other data, suggest a mercury-driven photochemical nucleation mechanism may be responsible for aerosol nucleation. Given the very low vapour pressures of the mercury species involved, this nucleation chemistry is likely only possible where pre-existing aerosol concentrations are low and both TGM concentrations and solar radiation levels are relatively high (&sim; 1.5 ng m−3 and &geq; 600 W m−2, respectively), such as those observed in the Antarctic sea ice boundary layer in this study or in the global free troposphere, particularly in the Northern Hemisphere.
Why does surface ozone peak before a typhoon landing in southeast China?

A high O3 episode with the large increases in surface ozone by 21–42 ppbv and the nocturnal surface O3 levels exceeding 70 ppbv was observed in the region between Xiamen and Quanzhou over the southeastern coast of China during 12–14 June 2014, before the Typhoon Hagibis landing. Variations in the surface O3, NO2, CO and meteorology during the Typhoon Hagibis event clearly suggest a substantial impact of the peripheral downdrafts in the large-scale typhoon circulation on such an O3 episode excluding the contributions of photochemical production and the horizontal transport. The influence of vertical O3 transport from the upper troposphere and lower stratosphere (UTLS) region on high surface O3 levels is further confirmed by a negative correlation between surface O3 and CO concentrations as well as dry surface air observed during the O3 episode. This study provides observational evidence of typhoon-driven intrusion of O3 from the UTLS region to surface air, revealing a significant effect of such a process of stratosphere–troposphere exchange (STE) of O3 on tropospheric O3 and ambient air quality.
Mixing state and sources of submicron regional background aerosols in the northern Qinghai–Tibet Plateau and the influence of biomass burning

Transmission electron microscopy (TEM) was employed to obtain morphology, size, composition, and mixing state of background aerosols with diameter less than 1 μm in the northern Qinghai–Tibet Plateau (QTP) during 15 September to 15 October 2013. Individual aerosol particles mainly contained secondary inorganic aerosols (SIA – sulfate and nitrate) and organics during clean periods (PM2.5 mass concentration less than 2.5 μg m−3). The presence of K–Na–Cl associated with organics and an increase in soot particles suggest that an intense biomass burning event caused the highest PM2.5 concentrations (> 30 μg m−3) during the study. A large number fraction of the fly-ash-containing particles (21.73 %) suggests that coal combustion emissions in the QTP significantly contributed to air pollutants at the medium pollution level (PM2.5: 10–30 μg m−3). We concluded that emissions from biomass burning and from coal combustion both constantly contribute to anthropogenic particles in the QTP atmosphere. Based on size distributions of individual particles at different pollution levels, we found that gas condensation on existing particles is an important chemical process for the formation of SIA with organic coating. TEM observations show that refractory aerosols (e.g., soot, fly ash, and visible organic particles) likely adhere to the surface of SIA particles larger than 200 nm due to coagulation. Organic coating and soot on surface of the aged particles likely influence their hygroscopic and optical properties, respectively, in the QTP. To our knowledge, this study reports the first microscopic analysis of fine particles in the background QTP air.
Organic nitrate aerosol formation via NO3 + biogenic volatile organic compounds in the southeastern United States

Gas- and aerosol-phase measurements of oxidants, biogenic volatile organic compounds (BVOCs) and organic nitrates made during the Southern Oxidant and Aerosol Study (SOAS campaign, Summer 2013) in central Alabama show that a nitrate radical (NO3) reaction with monoterpenes leads to significant secondary aerosol formation. Cumulative losses of NO3 to terpenes are correlated with increase in gas- and aerosol-organic nitrate concentrations made during the campaign. Correlation of NO3 radical consumption to organic nitrate aerosol formation as measured by aerosol mass spectrometry and thermal dissociation laser-induced fluorescence suggests a molar yield of aerosol-phase monoterpene nitrates of 23–44 %. Compounds observed via chemical ionization mass spectrometry (CIMS) are correlated to predicted nitrate loss to BVOCs and show C10H17NO5, likely a hydroperoxy nitrate, is a major nitrate-oxidized terpene product being incorporated into aerosols. The comparable isoprene product C5H9NO5 was observed to contribute less than 1 % of the total organic nitrate in the aerosol phase and correlations show that it is principally a gas-phase product from nitrate oxidation of isoprene. Organic nitrates comprise between 30 and 45 % of the NOy budget during SOAS. Inorganic nitrates were also monitored and showed that during incidents of increased coarse-mode mineral dust, HNO3 uptake produced nitrate aerosol mass loading at a rate comparable to that of organic nitrate produced via NO3 + BVOCs.
Sources of long-lived atmospheric VOCs at the rural boreal forest site, SMEAR II

In this study a long-term volatile organic compound (VOCs) concentration data set, measured at the SMEAR II (Station for Measuring Ecosystem–Atmosphere Relations) boreal forest site in Hyytiälä, Finland during the years 2006–2011, was analyzed in order to identify source areas and profiles of the observed VOCs. VOC mixing ratios were measured using proton transfer reaction mass spectrometry. Four-day HYSPLIT 4 (Hybrid Single Particle Lagrangian Integrated Trajectory) backward trajectories and the Unmix 6.0 receptor model were used for source area and source composition analysis. Two major forest fire events in Russia took place during the measurement period. The effect of these fires was clearly visible in the trajectory analysis, lending confidence to the method employed with this data set. Elevated volume mixing ratios (VMRs) of non-biogenic VOCs related to forest fires, e.g. acetonitrile and aromatic VOCs, were observed. Ten major source areas for long-lived VOCs (methanol, acetonitrile, acetaldehyde, acetone, benzene, and toluene) observed at the SMEAR II site were identified. The main source areas for all the targeted VOCs were western Russia, northern Poland, Kaliningrad, and the Baltic countries. Industrial areas in northern continental Europe were also found to be source areas for certain VOCs. Both trajectory and receptor analysis showed that air masses from northern Fennoscandia were less polluted with respect to both the VOCs studied and other trace gases (CO, SO2 and NOx), compared to areas of eastern and western continental Europe, western Russia, and southern Fennoscandia.
Decadal trends in global CO emissions as seen by MOPITT

Negative trends of carbon monoxide (CO) concentrations are observed in the recent decade by both surface measurements and satellite retrievals over many regions of the globe, but they are not well explained by current emission inventories. Here, we analyse the observed CO concentration decline with an atmospheric inversion that simultaneously optimizes the two main CO sources (surface emissions and atmospheric hydrocarbon oxidations) and the main CO sink (atmospheric hydroxyl radical OH oxidation). Satellite CO column retrievals from Measurements of Pollution in the Troposphere (MOPITT), version 6, and surface observations of methane and methyl chloroform mole fractions are assimilated jointly for the period covering 2002–2011. Compared to the model simulation prescribed with prior emission inventories, trends in the optimized CO concentrations show better agreement with that of independent surface in situ measurements. At the global scale, the atmospheric inversion primarily interprets the CO concentration decline as a decrease in the CO emissions (−2.3 % yr−1), more than twice the negative trend estimated by the prior emission inventories (−1.0 % yr−1). The spatial distribution of the inferred decrease in CO emissions indicates contributions from western Europe (−4.0 % yr−1), the United States (−4.6 % yr−1) and East Asia (−1.2 % yr−1), where anthropogenic fuel combustion generally dominates the overall CO emissions, and also from Australia (−5.3 % yr−1), the Indo-China Peninsula (−5.6 % yr−1), Indonesia (−6.7 % y−1), and South America (−3 % yr−1), where CO emissions are mostly due to biomass burning. In contradiction with the bottom-up inventories that report an increase of 2 % yr−1 over China during the study period, a significant emission decrease of 1.1 % yr−1 is inferred by the inversion. A large decrease in CO emission factors due to technology improvements would outweigh the increase in carbon fuel combustions and may explain this decrease. Independent satellite formaldehyde (CH2O) column retrievals confirm the absence of large-scale trends in the atmospheric source of CO. However, it should be noted that the CH2O retrievals are not assimilated and OH concentrations are optimized at a very large scale in this study.
Observations of the spectral dependence of linear particle depolarization ratio of aerosols using NASA Langley airborne High Spectral Resolution Lidar

Linear particle depolarization ratio is presented for three case studies from the NASA Langley airborne High Spectral Resolution Lidar-2 HSRL-2). Particle depolarization ratio from lidar is an indicator of non-spherical particles and is sensitive to the fraction of non-spherical particles and their size. The HSRL-2 instrument measures depolarization at three wavelengths: 355, 532, and 1064 nm. The three measurement cases presented here include two cases of dust-dominated aerosol and one case of smoke aerosol. These cases have partial analogs in earlier HSRL-1 depolarization measurements at 532 and 1064 nm and in literature, but the availability of three wavelengths gives additional insight into different scenarios for non-spherical particles in the atmosphere. A case of transported Saharan dust has a spectral dependence with a peak of 0.30 at 532 nm with smaller particle depolarization ratios of 0.27 and 0.25 at 1064 and 355 nm, respectively. A case of aerosol containing locally generated wind-blown North American dust has a maximum of 0.38 at 1064 nm, decreasing to 0.37 and 0.24 at 532 and 355 nm, respectively. The cause of the maximum at 1064 nm is inferred to be very large particles that have not settled out of the dust layer. The smoke layer has the opposite spectral dependence, with the peak of 0.24 at 355 nm, decreasing to 0.09 and 0.02 at 532 and 1064 nm, respectively. The depolarization in the smoke case may be explained by the presence of coated soot aggregates. We note that in these specific case studies, the linear particle depolarization ratio for smoke and dust-dominated aerosol are more similar at 355 nm than at 532 nm, having possible implications for using the particle depolarization ratio at a single wavelength for aerosol typing.
Biomass burning emissions of trace gases and particles in marine air at Cape Grim, Tasmania

Biomass burning (BB) plumes were measured at the Cape Grim Baseline Air Pollution Station during the 2006 Precursors to Particles campaign, when emissions from a fire on nearby Robbins Island impacted the station. Measurements made included non-methane organic compounds (NMOCs) (PTR-MS), particle number size distribution, condensation nuclei (CN) > 3 nm, black carbon (BC) concentration, cloud condensation nuclei (CCN) number, ozone (O3), methane (CH4), carbon monoxide (CO), hydrogen (H2), carbon dioxide (CO2), nitrous oxide (N2O), halocarbons and meteorology. During the first plume strike event (BB1), a 4 h enhancement of CO (max ~ 2100 ppb), BC (~ 1400 ng m-3) and particles > 3 nm (~ 13 000 cm-3) with dominant particle mode of 120 nm were observed overnight. A wind direction change lead to a dramatic reduction in BB tracers and a drop in the dominant particle mode to 50 nm. The dominant mode increased in size to 80 nm over 5 h in calm sunny conditions, accompanied by an increase in ozone. Due to an enhancement in BC but not CO during particle growth, the presence of BB emissions during this period could not be confirmed. The ability of particles > 80 nm (CN80) to act as CCN at 0.5 % supersaturation was investigated. The ΔCCN / ΔCN80 ratio was lowest during the fresh BB plume (56 ± 8 %), higher during the particle growth period (77 ± 4 %) and higher still (104 ± 3 %) in background marine air. Particle size distributions indicate that changes to particle chemical composition, rather than particle size, are driving these changes. Hourly average CCN during both BB events were between 2000 and 5000 CCN cm-3, which were enhanced above typical background levels by a factor of 6–34, highlighting the dramatic impact BB plumes can have on CCN number in clean marine regions. During the 29 h of the second plume strike event (BB2) CO, BC and a range of NMOCs including acetonitrile and hydrogen cyanide (HCN) were clearly enhanced and some enhancements in O3 were observed (ΔO3 / ΔCO 0.001–0.074). A short-lived increase in NMOCs by a factor of 10 corresponded with a large CO enhancement, an increase of the NMOC / CO emission ratio (ER) by a factor of 2–4 and a halving of the BC / CO ratio. Rainfall on Robbins Island was observed by radar during this period which likely resulted in a lower fire combustion efficiency, and higher emission of compounds associated with smouldering. This highlights the importance of relatively minor meteorological events on BB emission ratios. Emission factors (EFs) were derived for a range of trace gases, some never before reported for Australian fires, (including hydrogen, phenol and toluene) using the carbon mass balance method. This provides a unique set of EFs for Australian coastal heathland fires. Methyl halide EFs were higher than EFs reported from other studies in Australia and the Northern Hemisphere which is likely due to high halogen content in vegetation on Robbins Island. This work demonstrates the substantial impact that BB plumes can have on the composition of marine air, and the significant changes that can occur as the plume interacts with terrestrial, aged urban and marine emission sources.
Insights into the growth of newly formed particles in a subtropical urban environment

The role of different chemical compounds, particularly organics, involved in the new particle formation (NPF) and its consequent growth are not fully understood. Therefore, this study was conducted to investigate the chemical composition of aerosol particles during NPF events in an urban subtropical environment. Aerosol chemical composition was measured along with particle number size distribution (PNSD) and several other air quality parameters at five sites across an urban subtropical environment. An Aerodyne compact Time-of-Flight Aerosol Mass Spectrometer (c-ToF-AMS) and a TSI Scanning Mobility Particle Sizer (SMPS) measured aerosol chemical composition (particles above 50 nm in vacuum aerodynamic diameter) and PNSD (particles within 9–414 nm in mobility diameter), respectively. Five NPF events, with growth rates in the range 3.3–4.6 nm, were detected at two of the sites. The NPF events happened on relatively warmer days with lower condensation sink (CS). Temporal percent fractions of organics increased after the particles grew enough to have a significant contribution to particle volume, while the mass fraction of ammonium and sulfate decreased. This uncovered the important role of organics in the growth of newly formed particles. Three organic markers, factors f43, f44 and f57, were calculated and the f44 vs. f43 trends were compared between nucleation and non-nucleation days. K-means cluster analysis was performed on f44 vs. f43 data and it was found that they follow different patterns on nucleation days compared to non-nucleation days, whereby f43 decreased for vehicle-emission-generated particles, while both f44 and f43 decreased for NPF-generated particles. It was found for the first time that vehicle-generated and newly formed particles cluster in different locations on f44 vs. f43 plot, and this finding can be potentially used as a tool for source apportionment of measured particles.