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We describe an estimation technique for biomass burning emissions in South America based on a combination of remote-sensing fire products and field observations, the Brazilian Biomass Burning Emission Model (3BEM). For each fire pixel detected by remote sensing, the mass of the emitted tracer is calculated based on field observations of fire properties related to the type of vegetation burning. The burnt area is estimated from the instantaneous fire size retrieved by remote sensing, when available, or from statistical properties of the burn scars. The sources are then spatially and temporally distributed and assimilated daily by the Coupled Aerosol and Tracer Transport model to the Brazilian developments on the Regional Atmospheric Modeling System (CATT-BRAMS) in order to perform the prognosis of related tracer concentrations. Three other biomass burning inventories, including GFEDv2 and EDGAR, are simultaneously used to compare the emission strength in terms of the resultant tracer distribution. We also assess the effect of using the daily time resolution of fire emissions by including runs with monthly-averaged emissions. We evaluate the performance of the model using the different emission estimation techniques by comparing the model results with direct measurements of carbon monoxide both near-surface and airborne, as well as remote sensing derived products. The model results obtained using the 3BEM methodology of estimation introduced in this paper show relatively good agreement with the direct measurements and MOPITT data product, suggesting the reliability of the model at local to regional scales.
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To better understand the size-segregated chemical composition of aged organic aerosols in the western North Pacific rim, day- and night-time aerosol samples were collected in Sapporo, Japan during summer 2005 using an Andersen impactor sampler with 5 size bins: <I>D<sub>p</sub></I><1.1, 1.1–2.0, 2.0–3.3, 3.3–7.0, >7.0 μm. Samples were analyzed for the molecular composition of dicarboxylic acids, ketoacids, α-dicarbonyls, and sugars, together with water-soluble organic carbon (WSOC), organic carbon (OC), elemental carbon (EC) and inorganic ions. Based on the analyses of backward trajectories and chemical tracers, we found that during the campaign, air masses arrived from Siberia (a biomass burning source region) on 8–9 August, from China (an anthropogenic source region) on 9–10 August, and from the East China Sea/Sea of Japan (a mixed source receptor region) on 10–11 August. Most of the diacids, ketoacids, dicarbonyls, levoglucosan, WSOC, and inorganic ions (i.e., SO<sub>4</sub><sup>2−</sup>, NH<sub>4</sub><sup>+</sup> and K<sup>+</sup>) were enriched in fine particles (PM<sub>1.1</sub>) whereas Ca<sup>2+</sup>, Mg<sup>2+</sup> and Cl<sup>−</sup> peaked in coarse sizes (>1.1 μm). Interestingly, OC, most sugar compounds and NO<sub>3</sub><sup>−</sup> showed bimodal distributions in fine and coarse modes. In PM<sub>1.1</sub>, diacids in biomass burning-influenced aerosols transported from Siberia (mean: 252 ng m<sup>−3</sup>) were more abundant than those in the aerosols originating from China (209 ng m<sup>−3</sup>) and ocean (142 ng m<sup>−3</sup>), whereas SO<sub>4</sub><sup>2−</sup> concentrations were highest in the aerosols from China (mean: 3970 ng m<sup>−3</sup>) followed by marine- (2950 ng m<sup>−3</sup>) and biomass burning-influenced (1980 ng m<sup>−3</sup>) aerosols. Higher loadings of WSOC (2430 ng m<sup>−3</sup>) and OC (4360 ng m<sup>−3</sup>) were found in the fine mode, where biomass-burning products such as levoglucosan are abundant. This paper presents a case study of long-range transported aerosols illustrating that biomass burning episodes in the Siberian region have a significant influence on the chemical composition of carbonaceous aerosols in the western North Pacific rim.
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We report the first measurements of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), a substitute for ozone depleting compounds, in air samples originating from remote regions of the atmosphere and present evidence for its accelerating growth. Observed mixing ratios ranged from below 0.01 ppt in deep firn air to 0.59 ppt in the current northern mid-latitudinal upper troposphere. Firn air samples collected in Greenland were used to reconstruct a history of atmospheric abundance. Year-on-year increases were deduced, with acceleration in the growth rate from 0.029 ppt per year in 2000 to 0.056 ppt per year in 2007. Upper tropospheric air samples provide evidence for a continuing growth until late 2009. Furthermore we calculated a stratospheric lifetime of 370 years from measurements of air samples collected on board high altitude aircraft and balloons. Emission estimates were determined from the reconstructed atmospheric trend and suggest that current "bottom-up" estimates of global emissions for 2005 are too high by a factor of three.
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Within the framework of the Natural Environment Research Council (NERC) Oxidant and Particle Photochemical Processes (OP3) project, a pulsed Doppler lidar was deployed for a 3 month period in the tropical rain forest of Borneo to remotely monitor vertical and horizontal transport, aerosol distributions and clouds in the lower levels of the atmosphere. The Doppler velocity measurements reported here directly observe the mixing process and it is suggested that this is the most appropriate methodology to use in analysing the dispersion of canopy sourced species into the lower atmosphere. These data are presented with a view to elucidating the scales and structures of the transport processes, which effect the chemical and particulate concentrations in and above the forest canopy, for applications in the parameterisation of climate models.
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Light absorption of fine particle (PM<sub>2.5</sub>) aqueous extracts between wavelengths of 200 and 800 nm were investigated from two data sets: 24-h Federal Reference Method (FRM) filter extracts from 15 Southeastern US monitoring sites over the year of 2007 (900 filters), and online measurements from a Particle-Into-Liquid Sampler deployed from July to mid-August 2009 in Atlanta, Georgia. Three main sources of soluble chromophores were identified: biomass burning, mobile source emissions, and compounds linked to secondary organic aerosol (SOA) formation. Absorption spectra of aerosol solutions from filter extracts were similar for different sources. Angstrom exponents were ~7±1 for biomass burning and non-biomass burning-impacted 24-h filter samples (delineated by a levoglucosan concentration of 50 ng m<sup>−3</sup>) at both rural and urban sites. The absorption coefficient from measurements averaged between wavelength 360 and 370 nm (Abs<sub>365</sub>, in units m<sup>−1</sup>) was used as a measure of overall brown carbon light absorption. Biomass-burning-impacted samples were highest during winter months and Abs<sub>365</sub> was correlated with levoglucosan at all sites. During periods of little biomass burning in summer, light absorbing compounds were still ubiquitous and correlated with fine particle Water-Soluble Organic Carbon (WSOC), but comprised a much smaller fraction of the WSOC, where Abs<sub>365</sub>/WSOC (i.e., mass absorption efficiency) was typically ~3 times higher in biomass burning-impacted samples. Factor analysis attributed 50% of the yearly average Abs<sub>365</sub> to biomass burning sources. Brown carbon from primary urban emissions (mobile sources) was also observed and accounted for ~10% of the regional yearly average Abs<sub>365</sub>. Summertime diurnal profiles of Abs<sub>365</sub> and WSOC showed that morning to midday increases in WSOC from photochemical production were associated with a decrease in Abs<sub>365</sub>/WSOC. After noon, this ratio substantially increased, indicating that either some fraction of the non-light absorbing fresh SOA was rapidly (within hours) converted to chromophores heterogeneously, or that SOA from gas-particle partitioning later in the day was more light-absorbing. Factor analysis on the 24-h integrated filter data associated ~20 to 30% of Abs<sub>365</sub> over 2007 with a secondary source that was highest in summer and also the main source for oxalate, suggesting that aqueous phase reactions may account for the light-absorbing fraction of WSOC observed throughout the Southeastern US in summer.
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This paper provides an up-to-date assessment of global mercury emissions from anthropogenic and natural sources. On an annual basis, natural sources account for 5207 Mg of mercury released to the global atmosphere, including the contribution from re-emission processes, which are emissions of previously deposited mercury originating from anthropogenic and natural sources, and primary emissions from natural reservoirs. Anthropogenic sources, which include a large number of industrial point sources, are estimated to account for 2320 Mg of mercury emitted annually. The major contributions are from fossil-fuel fired power plants (810 Mg yr<sup>−1</sup>), artisanal small scale gold mining (400 Mg yr<sup>−1</sup>), non-ferrous metals manufacturing (310 Mg yr<sup>−1</sup>), cement production (236 Mg yr<sup>−1</sup>), waste disposal (187 Mg yr<sup>−1</sup>) and caustic soda production (163 Mg yr<sup>−1</sup>). Therefore, our current estimate of global mercury emissions suggests that the overall contribution from natural sources (primary emissions + re-emissions) and anthropogenic sources is nearly 7527 Mg per year, the uncertainty associated with these estimates are related to the typology of emission sources and source regions.
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The effect of wind speed on aerosol optical depth (AOD) at 0.55 μm over remote ocean regions is investigated. Remote ocean regions are defined by the combination of AOD from satellite observation and wind direction from ECMWF. According to our definition, many ocean regions cannot be taken as remote ocean regions due to long-range transportation of aerosol from continents. Highly correlated linear relationships are found in remote ocean regions with a wind speed range of 0–20 ms<sup>−1</sup>. The enhancement of AOD at high wind speed is explained as the increase of sea salt aerosol production.
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In conjunction with hosting the 2008 Beijing Olympics, the municipal government implemented a series of stringent air quality control measures. To assess the impacts on variation of ambient non-methane hydrocarbons (NMHCs), the whole air was sampled by canisters at one urban site and two suburban sites in Beijing, and 55 NMHC species were quantified by gas chromatography equipped with a quadrupole mass spectrometer and a flame ionization detector (GC/MSD/FID) as parts of the field Campaign for the Beijing Olympic Games Air Quality program (CareBeijing). According to the control measures, the data were presented according to four periods: 18–30 June, 8–19 July, 15–24 August (during the Olympic Games), and 6–15 September (during the Paralympic Games). Compared with the levels in June, the mixing ratios of NMHCs obtained in the Olympic and Paralympic Games periods were reduced by 35% and 25%, respectively. Source contributions were calculated using a chemical mass balance model (CMB 8.2). After implementing the control measures, emissions from target sources were obviously reduced, and reductions in vehicle exhaust could explain 48–82% of the reductions of ambient NMHCs. Reductions in emissions from gasoline evaporation, paint and solvent use, and the chemical industry contributed 9–40%, 3–24%, and 1–5%, respectively, to reductions of ambient NMHCs. Sources of liquefied petroleum gas (LPG) and biogenic emissions were not controlled, and contributions from these sources from July to September were stable or even higher than in June. Ozone formation potentials (OFPs) were calculated for the measured NMHCs. The total OFPs during the Olympic and Paralympic Games were reduced by 48% and 32%, respectively, compared with values in June. Reductions in the OFPs of alkenes and aromatics explained 77–92% of total OFP reductions. The alkenes and aromatics were mainly from vehicle exhausts, and reductions of vehicle exhaust gases explained 67–87% of reductions in alkenes and 38–80% of reductions in aromatics. These findings demonstrate the effectiveness of the air quality control measures enacted for the 2008 Olympics and indicate that controlling vehicular emissions could be the most important measure to improve air quality in Beijing.
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We have investigated the thermodynamic properties of four aliphatic oxo-dicarboyxlic acids identified or thought to be present in atmospheric particulate matter: oxosuccinic acid, 2-oxoglutaric acid, 3-oxoglutaric acid, and 4-oxopimelic acid. The compounds were characterized in terms of their cloud condensation nuclei (CCN) activity, vapor pressure, density, and tendency to decarboxylate in aqueous solution. We deployed a variety of experimental techniques and instruments: a CCN counter, a Tandem Differential Mobililty Analyzer (TDMA) coupled with a laminar flow-tube, and liquid chromatography/mass spectrometry (LC/MS). The presence of the oxo functional group in the α-position causes the vapor pressure of the compounds to diminish by an order of magnitude with respect to the parent dicarboxylic acid, while the CCN activity is similar or increased. Dicarboxylic acids with an oxo-group in the β-position decarboxylate in aqueous solution. We studied the effects of this process on our measurements and findings.
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Intense anthropogenic emissions over the Indian sub-continent lead to the formation of layers of particulate pollution that can be transported to the high altitude regions of the Himalaya-Hindu-Kush (HKH). Aerosol particles contain a substantial fraction of strongly absorbing material, including black carbon (BC), organic compounds (OC), and dust all of which can contribute to atmospheric warming, in addition to greenhouse gases. Using a 3-year record of continuous measurements of aerosol optical properties, we present a time series of key climate relevant aerosol properties including the aerosol absorption (σ<sub>ap</sub>) and scattering (σ<sub>sp</sub>) coefficients as well as the single-scattering albedo (<i>w</i><sub>0</sub>). Results of this investigation show substantial seasonal variability of these properties, with long range transport during the pre- and post-monsoon seasons and efficient precipitation scavenging of aerosol particles during the monsoon season. The monthly averaged scattering coefficients range from 0.1 Mm<sup>−1</sup> (monsoon) to 20 Mm<sup>−1</sup> while the average absorption coefficients range from 0.5 Mm<sup>−1</sup> to 3.5 Mm<sup>−1</sup>. Both have their maximum values during the pre-monsoon period (April) and reach a minimum during Monsoon (July–August). This leads to dry <i>w</i><sub>0</sub> values from 0.86 (pre-monsoon) to 0.79 (monsoon) seasons. Significant diurnal variability due to valley wind circulation is also reported. Using aerosol optical depth (AOD) measurements, we calculated the resulting direct local radiative forcing due to aerosols for selected air mass cases. We found that the presence of absorbing particulate material can locally induce an additional top of the atmosphere (TOA) forcing of 10 to 20 W m<sup>−2</sup> for the first atmospheric layer (500 m above surface). The TOA positive forcing depends on the presence of snow at the surface, and takes place preferentially during episodes of regional pollution occurring on a very regular basis in the Himalayan valleys. Warming of the first atmospheric layer is paralleled by a substantial decrease of the amount of radiation reaching the surface. The surface forcing is estimated to range from −4 to −20 W m<sup>−2</sup> for small-scale regional pollution events and large-scale pollution events, respectively. The calculated surface forcing is also very dependent on surface albedo, with maximum values occurring over a snow-covered surface. Overall, this work presents the first estimates of aerosol direct radiative forcing over the high Himalaya based on in-situ aerosol measurements, and results suggest a TOA forcing significantly greater than the IPCC reported values for green house gases.
