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We quantify the hygroscopic properties of particles freshly emitted from biomass burning and after several hours of photochemical aging in a smog chamber. Values of the hygroscopicity parameter, κ, were calculated from cloud condensation nuclei (CCN) measurements of emissions from combustion of 12 biomass fuels commonly burned in North American wildfires. Prior to photochemical aging, the κ of the fresh primary aerosol varied widely, between 0.06 (weakly hygroscopic) and 0.6 (highly hygroscopic). The hygroscopicity of the primary aerosol was positively correlated with the inorganic mass fraction of the particles. Photochemical processing reduced the range of κ values to between 0.08 and 0.3. The changes in κ were driven by the photochemical production of secondary organic aerosol (SOA). SOA also contributed to growth of particles formed during nucleation events. Analysis of the nucleation mode particles enabled the first direct quantification of the hygroscopicity parameter κ for biomass burning SOA, which was on average 0.11, similar to values observed for biogenic SOA. Although initial CCN activity of biomass burning aerosol emissions are highly variable, after a few hours of photochemical processing κ converges to a value of 0.2 ± 0.1. Therefore, photochemical aging reduces the variability of biomass burning CCN κ, which should simplify analysis of the potential effects of biomass burning aerosol on climate.
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The gas-phase oxidation of α-pinene produces a large amount of secondary organic aerosol (SOA) in the atmosphere. A number of carboxylic acids, organosulfates and nitrooxy organosulfates associated with α-pinene have been found in field samples and some are used as tracers of α-pinene oxidation. α-pinene reacts readily with OH and O<sub>3</sub> in the atmosphere followed by reactions with both HO<sub>2</sub> and NO. Due to the large number of potential reaction pathways, it can be difficult to determine what conditions lead to SOA. To better understand the SOA yield and chemical composition from low- and high-NO<sub>x</sub> OH oxidation of α-pinene, studies were conducted in the Caltech atmospheric chamber under controlled chemical conditions. Experiments used low O<sub>3</sub> concentrations to ensure that OH was the main oxidant and low α-pinene concentrations such that the peroxy radical (RO<sub>2</sub>) reacted primarily with either HO<sub>2</sub> under low-NO<sub>x</sub> conditions or NO under high-NO<sub>x</sub> conditions. SOA yield was suppressed under conditions of high-NO<sub>x</sub>. SOA yield under high-NO<sub>x</sub> conditions was greater when ammonium sulfate/sulfuric acid seed particles (highly acidic) were present prior to the onset of growth than when ammonium sulfate seed particles (mildly acidic) were present; this dependence was not observed under low-NO<sub>x</sub> conditions. When aerosol seed particles were introduced after OH oxidation, allowing for later generation species to be exposed to fresh inorganic seed particles, a number of low-NO<sub>x</sub> products partitioned to the highly acidic aerosol. This indicates that the effect of seed acidity and SOA yield might be under-estimated in traditional experiments where aerosol seed particles are introduced prior to oxidation. We also identify the presence of a number of carboxylic acids that are used as tracer compounds of α-pinene oxidation in the field as well as the formation of organosulfates and nitrooxy organosulfates. A number of the carboxylic acids were observed under all conditions, however, pinic and pinonic acid were only observed under low-NO<sub>x</sub> conditions. Evidence is provided for particle-phase sulfate esterification of multi-functional alcohols.
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Ozone data retrieved in the Arctic region from infrared radiance spectra recorded by the Infrared Atmospheric Sounding Interferometer (IASI) on board the MetOp-A European satellite are presented. They are compared with in situ and lidar observations obtained during a series of aircraft measurement campaigns as part of the International Polar Year POLARCAT activities in spring and summer 2008. Different air masses were sampled during the campaigns including clean air, polluted plumes originating from anthropogenic sources, forest fire plumes from the three northern continents, and stratospheric-influenced air masses. The comparison between IASI O<sub>3</sub> [0–8 km], [0–12 km] partial columns and profiles with collocated aircraft observations is achieved by taking into account the different sensitivity and geometry of the sounding instruments. A detailed analysis is provided and the agreement is discussed in terms of vertical sensitivity and surface properties at the location of the observations. Overall, IASI O<sub>3</sub> profiles are found to be in relatively good agreement with smoothed in situ and lidar profiles in the free troposphere with differences of less than 40% (25% over sea for both seasons) and 10%, respectively. The correlation between IASI O<sub>3</sub> retrieved partial columns and the smoothed aircraft partial columns is good with DC-8 in situ data in spring over North America (<i>r</i> = 0.68), and over Greenland with ATR-42 lidar measurements in summer (<i>r</i> = 0.67). Correlations with other data are less significant highlighting the difficulty of IASI to capture precisely the O<sub>3</sub> variability in the Arctic upper troposphere and lower stratosphere (UTLS). This is particularly noted in comparison with the [0–12 km] partial columns. The IASI [0–8 km] partial columns display a low negative bias (by less than 26% over snow) compared to columns derived from in situ measurements. Despite the relatively high biases of the IASI retrievals in the Arctic UTLS, our analysis shows that IASI can be used to identify, using O<sub>3</sub> / CO ratios, stratospheric intrusions.
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The global distribution of dust column burden derived from MODIS Deep Blue aerosol products is compared to NH<sub>3</sub> column burden retrieved from IASI infrared spectra. We found similarities in their spatial distributions, in particular their hot spots are often collocated over croplands and to a lesser extent pastures. Globally, we found 22% of dust burden collocated with NH<sub>3</sub>, with only 1% difference between land-use databases. This confirms the importance of anthropogenic dust from agriculture. Regionally, the Indian subcontinent has the highest amount of dust mixed with NH<sub>3</sub> (26%), mostly over cropland and during the pre-monsoon season. North Africa represents 50% of total dust burden but accounts for only 4% of mixed dust, which is found over croplands and pastures in Sahel and the coastal region of the Mediterranean. In order to evaluate the radiative effect of this mixing on dust optical properties, we derive the mass extinction efficiency for various mixtures of dust and NH<sub>3</sub>, using AERONET sunphotometers data. We found that for dusty days the coarse mode mass extinction efficiency decreases from 0.62 to 0.48 m<sup>2</sup> g<sup>−1</sup> as NH<sub>3</sub> burden increases from 0 to 40 mg m<sup>−2</sup>. The fine mode extinction efficiency, ranging from 4 to 16 m<sup>2</sup> g<sup>−1</sup>, does not appear to depend on NH<sub>3</sub> concentration or relative humidity but rather on mineralogical composition and mixing with other aerosols. Our results imply that a significant amount of dust is already mixed with ammonium salt before its long range transport. This in turn will affect dust lifetime, and its interactions with radiation and cloud properties.
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In addition to its mass concentration, the health effects of urban particulate matter may depend on its particle size distribution and chemical composition. Yet air pollution regulations rely on exclusively bulk PM<sub>10</sub> concentration measurements, without regard to their potentially different health effects under different conditions. Aerosols from various sources are well known to contain a plethora of toxic, carcinogenic, mutagenic or teratogenic constituents such as heavy metals and polycyclic aromatic hydrocarbons. Extensive public health studies established the link between mass concentrations of PM<sub>2.5</sub> / PM<sub>10</sub> and health problems within the population. However, little is known about the relative importance of PM from different sources and the effect of seasonality on the toxicity. Here we present the application of a simple and sensitive method for the direct assessment of the overall ecotoxicity of various PM<sub>2.5</sub> / PM<sub>10</sub> samples collected on filters. The method is based on the <i>Vibrio fischeri</i> bioluminescence inhibition bioassay that has been standardized for solid samples, representing a relevant biological exposure route. Direct emission samples proved to be significantly more ecotoxic than photochemically processed aerosol, thus marked differences were observed between the ecotoxicities of urban PM<sub>10</sub> in summer and winter. These effects of urban PM<sub>10</sub> may be useful supplementary indicators besides the mass concentrations of PM<sub>2.5</sub> / PM<sub>10</sub> in cities.
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The distribution of gaseous elemental mercury (GEM) was determined in the surface atmosphere of the northern South China Sea (SCS) during 12 SEATS cruises between May 2003 and December 2005. The sampling and analysis of GEM were performed on board ship by using an on-line mercury analyzer (GEMA). Distinct annual patterns were observed for the GEM with a winter maximum of 5.7 ± 0.2 ng m<sup>−3</sup> (<i>n</i> = 3) and minimum in summer (2.8 ± 0.2; <i>n</i> = 3), with concentrations elevated 2–3 times global background values. Source tracking through backward air trajectory analysis demonstrated that during the northeast monsoon (winter), air masses came from Eurasia, bringing continental- and industrial-derived GEM to the SCS. In contrast, during summer southwest monsoon and inter-monsoon, air masses were from the Indochina Peninsula and Indian Ocean and west Pacific Ocean. This demonstrates the impact that long-range transport, as controlled by seasonal monsoons, has on the Hg atmospheric distribution and cycling in the SCS.
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Observations and models have shown that continuously degassing volcanoes have a potentially large effect on the natural background aerosol loading and the radiative state of the atmosphere. We use a global aerosol microphysics model to quantify the impact of these volcanic emissions on the cloud albedo radiative forcing under pre-industrial (PI) and present-day (PD) conditions. We find that volcanic degassing increases global annual mean cloud droplet number concentrations by 40% under PI conditions, but by only 10% under PD conditions. Consequently, volcanic degassing causes a global annual mean cloud albedo effect of −1.06 W m<sup>−2</sup> in the PI era but only −0.56 W m<sup>−2</sup> in the PD era. This non-equal effect is explained partly by the lower background aerosol concentrations in the PI era, but also because more aerosol particles are produced per unit of volcanic sulphur emission in the PI atmosphere. The higher sensitivity of the PI atmosphere to volcanic emissions has an important consequence for the anthropogenic cloud radiative forcing because the large uncertainty in volcanic emissions translates into an uncertainty in the PI baseline cloud radiative state. Assuming a −50/+100% uncertainty range in the volcanic sulphur flux, we estimate the annual mean anthropogenic cloud albedo forcing to lie between −1.16 W m<sup>−2</sup> and −0.86 W m<sup>−2</sup>. Therefore, the volcanically induced uncertainty in the PI baseline cloud radiative state substantially adds to the already large uncertainty in the magnitude of the indirect radiative forcing of climate.
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We investigated the ice nucleating properties of mineral dust particles to understand the sensitivity of simulated cloud properties to two different representations of contact angle in the Classical Nucleation Theory (CNT). These contact angle representations are based on two sets of laboratory deposition ice nucleation measurements: Arizona Test Dust (ATD) particles of 100, 300 and 500 nm sizes were tested at three different temperatures (−25, −30 and −35 °C), and 400 nm ATD and kaolinite dust species were tested at two different temperatures (−30 and −35 °C). These measurements were used to derive the onset relative humidity with respect to ice (RH<sub>ice</sub>) required to activate 1% of dust particles as ice nuclei, from which the onset single contact angles were then calculated based on CNT. For the probability density function (PDF) representation, parameters of the log-normal contact angle distribution were determined by fitting CNT-predicted activated fraction to the measurements at different RH<sub>ice</sub>. Results show that onset single contact angles vary from ~18 to 24 degrees, while the PDF parameters are sensitive to the measurement conditions (i.e. temperature and dust size). Cloud modeling simulations were performed to understand the sensitivity of cloud properties (i.e. ice number concentration, ice water content, and cloud initiation times) to the representation of contact angle and PDF distribution parameters. The model simulations show that cloud properties are sensitive to onset single contact angles and PDF distribution parameters. The comparison of our experimental results with other studies shows that under similar measurement conditions the onset single contact angles are consistent within ±2.0 degrees, while our derived PDF parameters have larger discrepancies.
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We develop a parameterization scheme of convective dust emission for regional and global atmospheric models. Convective dust emission occurs in the absence of saltation as large eddies intermittently produce strong shear stresses on the surface and entrain dust particles into the air. This dust emission mechanism has not been included in the traditional dust models. The scheme presented in this study is a new approach which takes account of the stochastic nature of convective dust emission. It consists of the statistical representations of soil particle size, inter-particle cohesion, and instantaneous surface shear stress. A method of determining the probability density function of the latter quantity is proposed. Dust emission is then estimated from the overlap of the probability density functions of the aerodynamic lifting and inter-particle cohesive forces. The new scheme is implemented into the WRF/Chem model and applied to dust modeling in the Taklimakan Desert. A comparison with lidar data shows that the model can reproduce the main features of the dust patterns and their diurnal variations. For the case studied, convective dust emission is typically several μg m<sup>−2</sup> s<sup>−1</sup> and at times up to 50 μg m<sup>−2</sup> s<sup>−1</sup>.
