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Black carbon over Mexico: the effect of atmospheric transport on mixing state, mass absorption cross-section, and BC/CO ratios

A single particle soot photometer (SP2) was operated on the NCAR C-130 during the MIRAGE campaign (part of MILAGRO), sampling black carbon (BC) over Mexico. The highest BC concentrations were measured over Mexico City (sometimes as much as 2 μg/m3) and over hill-fires to the south of the city. The age of plumes outside of Mexico City was determined using a combination of HYSPLIT trajectories, WRF-FLEXPART modeling and CMET balloon tracks. As expected, older, diluted air masses had lower BC concentrations. A comparison of carbon monoxide (CO) and BC suggests a CO background of around 65 ppbv, and a background-corrected BC/COnet ratio of 2.89±0.89 (ng/m3-STP)/ppbv (average ± standard deviation). This ratio is similar for fresh emissions over Mexico City, as well as for aged airmasses. Comparison of light absorption measured with a particle soot absorption photometer (PSAP) and the SP2 BC suggests a BC mass-normalized absorption cross-section (MAC) of 10.9±2.1 m2/g at 660 nm (or 13.1 m2/g @ 550 nm, assuming MAC is inversely dependent on wavelength). This appears independent of aging and similar to the expected absorption cross-section for aged BC, but values, particularly in fresh emissions, could be biased high due to instrument artifacts. SP2-derived BC coating indicators show a prominent thinly-coated BC mode over the Mexico City Metropolitan Area (MCMA), while older air masses show both thinly-coated and thickly-coated BC. Some 2-day-old plumes do not show a prominent thickly-coated BC mode, possibly due to preferential wet scavenging of the likely-hydrophilic thickly-coated BC.
Stochastic fields method for sub-grid scale emission heterogeneity in mesoscale atmospheric dispersion models

The stochastic fields method for turbulent reacting flows has been applied to the issue of sub-grid scale emission heterogeneity in a mesoscale model. This method is a solution technique for the probability density function (PDF) transport equation and can be seen as a straightforward extension of currently used mesoscale dispersion models. It has been implemented in an existing mesoscale model and the results are compared with Large-Eddy Simulation (LES) data devised to test specifically the effect of sub-grid scale emission heterogeneity on boundary layer concentration fluctuations. The sub-grid scale emission variability is assimilated in the model as a PDF of the emissions. The stochastic fields method shows excellent agreement with the LES data without adjustment of the constants used in the mesoscale model. The stochastic fields method is a stochastic solution of the transport equations for the concentration PDF of dispersing scalars, therefore it possesses the ability to handle chemistry of any complexity without the need to introduce additional closures for the high order statistics of chemical species. This study shows for the first time the feasibility of applying this method to mesoscale chemical transport models.
Physical and optical properties of aerosols over an urban location in Spain: seasonal and diurnal variability

Measurements of aerosol optical properties and aerosol number size distribution obtained during the period from December 2005 to November 2007 at Granada, an urban site in south-eastern Spain, are analyzed. Large variations of the measured variables have been found, and related to variations in emissions sources and meteorological conditions. High values of aerosol absorption and scattering coefficients are obtained during winter and low values are measured during summer. This seasonal pattern in the surface aerosol optical properties is opposite to the seasonal cycle showed by columnar aerosol optical depth. The differences in the seasonal features of the surface and column-integrated data are related to seasonal variations in the aerosol vertical distribution, aerosol sources and boundary layer height. In winter the number density of "fine" particles (0.5<particle diameter<1 μm) is significantly larger than in summer while the number density of "coarse" particles (1<particle diameter<20 μm) is slightly larger during summer and spring than during winter and autumn. The scattering Angström exponent, αs, presents an evident seasonal cycle with values of 1.8±0.2, 1.6±0.3, 1.3±0.3 and 1.4±0.3 in winter, spring, summer and autumn, respectively. This suggests the presence of a large fraction of submicron particles at the site, especially during winter. The aerosols measured in this study contain a large fraction of absorbing material as indicated by the average single-scattering albedo that has values of 0.65±0.07, 0.66±0.06, 0.70±0.06 and 0.73±0.06 in autumn, winter, spring and summer, respectively. The aerosol scattering albedo obtained in the surface boundary layer of Granada is below the critical value of 0.86 that determines the shift from cooling to warming. These results put in evidence the need of efforts to reduce absorbing particles (black carbon) emissions to avoid the possible warming that would result from the reductions of the cooling aerosols only. The aerosol absorption and scattering coefficients present a clear diurnal pattern, in all seasons, with two local maxima, one early in the morning and the second one in the evening. This diurnal cycle is mainly attributed to the diurnal evolution of atmospheric boundary layer and local anthropogenic activities.
Simultaneous coastal measurements of ozone deposition fluxes and iodine-mediated particle emission fluxes with subsequent CCN formation

Here we present the first observations of simultaneous ozone deposition fluxes and ultrafine particle emission fluxes over an extensive infra-littoral zone. Fluxes were measured by the eddy covariance technique at the Station Biologique de Roscoff, on the coast of Brittany, north-west France. This site overlooks a very wide (3 km) littoral zone controlled by very deep tides (9.6 m) exposing extensive macroalgae beds available for significant iodine mediated photochemical production of ultrafine particles. The aspect at the Station Biologique de Roscoff provides an extensive and relatively flat, uniform fetch within which micrometeorological techniques may be utilized to study links between ozone deposition to macroalgae (and sea water) and ultrafine particle production. Ozone deposition to seawater at high tide was significantly slower (vd[O3]=0.302±0.095 mm s−1) than low tidal deposition. A statistically significant difference in the deposition velocities to macroalgae at low tide was observed between night time (vd[O3]=1.00±0.10 mm s−1) and daytime (vd[O3]=2.05±0.16 mm s−1) when ultrafine particle formation results in apparent particle emission. Very high emission fluxes of ultrafine particles were observed during daytime periods at low tides ranging from 50 000 particles cm−2 s−1 to greater than 200 000 particles cm−2 s−1 during some of the lowest tides. These emission fluxes exhibited a significant relationship with particle number concentrations comparable with previous observations at another location. Apparent particle growth rates were estimated to be in the range 17–150 nm h−1 for particles in the size range 3–10 nm. Under certain conditions, particle growth may be inferred to continue to greater than 120 nm over tens of hours; sizes at which they may readily behave as cloud condensation nuclei (CCN) under reasonable supersaturations that may be expected to pertain at the top of the marine boundary layer. These results link direct depositional loss and photochemical destruction of ozone to the formation of particles and hence CCN from macroalgal emissions at a coastal location.
Slower CCN growth kinetics of anthropogenic aerosol compared to biogenic aerosol observed at a rural site

Growth rates of water droplets were measured with a static diffusion cloud condensation chamber in May–June 2007 at a rural field site in Southern Ontario, Canada, 70 km north of Toronto. The observations include periods when the winds were from the south and the site was impacted by anthropogenic air from the U.S. and Southern Ontario as well as during a 5-day period of northerly wind flow when the aerosol was dominated by biogenic sources. The growth of droplets on anthropogenic size-selected particles centred at 0.1 μm diameter and composed of approximately 40% organic and 60% ammonium sulphate (AS) by mass, was delayed by on the order of 1 s compared to a pure AS aerosol. Simulations of the growth rate on monodisperse particles indicate that a lowering of the water mass accommodation coefficient from αc=1 to an average of αc=0.04 is needed (assuming an insoluble organic with hygroscopicity parameter, κorg, of zero). Simulations of the initial growth rate on polydisperse anthropogenic particles agree best with observations for αc=0.07. In contrast, the growth rate of droplets on size-selected aerosol of biogenic character, consisting of >80% organic, was similar to that of pure AS. Simulations of the predominantly biogenic polydisperse aerosol show agreement between the observations and simulations when κorg=0.2 (with upper and lower limits of 0.5 and 0.07, respectively) and αc=1. Inhibition of water uptake by the anthropogenic organic applied to an adiabatic cloud parcel model in the form of a constant low αc increases the number of droplets in a cloud compared to pure AS. If the αc is assumed to increase with increasing liquid water on the droplets, then the number of droplets decreases which could diminish the indirect climate forcing effect. The slightly lower κorg in the biogenic case decreases the number of droplets in a cloud compared to pure AS.
Technical Note: Ensuring consistent, global measurements of very short-lived halocarbon gases in the ocean and atmosphere

Very short-lived halocarbons are significant sources of reactive halogen in the marine boundary layer, and likely in the upper troposphere and lower stratosphere. Quantifying ambient concentrations in the surface ocean and atmosphere is essential for understanding the atmospheric impact of these trace gas fluxes. Despite the body of literature increasing substantially over recent years, calibration issues complicate the comparison of results and limit the utility of building larger-scale databases that would enable further development of the science (e.g. sea-air flux quantification, model validation, etc.). With this in mind, thirty-one scientists from both atmospheric and oceanic halocarbon communities in eight nations gathered in London in February 2008 to discuss the scientific issues and plan an international effort toward developing common calibration scales (<a href="http://tinyurl.com/c9cg58"target="_blank">http://tinyurl.com/c9cg58</a>). Here, we discuss the outputs from this meeting, suggest the compounds that should be targeted initially, identify opportunities for beginning calibration and comparison efforts, and make recommendations for ways to improve the comparability of previous and future measurements.
Aerosol Single Scattering Albedo retrieval in the UV range: an application to OMI satellite validation

The aerosol Single Scattering Albedo (SSA) and Absorbing Aerosol Optical Depth (AAOD) at 320.1 nm are derived at Rome site by the comparison between Brewer and modelled spectra. The UVSPEC radiative transfer model is used to calculate the UV irradiances for different SSA values, taking into account as input data total ozone and Aerosol Optical Depth (AOD) obtained from Brewer spectral measurements. The accuracy in determining SSA depends on the aerosol amount and on Solar Zenith Angle (SZA) value: SSA uncertainty increases when AOD and SZA decrease. The monthly mean values of SSA and AAOD during the period January 2005–June 2008 are analysed, showing a monthly and seasonal variability. It is found that the SSA and AAOD averages are 0.80±0.08 and 0.056±0.028, respectively. AAOD retrievals are also used to quantify the error in the Ozone Monitoring Instrument (OMI) surface UV products due to absorbing aerosols, not included in the current OMI UV algorithm. OMI and Brewer UV irradiances at 324.1 nm and Erythemal Dose Rates (EDRs) under clear sky conditions, are compared as a function of AAOD. Three methods are considered to investigate on the applicability of an absorbing aerosol correction on OMI UV data at Rome site. Depending on the correction methodology, the bias value decreases from 18% to 2% for spectral irradiance at 324.1 nm and from 25% to 8% for EDR.
More evidence for very short-lived substance contribution to stratospheric chlorine inferred from HCl balloon-borne in situ measurements in the tropics

Volume mixing ratio (vmr) vertical profiles of hydrogen chloride (HCl) are retrieved from in situ measurements performed by a balloon-borne infrared tunable diode laser absorption spectrometer (SPIRALE) during two balloon flights in the tropics (Teresina, Brazil, 5.1° S–42.9° W) in June 2005 and June 2008. HCl vertical profiles obtained from 15 to 31 km are presented and analysed to estimate the contribution of very short-lived substances (VSLS) to total stratospheric chlorine. Both retrieved vertical profiles of HCl from these flights agree very well with each other, with estimated overall uncertainties of 6% on vmr between 23 and 31 km. Upper limits of HCl vmr as low as 20 pptv in June 2008 and 30 pptv in June 2005 are inferred in the upper part of the tropical tropopause layer (TTL). Backward trajectory calculations and such low amounts suggest that the air masses sampled correspond to typical background conditions, i.e. neither influenced by recent tropospheric nor stratospheric air. Taking into account the recently reported VSL source gas measurements obtained in similar conditions (Laube et al., 2008) and the main intermediate degradation product gas COCl2 (Fu et al., 2007), a total VSLS contribution of 85±40 pptv to stratospheric chlorine is inferred. This refines the WMO (2007) estimation of 50 to 100 pptv, which was not taking into account any HCl contribution. In addition, comparisons of HCl measurements between SPIRALE and the Aura MLS satellite instrument in the tropical lower and middle stratosphere lead to a very good agreement. The previous agreement between MLS-deduced upper stratospheric total chlorine content and modelled values including 100 pptv of VSLS (Froidevaux et al., 2006) is thus supported by our present result about the VSLS contribution.
The impact of dust on sulfate aerosol, CN and CCN during an East Asian dust storm

A global model of aerosol microphysics is used to simulate a large East Asian dust storm during the ACE-Asia experiment. We use the model together with size resolved measurements of aerosol number concentration and composition to examine how dust modified the production of sulfate aerosol and the particle size distribution in East Asian outflow. Simulated size distributions and mass concentrations of dust, sub- and super-micron sulfate agree well with observations from the C-130 aircraft. Modeled mass concentrations of fine sulfate (Dp<1.3 μm) decrease by ~10% due to uptake of sulfur species onto super-micron dust. We estimate that dust enhanced the mass concentration of coarse sulfate (Dp>1.0 μm) by more than an order of magnitude, but total sulfate concentrations increase by less than 2% because decreases in fine sulfate have a compensating effect. Our analysis shows that the sulfate associated with dust can be explained largely by the uptake of H2SO4 rather than reaction of SO2 on the dust surface, which we assume is suppressed once the particles are coated in sulfate. We suggest that many previous model investigations significantly overestimated SO2 oxidation on East Asian dust, possibly due to the neglect of surface saturation effects. We extend previous model experiments by examining how dust modified existing particle concentrations in Asian outflow. Total particle concentrations (condensation nuclei, CN) modeled in the dust-pollution plume are reduced by up to 20%, but we predict that dust led to less than 10% depletion in particles large enough to act as cloud condensation nuclei (CCN). Our analysis suggests that E. Asian dust storms have only a minor impact on sulfate particles present at climate-relevant sizes.
Single ice crystal measurements during nucleation experiments with the depolarization detector IODE

In order to determine the efficiency of different aerosol particles to nucleate ice, an Ice Optical DEpolarization detector (IODE) was developed to distinguish between water droplets and ice crystals in ice nucleation chambers. A laser beam polarized linearly (power: 50 mW, wavelength: 407 nm) is directed through the chamber. The scattered light intensity from particles is measured at a scattering angle of Θ=175° in both polarization components (parallel and perpendicular). The ratio between the perpendicular intensity over the total one yields the depolarization ratio δ. Single particle detection is possible, using a peak detection algorithm. For high particle concentrations, a real-time signal averaging method can also be run simultaneously. The IODE detector was used in connection with the Zurich ice nucleation chamber during the ICIS 2007 workshop where ice nucleation experiments were performed with several aerosol types. In presence of ice crystals, a depolarization ratio could be measured on a particle-by-particle basis. Mean values of δ ranged from 0.24 to 0.37 and agree well with theoretical calculations.