The radiative properties of soot particles depend on their morphology and mixing state, but their evolution during transport is still elusive. Here we report observations from an electron microscopy analysis of individual particles transported in the free troposphere over long distances to the remote Pico Mountain Observatory in the Azores in the North Atlantic. Approximately 70% of the soot particles were highly compact and of those 26% were thinly coated. Discrete dipole approximation simulations indicate that this compaction results in an increase in soot single scattering albedo by a factor of ≤2.17. The top of the atmosphere direct radiative forcing is typically smaller for highly compact than mass-equivalent lacy soot. The forcing estimated using Mie theory is within 12% of the forcing estimated using the discrete dipole approximation for a high surface albedo, implying that Mie calculations may provide a reasonable approximation for compact soot above remote marine clouds.

Abstract. According to recent studies, internal mixing of black carbon (BC) with other aerosol materials in the atmosphere alters its aggregate shape, absorption of solar radiation, and radiative forcing. These mixing state effects are not yet fully understood. In this study, we characterize the morphology and mixing state of bare BC and BC internally mixed with sodium chloride (NaCl) using electron microscopy and examine the sensitivity of optical properties to BC mixing state and aggregate morphology using a discrete dipole approximation model (DDSCAT). DDSCAT is flexible in simulating the geometry and refractive index of particle aggregates. DDSCAT predicts a higher mass absorption coefficient (MAC), lower single scattering albedo (SSA), and higher absorption Angstrom exponent (AAE) for bare BC aggregates that are lacy rather than compact. Predicted values of SSA at 550 nm range between 0.16 and 0.27 for lacy and compact aggregates, respectively, in agreement with reported experimental values of 0.25 ± 0.05. The variation in absorption with wavelength does not adhere precisely to a power law relationship over the 200 to 1000 nm range. Consequently, AAE values depend on the wavelength region over which they are computed. The MAC of BC (averaged over the 200–1000 nm range) is amplified when internally mixed with NaCl (100–300 nm in radius) by factors ranging from 1.0 for lacy BC aggregates partially immersed in NaCl to 2.2 for compact BC aggregates fully immersed in NaCl. The SSA of BC internally mixed with NaCl is higher than for bare BC and increases with the embedding in the NaCl. Internally mixed BC SSA values decrease in the 200–400 nm wavelength range, a feature also common to the optical properties of dust and organics. Linear polarization features are also predicted in DDSCAT and are dependent on particle size and morphology. This study shows that DDSCAT predicts complex morphology and mixing state dependent aerosol optical properties that have been reported previously and are relevant to radiative transfer, climate modeling, and interpretation of remote sensing measurements.

[1] There is a worldwide tendency to replace Dobson spectrophotometers in groundbased total ozone (TOZ) measurements by more advanced Brewer spectrophotometers. Ensuring the homogeneity of these data sets is of utmost importance if changes in TOZ of a few percent over long time periods are to be diagnosed accurately. Previous studies have identified a seasonal bias of a few percent between midlatitude Brewer and Dobson measurements. At Arosa (Switzerland), two Dobson and three Brewer instruments have been colocated since 1998, providing a unique data set of quasi-simultaneous observations, invaluable to study systematic differences between these measurements. The differences are partially attributed to the seasonal variability in atmospheric temperatures and ozone slant paths (OSP). The sensitivity to the temperature dependence of the ozone absorption cross section is calculated for each operational Brewer spectrophotometers at Arosa by using different high-and low-resolution reference spectra appropriately weighted with the instruments' slit functions, whereas the information on the primary standard instruments is used for all the Dobson instruments. The Brewer retrieval algorithm reveals a higher sensitivity to the reference spectra applied than the Dobson. When adopting the Bass and Paur (1985) or Malicet et al. (1995) ozone absorption spectra with their specific temperature dependence, and correcting for the OSP effect, the seasonal bias between Dobson and Brewer TOZ measurements is reduced to 0.6%. Conversely, these differences increase when using the spectral data of Burrows et al. (1999). This finding illustrates that the accuracy of ground-based spectrophotometric TOZ measurements is limited by the uncertainty in the ozone cross sections measured by different internationally leading laboratories.

According to recent studies, internal mixing of black carbon (BC) with other aerosol materials in the atmosphere alters its aggregate shape, absorption of solar radiation, and radiative forcing. These mixing state effects are not yet fully understood. In this study, we characterize the morphology and mixing state of bare BC and BC internally mixed with sodium chloride (NaCl) using electron microscopy and examine the sensitivity of optical properties to BC mixing state and aggregate morphology using a discrete dipole approximation model (DDSCAT). DDSCAT predicts a higher mass absorption coefficient, lower single scattering albedo (SSA), and higher absorption Angstrom exponent (AAE) for bare BC aggregates that are lacy rather than compact. Predicted values of SSA at 550 nm range between 0.18 and 0.27 for lacy and compact aggregates, respectively, in agreement with reported experimental values of 0.25 ± 0.05. The variation in absorption with wavelength does not adhere precisely to a power law relationship over the 200 to 1000 nm range. Consequently, AAE values depend on the wavelength region over which they are computed. In the 300 to 550 nm range, AAE values ranged in this study from 0.70 for compact to 0.95 for lacy aggregates. The SSA of BC internally mixed with NaCl (100–300 nm in radius) is higher than for bare BC and increases with the embedding in the NaCl. Internally mixed BC SSA values decrease in the 200–400 nm wavelength range, a feature also common to the optical properties of dust and organics. Linear polarization features are also predicted in DDSCAT and are dependent on particle morphology. The bare BC (with a radius of 80 nm) presents in the linear polarization a bell shape feature, which is a characteristic of the Rayleigh regime (for particles smaller than the wavelength of incident radiation). When BC is internally mixed with NaCl (100–300 nm in radius), strong depolarization features for near-VIS incident radiation are evident, such as a decrease in the intensity and multiple modes at different angles corresponding to different mixing states. <br><br> DDSCAT, being flexible on the geometry and refractive index of the particle, can be used to study the effect of mixing state and complex morphology on optical properties of realistic BC aggregates. This study shows that DDSCAT predicts morphology and mixing state dependent optical properties that have been reported previously and are relevant to radiative transfer and climate modeling and interpretation of remote sensing measurements

Abstract.A physicochemical characterization, including aerosol number size distribution, chemical composition and mass concentrations, of the urban fine aerosol captured in MILAN, BARCELONA and LONDON is presented in this article. The objective is to obtain a comprehensive picture of the microphysical processes involved in aerosol dynamics during the: 1) regular evolution of the urban aerosol (daily, weekly and seasonal basis) and in the day-to-day variations (from clean-air to pollution-events), and 2) the link between "aerosol chemistry and mass concentrations" with the "number size distribution".The mass concentrations of the fine PM 2.5 aerosol exhibit a high correlation with the number concentration of >100 nm particles N>100 (nm) ("accumulation mode particles") which only account for <20% of the total number concentration N of fine aerosols; but do not correlate with the number of <100 nm particles ("ultrafine particles"), which accounts for >80% of fine particles number concentration. Organic matter and black-carbon are the only aerosol components showing a significant correlation with the ultrafine particles, attributed to vehicles exhausts emissions; whereas ammonium-nitrate, ammonium-sulphate and also organic matter and black-carbon correlate with N>100 (nm) and attributed to condensation mechanisms, other parCorrespondence to: S. Rodríguez (srodriguez@inm.es) ticle growth processes and some primary emissions. Time series of the aerosol DpN diameter (dN/dlogD mode), mass PM 2.5 concentrations and number N>100 (nm) concentrations exhibit correlated day-to-day variations, which point to a significant involvement of condensation of semi-volatile compounds during urban pollution events. This agrees with the observation that ammonium-nitrate is the component exhibiting the highest increases from mid-to-high pollution episodes, when the highest DpN increases are observed. The results indicates that "fine PM 2.5 particles urban pollution events" tend to occur when condensation processes have made particles grow large enough to produce significant number concentrations of N>100 (nm) ("accumulation mode particles"). In contrast, because the low contribution of ultrafine particles to the fine aerosol mass concentrations, high "ultrafine particles N<100(nm) events" frequently occurs under low PM 2.5 conditions. The results of this study demonstrate that vehicles exhausts emissions are strongly involved in this ultrafine particles aerosol pollution.

[1] Dobson and Brewer spectrophotometers are the standard instruments for ground-based total ozone monitoring under the World Meteorological Organization's Global Atmosphere Watch program. Both types of instruments have been simultaneously used at Arosa station (Switzerland) since 1988; presently two Dobson and three Brewer instruments (one of which is type Mark III) are in operation. The large data set of quasi-simultaneous measurements (defined here as observations performed less than 10 min apart) allows for the determination of both inter-and intrainstrumental precision. The results for one standard deviation of total ozone are ±0.5% for Dobson standard wavelength pair observations and ±0.15% for Brewer total ozone measurements. To transform Dobson data into Brewer total ozone observations, empirical transfer functions are used to describe the observed difference in seasonal variations of total ozone data derived from the two types of instruments (amounting to a seasonal amplitude of approximately 2% with maximum deviation in winter). The statistical model (applied to quasisimultaneous measurements) includes the ozone effective temperature and the air mass multiplied by total ozone (ozone slant path) as explanatory variables; it removes the seasonal cycle in the difference and it allows the significance of the proxies introduced and systematic errors in the data to be determined. However, even when these transfer functions are applied, a 3% drift over about a 10 year period (1988)(1989)(1990)(1991)(1992)(1993)(1994)(1995)(1996)(1997)) between Arosa's Dobson and Brewer derived total ozone data series remains unexplained, adding to the model an aerosol proxy for which only part of the drift can be removed (related to the period 1992-1996).

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after evaporating the cloud droplets, are significantly more compact than freshly emitted and interstitial soot, confirming that cloud processing, not just exposure to high humidity, compacts soot. Our findings have implications for how the radiative, surface, and aerodynamic properties, and the fate of soot particles are represented in numerical models.

Freshly emitted soot particles are fractal-like aggregates, but atmospheric processes often transform their morphology. Morphology of soot particles plays an important role in determining their optical properties, life cycle and hence their effect on Earth's radiative balance. However, little is known about the morphology of soot particles that participated in cold cloud processes. Here we report results from laboratory experiments that simulate cold cloud processing of diesel soot particles by allowing them to form supercooled droplets and ice crystals at −20 and −40°C, respectively. Electron microscopy revealed that soot residuals from ice crystals were more compact (roundness ∼0.55) than those from supercooled droplets (roundness ∼0.45), while nascent soot particles were the least compact (roundness ∼0.41). Optical simulations using the discrete dipole approximation showed that the more compact structure enhances soot single scattering albedo by a factor up to 1.4, thereby reducing the top-of-the-atmosphere direct radiative forcing by ∼63%. These results underscore that climate models should consider the morphological evolution of soot particles due to cold cloud processing to improve the estimate of direct radiative forcing of soot.