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.