Sea spray is one of the largest natural aerosol sources and plays an important role in the Earth’s radiative budget. These particles are inherently hygroscopic, that is, they take-up moisture from the air, which affects the extent to which they interact with solar radiation. We demonstrate that the hygroscopic growth of inorganic sea salt is 8–15% lower than pure sodium chloride, most likely due to the presence of hydrates. We observe an increase in hygroscopic growth with decreasing particle size (for particle diameters <150 nm) that is independent of the particle generation method. We vary the hygroscopic growth of the inorganic sea salt within a general circulation model and show that a reduced hygroscopicity leads to a reduction in aerosol-radiation interactions, manifested by a latitudinal-dependent reduction of the aerosol optical depth by up to 15%, while cloud-related parameters are unaffected. We propose that a value of κ_s=1.1 (at RH=90%) is used to represent the hygroscopicity of inorganic sea salt particles in numerical models.

Knowledge of the optical properties of soot black carbon (BC) is required for the prediction of the radiative effects of freshly-emitted and aged BC particles. Here we review BC mass absorption cross section (MAC) and absorption function E(m) measurements, focussing on freshly-emitted BC. First, we review recently reported MACs at 550 nm wavelength as obtained from direct measurements of particulate absorption and mass concentration; we find an average of 8.0 ± 0.7 m²/g from ten measurements, not significantly higher (p > 0.26) than the widely used MAC of 7.5 ± 1.2 m²/g recommended by Bond and Bergstrom (2006). Second, we review recently reported E(m), whose retrieval is more complex due to the need to combine measurements with numerical models to estimate the contribution of scattering to extinction. Third, we review recent numerical studies that have aimed to predict the BC MAC using various complex refractive indices (m = n + ik). Most of these studies have used m = 1.95 + 0.79i recommended by Bond and Bergstrom (2006), yet failed to predict a MAC as high as 7.5 or 8.0 m²/g at 550 nm wavelength. Fourth, we summarize a selected range of alternative values of m that have been reported by recent studies and place them in the context of measurements using a contour plot of E(m) on the n–k plane. We show that the widely used m = 1.95 + 0.79i corresponds to an E(m) that is too low to be consistent with the measured MAC values. We conclude that the E(m) of BC in the visible and near infrared should be greater than 0.32, and that the commonly used BC models or the refractive index, or both, are still in need of improvement.

Heavy fuel oil (HFO) particulate matter (PM) emitted by marine engines is known to contain toxic heavy metals including vanadium (V) and nickel (Ni). The toxicity of such metals will depend on the their chemical state, size distribution, and mixing state. Using online soot-particle aerosol mass spectrometry (SP-AMS), we quantified the mass of five metals (V, Ni, Fe, Na, and Ba) in HFO-PM soot particles produced by a marine diesel research engine. The in-soot metal concentrations were compared to 25 in-PM 2.5 measurements by inductively-coupled plasma–optical-emission spectroscopy (ICP-OES). We found that < 3% of total PM 2.5 metals was associated with soot particles, which may still be sufficient to influence in-cylinder soot burnout rates. Since these metals were most likely present as oxides, whereas studies on lower-temperature boilers report a predominance of sulfates, this result implies that the toxicity of HFO PM depends on its combustion conditions. Finally, we observed a 4–25-fold enhancement in the ratio V:Ni in soot particles versus PM 2.5, indicating an enrichment of V in soot due to its lower nucleation/condensation temperature. 30 As this enrichment mechanism is not dependent on soot formation, V is expected to be generally enriched within smaller HFO-PM particles from marine engines, enhancing its toxicity.

Ship engines in the open ocean and Arctic typically combust heavy fuel oil (HFO), resulting in light-absorbing particulate matter (PM) emissions that have been attributed to black carbon (BC) and conventional, soluble brown carbon (brC). We show here that neither BC nor soluble brC is the major light-absorbing carbon (LAC) species in HFO-combustion PM. Instead, “tar brC” dominates. This tar brC, previously identified only in open-biomass-burning emissions, shares key defining properties with BC: it is insoluble, refractory, and substantially absorbs visible and near-infrared light. Relative to BC, tar brC has a higher Angstrom absorption exponent (AAE) (2.5–6, depending on the considered wavelengths), a moderately-high mass absorption efficiency (up to 50% of that of BC), and a lower ratio of sp²- to sp³-bonded carbon. Based on our results, we present a refined classification of atmospheric LAC into two sub-types of BC and two sub-types of brC. We apply this refined classification to demonstrate that common analytical techniques for BC must be interpreted with care when applied to tar-containing aerosols. The global significance of our results is indicated by field observations which suggest that tar brC already contributes to Arctic snow darkening, an effect which may be magnified over upcoming decades as Arctic shipping continues to intensify.

We investigate the optical properties of light-absorbing organic carbon (brown carbon) from domestic wood combustion as a function of simulated atmospheric aging. At shorter wavelengths (370–470 nm), light absorption by brown carbon from primary organic aerosol (POA) and secondary organic aerosol (SOA) formed during aging was around 10 % and 20 %, respectively, of the total aerosol absorption (brown carbon plus black carbon). The mass absorption cross section (MAC) determined for black carbon (BC, 13.7 m² g⁻¹ at 370 nm, with geometric standard deviation GSD =1.1) was consistent with that recommended by Bond et al. (2006). The corresponding MAC of POA (5.5 m² g⁻¹; GSD =1.2) was higher than that of SOA (2.4 m² g⁻¹; GSD =1.3) at 370 nm. However, SOA presents a substantial mass fraction, with a measured average SOA ∕ POA mass ratio after aging of ∼5 and therefore contributes significantly to the overall light absorption, highlighting the importance of wood-combustion SOA as a source of atmospheric brown carbon. The wavelength dependence of POA and SOA light absorption between 370 and 660 nm is well described with absorption Ångström exponents of 4.6 and 5.6, respectively. UV-visible absorbance measurements of water and methanol-extracted OA were also performed, showing that the majority of the light-absorbing OA is water insoluble even after aging.