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 κs=1.1 (at RH=90%) is used to represent the hygroscopicity of inorganic sea salt particles in numerical models.

Abstract. A variety of tools are used to simulate atmospheric aging, including smog chambers and flow reactors. Traditional, large-scale smog chambers age emissions over the course of hours to days, whereas flow reactors rapidly age emissions using high oxidant concentrations to reach higher degrees of oxygenation than typically attained in smog chamber experiments. The atmospheric relevance of the products generated under such rapid oxidation warrants further study. However, no previously published studies have compared the yields and chemical composition of products generated in flow reactors and smog chambers from the same starting mixture. The yields and composition of the organic aerosol formed from the photo-oxidation of α-pinene and of wood-combustion emissions in a smog chamber (SC) and two flow reactors: a potential aerosol mass reactor (PAM) and a micro-smog chamber (MSC), were determined using aerosol mass spectrometry. Reactants were sampled from the SC and aged in the MSC and the PAM using a range of hydroxyl radical (OH) concentrations and then photo-chemically aged in the SC. The chemical composition, as well as the maximum yields and emission factors, of the products in both the α-pinene and wood-combustion systems determined with the PAM and the SC agreed reasonably well. High OH exposures have been shown previously to lower yields by breaking carbon–carbon bonds and forming higher volatility species, which reside largely in the gas phase; however, fragmentation in the PAM was not observed. The yields determined using the PAM for the α-pinene system were slightly lower than in the SC, possibly from increased wall losses of gas phase species due to the higher surface area to volume ratios in the PAM, even when offset with better isolation of the sampled flow from the walls. The α-pinene SOA results for the MSC were not directly comparable, as particles were smaller than the optimal AMS transmission range. The higher supersaturation in the flow reactors resulted in more nucleation than in the SC. For the wood-combustion system, emission factors measured from the MSC were typically lower than those measured from the SC. Lower emission factors in the MSC may have been due to considerable nucleation mode particles formed in the MSC which were not detected by the AMS or due to condensational loss of gases to the walls inside or after the MSC. More comprehensive coverage of the potential particle size range is needed in future SOA measurements to improve our understanding of the differences in yields when comparing the MSC to the SC. The PAM and the SC agreed within measurement uncertainties in terms of yields and composition for the systems and conditions studied here and this agreement supports the continued use of the PAM to study atmospheric aging.

Light-absorbing organic carbon (i.e., brown carbon or BrC) in the atmospheric aerosol has significant contribution to light absorption and radiative forcing. However, the link between BrC optical properties and chemical composition remains poorly constrained. In this study, we combine spectrophotometric measurements and chemical analyses of BrC samples collected from July 2008 to June 2009 in urban Xi'an, Northwest China. Elevated BrC was observed in winter (5 times higher than in summer), largely due to increased emissions from wintertime domestic biomass burning. The light absorption coefficient of methanol-soluble BrC at 365 nm (on average approximately twice that of water-soluble BrC) was found to correlate strongly with both parent polycyclic aromatic hydrocarbons (parent-PAHs, 27 species) and their carbonyl oxygenated derivatives (carbonyl-OPAHs, 15 species) in all seasons ( r > 0.61). These measured parent-PAHs and carbonyl-OPAHs account for on average ∼1.7% of the overall absorption of methanol-soluble BrC, about 5 times higher than their mass fraction in total organic carbon (OC, ∼0.35%). The fractional solar absorption by BrC relative to element carbon (EC) in the ultraviolet range (300-400 nm) is significant during winter (42 ± 18% for water-soluble BrC and 76 ± 29% for methanol-soluble BrC), which may greatly affect the radiative balance and tropospheric photochemistry and therefore the climate and air quality.

This study reports the first of a kind data on aircraft engine non-volatile particulate matter (nvPM) number-and massbased emissions using standardized systems. Two compliant sampling and measurement systems operated by Missouri University of Science and Technology (Missouri S&T) and Empa were evaluated during the Aviation-Particle Regulatory Instrumentation Demonstration Experiment (A-PRIDE) 4 campaign at the SR Technics facilities in Z€ urich, Switzerland, in November 2012. The Missouri S&T and Empa systems were compared during a series of dedicated engine tests using a CFM56-5B4/2P engine source, and maintenance engine testing using CFM56-7B24/3 and PW4168A engine sources at a range of engine operating conditions. These two compliant systems were found to agree within 6% of each other in terms of nvPM number-based emissions, and within 15% for nvPM mass-based emissions. For the three engine sources studied, at several engine power conditions the mass instruments approached their limit of detection, resulting in high measurement uncertainties. Ancillary instrumentation was used to determine PM size distributions, chemical composition, and effective density from mass-mobility experiments. Particle geometric mean mobility diameter ranged 20-45 nm, and geometric standard deviation varied from 1.55 to 1.9 for the three engine types studied. The fraction of PM organic content measured in the emissions from the CFM56-5B4/2P engine was »4% while the size-dependent particle effective density was parameterized with a massmobility exponent of 2.57 and a pre-factor of 0.606. Results of this study will contribute to the development of the new nvPM emissions certification standard and emissions inventories from commercial aviation operations.

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 sp 2-to sp 3-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.

An aerosol time-of-flight mass spectrometer (ATOFMS) was used to detect trimethylamine (TMA) in 0.52-1.9 μm particles at urban and rural sites in Southern Ontario during the summer and winter of 2007. During the summer, TMA-containing particles were observed exclusively during high relative humidity or fog events at both the urban and rural sites. In the wintertime, greater concentrations of TMA-containing particles were linked to cloud processing of aerosol in air masses originating from over agricultural and livestock areas. A laboratory study revealed that, at high relative humidity (∼ 100%), gas phase TMA at concentrations ranging from 2 to 20,000 ppt partitions preferentially to acidic particles present in the ambient air. On the basis of the field and laboratory studies, it appears that gas phase TMA present in ambient air partitions onto pre-existing particles preferentially during periods of acidic cloud/fog processing, leading to the presence of TMA-containing particles in the 0.52-1.9 μm size range.

Abstract. 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.

We characterized the chemical composition and optical properties of particulate matter (PM) emitted by a marine diesel engine operated on heavy fuel oil (HFO), marine gas oil (MGO), and diesel fuel (DF). For all three fuels, ∼80% of submicron PM was organic (and sulfate, for HFO at higher engine loads). Emission factors varied only slightly with engine load. Refractory black carbon (rBC) particles were not thickly coated for any fuel; rBC was therefore externally mixed from organic and sulfate PM. For MGO and DF PM, rBC particles were lognormally distributed in size (mode at d rBC ≈120 nm). For HFO, much larger rBC particles were present. Combining the rBC mass concentrations with in situ absorption measurements yielded an rBC mass absorption coefficient MAC BC,780 nm of 7.8 ± 1.8 m 2 /g at 780 nm for all three fuels. Using positive deviations of the absorption Ångström exponent (AAE) from unity to define brown carbon (brC), we found that brC absorption was negligible for MGO or DF PM (AAE(370,880 nm) ≈ 1.0 ± 0.1) but typically 50% of total 370-nm absorption for HFO PM. Even at 590 nm, ∼20 of the total absorption was due to brC. Using absorption at 880 nm as a reference for BC absorption and normalizing to organic PM mass, we obtained a MAC OM,370 nm of 0.4 m 2 /g at typical operating conditions. Furthermore, we calculated an imaginary refractive index of (0.045 ± 0.025)( ∕370 nm) −3 for HFO PM at 370 nm> > 660 nm, more than twofold greater than previous recommendations. Climate models should account for this substantial brC absorption in HFO PM. Plain Language SummaryWe characterized the fundamental properties of marine engine exhaust that are relevant to its aerosol-radiation interactions in climate models. In particular, we focussed on "brown carbon" light absorption (i.e., absorption in excess of that expected for the black carbon in canonical soot). We found that brown carbon can increase the direct radiative forcing of heavy-fuel-oil ship exhaust by 18% over snow.