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[1] A combined field and laboratory study was conducted to improve our understanding of the chemical and hygroscopic properties of organic compounds in aerosols sampled in the background continental atmosphere. PM 2.5 (particles with aerodynamic diameters smaller than 2.5 mm) aerosols were collected from 24 June to 28 July 2010 at Storm Peak Laboratory (SPL) in the Park Range of northwestern Colorado. New particle formation (NPF) was frequent at SPL during this campaign, and the samples were not influenced by regional dust storms. Filter samples were analyzed for organic carbon (OC) and elemental carbon (EC), water soluble OC (WSOC), major inorganic ions, and detailed organic speciation. WSOC was isolated from inorganic ions using solid phase absorbents. Hygroscopic growth factors (GFs) and cloud condensation nucleus (CCN) activity of the WSOC were measured in the laboratory. Organic compounds compose the majority (average of 64% with a standard deviation (SD) of 9%) of the mass of measured species and WSOC accounted for an average of 89% (with a SD of 21%) of OC mass. Daily samples were composited according to back trajectories. On average, organic acids, sugars, and sugar alcohols accounted for 12.5 AE 6.2% (average AE SD) of WSOC. Based on the composition of these compounds and that of high molecular weight compounds identified using ultra high resolution mass spectrometry, the organic mass to OC ratio of the WSOC is estimated to be 2.04. The average hygroscopic GFs at RH = 80% (GF 80 ) were 1.10 AE 0.03 for particles derived from isolated WSOC and 1.27 AE 0.03 for particles derived from the total water-soluble material (WSM). CCN activity followed a similar pattern. The critical diameters at a super-saturation of 0.35% were 0.072 AE 0.009 and 0.094 AE 0.006 mm for particles derived from WSM and isolated WSOC, respectively. These GF results compare favorably with estimates from thermodynamic models, which explicitly relate the water activity (RH) to concentration for the total soluble material identified in this study.

.[1] Humic-like substances (HULIS) constitute a significant fraction of aerosol particles in different environments. Studies of the role of HULIS in hygroscopic growth and cloud condensation nuclei (CCN) activity of aerosol particles are scarce, and results differ significantly. In this work the hygroscopic growth and CCN activity of water extracts (WE) and HULIS extracted from particulate matter (PM) collected at a polluted urban site (Copenhagen, Denmark), a rural site (Melpitz, Germany) and the remote site Storm Peak Laboratory (Colorado, USA) were investigated. Measurements of inorganic ions, elemental carbon, organic carbon and water soluble organic carbon (WSOC) within the PM confirmed that the sources of aerosol particles most likely differed for the three samples. The hygroscopic properties of the filtered WE were characterized by hygroscopicity parameters for subsaturated conditions (k GF ) of 0.25, 0.41 and 0.22, and for supersaturated conditions k CCN were 0.23, 0.29 and 0.22 respectively for the urban, rural and remote WE samples. The measured hygroscopic growth and CCN activity were almost identical for the three HULIS samples and could be well represented by k GF = 0.07 and k CCN = 0.08-0.10 respectively. Small amounts of inorganic ions were present in the HULIS samples so the actual values for pure HULIS are expected to be slightly lower (k GF * = 0.04-0.06 and k CCN * = 0.07-0.08). The HULIS samples are thus less hygroscopic compared to most previous studies. To aid direct comparison of hygroscopic properties of HULIS from different studies, we recommend that the fraction of inorganic species in the HULIS samples always is measured and reported.Citation: Kristensen, T. B., et al. (2012), Hygroscopic growth and CCN activity of HULIS from different environments,

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Time-evolving partitioning effects on surface tension and bulk water activity cancel out in Köhler predictions of CCN activation of mixed NAFA–NaCl particles.

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Humic-like substances (HULIS) are a complex group of relatively high molecular weight organic compounds which contribute considerably to the mass of organic carbon (OC) and influence the light-absorbing properties of aerosols. In this work, HULIS were investigated for the first time in the high-Arctic atmosphere, focusing on the chemical characterization and mass contribution of HULIS to the total suspended particle (TSP) mass using weekly aerosol samples collected at Station Nord, northeast Greenland every fourth week during 2010. Average HULIS-C concentration was 11 ng C m À3 during the darker months (November-April) and 4 ng C m À3during the other months (May-October) with an annual mass concentration of 0.02 ± 0.01 μg m À3. HULIS-C contributed to 3-16% of water-soluble organic carbon (WSOC), whereas HULIS accounted for 0.7-4.1% of TSP mass, with TSP typically below 1.0 μg m À3. Concentrations of OC, WSOC, HULIS, selected HULIS functional groups (carboxylic acids, aromatic carboxylic acids, and organosulfates) and levoglucosan overlapped with the typical Arctic haze pattern with elevated concentrations during winter to early spring. The aromatic carboxylic acid portion accounted for a larger share of total carboxylic acid of HULIS during the darker months (7%) compared to the brighter months (3%). The more abundant aromatic carboxylic acid functional groups and the moderate correlation between HULIS and levoglucosan concentrations during the darker months both indicate that biomass burning aerosols and thereby emissions of aromatic compounds could contribute to HULIS in the Arctic, especially during late winter. During the brighter months, relatively higher average molecular weight of HULIS was observed.

Abstract. The growth of aerosol due to the aqueous phase oxidation of sulfur dioxide by ozone was measured in laboratory-generated clouds created in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). Experiments were performed at 10 and − 10 • C, on acidic (sulfuric acid) and on partially to fully neutralised (ammonium sulfate) seed aerosol. Clouds were generated by performing an adiabatic expansion -pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted using oxidation rate constants previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and −10 • C, indicating that, in contrast to some previous studies, the oxidation rates of SO 2 in a dispersed aqueous system can be well represented by using accepted rate constants, based on bulk measurements. To the best of our knowledge, these are the first laboratory-based measurements of aqueous phase oxidation in a dispersed, supercooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rate constants to temperatures below 0 • C is correct.