Journal of Atmospheric Chemistry

The chemistry of cloud multiphase systems was studied within the Kleiner Feldberg Cloud Experiment 1990. The clouds encountered during this experimental campaign could be divided into two categories according to the origin of air masses in which the clouds formed. From the chemical point of view, clouds passing the sampling site during the first period of the campaign (26 October-4 November) were characterized by lower pollutant loading and higher pH, as compared to clouds during the final period of the experimental campaign (10–13 November). The study of multiphase partitioning of the main chemical constituents of the cloud systems and of atmospheric acidity within the multiphase systems themselves (gas + interstitial aerosol + liquid droplets) are presented in this paper. A general lack of gaseous NH3 was found in these cloud systems, which caused a lack of buffer capacity toward acid addition. Evidence supports the hypothesis that the higher acidity of the cloud systems during this final period of the campaign was due to input of HNO3. Our measurements, however, could not determine whether the observed input was due to scavenging of gaseous HNO3 from the air feeding into the cloud, or to heterogeneous HNO3 formation via NO2 oxidation by O3 to NO3 and N2O5. Sulfate in cloud droplets mainly originated from aerosol SO 4 2− scavenging, since S(IV) to S(VI) liquid phase conversion was inhibited due to both lack of H2O2 and low pH of cloud droplets, which made O3 and metal catalyzed S(IV) oxidation inefficient.

Size-segregated particle samples were collected using a Berner 5-stage impactor (stages 1–5: 0.05–0.14–0.42–1.2–3.5–10 μm aerodynamic diameter). The means for all 169 days and for different categories of days were used for a characterization. The sorting criteria were (a) the distinction between winter (Wi, November to April) and summer (Su, May to October), (b) the distinction between air mass inflow from a sector West (W, 210 °–320 °) and from a sector East (E, 35 °–140 °). For the assignment of the air mass origin 96-h backward trajectories were used and four categories (WiW, WiE, SuW and SuE) with 48, 18, 42 and 29 days were established. The lowest mean particle mass concentrations were found for SuW and the highest for WiE with relative mass concentration distributions of 5.9, 28.2, 36.5, 18.0, and 11.4 % and 3.5, 22.7, 52.6, 16.7, and 4.5 % for stages 1–5, respectively. The mass closure for water soluble ions, water, organic material (OM) and elemental carbon (EC) accounts for 81–99 % of the gravimetric mass in Wi and for 60–81 % for Su, depending on the stage. The fractions of nitrate were relatively high for WiW while sulphate fractions are high for WiE. The estimated concentrations of secondary organic carbon (SOA) on stage 3 for WiW, WiE, SuW and SuE were 0.32, 1.25, 0.27 and 0.58 μgm−³, respectively. The highest amount of SOA is found for WiE, representing 59 % of organic carbon (OC). The highest difference in the percentages of SOA in OC was found between winter (WiW 55 %, WiE 59 %) and summer (SuW and SuE 74 %) indicating photochemical processes during long-range transport. The mean Carbon Preference Indices (CPI) are highest for SuE (stage 4: 7.57 and stage 5: 9.82) resulting mainly from plant wax abrasion in the surrounding forests. For WiE the mean PAH concentration on stage 3 (9.7 ngm−3) is about five times higher than for WiW, indicating long range transport following domestic heating and other combustion processes.

Near real-time measurements of PM2.5 ionic compositions were performed at the summit of the highest mountain in the central-eastern plains in the spring and summer of 2007 in order to characterize aerosol composition and its interaction with clouds. The average concentrations of total water soluble ions were 27.5 and 36.7 μg m−3, accounting for 44% and 62% of the PM2.5 mass concentration in the spring and summer, respectively. A diurnal pattern of SO 4 2- , NH 4 + and NO 3 - was observed in both campaigns and attributed to the upslope/downslope transport of air mass and the development of the planetary boundary layer (PBL). The average SO2 oxidation ratio (SOR) in summer was 57% (±27%), more than twice that in spring 24% (±16%); the fine nitrate oxidation ratio (NOR) was comparable in the two seasons (9 ± 6% and 11 ± 10% in summer and spring, respectively). This result indicates strong summertime production of sulfate aerosol. A principal component analysis shows that short-range and long-range transport of pollution, cloud processing, and crustal source were the main factors affecting the variability of the measured ions (and other trace gases and aerosols) at Mt. Tai. Strong indications of biomass burning were observed in summer. Cloud scavenging rates showed larger variations for different ions and in different cloud events. The elevated concentrations of the water soluble ions at Mt. Tai indicate serious aerosol pollution over the North China plain of eastern China.

Measurements of Hg (total gas-phase, precipitation-phase andparticulate-phase), aerosol mass, particulate 210Pb and7Be and precipitation 210Pb were made at an atmosphericcollection station located in a near remote area of northcentral Wisconsin,U.S.A. (46°10′N, 89°50′W) during the summers of 1993, 1994and 1995. Total Hg and 210Pb were observed to correlate strongly(slope = 0.06 ± 0.03 ng mBq-1; r 2 =0.72) in rainwater. Mercury to 210Pb ratios in particulate matter(0.03 ± 0.02 ng mBq-1; r 2 = 0.06) wereconsistent with the ratio in rain. Enrichment of the Hg/mass ratio (approx.5–50×) relative to soil and primary pollutant aerosols indicatedthat gas-to-particle conversion had taken place during transport. Comparisonof these results with models for the incorporation of Hg into precipitationindicates that atmospheric particles deliver more Hg to precipitation than canbe explained by the presence of soot. A lack of correlation between totalgas-phase Hg (TGM) and a 7Be/210Pb function suggests novertical concentration gradient within the troposphere, and allows an estimateof TGM residence time of 1.5 ± 0.6 yr be made based on surface airsamples.

Atmospheric oxidation of monoterpenes contributes to formation of tropospheric ozone and secondary organic aerosol, but their products are poorly characterized. In this work, we report a series of outdoor smog chamber experiments to investigate both gaseous and particulate products in the ozone oxidation of four monoterpenes: α-pinene, β-pinene, Δ3-carene, and sabinene. More than ten oxygenated products are detected and identified in each monoterpene/O3 reaction by coupling derivatization techniques and GC/MS detection. A denuder/filter pack sampling system is used to separate and simultaneously collect gas and aerosol samples. The identified products, consisting of compounds containing carbonyl, hydroxyl, and carboxyl functional groups, are estimated to account for about 34–50%, 57%, 29–67%, and 24% of the reacted carbon mass for β-pinene, sabinene, α-pinene, and Δ3-carene, respectively. The identified individual products account for >83%, ∼100%, >90%, and 61% of the aerosol mass produced in the ozone reaction of β-pinene, sabinene, α-pinene, and Δ3-carene. The uncertainty in the yield data is estimated to be ∼ ±50%. Many of the products partition between gas and aerosol phases, and their gas-aerosol partitioning coefficients are determined and reported here. Reaction schemes are suggested to account for the products observed.

An extensive aerosol sampling program was conducted during January-December 2006 over Kolkata (22º33′ N and 88º20′ E), a mega-city in eastern India in order to understand the sources, distributions and properties of atmospheric fine mode aerosol (PM2.5). The primary focus of this study is to determine the relative contribution of natural and anthropogenic as well as local and transported components to the total fine mode aerosol loading and their seasonal distributions over the metropolis. The average concentrations of fine mode aerosol was found to be 71.2 ± 25.2 μgm-3 varying between 34.5 μgm-3 in monsoon and 112.6 μgm-3 in winter. The formation pathways of major secondary aerosol components like nitrate and sulphate in different seasons are discussed. A long range transport of dust aerosol from arid and semi-arid regions of western India and beyond was observed during pre-monsoon which significantly enriched the total aerosol concentration. Vehicular emissions, biomass burning and transported dust particles were the major sources of PM2.5 from local and continental regions whereas sea-salt aerosol was the major source of PM2.5 from marine source regions.