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We use 30 years of intercalibrated HIRS (High-Resolution Infrared Radiation Sounder) data to produce a 30-year data set of upper tropospheric humidity with respect to ice (UTH<sub>i</sub>). Since the required brightness temperatures (channels 12 and 6, <i>T</i><sub>12</sub> and <i>T</i><sub>6</sub>) are intercalibrated to different versions of the HIRS sensors (HIRS/2 and HIRS/4) it is necessary to convert the channel 6 brightness temperatures which are intercalibrated to HIRS/4 into equivalent brightness temperatures intercalibrated to HIRS/2, which is achieved using a linear regression. Using the new regression coefficients we produce daily files of UTH<sub>i</sub>, <i>T</i><sub>12</sub> and <i>T</i><sub>6</sub>, for each NOAA satellite and METOP-A (Meteorological Operational Satellite Programme), which carry the HIRS instrument. From this we calculate daily and monthly means in 2.5° × 2.5° resolution for the northern midlatitude zone 30–60° N. As a first application we calculate decadal means of UTH<sub>i</sub> and the brightness temperatures for the two decades 1980–1989 and 2000–2009. We find that the humidity mainly increased from the 1980s to the 2000s and that this increase is highly statistically significant in large regions of the considered midlatitude belt. The main reason for this result and its statistical significance is the corresponding increase of the <i>T</i><sub>12</sub> variance. Changes of the mean brightness temperatures are less significant.
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The fate of nitrogen oxide pollution during high-latitude winter is controlled by reactions of dinitrogen pentoxide (N<sub>2</sub>O<sub>5</sub>) and is highly affected by the competition between heterogeneous atmospheric reactions and deposition to the snowpack. MISTRA (MIcrophysical STRAtus), a 1-D photochemical model, simulated an urban pollution plume from Fairbanks, Alaska to investigate this competition of N<sub>2</sub>O<sub>5</sub> reactions and explore sensitivity to model parameters. It was found that dry deposition of N<sub>2</sub>O<sub>5</sub> made up a significant fraction of N<sub>2</sub>O<sub>5</sub> loss near the snowpack, but reactions on aerosol particles dominated loss of N<sub>2</sub>O<sub>5</sub> over the integrated atmospheric column. Sensitivity experiments found the fate of NO<sub>x</sub> emissions were most sensitive to NO emission flux, photolysis rates, and ambient temperature. The results indicate a strong sensitivity to urban area density, season and clouds, and temperature, implying a strong sensitivity of the results to urban planning and climate change. Results suggest that secondary formation of particulate (PM<sub>2.5</sub>) nitrate in the Fairbanks downtown area does not contribute significant mass to the total PM<sub>2.5</sub> concentration, but appreciable amounts are formed downwind of downtown due to nocturnal NO<sub>x</sub> oxidation and subsequent reaction with ammonia on aerosol particles.
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Dynamical and microphysical processes in pyroconvective clouds in mid-latitude conditions are investigated using idealized three-dimensional simulations with the Active Tracer High resolution Atmospheric Model (ATHAM). A state-of-the-art two-moment microphysical scheme building upon a realistic parameterization of cloud condensation nuclei (CCN) activation has been implemented in order to study the influence of aerosol concentration on cloud development. The results show that aerosol concentration influences the formation of precipitation. For low aerosol concentrations (<i>N</i><sub>CN</sub> = 200 cm<sup>−3</sup>), rain droplets are rapidly formed by autoconversion of cloud droplets. This also triggers the formation of large graupel and hail particles, resulting in an early onset of precipitation. With increasing aerosol concentration (<i>N</i><sub>CN</sub> = 1000 cm<sup>−3</sup> and <i>N</i><sub>CN</sub> = 20 000 cm<sup>−3</sup>) the formation of rain droplets is delayed due to more but smaller cloud droplets. Therefore, the formation of ice crystals and snowflakes becomes more important for the eventual formation of graupel and hail, which is delayed at higher aerosol concentrations. This results in a delay of the onset of precipitation and a reduction of its intensity with increasing aerosol concentration. This study is the first detailed investigation of the interaction between cloud microphysics and the dynamics of a pyroconvective cloud using the combination of a high-resolution atmospheric model and a detailed microphysical scheme.
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Loss of summertime Arctic sea ice will lead to a large increase in the emission of aerosols and precursor gases from the ocean surface. It has been suggested that these enhanced emissions will exert substantial aerosol radiative forcings, dominated by the indirect effect of aerosol on clouds. Here, we investigate the potential for these indirect forcings using a global aerosol microphysics model evaluated against aerosol observations from the Arctic Summer Cloud Ocean Study (ASCOS) campaign to examine the response of Arctic cloud condensation nuclei (CCN) to sea-ice retreat. In response to a complete loss of summer ice, we find that north of 70° N emission fluxes of sea salt, marine primary organic aerosol (OA) and dimethyl sulfide increase by a factor of ~ 10, ~ 4 and ~ 15 respectively. However, the CCN response is weak, with negative changes over the central Arctic Ocean. The weak response is due to the efficient scavenging of aerosol by extensive drizzling stratocumulus clouds. In the scavenging-dominated Arctic environment, the production of condensable vapour from oxidation of dimethyl sulfide grows particles to sizes where they can be scavenged. This loss is not sufficiently compensated by new particle formation, due to the suppression of nucleation by the large condensation sink resulting from sea-salt and primary OA emissions. Thus, our results suggest that increased aerosol emissions will not cause a climate feedback through changes in cloud microphysical and radiative properties.
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Particulate matter (PM) emissions were measured in July 2010 from on-road motor vehicles driving through a highway tunnel in the San Francisco Bay area. A soot particle aerosol mass spectrometer (SP-AMS) was used to measure the chemical composition of PM emitted by gasoline and diesel vehicles at high time resolution. Organic aerosol (OA) and black carbon (BC) concentrations were measured during various time periods that had different levels of diesel influence, as well as directly in the exhaust plumes of individual heavy-duty (HD) diesel trucks. BC emission factor distributions for HD trucks were more skewed than OA distributions (<i>N</i> = 293), with the highest 10% of trucks accounting for 56 and 42% of total measured BC and OA emissions, respectively. OA mass spectra measured for HD truck exhaust plumes show cycloalkanes are predominate in exhaust OA emissions relative to saturated alkanes (i.e., normal and iso-paraffins), suggesting that lubricating oil rather than fuel is the dominant source of primary organic aerosol (POA) emissions in diesel vehicle exhaust. This finding is supported by the detection of trace elements such as zinc and phosphorus in the exhaust plumes of individual trucks. Trace elements were emitted relative to total OA at levels that are consistent with typical weight fractions of commonly used additives present in lubricating oil. A comparison of measured OA and BC mass spectra across various sampling periods revealed a high degree of similarity in OA and BC emitted by gasoline and diesel engines. This finding indicates a large fraction of OA in gasoline exhaust is lubricant-derived as well. The similarity in OA and BC mass spectra for gasoline and diesel engine exhaust is likely to confound ambient source apportionment efforts to determine contributions to air pollution from these two important sources.
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Measurements of cloud condensation nuclei (CCN), aerosol size distribution and non-refractory chemical composition were performed from 16 to 31 October 2012 in the São Paulo Metropolitan Area (SPMA), Brazil. CCN measurements were performed at 0.23, 0.45, 0.68, 0.90 and 1.13% water supersaturation and were subsequently compared with the Köhler theory, considering the chemical composition. Real-time chemical composition has been obtained by deploying, for the first time in the SPMA, an aerosol chemical ionization monitor (ACSM). CCN closure analyses were performed considering internal mixtures. <br><br> Average aerosol composition during the studied period yielded (arithmetic mean~± standard deviation) 4.81 ± 3.05, 3.26 ± 2.10, 0.30 ± 0.27, 0.52 ± 0.32, 0.37 ± 0.21 and 0.04 ± 0.04 μg m<sup>−3</sup> for organics, BC, NH<sub>4</sub>, SO<sub>4</sub>, NO<sub>3</sub> and Cl, respectively. Particle number concentration was 12 813 ± 5350 cm<sup>−3</sup>, with a dominant nucleation mode. CCN concentrations were on average 1090 ± 328 and 3570 ± 1695 cm<sup>−3</sup> at SS = 0.23% and SS = 1.13%, respectively. <br><br> Results show an increase in aerosol hygroscopicity in the afternoon as a result of aerosol photochemical processing, leading to an enhancement of both organic and inorganic secondary aerosols in the atmosphere, as well as an increase in aerosol average diameter. <br><br> Considering the bulk composition alone, observed CCN concentrations were substantially overpredicted when compared with the Köhler theory (44.1 ± 47.9% at 0.23% supersaturation and 91.4 ± 40.3% at 1.13% supersaturation). Overall, the impact of composition on the calculated CCN concentration (<i>N</i><sub>CCN</sub>) decreases with decreasing supersaturation, partially because using bulk composition introduces less bias for large diameters and lower critical supersaturations, defined as the supersaturation at which the cloud droplet activation will take place. Results suggest that the consideration of only inorganic fraction improves the calculated <i>N</i><sub>CCN</sub>. <br><br> Introducing a size-dependent chemical composition based on filter measurements from previous campaigns has considerably improved simulated values for <i>N</i><sub>CCN</sub> (average overprediction error 14.8 ± 38.6% at 0.23% supersaturation and 3.6 ± 21.6% at 1.13% supersaturation). This study provides the first insight on aerosol real-time composition and hygroscopicity at a site strongly impacted by emissions of a unique vehicular fleet due to the extensive biofuel usage.
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In this work a new thermodynamic framework is developed and used to investigate the effect of water activity on the formation of ice within supercooled droplets. The new framework is based on a novel concept where the interface is assumed to be made of liquid molecules "trapped" by the solid matrix. It also accounts for the change in the composition of the liquid phase upon nucleation. Using this framework, new expressions are developed for the critical ice germ size and the nucleation work with explicit dependencies on temperature and water activity. However unlike previous approaches, the new model does not depend on the interfacial tension between liquid and ice. The thermodynamic framework is introduced within classical nucleation theory to study the effect of water activity on the ice nucleation rate. Comparison against experimental results shows that the new approach is able to reproduce the observed effect of water activity on the nucleation rate and the freezing temperature. It allows for the first time a phenomenological derivation of the constant shift in water activity between melting and nucleation. The new framework offers a consistent thermodynamic view of ice nucleation, simple enough to be applied in atmospheric models of cloud formation.
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The Whole Atmosphere Community Climate Model (WACCM) is utilised to study the daily ozone cycle and underlying photochemical and dynamical processes. The analysis is focused on the daily ozone cycle in the middle stratosphere at 5 hPa where satellite-based trend estimates of stratospheric ozone are most biased by diurnal sampling effects and drifting satellite orbits. The simulated ozone cycle shows a minimum after sunrise and a maximum in the late afternoon. Further, a seasonal variation of the daily ozone cycle in the stratosphere was found. Depending on season and latitude, the peak-to-valley difference of the daily ozone cycle varies mostly between 3 and 5% (0.4 ppmv) with respect to the midnight ozone volume mixing ratio. The maximal variation of 15% (0.8 ppmv) is found at the polar circle in summer. The global pattern of the strength of the daily ozone cycle is mainly governed by the solar zenith angle and the sunshine duration. In addition, we find synoptic-scale variations in the strength of the daily ozone cycle. These variations are often anti-correlated to regional temperature anomalies and are due to the temperature dependence of the rate coefficients <i>k</i><sub>2</sub> and <i>k</i><sub>3</sub> of the Chapman cycle reactions. Further, the NO<sub>x</sub> catalytic cycle counteracts the accumulation of ozone during daytime and leads to an anti-correlation between anomalies in NO<sub>x</sub> and the strength of the daily ozone cycle. Similarly, ozone recombines with atomic oxygen which leads to an anti-correlation between anomalies in ozone abundance and the strength of the daily ozone cycle. At higher latitudes, an increase of the westerly (easterly) wind cause a decrease (increase) in the sunshine duration of an air parcel leading to a weaker (stronger) daily ozone cycle.
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Light scattering by size-resolved aerosols in near-surface air at Tudor Hill, Bermuda, was measured between January and June 2009. Vertical distributions of aerosol backscattering and column-averaged aerosol optical properties were characterized in parallel with a micro-pulse lidar (MPL) and an automated sun–sky radiometer. Comparisons were made between extensive aerosol parameters in the column, such as the lidar-retrieved extinction at 400 m and the aerosol optical depth (AOD), and scattering was measured with a surface nephelometer. Comparisons were also made for intensive parameters such as the Ångström exponent and calculations using AERONET(Aerosol Robotic Network)-derived aerosol physical parameters (size distribution, index of refraction) and Mie theory, and the ratio of submicron scattering to total scattering for size-segregated nephelometer measurements. In these comparisons the <i>r</i><sup>2</sup> was generally around 0.50. Data were also evaluated based on back trajectories. The correlation between surface scattering and lidar extinction was highest for flows when the surface scattering was dominated by smaller particles and the flow had a longer footprint over land then over the ocean. The correlation of AOD with surface scatter was similar for all flow regimes. There was also no clear dependence of the atmospheric lapse rate, as determined from a nearby radiosonde station, on flow regime. The Ångström exponent for most flow regimes was 0.9–1.0, but for the case of air originating from North America, but with significant time over the ocean, the Ångström exponent was 0.57 ± 0.18. The submicron fraction of aerosol near the surface (<i>R</i><sub>sub-surf</sub>) was significantly greater for the flows from land (0.66 ± 0.11) than for the flows which spent more time over the ocean (0.40 ± 0.05). When comparing <i>R</i><sub>sub-surf</sub> and the column-integrated submicron scattering fraction, <i>R</i><sub>sub-col</sub>, the correlation was similar, <i>r</i><sup>2</sup> = 0.50, but <i>R</i><sub>sub-surf</sub> was generally less than <i>R</i><sub>sub-col</sub>, indicating more large particles contributing to light scattering at the surface, contrary to conditions over continents and for polluted continental transport over the ocean. In general, though, the marginal correlations indicate that the column optical properties are weakly correlated with the surface optical measurements. Thus, if it is desired to associate aerosol chemical/physical properties with their optical properties, it is best to use optical and chemical/physical measurements with both collected at the surface or both collected in the column.
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A method was developed to estimate hygroscopic growth factor (<i>f</i>(RH)) of aerosol light-scattering coefficient (<i>b</i><sub>sp</sub>), making use of the measured size- and chemically resolved aerosol samples. In this method, chemical composition of the measured aerosol samples were first reconstructed using the equilibrium model ISORROPIA II. The reconstructed chemical composition, which varies with relative humidity (RH), was then employed to calculate <i>b</i><sub>sp</sub> and hygroscopic growth factor of <i>b</i><sub>sp</sub> (<i>f</i><sub>sp</sub>(RH)) using the Mie model. Furthermore, the calculated <i>f</i><sub>sp</sub>(RH) was fitted with an empirical curve. To evaluate the applicability of <i>f</i><sub>sp</sub>(RH), the curve of <i>f</i><sub>sp</sub>(RH) was used to correct the long-term records of the measured <i>b</i><sub>sp</sub> from the values under comparative dry conditions to the ones under ambient RH conditions. Compared with the original <i>b</i><sub>sp</sub> data, the <i>f</i><sub>sp</sub>(RH)-corrected <i>b</i><sub>sp</sub> had a higher linear correlation with, and a smaller discrepancy from, the <i>b</i><sub>sp</sub> derived directly from visibility and absorption measurements. The <i>f</i><sub>sp</sub>(RH) determined here was further compared with that reported in previous studies. The method described in this manuscript provides an alternative approach to derive credible <i>f</i><sub>sp</sub>(RH) with high accuracy and has many potential applications in aerosol-related research.
