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Peroxynitrates are responsible for global scale transport of reactive nitrogen. Recent laboratory observations suggest that they may also play an important role in delivery of nutrients to plant canopies. We measured eddy covariance fluxes of total peroxynitrates (ΣPNs) and three individual peroxynitrates (APNs ≡ PAN + PPN + MPAN) over a ponderosa pine forest during the Biosphere Effects on AeRosols and Photochemistry EXperiment 2009 (BEARPEX 2009). Concentrations of these species were also measured at multiple heights above and within the canopy. While the above-canopy daytime concentrations are nearly identical for ΣPNs and APNs, we observed the downward flux of ΣPNs to be 30–60% slower than the flux of APNs. The vertical concentration gradients of ΣPNs and APNs vary with time of day and exhibit different temperature dependencies. These differences can be explained by the production of peroxynitrates other than PAN, PPN, and MPAN within the canopy (presumably as a consequence of biogenic VOC emissions) and upward fluxes of these PN species. The impact of this implied peroxynitrate flux on the interpretation of NO<sub>x</sub> fluxes and ecosystem N exchange is discussed.
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Arctic ozone depletion events (ODEs) are caused by halogen catalyzed ozone loss. In situ chemistry, advection of ozone-poor air mass, and vertical mixing in the lower troposphere are important factors affecting ODEs. To better characterize the ODEs, we analyze the combined set of surface, ozonesonde, and aircraft in situ measurements of ozone and bromine compounds during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS), the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC), and the Arctic Intensive Ozonesonde Network Study (ARCIONS) experiments (April 2008). Tropospheric BrO columns retrieved from satellite measurements and back trajectory calculations are also used to investigate the characteristics of observed ODEs. In situ observations from these field experiments are inadequate to validate tropospheric BrO columns derived from satellite measurements. In view of this difficulty, we construct an ensemble of tropospheric column BrO estimates from two satellite (OMI and GOME-2) measurements and with three independent methods of calculating stratospheric BrO columns. Furthermore, we select analysis methods that do not depend on the absolute magnitude of column BrO, such as time-lagged correlation analysis of ozone and tropospheric column BrO, to understand characteristics of ODEs. Time-lagged correlation analysis between in situ (surface and ozonesonde) measurements of ozone and satellite derived tropospheric BrO columns indicates that the ODEs are due to either local halogen-driven ozone loss or short-range (∼1 day) transport from nearby regions with ozone depletion. The effect of in situ ozone loss is also evident in the diurnal variation difference between low (10th and 25th percentiles) and higher percentiles of surface ozone concentrations at Alert, Canada. Aircraft observations indicate low-ozone air mass transported from adjacent high-BrO regions. Correlation analyses of ozone with potential temperature and time-lagged tropospheric BrO column show that the vertical extent of local ozone loss is surprisingly deep (1–2 km) at Resolute and Churchill, Canada. The unstable boundary layer during ODEs at Churchill could potentially provide a source of free-tropospheric BrO through convective transport and explain the significant negative correlation between free-tropospheric ozone and tropospheric BrO column at this site.
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The time dependence of immersion freezing was studied for temperatures between 236 K and 243 K. Droplets with single immersed, size-selected 400 nm and 800 nm kaolinite particles were produced at 300 K, cooled down to supercooled temperatures, and the fraction of frozen droplets with increasing residence time was detected. To simulate the conditions of immersion freezing in mixed-phase clouds we used the Zurich Ice Nucleation Chamber (ZINC) and its vertical extension, the Immersion Mode Cooling chAmber (IMCA). We observed that the frozen fraction of droplets increased with increasing residence time in the chamber. This suggests that there is a time dependence of immersion freezing and supports the importance of a stochastic component in the ice nucleation process. The rate at which droplets freeze was observed to decrease towards higher temperatures and smaller particle sizes. Comparison of the laboratory data with four different ice nucleation models, three based on classical nucleation theory with different representations of the particle surface properties and one singular, suggest that the classical, stochastic approach combined with a distribution of contact angles is able to reproduce the ice nucleation observed in these experiments most accurately. Using the models to calculate the increase in frozen fraction at typical mixed-phase cloud temperatures over an extended period of time, yields an equivalent effect of −1 K temperature shift for an increase in times scale by one order of magnitude. This suggests that temperature is more important than time.
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A small subset of the atmospheric aerosol population has the ability to induce ice formation at conditions under which ice would not form without them (heterogeneous ice nucleation). While no closed theoretical description of this process and the requirements for good ice nuclei is available, numerous studies have attempted to quantify the ice nucleation ability of different particles empirically in laboratory experiments. In this article, an overview of these results is provided. Ice nucleation "onset" conditions for various mineral dust, soot, biological, organic and ammonium sulfate particles are summarized. Typical temperature-supersaturation regions can be identified for the "onset" of ice nucleation of these different particle types, but the various particle sizes and activated fractions reported in different studies have to be taken into account when comparing results obtained with different methodologies. When intercomparing only data obtained under the same conditions, it is found that dust mineralogy is not a consistent predictor of higher or lower ice nucleation ability. However, the broad majority of studies agrees on a reduction of deposition nucleation by various coatings on mineral dust. The ice nucleation active surface site (INAS) density is discussed as a simple and empirical normalized measure for ice nucleation activity. For most immersion and condensation freezing measurements on mineral dust, estimates of the temperature-dependent INAS density agree within about two orders of magnitude. For deposition nucleation on dust, the spread is significantly larger, but a general trend of increasing INAS densities with increasing supersaturation is found. For soot, the presently available results are divergent. Estimated average INAS densities are high for ice-nucleation active bacteria at high subzero temperatures. At the same time, it is shown that INAS densities of some other biological aerosols, like certain pollen grains, fungal spores and diatoms, tend to be similar to those of dust. These particles may owe their high ice nucleation onsets to their large sizes. Surface-area-dependent parameterizations of heterogeneous ice nucleation are discussed. For immersion freezing on mineral dust, fitted INAS densities are available, but should not be used outside the temperature interval of the data they were based on. Classical nucleation theory, if employed with only one fitted contact angle, does not reproduce the observed temperature dependence for immersion nucleation, the temperature and supersaturation dependence for deposition nucleation, and the time dependence of ice nucleation. Formulations of classical nucleation theory with distributions of contact angles offer possibilities to overcome these weaknesses.
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In this paper, aircraft measurements are presented of liquid phase (ice-free) wave clouds made at temperatures greater than −5°C that formed over Scotland, UK. The horizontal variations of the vertical velocity across wave clouds display a distinct pattern. The maximum updraughts occur at the upshear flanks of the clouds and the strong downdraughts at the downshear flanks. The cloud droplet concentrations were a couple of hundreds per cubic centimetres, and the drops generally had a mean diameter between 15–45 μm. A small proportion of the drops were drizzle. The measurements presented here and in previous recent studies suggest a different interaction of dynamics and microphysics in wave clouds from the accepted model. The results in this paper provide a case for future numerical simulation of wave cloud and the interaction between wave and cloud.
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Three configurations of a bulk microphysics scheme in conjunction with a detailed bin scheme are implemented in the Weather Research and Forecasting (WRF) model to specifically address the role of the saturation adjustment assumption (i.e., condensing/evaporating the surplus/deficit water vapor relative to saturation in one time step) on aerosol-induced invigoration of deep convective clouds. The bulk model configurations are designed to treat cloud droplet condensation/evaporation using either saturation adjustment, as employed in most bulk models, or an explicit representation of supersaturation over a time step, as used in bin models. Results demonstrate that the use of saturation adjustment artificially enhances condensation and latent heating at low levels and limits the potential for an increase in aerosol concentration to increase buoyancy at mid to upper levels. This leads to a small weakening of the time- and domain-averaged convective mass flux (~-3%) in polluted compared to clean conditions. In contrast, the bin model and bulk scheme with explicit prediction of supersaturation simulate an increase in latent heating aloft and the convective updraft mass flux is weakly invigorated (~5%). The bin model also produces a large increase in domain-mean cumulative surface precipitation in polluted conditions (~18%), while all of the bulk model configurations simulate little change in precipitation. Finally, it is shown that the cold pool weakens substantially with increased aerosol loading when saturation adjustment is applied, which acts to reduce the low-level convergence and weaken the convective dynamics. With an explicit treatment of supersaturation in the bulk and bin models there is little change in cold pool strength, so that the convective response to polluted conditions is influenced more by changes in latent heating aloft. It is concluded that the use of saturation adjustment can explain differences in the response of cold pool evolution and convective dynamics with aerosol loading simulated by the bulk and bin models, but cannot explain large differences in the response of surface precipitation between these models.
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In order to investigate the formation and growth processes of nucleation mode particles, and to quantify the particle number (PN) concentration and size distributions in Hong Kong, an intensive field measurement was conducted from 25 October to 29 November in 2010 near the mountain summit of Tai Mo Shan, a suburban site approximately the geographical centre of the New Territories in Hong Kong. Based on observations of the particle size distribution, new particle formation (NPF) events were found on 12 out of 35 days with the estimated formation rate <i>J</i><sub>5.5</sub> from 0.97 to 10.2 cm<sup>−3</sup> s<sup>−1</sup>, and the average growth rates from 1.5 to 8.4 nm h<sup>−1</sup>. The events usually began at 10:00–11:00 LT characterized by the occurrence of a nucleation mode with a peak diameter of 6–10 nm. Solar radiation, wind speed, sulfur dioxide (SO<sub>2</sub>) and ozone (O<sub>3</sub>) concentrations were on average higher, whereas temperature, relative humidity and daytime nitrogen dioxide (NO<sub>2</sub>) concentration were lower on NPF days than on non-NPF days. Back trajectory analysis suggested that in majority of the NPF event days, the air masses originated from the northwest to northeast directions. The concentrations of gaseous sulfuric acid (SA) showed good power-law relationship with formation rates, with exponents ranging from 1 to 2. The result suggests that the cluster activation theory and kinetic nucleation could potentially explain the observed NPF events in this mountainous atmosphere of Hong Kong. Meanwhile, in these NPF events, the contribution of sulfuric acid vapor to particle growth rate (GR<sub>5.5–25</sub>) ranged from 9.2 to 52.5% with an average of 26%. Measurement-based calculated oxidation rates of monoterpenes (i.e. α-pinene, β-pinene, myrcene and limonene) by O<sub>3</sub> positively correlated with the GR<sub>5.5–25</sub> (<i>R</i> = 0.80, <i>p</i> < 0.05). The observed associations of the estimated formation rate <i>J</i><sub>5.5</sub> and the growth rate GR<sub>5.5–25</sub> with gaseous sulfuric acid and volatile organic compounds (VOCs) suggested the critical roles of sulfuric acid and biogenic VOCs (e.g. α-pinene and β-pinene) in these NPF events.
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Volcanic aerosols resulting from the Eyjafjallajökull eruption were detected in south-eastern Italy from 20 to 22 April 2010, at a distance of approximately 4000 km from the volcano, and have been characterized by lidar, sun/sky photometer, and surface in-situ measurements. Volcanic particles added to the pre-existing aerosol load and measurement data allow quantifying the impact of volcanic particles on the aerosol vertical distribution, lidar ratios, the aerosol size distribution, and the ground-level particulate-matter concentrations. Lidar measurements reveal that backscatter coefficients by volcanic particles were about one order of magnitude smaller over south-eastern Italy than over Central Europe. Mean lidar ratios at 355 nm were equal to 64 ± 5 sr inside the volcanic aerosol layer and were characterized by smaller values (47 ± 2 sr) in the underlying layer on 20 April, 19:30 UTC. Lidar ratios and their dependence with the height reduced in the following days, mainly because of the variability of the volcanic particle contributions. Size distributions from sun/sky photometer measurements reveal the presence of volcanic particles with radii <i>r</i> > 0.5 μm on 21 April and that the contribution of coarse volcanic particles increased from 20 to 22 April. The aerosol fine mode fraction from sun/sky photometer measurements varied between values of 0.85 and 0.94 on 20 April and decreased to values between 0.25 and 0.82 on 22 April. Surface measurements of particle size distributions were in good accordance with column averaged particle size distributions from sun/sky photometer measurements. PM<sub>1</sub>/PM<sub>2.5</sub> mass concentration ratios of 0.69, 0.66, and 0.60 on 20, 21, and 22 April, respectively, support the increase of super-micron particles at ground. Measurements from the Regional Air Quality Agency show that PM<sub>10</sub> mass concentrations on 20, 21, and 22 April 2010 were enhanced in the entire Apulia Region. More specifically, PM<sub>10</sub> mass concentrations have on average increased over Apulia Region 22%, 50%, and 28% on 20, 21, and 22 April, respectively, compared to values on 19 April. Finally, the comparison of measurement data with numerical simulations by the FLEXPART dispersion model demonstrates the ability of FLEXPART to model the advection of the volcanic ash over the 4000 km from the Eyjafjallajökull volcano to Southern Italy.
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A surface solar radiation parameterization based on deviations between 3-D and conventional plane-parallel radiative transfer models has been incorporated into the Weather Research and Forecasting (WRF) model to understand the solar insolation over mountain/snow areas and to investigate the impact of the spatial and temporal distribution and variation of surface solar fluxes on land-surface processes. Using the Sierra-Nevada in the western United States as a testbed, we show that mountain effect could produce up to −50 to + 50 W m<sup>−2</sup> deviations in the surface solar fluxes over the mountain areas, resulting in a temperature increase of up to 1 °C on the sunny side. Upward surface sensible and latent heat fluxes are modulated accordingly to compensate for the change in surface solar fluxes. Snow water equivalent and surface albedo both show decreases on the sunny side of the mountains, indicating more snowmelt and hence reduced snow albedo associated with more solar insolation due to mountain effect. Soil moisture increases on the sunny side of the mountains due to enhanced snowmelt, while decreases on the shaded side. Substantial differences are found in the morning hours from 8–10 a.m. and in the afternoon around 3–5 p.m., while differences around noon and in the early morning and late afternoon are comparatively smaller. Variation in the surface energy balance can also affect atmospheric processes, such as cloud fields, through the modulation of vertical thermal structure. Negative changes of up to −40 g m<sup>−2</sup> are found in the cloud water path, associated with reductions in the surface insolation over the cloud region. The day-averaged deviations in the surface solar flux are positive over the mountain areas and negative in the valleys, with a range between −12~12 W m<sup>−2</sup>. Changes in sensible and latent heat fluxes and surface skin temperature follow the solar insolation pattern. Differences in the domain-averaged diurnal variation over the Sierras show that the mountain area receives more solar insolation during early morning and late afternoon, resulting in enhanced upward sensible heat and latent heat fluxes from the surface and a corresponding increase in surface skin temperature. During the middle of the day, however, the surface insolation and heat fluxes show negative changes, indicating a cooling effect. Hence overall, the diurnal variations of surface temperature and surface fluxes in the Sierra-Nevada are reduced through the interactions of radiative transfer and mountains. The hourly differences of the surface solar insolation in higher elevated regions, however, show smaller magnitude in negative changes during the middle of the day and possibly more solar fluxes received during the whole day.
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The photolysis of HONO is important for the atmospheric HO<sub>x</sub> (OH + HO<sub>2</sub>) radical budget and ozone formation, especially in polluted air. Nevertheless, owing to the incomplete knowledge of HONO sources, realistic HONO mechanisms have not yet been implemented in global models. We investigated measurement data sets from 15 field measurement campaigns conducted in different countries worldwide. It appears that the HONO/NO<sub>x</sub> ratio is a good proxy predictor for HONO mixing ratios under different atmospheric conditions. From the robust relationship between HONO and NO<sub>x</sub>, a representative mean HONO/NO<sub>x</sub> ratio of 0.02 has been derived. Using a global chemistry-climate model and employing this HONO/NO<sub>x</sub> ratio, realistic HONO levels are simulated, being about one order of magnitude higher than the reference calculations that only consider the reaction OH + NO → HONO. The resulting enhancement of HONO significantly impacts HO<sub>x</sub> levels and photo-oxidation products (e.g, O<sub>3</sub>, PAN), mainly in polluted regions. Furthermore, the relative enhancements in OH and secondary products are higher in winter than in summer, thus enhancing the oxidation capacity in polluted regions, especially in winter when other photolytic OH sources are of minor importance. Our results underscore the need to improve the understanding of HONO chemistry and its representation in atmospheric models.
