A relationship between liquid water content and chemical composition in clouds (original) (raw)
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Atmospheric Chemistry and Physics Discussions, 2004
In order to estimate the anthropogenic influence of gas and aerosol emissions from the Petroleum Industry in maritime zones with clouds of small vertical extent, a numerical 1D Eulerian cloud-chemical model with detailed microphysics (Alfonso and Raga, 2002) is used to simulate the influence of water soluble organic compounds (WSOC) and organic+inorganic gas emissions on cloud development. Following Mircea et al. (2002), we tested the sensitivity of the cloud and precipitation development in the classical inorganic case (CIC) and the inorganic+organic case (IOC) with respect to CCN compositions. The results indicate an increase in the droplet concentration for the IOC, and a delay in the development of precipitation. The pH spectral evolution was studied during both the development and precipitation stages. The influence of the diffusion of formic acid and its generation by oxidation of hydrated formaldehyde in the aqueous phase result in a reduction in the pH of precipitation in th...
Atmospheric Chemistry and Physics, 2014
ABSTRACT Long-term monitoring of the chemical composition of clouds (73 cloud events representing 199 individual samples) sampled at the puy de Dôme (pdD) station (France) was performed between 2001 and 2011. Physicochemical parameters, as well as the concentrations of the major organic and inorganic constituents, were measured and analyzed by multicomponent statistical analysis. Along with the corresponding back-trajectory plots, this allowed for distinguishing four different categories of air masses reaching the summit of the pdD: polluted, continental, marine and highly marine. The statistical analysis led to the determination of criteria (concentrations of inorganic compounds, pH) that differentiate each category of air masses. Highly marine clouds exhibited high concentrations of Na+ and Cl−; the marine category presented lower concentration of ions but more elevated pH. Finally, the two remaining clusters were classified as "continental" and "polluted"; these clusters had the second-highest and highest levels of NH4+, NO3−, and SO24−, respectively. This unique data set of cloud chemical composition is then discussed as a function of this classification. Total organic carbon (TOC) is significantly higher in polluted air masses than in the other categories, which suggests additional anthropogenic sources. Concentrations of carboxylic acids and carbonyls represent around 10% of the organic matter in all categories of air masses and are studied for their relative importance. Iron concentrations are significantly higher for polluted air masses and iron is mainly present in its oxidation state (+II) in all categories of air masses. Finally, H2O2 concentrations are much more varied in marine and highly marine clouds than in polluted clouds, which are characterized by the lowest average concentration of H2O2. This data set provides concentration ranges of main inorganic and organic compounds for modeling purposes on multiphase cloud chemistry.
On the Relationship Between Cloud Water Composition and Cloud Droplet Number Concentration
Aerosol-cloud interactions are the largest source of uncertainty in quantifying anthropogenic radiative forcing. The large uncertainty is, in part, due to the difficulty of predicting cloud microphysical parameters, such as the cloud droplet number concentration (N d). Even though rigorous first-principle approaches exist to calculate N d , the cloud and aerosol research community also relies on empirical approaches such as relating N d to aerosol mass concentration. Here we analyze relationships between N d and cloud water chemical composition, in addition to the effect of environmental factors on the degree of the relationships. Warm, marine, stratocumulus clouds off the California coast were sampled throughout four summer campaigns between 2011 and 2016. A total of 385 cloud water samples were collected and analyzed for 80 chemical species. Single-and multispecies log-log linear regressions were performed to predict N d using chemical composition. Single-species regressions reveal that the species that best predicts N d is total sulfate (R 2 adj = 0.40). Multispecies regressions reveal that adding more species does not necessarily produce a better model, as six or more species yield regressions that are statistically insignificant. A commonality among the multispecies regressions that produce the highest correlation with N d was that most included sulfate (either total or non-seasalt), an ocean emissions tracer (such as sodium), and an organic tracer (such as oxalate). Binning the data according to turbulence, smoke influence, and in-cloud height allowed for examination of the effect of these environmental factors on the composition-N d correlation. Accounting for turbulence, quantified as the standard deviation of vertical wind speed, showed that the correlation between N d with both total sulfate and sodium increased at higher turbulence conditions, consistent with turbulence promoting the mixing between ocean surface and cloud base. Considering the influence of smoke significantly improved the correlation with N d for two biomass burning tracer species in the study region, specifically oxalate and iron. When binning by in-cloud height, non-sea-salt sulfate and sodium correlated best with N d at cloud top, whereas iron and oxalate correlated best with N d at cloud base.
Cloud chemistry at the Puy de D�me: variability and relationships with environmental factors
Atmos Chem Phys, 2004
The chemical composition of cloud water was investigated during the winter-spring months of 2001 and 2002 at the Puy de Dôme station (1465 m above sea level, 45°46'22'' N, 2°57'43'' E) in an effort to characterize clouds in the continental free troposphere. Cloud droplets were sampled with single-stage cloud collectors (cut-off diameter approximately 7 µm) and analyzed for inorganic and organic ions, as well as total dissolved organic carbon. Results show a very large variability in chemical composition and total solute concentration of cloud droplets, ranging from a few mg l-1 to more than 150 mg l-1. Samplings can be classified in three different categories with respect to their total ionic content and relative chemical composition: background continental (BG, total solute content lower than 18 mg l-1), anthropogenic continental (ANT, total solute content from 18 to 50 mg l-1), and special events (SpE, total solute content higher than 50 mg l-1). The relative chemical composition shows an increase in anthropogenic-derived species (NO3-, SO42- and NH4+) from BG to SpE, and a decrease in dissolved organic compounds (ionic and non-ionic) that are associated with the anthropogenic character of air masses.
We observed a high contribution of solute in cloud water derived from the dissolution of gas phase species in all cloud events. This was evident from large solute fractions of nitrate, ammonium and mono-carboxylic acids in cloud water, relative to their abundance in the aerosol phase. The comparison between droplet and aerosol composition clearly shows the limited ability of organic aerosols to act as cloud condensation nuclei. The strong contribution of gas-phase species limits the establishment of direct relationships between cloud water solute concentration and LWC that are expected from nucleation scavenging.
Cloud chemistry at the Puy de Dôme: variability and relationships with environmental factors
Atmospheric Chemistry and Physics, 2004
The chemical composition of cloud water was investigated during the winter-spring months of 2001 and 2002 at the Puy de Dôme station (1465 m above sea level, 45 • 46 22 N, 2 • 57 43 E) in an effort to characterize clouds in the continental free troposphere. Cloud droplets were sampled with single-stage cloud collectors (cut-off diameter approximately 7 µm) and analyzed for inorganic and organic ions, as well as total dissolved organic carbon. Results show a very large variability in chemical composition and total solute concentration of cloud droplets, ranging from a few mg l −1 to more than 150 mg l −1 . Samplings can be classified in three different categories with respect to their total ionic content and relative chemical composition: background continental (BG, total solute content lower than 18 mg l −1 ), anthropogenic continental (ANT, total solute content from 18 to 50 mg l −1 ), and special events (SpE, total solute content higher than 50 mg l −1 ). The relative chemical composition shows an increase in anthropogenic-derived species (NO − 3 , SO 2− 4 and NH + 4 ) from BG to SpE, and a decrease in dissolved organic compounds (ionic and non-ionic) that are associated with the anthropogenic character of air masses.
Atmospheric Research, 1994
We propose a mechanism by which condensed water within clouds becomes chemically heterogeneous due to the turbulent nature of entrainment of noncloudy air into a rising cloudy parcel. We hypothesize that the observed small-scale variability of cloud microphysics, temperature and vertical velocity results from the formation of turbulent-scale sub-regions composed of varying proportions of undiluted cloudy air mixed with dry, cloudfree air above cloud base. Cloudy regions that are exposed to a higher degree of entrainment will contain lower condensed water contents, lower temperatures, lower droplet number concentrations at smaller sizes, and lower vertical velocities as a result of e~ntrainment-induced dilution and evaporation. Greater entrainment will also increase concentrations of sulfate, nitrate and ammonium in cloudwater, and will lead to a size-dependent chemical composition of cloudwater across the range of entrainment mixtures. We find significant discrepancies between calculated SO2 oxidation rates that account for turbulent-scale variability, relative to simpler calculations that ignore turbulent-induced variability. The more exact description of a cloud composed of a heterogeneous mix of parcels yields higher sulfur oxidation rates and lower dissolved concentrations of highly soluble sulfate, nitrate and ammonia. Most current measurements and models of cloudwater chemical composition cannot resolve the fine structure of entrainment-induced fluctuations in cloud microphysics, and therefore implicitly "average out" small-scale fluctuations of momentum, heat, buoyancy and water substance within the measurement volume or numerical grid. This averaging can lead to erroneous interpretations of measurements, and may yield biased calculations of SO2 oxidation within clouds. Using measured concentrations of pertinent air quality concentrations in conjunction with a relatively simple regional-scale atmospheric chemistry model, we find that during most of the year, the neglect of small-scale cloud variability produces errors of less than 10% in calculated SO2 oxidation rates. However, errors maximize during spring and autumn when cloudwater acidities and hydrogen peroxide concentrations are relatively low. During these periods, the SO2 oxidation potential within clouds may only be ~ 70% of the potential when small-scale cloud variability is accounted for. These results suggest that measurements and model cal
Arhiv za higijenu rada i toksikologiju, 2003
Clouds play an immense role in transport and transformation of atmospheric trace species. In the joint project FEBUKO (Field investigations of budgets and conversions of particle phase organics in tropospheric cloud processes) the microphysics and chemistry of different types of aerosols, the role of aerosol chemical composition for cloud formation as well as the chemical transformation in cloud processes have been investigated by means of ground-based cloud experiments at Mt. Schmücke in the Thuringian Forest (Germany). The groups involved used a wide range of measurements of trace gases, aerosol particles and cloud droplets at three sites to study their sources and sinks, especially those in cloud. Although kind and behaviour of organic substances were of special interest (e.g., organic acids, peroxides, organic carbon, soot) attention was paid to the role of inorganic soluble material being the main part of the cloud condensation nuclei. In this paper we present selected results ...
Atmospheric Chemistry and Physics, 2008
Physical and chemical properties of boundary layer clouds, together with relevant aerosol properties, were investigated during the first Pallas Cloud Experiment (First Pace) conducted in northern Finland between 20 October and 9 November 2004. Two stations located 6 km apart from each other at different altitudes were employed in measurements. The low-altitude station was always below the cloud layer, whereas the high-altitude station was inside clouds about 75% of the time during the campaign. Direct measurements of cloud droplet populations showed that our earlier approach of determining cloud droplet residual particle size distributions and corresponding activated fractions using continuous aerosol number size distribution measurements at the two stations is valid, as long as the cloud events are carefully screened to exclude precipitating clouds and to make sure the same air mass has been measured at both stations. We observed that a non-negligible fraction of cloud droplets originated from Aitken mode particles even at moderatelypolluted air masses. We found clear evidence on first indirect aerosol effect on clouds but demonstrated also that no simple relation between the cloud droplet number concentration and aerosol particle number concentration exists for this type of clouds. The chemical composition of aerosol particles was dominated by particulate organic matter (POM) and sulphate in continental air masses and POM, sodium and chlorine in marine air masses. The inorganic composition of cloud water behaved similarly to that of the aerosol phase and was not influenced by inorganic trace gases.
Vertical gradients of dissolved chemical constituents in evaporating clouds
1997
Vertical gradients in cloud-water composition were investigated during the Ground-based Cloud Experiment at Great Dun Fell (GDF) 1993. The cloud-water measurements were performed at two heights above the cloud base. The observed changes in cloud-water concentration were not only induced by dilution or concentration due to an increasing or decreasing liquid water content (LWC), but also by loss or uptake of chemical compounds, and, under appropriate meteorological conditions (downslope flow), by evaporation of small droplets between the two heights. The observed vertical gradients were found to be ion-specific. Higher amounts of total dissolved material were measured at greater distances above the cloud base, e.g. SO-during most of the time of the monitored cloud events. Thus, vertical gradients may be important for deposition calculations of trace substances onto vegetation via cloud-water interception. In any case, the cloud base is a very important parameter relevant for the cloud chemical studies, because it is of importance for data interpretation.