Chemical Composition Of Cloud Water Research Articles

Comparison of acidity and chemical composition of summertime cloud water and aerosol at an alpine site in Northwest China: Implications for the neutral property of clouds in the free troposphere

Aerosol and cloud acidity are essential to human health, ecosystem health and productivity, as well as climate effects. The main chemical composition of cloud water greatly varies in different regions, resulting in substantial differences in the pH of cloud water. However, the influences of the anthropogenic emissions of acidic gases and substances, alkaline dust components, and dicarboxylic acids (diacids) on the ground concerning the acidity of cloud water in the free troposphere of the Guanzhong Plain, China, remain clear. In this study, cloud water and PM2.5 samples were simultaneously collected in the troposphere (Mt. Hua, 2060 m a.s.l). The results indicated that the cloud water was alkaline (pH = 7.6) and PM2.5 was acidic (pH = 3.2). These results showed the neutral property of clouds collected in the heavily polluted Guanzhong Plain, although most previous studies always considered acidity as a marker of pollution. The sulfate (SO42−), nitrate (NO3−), and ammonium (NH4+) (SNA) of particulate matter and cloud water in the same period were compared. SO42− was dominant in particulate matters (accounting for 63.4 % of the total SNA) but substantially decreased in cloud water (only 30.1 % of the total SNA), whereas NO3− and NH4+ increased from 28.5 % and 8.2 % to 39.8 % and 30.2 %, respectively. This could be attributed to the complex formation mechanism and sources of SO42− and NO3− in the cloud. The results of ion balance indicated that a significant deficit of inorganic anion equivalents was observed in the cloud water samples. The high concentration of diacids in the cloud phase (1237.4 μg L−1) may facilitate the formation of salt complexes with NH4+, thus influencing the acidity of the cloud water. The pH of cloud water has increased in recent decades due to the sustained reduction of sulfur dioxide, which may also affect the acidity of future precipitation.

Effects of pH and light exposure on the survival of bacteria and their ability to biodegrade organic compounds in clouds: implications for microbial activity in acidic cloud water

Abstract. Recent studies have reported that interactions between live bacteria and organic matter can potentially affect the carbon budget in clouds, which has important atmospheric and climate implications. However, bacteria in clouds are subject to a variety of atmospheric stressors, which can adversely affect their survival and energetic metabolism and, consequently, their ability to biodegrade organic compounds. At present, the effects of cloud water pH and solar radiation on bacteria are not well understood. In this study, we investigated how cloud water pH (pH 3 to 6) and exposure to solar radiation impact the survival and energetic metabolism of two Enterobacter bacterial strains that were isolated from ambient air collected in Hong Kong and their ability to biodegrade organic acids. Experiments were conducted using simulated sunlight (wavelength from 320 to 700 nm) and microcosms comprised of artificial cloud water that mimicked the pH and chemical composition of cloud water in Hong Kong, South China. Our results showed that the energetic metabolism and survival of both strains depended on the pH. Low survival rates were observed for both strains at pH<4, regardless of whether the strains were exposed to simulated sunlight. At pH 4 to 5, the energetic metabolism and survival of both strains were negatively impacted only when they were exposed to simulated sunlight. Organic compounds such as lipids and peptides were detected during exposure to simulated sunlight at pH 4 to 5. In contrast, there were minimal effects on the energetic metabolism and the survival of both strains when they were exposed to simulated sunlight at pH>5. The biodegradation of organic acids was found to depend on the presence (or absence) of simulated sunlight and the pH of the artificial cloud water medium. Overall, this study provides new insights into how two common atmospheric stressors, cloud water pH and exposure to solar radiation, can influence the survival and energetic metabolism of bacteria, and consequently the roles that they play in cloud processes.

Emerging investigator series: aqueous photooxidation of live bacteria with hydroxyl radicals under cloud-like conditions: insights into the production and transformation of biological and organic matter originating from bioaerosols.

Live bacteria in clouds are exposed to free radicals such as the hydroxyl radical (˙OH), which is the main driver of many photochemical processes. While the ˙OH photooxidation of organic matter in clouds has been widely studied, equivalent investigations on the ˙OH photooxidation of bioaerosols are limited. Little is known about the daytime encounters between ˙OH and live bacteria in clouds. Here we investigated the aqueous ˙OH photooxidation of four bacterial strains, B. subtilis, P. putida, E. hormaechei B0910, and E. hormaechei pf0910, in microcosms composed of artificial cloud water that mimicked the chemical composition of cloud water in Hong Kong. The survival rates for the four bacterial strains decreased to zero within 6 hours during exposure to 1 × 10-16 M of ˙OH under artificial sunlight. Bacterial cell damage and lysis released biological and organic compounds, which were subsequently oxidized by ˙OH. The molecular weights of some of these biological and organic compounds were >50 kDa. The O/C, H/C, and N/C ratios increased at the initial onset of photooxidation. As the photooxidation progressed, there were few changes in the H/C and N/C, whereas the O/C continued to increase for hours after all the bacterial cells had died. The increase in the O/C was due to functionalization and fragmentation reactions, which increased the O content and decreased the C content, respectively. In particular, fragmentation reactions played key roles in transforming biological and organic compounds. Fragmentation reactions cleaved the C-C bonds of carbon backbones of higher molecular weight proteinaceous-like matter to form a variety of lower molecular weight compounds, including HULIS of molecular weight <3 kDa and highly oxygenated organic compounds of molecular weight <1.2 kDa. Overall, our results provided new insights at the process level into how daytime reactive interactions between live bacteria and ˙OH in clouds contribute to the formation and transformation of organic matter.

Wildfire Smoke Influence on Cloud Water Chemical Composition at Whiteface Mountain, New York.

Wildfires significantly impact air quality and climate, including through the production of aerosols that can nucleate cloud droplets and participate in aqueous-phase reactions. Cloud water was collected during the summer months (June-September) of 2010-2017 at Whiteface Mountain, New York and examined for biomass burning influence. Cloud water samples were classified by their smoke influence based on backward air mass trajectories and satellite-detected smoke. A total of 1,338 cloud water samples collected over 485days were classified by their probability of smoke influence, with 49% of these days categorized as having moderate to high probability of smoke influence. Carbon monoxide and ozone levels were enhanced during smoke influenced days at the summit of Whiteface Mountain. Smoke-influenced cloud water samples were characterized by enhanced concentrations of potassium, sulfate, ammonium, and total organic carbon, compared to samples lacking identified influence. Five cloud water samples were examined further for the presence of dissolved organic compounds, insoluble particles, and light-absorbing components. The five selected cloud water samples contained the biomass burning tracer levoglucosan at 0.02-0.09μM. Samples influenced by air masses that remained aloft, above the boundary layer during transport, had lower insoluble particle concentrations, larger insoluble particle diameters, and larger oxalate:sulfate ratios, suggesting cloud processing had occurred. These findings highlight the influence that local and long-range transported smoke have on cloud water composition.

Insights into tropical cloud chemistry in Réunion (Indian Ocean): results from the BIO-MAÏDO campaign

Abstract. We present here the results obtained during an intensive field campaign conducted in the framework of the French “BIO-MAÏDO” (Bio-physico-chemistry of tropical clouds at Maïdo (Réunion Island): processes and impacts on secondary organic aerosols' formation) project. This study integrates an exhaustive chemical and microphysical characterization of cloud water obtained in March–April 2019 in Réunion (Indian Ocean). Fourteen cloud samples have been collected along the slope of this mountainous island. Comprehensive chemical characterization of these samples is performed, including inorganic ions, metals, oxidants, and organic matter (organic acids, sugars, amino acids, carbonyls, and low-solubility volatile organic compounds, VOCs). Cloud water presents high molecular complexity with elevated water-soluble organic matter content partly modulated by microphysical cloud properties. As expected, our findings show the presence of compounds of marine origin in cloud water samples (e.g. chloride, sodium) demonstrating ocean–cloud exchanges. Indeed, Na+ and Cl− dominate the inorganic composition contributing to 30 % and 27 %, respectively, to the average total ion content. The strong correlations between these species (r2 = 0.87, p value: &lt; 0.0001) suggest similar air mass origins. However, the average molar Cl-/Na+ ratio (0.85) is lower than the sea-salt one, reflecting a chloride depletion possibly associated with strong acids such as HNO3 and H2SO4. Additionally, the non-sea-salt fraction of sulfate varies between 38 % and 91 %, indicating the presence of other sources. Also, the presence of amino acids and for the first time in cloud waters of sugars clearly indicates that biological activities contribute to the cloud water chemical composition. A significant variability between events is observed in the dissolved organic content (25.5 ± 18.4 mg C L−1), with levels reaching up to 62 mg C L−1. This variability was not similar for all the measured compounds, suggesting the presence of dissimilar emission sources or production mechanisms. For that, a statistical analysis is performed based on back-trajectory calculations using the CAT (Computing Atmospheric Trajectory Tool) model associated with the land cover registry. These investigations reveal that air mass origins and microphysical variables do not fully explain the variability observed in cloud chemical composition, highlighting the complexity of emission sources, multiphasic transfer, and chemical processing in clouds. Even though a minor contribution of VOCs (oxygenated and low-solubility VOCs) to the total dissolved organic carbon (DOC) (0.62 % and 0.06 %, respectively) has been observed, significant levels of biogenic VOC (20 to 180 nmol L−1) were detected in the aqueous phase, indicating the cloud-terrestrial vegetation exchange. Cloud scavenging of VOCs is assessed by measurements obtained in both the gas and aqueous phases and deduced experimental gas-/aqueous-phase partitioning was compared with Henry's law equilibrium to evaluate potential supersaturation or unsaturation conditions. The evaluation reveals the supersaturation of low-solubility VOCs from both natural and anthropogenic sources. Our results depict even higher supersaturation of terpenoids, evidencing a deviation from thermodynamically expected partitioning in the aqueous-phase chemistry in this highly impacted tropical area.

The development of a miniaturised balloon-borne cloud water sampler and its first deployment in the high Arctic

The chemical composition of cloud water can be used to infer the sources of particles upon which cloud droplets and ice crystals have formed. In order to obtain cloud water for analysis of chemical composition for elevated clouds in the pristine high Arctic, balloon-borne active cloud water sampling systems are the optimal approach. However, such systems have not been feasible to deploy previously due to their weight and the challenging environmental conditions. We have taken advantage of recent developments in battery technology to develop a miniaturised cloud water sampler for balloon-borne collection of cloud water. Our sampler is a bulk sampler with a cloud drop cutoff diameter of approximately 8 µm and an estimated collection efficiency of 70%. The sampler was heated to prevent excessive ice accumulation and was able to operate for several hours under the extreme conditions encountered in the high Arctic. We have tested and deployed the new sampler on a tethered balloon during the Microbiology-Ocean-Cloud-Coupling in the High Arctic (MOCCHA) campaign in August and September 2018 close to the North pole. The sampler was able to successfully retrieve cloud water samples that were analysed to determine their chemical composition as well as their ice-nucleating activity. Given the pristine conditions found in the high Arctic we have placed significant emphasis on the development of a suitable cleaning procedure to minimise background contamination by the sampler itself.

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 (Nd). Even though rigorous first-principle approaches exist to calculate Nd, the cloud and aerosol research community also relies on empirical approaches such as relating Nd to aerosol mass concentration. Here we analyze relationships between Nd 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 Nd using chemical composition. Single-species regressions reveal that the species that best predicts Nd is total sulfate (). 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 Nd was that most included sulfate (either total or non-sea-salt), 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-Nd correlation. Accounting for turbulence, quantified as the standard deviation of vertical wind speed, showed that the correlation between Nd 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 Nd 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 Nd at cloud top, whereas iron and oxalate correlated best with Nd at cloud base.

Screening of cloud microorganisms isolated at the Puy de Dôme (France) station for the production of biosurfactants

Abstract. A total of 480 microorganisms collected from 39 clouds sampled at the Puy de Dôme station (alt. 1465 m; 45°46′19′′ N, 2°57′52′′ E; Massif Central, France) were isolated and identified. This unique collection was screened for biosurfactant (surfactants of microbial origin) production by measuring the surface tension (σ) of the crude extracts, comprising the supernatants of the pure cultures, using the pendant drop technique. The results showed that 41 % of the tested strains were active producers (σ &lt; 55 mN m−1), with 7 % being extremely active (σ &lt; 30 mN m−1). The most efficient biosurfactant producers (σ &lt; 45 mN m−1) belong to a few bacterial genera (Pseudomonas and Xanthomonas) from the Υ-Proteobacteria class (78 %) and a yeast genus (Udeniomyces) from the Basidiomycota phylum (11 %). Some Bacillus strains from the Firmicutes phylum were also active but represented a small fraction of the collected population. Strains from the Actinobacteria phylum in the collection examined in the present study showed moderate biosurfactant production (45&lt;σ &lt; 55 mN m−1). Pseudomonas (Υ-Proteobacteria), the most frequently detected genus in clouds, with some species issued from the phyllosphere, was the dominant group for the production of biosurfactants. We observed some correlations between the chemical composition of cloud water and the presence of biosurfactant-producing microorganisms, suggesting the “biogeography” of this production. Moreover, the potential impact of the production of biosurfactants by cloud microorganisms on atmospheric processes is discussed.

Speciation of water-soluble inorganic, organic, and total nitrogen in a background marine environment: Cloud water, rainwater, and aerosol particles

[1] Cloud water, rainwater, and aerosol particles were collected in Puerto Rico from December 2004 to March 2007 in order to investigate their chemical composition, relation to sources, and removal processes. The species analyzed were inorganic ions, metals, total and dissolved organic carbon (TOC, DOC), total nitrogen (TN), and organic acids. For all samples, the dominant species were marine (Na+, Cl−), representing about 50%–65% of total content. Non-sea-salt fraction was dominated by SO42− (17%–25%), followed by water-soluble organic (2%–8%) and total nitrogen (2% –6%) compounds. Organic acids represented contributions to the organic fraction in cloud water of 20% and 6% for aerosol particles. Inorganic species were predominant in total nitrogen portion. The chemical composition of cloud water, rainwater, and aerosol particles were observed to be sensitive to transport patterns. Air masses from northwest Africa showed the highest concentrations of nss-Ca2+, Fe, and Al, suggesting a crustal origin. The pH values for cloud water and rainwater observed under this transport pattern were higher than background conditions, probably due to the alkalinity associated with nss-Ca2+. The highest concentrations of Cl− and SO42−, with lower pH, were measured during periods of influence from Soufriere Hills volcano eruptions, most likely due to emitted SO2 and HCl. Air masses from North America had an anthropogenic influence, where levels of nss-SO42−, TOC, and TN were higher (∼4 times) than in clean air masses. These results suggest that long-range transport could be an extra source of metals and organic/nitrogen species to the Caribbean region ecosystems.

Cloud and the corresponding precipitation chemistry in south China: Water‐soluble components and pollution transport

To investigate the transport and deposition of pollutants in south China, the chemical composition of cloud water and rainwater was studied at Mount Heng, which is located in the heart of China's acid rain affected region. A total of 194 cloud samples and 38 event‐based precipitation samples from March to May 2009 were analyzed for a wide variety of water‐soluble compounds. The volume‐weighted mean (VWM) pH of cloud water was 3.80, indicating an acidic nature. Compared with cloud water, precipitation was much less acidic with a VWM pH value of 4.35. The concentration results show that in cloud water, SO42− was the dominant anion, followed by NO3−, controlling the acidity, while NH4+ accounted for 69.8% of the total cations, dominating the cloud water neutralization. In rainwater, a similar situation appeared, but with a slightly higher Ca2+concentration. In both cloud water and precipitation the acidities were found to be mainly due to sulfuric acid, followed by nitric acid. The calculation of neutralization factors and the application of multiple linear regression analysis showed the higher NH4+ contribution to the neutralization process in both types of samples. The very weak correlations of ions in rain with the ones in cloud water on the event basis suggested that cloud and precipitation events may be associated with different air masses. With relatively high ionic concentrations and higher frequency, air masses from the east and south directions were associated with the high cloud deposition of the major species at our site.

Chemical Composition of Cloud Water in the Puerto Rican Tropical Trade Wind Cumuli

As part of the Rain In Cumulus over the Ocean Experiment (RICO) and the Puerto Rico Aerosol and Cloud Study (PRACS), cloud water was collected at East Peak (EP) in Puerto Rico. The main objective of this study was to determine the concentrations of water-soluble species (Cl−, NO3 −, SO4 2−, NH4 +, Ca2+, H+, Mg2+, K+, and Na+) in water samples taken from clouds influenced by tropical trade winds. The most abundant inorganic species were Na+ (average 465 µeq l−1) and Cl− (434 µeq l−1), followed by Mg2+ (105 µeq l−1), SO4 2− (61 µeq l−1), and NO3 − (25 µeq l−1). High concentrations of nss–SO4 2 (28 µeq l−1), NO3 − (86 µeq l−1), and H+ (14.5 µeq l−1) were measured with a shift in air masses origin from the North Atlantic to North American continent, which reflected a strong anthropogenic influence on cloud chemistry at EP. Long-range transport of particles and acid gases seems to be the factor responsible for fluctuations in concentrations and pH of cloud water at East Peak. When under trade wind influences the liquid phase concentrations of all inorganic substances were similar to those found in clouds in other clean maritime environments.

Changes of cloud water chemical composition in the Western Sudety Mountains, Poland

The changing chemical composition of cloud water and precipitation in the Western Sudety Mountains are discussed against the background of air-pollution changes in the Black Triangle since the 1980s until September 2004. A marked reduction of sulphur dioxide emissions between the early 1990's and the present (from almost 2 million tons to around 0.2 million tons) has been observed, with a substantial decline of sulphate and hydrogen concentration in cloud water (SO 4 2− from more than 200 to around 70 μmol l − 1 ; H + from 150 to 50 μmol l − 1 ) and precipitation (SO 4 2− from around 80 to 20–30 μmol l − 1 ; H + from around 60 to 10–15 μmol l − 1 ) samples. At some sites, where fog/cloud becomes the major source of pollutants, deposition hot spots are still observed where, for example, nitrogen deposition can exceed 20 times the relevant critical load. The results show that monitoring of cloud water chemistry can be a sensitive indicator of pollutant emissions.

An important oceanic source of micro-organisms for cloud water at the Puy de Dôme (France)

A description of the microbial content of cloud water based on samples collected along an almost 2-year-period is presented. Cloud water from 14 events was sampled at the Puy de Dôme summit (1465 m a.s.l.). Total bacterial and fungal cells were about, respectively, 8.1×10 4 and 5.9×10 3 mL −1, with more than 10% of the fungi but <1% of bacteria recovered by cultivation at 15 or 27 °C. However, ATP concentration of about 0.40 pmol mL −1 shows that a large majority of these cells are likely viable but not cultivable and remain alive in clouds. A high variability is noticed in the microbial content, and local meteorological variations are not involved. A seasonal effect is shown, with a general increase in the concentrations of cultivable micro-organism and of total fungal cells during summer and autumn. Moreover, psychrotolerant micro-organisms, with respect to those growing only at 27 °C, are more numerous during winter. The concentrations of micro-organisms (total and cultivable) were clearly linked to the chemical composition of cloud water: an increase with increasing oceanic contribution is pointed, and bacteria concentration decreases with increasing anthropic influence. A preferential integration of micro-organisms emitted by the ocean into cloud droplets, compared to micro-organisms from other sources, is likely to occur, making the ocean a major source of micro-organisms for cloud water. It also suggests that the toxicity of polluted cloud water could disturb an eventual multiplication of cells in atmospheric droplets.

Numerical quantification of sources and phase partitioning of chemical species in cloud: application to wintertime anthropogenic air masses at the Puy de Dôme station

The Model of Multiphase Cloud Chemistry M2C2 has recently been extended to account for nucleation scavenging of aerosol particles in the cloud water chemical composition. This extended version has been applied to multiphase measurements available at the Puy de Dôme station for typical wintertime anthropogenic air masses. The simulated ion concentrations in cloud water are in reasonable agreement with the experimental data. The analysis of the sources of the chemical species in cloud water shows an important contribution from nucleation scavenging of particles which prevails for nitrate, sulphate and ammonium. Moreover, the simulation shows that iron, which comes only from the dissolution of aerosol particles in cloud water, has a significant contribution in the hydroxyl radical production. Finally, the simulated phase partitioning of chemical species in cloud are compared with measurements. Numerical results show an underestimation of interstitial particulate phase fraction with respect to the measurements, which could be due to an overestimation of activated mass by the model. However, the simulated number scavenging efficiency of particles agrees well with the measured value of 40% of total number of aerosol particles activated in cloud droplets. Concerning the origin of chemical species in cloud water, the model reproduces quite well the contribution of gas and aerosol scavenging estimated from measurements. In addition, the simulation provides the contribution of in-cloud chemical reactivity to cloud water concentrations.

Cloud chemistry at the Puy de Dôme: variability and relationships with environmental factors

Abstract. 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.

Chemical attributes of some clouds amid a forest ecosystem's trees

Simultaneous physical and chemical characteristics of clouds amid and above the trees of a montane forest, located about 3.3 km southwest of Mt. Mitchell, NC, were collected between 13 and 22 June 1993. This paper summarizes the chemical characteristics of the cloud droplets amid the trees. The ionic composition and pH of the analyzed amid-canopy cloud water samples are generally consistent with those of previous above-canopy cloud water samples obtained at this site. Magnesium, sodium, and calcium are highly correlated to each other amid the canopy as compared to above the canopy. Above-canopy and amid-canopy cloud-only episodes, with concurrent event-averaged cloud water pH values at or below 3.1, generally contain more magnesium, sodium, and calcium in the amid-canopy cloud water samples compared to concurrent above-canopy cloud water samples. The observed chemical differences between the amid-canopy cloud and the above-canopy cloud suggest an unhealthier environment for the tree canopy when the cloud water traversing this site has a pH value at or below 3.1. The predominant ion deposition fluxes were calculated to provide preliminary data for studies designed to explicitly quantify how the chemical composition of cloud water affects tree health.

Spring time sources and sinks of Peroxyacetyl Nitrate in the UK and its contribution to acidification and nitrification of cloud water

During spring the atmospheric concentration of Peroxyacetyl Nitrate, PAN, in the UK varies over three orders of magnitude due to long range transport and local photochemical production. An experiment at Great Dun Fell was used to determine which of these sources of PAN controlled spring time concentrations and to quantify the contribution of PAN to oxidised nitrogen in cloud water. The gas phase mixing ratio of a wide range of trace gas pollutants, including PAN, along with cloud water chemical composition and aerosol/cloud droplet distributions were measured. A chemical model was developed to determine the contribution of PAN hydrolysis to cloud water nitrification and to quantify the sink strengths of PAN. Chemical reaction following thermal decomposition was found to be the dominant sink mechanism in the model but transport was the most important factor controlling PAN concentration. During cloud episodes PAN concentrations varied from 100 ppt to over 1 ppb but the calculated inorganic oxidised nitrogen loading in the cloud due to PAN dissolution and hydrolysis was an insignificant fraction of the observed total oxidised nitrogen loading of the cloud. Extrapolation of the model to persistent cloud in marine conditions showed that PAN has a negligible effect on cloud nitrification. It was concluded that PAN concentrations were heavily influenced by regional concentrations and that the hydrolysis of PAN in cloud water was an insignificant source of oxidised nitrogen in cloud water.

A relationship between liquid water content and chemical composition in clouds

In this paper we present two-year results from the Cloud Chemistry Measurements Programme, carried out at Mt. Brocken/Hart (Germany) to assess the influence of cloud physical parameters on the chemical composition of clouds. There are large variations in the chemical composition of cloud water. We found that the liquid water content of clouds predominantly determines the ionic content. The relationship is best approximated by a power function, nearly identical for all chemical species. We identified deviations of data points from the general relationship accompanying events with different air pollution situations. An important conclusion is that cloud chemistry monitoring in the sense of air pollution studies is meaningless without measurement of cloud physical parameters. These are liquid water content, cloud base altitudes, and to some extent, droplet size distribution.

A climatology of cloud chemistry for the eastern United States derived from the mountain cloud chemistry project

The chemical composition of clouds collected in the eastern United States has been intensely monitored over a 4-year period as part of the Mountain Cloud Chemistry Project. On the basis of these measurements we prepared a climatology for cloud chemistry, using simple statistical analyses tools and incorporating meteorological and cloud physical and chemical information. Five mountain stations have been established for cloud collection covering the northern and southern Appalachian Mountain range: Whiteface Mountain, New York; Mount Moosilauke, New Hampshire; Shenandoah Mountain, Virginia; Whitetop Mountain, Virginia; and Mount Mitchell, North Carolina. This review presents the major result from this 4-year measurement program. Cloud cover and cloud base over the eastern United States were deduced from the global real-time nephanalysis archives produced by the U.S. Air Force, augmented by local observations. Both active and passive cloud collectors were deployed to sample cloud water on an hourly basis, i.e., with sufficient time resolution to resolve synoptic scale phenomena. Chemical analysis of cloud water was performed by a central analytical laboratory with occasional on-site analysis to satisfy quality control procedures. Reliable methods now exist for collecting cloud-water samples in sufficient quantities for detailed chemical analysis. The chemical composition of cloud water varied significantly between sites. However, the differences in cloud-water ion concentration do not necessarily establish a geographic gradient between the sites but rather reflect differences in air-mass trajectories associated with the synoptic air-flow pattern and differences in sample location above cloud base. The dependence of cloud-water ion concentrations on synoptic weather type and observed differences in relative frequencies of warm sector, marine flow, and post-cold frontal synoptic types between northern and southern sites suggest that the north–south differences in cloud-water ion concentrations are related to cloud climatology at the northern sites. When air-mass trajectories shift from southwest to northwest, the concentrations of H+, SO42−, NO3− and NH4+ normally decrease but the southern sites continue to receive high concentrations under northwest flow. The height of cloud-water sample collection above cloud base was found to be an additional source of variability in both cloud-water chemistry and liquid-water content. Seasonal variation in cloud-water chemical composition was investigated at one site only. Sulfate levels were found to be significantly lower in supercooled clouds (i.e., during the 'cold' season) than in 'warm' clouds, but nitrate levels remained about the same.Key words: cloud chemistry, cloud frequency, air-mass trajectories, ANOVA.

The chemical composition of intercepted cloudwater in the Sierra Nevada

The chemical composition of cloudwater in the Sierra Nevada is dominated by NO 3 −, SO 4 2−, and NH 4 +. Cloudwater pH is determined largely by the balance between the concentrations of these three species, although inputs of formic and acetic acid also are believed to be important, particularly when anthropogenic inputs are small. Cloudwater samples collected in Sequoia National Park (SNP) exhibited pH values ranging from 3.9 to 6.5; Yosemite National Park (YNP) cloudwater samples had pH values ranging from 3.8 to 5.2. Samples collected at YNP were more acidic than those collected at SNP. The difference in pH between the two regions appears to be due to relatively small differences in inputs of NO 3 −, SO 4 2−, and NH 4 +. In the absence of inputs of NH 3, cloudwater pH values in the Sierra may fall below 3. Over 250 h of cloud interception were observed during a 12 month period at a cloud monitoring site at 1856 m elevaton in SNP. Estimates of cloudwater deposition of NO 3 −, SO 4 2−, and NH 4 + indicate that cloud interception contributes significantly to regional acid deposition for closed forest canopies. Cloud interception may be the dominant deposition mechanism for isolated conifers and ridgetop canopies, where wind speeds are higher and cloudy air parcels can impact directly on foliar surfaces.