Cloud Water Samples Research Articles

Molecular composition of clouds: a comparison between samples collected at tropical (Réunion Island, France) and mid-north (Puy de Dôme, France) latitudes

Abstract. The composition of dissolved organic matter of cloud water has been investigated through non-targeted high-resolution mass spectrometry on only a few samples that were mostly collected in the Northern Hemisphere in the USA, Europe and China. There remains, therefore, a lack of measurements for clouds located in the Southern Hemisphere, under tropical conditions and influenced by forest emissions. As a matter of fact, the comparison of the composition of clouds collected in different locations is challenging since the methodology for the analysis and data treatment is not standardized. In this work, the chemical composition of three samples collected at Réunion Island (REU) during the BIO-MAÏDO field campaign, in the Indian Ocean, with influences from marine, anthropogenic and biogenic (tropical) emissions, is investigated and compared to the chemical composition of samples collected at the Puy de Dôme (PUY) observatory in France. The same methodology of analysis and data treatment was employed, producing a unique dataset for the investigation of the molecular composition of organic matter in cloud water. Besides the analysis of elemental composition, we investigated the carbon oxidation state (OSC) of dissolved organic matter, finding that overall samples collected at PUY are more oxidized than those collected at REU. Molecular formulas were also classified based on stoichiometric elemental ratios, showing the high frequency and abundance of reduced organic compounds, classified as lipids (LipidC), in this matrix, which led to a search for terpene oxidation products in cloud water samples. To better discriminate between samples collected at PUY and REU, statistical analysis (principal component analysis and agglomerative hierarchical clustering) was performed on the ensemble of molecular formulas and their intensities. Samples collected at REU have a different composition from samples collected at PUY, which is mainly linked to different primary sources, the processing of organic matter in cloud water and the influence of different primary emissions at the two locations.

Formation of In‐Cloud Aqueous‐Phase Secondary Organic Matter and Related Characteristic Molecules

AbstractThe formation process of in‐cloud aqueous‐phase secondary organic matter (aqSOM) and its characteristics are unclear. Herein, water‐soluble inorganic ions, oxalate, and water‐soluble organic carbon (WSOC) were determined in cloud water and aerosol (PM2.5) samples simultaneously collected at a remote mountain site in southern China during spring 2018 and winter 2020. The molecular compositions of water‐soluble organic matter (WSOM) in cloud water and aerosols were analyzed by a Fourier transform ion cyclotron resonance mass spectrometer in negative electrospray ionization (ESI‐) mode. The results showed that the mean concentration of WSOC was 6.27–8.54 mg C L−1 in cloud water and 0.60–1.37 μg C m−3 in aerosols. The strong correlation observed between WSOM and aqueous secondary matter (e.g., NO3− and oxalate), the positive matrix factorization results, and the elevated WSOM/K+ ratios observed in cloud water suggested enhanced aqSOM formation in cloud water. According to random forest analysis, the factors related to in‐cloud WSOM variation mainly included secondary ions, K+, cloud water pH, and atmospheric NOx. Additionally, 37 characteristic in‐cloud aqSOM molecules, classified as ‐Ox, ‐NOx, ‐N2Ox, and ‐N1‐2OxS, mainly consisting of dicarboxylic acids, nitrophenols, and dinitrophenols, were identified using linear discriminant analysis effect size (LefSe). The characteristic N‐ and S‐containing molecules in in‐cloud aqSOM with carbon numbers >10 had low or extremely low volatility; therefore, they might contribute to secondary organic aerosol formation after droplet evaporation. The results revealed the modifying effects of in‐cloud processes on aerosol organic composition at the molecular level and could improve our understanding of aerosol–cloud interactions.

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.

Influences of sources and weather dynamics on atmospheric deposition of Se species and other trace elements

Abstract. Atmospheric deposition is an important source of the micronutrient selenium for terrestrial ecosystems and food chains. However, the factors determining the total concentrations and chemical forms (speciation) of selenium in atmospheric deposition remain poorly understood. Here, aerosol samples were collected weekly over 5 years at Pic du Midi Observatory (French Pyrenees), alongside highly temporally resolved samples of aerosols, precipitation, and cloud water taken during a 2-month campaign. Firstly, measurements of selenium, other elements, and water isotopes were combined with sophisticated modelling approaches (aerosol–chemistry–climate SOCOL-AERv2 model and air parcel backward trajectories and Lagrangian moisture source analyses). Aerosol selenium measurements agreed well with SOCOL-AERv2-predicted values, and interestingly, higher fluxes of selenium and other elements were associated with deep convective activity during thunderstorms, highlighting the importance of local cloud dynamics in high deposition fluxes. Our results further indicate the coupling of element and water cycles from source to cloud formation, with decoupling during precipitation due to below-cloud scavenging. Secondly, selenium speciation was investigated in relation to sulfur speciation, organic composition, and moisture sources. While in the 5-year aerosol series, selenite (SeIV) was linked to anthropogenic source factors, in wet deposition it was related to pH and Atlantic moisture sources. We also report an organic selenium fraction, tracing it back to a marine biogenic source in both aerosols and wet deposition. With a comprehensive set of observations and model diagnostics, our study underscores the role of weather system dynamics alongside source contributions in explaining the atmospheric supply of trace elements to surface environments.

Seasonal variation of mercury in cloud water at a mountaintop in subtropical Hong Kong: Influences of transboundary transport and sea-salt aerosol

Understanding the distribution and controlling factors of mercury (Hg) speciation in cloud water is crucial for predicting the fate of atmospheric Hg and assessing the environmental impacts of Hg in cloud water. In this study, we collected 85 cloud water samples during autumn and spring at a mountaintop (957 m a.s.l.) in Hong Kong, China. The concentrations of total Hg (THg) in cloud water varied from 3.6 to 225.3 ng L−1, with volume-weighted mean values of 32.1 ng L−1 in autumn and 24.4 ng L−1 in spring. Due to the strong acidic condition of the cloud water, dissolved Hg (DHg) contributed to two-thirds of THg, with Hg complexes by dissolved organic matter (DOM) and chloride being the predominant species of DHg according to chemical equilibrium modeling simulations. Moreover, the levels of Hg-DOM were significantly higher in autumn cloud water compared to spring, and the latter contained more Hg(II)-halide complexes. These differences could be attributed to the different air mass pathways and their emission sources. By combining backward trajectories and Positive Matrix Factorization (PMF) models, we found that air masses originating from the inland Pearl River Delta region, which were only present in autumn cloud water and strongly influenced by stationary coal combustion, were responsible for the highest concentrations of THg, DHg, particulate Hg (PHg) and Hg-DOM. Additionally, air masses originating from regions in China-Indochina Peninsula were only found in spring samples and were significantly influenced by stationary coal combustion, industrial and biogenic sources, contributing to elevated proportions of methylmercury (MeHg) and PHg. In contrast, marine air masses mainly from the western Pacific Ocean contributed to high levels of Hg(II)-halide complexes, especially in spring cloud water. The dissolution and conversion of Hg from sea salt aerosols played a significant role in the enhanced DHg levels observed during cloud processing.

Changed mercury speciation in clouds driven by changing cloud water chemistry and impacts on photoreduction: Field evidence at Mt. Tai in eastern China

Chemical speciation of mercury (Hg) in clouds largely determines the photochemistry of Hg in the atmosphere and consequently influences Hg deposition on the surface through precipitation. Cloud water chemistry has notably changed over the last decade in response to global changes, however, the effects on Hg speciation remain poorly understood. During summer 2021, we collected sixty cloud water samples at Mt. Tai in eastern China and compared the cloud chemistry and Hg speciation with our previous findings during summer 2015. The results showed that although there were no statistically significant differences in the concentrations of total Hg (THg), dissolved Hg (DHg), and particulate Hg (PHg), there was a distinct shift in DHg species from the predominated Hg-DOM (78.6% in 2015 campaign) to the more homogeneously distributed Hg(OH)2 (28.4% in 2021 campaign), HgBr2 (26.5%), Hg-DOM (17.3%) and HgBrOH (17.0%). Changes in cloud water chemistry, particularly the significant increase in pH values to 6.49 ± 0.27 and unexpectedly high levels of bromide ions (Br−, 0.19 ± 0.22 mg L−1), were found to drive the changing of Hg speciation by enhancing Hg(II) hydrolysis and binding by Br−. Elevated Br− originating primarily from the continent likely caused noticeable differences in the dominating DHg species between cloud water sourced from marine and continental regions. The changes in chemical speciation of DHg were estimated to result in a 2.6-fold decrease in Hg(II) photoreduction rate between 2015 and 2021 campaigns (0.178 ± 0.054 h−1 vs. 0.067 ± 0.027 h−1), implying a shortened lifetime of atmospheric Hg and increased ecological risks associated with Hg wet deposition.

Experimental Determination of Mercury Photoreduction Rates in Cloudwater

AbstractRedox chemistry controls the behavior of mercury during long‐range atmospheric transport. Despite major progress in understanding the oxidation process in the atmosphere, the mechanism of mercury reduction, especially the aqueous‐phase and multi‐phase reactions in cloudwater, remains poorly known. Here we report experimentally determined rates of in‐cloud mercury photoreduction using cloudwater samples collected from a forested area in the Canary Islands, Spain. Mercury concentrations in cloudwater varied greatly from 0.04 to 19.9 nM (7.89 ± 6.11 nM) for total mercury and 0.02 to 4.98 nM (1.16 ± 1.49 nM) for the dissolved fraction, with particulate mercury being the dominant fraction in most of the samples. The mercury concentrations were elevated in comparison with those previously reported for atmospheric waters, reflecting the impact of a large‐scale forest wildfire that occurred shortly before the sampling campaign on a neighboring island. Mercury photoreduction was determined by two independent methods: under natural solar radiation at a nearby mountain site located in the free troposphere and under UV radiation in the laboratory. In addition to aqueous‐phase photoreduction, multi‐phase photoreduction involving particulate mercury also occurred in cloudwater, with the latter becoming dominant once dissolved mercury had been depleted. Overall, the pseudo‐first‐order rate constants for in‐cloud mercury photoreduction varied from 0.07 to 0.21 hr−1, which are one order of magnitude lower than the values presumed in global mercury transport models. Our results suggest that in‐cloud reactions alone are insufficient to account for mercury reduction in the atmosphere and that other pathways, such as gas‐phase reactions, must exist and need to be properly incorporated into future models.

Recent Progress and Applications of Thermal Lens Spectrometry and Photothermal Beam Deflection Techniques in Environmental Sensing.

This paper presents recent development and applications of thermal lens microscopy (TLM) and beam deflection spectrometry (BDS) for the analysis of water samples and sea ice. Coupling of TLM detection to a microfluidic system for flow injection analysis (μFIA) enables the detection of microcystin-LR in waters with a four samples/min throughput (in triplicate injections) and provides an LOD of 0.08 µg/L which is 12-times lower than the MCL for microcystin-LR in water. μFIA-TLM was also applied for the determination of total Fe and Fe(II) in 3 µL samples of synthetic cloudwater. The LODs were found to be 100 nM for Fe(II) and 70 nM for total Fe. The application of µFIA-TLM for the determination of ammonium in water resulted in an LOD of 2.3 µM for injection of a 5 µL sample and TLM detection in a 100 µm deep microfluidic channel. For the determination of iron species in sea ice, the BDS was coupled to a diffusive gradient in the thin film technique (DGT). The 2D distribution of Fe(II) and total Fe on DGT gels provided by the BDS (LOD of 50 nM) reflected the distribution of Fe species in sea ice put in contact with DGT gels.

How Well Do We Handle the Sample Preparation, FT-ICR Mass Spectrometry Analysis, and Data Treatment of Atmospheric Waters?

FT-ICR MS (Fourier-transform ion cyclotron resonance mass spectrometry) analysis has shown great potential to aid in the understanding of the extremely high molecular diversity of cloud water samples. The main goal of this work was to determine the differences in terms of formula assignment for analytical (i.e., measurement replicates) and experimental replicates of a given cloud water sample. The experimental replicates, obtained by solid phase extraction, were also compared to the results obtained for freeze-dried samples to evaluate whether the presence of salts interferes with the analysis. Two S/N ratios, generally adopted for atmospheric samples, were evaluated, and three different algorithms were used for assignment: DataAnalysis 5.3 (Bruker), Composer (Sierra Analytics), and MFAssignR (Chemical Advanced Resolution Methods Lab). In contrast to other works, we wanted to treat this comparison from the point of view of users, who usually must deal with a simple list of m/z ratios and intensity with limited access to the mass spectrum characteristics. The aim of this study was to establish a methodology for the treatment of atmospheric aqueous samples in light of the comparison of three different software programs, to enhance the possibility of data comparison within samples.

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.

Atmospheric Nitrated Phenolic Compounds in Particle, Gaseous, and Aqueous Phases During Cloud Events at a Mountain Site in North China: Distribution Characteristics and Aqueous‐Phase Formation

AbstractNitrated phenolic compounds in the atmosphere are receiving increasing attention due to their light absorption and biological toxicity. In this study, particulate, gaseous, and cloud water samples were simultaneously collected during cloud events at the summit of Mount Tai in northern China in spring, summer, and winter and the contents of 11 nitrated phenolic compounds were determined. The seasonal average concentrations of the total nitrated phenolic compounds in particles were in the range of 7.3–27.1 ng m−3, a little lower than those measured in the gas‐phase (18.3–70.6 ng m−3). Their concentrations in cloud water were at the levels of 168.4–438.5 μg L−1. 4‐Nitrophenol and nitrosalicylic acids were the dominant compounds in particles, while 4‐nitrophenol and 2,4‐dinitrophenol were the most abundant in the gas phase and cloud water samples. During cloud events, most nitrated phenolic compounds were mainly distributed in the particle phase, except dinitrophenols which were mainly distributed in the gas phase in winter. The field‐derived effective Henry's law coefficients were several orders of magnitude higher than their theoretical values in pure water. Moreover, the measured concentrations of particulate nitrated phenolic compounds were substantially greater than the theoretical predictions, especially in spring. The above results indicate that nitrated phenolic compounds were partly formed via aqueous‐phase reactions inside the cloud droplets or on the wet particle surfaces, which changed their distribution patterns. The much higher ratios of 2,4‐dinitrophenol to the sum of 4‐nitrophenol and 5‐nitrosalicylic acid in cloud water than those in particles further confirm the enhanced formation via aqueous processes.

Puy de Dôme Station (France): A Stoichiometric Approach to Compound Classification in Clouds

AbstractSeven cloud water samples were collected from May to October 2018 at the Puy de Dôme station (PUY) in France and analyzed by positive‐ion atmospheric pressure photoionization [(+)APPI] Fourier transform ion cyclotron resonance mass spectrometry. The assigned formulas (ranging from 3,865 to 6,380) were attributed using the multidimensional stoichiometric constraint classification of Rivas‐Ubach et al. (2018, https://doi.org.10.1021/acs.analchem.8b00529) to six main categories (RUCs): LipidC, ProteinC, Amino‐sugarC, CarbohydrateC, NucleotideC, and OxyaromaticC. Back trajectories were calculated by the computing atmospheric trajectory tool (CAT) model to obtain information on the air mass history. Partial least square regressions were performed using chemical data, CAT back‐trajectory calculations and FT‐ICR MS data to analyze the environmental variability of the organic sample composition. ProteinC is correlated with the continental surface for air masses transported within the boundary layer, and Amino‐sugarC is strongly correlated with acetate, NO3− and NH4+, suggesting Anthropogenic sources for amino sugars and proteins. LipidC is correlated with the sea surface for air masses transported within the free troposphere, confirming the long‐range transport of marine biogenic sources. Concerning Oxy‐aromaticC, given the correlations with oxidants and pollutants, as well as anti‐correlations with local influence, we proposed a mechanism of oxidation from remote anthropogenic sources.

High number concentrations of transparent exopolymer particles in ambient aerosol particles and cloud water – a case study at the tropical Atlantic Ocean

Abstract. Transparent exopolymer particles (TEPs) exhibit the properties of gels and are ubiquitously found in the world oceans. TEPs may enter the atmosphere as part of sea-spray aerosol. Here, we report number concentrations of TEPs with a diameter > 4.5 µm, hence covering a part of the supermicron particle range, in ambient aerosol and cloud water samples from the tropical Atlantic Ocean as well as in generated aerosol particles using a plunging waterfall tank that was filled with the ambient seawater. The ambient TEP concentrations ranged between 7×102 and 3×104 #TEP m−3 in the aerosol particles and correlations with sodium (Na+) and calcium (Ca2+) (R2=0.5) suggested some contribution via bubble bursting. Cloud water TEP concentrations were between 4×106 and 9×106 #TEP L−1 and, according to the measured cloud liquid water content, corresponding to equivalent air concentrations of 2–4×103 #TEP m−3. Based on Na+ concentrations in seawater and in the atmosphere, the enrichment factors for TEPs in the atmosphere were calculated. The tank-generated TEPs were enriched by a factor of 50 compared with seawater and, therefore, in-line with published enrichment factors for supermicron organic matter in general and TEPs specifically. TEP enrichment in the ambient atmosphere was on average 1×103 in cloud water and 9×103 in ambient aerosol particles and therefore about two orders of magnitude higher than the corresponding enrichment from the tank study. Such high enrichment of supermicron particulate organic constituents in the atmosphere is uncommon and we propose that atmospheric TEP concentrations resulted from a combination of enrichment during bubble bursting transfer from the ocean and a secondary TEP in-situ formation in atmospheric phases. Abiotic in-situ formation might have occurred from aqueous reactions of dissolved organic precursors that were present in particle and cloud water samples, whereas biotic formation involves bacteria, which were abundant in the cloud water samples. The ambient TEP number concentrations were two orders of magnitude higher than recently reported ice nucleating particle (INP) concentrations measured at the same location. As TEPs likely possess good properties to act as INPs, in future experiments it is worth studying if a certain part of TEPs contributes a fraction of the biogenic INP population.

Influence of strong iron-binding ligands on cloud water oxidant capacity

Iron (Fe) plays a dual role in atmospheric chemistry: it is involved in chemical and photochemical reactivity and serves as a micronutrient for microorganisms that have recently been shown to produce strong organic ligands. These ligands control the reactivity, mobility, solubility and speciation of Fe, which have a potential impact on Fe bioavailability and cloud water oxidant capacity.In this work, the concentrations of Fe-binding ligands and the conditional stability constants were experimentally measured for the first time by Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) technique in cloud water samples collected at puy de Dôme (France). The conditional stability constants, which indicate the strength of the Fe-ligand complexes, are higher than those considered until now in cloud chemistry (mainly Fe-oxalate). To understand the effect of Fe complexation on cloud water reactivity, we used the CLEPS cloud chemistry model. According to the model results, we found that Fe complexation impacts the hydroxyl radical formation rate: contrary to our expectations, Fe complexation by natural organic ligands led to an increase in hydroxyl radical production. These findings have important impacts on cloud chemistry and the global iron cycle.

Cloud and fog deposition: Monitoring in high elevation and coastal ecosystems. The past, present, and future

Deposition of pollutants by cloud water exceeds deposition by precipitation and dry deposition in many high elevation settings. This larger loading of pollutants in these environments is due to a combination of factors such as high frequency of cloud immersion, high wind speeds, orographic enhancement of precipitation, and large leaf area of tree species typical in these environments. Fog-impacted coastal ecosystems also experience increased pollutant deposition similar to cloud-impacted high elevation sites. Therefore, development of meaningful critical load values and total nitrogen budgets for high-elevation and fog-impacted sites requires reliable cloud and fog water deposition estimates. The cost and labor intensity of cloud/fog water sample collection have made it difficult to conduct long-term studies that would provide the data needed to develop accurate estimates. Current understanding of fog formation, transport, and the role of fog and cloud deposition in hydrogeological and biogeochemical cycles is incomplete due, in part, to lack of a concerted interdisciplinary approach to the problem. Historically, these obstacles have limited interest in and collection of cloud and fog water samples. In addition to measurements of cloud/fog chemical composition, documenting fog/cloud deposition fluxes of pollutant and nutrient species requires knowledge of cloud/fog physical properties, frequency and duration of fog/cloud interception with landscapes, properties of vegetation on those landscapes, and properties of the wind that drive droplet/vegetation interactions. Because drop deposition efficiency is dependent on drop size, it is also important to consider variations in fog/cloud drop composition with drop size as species enriched in larger/smaller drops will experience enhanced/reduced deposition rates.This paper presents summary results from a small U.S. cloud water monitoring network that operated from the mid-nineties through 2011, as well as a brief qualitative review of other cloud and fog water studies conducted in the United States (including Puerto Rico), Europe, South America/Pacific, and Asia. Current collection methods are also reviewed. Recent scientific efforts by the National Atmospheric Deposition Program's (NADP) Total Deposition Science Committee and NADP's Critical Loads of Atmospheric Deposition Science Committee have identified occult (cloud/fog) deposition as a “need” in developing critical loads for ecosystems that experience significant cloud and fog impaction. To this end, remaining knowledge gaps and suggestions for future research to investigate these gaps are explored.

The number fraction of iron-containing particles affects OH, HO<sub>2</sub> and H<sub>2</sub>O<sub>2</sub> budgets in the atmospheric aqueous phase

Abstract. Reactive oxygen species (ROS), such as OH, HO2 and H2O2, affect the oxidation capacity of the atmosphere and cause adverse health effects of particulate matter. The role of transition metal ions (TMIs) in impacting the ROS concentrations and conversions in the atmospheric aqueous phase has been recognized for a long time. Model studies usually assume that the total TMI mass as measured in bulk aerosol or cloud water samples is distributed equally across all particles or droplets. This assumption is contrary to single-particle measurements that have shown that only a small number fraction of particles contain iron and other TMIs (FN,Fe<100 %), which implies that also not all cloud droplets contain TMIs. In the current study, we apply a box model with an explicit multiphase chemical mechanism to simulate ROS formation and cycling in aqueous aerosol particles and cloud droplets. Model simulations are performed for the range of 1 % ≤ FN,Fe ≤ 100 % for constant pH values of 3, 4.5 and 6 and constant total iron mass concentration (10 or 50 ng per cubic meter of air). Model results are compared for two sets of simulations with FN,Fe<100 % (FeN<100) and 100 % (FeBulk). We find the largest differences between model results in OH and HO2 / O2- concentrations at pH = 6. Under these conditions, HO2 is subsaturated in the aqueous phase because of its high effective Henry's law constant and the fast chemical loss reactions of the O2- radical anion. As the main reduction process of Fe(III) is its reaction with HO2 / O2-, we show that the HO2 subsaturation leads to Fe(II) / Fe(total) ratios for FN,Fe<100 % that are lower by a factor of ≤ 2 as compared to bulk model approaches. This trend is largely independent of the total iron concentration, as both chemical source and sink rates of HO2 / O2- scale with the iron concentration. We compare model-derived reactive uptake parameters γOH and γHO2 for the full range of FN,Fe. While γOH is not affected by the iron distribution, the calculated γHO2 values range from 0.0004 to 0.03 for FN,Fe = 1 % and 100 %, respectively. Implications of these findings are discussed for the application of lab-derived γHO2 in models to present reactive HO2 uptake on aerosols. We conclude that the iron distribution (FN,Fe) should be taken into account to estimate the ROS concentrations and oxidation potential of particulate matter that might be overestimated by bulk sampling and model approaches. Our study suggests that the number concentration of iron-containing particles FN,Fe may be more important than the total iron mass concentration in determining ROS budgets and uptake rates in cloud and aerosol water.

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: < 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.

Anomalous Noble Gas Solubility in Liquid Cloud Water: Possible Implications for Noble Gas Temperatures and Cloud Physics

AbstractThe noble gas temperature climate proxy is an established tool that has previously been applied to determine the source of groundwater recharge, however, unanswered questions remain. In fractured media (e.g., volcanic islands) recharge can be so rapid that groundwater is significantly depleted in heavy noble gases, indicating that the water has retained noble gas concentrations from higher elevations. Previous studies of rain samples have confirmed a match to patterns seen in fractured‐rock groundwater for heavy noble gases along with a significant helium excess. Snow has been shown to be a credible source for both the helium excess and the observed heavy noble gas pattern. Here, liquid cloud water samples were collected at two mountainous sites and analyzed for noble gas concentrations. A pattern like that of rainwater was found. However, an analysis of diffusive uptake of noble gases into cloud water demonstrates that droplets of 1 mm diameter and smaller should be in constant solubility equilibrium with the atmosphere. To explain this, we present a novel hypothesis that relies on the assumption that liquid water consists of two types of water molecule clusters bounded by hydrogen bonds: a low‐density ice‐like structure and a high‐density condensed structure. In this model, the pressure gradient near the surface of a droplet resulting from surface tension could allow for the formation of a surface layer that is rich in ice‐like low density clusters. This can explain both the helium excess and the heavy noble gas depletion seen in the samples.

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.

Characterization of ice nucleating particles in rainwater, cloud water, and aerosol samples at two different tropical latitudes

Ice nucleating particles (INPs) induce ice crystal formation and therefore, they are able to influence precipitation development. INP sources remain highly uncertain, with most of the observational studies performed in mid- and high-latitudes, bypassing the Tropics. In the present study, rainwater, cloud water, and aerosol samples were collected during the rainy seasons in 2018 and 2019 in two major tropical capital cities: Quito and Mexico City, and at the high-altitude rural site Altzomoni (Mexico). The ice nucleating abilities of the rainwater samples from the urban sites (INP concentrations varying between 1.1 × 102 and 105 L−1 water at −9 °C and −24 °C) were not influenced by the pollution levels, consistent with the literature for other cities (e.g., Beijing and New Delhi), suggesting similarities in the behavior of INPs in densely populated and polluted cities. On the other hand, although the INP concentrations of the rural site samples were similar to those found in Quito and Mexico City (i.e., 7.1 × 101 and 1.1 × 105), their onset freezing temperatures (T0) were found to be higher (−7.5 °C as the highest). In terms of T50 (the temperature at which 50% of the droplets freeze), the rainwater and the cloud water samples were found to be more efficient than the aerosol samples. The ice nucleating abilities of the rural site samples were reduced when applying the heating test, resulting in lower T0 values, by more than 5 °C. Moreover, the presence of bacteria and fungal propagules on the rainwater and cloud water samples was also confirmed. Therefore, the high ice nucleating abilities observed on the samples from the rural site are likely related to biological material. Although K, Ca, S, Zn, and NO3− were found to be enriched in the cloud water samples in comparison to the aerosol particles, only Cu, Mn, and Zn were found to moderately correlate with the INP concentrations at −15 °C and −17 °C out of all the elements detected. Finally, the rainwater samples collected at those tropical sites were found to contain INPs concentrations lower than those found in other mid- and high-latitude sites. The information herein will improve the knowledge of INPs' contained in precipitation, their influence in tropical latitudes, and the development of new parameterizations.