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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. [ABSTRACT FROM AUTHOR]

The composition of cloud water dissolved organic matter has been investigated through non-targeted high resolution mass spectrometry only on few samples, mostly collected in the Northern hemisphere, in USA, Europe and China. Nevertheless, there is a lack of measurements for clouds located in the Southern Hemisphere, under tropical conditions and influenced by forest emissions. Moreover, the comparison of the composition of cloud samples collected in different locations is not trivial, since the methodology for the analysis and data treatment are not standardized. In this work, the chemical composition of three samples collected at Reunion 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 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 search for terpenes oxidation products in cloud water samples. To better discriminate between samples collected at PUY and at 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, mainly linked to the processing of organic matter in cloud water, but also to the influence of different primary emissions at the two locations. [ABSTRACT FROM AUTHOR]

Eighteen free amino acids (FAAs) were quantified in cloud water sampled at the Puy de Dôme station (PUY – France) during 13 cloud events. This quantification has been performed without concentration or derivatization, using liquid chromatography hyphened to mass spectrometry (LC-MS) and the standard addition method to correct for matrix effects. Total concentrations of FAAs (TCAAs) vary from 1.2 to 7.7 µ M, Ser (serine) being the most abundant AA (23.7 % on average) but with elevated standard deviation, followed by glycine (Gly) (20.5 %), alanine (Ala) (11.9 %), asparagine (Asn) (8.7 %), and leucine/isoleucine (Leu/I)​​​​​​​ (6.4 %). The distribution of AAs among the cloud events reveals high variability. TCAA constitutes between 0.5 and 4.4 % of the dissolved organic carbon measured in the cloud samples. AA quantification in cloud water is scarce, but the results agree with the few studies that investigated AAs in this aqueous medium. The environmental variability is assessed through a statistical analysis. This work shows that AAs are correlated with the time spent by the air masses within the boundary layer, especially over the sea surface before reaching the PUY. The cloud microphysical properties' fluctuation does not explain the AA variability in our samples, confirming previous studies at the PUY. We finally assessed the sources and the atmospheric processes that potentially explain the prevailing presence of certain AAs in the cloud samples. The initial relative distribution of AAs in biological matrices (proteins extracted from bacterial cells or mammalian cells, for example) could explain the dominance of Ala, Gly, and Leu/I. AA composition of aquatic organisms (i.e., diatom species) could also explain the high concentrations of Ser in our samples. The analysis of the AA hygroscopicity also indicates a higher contribution of AAs (80 % on average) that are hydrophilic or neutral, revealing the fact that other AAs (hydrophobic) are less favorably incorporated into cloud droplets. Finally, the atmospheric aging of AAs has been evaluated by calculating atmospheric lifetimes considering their potential transformation in the cloud medium by biotic or abiotic (mainly oxidation) processes. The most concentrated AAs encountered in our samples present the longest atmospheric lifetimes, and the less dominant ones are clearly efficiently transformed in the atmosphere, potentially explaining their low concentrations. However, this cannot fully explain the relative contribution of several AAs in the cloud samples. This reveals the high complexity of the bio-physico-chemical processes occurring in the multiphase atmospheric environment. [ABSTRACT FROM AUTHOR]

Bacteria circulate in the atmosphere, through clouds and precipitation to surface ecosystems. Here, we conducted a coordinated study of bacteria assemblages in clouds and precipitation at two sites distant of ∼800 m in elevation in a rural vegetated area around puy de Dôme Mountain, France, and analysed them in regard to meteorological, chemical and air masses' history data. In both clouds and precipitation, bacteria generally associated with vegetation or soil dominated. Elevated ATP-to-cell ratio in clouds compared with precipitation suggested a higher proportion of viable cells and/or specific biological processes. The increase of bacterial cell concentration from clouds to precipitation indicated strong below-cloud scavenging. Using ions as tracers, we derive that 0.2 to 25.5% of the 1.1 × 107 to 6.6 × 108 bacteria cell/m2/h1 deposited with precipitation originated from the source clouds. Yet, the relative species richness decreased with the proportion of inputs from clouds, pointing them as sources of distant microbial diversity. Biodiversity profiles, thus, differed between clouds and precipitation in relation with distant/local influencing sources, and potentially with bacterial phenotypic traits. Notably Undibacterium , Bacillus and Staphylococcus were more represented in clouds, while epiphytic bacteria such as Massilia , Sphingomonas , Rhodococcus and Pseudomonas were enriched in precipitation. [ABSTRACT FROM AUTHOR]

For the last 25 years, CO-PDD (Cézeaux-Aulnat-Opme-puy de Dôme) has evolved to become a full instrumented platform for atmospheric research. It has received credentials as a national observing platform in France and is internationally recognized as a global station in the GAW (Global Atmosphere Watch) network. It is a reference site of European and national research infrastructures ACTRIS (Aerosol Cloud and Trace gases Research Infrastructure) and ICOS (Integrated Carbon Observing System). The site located on top of the puy de Dôme mountain (1465 m a.s.l.) is completed by additional sites located at lower altitudes and adding the vertical dimension to the atmospheric observations: Opme (660 m a.s.l.), Cézeaux (410 m), and Aulnat (330 m). The integration of different sites offers a unique combination of in situ and remote sensing measurements capturing and documenting the variability of particulate and gaseous atmospheric composition, but also the optical, biochemical, and physical properties of aerosol particles, clouds, and precipitations. Given its location far away from any major emission sources, its altitude, and the mountain orography, the puy de Dôme station is ideally located to sample different air masses in the boundary layer or in the free troposphere depending on time of day and seasons. It is also an ideal place to study cloud properties with frequent presence of clouds at the top in fall and winter. As a result of the natural conditions prevailing at the site and of the very exhaustive instrumental deployment, scientific studies at the puy de Dôme strongly contribute to improving knowledge in atmospheric sciences, including the characterization of trends and variability, the understanding of complex and interconnected processes (microphysical, chemical, biological, chemical and dynamical), and the provision of reference information for climate/chemistry models. In this context, CO-PDD is a pilot site to conduct instrumental development inside its wind tunnel for testing liquid and ice cloud probes in natural conditions, or in situ systems to collect aerosol and cloud. This paper reviews 25 years (1995–2020) of atmospheric observation at the station and related scientific research contributing to atmospheric and climate science. [ABSTRACT FROM AUTHOR]

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 < 55 mN m-1), with 7% being extremely active (σ < 30 mN m-1). The most efficient biosurfactant producers (σ < 45 mN m-1) belong to a few bacterial genera (Pseudomonas and Xanthomonas) from the -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<σ < 55 mN m-1). Pseudomonas (γ-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. [ABSTRACT FROM AUTHOR]

We present a simple algorithm that calculates the cloud occurrence frequency at an altitude site using automatic camera image analysis. This algorithm was applied at the puy de Dôme station (PUY, 1465 m. a.s.l., France) over 2013–2018. Cloud detection thresholds were determined by direct comparison with simultaneous in situ cloud probe measurements (particulate volume monitor (PVM) Gerber). The cloud occurrence frequency has a seasonal cycle, with higher values in winter (60%) compared to summer (24%). A cloud diurnal cycle is observed only in summer. Comparisons with the larger scale products from satellites and global model reanalysis are also presented. The NASA cloud-aerosol transport system (CATS) cloud fraction shows the same seasonal and diurnal variations and is, on average, 11% higher. Monthly variations of the ECMWF ERA-5 fraction of cloud cover are also highly correlated with the camera cloud occurrence frequency, but the values are 19% lower and up to 40% for some winter months. The METEOSAT-SEVIRI cloud occurrence frequency also follows the same seasonal cycle but with a much smaller decrease in summer. The all-sky imager cloud fraction (CF) presents larger variability than the camera cloud occurrence but also follows similar seasonal variations (67% in winter and 44% in summer). This automatic low-cost detection of cloud occurrence is of interest in characterizing altitude observation sites, especially those that are not yet equipped with microphysical instruments and can be deployed to other high-altitude sites equipped with cameras. [ABSTRACT FROM AUTHOR]

Abstract: Despite the enormous volume they represent and the importance they have for Earth’s climate, clouds remain environments where the microbiological features are still poorly understood. Studies of the microbial content existing in the atmosphere have demonstrated extreme quantitative and qualitative variability, of which the drivers yet need to be determined. Between 2007 and 2010, we collected cloud water from the puy de Dôme summit in France (1465m a.s.l.) for chemical and microbiological analysis. These data were combined with cloud data collected between 2004 and 2005 following similar protocols. Overall, the cultivable community of chemotrophic aerobic microorganisms was dominated by pigmented colonies and accounted for <1% of the 3.3×103 to 2.5×105 total bacteria mL−1, but up to 41% of the 8.9×102 to 3.2×104 fungal cells mL−1. None of the concentrations of the chemical compounds measured was linked to the variations observed for the microbiological content, suggesting distinct sources and/or distinct modes of incorporation into cloud water. However, the overall dataset indicated that microorganisms in clouds were mostly originating from continental areas, especially from vegetation. We isolated and identified 185 heterotrophic bacteria and 150 yeasts from our samples (including -Alpha, -Beta and Gamma-Proteobacteria, Bacteroidetes, Firmicutes and Actinobacteria, and Basidiomycetous and Ascomycetous yeasts), the corresponding 16S and 26S rRNA gene sequences of which have been deposited in GenBank. A few genera largely dominated the pool of cultivable microorganisms in clouds, such as Pseudomonas and Sphingomonas for bacteria, which were detected in more than 40% of the clouds sampled, and Dioszegia and Udeniomyces for yeasts, detected in more than 60% of the samples. The recurring presence of some groups of microorganisms suggests that they have elaborated strategies of increased survival in the atmosphere and clouds. [Copyright &y& Elsevier]

VOC precursors play a key role in air quality and climate by contributing to ozone productionand by modifying the physicochemical properties of aerosols, one of the main agents of theEarth&#x2019;s radiative forcing. Among VOCs, oxygenated VOC (OVOC) and biogenic VOC(BVOC) are of particular interest due to their high reactivity. Meanwhile, the cloud systemrepresents a multiphase medium (gas, aerosol, water) for transformations of VOC andparticularly of OVOC, highly soluble. Indeed, cloud droplets, which are able to trap and dissolve many gaseous and particulatecompounds, represent a very reactive media in the atmosphere. Microphysical processescontrol formation, lifetime and dissipation of the clouds and consequently modify thedistribution of the chemical species between the different reservoirs (cloud water, rain,particle phase, gaseous phase, and solid ice phase). Meanwhile, photochemical processesinside the droplets are strongly amplified when compared with the interstitial air.However, speciation and concentrations of organic compounds between gaseousphase (interstitial air) and atmospheric liquid phase (cloud droplets) are still poorlydescribed. Our objectives are to collect air and cloud water simultaneously by using differentsamplers and to characterize the gas/liquid partitioning of target organic compounds (OVOC,BVOC) that are considered as efficient SOA precursors both in the aqueous phase andgaseous phase. Several cloud events were sampled at the puy de Dôme station (PUY) in thecentre of France (1465 m a.s.l.) belonging to the GAW/ACTRIS network. Air massesreaching the summit present contrasted origins (from the marine influence to theanthropogenic one). A new analytical approach has been optimized (i.e., linearity, repeatability, sensitivity andrelative humidity) to explore VOCs in both gas and liquid phases by taking into account realcloud conditions. First, a newly developed gas sampler (AEROVOCC) collectsgaseous VOCs/OVOCs (–C=O and –OH functional groups) simultaneously bydeploying three types of Tenax TA sorbent tubes pre-coated with different derivatisationreagents. Simultaneously, cloud sampling is performed with a cloud collector. Then,(O)VOC concentrations in the cloud water samples are evaluated by using directliquid derivatization and extraction by Stir Bar Sorptive Extraction (SBSE). Finally,collected both gas and aqueous samples are analysed by desorption (TD) coupledwith gas chromatography (GC) and mass spectrometry (MS) at the laboratory. Thewhole set-up has been deployed on the field to study the partitioning of VOCs; thisexperimental partitioning is evaluated towards the theoretical one described bythe Henry&#x2019;s Law constants. Our results show that even observed concentrations ofhydrophobic VOCs are significant in the cloud droplet and supersaturated by afactor of 10-10000. Larger and less soluble carbonyl compounds were found to besupersaturated by a factor of 100-1000 in other studies. This result suggests that thepool of reactive organic compounds in the cloud phase is largely underestimated. [ABSTRACT FROM AUTHOR]

Antibiotic resistance in bacteria is becoming a major sanitary concern worldwide. The extensive use of large quantities of antibiotics to sustain human activity has led to the rapid acquisition and maintenance of antibiotic resistant genes (ARGs) in bacteria and to their spread into the environment. Eventually, these can be disseminated over long distances by atmospheric transport. Here, we assessed the presence of ARGs in clouds as an indicator of long-distance travel potential of antibiotic resistance in the atmosphere. We hypothesized that a variety of ARGs can reach the altitude of clouds mainly located within the free troposphere. Once incorporated in the atmosphere, they are efficiently transported and their respective concentrations should differ depending on the sources and the geographical origin of the air masses. We deployed high-flow rate impingers and collected twelve clouds between September 2019 and October 2021 at the meteorological station of the puy de Dôme summit (1465 m a.s.l., France). Total airborne bacteria concentration was assessed by flow cytometry, and ARGs subtypes of the main families of antibiotic resistance (quinolone, sulfonamide, tetracycline; glycopeptide, aminoglycoside, β-lactamase, macrolide) including one mobile genetic element (transposase) were quantified by qPCR. Our results indicate the presence of 29 different ARGs' subtypes at concentrations ranging from 1.01 × 10 3 to 1.61 × 10 4 copies m -3 of air. Clear distinctions could be observed between clouds in air masses transported over marine areas (Atlantic Ocean) and clouds influenced by continental surfaces. Specifically, quinolones (mostly qepA) resistance genes were prevalent in marine clouds (54 % of the total ARGs on average), whereas higher contributions of sulfonamide, tetracycline; glycopeptide, β-lactamase and macrolide were found in continental clouds. This study constitutes the first evidence for the presence of microbial ARGs in clouds at concentrations comparable to other natural environments. This highlights the atmosphere as routes for the dissemination of ARGs at large scale., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Cloud droplets contain dynamic and complex pools of highly heterogeneous organic matter, resulting from the dissolution of both water-soluble organic carbon in atmospheric aerosol particles and gas-phase soluble species, and are constantly impacted by chemical, photochemical, and biological transformations. Cloud samples from two summer events, characterized by different air masses and physicochemical properties, were collected at the Puy de Dôme station in France, concentrated on a strata-X solid-phase extraction cartridge and directly infused using electrospray ionization in the negative mode coupled with ultrahigh-resolution mass spectrometry. A significantly higher number (n = 5258) of monoisotopic molecular formulas, assigned to CHO, CHNO, CHSO, and CHNSO, were identified in the cloud sample whose air mass had passed over the highly urbanized Paris region (J1) compared to the cloud sample whose air mass had passed over remote areas (n = 2896; J2). Van Krevelen diagrams revealed that lignins/CRAM-like, aliphatics/proteins-like, and lipids-like compounds were the most abundant classes in both samples. Comparison of our results with previously published data sets on atmospheric aqueous media indicated that the average O/C ratios reported in this work (0.37) are similar to those reported for fog water and for biogenic aerosols but are lower than the values measured for aerosols sampled in the atmosphere and for aerosols produced artificially in environmental chambers.

Within cloud water, microorganisms are metabolically active and, thus, are expected to contribute to the atmospheric chemistry. This article investigates the interactions between microorganisms and the reactive oxygenated species that are present in cloud water because these chemical compounds drive the oxidant capacity of the cloud system. Real cloud water samples with contrasting features (marine, continental, and urban) were taken from the puy de Dôme mountain (France). The samples exhibited a high microbial biodiversity and complex chemical composition. The media were incubated in the dark and subjected to UV radiation in specifically designed photo-bioreactors. The concentrations of H(2)O(2), organic compounds, and the ATP/ADP ratio were monitored during the incubation period. The microorganisms remained metabolically active in the presence of ()OH radicals that were photo-produced from H(2)O(2). This oxidant and major carbon compounds (formaldehyde and carboxylic acids) were biodegraded by the endogenous microflora. This work suggests that microorganisms could play a double role in atmospheric chemistry; first, they could directly metabolize organic carbon species, and second, they could reduce the available source of radicals through their oxidative metabolism. Consequently, molecules such as H(2)O(2) would no longer be available for photochemical or other chemical reactions, which would decrease the cloud oxidant capacity.