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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]

For the last twenty-five years, CO-PDD (Cézeaux-Aulnat-Opme-puy de Dôme) has evolved to become a full instrumented platform for atmospheric research. It is nationally accredited by CNRS, the French national center for scientific research, and recognized as a global station in the GAW network (Global Atmospheric Watch). It is a reference site of the 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). On the sites has been developed 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 situated 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 autumn and winter. As a result of the natural conditions prevailing at the site and of the very exhaustive instrumental deployment, scientific studies at puy de Dôme strongly contribute to improving the 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 providing a reference point for climate models. In this context, CO-PDD is a pilot site to conduct instrumental development inside its wind tunnel for testing liquid/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 new detailed aqueous phase mechanism named the Cloud Explicit Physico-chemical Scheme (CLEPS 1.0) is proposed to describe the oxidation of water soluble organic compounds resulting from isoprene oxidation. It is based on structure activity relationships (SARs) which provide global rate constants together with branching ratios for HO· abstraction and addition on atmospheric organic compounds. The GROMHE SAR allows the evaluation of Henry's law constants for undocumented organic compounds. This new aqueous phase mechanism is coupled with the MCM v3.3.1 gas phase mechanism through a mass transfer scheme between gas phase and aqueous phase. The resulting multiphase mechanism has then been implemented in a model based on the Dynamically Simple Model for Atmospheric Chemical Complexity (DSMACC) using the Kinetic PreProcessor (KPP) that can serve to analyze data from cloud chamber experiments and field campaigns. The simulation of permanent cloud under low-NOx conditions describes the formation of oxidized monoacids and diacids in the aqueous phase as well as a significant influence on the gas phase chemistry and composition and shows that the aqueous phase reactivity leads to an efficient fragmentation and functionalization of organic compounds. [ABSTRACT FROM AUTHOR]

Organic compounds of both anthropogenic and natural origin are ubiquitous in the multiphasic atmospheric medium. Their transformation in the atmosphere affects air quality and the global climate. Modelling provides a useful tool to investigate the chemistry of organic compounds in the tropospheric multiphase system. While several comprehensive explicit mechanisms exist in the gas phase, explicit mechanisms are much more limited in the aqueous phase. Recently, new empirical methods have been developed to estimate HO• reaction rates in the aqueous phase: structure-activity relationships (SARs) provide global rate constants and branching ratios for HO• abstraction from and addition to atmospheric organic compounds. Based on these SARs, a new detailed aqueous-phase mechanism, named the cloud explicit physico-chemical scheme (CLEPS), to describe the oxidation of hydrosoluble organic compounds resulting from isoprene oxidation is proposed. In this paper, a protocol based on reviewed experimental data and evaluated prediction methods is described in detail. The current version of the mechanism includes approximately 850 aqueous reactions and 465 equilibria. Inorganic reactivity is described for 67 chemical species (e.g., transition metal ions, HxOy, sulphur species, nitrogen species, and chlorine). For organic compounds, 87 chemical species are considered in the mechanism, corresponding to 657 chemical forms that are individually followed (e.g., hydrated forms, anionic forms). This new aqueous-phase mechanism is coupled with the detailed gas phase mechanism MCM v3.3.1 through mass transfer parameterization for the exchange between the gas phase and aqueous phase. The GROMHE SAR enables the evaluation of the Henry's law constants for undocumented organic compounds. The resulting multiphase mechanism is implemented in a model based on the Dynamically Simple Model for Atmospheric Chemical Complexity (DSMACC) using the Kinetic PreProcessor (KPP). This model allows simulation of the time evolution of the concentrations of each individual chemical species in addition to detailed time-resolved flux analyses. The variable photolysis in both phases is calculated using the TUV 4.5 radiative transfer model. To evaluate our chemical mechanism, an idealized cloud event with fixed microphysical cloud parameters is simulated. The simulation is performed for a low-NOx situation. The results indicate the formation of oxidized mono- and diacids in the aqueous phase, as well as a significant influence on the gas phase chemistry and composition. For this particular simulation, the aqueous phase mechanism is responsible for the efficient fragmentation and functionalization of organic compounds. This new cloud chemistry model allows for the analysis of individual aqueous sub systems and can be used to analyze the results from cloud chamber experiments and field campaigns. [ABSTRACT FROM AUTHOR]

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 H2O2, 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 H2O2. 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 H2O2 would no longer be available for photochemical or other chemical reactions, which would decrease the cloud oxidant capacity. [ABSTRACT FROM AUTHOR]

Mechanism reductions of the detailed aqueous phase chemistry mechanism CAPRAM 3.0i are performed. Manual methods and automatic techniques are both applied in order to provide a less computationally intensive mechanism which is operational in regional chemistry transport models (CTMs). The finally reduced mechanism contains less than 200 reactions (4 times smaller than the detailed CAPRAM 3.0i) and describes the main characteristics of inorganic and organic aqueous phase processes occurring in tropospheric warm clouds. Most of the chemical reduction potential is realized in the CAPRAM 3.0i organic chemistry. The number of aqueous phase species decreases from 380 in the full mechanism to 130 in the final reduced version. The calculated percentage deviations between the full and reduced mechanism are on average below 5% for the most important organic and inorganic target compounds such as oxidants, inorganic and organic acids, carbonyls and alcohols. Comparisons of the required CPU times between the full and reduced mechanisms show reductions of approximately 40%. 2-D test simulations with the CTM MUSCAT were performed using prescribed meteorological conditions in order to examine the applicability of the reduced mechanism at regional scale. Simulations with the reduced CAPRAM 3.0i mechanism and a much less complex mechanism with only limited inorganic chemistry (INORG) were compared to evaluate the effects of more detailed chemistry. The model results show large differences in the level of oxidants and the inorganic and organic mass processing. Prospectively, the reduced mechanism represents the basis for studying aerosol cloud processing effects at regional scale with future CTMs and will allow more adequate interpretation of field data. [ABSTRACT FROM AUTHOR]

Evaluates multiphase chemistry versus the overall tropospheric chemistry and its role in the earth's radiative budget. Effect of multiphase chemistry on cloud optical properties; Aspects of chemical reactivity within the cloud; Source of metals in the atmospheric aqueous phase.

Abstract: Modeling studies have shown that the Fenton reaction of iron(II) with H2O2 can contribute, in a significant amount, to OH radicals production in cloud droplets. However, the destruction mechanism of hydrogen peroxide by iron(II) is still uncertain. Two reaction pathways for the first step of Fenton chemistry have been advanced: a radical pathway which considers an OH radical production and a non-radical pathway considering ferryl ion production. The aim of this work is to evaluate the impact of these two possible reaction pathways for Fenton chemistry on the iron redox cycle in cloud droplets. For this purpose, the numerical model of multiphase chemistry M2C2 has been applied to a rural chemical scenario representative of continental conditions. This study highlights that the iron redox cycling is driven by Fenton reaction whatever Fenton mechanism is considered. The ferryl ion chemistry becomes significant in the iron redox cycling when this species is considered as an active intermediate in Fenton chemistry and under night time conditions the iron redox chemistry is controlled by the ferryl ion reactivity. The partitioning of iron between its two main oxidation states (+II and +III) in cloud droplets, which is the indicator of the iron oxido-reduction potential, does not change significantly between the two cases. However, for the non-radical case, the ferryl ion concentration is up to four orders of magnitude higher than the OH concentration highlighting its potential role in oxidative capacity of cloud droplets. [Copyright &y& Elsevier]

Cloud/fog droplets comprise a myriad of chemical compounds and are living environments in which microorganisms are present and active. These chemical and biological elements can evolve in various ways within the cloud system, and the aqueous transformation of chemicals contributes to atmospheric chemistry. In situ cloud studies are fundamental in this sense, because they enable us to study the variability in cloud chemical composition as a function of environmental conditions and assess their potential for transforming chemical compounds. To achieve this objective, cloud water collectors have been developed in recent decades to recover water from clouds and fogs using different designs and collection methods. In this study, a new active ground-based cloud collector was developed and tested for sampling cloud water to assess the cloud microbiology and chemistry. This new instrument, BOOGIE, is an easy mobile sampler for cloud water collection with the objective of being cleanable and sterilisable, respecting chemical and microbial cloud integrity, and presenting an efficient collection rate of cloud water. Computational fluid dynamics simulations were performed to theoretically assess the capture of cloud droplets by this new sampler. Few turbulences have been observed inside the collector and a 50 % collection efficiency cutoff of 10 µm has been estimated. The collector was deployed at Puy de Dôme station under cloudy conditions for evaluation. The water collection rates were measured at 156 ± 52 mL h-1 for a collection of 17 cloud events; considering the measured liquid water content, the sampling efficiency of this new collector has been estimated at 87.2 ± 8.6 % over the same set of cloud events. BOOGIE was compared with other active cloud collectors commonly used by the scientific community (Cloud Water Sampler and Caltech Active Strand Cloud Collector version 2). Four cloud events were collected; the three samplers presented similar collection efficiencies (between 79 % and 88 % on average). The measured ionic composition was comparable even if differences were highlighted between collectors, the consequence of different designs, and the intrinsic homogeneity in the chemical composition within the cloud system. [ABSTRACT FROM AUTHOR]

An amendment to this paper has been published and can be accessed via a link at the top of the paper. [ABSTRACT FROM AUTHOR]

This work investigates the occurrence and photochemical behaviour of tryptophan (TRP) in the cloud aqueous phase. The concentrations of tryptophan, TRYptophan LIke Substances (TRYLIS) and HUmic LIke Substances (HULIS) in real cloud water, collected between October 2013 and November 2014 at the top of the puy de Dôme station, were determined using the Excitation-Emission-Matrix (EEM) technique. The amount of free and complexed tryptophan (TRP) up to 10 −7 M in cloud aqueous phase was quantified by HPLC-UV-fluorescence analysis, and its photoreactivity under sun-simulated conditions was investigated in synthetic water samples mimicking cloud aqueous phase compositions (oceanic and continental origins). TRP undergoes direct photolysis, and its degradation is enhanced in the presence of naturally occurring species able to photo-generate hydroxyl radicals (HO ). The polychromatic quantum yield of TRP ( ϕ 290 − 340 n m T R P ) is estimated to be 8.37 × 10 −4 between 290 and 340 nm, corresponding to the degradation rate ( R TRP d ) of 1.29 × 10 −11 M s −1 under our irradiation conditions. The degradation is accelerated up to 3.65 × 10 −10 and 8.26 × 10 −10 M s −1 in synthetic oceanic and continental cloud water samples doped with 100 μM hydrogen peroxide, respectively. Hydroxyl radical-mediated transformation leads to the generation of different functionalized and oxidized products, as well as small carboxylic acids, such as formate and acetate. Moreover, fluorescent signals of irradiated solutions indicate the formation of HULIS. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

In the present study, we investigated the correlation between the hydroxyl radical formation rate (R˙OH) and the degradation of a pesticide (mesotrione) in synthetic cloud water solutions and in two real atmospheric cloud waters collected at the top of puy de Dôme station (France). Using terephthalic acid as the hydroxyl radical chemical probe, we established the linear correlation between the photogenerated hydroxyl radical under polychromatic wavelengths and the pesticide degradation rate: ( m s−1) = (1.61 ± 0.15) × 10−1 R˙OH( m s−1). Moreover, the formation rate of hydroxyl radical in two natural cloud waters was estimated considering H2O2 and NO3− and the difference between the predicted values and those experimentally obtained could be attributed to the presence of other photochemical sources: iron-complexes and total organic matter. The organic constituents could play a dual role of sources and scavengers of photoformed hydroxyl radicals in the aqueous phase. [ABSTRACT FROM AUTHOR]

Abstract: The kinetics of biodegradation of methanol and formaldehyde in phosphate buffer at pH 7 by 4 bacterial strains (Pseudomonas spp., Bacillus sp. and Frigoribacterium sp.) isolated from cloud water at the puy de Dôme mountain have been investigated using 1H and 13C NMR spectroscopy. We showed that biodegradation occurred at 5°C and 17°C, respectively average and summertime temperature considered within the cloud system at this site. They ranged from 10−19 to 10−21 mol cell−1 s−1 both at 5 and 17°C for formaldehyde, and from 10−21 to 10−23 mol cell−1 s−1 at 5 and 17°C for methanol. Metabolic intermediates were identified, with notably production of C3 compounds (glycerol, 1,2- and 1,3-propanediol) from formaldehyde by the strain Bacillus sp. In order to evaluate to which extent microbiological oxidation of organic compounds has to be considered as an alternative route to radical chemistry in cloud water, the biodegradation rates measured were compared with rates related to the reactivity of organic species with free radicals OH (daytime chemistry) and NO3 (nighttime chemistry) under two cloud situations (urban and remote cases). Clearly, measured biological and chemical reaction rates were in the same range of magnitude and their relative contribution varies according to the scenarios we tested, including the temperature of the clouds (5 or 17°C), the category of the clouds (urban and remote) and the diurnal cycle (day and nighttime). Except for the degradation of methanol at 5°C in remote clouds, our results show that biotransformation processes could be the main sink for C1 compounds in liquid clouds (T ≥5°C≡“warm cloud”) during the night and both in polluted and non polluted clouds. [Copyright &y& Elsevier]

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. [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]

Concentrations of 33 metal elements were determined by ICP-MS (Inductively Coupled Plasma Mass Spectrometry) analysis for 24 cloud water samples (corresponding to 10 cloud events) collected at the puy de Dôme station. Clouds present contrasted chemical composition with mainly marine and continental characteristics; for some cloud events, a further anthropogenic source can be superimposed on the background level. In this context, measurements of trace metals may help to evaluate the impact of anthropogenic and natural sources on the cloud and to better discriminate the origin of the air masses. The metal concentrations in the samples are low (between 16.4 μg L-1 and 1.46 mg L-1). This could be explained by the remoteness of the puy de Dôme site from local sources. Trace metals are then used to confirm and refine a previous sample classification. A principal component analysis (PCA) using the pH value and the concentrations of Cl-, NO3-, SO42-, Na+ and NH4+ is performed considering 24 cloud samples. This first analysis shows that 18 samples are of marine origin and 6 samples are classified as continental. The same statistical approach is used adding trace metal concentration. Zn and Mg elements are the most abundant trace metals for all clouds. A higher concentration of Cd is mainly associated to clouds from marine origins. Cu, As, Tl and Sb elements are rather found in the continental samples than in the marine ones. Mg, V, Mn and Rb elements mainly found in soil particles are also more concentrated in the samples from continental air mass. This new PCA including trace metal confirms the classification between marine and continental air masses but also indicates that one sample presenting low pH and high concentrations of SO42-, Fe, Pb and Cu could be rather attributed to a polluted event. [ABSTRACT FROM AUTHOR]

Clouds are key components in Earth’s functioning. In addition of acting as obstacles to light radiations and chemical reactors, they are possible atmospheric oases for airborne microorganisms, providing water, nutrients and paths to the ground. Microbial activity was previously detected in clouds, but the microbial community that is active in situ remains unknown. Here, microbial communities in cloud water collected at puy de Dôme Mountain’s meteorological station (1465 m altitude, France) were fixed upon sampling and examined by high-throughput sequencing from DNA and RNA extracts, so as to identify active species among community members. Communities consisted of ~103−104 bacteria and archaea mL-1 and ~102−103 eukaryote cells mL-1. They appeared extremely rich, with more than 28 000 distinct species detected in bacteria and 2 600 in eukaryotes. Proteobacteria and Bacteroidetes largely dominated in bacteria, while eukaryotes were essentially distributed among Fungi, Stramenopiles and Alveolata. Within these complex communities, the active members of cloud microbiota were identified as Alpha- (Sphingomonadales, Rhodospirillales and Rhizobiales), Beta- (Burkholderiales) and Gamma-Proteobacteria (Pseudomonadales). These groups of bacteria usually classified as epiphytic are probably the best candidates for interfering with abiotic chemical processes in clouds, and the most prone to successful aerial dispersion. [ABSTRACT FROM AUTHOR]

Improving our understanding of cloud chemistry depends on achieving better chemical characterization (90% of the organic carbon [OC] fraction remains uncharacterized) and, consequently, assessing the reactivity of this complex system. In this manuscript, we report for the first time the concentrations of 16 amino acids (AAs) in 25 cloud water samples. The concentrations of individual AAs ranged from a few nM up to ~2.0 μM, and the average contribution of AAs corresponded to 9.1% (4.4 to 21.6%) of the dissolved OC (DOC) concentration. Considering their occurrence and concentrations, AAs were expected to represent an important hydroxyl radical (HO•) sink in aqueous cloud samples. In this work, we estimated that approximately 17% (from 7 to 36%) of the hydroxyl radical-scavenging ability of the DOC could be attributed to the presence of AAs, whereas comparing the AAs suggested that an average of 51% (from 22 to 80%) of their reactivity with HO• could account for the presence of tryptophan. These results clearly demonstrate that the occurrence and reactivity of AAs must be considered to better estimate the chemical composition and oxidant capacity of the cloud aqueous phase. [ABSTRACT FROM AUTHOR]

A total of 450 bacteria and yeast strains isolated from cloud waters sampled at the puy de Dôme station in France (1465 m) were screened for their ability to produce siderophores. To achieve this, a high-throughput method in 96-well plates was adapted from the CAS (chrome azurol S) method. Notably, 42% of the isolates were siderophore producers. This production was examined according to the phyla of the tested strains and the type of chelating functional groups (i.e., hydroxamate, catechol, and mixed type). The most active bacteria in the clouds belong to the γ-Proteobacteria class, among which the Pseudomonas genus is the most frequently encountered. γ-Proteobacteria are produced in the majority of mixed function siderophores, such as pyoverdines, which bear a photoactive group. Finally, siderophore production was shown to vary with the origin of the air masses. The organic speciation of iron remains largely unknown in warm clouds. Our results suggest that siderophores could partly chelate Fe(III) in cloud waters and thus potentially impact the chemistry of the atmospheric aqueous phase. [ABSTRACT FROM AUTHOR]

In the atmosphere, airborne microbial cells are exposed to conditions that are thought to affect their survival. Here, we investigated the survival of 5 microorganisms among the most represented in the cultivable community of clouds (4 bacteria affiliated to Pseudomonas , Sphingomonas and Arthrobacter and 1 yeast of Dioszegia ) after exposition to different atmospheric factors generally considered stressful for cells: artificial solar light (10 h), oxidant (hydrogen peroxide: 0–1 mM for 90 min), osmotic shocks (0.1–2.5 M NaCl) and freeze-thaw cycles (6 cycles of 5 °C/-40 °C). Each condition was applied separately to cell suspensions, and survival rates were examined by culture. Survival was highly strain and stress dependent, with no relationship with pigmentation or ice nucleation activity. In all strains, solar light had no or mitigated influence, and exposition to H 2 O 2 at the concentration measured in cloud water only slightly impacted viability (>70% of the cells survived). The strain Sphingomonas sp. was particularly impacted by osmotic shocks while repeated freeze-thaw was particularly damaging for Arthrobacter and Pseudomonas species. Overall, our results tend to indicate that in the atmosphere, the most stringent selection factors on living organisms are probably freeze-thaw and condensation/evaporation (osmotic shocks) cycles, whereas the impacts of oxidants and of solar light are limited. [ABSTRACT FROM AUTHOR]

Abstract: Currently, cloud chemistry models are including more detailed and explicit multiphase mechanisms based on laboratory experiments that determine such values as kinetic constants, stability constants of complexes and hydration constants. However, these models are still subject to many uncertainties related to the aqueous chemical mechanism they used. Particularly, the role of oxidants such as iron and hydrogen peroxide in the oxidative capacity of the cloud aqueous phase has typically never been validated against laboratory experimental data. To fill this gap, we adapted the M2C2 model (Model of Multiphase Cloud Chemistry) to simulate irradiation experiments on synthetic aqueous solutions under controlled conditions (e.g., pH, temperature, light intensity) and for actual cloud water samples. Various chemical compounds that purportedly contribute to the oxidative budget in cloud water (i.e., iron, oxidants, such as hydrogen peroxide: H2O2) were considered. Organic compounds (oxalic, formic and acetic acids) were taken into account as target species because they have the potential to form iron complexes and are good indicators of the oxidative capacity of the cloud aqueous phase via their oxidation in this medium. The range of concentrations for all of the chemical compounds evaluated was representative of in situ measurements. Numerical outputs were compared with experimental data that consisted of a time evolution of the concentrations of the target species. The chemical mechanism in the model describing the “oxidative engine” of the H x O y /iron (H x O y = H2O2, HO2 /O2 − and HO ) chemical system was consistent with laboratory measurements. Thus, the degradation of the carboxylic acids evaluated was closely reproduced by the model. However, photolysis of the Fe(C2O4)+ complex needs to be considered in cloud chemistry models for polluted conditions (i.e., acidic pH) to correctly reproduce oxalic acid degradation. We also show that iron and formic acid lead to a stable complex whose photoreactivity has currently not been investigated. The updated aqueous chemical mechanism was compared with data from irradiation experiments using natural cloud water. The new reactions considered in the model (i.e., iron complex formation with oxalic and formic acids) correctly reproduced the experimental observations. [Copyright &y& Elsevier]

Abstract: Some Gamma–Proteobacteria can catalyze ice formation thereby potentially contributing to the induction of precipitation in supercooled clouds and subsequently to bacterial deposition. Forty-four bacterial strains from cloud water were screened for their capacity to induce freezing. Seven strains (16%) were active at −8 °C or warmer and were identified as Pseudomonas syringae, Xanthomonas spp. and Pseudoxanthomonas sp. Phylogenetic analysis revealed that the P. syringae strains in clouds at the Puy de Dôme belonged to clades that are among the most infrequently detected in the environment, while widespread clades were absent suggesting some extent of selection or unusual biogeography of the bacteria at the sampling site. Three strains induced freezing at −3 °C while the others nucleated ice at −4 °C to −6 °C. The freezing profiles revealed that the peaks of activity were centered around −3.5 °C, −5 °C and/or −8.5 °C depending on the strain. The frequency of ice-nuclei (IN) per cell at −6 °C was generally below 0.5% and reached up to 4.2% in one strain. We estimated that clouds influenced by vegetated areas would carry between less than 1 and ∼500 bacterial IN mL−1 of water active between −3 °C and −10 °C depending on the season. These data will contribute to modeling the impact of bacterial IN on precipitation at regional scales. [Copyright &y& Elsevier]

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]

Abstract: In the first part of the work, we investigated the reactivity toward photogenerated hydroxyl radicals ( OH) of seven monocarboxylic acids and six dicarboxylic acids found in natural cloud water. This leads to the proposition of a schematic degradation pathway linking glutaric acid (C5) to complete mineralization into CO2. We report a detailed mechanism on the succinic acid reactivity toward OH leading to the formation of malonic, glyoxylic and consequently oxalic acids and a comparison with reported pathways proposed by the CAPRAM (Chemical Aqueous Phase RAdical Mechanism) is discussed. We also investigated the photooxidation of formic acid under atmospherically relevant conditions leading to the possible formation of oxalic acid via radical mediated recombination. The second part focuses on the polychromatic irradiation (closed to solar irradiation) of a collected cloud aqueous phase showing that irradiation of cloud water leads to the formation of both formic and acetic acids. Carboxylic acid formation increases in the presence of photogenerated hydroxyl radicals from hydrogen peroxide, showing that photooxidation could play a key role in the formation of carboxylic acids under atmospherically relevant conditions. [Copyright &y& Elsevier]

Abstract: In this study we improved the dansylacetamidooxyamine (DNSAOA)–LC–fluorescence method for the determination of aqueous-phase glyoxal (GL), methylglyoxal (MG) and hydroxyacetaldehyde (HA). As derivatization of dicarbonyls can potentially lead to complex mixtures, a thorough study of the reaction patterns of GL and MG with DNSAOA was carried out. Derivatization of GL and MG was shown to follow the kinetics of successive reactions, yielding predominantly doubly derivatized compounds. We verified that the bis-DNSAOA structure of these adducts exerted only minor influence on their fluorescence properties. Contrary to observations made with formaldehyde, derivatization of GL, MG and, to a lesser extent of HA, was shown to be faster in acidic (H2SO4) medium with a maximum of efficiency for acid concentrations of ca. 2.5mM. Concomitant separation of GL, MG, HA and of single carbonyls was achieved within 20min by using C18 chromatography and a gradient of CH3CN in water. Detection limits of 0.27, 0.17 and 0.12nM were determined for GL, MG and HA, respectively. Consequently, low sample volumes are sufficient and, unlike numerous published methods, neither preconcentration nor large injection volumes are necessary to monitor trace-level samples. The method shows relative measurement uncertainties better than ±15% at the 95% level of confidence and good dynamic ranges (R 2 >0.99) from 0.01 to 1.5μM for all carbonyls. GL, MG and HA were identified for the first time in polar snow samples, but also in saline frost flowers for which unexpected levels of 0.1–0.6μM were measured. Concentrations in the 0.02–2.3μM range were also measured in cloud water. In most samples, a predominance of HA over GL and MG was observed. [Copyright &y& Elsevier]

Abstract: The photochemical behaviour of H2O2 in cloud aqueous phase was investigated from a large amount of in situ cloud droplet sampling data. Then we performed laboratory irradiation experiments of real cloud samples, free from gaseous chemistry, in order to factorise between gas phase and liquid phase photochemical reactions. H2O2 was revealed to be sensitive to solar radiation, with higher concentrations during the day. H2O2 was dependent on the degree of air mass pollution with anthropogenic influences leading to lower values of aqueous H2O2. We observed higher differences between day and night of H2O2 concentrations for air masses influenced by anthropogenic activities (mainly Northern direction) compared to those form remote areas (oceanic). Contrary to this field diurnal trend, during laboratory irradiation experiments of the cloud aqueous phase, the concentration showed a regular linear decrease leading to the conclusion that photolysis is more important than photoproduction in cloud aqueous phase. So the diurnal cycle observed during field measurements is due to the high mass transfer from gas phase to liquid phase favoured by the high dispersion of liquid phase and the high solubility of hydrogen peroxide. As a consequence, H2O2 can act as a photochemical source of ls in cloud aqueous phase. [Copyright &y& Elsevier]

Abstract: Recent studies showed that living microorganisms, including bacteria, fungi and yeasts, are present in the atmospheric water phase (fog and clouds) and their role in chemical processes may have been underestimated. At the interface between atmospheric science and microbiology, information about this field of science suffers from the fact that not all recent findings are efficiently conveyed to both scientific communities. The purpose of this paper is therefore to provide a short overview of recent work linked to living organisms in the atmospheric water phase, from their activation to cloud droplets and ice crystal, to their potential impact on atmospheric chemical processes. This paper is focused on the microorganisms present in clouds and on the role they could play in atmospheric chemistry and nucleation processes. First, the life cycle of microorganisms via the atmosphere is examined, including their aerosolization from sources, their integration into clouds and their wet deposition on the ground. Second, special attention is paid to the possible impacts of microorganisms on liquid and ice nucleation processes. Third, a short description of the microorganisms that have been found in clouds and their variability in numbers and diversity is presented, emphasizing some specific characteristics that could favour their occurrence in cloud droplets. In the last section, the potential role of microbial activity as an alternative route to photochemical reaction pathways in cloud chemistry is discussed. [Copyright &y& Elsevier]

Cloud droplets are able to trap many gaseous compounds and represent a very reactive media in the atmosphere. However, phase-partitioning of Volatile Organic Compounds (VOCs) between gaseous phase (interstitial air) and atmospheric liquid phase (cloud droplets) is still poorly characterized. In the present work, air samples and cloud water were collected simultaneously and hydrophobic organic compounds from anthropogenic and biogenic origins were quantified in order to evaluate their air/water partitioning. For this, cloud events were sampled at the puy de Dôme station (PUY). A new analytical approach was optimized to explore dissolved VOCs in the aqueous phase by Stir Bar Sorptive Extraction (SBSE) and gaseous samples were collected using sorbent tubes. All samples were analyzed by Thermal Desorption (TD) Gas Chromatography (GC) coupled with Mass Spectrometry (MS). Extraction efficiencies by SBSE vary between 22% and 97% and the detection limit of VOCs in aqueous cloud samples lies between 1.0 and 8.7 ng L−1. Experimental partitioning is evaluated towards the theoretical one described by the Henry's Law constants. Our results show that observed concentrations of hydrophobic VOCs are supersaturated by a factor of 10–103 in comparison with Henry's law equilibrium. Calculations have been performed to evaluate the potential role of adsorption at the air/water interface and of sorption with non-dissolved organic carbon. However, the supersaturation in the cloud droplets requires more laboratory experiments to understand processes at the air/water interface and constrain cloud chemistry models. • Cloud and air samples were collected at the puy de Dôme station in parallel. • Extraction of VOCs in cloud waters by Stir Bar Sorptive Extraction was optimized. • Hydrophobic VOCs from anthropogenic and biogenic sources detected in cloud waters. • Strong super-saturations in cloud waters in comparison to Henry's law predictions [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]

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]