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 µM, 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.

Global contamination of streams by a large variety of compounds, such as nutrients and pesticides, may exert a high pressure on aquatic organisms, including microbial communities and their activity of organic matter decomposition. In this study, we assessed the potential interaction between nutrients and a fungicide and herbicide [tebuconazole (TBZ) and S-metolachlor (S-Met), respectively] at realistic environmental concentrations on the structure (biomass, diversity) and decomposition activity of fungal and bacterial communities (leaf decay rates, extracellular enzymatic activities) associated with Alnus glutinosa (Alnus) leaves. A 40-day microcosm experiment was used to combine two nutrient conditions (mesotrophic and eutrophic) with four pesticide treatments at a nominal concentrations of 15 μg L^-1 (control, TBZ and S-Met, alone or mixed) following a 2 × 4 full factorial design. We also investigated resulting indirect effects on Gammarus fossarum feeding rates using leaves previously exposed to each of the treatments described above. Results showed interactive effects between nutrients and pesticides, only when nutrient (i.e., nitrogen and phosphorus) concentrations were the highest (eutrophic condition). Specifically, slight decreases in Alnus leaf decomposition rates were observed in channels exposed to TBZ (0.01119 days^-1) and S-Met (0.01139 days^-1) than in control ones (0.01334 days^-1) that can partially be explained by changes in the structure of leaf-associated microbial communities. However, exposition to both TBZ and S-Met in mixture (MIX) led to comparable decay rates to those exposed to the pesticides alone (0.01048 days^-1), suggesting no interaction between these two compounds on microbial decomposition. Moreover, stimulation in ligninolytic activities (laccase and phenol oxidase) was observed in presence of the fungicide, possibly highlighting detoxification mechanisms employed by microbes. Such stimulation was not observed for laccase activity exposed to the MIX, suggesting antagonistic interaction of these two compounds on the ability of microbial communities to cope with stress by xenobiotics. Besides, no effects of the treatments were observed on leaf palatability for macroinvertebrates. Overall, the present study highlights that complex interactions between nutrients and xenobiotics in streams and resulting from global change can negatively affect microbial communities associated with leaf litter, although effects on higher trophic-level organisms remains unclear.