[1] As part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA)-Cooperative LBA Airborne Regional Experiment (CLAIRE) 2001 campaign, separate day and nighttime aerosol samples were collected in July 2001 at a ground-based site in Amazonia, Brazil, in order to examine the composition and temporal variability of the natural ''background'' aerosol. A combination of analytical techniques was used to characterize the elemental and ionic composition of the aerosol. Major particle types larger than $0.5 mm were identified by electron and light microscopy. Both the coarse and fine aerosol were found to consist primarily of organic matter ($70 and 80% by mass, respectively), with the coarse fraction containing small amounts of soil dust and sea-salt particles and the fine fraction containing some non-sea-salt sulfate. Coarse particulate mass concentrations (CPM % PM 10 À PM 2 ) were found to be highest at night (average = 3.9 ± 1.4 mg m À3 , mean night-to-day ratio = 1.9 ± 0.4), while fine particulate mass concentrations (FPM % PM 2 ) increased during the daytime (average = 2.6 ± 0.8 mg m À3 , mean night-to-day ratio = 0.7 ± 0.1). The nocturnal increase in CPM coincided with an increase in primary biological particles in this size range (predominantly yeasts and other fungal spores), resulting from the trapping of surface-derived forest aerosol under a shallow nocturnal boundary layer and a lake-land breeze effect at the site, although active nocturnal sporulation may have also contributed. Associated with this, we observed elevated nighttime concentrations of biogenic elements and ions (P, S, K, Cu, Zn, NH 4 + ) in the CPM fraction. For the FPM fraction a persistently higher daytime concentration of organic carbon was found, which indicates that photochemical production of secondary organic aerosol from biogenic volatile organic compounds may have made a significant contribution to the fine aerosol. Dust and sea-salt-associated elements/ions in the CPM fraction, and non-sea-salt sulfate in the FPM fraction, showed higher daytime concentrations, most likely due to enhanced convective downward mixing of long-range transported aerosol.

Abstract. The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM2.5 aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagrams, carbon oxidation state and aromaticity equivalent) were used to identify compound classes and mass distributions of the detected species. Nitrogen- and/or sulfur-containing organic species contributed up to 60 % of the total identified number of formulae. A large number of molecular formulae in organic aerosol (OA) were attributed to later-generation nitrogen- and sulfur-containing oxidation products, suggesting that OA composition is affected by biomass burning and other, potentially anthropogenic, sources. Isoprene-derived organosulfate (IEPOX-OS) was found to be the most dominant ion in most of the analysed samples and strongly followed the concentration trends of the gas-phase anthropogenic tracers confirming its mixed anthropogenic–biogenic origin. The presence of oxidised aromatic and nitro-aromatic compounds in the samples suggested a strong influence from biomass burning especially during the dry period. Aerosol samples from the dry period and under enhanced biomass burning conditions contained a large number of molecules with high carbon oxidation state and an increased number of aromatic compounds compared to that from the wet period. The results of this work demonstrate that the studied site is influenced not only by biogenic emissions from the forest but also by biomass burning and potentially other anthropogenic emissions from the neighbouring urban environments.

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The intercontinental transport of aerosols from the Sahara desert plays a significant role in nutrient cycles in the Amazon rainforest, since it carries many types of minerals to these otherwise low-fertility lands. Iron is one of the micronutrients essential for plant growth, and its long-range transport might be an important source for the iron-limited Amazon rainforest. This study assesses the bioavailability of iron Fe(II) and Fe(III) in the particulate matter over the Amazon forest, which was transported from the Sahara desert (for the sake of our discussion, this term also includes the Sahel region). The sampling campaign was carried out above and below the forest canopy at the ATTO site (Amazon Tall Tower Observatory), a near-pristine area in the central Amazon Basin, from March to April 2015. Measurements reached peak concentrations for soluble Fe(III) (48 ng m−3), Fe(II) (16 ng m−3), Na (470 ng m−3), Ca (194 ng m−3), K (65 ng m−3), and Mg (89 ng m−3) during a time period of dust transport from the Sahara, as confirmed by ground-based and satellite remote sensing data and air mass backward trajectories. Dust sampled above the Amazon canopy included primary biological aerosols and other coarse particles up to 12 µm in diameter. Atmospheric transport of weathered Saharan dust, followed by surface deposition, resulted in substantial iron bioavailability across the rainforest canopy. The seasonal deposition of dust, rich in soluble iron, and other minerals is likely to assist both bacteria and fungi within the topsoil and on canopy surfaces, and especially benefit highly bioabsorbent species. In this scenario, Saharan dust can provide essential macronutrients and micronutrients to plant roots, and also directly to plant leaves. The influence of this input on the ecology of the forest canopy and topsoil is discussed, and we argue that this influence would likely be different from that of nutrients from the weathered Amazon bedrock, which otherwise provides the main source of soluble mineral nutrients

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