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The Amazon Basin plays key roles in the carbon and water cycles, climate change, atmospheric chemistry, and biodiversity. It has already been changed significantly by human activities, and more pervasive change is expected to occur in the coming decades. It is therefore essential to establish long-term measurement sites that provide a baseline record of present-day climatic, biogeochemical, and atmospheric conditions and that will be operated over coming decades to monitor change in the Amazon region, as human perturbations increase in the future. The Amazon Tall Tower Observatory (ATTO) has been set up in a pristine rain forest region in the central Amazon Basin, about 150 km northeast of the city of Manaus. Two 80 m towers have been operated at the site since 2012, and a 325 m tower is nearing completion in mid-2015. An ecological survey including a biodiversity assessment has been conducted in the forest region surrounding the site. Measurements of micrometeorological and atmospheric chemical variables were initiated in 2012, and their range has continued to broaden over the last few years. The meteorological and micrometeorological measurements include temperature and wind profiles, precipitation, water and energy fluxes, turbulence components, soil temperature profiles and soil heat fluxes, radiation fluxes, and visibility. A tree has been instrumented to measure stem profiles of temperature, light intensity, and water content in cryptogamic covers. The trace gas measurements comprise continuous monitoring of carbon dioxide, carbon monoxide, methane, and ozone at five to eight different heights, complemented by a variety of additional species measured during intensive campaigns (e.g., VOC, NO, NO2, and OH reactivity). Aerosol optical, microphysical, and chemical measurements are being made above the canopy as well as in the canopy space. They include aerosol light scattering and absorption, fluorescence, number and volume size distributions, chemical composition, cloud condensation nuclei (CCN) concentrations, and hygroscopicity. In this paper, we discuss the scientific context of the ATTO observatory and present an overview of results from ecological, meteorological, and chemical pilot studies at the ATTO site. © Author(s) 2015.

A new continuous integrated cavity output spectroscopy analyzer and an automated soil chamber system were used to investigate the exchange processes of carbonyl sulfide (OCS) between soils and the atmosphere under laboratory conditions. The exchange patterns of OCS between soils and the atmosphere were found to be highly dependent on soil moisture and ambient CO2 concentration. With increasing soil moisture, OCS exchange ranged from emission under dry conditions to an uptake within an optimum moisture range, followed again by emission at high soil moisture. Elevated CO2 was found to have a significant impact on the exchange rate and direction as tested with several soils. There is a clear tendency toward a release of OCS at higher CO2 levels (up to 7600 ppm), which are typical for the upper few centimeters within soils. At high soil moisture, the release of OCS increased sharply. Measurements after chloroform vapor application show that there is a biotic component to the observed OCS exchange. Furthermore, soil treatment with the fungi inhibitor nystatin showed that fungi might be the dominant OCS consumers in the soils we examined. We discuss the influence of soil moisture and elevated CO2 on the OCS exchange as a change in the activity of microbial communities. Physical factors such as diffusivity that are governed by soil moisture also play a role. Comparing KM values of the enzymes to projected soil water CO2 concentrations showed that competitive inhibition is unlikely for carbonic anhydrase and PEPCO but might occur for RubisCO at higher CO2 concentrations.

Size-resolved long-term measurements of atmospheric aerosol and cloud condensation nuclei (CCN) concentrations as well as hygroscopicity were conducted at the remote Amazon Tall Tower Observatory (ATTO) in the central Amazon Basin over a one-year period and full seasonal cycle (March 2014–February 2015). The presented measurements provide a climatology of CCN properties for a characteristic central Amazonian rain forest site. The CCN measurements were continuously cycled through 10 levels of supersaturation (S = 0.11 to 1.10 %) and span the aerosol particle size range from 20 to 245 nm. The observed mean critical diameters of CCN activation range from 43 nm at S = 1.10 % to 172 nm at S = 0.11 %. The particle hygroscopicity exhibits a pronounced size dependence with lower values for the Aitken mode (κAit = 0.14 ± 0.03), elevated values for the accumulation mode (κAcc = 0.22 ± 0.05), and an overall mean value of κmean = 0.17 ± 0.06, consistent with high fractions of organic aerosol. The hygroscopicity parameter κ exhibits remarkably little temporal variability: no pronounced diurnal cycles, weak seasonal trends, and few short-term variations during long-range transport events. In contrast, the CCN number concentrations exhibit a pronounced seasonal cycle, tracking the pollution-related seasonality in total aerosol concentration. We find that the variability in the CCN concentrations in the central Amazon is mostly driven by aerosol particle number concentration and size distribution, while variations in aerosol hygroscopicity and chemical composition matter only during a few episodes. For modelling purposes, we compare different approaches of predicting CCN number concentration and present a novel parameterization, which allows accurate CCN predictions based on a small set of input data.

We describe a dynamic chamber system to determine reactive trace gas exchange fluxes between plants and the atmosphere under laboratory and, with small modifications, also under field conditions. The system allows measurements of the flux density of the reactive NO-NO2-O3 triad and additionally of the non-reactive trace gases CO2 and H2O. The chambers are made of transparent and chemically inert wall material and do not disturb plant physiology. For NO2 detection we used a highly NO2 specific blue light converter coupled to chemiluminescence detection of the photolysis product, NO. Exchange flux densities derived from dynamic chamber measurements are based on very small concentration differences of NO2 (NO, O3) between inlet and outlet of the chamber. High accuracy and precision measurements are therefore required, and high instrument sensitivity (limit of detection) and the statistical significance of concentration differences are important for the determination of corresponding exchange flux densities, compensation point concentrations, and deposition velocities. The determination of NO2 concentrations at sub-ppb levels (2 analyzer with a lower detection limit (3σ-definition) of 0.3 ppb or better. Deposition velocities and compensation point concentrations were determined by bi-variate weighted linear least-squares fitting regression analysis of the trace gas concentrations, measured at the inlet and outlet of the chamber. Performances of the dynamic chamber system and data analysis are demonstrated by studies of Picea abies L. (Norway Spruce) under field and laboratory conditions. Our laboratory data show that the quality selection criterion based on the use of only significant NO2 concentration differences has a considerable impact on the resulting compensation point concentrations yielding values closer to zero. The results of field experiments demonstrate the need to consider photo-chemical reactions of NO, NO2, and O3 inside the chamber for the correct determination of the exchange flux densities, deposition velocities, as well as compensation point concentrations. Under our field conditions NO2 deposition velocities would have been overestimated up to 80%, if NO2 photolysis has not been considered. We also quantified the photolysis component for some previous NO2 flux measurements. Neglecting photo-chemical reactions may have changed reported NO2 compensation point concentration by 10%. However, the effect on NO2 deposition velocity was much more intense, ranged between 50 and several hundreds percent. Our findings may have consequences for the results from previous studies and ongoing discussion of NO2 compensation point concentrations.

The effect of root inundation on the leaf emissions of ethanol, acetaldehyde and acetic acid in relation to assimilation and transpiration was investigated with 2–3 years old tree seedlings of four Amazonian floodplain species by applying dynamic cuvette systems under greenhouse conditions. Emissions were monitored over a period of several days of inundation using a combination of Proton Transfer Reaction Mass Spectrometry (PTR-MS) and conventional techniques (HPLC, ion chromatography). Under non-flooded conditions, none of the species exhibited measurable emissions of any of the compounds, but rather low deposition of acetaldehyde and acetic acid was observed instead. Tree species specific variations in deposition velocities were largely due to variations in stomatal conductance. Flooding of the roots resulted in leaf emissions of ethanol and acetaldehyde by all species, while emissions of acetic acid were only observed from the species exhibiting the highest ethanol and acetaldehyde emission rates. All three compounds showed a similar diurnal emission profile, each displaying an emission burst in the morning, followed by a decline in the evening. This concurrent behavior supports the conclusion, that all three compounds emitted by the leaves are derived from ethanol produced in the roots by alcoholic fermentation, transported to the leaves with the transpiration stream and finally partly converted to acetaldehyde and acetic acid by enzymatic processes. Co-emissions and peaking in the early morning suggest that root ethanol, after transportation with the transpiration stream to the leaves and enzymatic oxidation to acetaldehyde and acetate, is the metabolic precursor for all compounds emitted, though we can not totally exclude other production pathways. Emission rates substantially varied among tree species, with maxima differing by up to two orders of magnitude (25–1700 nmol m−2 min−1 for ethanol and 5–500 nmol m−2 min−1 for acetaldehyde). Acetic acid emissions reached 12 nmol m−2 min−1. The observed differences in emission rates between the tree species are discussed with respect to their root adaptive strategies to tolerate long term flooding, providing an indirect line of evidence that the root ethanol production is a major factor determining the foliar emissions. Species which develop morphological root structures allowing for enhanced root aeration produced less ethanol and showed much lower emissions compared to species which lack gas transporting systems, and respond to flooding with substantially enhanced fermentation rates and a non-trivial loss of carbon to the atmosphere. The pronounced differences in the relative emissions of ethanol to acetaldehyde and acetic acid between the tree species indicate that not only the ethanol production in the roots but also the metabolic conversion in the leaf is an important factor determining the release of these compounds to the atmosphere.

International audience; The Amazonian rainforest is a large tropical ecosystem, which is one of the last pristine continental terrains. This ecosystem is ideally located for the study of diel and seasonal behaviour of biogenic volatile organic compounds (BVOCs) in the absence of local human interference. In this study, we report the first atmospheric BVOC measurements at the Amazonian Tall Tower Observatory (ATTO) site, located in central Amazonia. A quadrupole proton-transfer-reaction mass spectrometer (PTR-MS), with seven ambient air inlets, positioned from near ground to about 80 m (0.05, 0.5, 4, 24, 38, 53 and 79 m above the forest floor), was deployed for BVOC monitoring. We report diel and seasonal (February–March 2013 as wet season and September 2013 as dry season) ambient mixing ratios for iso-prene, monoterpenes, isoprene oxidation products, acetalde-hyde, acetone, methyl ethyl ketone (MEK), methanol and acetonitrile. Clear diel and seasonal patterns were observed for all compounds. In general, lower mixing ratios were observed during night, while maximum mixing ratios were observed during the wet season (February–March 2013), with the peak in solar irradiation at 12:00 LT (local time) and during the dry season (September 2013) with the peak in temperature at 16:00 LT. Isoprene and monoterpene mixing ratios were the highest within the canopy with a median of 7.6 and 1 ppb, respectively (interquartile range (IQR) of 6.1 and 0.38 ppb) during the dry season (at 24 m, from 12:00 to 15:00 LT). The increased contribution of oxygenated volatile organic compounds (OVOCs) above the canopy indicated a transition from dominating forest emissions during the wet season (when mixing ratios were higher than within the canopy), to a blend of biogenic emission, photochemical production and advection during the dry season when mixing ratios were higher above the canopy. Our observations suggest strong seasonal interactions between environmental (in-solation, temperature) and biological (phenology) drivers of leaf BVOC emissions and atmospheric chemistry. Considerable differences in the magnitude of BVOC mixing ratios, as compared to other reports of Amazonian BVOC, demonstrate the need for long-term observations at different sites and more standardized measurement procedures, in order to better characterize the natural exchange of BVOCs between the Amazonian rainforest and the atmosphere.

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As volatile organic compounds (VOCs) significantly affect atmospheric chemistry (oxidative capacity) and physics (secondary organic aerosol formation and effects), emission inventories defining regional and global biogenic VOC emission strengths are important. The aim of this work was to achieve a description of VOC emissions from poorly described tropical vegetation to be compared with the quite well investigated and highly heterogeneous emissions from Mediterranean vegetation. For this task, common plant species of both ecosystems were investigated. Sixteen plant species from the Mediterranean area, which is known for its special diversity in VOC emitting plant species, were chosen. In contrast, little information is currently available regarding emissions of VOCs from tropical tree species at the leaf level. Twelve plant species from different environments of the Amazon basin, i.e. Terra firme, Várzea and Igapó, were screened for emission of VOCs at leaf level with a branch enclosure system. Analysis of the volatile organics was performed online by a proton-transfer-reaction mass spectrometer (PTR-MS) and offline by collection on adsorbent tubes and subsequent gas chromatographic analysis. Isoprene was quantitatively the most dominant compound emitted followed by monoterpenes, methanol and acetone. Most of the Mediterranean species emitted a variety of monoterpenes, whereas only five tropical species were monoterpene emitters exhibiting a quite conservative emission pattern (α-pinene > limonene > sabinene > β-pinene). Mediterranean plants showed additional emissions of sesquiterpenes, whereas in the case of plants from the Amazon region no sesquiterpenes were detected probably due to a lack of sensitivity in the measuring systems. On the other hand methanol emissions, an indicator of growth, were common in most of the tropical and Mediterranean species. A few species from both ecosystems showed acetone emissions. The observed heterogeneous emissions including reactive VOC species which are not easily detected by flux measurements, give reason to perform more screening at leaf level and, whenever possible, within the forests under ambient conditions.

We measured the mixing ratios of NO, NO2, O-3, and volatile organic carbon as well as the aerosol light-scattering coefficient on a boat platform cruising on rivers downwind of the city of Manaus (Amazonas State, Brazil) in July 2001 (Large-Scale Biosphere-Atmosphere Experiment in Amazonia-Cooperative LBA Airborne Regional Experiment-2001). The dispersion and impact of the Manaus plume was investigated by a combined analysis of ground-based (boat platform) and airborne trace gas and aerosol measurements as well as by meteorological measurements complemented by dispersion calculations (Hybrid Single-Particle Lagrangian Integrated Trajectory model). For the cases with the least anthropogenic influence (including a location in a so far unexplored region similar to 150 km west of Manaus on the Rio Manacapuru), the aerosol scattering coefficient, sigma(s), was below 11 Mm(-1), NOx mixing ratios remained below 0.6 ppb, daytime O-3 mixing ratios were mostly below 20 ppb and maximal isoprene mixing ratios were about 3 ppb in the afternoon. The photostationary state (PSS) was not established for these cases, as indicated by values of the Leighton ratio, Phi, well above unity. Due to the influence of river breeze systems and other thermally driven mesoscale circulations, a change of the synoptic wind direction from east-northeast to south-southeast in the afternoon often caused a substantial increase of ss and trace gas mixing ratios (about threefold for sigma(s), fivefold for NOx, and twofold for O-3), which was associated with the arrival of the Manaus pollution plume at the boat location. The ratio F reached unity within its uncertainty range at NOx mixing ratios of about 3 ppb, indicating "steady-state" conditions in cases when radiation variations, dry deposition, emissions, and reactions mostly involving peroxy radicals (XO2) played a minor role. The median midday/afternoon XO2 mixing ratios estimated using the PSS method range from 90 to 120 parts per trillion (ppt) for the remote cases (sigma(s) < 11 Mm(-1) and NOx < 0.6 ppb), while for the polluted cases our estimates are 15 to 60 ppt. These values are within the range of XO2 estimated by an atmospheric chemistry box model (Chemistry As A Box model Application-Module Efficiently Calculating the Chemistry of the Atmosphere (CAABA/MECCA)-3.0).