[1] We measured atmospheric gas-phase volatile organic compounds (VOCs) at the end of the wet and end of the dry season at a tropical rainforest site in Rondônia, Brazil, using various sampling techniques such as trapping on different adsorbents or cryogenic trapping combined with appropriate analysis techniques. The measuring sites were located inside the forest of a biological reserve near Ji-Paraná. Sampling was performed from 3 May 1999 to 17 May 1999 and from 24 September 1999 to 2 November 1999 during the ''wet-to-dry season transition'' and ''dry-to-wet season transition'' periods in Rondônia, respectively. Samples were obtained at the canopy top close to the potential sources/sinks for these compounds as well as above the forest. We report the measured concentrations of a large number of different VOCs and their oxidation products, such as isoprenoids, organic acids, carbonyls, aromatics, and alcohols. The most prominent VOCs present in air over the last part of the wet season were isoprene, formaldehyde, and formic acid, with mixing ratios of each ranging up to several parts per billion (ppb). Methyl vinyl ketone as well as methacrolein, both oxidation products of isoprene, ranged around 1 ppb. The sum of the measured monoterpene concentrations was below 1 ppb. At the end of the dry season, the amount of C 1 -C 2 organic acids and C 1 -C 2 aldehydes increased significantly up to 17 and 25 ppb, respectively, which is thought to result significantly from vegetation fire emissions. High methanol concentrations also support this scenario. At the same time, however, atmospheric mixing ratios of biogenic compounds such as isoprene increased up to 30 ppb near the crown region and well above 10 ppb at 10-20 m over the forest, whereas monoterpene species seem to decrease. We discuss seasonal development of the vegetation and climatological factors to be responsible for such concentration pattern. The results give an impression about the variability and concentration of VOCs during the different seasons.

As a part of the LBA‐EUSTACH (EUropean Studies on Trace Gases and Atmospheric CHemistry as a contribution of the Large‐scale Biosphere–Atmosphere experiment in Amazonia) project, the exchanges of formaldehyde (HCHO) and acetaldehyde (CH3CHO) between Amazonian vegetation and the atmosphere were investigated by branch enclosures and compared with gradient measurements during the wet‐to‐dry transition and dry‐to‐wet‐transition periods at a remote forest site in Brazil, 1999. Branch enclosure measurements of several tree species showed emission as well as deposition of short‐chain aldehydes, but fluxes were clearly dominated by deposition during both seasons. This bidirectional exchange was found to depend mainly on the actual ambient concentrations of these compounds and to exhibit a compensation point below 0.6 ppb of the compound in air with deposition velocities between 0.16 and 0.21 cm/s during the wet‐to‐dry season. During the dry‐to‐wet season, the deposition velocities and the compensation point increased. Under the clean air conditions of the wet‐to‐dry season, the major pathway for the aldehyde uptake was via leaf stomata. For HCHO, a mesophyll resistance of the same order of magnitude as the stomatal resistance contributed to the total leaf surface resistance, whereas the mesophyll resistance for CH3CHO was small, allowing a rapid uptake. This finding indicates a major contribution of metabolic consumption processes in addition to physical and chemical processes to the overall resistance. During the dry‐to‐wet period, when ambient air concentrations substantially increased, we found indications for an additional deposition to the leaf cuticle. Vertical gradient measurements of ambient air concentrations in and above the canopy closely agreed with the branch enclosure studies and confirmed that the forest acts rather as a sink than as a direct source for HCHO and CH3CHO. Diel courses of ambient air concentrations and ratios of HCHO and CH3CHO above the canopy suggest photochemical oxidation of biogenically or pyrogenically emitted precursor compounds as the major sources for short‐chain aldehydes in the tropical atmosphere.

[1] As part of the project LBA-EUSTACH (European Studies on Trace gases and Atmospheric Chemistry as a contribution to the Large-Scale Biosphere-Atmosphere experiment in Amazonia), the exchange of formic acid and acetic acid between vegetation and the atmosphere was investigated in the wet-to-dry season transition and the dry-to-wet season transition periods in 1999 in Rondônia, Brazil. Direct exchange measurements on the branch level mainly exhibited uptake of formic acid and acetic acid for all plant species in both seasons, although diel, seasonal, and interspecies variations were observed. Even though other physiological and physico-chemical parameters may have contributed, the uptake of organic acids was found to be primarily a function of the ambient atmospheric mixing ratios. The linear dependence suggests a bidirectional exchange behavior of the plants and calculated deposition velocities (0.17-0.23 cm s À1 ), compensation point mixing ratios (0.16-0.30 ppb), and potential emission rates under purified air conditions (0.013-0.031 nmol m À2 s À1 ) are discussed. Vertical profile measurements in and above the primary forest canopy further strengthened the assumption that the forest is rather a sink than a source for organic acids. The generally lower mixing ratios observed within the canopy were indicative of an uptake by vegetation and/or the soil surface. Continuous measurements of the ambient atmospheric mixing ratios at the canopy top revealed strong diel variations in both seasons and a marked seasonality with higher mixing ratios during the dry season, both being mirrored in the variation of observed uptake rates of the plants. High atmospheric concentrations during the dry season were attributed to biomass burning. During the wet season, when biomass burning activity was low, indirect emission by the vegetation, i.e., photochemical oxidation of primarily emitted biogenic reactive hydrocarbons, was assumed to dominantly contribute to the atmospheric burden of the organic acids. The high degree of correlation between atmospheric formic acid and acetic acid indicated that similar atmospheric processes were affecting their mixing ratios.

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