Abstract. We measured the mixing ratios of ammonia (NH3), nitric acid (HNO3), nitrous acid (HONO), hydrochloric acid (HCl), sulfur dioxide (SO2) and the corresponding water-soluble inorganic aerosol species, ammonium (NH4+), nitrate (NO3−), nitrite (NO2−), chloride (Cl−) and sulfate (SO42−), and their diel and seasonal variations at a pasture site in the Amazon Basin (Rondônia, Brazil). This study was conducted within the framework of LBA-SMOCC (Large Scale Biosphere Atmosphere Experiment in Amazonia Smoke Aerosols, Clouds, Rainfall and Climate). Sampling was performed from 12 September to 14 November 2002, extending from the dry season (extensive biomass burning activity), through the transition period to the wet season (background conditions). Measurements were made continuously using a wet-annular denuder in combination with a Steam-Jet Aerosol Collector (SJAC) followed by suitable on-line analysis. A detailed description and verification of the inlet system for simultaneous sampling of soluble gases and aerosol compounds is presented. Overall measurement uncertainties of the ambient mixing ratios usually remained below 15%. The limit of detection (LOD) was determined for each single data point measured during the field experiment. Median LOD values (3σ-definition) were ≤0.015 ppb for acidic trace gases and aerosol anions and ≤0.118 ppb for NH3 and aerosol NH4+. Mixing ratios of acidic trace gases remained below 1ppb throughout the measurement period, while NH3 levels were an order of magnitude higher. Accordingly, mixing ratios of NH4+ exceeded those of other inorganic aerosol contributors by a factor of 4 to 10. During the wet season, mixing ratios decreased by nearly a factor of 3 for all compounds compared to those observed when intensive biomass burning took place. Additionally, N-containing gas and aerosol species featured pronounced diel variations. This is attributed to strong relative humidity and temperature variations between day and night as well as to changing photochemistry and stability conditions of the planetary boundary layer. HONO exhibited a characteristic diel cycle with high mixing ratios at nighttime and was not completely depleted by photolysis during daylight hours.
Abstract. The input of nitrogen (N) to ecosystems has increased dramatically over the past decades. While total N deposition (wet + dry) has been extensively determined in temperate regions, only very few data sets exist about wet N deposition in tropical ecosystems, and moreover, experimental information about dry N deposition in tropical environments is lacking. In this study we estimate dry and wet deposition of inorganic N for a remote pasture site in the Amazon Basin based on in-situ measurements. The measurements covered the late dry (biomass burning) season, a transition period and the onset of the wet season (clean conditions) (12 September to 14 November 2002, LBA-SMOCC). Ammonia (NH3), nitric acid (HNO3), nitrous acid (HONO), nitrogen dioxide (NO2), nitric oxide (NO), ozone (O3), aerosol ammonium (NH4+) and aerosol nitrate (NO3-) were measured in real-time, accompanied by simultaneous (micro-)meteorological measurements. Dry deposition fluxes of NO2 and HNO3 are inferred using the ''big leaf multiple resistance approach'' and particle deposition fluxes are derived using an established empirical parameterization. Bi-directional surface-atmosphere exchange fluxes of NH3 and HONO are estimated by applying a ''canopy compensation point model''. Dry and wet N deposition is dominated by NH3 and NH4+, which is largely the consequence of biomass burning during the dry season. The grass surface appeared to have a strong potential for daytime NH3 (re-)emission, owing to high canopy compensation points, which are related to high surface temperatures and to direct NH3 emissions from cattle excreta. NO2 also significantly accounted for dry N deposition, whereas HNO3, HONO and N-containing aerosol species were only minor contributors. We estimated a total (dry + wet) N deposition of 7.3–9.8 kgN ha-1 yr-1 to the tropical pasture site, whereof 2–4.5 kgN ha-1 yr-1 are attributed to dry N deposition and ~5.3 kgN ha-1 yr-1 to wet N deposition. Our estimate exceeds total (wet + dry) N deposition to tropical ecosystems predicted by global chemistry and transport models by at least factor of two.
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