The NH4+-NO3--Cl--SO42--H2O aerosol system and its gas phase precursors at a pasture site in the Amazon Basin: How relevant are mineral cations and soluble organic acids?

Real-time measurements of ammonia, nitric acid, hydrochloric acid, sulfur dioxide and the water-soluble inorganic aerosol species, ammonium, nitrate, chloride, and sulfate were performed at a pasture site in the Amazon Basin (Rondônia, Brazil). The measurements were made during the late dry season (biomass burning), the transition period, and the onset of the wet season (clean conditions) using a wet-annular denuder (WAD) in combination with a Steam-Jet Aerosol Collector (SJAC). Measurements were conducted from 12 September to 14 November 2002 within the framework of LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazonia - Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate). Real-time data were combined with measurements of sodium, potassium, calcium, magnesium, and low-molecular weight (LMW) polar organic acids determined on 12-, 24-, and 48-hours integrated filter samples. The contribution of inorganic species to the fine particulate mass (Dp = 2.5 µm) was frequently below 20% by mass, indicating the preponderance of organic matter. The measured concentration products of NH3 × HNO3 and NH3 × HCl persistently remained below the theoretical equilibrium dissociation constants of the NH3/HNO3/NH4NO3 and NH3/HCl/NH4Cl systems during daytime (RH <90%). The application of four thermodynamic equilibrium models (EQMs) indicates that the fine mode aerosol anions NO3 -, Cl-, and SO4 2- were balanced predominantly by mineral cations (particularly pyrogenic K+) during daytime. At nighttime (RH > 90%) fine-mode NH4NO3 and NH4Cl are predicted to be formed in the aqueous aerosol phase. Probably, Cl- was driven out of the aerosol phase largely by reaction of pyrogenic KCl with HNO3 and H2SO4. As shown by an updated version of the equilibrium simplified aerosol model (EQSAM2), which incorporates mineral aerosol species and lumped LMW polar organic acids, daytime aerosol NH4 + was mainly balanced by organic co