In the wet season, a large portion of the Amazon region constitutes one of the most pristine continental areas, with very low concentrations of atmospheric trace gases and aerosol particles. However, land use change modifies the biosphere–atmosphere interactions in such a way that key processes that maintain the functioning of Amazonia are substantially altered. This study presents a comparison between aerosol properties observed at a preserved forest site in Central Amazonia (TT34 North of Manaus) and at a heavily biomass burning impacted site in south-western Amazonia (PVH, close to Porto Velho). Amazonian aerosols were characterized in detail, including aerosol size distributions, aerosol light absorption and scattering, optical depth and aerosol inorganic and organic composition, among other properties. The central Amazonia site (TT34) showed low aerosol concentrations (PM_2.5 of 1.3 ± 0.7 μg m⁻³ and 3.4 ± 2.0 μg m⁻³ in the wet and dry seasons, respectively), with a median particle number concentration of 220 cm⁻³ in the wet season and 2200 cm⁻³ in the dry season. At the impacted site (PVH), aerosol loadings were one order of magnitude higher (PM_2.5 of 10.2 ± 9.0 μg m⁻³ and 33.0 ± 36.0 μg m⁻³ in the wet and dry seasons, respectively). The aerosol number concentration at the impacted site ranged from 680 cm⁻³ in the wet season up to 20 000 cm⁻³ in the dry season. An aerosol chemical speciation monitor (ACSM) was deployed in 2013 at both sites, and it shows that organic aerosol account to 81% to the non-refractory PM1 aerosol loading at TT34, while biomass burning aerosols at PVH shows a 93% content of organic particles. Three years of filter-based elemental composition measurements shows that sulphate at the impacted site decreases, on average, from 12% of PM_2.5 mass during the wet season to 5% in the dry season. This result corroborates the ACSM finding that the biomass burning contributed overwhelmingly to the organic fine mode aerosol during the dry season in this region. Aerosol light scattering and absorption coefficients at the TT34 site were low during the wet season, increasing by a factor of 5, approximately, in the dry season due to long range transport of biomass burning aerosols reaching the forest site in the dry season. Aerosol single scattering albedo (SSA) ranged from 0.84 in the wet season up to 0.91 in the dry. At the PVH site, aerosol scattering coefficients were 3–5 times higher in comparison to the TT34 site, an indication of strong regional background pollution, even in the wet season. Aerosol absorption coefficients at PVH were about 1.4 times higher than at the forest site. Ground-based SSA at PVH was around 0.92 year round, showing the dominance of scattering aerosol particles over absorption, even for biomass burning aerosols. Remote sensing observations from six AERONET sites and from MODIS since 1999, provide a regional and temporal overview. Aerosol Optical Depth (AOD) at 550 nm of less than 0.1 is characteristic of natural conditions over Amazonia. At the perturbed PVH site, AOD₅₅₀ values greater than 4 were frequently observed in the dry season. Combined analysis of MODIS and CERES showed that the mean direct radiative forcing of aerosols at the top of the atmosphere (TOA) during the biomass burning season was −5.6 ± 1.7 W m⁻², averaged over whole Amazon Basin. For high AOD (larger than 1) the maximum daily direct aerosol radiative forcing at the TOA was as high as −20 W m⁻² locally. This change in the radiation balance caused increases in the diffuse radiation flux, with an increase of Net Ecosystem Exchange (NEE) of 18–29% for high AOD. From this analysis, it is clear that land use change in Amazonia shows alterations of many atmospheric properties, and these changes are affecting the functioning of the Amazonian ecosystem in significant ways.

Carbon cycling in the Amazon is closely linked to atmospheric processes and climate in the region as a consequence of the strong coupling between the atmosphere and biosphere. This work examines the effects of changes in net radiation due to atmospheric aerosol particles and clouds on the net ecosystem exchange (NEE) of CO₂ in the Amazon region. Some of the major environmental factors affecting the photosynthetic activity of plants, such as air temperature and relative humidity, were also examined. An algorithm for clear-sky irradiance was developed and used to determine the relative irradiance, f, which quantifies the percentage of solar radiation absorbed and scattered due to atmospheric aerosol particles and clouds. Aerosol optical depth (AOD) was calculated from irradiances measured with the MODIS (Moderate Resolution Imaging Spectroradiometer) sensor, onboard the Terra and Aqua satellites, and was validated with ground-based AOD measurements from AERONET (Aerosol Robotic Network) sun photometers. Carbon fluxes were measured using eddy covariance technique at the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA) flux towers. Two sites were studied: the Jaru Biological Reserve (RBJ), located in Rondonia, and the Cuieiras Biological Reserve at the K34 LBA tower (located in a preserved region in the central Amazon). Analysis was performed continuously from 1999 to 2009 at K34 and from 1999 to 2002 at RBJ, and includes wet, dry and transition seasons. In the Jaru Biological Reserve, a 29% increase in carbon uptake (NEE) was observed when the AOD ranged from 0.10 to 1.5 at 550 nm. In the Cuieiras Biological Reserve, the aerosol effect on NEE was smaller, accounting for an approximate 20% increase in NEE. High aerosol loading (AOD above 3 at 550 nm) or high cloud cover leads to reductions in solar flux and strong decreases in photosynthesis up to the point where NEE approaches zero. The observed increase in NEE is attributed to an enhancement (~50%) in the diffuse fraction of photosynthetic active radiation (PAR). The enhancement in diffuse PAR can be done through increases in aerosols and/or clouds. In the present study, it was not possible to separate these two components. Significant changes in air temperature and relative humidity resulting from changes in solar radiation fluxes under high aerosol loading were also observed at both sites. Considering the long-range transport of aerosols in the Amazon, the observed changes in NEE for these two sites may occur over large areas in the Amazon, significantly altering the carbon balance in the largest rainforest in the world.

A long term experiment was conducted in a primary forest area in Amazonia, with continuous in-situ measurements of aerosol optical properties between February 2008 and April 2011, comprising, to our knowledge, the longest database ever in the Amazon Basin. Two major classes of aerosol particles, with significantly different optical properties were identified: coarse mode predominant biogenic aerosols in the wet season (January–June), naturally released by the forest metabolism, and fine mode dominated biomass burning aerosols in the dry season (July–December), transported from regional fires. Dry particle median scattering coefficients at the wavelength of 550 nm increased from 6.3 Mm⁻¹ to 22 Mm⁻¹, whereas absorption at 637 nm increased from 0.5 Mm⁻¹ to 2.8 Mm⁻¹ from wet to dry season. Most of the scattering in the dry season was attributed to the predominance of fine mode (PM₂) particles (40–80% of PM₁₀ mass), while the enhanced absorption coefficients are attributed to the presence of light absorbing aerosols from biomass burning. As both scattering and absorption increased in the dry season, the single scattering albedo (SSA) did not show a significant seasonal variability, in average 0.86 ± 0.08 at 637 nm for dry aerosols. Measured particle optical properties were used to estimate the aerosol forcing efficiency at the top of the atmosphere. Results indicate that in this primary forest site the radiative balance was dominated by the cloud cover, particularly in the wet season. Due to the high cloud fractions, the aerosol forcing efficiency absolute values were below −3.5 W m⁻² in 70% of the wet season days and in 46% of the dry season days. Besides the seasonal variation, the influence of out-of-Basin aerosol sources was observed occasionally. Periods of influence of the Manaus urban plume were detected, characterized by a consistent increase on particle scattering (factor 2.5) and absorption coefficients (factor 5). Episodes of biomass burning and mineral dust particles advected from Africa were observed between January and April, characterized by enhanced concentrations of crustal elements (Al, Si, Ti, Fe) and potassium in the fine mode. During these episodes, median particle absorption coefficients increased by a factor of 2, whereas median SSA values decreased by 7%, in comparison to wet season conditions.

The occurrence of nonliquid and liquid physical states of submicron atmospheric particulate matter (PM) downwind of an urban region in central Amazonia was investigated. Measurements were conducted during two intensive operating periods (IOP1 and IOP2) that took place during the wet and dry seasons of the GoAmazon2014/5 campaign. Air masses representing variable influences of background conditions, urban pollution, and regional- and continental-scale biomass burning passed over the research site. As the air masses varied, particle rebound fraction, an indicator of physical state, was measured in real time at ground level using an impactor apparatus. Micrographs collected by transmission electron microscopy confirmed that liquid particles adhered, while nonliquid particles rebounded. Relative humidity (RH) was scanned to collect rebound curves. When the apparatus RH matched ambient RH, 95 % of the particles adhered as a campaign average. Secondary organic material, produced for the most part by the oxidation of volatile organic compounds emitted from the forest, produces liquid PM over this tropical forest. During periods of anthropogenic influence, by comparison, the rebound fraction dropped to as low as 60 % at 95 % RH. Analyses of the mass spectra of the atmospheric PM by positive-matrix factorization (PMF) and of concentrations of carbon monoxide, total particle number, and oxides of nitrogen were used to identify time periods affected by anthropogenic influences, including both urban pollution and biomass burning. The occurrence of nonliquid PM at high RH correlated with these indicators of anthropogenic influence. A linear model having as output the rebound fraction and as input the PMF factor loadings explained up to 70 % of the variance in the observed rebound fractions. Anthropogenic influences can contribute to the presence of nonliquid PM in the atmospheric particle population through the combined effects of molecular species that increase viscosity when internally mixed with background PM and increased concentrations of nonliquid anthropogenic particles in external mixtures of anthropogenic and biogenic PM.

An understanding of how anthropogenic emissions affect the concentrations and composition of airborne particulate matter (PM) is fundamental to quantifying the influence of human activities on climate and air quality. The central Amazon Basin, especially around the city of Manaus, Brazil, has experienced rapid changes in the past decades due to ongoing urbanization. Herein, changes in the concentration and composition of submicron PM due to pollution downwind of the Manaus metropolitan region are reported as part of the GoAmazon2014/5 experiment. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a suite of other gas- and particle-phase instruments were deployed at the T3 research site, 70 km downwind of Manaus, during the wet season. At this site, organic components represented 79±7 % of the non-refractory PM₁ mass concentration on average, which was in the same range as several upwind sites. However, the organic PM₁ was considerably more oxidized at T3 compared to upwind measurements. Positive-matrix factorization (PMF) was applied to the time series of organic mass spectra collected at the T3 site, yielding three factors representing secondary processes (73±15 % of total organic mass concentration) and three factors representing primary anthropogenic emissions (27±15 %). Fuzzy c-means clustering (FCM) was applied to the afternoon time series of concentrations of NO_y, ozone, total particle number, black carbon, and sulfate. Four clusters were identified and characterized by distinct air mass origins and particle compositions. Two clusters, Bkgd-1 and Bkgd-2, were associated with background conditions. Bkgd-1 appeared to represent near-field atmospheric PM production and oxidation of a day or less. Bkgd-2 appeared to represent material transported and oxidized for two or more days, often with out-of-basin contributions. Two other clusters, Pol-1 and Pol-2, represented the Manaus influence, one apparently associated with the northern region of Manaus and the other with the southern region of the city. A composite of the PMF and FCM analyses provided insights into the anthropogenic effects on PM concentration and composition. The increase in mass concentration of submicron PM ranged from 25 % to 200 % under polluted compared with background conditions, including contributions from both primary and secondary PM. Furthermore, a comparison of PMF factor loadings for different clusters suggested a shift in the pathways of PM production under polluted conditions. Nitrogen oxides may have played a critical role in these shifts. Increased concentrations of nitrogen oxides can shift pathways of PM production from HO₂-dominant to NO-dominant as well as increase the concentrations of oxidants in the atmosphere. Consequently, the oxidation of biogenic and anthropogenic precursor gases as well as the oxidative processing of preexisting atmospheric PM can be accelerated. This combined set of results demonstrates the susceptibility of atmospheric chemistry, air quality, and associated climate forcing to anthropogenic perturbations over tropical forests.