Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX), key isoprene oxidation products, with inorganic sulfate aerosol yields substantial amounts of secondary organic aerosol (SOA) through the formation of organosulfur compounds. The extent and implications of inorganic-to-organic sulfate conversion, however, are unknown. In this article, we demonstrate that extensive consumption of inorganic sulfate occurs, which increases with the IEPOX-to-inorganic sulfate concentration ratio (IEPOX/Sulfinorg), as determined by laboratory measurements. Characterization of the total sulfur aerosol observed at Look Rock, Tennessee, from 2007 to 2016 shows that organosulfur mass fractions will likely continue to increase with ongoing declines in anthropogenic Sulfinorg, consistent with our laboratory findings. We further demonstrate that organosulfur compounds greatly modify critical aerosol properties, such as acidity, morphology, viscosity, and phase state. These new mechanistic insights demonstrate that changes in SO2 emissions, especially in isoprene-dominated environments, will significantly alter biogenic SOA physicochemical properties. Consequently, IEPOX/Sulfinorg will play an important role in understanding the historical climate and determining future impacts of biogenic SOA on the global climate and air quality.

The emissions, deposition, and chemistry of volatile organic compounds (VOCs) are thought to be influenced by underlying landscape heterogeneity at intermediate horizontal scales of several hundred meters across different forest subtypes within a tropical forest. Quantitative observations and scientific understanding at these scales, however, remain lacking, in large part due to a historical absence of canopy access and suitable observational approaches. Herein, horizontal heterogeneity in VOC concentrations in the near-canopy atmosphere was examined by sampling from an unmanned aerial vehicle (UAV) flown horizontally several hundred meters over the plateau and slope forests in central Amazonia during the morning and early afternoon periods of the wet season of 2018. Unlike terpene concentrations, the isoprene concentrations in the near-canopy atmosphere over the plateau forest were 60% greater than those over the slope forest. A gradient transport model constrained by the data suggests that isoprene emissions differed by 220 to 330% from these forest subtypes, which is in contrast to a 0% difference implemented in most present-day biosphere emissions models (i.e., homogeneous emissions). Quantifying VOC concentrations, emissions, and other processes at intermediate horizontal scales is essential for understanding the ecological and Earth system roles of VOCs and representing them in climate and air quality models.

Abstract. 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 PM 1 mass concentration on average, which was in the same range as several upwind sites. However, the organic PM 1 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 Published by Copernicus Publications on behalf of the European Geosciences Union. S. S. de Sá et al.: Urban influence on submicron PM in central AmazoniaT3 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 HO 2 -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 preexi...

<p><strong>Abstract.</strong> Fundamental to quantifying the influence of human activities on climate and air quality is an understanding of how anthropogenic emissions affect the concentrations and composition of airborne particulate matter (PM). 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 <q>T3</q> research site, 70 km downwind of Manaus, during the wet season. At this site, organic components represented on average 79 ± 7 % of the non-refractory PM1 mass concentration, which was in the same range as several upwind sites. The organic PM<sub>1</sub> was, however, 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<sub>y</sub>, ozone, total particle number, black carbon, and sulfate. Four clusters were identified and characterized by distinct airmass 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 to 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 HO<sub>2</sub>-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 pre-existing atmospheric PM can be accelerated. The combined set of results demonstrates the susceptibility of atmospheric chemistry, air quality, and associated climate forcing to anthropogenic perturbations over tropical forests.</p>