The rhizosphere is a highly dynamic zone bridging plant roots with needed nutrient resources in soil. While the rhizosphere may be small, it has a disproportionally large impact on plant success and biomass production. A suite of rhizosphere-hosted microbial and geochemical interactions facilitate nutrient acquisition by plant roots, and, in turn, the roots stimulate these processes by supplying organic carbon into the rhizosphere. The small physical dimensions of the rhizosphere, however, can constrain efforts to elucidate key carbon exchange processes and their spatial extent and localization. We present a method for spatially resolved delta C-13 analysis of rhizosphere samples by coupling laser ablation (LA) sampling with isotopic analysis using capillary absorption spectroscopy (CAS) which differs from conventional mass spectrometer (MS) approaches. The CAS system has high sensitivity (requires fewer nanomoles of CO2 per analysis) than comparable MS systems, which enables reduced sample size requirements to thereby improve spatial resolution (from 25 mu m to as low as a projected 5 mu m spatial resolution). We demonstrate the utility of CAS using rhizosphere samples from switchgrass plants exposed to (CO2)-C-13. This technique will provide a capability for tracking the extent and spatial distribution of root exudate into the rhizosphere at highly detailed spatial scales.

Anthropogenic emissions alter secondary organic aerosol (SOA) formation chemistry from naturally emitted isoprene. We use correlations of tracers and tracer ratios to provide new perspectives on sulfate, NOx, and particle acidity influencing isoprene-derived SOA in two isoprene-rich forested environments representing clean to polluted conditions-wet and dry seasons in central Amazonia and Southeastern U.S. summer. We used a semivolatile thermal desorption aerosol gas chromatograph (SV-TAG) and filter samplers to measure SOA tracers indicative of isoprene/HO2 (2-methyltetrols, C5-alkene triols, 2-methyltetrol organosulfates) and isoprene/NOx (2-methylglyceric acid, 2-methylglyceric acid organosulfate) pathways. Summed concentrations of these tracers correlated with particulate sulfate spanning three orders of magnitude, suggesting that 1 μg m-3 reduction in sulfate corresponds with at least ∼0.5 μg m-3 reduction in isoprene-derived SOA. We also find that isoprene/NOx pathway SOA mass primarily comprises organosulfates, ∼97% in the Amazon and ∼55% in Southeastern United States. We infer under natural conditions in high isoprene emission regions that preindustrial aerosol sulfate was almost exclusively isoprene-derived organosulfates, which are traditionally thought of as representative of an anthropogenic influence. We further report the first field observations showing that particle acidity correlates positively with 2-methylglyceric acid partitioning to the gas phase and negatively with the ratio of 2-methyltetrols to C5-alkene triols.

Shallow convective clouds are common, occurring over many areas of the world, and are an important component in the atmospheric radiation budget. In addition to synoptic and mesoscale meteorological conditions, land-atmosphere interactions and aerosol-radiation-cloud interactions can influence the formation of shallow clouds and their properties. These processes exhibit large spatial and temporal variability and occur at the subgrid scale for all current climate, operational forecast, and cloud-system-resolving models; therefore, they must be represented by parameterizations. Uncertainties in shallow cloud parameterization predictions arise from many sources, including insufficient coincident data needed to adequately represent the coupling of cloud macrophysical and microphysical properties with inhomogeneity in the surface-layer, boundary layer, and aerosol properties. Predictions of the transition of shallow to deep convection and the onset of precipitation are also affected by errors in simulated shallow clouds. Coincident data are a key factor needed to achieve a more complete understanding of the life cycle of shallow convective clouds and to develop improved model parameterizations. To address these issues, the Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems (HI-SCALE) campaign was conducted near the Atmospheric Radiation Measurement (ARM) Southern Great Plains site in north-central Oklahoma during the spring and summer of 2016. We describe the scientific objectives of HI-SCALE as well as the experimental approach, overall weather conditions during the campaign, and preliminary findings from the measurements. Finally, we discuss scientific gaps in our understanding of shallow clouds that can be addressed by analysis and modeling studies that use HI-SCALE data.

Urbanization and deforestation have important impacts on atmospheric particulate matter (PM) over Amazonia. This study presents observations and analysis of PM1 concentration, composition, and optical properties in central Amazonia during the dry season, focusing on the anthropogenic impacts. The primary study site was located 70 km downwind of Manaus, a city of over 2 million people in Brazil, as part of the GoAmazon2014/5 experiment. A high-resolution time-of-flight aerosol mass spectrometer (AMS) provided data on PM1 composition, and aethalometer measurements were used to derive the absorption coefficient babs,BrC of brown carbon (BrC) at 370 nm. Non-refractory PM1 mass concentrations averaged 12.2 µg m−3 at the primary study site, dominated by organics (83 %), followed by sulfate (11 %). A decrease in babs,BrC was observed as the mass concentration of nitrogen-containing organic compounds decreased and the organic PM1 O:C ratio increased, suggesting atmospheric bleaching of the BrC components. The organic PM1 was separated into six different classes by positive-matrix factorization (PMF), and the mass absorption efficiency Eabs associated with each factor was estimated through multivariate linear regression of babs,BrC on the factor loadings. The largest Eabs values were associated with urban (2.04±0.14 m2 g−1) and biomass-burning (0.82±0.04 to 1.50±0.07 m2 g−1) sources. Together, these sources contributed at least 80 % of babs,BrC while accounting for 30 % to 40 % of the organic PM1 mass concentration. In addition, a comparison of organic PM1 composition between wet and dry seasons revealed that only part of the 9-fold increase in mass concentration between the seasons can be attributed to biomass burning. Biomass-burning factor loadings increased by 30-fold, elevating its relative contribution to organic PM1 from about 10 % in the wet season to 30 % in the dry season. However, most of the PM1 mass (>60 %) in both seasons was accounted for by biogenic secondary organic sources, which in turn showed an 8-fold seasonal increase in factor loadings. A combination of decreased wet deposition and increased emissions and oxidant concentrations, as well as a positive feedback on larger mass concentrations are thought to play a role in the observed increases. Furthermore, fuzzy c-means clustering identified three clusters, namely “baseline”, “event”, and “urban” to represent different pollution influences during the dry season. The baseline cluster, representing the dry season background, was associated with a mean mass concentration of 9±3 µg m−3. This concentration increased on average by 3 µg m−3 for both the urban and the event clusters. The event cluster, representing an increased influence of biomass burning and long-range transport of African volcanic emissions, was characterized by remarkably high sulfate concentrations. The urban cluster, representing the influence of Manaus emissions on top of the baseline, was characterized by an organic PM1 composition that differed from the other two clusters. The differences discussed suggest a shift in oxidation pathways as well as an accelerated oxidation cycle due to urban emissions, in agreement with findings for the wet season.

Organosulfates are formed in the atmosphere from reactions between reactive organic compounds (such as oxidation products of isoprene) and acidic sulfate aerosol. Here we investigated speciated organosulfates in an area typically downwind of the city of Manaus situated in the Amazon forest in Brazil during "GoAmazon2014/5" in both the wet season (February-March) and dry season (August-October). We observe products consistent with the reaction of isoprene photooxidation products and sulfate aerosols, leading to formation of several types of isoprene-derived organosulfates, which contribute 3% up to 42% of total sulfate aerosol measured by aerosol mass spectrometry. During the wet season the average contribution of summed organic sulfate concentrations to total sulfate was 19 ± 10% and similarly during the dry season the contribution was 19 ± 8%. This is the highest fraction of speciated organic sulfate to total sulfate observed at any reported site. Organosulfates appeared to be dominantly formed from isoprene epoxydiols (IEPOX), averaging 104 ± 73 ng m-3 (range 15-328 ng m-3) during the wet season, with much higher abundance 610 ± 400 ng m-3 (range 86-1962 ng m-3) during the dry season. The concentration of isoprene-derived organic sulfate correlated with total inorganic sulfate (R2 = 0.35 and 0.51 during the wet and dry seasons, respectively), implying the significant influence of inorganic sulfate aerosol for the heterogeneous reactive uptake of IEPOX. Organosulfates also contributed to organic matter in aerosols (3.5 ± 1.9% during the wet season and 5.1 ± 2.5% during the dry season). The present study shows that an important fraction of sulfate in aerosols in the Amazon downwind of Manaus consists of multifunctional organic chemicals formed in the atmosphere, and that increased SO2 emissions would substantially increase SOA formation from isoprene.

Biogenic volatile organic compounds (BVOCs) from the Amazon forest region represent the largest source of organic carbon emissions to the atmosphere globally. These BVOC emissions dominantly consist of volatile and intermediate-volatility terpenoid compounds that undergo chemical transformations in the atmosphere to form oxygenated condensable gases and secondary organic aerosol (SOA). We collected quartz filter samples with 12 h time resolution and performed hourly in situ measurements with a semi-volatile thermal desorption aerosol gas chromatograph (SV-TAG) at a rural site ("T3") located to the west of the urban center of Manaus, Brazil as part of the Green Ocean Amazon (GoAmazon2014/5) field campaign to measure intermediate-volatility and semi-volatile BVOCs and their oxidation products during the wet and dry seasons. We speciated and quantified 30 sesquiterpenes and 4 diterpenes with mean concentrations in the range 0.01-6.04 ngm-3 (1-670ppqv). We estimate that sesquiterpenes contribute approximately 14 and 12% to the total reactive loss of O3 via reaction with isoprene or terpenes during the wet and dry seasons, respectively. This is reduced from ~ 50-70 % for within-canopy reactive O3 loss attributed to the ozonolysis of highly reactive sesquiterpenes (e.g., β-caryophyllene) that are reacted away before reaching our measurement site. We further identify a suite of their oxidation products in the gas and particle phases and explore their role in biogenic SOA formation in the central Amazon region. Synthesized authentic standards were also used to quantify gas- and particle-phase oxidation products derived from β-caryophyllene. Using tracer-based scaling methods for these products, we roughly estimate that sesquiterpene oxidation contributes at least 0.4-5 % (median 1 %) of total submicron OA mass. However, this is likely a low-end estimate, as evidence for additional unaccounted sesquiterpenes and their oxidation products clearly exists. By comparing our field data to laboratory-based sesquiterpene oxidation experiments we confirm that more than 40 additional observed compounds produced through sesquiterpene oxidation are present in Amazonian SOA, warranting further efforts towards more complete quantification.

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 NOy, 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.

Oxidation flow reactors (OFRs) allow the concentration of a given atmospheric oxidant to be increased beyond ambient levels in order to study secondary organic aerosol (SOA) formation and aging over varying periods of equivalent aging by that oxidant. Previous studies have used these reactors to determine the bulk OA mass and chemical evolution. To our knowledge, no OFR study has focused on the interpretation of the evolving aerosol size distributions. In this study, we use size-distribution measurements of the OFR and an aerosol microphysics model to learn about size-dependent processes in the OFR. Specifically, we use OFR exposures between 0.09 and 0.9 equivalent days of OH aging from the 2011 BEACHON-RoMBAS and GoAmazon2014/5 field campaigns. We use simulations in the TOMAS (TwO-Moment Aerosol Sectional) microphysics box model to constrain the following parameters in the OFR: (1) the rate constant of gas-phase functionalization reactions of organic compounds with OH, (2) the rate constant of gas-phase fragmentation reactions of organic compounds with OH, (3) the reactive uptake coefficient for heterogeneous fragmentation reactions with OH, (4) the nucleation rate constants for three different nucleation schemes, and (5) an effective accommodation coefficient that accounts for possible particle diffusion limitations of particles larger than 60 nm in diameter. We find the best model-to-measurement agreement when the accommodation coefficient of the larger particles (Dp > 60 nm) was 0.1 or lower (with an accommodation coefficient of 1 for smaller particles), which suggests a diffusion limitation in the larger particles. When using these low accommodation-coefficient values, the model agrees with measurements when using a published H2SO4-organics nucleation mechanism and previously published values of rate constants for gas-phase oxidation reactions. Further, gas-phase fragmentation was found to have a significant impact upon the size distribution, and including fragmentation was necessary for accurately simulating the distributions in the OFR. The model was insensitive to the value of the reactive uptake coefficient on these aging timescales. Monoterpenes and isoprene could explain 24 %–95 % of the observed change in total volume of aerosol in the OFR, with ambient semivolatile and intermediate-volatility organic compounds (S/IVOCs) appearing to explain the remainder of the change in total volume. These results provide support to the mass-based findings of previous OFR studies, give insight to important size-distribution dynamics in the OFR, and enable the design of future OFR studies focused on new particle formation and/or microphysical processes.

Secondary organic aerosol (SOA) formation from ambient air was studied using an oxidation flow reactor (OFR) coupled to an aerosol mass spectrometer (AMS) during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O3, over ranges from hours to days (O3) or weeks (OH) of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to as much as 10 µg m−3, depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O3 oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air and were confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA) after OH oxidation showed formation of typical oxidized OA factors and a loss of primary OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O : C up to O : C ∼ 1.0, and then decreased as O : C increased further. Possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. While measured ambient precursors were sufficient to explain the amount of SOA formed from O3, they could only explain 10–50 % of the SOA formed from OH. This is consistent with previous OFR studies, which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C = C bonds) are present in ambient air and can explain such additional SOA formation. To investigate the sources of the unmeasured SOA-forming gases during this campaign, multilinear regression analysis was performed between measured SOA formation and the concentration of gas-phase tracers representing different precursor sources. The majority of SOA-forming gases present during both seasons were of biogenic origin. Urban sources also contributed substantially in both seasons, while biomass burning sources were more important during the dry season. This study enables a better understanding of SOA formation in environments with diverse emission sources.

During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, size-resolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60 km downwind of the city of Manaus, Brazil, in central Amazonia for 1 year (12 March 2014 to 3 March 2015). Particle hygroscopicity (κCCN) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (κorg) was then calculated from κCCN and concurrent chemical composition measurements. The annual average κCCN increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely due to an increase in sulfate volume fraction. During both wet and dry seasons, κCCN, κorg, and particle composition under background conditions exhibited essentially no diel variations. The constant κorg of ∼ 0. 15 is consistent with the largely uniform and high O : C value (∼ 0. 8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of κorg and organic O : C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O : C, κorg, and κCCN increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into a deeper boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF (positive matrix factorization) analysis of AMS (aerosol mass spectrometry) spectra, were estimated through multivariable linear regression. For the SOA factors, the variation of the κ value with O : C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O : C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O : C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O : C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase in κorg with O : C, as observed during this and earlier field studies. This finding helps better understand and reconcile the differences in the relationships between κorg and O : C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.

Inherent soil heterogeneity makes tracking carbon (C) through these dynamic environments very difficult. Here we discuss three emerging techniques for spatially resolved analysis of organic components in soil. Laser ablation isotope ratio mass spectrometry (LA-IRMS) is a method for performing stable isotope analysis on solid samples. The laser-based sampling associated with LA-IRMS allows targeting of specific regions along a solid surface, with resulting isotope analysis at a spatial resolution of up to 50 mu m. Laser ablation aerosol mass spectrometry (LA-AMS) uses a similar, laser ablation-based, sampling approach with up to 2 mu m spatial resolution. In contrast to LA-IRMS, which provides isotope measurement but no chemical identification, the high resolution mass spectrometry capabilities of the AMS enable basic identification and classification of organics based on their elemental ratios (C/N, O/C, H/C, etc.), degree of oxidation, or inclusion of functional groups (e.g., amines, hydrated species, etc.). Nanospray desorption electrospray ionization mass spectrometry (nano-DESI) offers additional detail to chemical identification above that provided by AMS. This technique applies a solvent bridge to dissolve organics off of a solid's surface. A high voltage applied between the solvent droplet and detector inlet then aspirates the analytes into the mass spectrometer for chemical identification. Translating the solvent bridge over a sample's surface enables spatial (similar to 100 mu m) resolution in organic compound analysis. Taken together, the spatial resolution of these emerging approaches, combined with their associated isotopic measurement and chemical identification, provides a suite of tools to enhance the understanding of C accumulation, localization, and transformation in soils.

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.

When secondary organic aerosol (SOA) particles are formed by ozonolysis in the presence of gas-phase polycyclic aromatic hydrocarbons (PAHs), their formation and properties are significantly different from SOA particles formed without PAHs. For all SOA precursors and all PAHs, discussed in this study, the presence of the gas-phase PAHs during SOA formation significantly affects particle mass loadings, composition, growth, evaporation kinetics, and viscosity. SOA particles formed in the presence of PAHs have, as part of their compositions, trapped unreacted PAHs and products of heterogeneous reactions between PAHs and ozone. Compared to 'pure' SOA particles, these particles exhibit slower evaporation kinetics, have higher fractions of non-volatile components, like oligomers, and higher viscosities, assuring their longer atmospheric lifetimes. In turn, the increased viscosity and decreased volatility provide a shield that protects PAHs from chemical degradation and evaporation, allowing for the long-range transport of these toxic pollutants. The magnitude of the effect of PAHs on SOA formation is surprisingly large. The presence of PAHs during SOA formation increases mass loadings by factors of two to five, and particle number concentrations, in some cases, by more than a factor of 100. Increases in SOA mass, particle number concentrations, and lifetime have important implications to many atmospheric processes related to climate, weather, visibility, and human health, all of which relate to the interactions between biogenic SOA and anthropogenic PAHs. The synergistic relationship between SOA and PAHs presented here are clearly complex and call for future research to elucidate further the underlying processes and their exact atmospheric implications.

The atmospheric chemistry of isoprene contributes to the production of a substantial mass fraction of the particulate matter (PM) over tropical forests. Isoprene epoxydiols (IEPOX) produced in the gas phase by the oxidation of isoprene under HO2-dominant conditions are subsequently taken up by particles, thereby leading to production of secondary organic PM. The present study investigates possible perturbations to this pathway by urban pollution. The measurement site in central Amazonia was located 4 to 6 h downwind of Manaus, Brazil. Measurements took place from February through March 2014 of the wet season, as part of the GoAmazon2014/5 experiment. Mass spectra of organic PM collected with an Aerodyne Aerosol Mass Spectrometer were analyzed by positive-matrix factorization. One resolved statistical factor (IEPOX-SOA factor) was associated with PM production by the IEPOX pathway. The IEPOX-SOA factor loadings correlated with independently measured mass concentrations of tracers of IEPOX-derived PM, namely C5-alkene triols and 2-methyltetrols (R = 0. 96 and 0.78, respectively). The factor loading, as well as the ratio f of the loading to organic PM mass concentration, decreased under polluted compared to background conditions. For an increase in NOy concentration from 0.5 to 2 ppb, the factor loading and f decreased by two to three fold. Overall, sulfate concentration explained 37 % of the variability in the factor loading. After segregation of factor loading into subsets based on NOy concentration, the sulfate concentration explained up to 75 % of the variability. Considering both factors, the data sets show that the suppressing effects of increased NO concentrations dominated over the enhancing effects of higher sulfate concentrations. The pollution from Manaus elevated NOy concentrations more significantly than sulfate concentrations relative to background conditions. In this light, increased emissions of nitrogen oxides, as anticipated for some scenarios of Amazonian economic development, could significantly alter pathways of PM production that presently prevail over the tropical forest, implying changes to air quality and regional climate.