Chemical Signatures of Seasonally Unique Anthropogenic Influences on Organic Aerosol Composition in the Central Amazon.

Urbanization and fires perturb the quantities and composition of fine organic aerosol in the central Amazon, with ramifications for radiative forcing and public health. These disturbances include not only direct emissions of particulates and secondary organic aerosol (SOA) precursors but also changes in the pathways through which biogenic precursors form SOA. The composition of ambient organic aerosol is complex and incompletely characterized, encompassing millions of potential structures relatively few of which have been synthesized and characterized. Through analysis of submicron aerosol samples from the Green Ocean Amazon (GoAmazon2014/5) field campaign by two-dimensional gas chromatography coupled with machine learning, ∼1300 unique compounds were traced and characterized over two seasons. Fires and urban emissions produced chemically and interseasonally distinct impacts on product signatures, with only ∼50% of compounds observed in both seasons. Seasonally unique populations point to the importance of aqueous processing in Amazonian aerosol aging, but further mechanistic insights are impeded by limited product identity knowledge. Less than 10% of compounds were identifiable at an isomer-specific level. Overall, the findings (i) provide compositional characterization of anthropogenic influence on submicron organic aerosol in the Amazon, (ii) identify key season-to-season differences in chemical signatures, and (iii) highlight high-priority knowledge gaps in current speciated knowledge.

Assessing over decadal biomass burning influence on particulate matter composition in subequatorial Amazon: literature review, remote sensing, chemical speciation and machine learning application.

A study on aerosols in the Brazilian subequatorial Amazon region, Tangará da Serra (TS) and Alta Floresta (AF) was conducted and compared to findings in an additional site with background characteristics (Manaus, AM). TS and AF counties suffer from intense biomass burning periods in the dry season, and it accounts for high levels of particles in the atmosphere. Chemical characterization of fine and coarse particulate matter (PM) was performed to quantify water-soluble ions (WSI) and black carbon (BC). The importance of explanatory variables was assessed using three machine learning techniques. Average concentrations of PM in AF and TS were similar (PM2.0, 17±10 µg m-3 (AF) and 16±11 µg m-3 (TS) and PM10-2.0, 13±5 µg m-3 (AF) and 11±7 µg m-3 (TS)), but higher than the background site. BC and SO4 2- were the prevalent components as they represented 27%-68% of particulates chemical composition. The combination of the machine learning techniques provided a further understanding of the pathways for PM concentration variability, and the results highlighted the influence of biomass burning for key sample groups and periods. PM2.0, BC, and most WSI presented higher concentrations in the dry season, providing further support for the influence of biomass burning.

Major Regional-Scale Production of O3 and Secondary Organic Aerosol in Remote Amazon Regions from the Dynamics and Photochemistry of Urban and Forest Emissions.

The Amazon rainforest suffers increasing pressure from anthropogenic activities. A key aspect not fully understood is how anthropogenic atmospheric emissions within the basin interact with biogenic emissions and impact the forest's atmosphere and biosphere. We combine a high-resolution atmospheric chemical transport model with an improved emissions inventory and in-situ measurements to investigate a surprisingly high concentration of ozone (O3) and secondary organic aerosol (SOA) 150-200 km downwind of Manaus city in an otherwise pristine forested region. We show that atmospheric dynamics and photochemistry determine a gross production of secondary pollutants seen in the simulation. After sunrise, the erosion of the nocturnal boundary layer mixes natural forest emissions, rich in biogenic volatile organic compounds, with a lofted pollution layer transported overnight, rich in nitrogen oxides and formaldehyde. As a result, O3 and SOA concentrations greater than ∼47 ppbv and 1.8 µg m-3, respectively, were found, with maximum concentrations occurring at 2 pm LT, 150-200 km downwind of Manaus city. These high concentrations affect a large primary forested area of about 11,250 km2. These oxidative areas are under a NOx-limited regime so that changes in NOx emissions from Manaus have a significant impact on O3 and SOA production.

Amazon boundary layer aerosol concentration sustained by vertical transport during rainfall.

The nucleation of atmospheric vapours is an important source of new aerosol particles that can subsequently grow to form cloud condensation nuclei in the atmosphere. Most field studies of atmospheric aerosols over continents are influenced by atmospheric vapours of anthropogenic origin (for example, ref. 2) and, in consequence, aerosol processes in pristine, terrestrial environments remain poorly understood. The Amazon rainforest is one of the few continental regions where aerosol particles and their precursors can be studied under near-natural conditions, but the origin of small aerosol particles that grow into cloud condensation nuclei in the Amazon boundary layer remains unclear. Here we present aircraft- and ground-based measurements under clean conditions during the wet season in the central Amazon basin. We find that high concentrations of small aerosol particles (with diameters of less than 50 nanometres) in the lower free troposphere are transported from the free troposphere into the boundary layer during precipitation events by strong convective downdrafts and weaker downward motions in the trailing stratiform region. This rapid vertical transport can help to maintain the population of particles in the pristine Amazon boundary layer, and may therefore influence cloud properties and climate under natural conditions.

Amazonian biogenic volatile organic compounds under global change.

Biogenic volatile organic compounds (BVOCs) play important roles at cellular, foliar, ecosystem and atmospheric levels. The Amazonian rainforest represents one of the major global sources of BVOCs, so its study is essential for understanding BVOC dynamics. It also provides insights into the role of such large and biodiverse forest ecosystem in regional and global atmospheric chemistry and climate. We review the current information on Amazonian BVOCs and identify future research priorities exploring biogenic emissions and drivers, ecological interactions, atmospheric impacts, depositional processes and modifications to BVOC dynamics due to changes in climate and land cover. A feedback loop between Amazonian BVOCs and the trends of climate and land-use changes in Amazonia is then constructed. Satellite observations and model simulation time series demonstrate the validity of the proposed loop showing a combined effect of climate change and deforestation on BVOC emission in Amazonia. A decreasing trend of isoprene during the wet season, most likely due to forest biomass loss, and an increasing trend of the sesquiterpene to isoprene ratio during the dry season suggest increasing temperature stress-induced emissions due to climate change.

Natural and Anthropogenically Influenced Isoprene Oxidation in Southeastern United States and Central Amazon.

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.

Radical Formation by Fine Particulate Matter Associated with Highly Oxygenated Molecules.

Highly oxygenated molecules (HOMs) play an important role in the formation and evolution of secondary organic aerosols (SOA). However, the abundance of HOMs in different environments and their relation to the oxidative potential of fine particulate matter (PM) are largely unknown. Here, we investigated the relative HOM abundance and radical yield of laboratory-generated SOA and fine PM in ambient air ranging from remote forest areas to highly polluted megacities. By electron paramagnetic resonance and mass spectrometric investigations, we found that the relative abundance of HOMs, especially the dimeric and low-volatility types, in ambient fine PM was positively correlated with the formation of radicals in aqueous PM extracts. SOA from photooxidation of isoprene, ozonolysis of α- and ß-pinene, and fine PM from tropical (central Amazon) and boreal (Hyytiälä, Finland) forests exhibited a higher HOM abundance and radical yield than SOA from photooxidation of naphthalene and fine PM from urban sites (Beijing, Guangzhou, Mainz, Shanghai, and Xi'an), confirming that HOMs are important constituents of biogenic SOA to generate radicals. Our study provides new insights into the chemical relationship of HOM abundance, composition, and sources with the yield of radicals by laboratory and ambient aerosols, enabling better quantification of the component-specific contribution of source- or site-specific fine PM to its climate and health effects.

Satellite retrieval of cloud condensation nuclei concentrations by using clouds as CCN chambers.

Quantifying the aerosol/cloud-mediated radiative effect at a global scale requires simultaneous satellite retrievals of cloud condensation nuclei (CCN) concentrations and cloud base updraft velocities (Wb). Hitherto, the inability to do so has been a major cause of high uncertainty regarding anthropogenic aerosol/cloud-mediated radiative forcing. This can be addressed by the emerging capability of estimating CCN and Wb of boundary layer convective clouds from an operational polar orbiting weather satellite. Our methodology uses such clouds as an effective analog for CCN chambers. The cloud base supersaturation (S) is determined by Wb and the satellite-retrieved cloud base drop concentrations (Ndb), which is the same as CCN(S). Validation against ground-based CCN instruments at Oklahoma, at Manaus, and onboard a ship in the northeast Pacific showed a retrieval accuracy of ±25% to ±30% for individual satellite overpasses. The methodology is presently limited to boundary layer not raining convective clouds of at least 1 km depth that are not obscured by upper layer clouds, including semitransparent cirrus. The limitation for small solar backscattering angles of <25° restricts the satellite coverage to ∼25% of the world area in a single day.

Isoprene photochemistry over the Amazon rainforest.

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.

The Amazon basin in transition.

Agricultural expansion and climate variability have become important agents of disturbance in the Amazon basin. Recent studies have demonstrated considerable resilience of Amazonian forests to moderate annual drought, but they also show that interactions between deforestation, fire and drought potentially lead to losses of carbon storage and changes in regional precipitation patterns and river discharge. Although the basin-wide impacts of land use and drought may not yet surpass the magnitude of natural variability of hydrologic and biogeochemical cycles, there are some signs of a transition to a disturbance-dominated regime. These signs include changing energy and water cycles in the southern and eastern portions of the Amazon basin.

Fire and deforestation dynamics in Amazonia (1973-2014).

Consistent long-term estimates of fire emissions are important to understand the changing role of fire in the global carbon cycle and to assess the relative importance of humans and climate in shaping fire regimes. However, there is limited information on fire emissions from before the satellite era. We show that in the Amazon region, including the Arc of Deforestation and Bolivia, visibility observations derived from weather stations could explain 61% of the variability in satellite-based estimates of bottom-up fire emissions since 1997 and 42% of the variability in satellite-based estimates of total column carbon monoxide concentrations since 2001. This enabled us to reconstruct the fire history of this region since 1973 when visibility information became available. Our estimates indicate that until 1987 relatively few fires occurred in this region and that fire emissions increased rapidly over the 1990s. We found that this pattern agreed reasonably well with forest loss data sets, indicating that although natural fires may occur here, deforestation and degradation were the main cause of fires. Compared to fire emissions estimates based on Food and Agricultural Organization's Global Forest and Resources Assessment data, our estimates were substantially lower up to the 1990s, after which they were more in line. These visibility-based fire emissions data set can help constrain dynamic global vegetation models and atmospheric models with a better representation of the complex fire regime in this region.

Rupturing of Biological Spores As a Source of Secondary Particles in Amazonia.

Airborne biological particles, such as fungal spores and pollen, are ubiquitous in the Earth's atmosphere and may influence the atmospheric environment and climate, impacting air quality, cloud formation, and the Earth's radiation budget. The atmospheric transformations of airborne biological spores at elevated relative humidity remain poorly understood and their climatic role is uncertain. Using an environmental scanning electron microscope (ESEM), we observed rupturing of Amazonian fungal spores and subsequent release of submicrometer size fragments after exposure to high humidity. We find that fungal fragments contain elements of inorganic salts (e.g., Na and Cl). They are hygroscopic in nature with a growth factor up to 2.3 at 96% relative humidity, thus they may potentially influence cloud formation. Due to their hygroscopic growth, light scattering cross sections of the fragments are enhanced by up to a factor of 10. Furthermore, rupturing of fungal spores at high humidity may explain the bursting events of new particle formation in Amazonia.

Ambient Gas-Particle Partitioning of Tracers for Biogenic Oxidation.

Exchange of atmospheric organic compounds between gas and particle phases is important in the production and chemistry of particle-phase mass but is poorly understood due to a lack of simultaneous measurements in both phases of individual compounds. Measurements of particle- and gas-phase organic compounds are reported here for the southeastern United States and central Amazonia. Polyols formed from isoprene oxidation contribute 8% and 15% on average to particle-phase organic mass at these sites but are also observed to have substantial gas-phase concentrations contrary to many models that treat these compounds as nonvolatile. The results of the present study show that the gas-particle partitioning of approximately 100 known and newly observed oxidation products is not well explained by environmental factors (e.g., temperature). Compounds having high vapor pressures have higher particle fractions than expected from absorptive equilibrium partitioning models. These observations support the conclusion that many commonly measured biogenic oxidation products may be bound in low-volatility mass (e.g., accretion products, inorganic-organic adducts) that decomposes to individual compounds on analysis. However, the nature and extent of any such bonding remains uncertain. Similar conclusions are reach for both study locations, and average particle fractions for a given compound are consistent within ∼25% across measurement sites.

Vehicular Emission Ratios of VOCs in a Megacity Impacted by Extensive Ethanol Use: Results of Ambient Measurements in São Paulo, Brazil.

The São Paulo Metropolitan Area (SPMA) is a megacity with 20 million people and over 8 million vehicles. Over the past decade a large increase in biofuel usage, more notably ethanol by light-duty vehicles, has made Brazil, and in particular São Paulo, a unique case worldwide. This study presents the first assessment of emission ratios of a selected group of volatile organic compounds (VOCs) relative to carbon monoxide (CO) under ambient conditions. The VOCs studied here include aromatics such as benzene (1.03 pptv/ppbv CO), toluene (3.10 pptv/ppbv CO) and Oxygenated VOCs such as methanol (5.39 pptv/ppbv CO), acetaldehyde (3.93 pptv/ppbv CO), acetone (3.59 pptv/ppbv CO), methyl ethyl ketone (1.42 pptv/ppbv CO), and others. Despite the specificity of the fuel composition, emission ratios were in surprisingly close agreement with other megacities in Europe or in North America. Such results include species whose emission factors have been previously reported to decline (e.g., benzene) or increase (e.g., acetaldehyde) with ethanol usage. Furthermore, diurnal profiles and temperature analysis aid separating the primary anthropogenic, secondary or biogenic components of the species studied here. This study shows that a significant fraction of ethanol in gasoline blends does not result in a well-defined trend in VOC emission profile and certainly motivates further studies.

Optical and chemical characterization of aerosols emitted from coal, heavy and light fuel oil, and small-scale wood combustion.

Particle emissions affect radiative forcing in the atmosphere. Therefore, it is essential to know the physical and chemical characteristics of them. This work studied the chemical, physical, and optical characteristics of particle emissions from small-scale wood combustion, coal combustion of a heating and power plant, as well as heavy and light fuel oil combustion at a district heating station. Fine particle (PM1) emissions were the highest in wood combustion with a high fraction of absorbing material. The emissions were lowest from coal combustion mostly because of efficient cleaning techniques used at the power plant. The chemical composition of aerosols from coal and oil combustion included mostly ions and trace elements with a rather low fraction of absorbing material. The single scattering albedo and aerosol forcing efficiency showed that primary particles emitted from wood combustion and some cases of oil combustion would have a clear climate warming effect even over dark earth surfaces. Instead, coal combustion particle emissions had a cooling effect. Secondary processes in the atmosphere will further change the radiative properties of these emissions but are not considered in this study.

Genetic damage of organic matter in the Brazilian Amazon: a comparative study between intense and moderate biomass burning.

BACKGROUND: The biomass burning that occurs in the Amazon region has an adverse effect on environmental and human health. However, in this region, there are limited studies linking atmospheric pollution and genetic damage. OBJECTIVE: We conducted a comparative study during intense and moderate biomass burning periods focusing on the genetic damage and physicochemical analyses of the particulate matter (PM). METHOD: PM and black carbon (BC) were determined; organic compounds were identified and quantified using gas chromatography with flame ionization detection, the cyto-genotoxicity test was performed using two bioassays: cytokinesis-block micronucleus (CBMN) in A549 cells and Tradescantia pallida micronucleus (Trad-MCN) assay. RESULTS: The PM10 concentrations were lower than the World Health Organization air quality standard for 24h. The n-alkanes analyses indicate anthropogenic and biogenic influences during intense and moderate biomass burning periods, respectively. Retene was identified as the most abundant polycyclic aromatic hydrocarbon during both sampling periods. Carcinogenic and mutagenic compounds were identified. The genotoxic analysis through CBMN and Trad-MCN tests showed that the frequency MCN from the intense burning period is significantly higher compared to moderate burning period. CONCLUSIONS: This is the first study using human alveolar cells to show the genotoxic effects of organic PM from biomass burning samples collected in Amazon region. The genotoxicity of PM can be associated with the presence of several mutagenic and carcinogenic compounds, mainly benzo[a]pyrene. These findings have potential implications for the development of pollution abatement strategies and can minimize negative impact on health.

Process-evaluation of forest aerosol-cloud-climate feedback shows clear evidence from observations and large uncertainty in models.

Natural aerosol feedbacks are expected to become more important in the future, as anthropogenic aerosol emissions decrease due to air quality policy. One such feedback is initiated by the increase in biogenic volatile organic compound (BVOC) emissions with higher temperatures, leading to higher secondary organic aerosol (SOA) production and a cooling of the surface via impacts on cloud radiative properties. Motivated by the considerable spread in feedback strength in Earth System Models (ESMs), we here use two long-term observational datasets from boreal and tropical forests, together with satellite data, for a process-based evaluation of the BVOC-aerosol-cloud feedback in four ESMs. The model evaluation shows that the weakest modelled feedback estimates can likely be excluded, but highlights compensating errors making it difficult to draw conclusions of the strongest estimates. Overall, the method of evaluating along process chains shows promise in pin-pointing sources of uncertainty and constraining modelled aerosol feedbacks.

Oxidized organic molecules in the tropical free troposphere over Amazonia.

New particle formation (NPF) in the tropical free troposphere (FT) is a globally important source of cloud condensation nuclei, affecting cloud properties and climate. Oxidized organic molecules (OOMs) produced from biogenic volatile organic compounds are believed to contribute to aerosol formation in the tropical FT, but without direct chemical observations. We performed in situ molecular-level OOMs measurements at the Bolivian station Chacaltaya at 5240 m above sea level, on the western edge of Amazonia. For the first time, we demonstrate the presence of OOMs, mainly with 4-5 carbon atoms, in both gas-phase and particle-phase (in terms of mass contribution) measurements in tropical FT air from Amazonia. These observations, combined with air mass history analyses, indicate that the observed OOMs are linked to isoprene emitted from the rainforests hundreds of kilometers away. Based on particle-phase measurements, we find that these compounds can contribute to NPF, at least the growth of newly formed nanoparticles, in the tropical FT on a continental scale. Thus, our study is a fundamental and significant step in understanding the aerosol formation process in the tropical FT.