Molecular composition of organic aerosols in central Amazonia: An ultra-high-resolution mass spectrometry study

The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM2.5 aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagrams, carbon oxidation state and aromaticity equivalent) were used to identify compound classes and mass distributions of the detected species. Nitrogen-and/or sulfur-containing organic species contributed up to 60% of the total identified number of formulae. A large number of molecular formulae in organic aerosol (OA) were attributed to later-generation nitrogen-and sulfur-containing oxidation products, suggesting that OA composition is affected by biomass burning and other, potentially anthropogenic, sources. Isoprene-derived organosulfate (IEPOX-OS) was found to be the most dominant ion in most of the analysed samples and strongly followed the concentration trends of the gas-phase anthropogenic tracers confirming its mixed anthropogenic-biogenic origin. The presence of oxidised aromatic and nitro-aromatic compounds in the samples suggested a strong influence from biomass burning especially during the dry period. Aerosol samples from the dry period and under enhanced biomass burning conditions contained a large number of molecules with high carbon oxidation state and an increased number of aromatic compounds compared to that from the wet period. The results of this work demonstrate that the studied site is influenced not only by biogenic emissions from the forest but also by biomass burning and potentially other anthropogenic emissions from the neighbouring urban environments. © 2016 Author(s)

The Amazon Tall Tower Observatory (ATTO): Overview of pilot measurements on ecosystem ecology, meteorology, trace gases, and aerosols

The Amazon Basin plays key roles in the carbon and water cycles, climate change, atmospheric chemistry, and biodiversity. It has already been changed significantly by human activities, and more pervasive change is expected to occur in the coming decades. It is therefore essential to establish long-term measurement sites that provide a baseline record of present-day climatic, biogeochemical, and atmospheric conditions and that will be operated over coming decades to monitor change in the Amazon region, as human perturbations increase in the future. The Amazon Tall Tower Observatory (ATTO) has been set up in a pristine rain forest region in the central Amazon Basin, about 150 km northeast of the city of Manaus. Two 80 m towers have been operated at the site since 2012, and a 325 m tower is nearing completion in mid-2015. An ecological survey including a biodiversity assessment has been conducted in the forest region surrounding the site. Measurements of micrometeorological and atmospheric chemical variables were initiated in 2012, and their range has continued to broaden over the last few years. The meteorological and micrometeorological measurements include temperature and wind profiles, precipitation, water and energy fluxes, turbulence components, soil temperature profiles and soil heat fluxes, radiation fluxes, and visibility. A tree has been instrumented to measure stem profiles of temperature, light intensity, and water content in cryptogamic covers. The trace gas measurements comprise continuous monitoring of carbon dioxide, carbon monoxide, methane, and ozone at five to eight different heights, complemented by a variety of additional species measured during intensive campaigns (e.g., VOC, NO, NO2, and OH reactivity). Aerosol optical, microphysical, and chemical measurements are being made above the canopy as well as in the canopy space. They include aerosol light scattering and absorption, fluorescence, number and volume size distributions, chemical composition, cloud condensation nuclei (CCN) concentrations, and hygroscopicity. In this paper, we discuss the scientific context of the ATTO observatory and present an overview of results from ecological, meteorological, and chemical pilot studies at the ATTO site. © Author(s) 2015

Observations of atmospheric monoaromatic hydrocarbons at urban, semi-urban and forest environments in the Amazon region

The Amazon region is one of the most significant natural ecosystems on the planet. Of special interest as a major study area is the interface between the forest and Manaus city, a state capital in Brazil embedded in the heart of the Amazon forest. In view of the interactions between natural and anthropogenic processes, an integrated experiment was conducted measuring the concentrations of the volatile organic compounds (VOCs) benzene, toluene, ethylbenzene and meta, ortho, para-xylene (known as BTEX), all of them regarded as pollutants with harmful effects on human health and vegetation and acting also as important precursors of tropospheric ozone. Furthermore, these compounds also take part in the formation of secondary organic aerosols, which can influence the pattern of cloud formation, and thus the regional water cycle and climate. The samples were collected in 2012/2013 at three different sites: (i) The Amazon Tall Tower Observatory (ATTO), a pristine rain forest region in the central Amazon Basin; (ii) Manacapuru, a semi-urban site located southwest and downwind of Manaus as a preview of the Green Ocean Amazon Experiment (GoAmazon 2014/15); and (iii) the city of Manaus (distributed over three sites). Results indicate that there is an increase in pollutant concentrations with increasing proximity to urban areas. For instance, the benzene concentration ranges were 0.237-19.6 (Manaus), 0.036-0.948 (Manacapuru) and 0.018-0.313 μg m-3 (ATTO). Toluene ranges were 0.700-832 (Manaus), 0.091-2.75 μg m-3 (Manacapuru) and 0.011-4.93 (ATTO). For ethylbenzene, they were 0.165-447 (Manaus), 0.018-1.20 μg m-3 (Manacapuru) and 0.047-0.401 (ATTO). Some indication was found for toluene to be released from the forest. No significant difference was found between the BTEX levels measured in the dry season and the wet seasons. Furthermore, it was observed that, in general, the city of Manaus seems to be less impacted by these pollutants than other cities in Brazil and in other countries, near the coastline or on the continent. A risk analysis for the health of Manaus' population was performed and indicated that the measured concentrations posed a risk for development of chronic diseases and cancer for the population of Manaus. © 2015 Elsevier Ltd

Observations of particulate matter, NO2, SO2, O3, H2S and selected VOCs at a semi-urban environment in the Amazon region

This research aims to assess air quality in a transitional location between city and forest in the Amazon region. Located downwind of the Manaus metropolitan region, this study is part of the large-scale experiment GoAmazon2014/5. Based on their pollutant potential, inhalable particulate matter (PM2.5), nitrogen dioxide (NO2), sulfur dioxide (SO2), ozone (O3), hydrogen sulfide (H2S), benzene, toluene, ethylbenzene and meta-, orto-, para-xylene (BTEX) were selected for analysis. Sampling took place during the wet season (March–April 2014) and dry season (August–October 2014). The number of forest fires in the surroundings was higher during the dry wet season. Results show significant increase during the dry season in mass concentration (wet: <0.01–10 μg m−3; dry: 9.8–69 μg m−3), NH4 + soluble content (wet: 13–125 μg m−3; dry: 86–323 μg m−3) and K+ soluble content (wet: 11–168 μg m−3; dry 60–356 μg m−3) of the PM2.5, and O3 levels (wet: 1.4–14 μg m−3; dry: 1.0–40 μg m−3), indicating influence of biomass burning emissions. BTEX concentrations were low in both periods, but also increased during the dry season. A weak correlation in the time series of the organic and inorganic gaseous pollutants indicates a combination of different sources in both seasons and NO2 results suggest a spatial heterogeneity in gaseous pollutants levels beyond initial expectations. © 201

Impact of the biomass burning on methane variability during dry years in the Amazon measured from an aircraft and the AIRS sensor

The present study examines the spatiotemporal variability and interrelations of the atmospheric methane (CH4), carbon monoxide (CO) and biomass burning (BB) outbreaks retrieved from satellite data over the Amazon region during the 2003–2012 period. In the climatological context, we found consistent seasonal cycles of BB outbreaks and CO in the Amazon, both variables showing a peak during the dry season. The dominant CO variability mode features the largest positive loadings in the southern Amazon, and describes the interannual CO variations related to BB outbreaks along the deforestation arc during the dry season. In line with CO variability and BB outbreaks, the results show strong correspondence with the spatiotemporal variability of CH4 in the southern Amazon during years of intense drought. Indeed, the areas with the largest positive CH4 anomalies in southern Amazon overlap the areas with high BB outbreaks and positive CO anomalies. The analyses also showed that high (low) BB outbreaks in the southern Amazon occur during dry (wet) years. In consequence, the interannual climate variability modulates the BB outbreaks in the southern Amazon, which in turn have considerable impacts on CO and CH4 interannual variability in the region. Therefore, the BB outbreaks might play a major role in modulating the CH4 and CO variations, at least in the southern Amazon. This study also provides a comparison between the estimate of satellite and aircraft measurements for the CH4 over the southern Amazon, which indicates relatively small differences from the aircraft measurements in the lower troposphere, with errors ranging from 0.18% to 1.76%. © 2017 Elsevier B.V