Lightning patterns in the Pantanal: Untangling natural and anthropogenic-induced wildfires.

The identification of fire causes and characteristics is of fundamental importance to better understand fire regimes and drivers. Particularly for Brazil, there is a gap in the quantification of lightning-caused fires. Accordingly, this work is a novel probabilistic assessment of the spatial-temporal patterns of lightning-ignited wildfires in the Pantanal wetland. Here, remote sensing information such as VIIRS active fires, MODIS burned area (BA) and STARNET lightning observations from 2012 to 2017, were combined to estimate the location, number of scars and amount of BA associated with atmospheric discharges on a seasonal basis. The highest lightning activity occurs during summer (December-February), and the lowest during winter (June-August). Conversely, the highest fire activity occurred during spring (September-November) and the lowest during autumn (March-May). Our analysis revealed low evidence of an association between fires and lightning, suggesting that human-related activities are the main source of ignitions. Weak evidence of natural-caused fire occurrence is conveyed by the low spatial-temporal match of lightning and fire throughout the studied period. Natural-caused fires accounted for only 5% of the annual total scars and 83.8% of the BA was human-caused. Most of the fires with extension larger than 1000 ha were not related to lighting. Lightning-fires seem an important element of the summer fire regime given that around half of the total BA during this season may be originated by lightning. By contrast, in the rest of the year the lightning-fires represent a minor percentage of the fire activity in the region. The density of lightning-ignited fires varies considerably, being higher in the north part of the Pantanal. This work provides a basis for a better understanding of lightning-related fire outbreaks in tropical ecosystems, particularly wetlands, which is fundamental to improve region-based strategies for land management actions, ecological studies and modeling climatic and anthropogenic drivers of wildfires.

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.

Atomic Absorption Spectrometry Methods to Access the Metal Solubility of Aerosols in Artificial Lung Fluid.

Recent studies to quantify the health risks that fine particulate matter with an aerodynamic less than 2.5 µm (PM2.5) pose use in vitro approaches. One of these approaches is to incubate PM2.5 in artificial lysosomal fluid for a given period at body temperature. These body fluids used have a high ionic strength and as such can be challenging samples to analyze with atomic spectroscopy techniques. As PM2.5 is a primary health hazard because it is tiny enough to penetrate deep into the lungs and could, in addition, dissolve in the lung fluid it is important to quantify elements of toxic and/or carcinogenic concerns, reliably and accurately. Sophisticated instrumentation and expensive pre-treatment of challenging samples are not always available, especially in developing countries. To evaluate the applicability of graphite furnace atomic absorption spectrometry (GFAAS) without Zeeman correction capability to detect trace quantities of heavy metals leached from PM2.5 on to artificial lung fluid, univariate and multivariate approaches have been used for optimization purposes. The limits of quantification, LOQ, obtained by the optimized method were: 2 µg L-1 (Cu), 3 µg L-1 (Cr), 1 µg L-1 (Mn), and 10 µg L-1 (Pb). The addition/recovery experiments had a mean accuracy of: (Cu) 99 ± 7%; 110 ± 8% (Cr); 95 ± 9% (Mn), and 96 ± 11% (Pb). The average soluble fractions of PM2.5 incubated in artificial lysosomal fluid (ALF) for 1 h were: 1.2 ± 0.01 ng m-3 Cu, 0.4 ± 0.01 ng m-3 Cr, 0.6 ± 0.01 ng m-3 Mn, and 4.8 ± 0.03 ng m-3 Pb. Using historical elemental averages of PM2.5 in Curitiba (Cu 3.3 ng m-3, Cr 2.1 ng m-3, Mn 6.1 ng m-3, Pb 21 ng m-3), the percentage bioaccessibility were determined to be Cu 38%, Cr 20%, Mn 10%, and Pb 23%. The elemental values of the atmospheric soluble fraction of Cu, Cr, and Mn were below the inhalation risk concentrations. However, for Pb, the atmospheric soluble fraction exceeded the inhalation unit risk of 0.012 ng m-3. This robust and straightforward GF AAS method is pivotal for low and middle-income countries were most air pollution adverse effects occur and established lower-cost technologies are likely unavailable.

Impact of biomass burning on a metropolitan area in the Amazon during the 2015 El Niño: The enhancement of carbon monoxide and levoglucosan concentrations.

Extreme droughts associated with changes in the climate have occurred every 5 years in the Amazon during the 21st century, with the most severe being in 2015. The increase in biomass burning (BB) events that occurred during the 2015 drought had several negative socioeconomic and environmental impacts, one of which was a decrease in the air quality. This study is an investigation into the air quality in the Manaus Metropolitan Region (MMR) (central Amazon, Brazil) during the dry (September to October) and wet (April to May) seasons of 2015 and 2016. A strong El Niño event began during the wet season of 2015 and ended during the wet season of 2016. Particulate matter samples were collected in the MMR during 2015 and 2016, and analyses of the satellite-estimated total carbon monoxide (CO) column and observed levoglucosan concentrations were carried out. Levoglucosan has been shown to be significantly correlated with regional fires and is a well-established chemical tracer for the atmospheric particulates emitted by BB, and CO can be treated as a gaseous-phase tracer for BB. The number of BB events increased significantly during the El Niño period when compared to the average number during 2003-2016. Consequently, the total CO column and levoglucosan concentration values in the MMR increased by 15% and 500%, respectively, when compared to the normal conditions. These results indicate that during the period that was analyzed, the impacts of BB were exacerbated during the strong El Niño event as compared to the non-El Niño period. In this study, we provided evidence that the air quality in the MMR will degrade in the future if droughts and BB occurrences continue to increase.

The influence that different urban development models has on PM2.5 elemental and bioaccessible profiles.

Limited studies have reported on in-vitro analysis of PM2.5 but as far as the authors are aware, bioaccessibility of PM2.5 in artificial lysosomal fluid (ALF) has not been linked to urban development models before. The Brazilian cities Manaus (Amazon) and Curitiba (South region) have different geographical locations, climates, and urban development strategies. Manaus drives its industrialization using the free trade zone policy and Curitiba adopted a services centered economy driven by sustainability. Therefore, these two cities were used to illustrate the influence that these different models have on PM2.5 in vitro profile. We compared PM2.5 mass concentrations and the average total elemental and bioaccessible profiles for Cu, Cr, Mn, and Pb. The total average elemental concentrations followed Mn > Pb > Cu > Cr in Manaus and Pb > Mn > Cu > Cr in Curitiba. Mn had the lowest solubility while Cu showed the highest bioaccessibility (100%) and was significantly higher in Curitiba than Manaus. Cr and Pb had higher bioaccessibility in Manaus than Curitiba. Despite similar mass concentrations, the public health risk in Manaus was higher than in Curitiba indicating that the free trade zone had a profound effect on the emission levels and sources of airborne PM. These findings illustrate the importance of adopting sustainable air quality strategies in urban planning.

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.

Increasing Isoprene Epoxydiol-to-Inorganic Sulfate Aerosol Ratio Results in Extensive Conversion of Inorganic Sulfate to Organosulfur Forms: Implications for Aerosol Physicochemical Properties.

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.

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.

Development of a hydrophilic interaction liquid chromatography (HILIC) method for the chemical characterization of water-soluble isoprene epoxydiol (IEPOX)-derived secondary organic aerosol.

Acid-catalyzed multiphase chemistry of isoprene epoxydiols (IEPOX) on sulfate aerosol produces substantial amounts of water-soluble secondary organic aerosol (SOA) constituents, including 2-methyltetrols, methyltetrol sulfates, and oligomers thereof in atmospheric fine particulate matter (PM2.5). These constituents have commonly been measured by gas chromatography interfaced to electron ionization mass spectrometry (GC/EI-MS) with prior derivatization or by reverse-phase liquid chromatography interfaced to electrospray ionization high-resolution mass spectrometry (RPLC/ESI-HR-MS). However, both techniques have limitations in explicitly resolving and quantifying polar SOA constituents due either to thermal degradation or poor separation. With authentic 2-methyltetrol and methyltetrol sulfate standards synthesized in-house, we developed a hydrophilic interaction liquid chromatography (HILIC)/ESI-HR-quadrupole time-of-flight mass spectrometry (QTOFMS) protocol that can chromatographically resolve and accurately measure the major IEPOX-derived SOA constituents in both laboratory-generated SOA and atmospheric PM2.5. 2-Methyltetrols were simultaneously resolved along with 4-6 diastereomers of methyltetrol sulfate, allowing efficient quantification of both major classes of SOA constituents by a single non-thermal analytical method. The sum of 2-methyltetrols and methyltetrol sulfates accounted for approximately 92%, 62%, and 21% of the laboratory-generated ß-IEPOX aerosol mass, laboratory-generated δ-IEPOX aerosol mass, and organic aerosol mass in the southeastern U.S., respectively, where the mass concentration of methyltetrol sulfates was 171-271% the mass concentration of methyltetrol. Mass concentrations of methyltetrol sulfates were 0.39 and 2.33 µg m-3 in a PM2.5 sample collected from central Amazonia and the southeastern U.S., respectively. The improved resolution clearly reveals isomeric patterns specific to methyltetrol sulfates from acid-catalyzed multiphase chemistry of ß- and δ-IEPOX. We also demonstrate that conventional GC/EI-MS analyses overestimate 2-methyltetrols by up to 188%, resulting (in part) from the thermal degradation of methyltetrol sulfates. Lastly, C5-alkene triols and 3-methyltetrahydrofuran-3,4-diols are found to be largely GC/EI-MS artifacts formed from thermal degradation of 2-methyltetrol sulfates and 3-methyletrol sulfates, respectively, and are not detected with HILIC/ESI-HR-QTOFMS.

Substantial convection and precipitation enhancements by ultrafine aerosol particles.

Aerosol-cloud interactions remain the largest uncertainty in climate projections. Ultrafine aerosol particles smaller than 50 nanometers (UAP<50) can be abundant in the troposphere but are conventionally considered too small to affect cloud formation. Observational evidence and numerical simulations of deep convective clouds (DCCs) over the Amazon show that DCCs forming in a low-aerosol environment can develop very large vapor supersaturation because fast droplet coalescence reduces integrated droplet surface area and subsequent condensation. UAP<50 from pollution plumes that are ingested into such clouds can be activated to form additional cloud droplets on which excess supersaturation condenses and forms additional cloud water and latent heating, thus intensifying convective strength. This mechanism suggests a strong anthropogenic invigoration of DCCs in previously pristine regions of the world.