Pascal Guyon

Water-Soluble Organic Compounds in Biomass Burning Aerosols over Amazonia: 2. Apportionment of the Chemical Composition and Importance of the Polyacidic Fraction

[1]xa0Chemical characterization was performed on carbonaceous aerosols from Rondonia in the Brazilian Amazon region as part of the European contribution to the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA-EUSTACH). The sampling period (October 1999) included the peak of the burning season as well as the dry-to-wet season transition. Characterization of the carbonaceous material was performed by using a thermal combustion method. This enabled determination of aerosol total carbon (TC), black carbon (BC), and organic carbon (OC). A significant fraction of the BC material (on average about 50%) seemed to be highly refractory organic material soluble in water. A more detailed analysis of the water-soluble organic carbon (WSOC) fraction of the TC was undertaken, involving measurements of WSOC content, high-performance liquid chromatography (HPLC) separation (with UV detection) of the water-soluble components, and characterization of individual components by gas chromatography/mass spectrometry (GC/MS). The WSOC fraction accounted for 45−75% of the OC. This high WSOC fraction suggests an aerosol derived mainly from smoldering combustion. Using GC/MS, many different compounds, containing hydroxy, carboxylate, and carbonyl groups, were detected. The fraction of the WSOC identified by GC/MS was about 10%. Three classes of compounds were separated by HPLC/UV: neutral compounds (N), monocarboxylic and dicarboxylic acids (MDA), and polycarboxylic acids (PA). The sum of these three groups accounted for about 70% of the WSOC, with MDA and PA being most abundant (about 50%). Good correlations (r2 between 0.84 and 0.99) of BCwater (BC after water extraction) and levoglucosan (both indicators of biomass combustion) with the water-soluble species (i.e., WSOC, N, MDA, and PA), and their increase in concentrations during the burning period provided strong evidence that biomass burning is a major source of the WSOC. Particularly interesting is that PA and therefore, probably, humic-like substances (due to their polyacidic nature) are generated in significant amounts during biomass burning. These substances, due to their water solubility and surface tension-lowering effects, may play an important role in determining the overall cloud condensation nuclei activity of biomass burning aerosols and, consequently, could be important in cloud processes and climate forcing.

Water-soluble organic compounds in biomass burning aerosols over Amazonia 1. Characterization by NMR and GC-MS

[1]xa0As part of the European contribution to the Large-Scale Atmosphere-Biosphere Experiment in Amazonia (LBA-EUSTACH), aerosols were sampled at representative pasture and primary rainforest sites in Rondonia, Brazil, during the 1999 “burning season” and dry-to-wet season transition (September-October). Water-soluble organic compounds (WSOCs) within the samples were characterized using a combination of 1H Nuclear Magnetic Resonance (NMR) spectroscopy for chemical functional group analysis, and Gas Chromatography-Mass Spectrometry (GC-MS) for identification and quantification of individual low-molecular-weight compounds. The 1H NMR analysis indicates that WSOCs are predominantly aliphatic or oxygenated aliphatic compounds (alcohols, carboxylic acids, etc.), with a minor content of aromatic rings carrying carboxylic and phenolic groups. Levoglucosan (1,6-anhydro-β-D-glucose), a well-known cellulose combustion product, was the most abundant individual compound identified by GC-MS (0.04–6.90 μg m−3), accounting for 1–6% of the total carbon (TC) and 2–8% of the water-soluble organic carbon (WSOC). Other anhydrosugars, produced by hemicellulose breakdown, were detected in much smaller amounts, in addition to series of acids, hydroxyacids, oxoacids, and polyalcohols (altogether 2–5% of TC, 3–6% of WSOC). Most correlated well with organic carbon, black carbon, and potassium, indicating biomass burning to be the major source. A series of sugar alcohols (mannitol, arabitol, erythritol) and sugars (glucose, fructose, mannose, galactose, sucrose, trehalose) were identified as part of the natural background aerosol and are probably derived from airborne microbes and other biogenic material. The bulk of the WSOCs (86–91% WSOC) eluded analysis by GC-MS and may be predominantly high-molecular weight in nature.

Physical and chemical properties of aerosols in the wet and dry seasons in Rondônia, Amazonia

[1]xa0As part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA), a large study of aerosol and trace gas properties was conducted in Amazonia during the dry and wet seasons and for pasture and primary forest sites. Aerosol mass and elemental composition were measured on filters for both fine (dp 10 nm) every minute. A 55-m tower in a primary forest in Rondonia and a facility built on a pasture site were used to operate the instrumentation for 4 months in the wet season and 3 months in the dry season of 1999. Particle-Induced X-Ray Emission (PIXE) was used to measure the concentration of 22 trace elements for fine- and coarse-mode aerosol. During the wet season, very clean atmospheric conditions were observed at both sites. Particle concentration averaged 900 cm−3, black carbon averaged 250 ng m−3, and mean fine-mode mass concentration was 2.9 μg m−3. In sharp contrast, very high concentrations were observed in the dry season for all the parameters at both sampling sites. Aerosol mass concentrations up to 250 μg m−3 and particle number concentrations of more than 40,000 cm−3 were observed, while the CO peaked at 8 ppm and NO2 reached 16 ppb. High correlation was observed between BCE, NO2, CO, aerosol particle number, mass, aerosol optical thickness, and other properties linked to biomass-burning emissions. Relatively large concentrations of phosphorus in the coarse-mode particles were observed, especially at nighttime. The emission of biogenic particulate P could have an effect in the nutrient cycling of this essential and key nutrient, which is present almost exclusively in the form of aerosol particles. Phosphorus is exchanged in the aerosol phase and mostly for coarse-mode particles and during nighttime.

Organic compounds present in the natural Amazonian aerosol: Characterization by gas chromatography–mass spectrometry

As part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA)-Cooperative LBA Airborne Regional Experiment (CLAIRE) 2001 campaign in July 2001, separate day and nighttime aerosol samples were collected at a ground-based site in Amazonia, Brazil, in order to examine the composition and temporal variability of the natural “background” aerosol. We used a high-volume sampler to separate the aerosol into fine (aerodynamic diameter, AD 2.5 μm) size fractions and quantified a range of organic compounds in methanolic extracts of the samples by a gas chromatographic-mass spectrometric technique. The carbon fraction of the compounds could account for an average of 7% of the organic carbon (OC) in both the fine and coarse aerosol fractions. We observed the highest concentrations of sugars, sugar alcohols, and fatty acids in the coarse aerosol samples, which suggests that these compounds are associated with primary biological aerosol particles (PBAP) observed in the forest atmosphere. Of these, trehalose, mannitol, arabitol, and the fatty acids were found to be more prevalent at night, coinciding with a nocturnal increase in PBAP in the 2–10 μm size range (predominantly yeasts and other small fungal spores). In contrast, glucose, fructose, and sucrose showed persistently higher daytime concentrations, coinciding with a daytime increase in large fungal spores, fern spores, pollen grains, and, to a lesser extent, plant fragments (generally >20 μm in diameter), probably driven by lowered relative humidity and enhanced wind speeds/convective activity during the day. For the fine aerosol samples a series of dicarboxylic and hydroxyacids were detected with persistently higher daytime concentrations, suggesting that photochemical production of a secondary organic aerosol from biogenic volatile organic compounds may have made a significant contribution to the fine aerosol. Anhydrosugars (levoglucosan, mannosan, galactosan), which are specific tracers for biomass burning, were detected only at low levels in the fine aerosol samples. On the basis of the levoglucosan-to-OC emission ratio measured for biomass burning aerosol, we estimate that an average of ∼16% of the OC in the fine aerosol was due to biomass burning during CLAIRE 2001, indicating that the major fraction was associated with biogenic particles.

Overview of the inorganic and organic composition of size-segregated aerosol in Rondônia, Brazil, from the biomass-burning period to the onset of the wet season

The aerosol characterization experiment performed within the Large-Scale Biosphere-Atmosphere Experiment in Amazonia-Smoke, Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC) field experiment carried out in Rondonia, Brazil, in the period from September to November 2002 provides a unique data set of size-resolved chemical composition of boundary layer aerosol over the Amazon Basin from the intense biomass-burning period to the onset of the wet season. Three main periods were clearly distinguished on the basis of the PM10 concentration trend during the experiment: (1) dry period, with average PM10 well above 50 mu g m(-3); (2) transition period, during which the 24-hour-averaged PM10 never exceeded 40 mu g m(-3) and never dropped below 10 mg m(-3); (3) and wet period, characterized by 48-hour-averaged concentrations of PM10 below 12 mu g m(-3) and sometimes as low as 2 mu g m(-3). The trend of PM10 reflects that of CO concentration and can be directly linked to the decreasing intensity of the biomass- burning activities from September through November, because of the progressive onset of the wet season. Two prominent aerosol modes, in the submicron and supermicron size ranges, were detected throughout the experiment. Dry period size distributions are dominated by the fine mode, while the fine and coarse modes show almost the same concentrations during the wet period. The supermicron fraction of the aerosol is composed mainly of primary particles of crustal or biological origin, whereas submicron particles are produced in high concentrations only during the biomass-burning periods and are mainly composed of organic material, mostly water-soluble, and similar to 10% of soluble inorganic salts, with sulphate as the major anion. Size-resolved average aerosol chemical compositions are reported for the dry, transition, and wet periods. However, significant variations in the aerosol composition and concentrations were observed within each period, which can be classified into two categories: (1) diurnal oscillations, caused by the diurnal cycle of the boundary layer and the different combustion phase active during day (flaming) or night (smouldering); and (2) day-to-day variations, due to alternating phases of relatively wet and dry conditions. In a second part of the study, three subperiods representative of the conditions occurring in the dry, transition, and wet periods were isolated to follow the evolution of the aerosol chemical composition as a function of changes in rainfall rate and in the strength of the sources of particulate matter. The chemical data set provided by the SMOCC field experiment will be useful to characterize the aerosol hygroscopic properties and the ability of the particles to act as cloud condensation nuclei.

composition and diurnal variability of the natural Amazonian aerosol

As part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA)-Cooperative LBA Airborne Regional Experiment (CLAIRE) 2001 campaign, separate day and nighttime aerosol samples were collected in July 2001 at a ground-based site in Amazonia, Brazil, in order to examine the composition and temporal variability of the natural “background” aerosol. A combination of analytical techniques was used to characterize the elemental and ionic composition of the aerosol. Major particle types larger than ∼0.5 μm were identified by electron and light microscopy. Both the coarse and fine aerosol were found to consist primarily of organic matter (∼70 and 80% by mass, respectively), with the coarse fraction containing small amounts of soil dust and sea-salt particles and the fine fraction containing some non-sea-salt sulfate. Coarse particulate mass concentrations (CPM ≈ PM_(10) − PM_2) were found to be highest at night (average = 3.9 ± 1.4 μg m^(−3), mean night-to-day ratio = 1.9 ± 0.4), while fine particulate mass concentrations (FPM ≈ PM_2) increased during the daytime (average = 2.6 ± 0.8 μg m^(−3), mean night-to-day ratio = 0.7 ± 0.1). The nocturnal increase in CPM coincided with an increase in primary biological particles in this size range (predominantly yeasts and other fungal spores), resulting from the trapping of surface-derived forest aerosol under a shallow nocturnal boundary layer and a lake-land breeze effect at the site, although active nocturnal sporulation may have also contributed. Associated with this, we observed elevated nighttime concentrations of biogenic elements and ions (P, S, K, Cu, Zn, NH_4^+) in the CPM fraction. For the FPM fraction a persistently higher daytime concentration of organic carbon was found, which indicates that photochemical production of secondary organic aerosol from biogenic volatile organic compounds may have made a significant contribution to the fine aerosol. Dust and sea-salt-associated elements/ions in the CPM fraction, and non-sea-salt sulfate in the FPM fraction, showed higher daytime concentrations, most likely due to enhanced convective downward mixing of long-range transported aerosol.

Refractive index of aerosol particles over the Amazon tropical forest during LBA-EUSTACH 1999

Optical properties of aerosol particles were characterized during two :eld campaigns at a remote rainforest site in Rondonia, Brazil, as part of the project European Studies on Trace Gases and Atmospheric Chem- istry, a contribution to the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA-EUSTACH). The measurements included background (wet season), biomass burning (dry season), and transition period conditions. Optical measurements of light scattering and absorption were combined with data on number/size distributions in a new iterative method, which retrieves the e<ective imaginary refractive indexof the particles at a wavelength of 545 nm. For ambient relative humidities lower than 80%, background aerosols exhibited an average refractive indexof 1 :42 − 0:006i. Biomass burning aerosols displayed a much larger imaginary part, with an average refractive indexof 1 :41 − 0:013i. Other climate-relevant parameters were estimated from Mie calculations. These include single-scattering albedos of 0:93 ± 0:03 and 0:90 ± 0:03 (at ambient humidity), asymmetry parameters of 0:63 ± 0:02 and 0:70 ± 0:03, and backscatter ratios of 0:12 ± 0:01 and 0:08 ± 0:01 for background and biomass burning aerosols, respectively. ? 2003 Published by Elsevier Ltd.

In‐canopy gradients, composition, sources, and optical properties of aerosol over the Amazon forest

[1]xa0As part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia-European Studies on Trace Gases and Atmospheric Chemistry (LBA-EUSTACH), size-fractionated aerosol samples were collected at a primary rain forest in the Brazilian Amazon during two field campaigns in April–May and September–October 1999. These two periods encompassed parts of the wet and dry seasons, respectively. Daytime-nighttime-segregated sampling was carried out at three different heights (above, within, and below canopy level) on a 54-m meteorological tower at the forest site in order to better characterize the aerosol sources. The samples were analyzed for up to 19 trace elements by particle-induced X-ray emission analysis and for carbonaceous components by thermal-optical analysis. Equivalent black carbon (BCe) and gravimetric analyses were also performed. The average mass concentrations for particles <2 μm diameter were 2.2 and 33.5 μg m−3 for the wet and the dry seasons, respectively. The elements related to biomass burning and soil dust generally exhibited highest concentrations above the canopy and during daytime, while forest-derived aerosol was more concentrated underneath the canopy and during nighttime. These variations can be largely attributed to daytime convective mixing and the formation of a shallow nocturnal boundary layer, along with the possibility of enhanced nighttime release of biogenic aerosol particles. Mass scattering (αs) and mass absorption efficiency (αa) data indicate that scattering was dominated by fine aerosol, while fine and coarse aerosol both contributed significantly to absorption during both seasons. The data also suggest that components other than elemental carbon were responsible for a substantial fraction of the absorption.

Design and field application of an automated cartridge sampler for VOC concentration and flux measurements

One of the major limitations in advancing the understanding of tropospheric ozone and aerosol generation and developing strategies for their control is the technical ability to accurately measure volatile organic compounds (VOCs). This paper describes the design of a constant flow VOC sampler. The versatile sampler can be used for fully automated concentration and flux measurements of VOCs. The sampler incorporates a microprocessor control unit and provides highly accurate mass flow control and significant ease of operation. Sampling sequences can be programmed directly or by remote control through a PC. All important operational parameters necessary for a complete sampling audit trail are logged. Compact weatherproof housings and low power consumption allow operation at remote sites and locations which are sensitive to disturbances or have restricted access. Inner wetted surfaces of the sampler are constructed from non-contaminating materials that do not sorb or emit VOC, and thus permit the collection of representative samples even in environments with very low VOC concentrations. The cartridge magazine provides a maximum of 20 sequential cartridge samples, which allows for long-term air quality assessments. In the dual channel mode, two samples can be collected simultaneously through two independent sample loops, providing ten sequential sample pairs. This design allows the parallel collection of (a) quality assurance backup samples, (b) samples on two different types of cartridges/sorbents to allow a variety of analyses, or (c) differential samples for flux measurements using enclosure, aerodynamic profile, or relaxed eddy accumulation (REA) methods. Field applications including airplane profile measurements above a tropical rainforest area, as well as gradient and REA measurements over a mid-latitude mixed forest stand are described, and demonstrate the validity and flexibility of the system. In particular, the application of the VOC sampler as an integrated part of a REA system is emphasized.

Corrigendum to “Study of tropical organic aerosol by thermally assisted alkylation-gas chromatography mass spectrometry”: [J. Anal. Appl. Pyrolysis 68–69 (2003) 351–369]

a Research Laboratory of Materials and Environmental Chemistry, Chemical Research Centre, Hungarian Academy of Sciences, P.O. Box 17, H-1525 Budapest, Hungary b Department of Earth and Environmental Sciences, University of Veszprem, P.O. Box 158, H-8201 Veszprem, Hungary c Air Chemistry Group of the Hungarian Academy of Sciences, University of Veszprem, P.O. Box 158, H-8201 Veszprem, Hungary d Instituto de Fisica, Universidade de Sao Paulo, Rua do Matao, Travessa R, 187, CEP 05508-900 Sao Paulo, SP, Brazil e Max Planck Institute for Chemistry, P.O. Box 3060, 55020 Mainz, Germany f Institute for Nuclear Sciences, Ghent University, Gent, Belgium