Willy Maenhaut

Global distribution of atmospheric phosphorus sources, concentrations and deposition rates, and anthropogenic impacts

A worldwide compilation of atmospheric total phosphorus (TP) and phosphate (PO4) concentration and deposition flux observations are combined with transport model simulations to derive the global distribution of concentrations and deposition fluxes of TP and PO4. Our results suggest that mineral aerosols are the dominant source of TP on a global scale (82%), with primary biogenic particles (12%) and combustion sources (5%) important in nondusty regions. Globally averaged anthropogenic inputs are estimated to be similar to 5 and 15% for TP and PO4, respectively, and may contribute as much as 50% to the deposition over the oligotrophic ocean where productivity may be phosphorus-limited. There is a net loss of TP from many (but not all) land ecosystems and a net gain of TP by the oceans (560 Gg P a(-1)). More measurements of atmospheric TP and PO4 will assist in reducing uncertainties in our understanding of the role that atmospheric phosphorus may play in global biogeochemistry.

Organosulfate Formation in Biogenic Secondary Organic Aerosol

Organosulfates of isoprene, alpha-pinene, and beta-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive series of laboratory photooxidation (i.e., OH-initiated oxidation) and nighttime oxidation (i.e., NO3-initiated oxidation under dark conditions) experiments using nine monoterpenes (alpha-pinene, beta-pinene, d-limonene, l-limonene, alpha-terpinene, gamma-terpinene, terpinolene, Delta(3)-carene, and beta-phellandrene) and three monoterpenes (alpha-pinene, d-limonene, and l-limonene), respectively. Organosulfates were characterized using liquid chromatographic techniques coupled to electrospray ionization combined with both linear ion trap and high-resolution time-of-flight mass spectrometry. Organosulfates are formed only when monoterpenes are oxidized in the presence of acidified sulfate seed aerosol, a result consistent with prior work. Archived laboratory-generated isoprene SOA and ambient filter samples collected from the southeastern U.S. were reexamined for organosulfates. By comparing the tandem mass spectrometric and accurate mass measurements collected for both the laboratory-generated and ambient aerosol, previously uncharacterized ambient organic aerosol components are found to be organosulfates of isoprene, alpha-pinene, beta-pinene, and limonene-like monoterpenes (e.g., myrcene), demonstrating the ubiquity of organosulfate formation in ambient SOA. Several of the organosulfates of isoprene and of the monoterpenes characterized in this study are ambient tracer compounds for the occurrence of biogenic SOA formation under acidic conditions. Furthermore, the nighttime oxidation experiments conducted under highly acidic conditions reveal a viable mechanism for the formation of previously identified nitrooxy organosulfates found in ambient nighttime aerosol samples. We estimate that the organosulfate contribution to the total organic mass fraction of ambient aerosol collected from K-puszta, Hungary, a field site with a similar organosulfate composition as that found in the present study for the southeastern U.S., can be as high as 30%.

Characterization of the Gent Stacked Filter Unit PM10 Sampler

ABSTRACT An integral part of several International Atomic Energy Agency sponsored coordinated research programmes involving the sampling and analysis of ambient airborne particules was the development of a PM10 sampler. Each participant was provided with such a sampler so that comparable samples would be obtained by each of the participating groups. Thus, in order to understand the characteristics of this sampler, we undertoke several characterization studies in which we examined the aerodynamic collection characteristics of the impactor inlet and the reproducibility of the sample mass collection. One of the samplers machined in Belgium was compared with one built from the same design in the U.S. and comparable results were obtained. The sampler was operated side-by-side with a commercial PM10 beta gauge and an IMPROVE-design 2.5 μm cut-point cyclone. Although the sampler was not wind tunnel tested as required for certification as a reference sampler, it does provide a collection efficiency that generally...

The long-range transport of southern African aerosols to the tropical South Atlantic

Two episodes of long-range aerosol transport (4000 km) from southern Africa into the central tropical South Atlantic are documented. Stable nitrogen isotope analysis, multielemental analysis, and meteorological observations on local and regional scales are used to describe the observed surface aerosol chemistry during these transport episodes. The chemical, kinematic, and thermodynamic analyses suggest that for the central tropical South Atlantic, west Africa between 0° and 10°S is the primary air mass source region (over 50%) during austral spring. Over 70% of all air arriving in the lower and middle troposphere in the central tropical South Atlantic comes from a broad latitudinal band extending from 20°S to 10°N. Air coming from the east subsides and is trapped below the midlevel and trade wind inversion layers. Air from the west originates at higher levels (500 hPa) and contributes less than 30% of the air masses arriving in the central tropical South Atlantic. The source types of aerosols and precursor trace gases extend over a broad range of biomes from desert and savanna to the rain forest. During austral spring, over this broad region, processes include production from vegetation, soils, and biomass burning. The aerosol composition of air masses over and the atmospheric chemistry of the central South Atlantic is a function of the supply of biogenic, biomass burning, and aeolian emissions from tropical Africa. Rainfall is a common controlling factor for all three sources. Rain, in turn, is governed by the large-scale circulations which show pronounced interannual variability. The field measurements were taken in an extremely dry year and reflect the circulation and transport fields typical of these conditions.

Trace elements in tropical African savanna biomass burning aerosols

As a part of the FOS/DECAFE experiment, aerosol particles emitted during prescribed savanna fires were collected in January 1991 at Lamto (Ivory Coast), either close to the emission or in ambient air. Analytical transmission electron microscopy pointed out the presence of sub-micrometer soots, salt condensates, vegetation relicts and soil derived particles. The samples were also analyzed for their total particulate matter (TPM) content and elemental composition by PIXE or XRF. At the emission, high concentrations of soil derived elements (Fe and Al) pointed out an intense remobilization process during the fires. Biomass burning emissions contributed to more than 90% of the measured concentrations, of P, Cl, S, K, Cu and Zn, which were found primarily in the fine fraction with the exception of P. Near the emission, K was mainly present as KCl, evolving to K2SO4 in the ambient samples. Trace elements emission factors were obtained for the first time for the African savanna burning and their annual emissions were estimated: our median K emission factor (0.78 g/kg of C) is higher than estimates for other ecosystems (0.2–0.58 g/kg of C); Zn emissions (0.008 Tg/year) account for 4 to 11% of the global anthropogenic emissions.

Regional atmospheric aerosol composition and sources in the eastern Transvaal, South Africa, and impact of biomass burning

As part of the Southern Africa Fire-Atmosphere Research Initiative (SAFARI-92), size-fractionated aerosol samples were collected during September–October 1992 at three fixed ground-based sites in the eastern Transvaal, i.e., at two sites within the Kruger National Park (KNP) and at a third site on the Transvaal highveld (about 150 km WSW of the KNP sites), and near a number of prescribed fires in the KNP. The collection devices consisted of stacked filter units, which separate the aerosol into a coarse (2–10 μm equivalent aerodynamic diameter (EAD)) and a fine (<2 μm EAD) size fraction, and of eight-stage cascade impactors, which provide more detailed size fractionation. The samples were analyzed for particulate mass (PM), black carbon (BC), and up to 47 elements. The prescribed fires gave rise to high levels of airborne soil dust, but several species (elements) were particularly enriched in the pyrogenic emissions. This was the case for BC, P, K, Ca, Mn, Zn, Sr, and I in the coarse fraction, and for BC, the halogens (Cl, Br, I), K, Cu, Zn, Rb, Sb, Cs, and Pb (and in the flaming phase also Na and S) in the fine fraction. The aerosol concentrations, compositions, and time trends at the two KNP sites were quite similar, suggesting that regionally representative samples were collected. Receptor modeling calculations, using both absolute principal component analysis and chemical mass balance, indicated that the KNP coarse PM was essentially attributable to mineral dust and sea salt, with average relative apportionments of 75% and 25%, respectively. At the highveld site, mineral dust and sea salt contributed in a 99-to-1 ratio to the coarse PM. In the fine size fraction at all three fixed sites, four components were identified, i.e., mineral dust, sea salt, biomass burning products, and sulfate. The pyrogenic component was the dominant contributor to the atmospheric concentrations of BC, K, Zn, and I, a major source for PM, Cl, Cu, Br, and Cs, but only a minor source for S. About 40% of the fine PM was, on the average, attributed to the pyrogenic particles, and about one third of it to the sulfate component. Relation of the time trends of the various components with three-dimensional air mass back trajectories indicated that elevated levels of pyrogenic products were mostly found in air masses arriving from the north. The levels of the sulfate component tended to be higher at the highveld site than at the two KNP sites, and this component was generally associated with continental air. It was concluded that the major contribution to this fine sulfate came from fossil fuel burning and various industrial activities on the Transvaal highveld.

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.

Methyl halide emissions from savanna fires in southern Africa

The methyl halides, methyl chloride (CH3Cl), methyl bromide (CH3Br), and methyl iodide (CH3I), were measured in regional air samples and smoke from savanna fires in southern Africa during the Southern Africa Fire-Atmosphere Research Initiative-92 (SAFARI-92) experiment (August–October 1992). All three species were significantly enhanced in the smoke plumes relative to the regional background. Good correlations were found between the methyl halides and carbon monoxide, suggesting that emission was predominantly associated with the smoldering phase of the fires. About 90% of the halogen content of the fuel burned was released to the atmosphere, mostly as halide species, but a significant fraction (3–38%) was emitted in methylated form. On the basis of comparison with the composition of the regional background atmosphere, emission ratios to carbon dioxide and carbon monoxide were determined for the methyl halide species. The emission ratios decreased in the sequence CH3Cl > CH3Br > CH3I. Extrapolation of these results in combination with data from other types of biomass burning, e.g. forest fires, suggests that vegetation fires make a significant contribution to the atmospheric budget of CH3Cl and CH3Br. For tropospheric CH3I, on the other hand, fires appear to be a minor source. Our results suggest that pyrogenic emissions of CH3Cl and CH3Br need to be considered as significant contributors to stratospheric ozone destruction.

Large‐scale aerosol source apportionment in Amazonia

Aerosol particles were collected aboard two Brazilian Bandeirante EMB 110 planes, and the University of Washington Convair C-131A aircraft during the Smoke, Clouds, and Radiation-Brazil (SCAR-B) field project in the Amazon Basin in August and September 1995. Aerosols were collected on Nuclepore and Teflon filters. Aerosol size distribution was measured with a MOUDI cascade impactor. Sampling was performed mostly over areas heavily influenced by biomass burning smoke. Particle-induced X ray emission (PIXE) was used to measure concentrations of up to 20 elements (Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, Zr, and Pb). Black carbon (BC) and gravimetric mass analysis were also performed. Instrumental neutron activation analysis (INAA) determined the concentrations of about 15 elements on the Teflon filters. Electron probe X ray microanalysis (EPMA) was used to analyze individual aerosol particles. The average aerosol mass concentration was 105 μg m−3, with a maximum of 297 μg m−3. Black carbon (BC) averaged 5.49 μg m−3, or 1–7% of the aerosol mass load. Five aerosol components were revealed by absolute principal factor analysis: (1) a biomass burning component (responsible for 54% of the aerosol mass and associated with BC, K, Cl, Zn, I, S, Br, Rb, aerosol mass concentration, and other elements); (2) a soil dust aerosol component (15.6% of the aerosol mass); (3) a natural biogenic component (18.7% of the aerosol mass and associated with P, K, S, Ca, Sr, Mg, Mn, Cu and Zn); (4) a second soil dust (5.7% of the aerosol mass and enriched in Si, Ti, and Fe); and (5) a NaCl aerosol component (5.9% of the aerosol mass with Na, Cl, Br, and iodine). Electron microscopy analysis of individual aerosol particles confirmed these five aerosol types. Organic material dominated the aerosol mass and the number concentration of airborne particles. Aerosol size distributions show that the fine mode accounts for 78% of the aerosol mass, centered at 0.33 μm aerodynamic diameter. The coarse mode accounts for 22% of the mass, centered at about 3.2 μm. Black carbon size distributions show a consistent picture, with a mass median diameter centered at about 0.175-0.33 μm aerodynamic diameter. This study suggests that for modeling the optical properties of aerosol in the Amazon Basin, it is essential to use a model that includes the optical and physical properties of at least two aerosol components other than the biomass burning aerosol, namely, natural biogenic aerosol and soil dust.

Saharan dust in Brazil and Suriname during the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA)- Cooperative LBA Regional Experiment (CLAIRE) in March 1998

Advection of Saharan dust was observed via chemical and optical measurements during March 1998 in Brazil and Suriname during the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA)-Cooperative LBA Airborne Regional Experiment (CLAIRE)-98 experiment. In Brazil the dust outbreak produced an increase of a factor of 3 in the daily mean mass concentration (up to 26±7 μg m−3) of particles smaller than 10 μm equivalent aerodynamic diameter (EAD), and in the daily mean aerosol particle scattering coefficient σs (up to 26±8 Mm−1 STP, ambient humidity). Background levels of aerosol scattering (ambient) were σs ∼ 10 Mm−1. The effect of dust advection was evident for all major crustal elements (Al, Si, Ca, Ti, Mn, and Fe), as well as the sea-salt elements (Na, Cl, and S), as the dust layer was transported at low altitude (below 800 hPa). Coarse P and organic carbon (OC) concentrations were not influenced by the occurrence of dust, and were mainly emitted by the rain forest. The dry scattering mass efficiency of dust (particles smaller than 10 μm EAD) was estimated to be between 0.65 (±0.06) and 0.89 (±0.08) m2 g−1. Airborne profiles of aerosol scattering showed two distinct types of vertical structure in the dust layer over Suriname, either vertically uniform (15, 26 March), or plume-like (25 March). Dust layers extended generally up to 700 hPa, while scattering layers occasionally encountered at higher altitudes resulted from smoke emitted by biomass burning in Venezuela and Colombia. Observations in South America were supported by measurements in Israel and Tenerife (Canary Islands), where the dust outbreaks were also detected.