Abstract. Atmospheric tar balls are particles of special morphology and composition that are fairly abundant in the plumes of biomass smoke. These particles form a specific subset of brown carbon (BrC) which has been shown to play a significant role in atmospheric shortwave absorption and, by extension, climate forcing. Here we suggest that tar balls are produced by the direct emission of liquid tar droplets followed by heat transformation upon biomass burning. For the first time in atmospheric chemistry we generated tar-ball particles from liquid tar obtained previously by dry distillation of wood in an all-glass apparatus in the laboratory with the total exclusion of flame processes. The particles were perfectly spherical with a mean optical diameter of 300 nm, refractory, externally mixed, and homogeneous in the contrast of the transmission electron microscopy (TEM) images. They lacked any graphene-like microstructure and exhibited a mean carbon-to-oxygen ratio of 10. All of the observed characteristics of laboratory-generated particles were very similar to those reported for atmospheric tar-ball particles in the literature, strongly supporting our hypothesis regarding the formation mechanism of atmospheric tar-ball particles.
Abstract. Atmospheric tar balls are particles of special morphology and composition that are abundant in the plumes of biomass smoke. These particles form a specific subset of brown carbon (BrC) which has been shown to play a significant role in atmospheric shortwave absorption and thus climate forcing. Formerly tar balls were hypothesized to be formed in secondary processes in the atmosphere from lignin pyrolysis products. Based on their typical size distributions, morphology, chemical characteristics and other features we now suggest that tar balls are initially produced by the emission of primary tar droplets upon biomass burning. To verify our hypothesis tar balls were produced under laboratory conditions with the total exclusion of flame processes. An all-glass apparatus was designed and tar ball particles were generated from liquid tar obtained previously by dry distillation of wood. The size range, morphology and the chemical composition of the laboratory-generated tar ball particles were similar to those observed in biomass smoke plumes or elsewhere in the atmosphere. Based on our results and the chemical and physical characteristics of tar we suggest that tar balls can be formed by the chemical transformation of emitted primary tar droplets.
Abstract. Tar balls (TBs) are a specific particle type which is abundant in the global troposphere, in particular in biomass smoke plumes. These particles belong to the family of atmospheric brown carbon (BrC) which can absorb light in the visible range of the solar spectrum. Albeit TBs are typically present as individual particles in biomass smoke plumes, their absorption properties have been only indirectly inferred from field observations or calculations based on their electron energy-loss spectra. This is because in biomass smoke TBs coexist with various other particle types (e.g. organic particles with inorganic inclusions and soot, the latter is emitted mainly during flaming conditions) from which they cannot be physically separated; thus, a direct experimental determination of their absorption properties is not feasible. Very recently we have demonstrated that TBs can be generated in the laboratory from droplets of wood tar that resemble atmospheric TBs in all of their observed properties. As a follow-up study we have installed on-line instruments to our laboratory set-up generating pure TB particles to measure the absorption and scattering, as well as size distribution of the particles. In addition, samples were collected for transmission electron microscopy (TEM) and total carbon (TC) analysis. The effects of experimental parameters were also studied. The mass absorption coefficients of the laboratory generated TBs were found to be in the range of 0.8–3.0 m2 g−1 at 550 nm, with absorption Ångström exponents (AAE) between 2.7 and 3.4 (average 2.9) in the wavelength range 467–652 nm. The refractive index of TBs as derived from Mie calculations was about 1.84–0.21i at 550 nm. In the brown carbon continuum these values fall closer to those of soot than to other light-absorbing species such as humic-like substances (HULIS). Considering the abundance of TBs in biomass smoke and the global magnitude of biomass burning emissions, these findings may have substantial influence on the understanding of global radiative energy fluxes.
Urban air quality is severely affected by traffic related particulate matter, including direct emissions from exhaust, brake pad, tire wear and road dust resuspended by vehicular motions. Deposited road dust can also be resuspended by wind force or other anthropogenic activities, and overall it may contribute up to 30% to urban PM10. A mobile resuspended road dust PM10 sampler was developed and constructed which simulates the effects of traffic or gusting winds on road surfaces and collects resuspended PM1−10 samples in a cyclone separator and PM1 samples on filters. The sampler was tested by collecting resuspended road dust at kerbside locations in Veszprém, Hungary. The collected PM1 and PM1−10 fractions were analysed by various analytical methods to show the potential of size-selective on-line sample collection combined with the chemical characterization of resuspended road dust. The main constituents of the resuspended road dust were crustal elements, and it was also possible to determine the mineral phase composition of PM1−10 dust which is generally not feasible from samples collected on filter substrate. The application of the sampling and analysis methods may facilitate the evaluation of resuspended road dust sources in cities as well as help constrain a better source apportionment of urban PM10.
Minerals of the sediments of shallow lakes are in continuous interaction with the biota. In order to understand the role of algae in producing carbonate minerals in shallow Lake Balaton, we used electron microscopy to study the nanoscale processes of mineral formation and transformation in association with algal blooms. In the immediate vicinity of photosynthesizing cells, the first phase to precipitate was amorphous calcium carbonate (ACC). Also associated with some blooms were spindle-shaped calcite particles that invariably contained nm-scale flakes of clay minerals belonging to the smectite group. In contrast, carbonate particles collected from the sediment and from suspended matter during non-bloom periods contained only Mg-bearing calcite particles and minor protodolomite, both associated with smectite flakes. By comparing these observations with the results of laboratory carbonate precipitation experiments, we interpret the distinct carbonate phases as representing stages of a complex process: (1) algal photosynthesis creates high supersaturation near the cells, resulting in the fast nucleation of ACC; (2) ACC particles attach to nm-scale smectite flakes where they instantly transform into calcite through partial dissolution and reprecipitation. Step (2) can result either in calcite spindles, or aggregate-looking, Mg-bearing calcite particles that are typical for Lake Balaton sediments. Spindles form exclusively near algae, for reasons not yet known. (3) Further aging of Mg-bearing calcite by dissolution/reprecipitation produces protodolomite. The entire process appears to take place within hours to days; thus, the typical Lake Balaton sediment contains mainly Mg-bearing calcite and some protodolomite particles. Significantly, the above multistep process of carbonate formation involves several dissolution and reprecipitation cycles, and in most stages clay minerals play crucial roles.
Abstract. Tar balls (TBs) are a specific particle type that is abundant in the global troposphere, in particular in biomass smoke plumes. These particles belong to the family of atmospheric brown carbon (BrC), which can absorb light in the visible range of the solar spectrum. Albeit TBs are typically present as individual particles in biomass smoke plumes, their absorption properties have been only indirectly inferred from field observations or calculations based on their electron energy-loss spectra. This is because in biomass smoke TBs coexist with various other particle types (e.g., organic particles with inorganic inclusions and soot, the latter emitted mainly during flaming conditions) from which they cannot be physically separated; thus, a direct experimental determination of their absorption properties is not feasible. Very recently we have demonstrated that TBs can be generated in the laboratory from droplets of wood tar that resemble atmospheric TBs in all of their observed properties. As a follow-up study, we have installed on-line instruments to our laboratory set-up, which generate pure TB particles to measure the absorption and scattering, as well as the size distribution of the particles. In addition, samples were collected for transmission electron microscopy (TEM) and total carbon (TC) analysis. The effects of experimental parameters were also studied. The mass absorption coefficients of the laboratory-generated TBs were found to be in the range of 0.8–3.0 m2 g−1 at 550 nm, with absorption Ångström exponents (AAE) between 2.7 and 3.4 (average 2.9) in the wavelength range 467–652 nm. The refractive index of TBs as derived from Mie calculations was about 1.84 − 0.21i at 550 nm. In the brown carbon continuum, these values fall closer to those of soot than to other light-absorbing species such as humic-like substances (HULIS). Considering the abundance of TBs in biomass smoke and the global magnitude of biomass burning emissions, these findings may have substantial influence on the understanding of global radiative energy fluxes.
The origin of growth defects and epitaxial layers in nanocrystalline magnetite (Fe3O4) and its oxidation product, maghemite (γ-Fe2O3), was studied. In magnetite, two types of planar defects are identified, (111) spinel-law twin boundaries and (110) stacking faults (SF). The twinning in magnetite is related to magnetic-field-assisted self-assembly and the growth of octahedral nanocrystals throughout their crystallization period. Simple contact twins of crystals sharing common octahedral faces, or even plate-like twins develop when two adjoined crystals continue their growth as a unit. Crystallographically, twinned domains are related by 180° rotation about the [111]-axis and with the (111) plane as the interface, producing local hcp stacking in the oxygen sub-lattice. SFs are present in both single and twinned magnetite crystals, where they are pinned to (111) twin boundaries and are present only in one domain. The displacement vector corresponding to the observed translation is RSF = ¼·[110], pointing normal to the (110) plane of the SF. After the thermal treatment at 250 °C both types of planar defects are retained. In addition to planar defects, originating from magnetite, we identified a new formation of few-nanometers-thick epitaxial layers, of a hexagonal Fe(III)-oxide–hydroxide, feroxyhyte (δ-FeOOH), covering the octahedral faces of the maghemite crystals. The crystallographic relationship between maghemite and feroxyhyte is described by [10]·(222)mag||[010]·(002)fer.
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