Olga B. Popovicheva

Cloud condensation nuclei and ice nucleation activity of hydrophobic and hydrophilic soot particles

Cloud condensation nuclei (CCN) activity and ice nucleation behavior (for temperatures<or=-40 degrees C) of soot aerosols relevant for atmospheric studies were investigated. Soots were chosen to represent a range of physico-chemical properties, from hydrophobic through a range of hydrophilicity, to hygroscopic. These characteristics were achieved through generation by three different combustion sources; three soots from natural gas pyrolysis (original: TS; graphitized: GTS; and oxidized: TOS), soot from a diffusion flame in an oil lamp burning aviation kerosene (TC1), and soot from a turbulent diffusion flame in an aircraft engine combustor (AEC). All of the samples exhibited some heterogeneity in our experiments, which showed evidence of two or more particle sub-types even within a narrow size cut. The heterogeneity could have resulted from both chemical and sizing differences, the latter attributable in part to particle non-sphericity. Neither GTS nor TS, hydrophobic particles distinguished only by the lower porosity and polarity of the GTS surface, showed CCN activity at or below water supersaturations required for wettable, insoluble particles (the Kelvin limit). TC1 soot particles, despite classification as hydrophilic, did not show CCN activity at or below the Kelvin limit. We attribute this result to the microporosity of this soot. In contrast, oxidized, non-porous, and hydrophilic TOS particles exhibited CCN activation at very near the Kelvin limit, with a small percentage of these particles CCN-active even at lower supersaturations. Due to containing a range of surface coverage of organic and inorganic hydrophilic and hygroscopic compounds, up to approximately 35% of hygroscopic AEC particles were active as CCN, with a small percentage of these particles CCN-active at lower supersaturations. In ice nucleation experiments below -40 degrees C, AEC particles nucleated ice near the expected condition for homogeneous freezing of water from aqueous solutions. In contrast, GTS, TS, and TC1 required relative humidity well in excess of water saturation at -40 degrees C for ice formation. GTS particles required water supersaturation conditions for ice activation even at -51 degrees C. At -51 to -57 degrees C, ice formation in particles with electrical mobility diameter of 200 nm occurred in up to 1 in 1000 TS and TC1 particles, and 1 in 100 TOS particles, at relative humidities below those required for homogeneous freezing in aqueous solutions. Our results suggest that heterogeneous ice nucleation is favored in cirrus conditions on oxidized hydrophilic soot of intermediate polarity. Simple considerations suggest that the impact of hydrophilic soot particles on cirrus cloud formation would be most likely in regions of elevated atmospheric soot number concentrations. The ice formation properties of AEC soot are reasonably consistent with present understanding of the conditions required for aircraft contrail formation and the proportion of soot expected to nucleate under such conditions.

Water interaction with hydrophobic and hydrophilic soot particles

The interaction of water with laboratory soots possessing a range of properties relevant for atmospheric studies is examined by two complementary methods: gravimetrical measurement of water uptake coupled with chemical composition and porosity analysis and HTDMA (humidified tandem differential mobility analyzer) inference of water uptake accompanied by separate TEM (transmission electron microscopy) analysis of single particles. The first method clarifies the mechanism of water uptake for bulk soot and allows the classification of soot with respect to its hygroscopicity. The second method highlights the dependence of the soot aerosol growth factor on relative humidity (RH) for quasi-monodisperse particles. Hydrophobic and hydrophilic soot are qualitatively defined by their water uptake and surface polarity: laboratory soot particles are thus classified from very hydrophobic to very hydrophilic. Thermal soot particles produced from natural gas combustion are classified as hydrophobic with a surface of low polarity since water is found to cover only half of the surface. Graphitized thermal soot particles are proposed for comparison as extremely hydrophobic and of very low surface polarity. Soot particles produced from laboratory flame of TC1 aviation kerosene are less hydrophobic, with their entire surface being available for statistical monolayer water coverage at RH approximately 10%. Porosity measurements suggest that, initially, much of this surface water resides within micropores. Consequently, the growth factor increase of these particles to 1.07 at RH > 80% is attributed to irreversible swelling that accompanies water uptake. Hysteresis of adsorption/desorption cycles strongly supports this conclusion. In contrast, aircraft engine soot, produced from burning TC1 kerosene in a gas turbine engine combustor, has an extremely hydrophilic surface of high polarity. Due to the presence of water soluble organic and inorganic material it can be covered by many water layers even below water saturation conditions. This soot demonstrates a gradual diameter growth factor (D(wet)/D(dry)) increase up to 1.22 at 93% relative humidity, most likely due to the presence of single particles with water soluble material heterogeneously distributed over their surface.

Quantification of water uptake by soot particles

Quantification of atmospheric processes including the water uptake by soot particles of various origin, emitted from different sources, requires identification of hydrophobic and hydrophilic soot. Water uptake measurements are performed on well-characterized laboratory soots available for atmospheric studies. Comparative analysis of water adsorption isotherms on soots of various compositions allows us to suggest a concept of quantification. Systematic analysis demonstrates two mechanisms of water/soot interaction, namely, bulk dissolution into soot-water-soluble coverage (absorption mechanism) and water molecule adsorption on surface active sites (adsorption mechanism). The formation of water film extended over the surface is suggested as a quantification measure which separates hygroscopic from non-hygroscopic soot. Water uptake on hygroscopic soot takes place by the absorption mechanism: it significantly exceeds the formation of many surface layers. If soot particles are made mostly from elemental carbon and/or are covered by a water-insoluble organic layer, they are classified as non-hygroscopic. Low water adsorption on some active sites following cluster formation is a typical mechanism of water interaction with hydrophobic soot. If a water film extended over the surface is formed due to the cluster confluence it is suggested that soot is hydrophilic. A few classical models are applied for parameterization of water interactions on hydrophilic and hydrophobic soots.

Impact of Fe Content in Laboratory - Produced Soot Aerosol on its Composition, Structure, and Thermo-Chemical Properties

Soot aerosol, which is a major pollutant in the atmosphere of urban areas, often contains not only carbonaceous matter but also inorganic material. These species, for example, iron compounds, originated from impurities in fuel or lubricating oil, additives or engine wear may change the physico-chemical characteristics of soot and hence its environmental impact. We studied the change of composition, structure, and oxidation reactivity of laboratory-produced soot aerosol with varying iron content. Soot types of various iron contents were generated in a propane/air diffusion flame by adjusting the doping amount of iron pentacarbonyl Fe(CO)5 to the flame. Scanning electron microscopy (SEM)/energy-dispersive X-ray spectroscopy (EDX) was combined with cluster analysis (CA) to separate individual particles into definable groups of similar chemical composition representing the particle types in dependence of the iron content in soot. Raman microspectroscopy (RM) and infrared spectroscopy were applied for the characterization of the graphitic soot structure, hydrocarbons, and iron species. For the analysis of soot reactivity, temperature-programmed oxidation (TPO) was used. It is demonstrated that iron is most dominantly present in the form of amorphous Fe (III) oxide crystallizing to hematite α-Fe2O3 upon thermal treatment. Iron contaminations do not change the soot microstructure crucially, but Fe(CO)5 doping of the flame impacts hydrocarbon composition. Soot oxidation reactivity strongly depends on the iron content, as the temperature of maximum carbon (di)oxide emission T max follows an exponential decay with increasing iron content in soot. Based on the results of the thermo-chemical characterization of laboratory-produced internally mixed iron-containing soot, we can conclude that iron-containing combustion aerosol samples cannot be characterized unambiguously by current thermo-optical analysis protocols. Copyright 2012 American Association for Aerosol Research

Cerium dioxide nanoparticles can interfere with the associated cellular mechanistic response to diesel exhaust exposure

The aim of this study was to compare the biological response of a sophisticated in vitro 3D co-culture model of the epithelial airway barrier to a co-exposure of CeO(2) NPs and diesel exhaust using a realistic air-liquid exposure system. Independent of the individual effects of either diesel exhaust or CeO(2) NPs investigation observed that a combined exposure of CeO(2) NPs and diesel exhaust did not cause a significant cytotoxic effect or alter cellular morphology after exposure to diesel exhaust for 2h at 20μg/ml (low dose) or for 6h at 60μg/ml (high dose), and a subsequent 6h exposure to an aerosolized solution of CeO(2) NPs at the same doses. A significant loss in the reduced intracellular glutathione level was recorded, although a significant increase in the oxidative marker HMOX-1 was found after exposure to a low and high dose respectively. Both the gene expression and protein release of tumour necrosis factor-α were significantly elevated after a high dose exposure only. In conclusion, CeO(2) NPs, in combination with diesel exhaust, can significantly interfere with the cell machinery, indicating a specific, potentially adverse role of CeO(2) NPs in regards to the biological response of diesel exhaust exposure.

Ship particulate pollutants: Characterization in terms of environmental implication

A major aspect of monitoring the atmosphere is the quantification of man-made pollution and their interactions with the environment. Key physico-chemical characteristics of diesel exhaust particulates of sea-going ship emissions are presented with respect to morphology, microstructure, and chemical composition. Heavy fuel oil (HFO)-derived particles exhibit extremely complex chemistry. They demonstrate three distinct morphological structures with different chemical composition, namely soot, char and mineral/ash. The composition analysis investigates the content of environmentally-dangerous pollutants: metals, inorganic/mineral species, and soluble, volatile organic and ionic compounds. It is found that hazardous constituents from HFO combustion, such as transitional and alkali earth metals (V, Ni, Ca, Fe) and their soluble or insoluble chemical forms (sulfides, sulfates, oxides, carbides), are released together with particles into the atmosphere. The water soluble fraction, more than 27 wt%, is dominated by sulfates and calcium cations. They cause the high hygroscopicity of ship exhaust particles and their possible ability to act as cloud nuclei in humid marine environment.

Wetting and hydration of insoluble soot particles in the upper troposphere

Wettability and hydration are determined for aircraft combustor and laboratory-made soots which are used as surrogates for the insoluble part of aircraft-generated black carbon particles in the upper troposphere (UT). The measured water/ice contact angles on the soot surfaces are in the range 60-80 degrees. Factors influencing the soot wetting show a tremendous dependence on the surface chemical composition and microstructure. Wetting characteristics of soots are directly related to its hydrophilicity. The inverse Kelvin effect is considered as a mechanism of ice nucleation which is facilitated by the soot agglomerated structure with interparticle cavities in which condensation takes place on the insoluble surface with a high water contact angle. Estimations of the critical supersaturations needed for the ice condensation growth of particles are provided to determine which of the wetting characteristics are required for cirrus cloud formation in ice saturated regions of the UT.

Effect of black carbon particles on the efficiency of water droplet freezing

Black carbon particles emitted by natural and anthropogenic sources of combustion are potential nuclei of ice formation of cirri in troposphere. The freezing of the ensembles of water microdroplets containing black carbon particles of different origins, including those modified with organic substances, is studied. Ice-forming ability is shown to be predetermined by the density and sizes of black carbon agglomerates, as well as the chemistry and wettability of their surface. Ice formation is most efficient in dispersions of black carbon particles that are stable with respect to sedimentation and have a uniform distribution of particles over the droplet volume. In the presence of oxygen-containing groups on the particle surface, freezing temperature increases. The efficiency of the ice formation decreases in the presence of noticeable amounts of water-soluble substances on the particle surface. The maximum freezing ability is inherent in ensembles of water droplets containing hydrophilic particles. Characteristics ensuring a high ice forming ability of nuclei are determined.

FTIR analysis of surface functionalities on particulate matter produced by off-road diesel engines operating on diesel and biofuel

Fourier transform infrared spectroscopy is applied as a powerful analytic technique for the evaluation of the chemical composition of combustion aerosols emitted by off-road engines fuelled by diesel and biofuels. Particles produced by burning diesel, heated rapeseed oil (RO), RO with ethylhexylnitrate, and heated palm oil were sampled from exhausts of representative in-use diesel engines. Multicomponent composition of diesel and biofuel particles reveal the chemistry related to a variety of functional groups containing carbon, hydrogen, oxygen, sulfur, and nitrogen. The most intensive functionalities of diesel particles are saturated C–C–H and unsaturated C=C–H aliphatic groups in alkanes and alkenes, aromatic C=C and C=C–H groups in polyaromatics, as well as sulfates and nitrated ions. The distinguished features of biofuel particles were carbonyl C=O groups in carboxylic acids, ketones, aldehydes, esters, and lactones. NO2, C–N and -NH groups in nitrocompounds and amines are found to dominate biofuel particles. Group identification is confirmed by complementary measurements of organic carbon (OC), elemental carbon, and water-soluble ion species. The relationship between infrared bands of polar oxygenated and non-polar aliphatic functionalities indicates the higher extent of the surface oxidation of biofuel particles. Findings provide functional markers of organic surface structure of off-road diesel emission, allowing for a better evaluation of relation between engine, fuel, operation condition, and particle composition, thus improving the quantification of environmental impacts of alternative energy source emissions.

Ion–soot interaction: a possible mechanism of ion removal in aircraft plume

The phenomenon of the ion-soot interaction in the aircraft plume at the ground conditions is investigated. The ion-soot attachment coefficients, taking into account the polarization of the soot particles in the ion electric field, are calculated. It is shown that the ion-soot attachment may play the important role in the evolution of the ion concentrations in the plume. Comparison of the model results with the ground-based measurements for the ion depletion along the plume demonstrates that the concentration of the positive and negative ions at the nozzle exit for these observations is close to 1.2 x 10(8) cm(-3).