N. M. Persiantseva

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.

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.

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).

Optical-microphysical and physical-chemical characteristics of Siberian biomass burning: Experiments in Aerosol Chamber

A series of experiments aimed at studying the effect of combustion regimes of typical Siberian biomasses on the optical, microphysical, and physical-chemical properties of smoke aerosols was performed in the Large Aerosol Chambe, Institute of Atmospheric Optics, Siberian Branch, Russian Academy of Sciences. A comprehensive data analysis showed that temperature regime of Siberian pine and coniferous tree burning has a key effect on the formation and time dynamics of all smoke characteristics. The polarization spectronephelometer measurements of light scattering are used to determine the size distributions and absorption indices of particles. Particles in the smoldering phase are weakly absorbing, but the mixed phase contains a strongly absorbing fine component produced in open flame phases. We studied microstructure characteristics of aerosols by the analysis of morphology and elemental composition. Groups of soot and organic particles were determined as micromarkers of emissions in open flaming and smoldering phases, respectively. The organic and elemental carbon contents, origin and concentration of chemical compounds in the water-soluble ion fraction exhibit a strong dependence on the combustion phase. Sugar anhydride (levoglucosan) was determined in the smoldering phase as a stable molecular marker of Siberian pine burning. A number of specific markers of coniferous wood burning were identified among the chemical compounds. Smoke aging is accompanied by condensation of organic and inorganic compounds, transformation of aerosol surface chemistry, and the formation of the group of potassium-rich particles, all demonstrating the complexity and variability of the chemical composition and microstructure of atmospheric aerosol pollution during Siberian forest fires.

Aerosol composition and microstructure in the smoky atmosphere of Moscow during the August 2010 extreme wildfires

This is a comprehensive study of the physicochemical characterization of multicomponent aerosols in the smoky atmosphere of Moscow during the extreme wildfires of August 2010 and against the background atmosphere of August 2011. Thermal–optical analysis, liquid and ion chromatography, IR spectroscopy, and electron microscopy were used to determine the organic content (OC) and elemental content (EC) of carbon, organic/inorganic and ionic compounds, and biomass burning markers (anhydrosaccharides and the potassium ion) and study the morphology and elemental composition of individual particles. It has been shown that the fires are characterized by an increased OC/EC ratio and high concentrations of ammonium, potassium, and sulfate ions in correlation with an increased content of levoglucosan as a marker of biomass burning. The organic compounds containing carbonyl groups point to the process of photochemical aging and the formation of secondary organic aerosols in the urban atmosphere when aerosols are emitted from forest fires. A cluster analysis of individual particles has indicated that when the smokiest atmosphere is characterized by prevailing soot/tar ball particles, which are smoke-emission micromarkers.