Sources and source regions effecting the aerosol composition of the Eastern Mediterranean

Positive matrix factorization (PMF) was used to deduce the aerosol sources at a rural site on the Mediterranean coast of Turkey, using sample collected between February 1992 and December 1993. Approximately 600 daily aerosol samples were collected and 40 elements and compounds were analyzed by atomic absorption spectrometry, instrumental neutron activation analysis, ion chromatography and colorimetry.Seven factors were identified with PMF, namely local dust, Saharan dust, sea salt, long range transport, smelter, arsenic and fertilizer factors. The non-parametric bootstrapped potential source contribution function (PSCF) was then used to help identify likely locations of the regional sources of pollution. Besides, explained variance, enrichment factors, seasonal variation of G-score values and back trajectories were used to define the source regions of the factors. Results demonstrated that there are major potential source areas, for the pollution-derived component in aerosol mass, on the Aegean coast, Northwest Turkey, Balkan countries, Ukraine and regions located northern part of Ukraine.     

Chemical composition and reaction analysis of single aerosol particles

In situ measurements of gas-liquid surface reactions of single aerosol microdroplets are presented. By means of optical levitation in combination with elastic (Mie) and inelastic (Raman) light scattering it is possible to get information on the chemistry of e.g. acid/base reactions as well as the physical behavior of single microparticles.     

Chemical composition and reaction analysis of single aerosol particles

In situ measurements of gas-liquid surface reactions of single aerosol microdroplets are presented. By means of optical levitation in combination with elastic (Mie) and inelastic (Raman) light scattering it is possible to get information on the chemistry of e.g. acid/base reactions as well as the physical behavior of single microparticles.     

Effect of lipid headgroup composition on the interaction between melittin and lipid bilayers

The effect of the lipid polar headgroup on melittin-phospholipid interaction was investigated by cryo-TEM, fluorescence spectroscopy, ellipsometry, circular dichroism, electrophoresis and photon correlation spectroscopy. In particular, focus was placed on the effect of the lipid polar headgroup on peptide adsorption to, and penetration into, the lipid bilayer, as well as on resulting colloidal stability effects for large unilamellar liposomes. The effect of phospholipid headgroup properties on melittin-bilayer interaction was addressed by comparing liposomes containing phosphatidylcholine, -acid, and -inositol at varying ionic strength. Increasing the bilayer negative charge leads to an increased liposome tolerance toward melittin which is due to an electrostatic arrest of melittin at the membrane interface. Balancing the electrostatic attraction between the melittin positive charges and the phospholipid negative charges through a hydration repulsion, caused by inositol, reduced this surface arrest and increased liposome susceptibility to the disruptive actions of melittin. Furthermore, melittin was demonstrated to induce liposome structural destabilization on a colloidal scale which coincided with leakage induction for both anionic and zwitterionic systems. The latter findings thus clearly show that coalescence, aggregation, and fragmentation contribute to melittin-induced liposome leakage, and that detailed molecular analyses of melittin pore formation are incomplete without considering also these colloidal aspects.     

Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene

Recent work in our laboratory has shown that the photooxidation of isoprene (2-methyl-1,3-butadiene, C(5)H(8)) leads to the formation of secondary organic aerosol (SOA). In the current study, the chemical composition of SOA from the photooxidation of isoprene over the full range of NO(x) conditions is investigated through a series of controlled laboratory chamber experiments. SOA composition is studied using a wide range of experimental techniques: electrospray ionization-mass spectrometry, matrix-assisted laser desorption ionization-mass spectrometry, high-resolution mass spectrometry, online aerosol mass spectrometry, gas chromatography/mass spectrometry, and an iodometric-spectroscopic method. Oligomerization was observed to be an important SOA formation pathway in all cases; however, the nature of the oligomers depends strongly on the NO(x) level, with acidic products formed under high-NO(x) conditions only. We present, to our knowledge, the first evidence of particle-phase esterification reactions in SOA, where the further oxidation of the isoprene oxidation product methacrolein under high-NO(x) conditions produces polyesters involving 2-methylglyceric acid as a key monomeric unit. These oligomers comprise approximately 22-34% of the high-NO(x) SOA mass. Under low-NO(x) conditions, organic peroxides contribute significantly to the low-NO(x) SOA mass (approximately 61% when SOA forms by nucleation and approximately 25-30% in the presence of seed particles). The contribution of organic peroxides in the SOA decreases with time, indicating photochemical aging. Hemiacetal dimers are found to form from C(5) alkene triols and 2-methyltetrols under low-NO(x) conditions; these compounds are also found in aerosol collected from the Amazonian rainforest, demonstrating the atmospheric relevance of these low-NO(x) chamber experiments.     

Absolute modelling of urban aerosol elemental composition by factor analysis

Data on the elemental composition of urban aerosols from a Danish city are treated by R-mode factor analysis to identify and quantify contributions from different sources. The analysis produced a 6-factor solution. If it is assumed that all sources contributing to the total suspended particulates were determined, absolute calculations of emission profiles and source contributions are possible.     

Essential oil composition of wild growing Apiaceae from Europe and the Mediterranean

In this overview, the essential oil composition of more than 150 species from about 50 genera of the Apiaceae is reviewed. Essential oil components encountered in Apiaceae proved to be very diverse; they include monoterpenes, sesquiterpenes, rarely diterpenes, phenylpropanoids, phthalides, octanol and octyl esters, trimethylbenzaldehydes and aliphatic aldehydes. In assessing the data one has to keep in mind that the essential oil amount and composition is influenced by many factors, including geographic and genetic variation, physiological aspects and environmental conditions. In some species the occurrence of chemotypes could be demonstrated, but in many cases the data available do not allow the evaluation of infraspecific variability.     

The lipid composition determines the kinetics of adhesion and spreading of liposomes on mercury electrodes

The dependence of membrane properties on their composition was studied by following the adhesion and spreading of unilamellar and multilamellar liposomes on static mercury electrodes with the help of chronoamperometry. The analysis of the peak-shaped signals allows determining the kinetic parameters of the three-step adhesion-spreading process. The presence of cholesterol in the membrane stabilizes the bilayer in the liquid-crystalline phase, and destabilizes the gel phase. The kinetic parameters also show the effect of superlattice formation in the DMPC-cholesterol system. The detergent triton X-100 is only incorporated in the liquid-crystalline DMPC membranes, and it is expelled to the solution when the membrane is transformed to the gel phase. In the liquid-crystalline membrane, it enhances the adhesion-spreading of liposomes on mercury. The lytic peptides mastoparan X and melittin affect the adhesion-spreading in a similar manner. For the rupture-spreading step, their effect is explained by pore formation. The results obtained with lecithins of different length suggest that the bilayer opening process has much in common with flip-flop translocations. For this process the activation energies were found to be independent of the chain length of the lecithin molecules, while the preexponential factor in the Arrhenius equation decreases drastically for longer chains.     

Change in the lipid composition of lichens in the spring period

The dynamics of the amount of total lipids, the ratio of the main classes of lipids, the amount of fatty acids, and the ratio of individual phospholipids in three epiphytic species of lichens from the Zhigulevsk reserve have been followed. It has been shown that all the classes of lipids of the lichens change to some degree or other in this period. The dynamics of the fatty acids has also confirmed a known rule: an increase in the amount of saturated and a decrease in the number of unsaturated fatty acids of the membranes with a rise in the temperature of the environment. This is the first time that the dynamics of the hydroxy acids have been followed.Institute of the Ecology of the Volga Basin, Tol'yatti. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 660–664, September–October, 1993.     

Change in the lipid composition of lichens in the spring period

The dynamics of the amount of total lipids, the ratio of the main classes of lipids, the amount of fatty acids, and the ratio of individual phospholipids in three epiphytic species of lichens from the Zhigulevsk reserve have been followed. It has been shown that all the classes of lipids of the lichens change to some degree or other in this period. The dynamics of the fatty acids has also confirmed a known rule: an increase in the amount of saturated and a decrease in the number of unsaturated fatty acids of the membranes with a rise in the temperature of the environment. This is the first time that the dynamics of the hydroxy acids have been followed.     

Analysis of anthropogenic and biogenic lipids in the aerosol of a coastal area in East Mediterranean Sea

Summary The concentrations of lipids were determined in atmospheric particle samples, collected seasonally, in an urban coastal area of the Island of Crete. Lipid compound classes, such as n-alkanes, hopanes and steranes, PAH, fatty alcohols, fatty acids and fatty acids selts, were determined by GC-FID and GC-MS analysis. The concentrations ranged between 56–215 ng/m³ for n-alkanes, 10–52 ng/m³ for PAH, 2–31 ng/m³ for fatty alcohols, 13–279 ng/m³ for fatty acids and 24–220 ng/m³ for fatty acid salts. -Oxocarboxylic acids were also determined as salts, indicating the atmospheric oxidation of unsaturated fatty acids.     

Determination of the chemical composition of the South Pole aerosol by instrumental neutron activation analysis

Atmospheric particulate samples were collected at the geographic South pole, using cellulose and polycarbonate filters and cascade impactors. The samples were analysed for 40 elements by instrumental neutron activation analysis. From the filter samples atmospheric concentrations for 33 elements could be obtained. The highest atmospheric concentrations were found for S: 49 ng/standard cubic meter (SCM) of air, Na: 3.3 ng/SCM and Cl: 2.6 ng/SCM. In the cascade impactor samples, only a few elements were observed above blank. For these elements it could be concluded that they are associated for over 80–90% with submicron size paricles.     

Observation of inhomogeneity in the lipid composition of individual nanoscale liposomes

Liposomes, or vesicles, have been studied extensively both as models of biological membranes and as drug delivery vehicles. Typically it is assumed that all liposomes within the same preparation are identical. Here by employing pairs of fluorescently labeled lipids we demonstrated an up to 10-fold variation in the relative lipid composition of individual liposomes with diameters between 50 nm and 15 μm. Since the physicochemical properties of liposomes are directly linked to their composition, a direct consequence of compositional inhomogeneities is a polydispersity in the properties of the individual liposomes in an ensemble.     

Determination of elemental composition of atmospheric aerosol in the urban area of Islamabad, Pakistan

Summary This study provides useful information about the level and chemical composition of particulate matter and about the possible sources of the aerosol pollutant in Islamabad, the capital of Pakistan. Atmospheric aerosol samples were collected during winter (January and February) 1995, from two locations of Islamabad, namely of Sector F-7 and Sector I-9. Twenty-four elements were detected by using thermal neutron activation analysis (NAA) and atomic absorption spectrometry (AAS). The concentration of total suspended particulates (TSP) in the area around the industrial sector (I-9) was found to be more than twice higher (297 μg/m³) than in the Sector F-7 (133 μg/m³). The enrichment factor analysis revealed Zn, As, Br, Sb, I and Pb, originated mainly from anthropogenic sources. The elemental ratio analysis indicated that both Sectors I-9 and F-7 are under the influence of coal burning processes whereas transportation is responsible for the toxic pollutants Pb and Br. The present results were discussed and compared with those of the literature. The results may also serve as base line level as this work employed samples collected in 1995 and many of the air environmental change factors occurred after the sampling year.     

Vapor-particle partitioning of hydrocarbons in Western Mediterranean urban and marine atmospheres

An analytical procedure is described for a comprehensive determination of the composition of hydrocarbons in the atmosphere, based on: (a) aerosol filtration and subsequent adsorption of the vapor phase onto active charcoal and polyurethane foam; (b) GPC and HPLC fractionation of the extracts, and (c) analysis of the fractions by GC-MS under EI and NICI modes. Special emphasis is placed onn-alkanes, PAHs and their oxygenated derivatives.The characterization of samples collected in a coastal urban area (Barcelona city), and far away over the Western Mediterranean, at sea level and at 1100 m of altitude, revealed significant changes in the aerosol composition, mainly attributed to initial vapor-particle partitioning processes, influenced by ambient temperature variations, and to others taking place during long-range atmospheric transport, related with the different compound photoreactivities and with an unexplained source-decoupling phenomenon.     

Secondary organic aerosol formation during the photooxidation of toluene: NOx dependence of chemical composition

The photooxidation of toluene is a potential source of secondary organic aerosol (SOA) in urban air, but only a small portion of the compounds present in SOA have been identified. In this study, we analyzed the chemical compositions of SOA produced by photoirradiation of the toluene/NOx/air system in laboratory chamber experiments by a combination of liquid chromatography-mass spectrometry, hybrid high-performance liquid chromatography-mass spectrometry, and iodometry-spectrophotometry. The dependence of the chemical composition on the initial NOx concentration was examined at initial NO concentrations ([NO]0) of 0.2 and 1 ppmv. Fifteen semivolatile products, including aromatic and ring-cleavage compounds, were quantified. However, the quantified products comprised only a small portion ( approximately 1 wt %) of the total aerosol mass. The total SOA yield ( approximately 13 wt %), the ratio of organic peroxides to total SOA mass ( approximately 17 wt %), and the density of SOA ( approximately 1.4 g cm-3) were independent of the NOx level, suggesting that the reaction mechanisms of the formation of major SOA products at [NO]0 = 0.2 and 1 ppmv are essentially the same. The negative-ion mass spectra of SOA samples showed that ion signals attributed to hemiacetal oligomers and/or decomposition products of peroxy hemiacetal oligomers were detected in the range of mass-to-charge ratios (m/z) between 200 and 500. The highest signals were detected at m/z = 155 and 177, and these were tentatively assigned to C7 unsaturated oxacyclic oxocarboxylic acids and C7 unsaturated oxacyclic dicarboxylic acids, respectively. We conclude that the major chemical components of the aerosol are hemiacetal and peroxy hemiacetal oligomers and low-molecular-weight dicarboxylic acids.     

Combined application of INAA and PIXE for studying the regional aerosol composition in Southern Africa

As part of the SAFARI-92 biomass buming experiment, aerosol collections were carried out with several size-fractionating sampling devices at a number of sites in Southern Africa. One of the samplers used at all ground-based sites was a stacked filter unit (SFU). The SFU samples were analyzed by both INAA and PIXE analysis. The present paper gives an intercomparison of the analytical results obtained in order to assess the accuracy and to check the quality assurance of the analytical procedures. Twenty-one common elements were determined by both INAA and PIXE. Concentrations of 13 elements (i.e., Na, Mg, Al, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Zn and Br) were generally measured with sufficient precision in both techniques for performing the intercomparison. The INAA and PIXE data were compared in terms of PIXE/INAA concentration ratios on a sample by sample basis for the coarse and fine size fraction separately. the atmospheric concentrations for K, Mn and Fe agreed within 5–10%, the agreement between the data for the other common elements was typically better than 15%. Possible explanations for lower than 1.0 ratios for Cl, Br and Na are presented. The common elements were classified into groups according to their detectability and sensitivity in each technique.     

Elemental composition of laser ablation aerosol particles deposited in the transport tube to an ICP

The element ratios in aerosol particles produced by laser ablation (λ=266 nm, pulse length: 5 ns) of brass and steel in Ar and He and deposited in different segments of the transport tube to an ICP have been measured by ICP-MS. The data are compared with the ratios obtained by a corresponding bulk analysis. For brass, the element compositions of the aerosol particles deposited in different parts of the tube deviated from the bulk and varied along the tube. For steel, moderate agreement of the element ratios in the aerosols and the bulk was found. It is also shown that elemental ratios measured on-line by laser ablation ICP-MS with the laser-produced aerosol should not be calibrated by elemental ratios obtained with wet aerosols from aqueous solutions of the bulk.