Original article can be found at: http://www.sciencedirect.com/science/journal/13522310 Copyright Elsevier Ltd. DOI : 10.1016/j.atmosenv.2007.12.010There is an increasing concern about the occurrence of polycyclic aromatic hydrocarbons (PAHs) in the environment as they are ubiquitous in ambient air and some of them are among the strongest known carcinogens. PAHs and their derivatives are produced by the incomplete combustion of organic material arising, partly, from natural combustion such as forest and volcanic eruption, but with the majority due to anthropogenic emissions. The PAH concentration varies significantly in various rural and urban environments and is mainly influenced by vehicular and domestic emissions. The review serves as a database to identify and characterize the emission sources of PAHs and hence various approaches including diagnostic ratio (DR) and principal component analysis (PCA) are discussed in detail. These approaches allow individual PAHs to be associated with their origin sources. The factors that effect PAH emission and estimated emission rate are also discussed in this paper. Although the levels of low molecular weight PAHs are high in vapor phase, most of the probable human carcinogenic PAHs are found to be associated with particulate matter, especially in fine mode particles in ambient air. Many countries have proposed a non-mandatory concentration limit for PAHs, whereas the health risk studies conducted in relation to PAH exposure, urge that these pollutants should be given a high priority when considering air quality management and reduction of impacts. r 2007 Elsevier Ltd. All rights reserved

Accumulation of platinum group elements (PGEs) in the environment has been increased over the time. Catalytic converters of modern vehicles are considered to be the main sources of PGE pollution, since the correlation is between the Pt:Rh ratios in various environmental compartments and in converter units. The present literature survey shows that the concentration of these metals has increased significantly in the last decades in diverse environmental matrices; like airborne particulate matter, soil, roadside dust and vegetation, river, coastal and oceanic environment. Generally, PGEs are referred to behave in an inert manner and to be immobile. However, there is an evidence of spread and bioaccumulation of these elements in the environment. Platinum content of road dusts can be soluble, consequently, it enters the waters, sediments, soil and finally, the food chain. The effect of chronic occupational exposure to Pt compounds is well-documented, and certain Pt species are known to exhibit allergenic potential. However, the toxicity of biologically available anthropogenic Pt is not clear. Hence, there is a need to study the effect on human health of long-term chronic exposure to low levels of Pt compounds.

[1] As part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA)-Cooperative LBA Airborne Regional Experiment (CLAIRE) 2001 campaign, separate day and nighttime aerosol samples were collected in July 2001 at a ground-based site in Amazonia, Brazil, in order to examine the composition and temporal variability of the natural ''background'' aerosol. A combination of analytical techniques was used to characterize the elemental and ionic composition of the aerosol. Major particle types larger than $0.5 mm were identified by electron and light microscopy. Both the coarse and fine aerosol were found to consist primarily of organic matter ($70 and 80% by mass, respectively), with the coarse fraction containing small amounts of soil dust and sea-salt particles and the fine fraction containing some non-sea-salt sulfate. Coarse particulate mass concentrations (CPM % PM 10 À PM 2 ) were found to be highest at night (average = 3.9 ± 1.4 mg m À3 , mean night-to-day ratio = 1.9 ± 0.4), while fine particulate mass concentrations (FPM % PM 2 ) increased during the daytime (average = 2.6 ± 0.8 mg m À3 , mean night-to-day ratio = 0.7 ± 0.1). The nocturnal increase in CPM coincided with an increase in primary biological particles in this size range (predominantly yeasts and other fungal spores), resulting from the trapping of surface-derived forest aerosol under a shallow nocturnal boundary layer and a lake-land breeze effect at the site, although active nocturnal sporulation may have also contributed. Associated with this, we observed elevated nighttime concentrations of biogenic elements and ions (P, S, K, Cu, Zn, NH 4 + ) in the CPM fraction. For the FPM fraction a persistently higher daytime concentration of organic carbon was found, which indicates that photochemical production of secondary organic aerosol from biogenic volatile organic compounds may have made a significant contribution to the fine aerosol. Dust and sea-salt-associated elements/ions in the CPM fraction, and non-sea-salt sulfate in the FPM fraction, showed higher daytime concentrations, most likely due to enhanced convective downward mixing of long-range transported aerosol.

Individual aerosol particles from the remote marine atmosphere were investigated by scanning electron microscopy and electron microprobe analysis. A large fraction of the silicate mineral component of the aerosol was found to be internally mixed with sea-salt aerosol particles. This observation explains the unexpected similarity in the size distributions of silicates and sea salt that has been observed in remote marine aerosols. Reentrainment of dust particles previously deposited onto the sea surface and collision between aerosol particles can be excluded as possible source mechanisms for these internally mixed aerosols. The internal mixing could be produced by processes within clouds, including droplet coalescence. Cloud processes may also be responsible for the observed enrichment of excess (nonsea-salt) sulfate on sea-salt particles.

As a part of the NASA Global Tropospheric Experiment (GTE), aerosols were sampled in the tropical rain forest of the Amazon Basin during the Amazon Boundary Layer Experiment (ABLE 2B) in April and May 1987, in the wet season, when no forest burning occurs. Fine (dp < 2.0 μm) and coarse (2.0 < dp < 15 μm) aerosol fractions were collected using stacked filter units, at three sites under the forest canopy and at three levels of a tower inside the jungle. Particle‐induced X ray emission (PIXE) was used to measure concentrations of 22 elements (Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, Zr, and Pb). Morphological and trace element measurements of individual particles were carried out by automated electron probe X ray microanalysis. Gravimetric analysis was performed to obtain the fine and coarse aerosol mass concentration. Absolute factor analysis was used to interpret the large data set of the trace element concentrations and to obtain elemental source profiles. Hierarchical cluster analysis was used to derive groups of individual particles. The concentrations of soil dust related elements (Al, Si, Ti, Fe, Mn) were 5 times larger in the wet season compared to the 1985 ABLE 2A dry season experiment. Biogenic aerosol related elements in the fine fraction showed lower concentrations in the wet season. Fine aerosol mass concentration averaged only 2.1±0.7 μg m−3, while the average coarse mass concentration was 6.1±1.8 μg m −3. Sulphur concentrations averaged 76±14 ng m −3 in the fine fraction and 37±9 ng m −3 in the coarse fraction. Biogenic aerosol‐related elements were dominant under the forest canopy, while soil dust dominated at the top of the forest canopy. Only two factors explained about 90% of the data variability for the fine and coarse aerosol fractions. These were soil dust (represented mainly by Al, Si, Ti, Mn, and Fe) and biogenic aerosol (represented by K, P, Cl, S, Zn, and the aerosol mass concentration). Source profiles showed a homogeneous aerosol distribution with similar elemental compositions at the different sampling sites. Enrichment factor calculations revealed a soil dust elemental profile similar to the average bulk soil composition, and a biogenic component similar to the plant bulk elemental composition. Total aerosol mass source apportionment showed that biogenic particles account for 55–95% of the airborne concentrations. The analysis of individual aerosol particles showed that the biogenic particles consist of leaf fragments, pollen grains, fungi, algae, and other types of particles. Several groups of particles with K, Cl, P, S, and Ca as minor elements could easily be identified as biogenic particles on the basis of their morphology. Considering the vast area of tropical rain forests and the concentrations measured in this work, it is possible that biogenic particles can play an important role in the global aerosol budget and in the global biogeochemical cycles of various elements.

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The advances in the characterization of amorphous carbons by Raman spectroscopy over the last four decades are of interest to many industries, especially those involving the combustion, gasification and pyrolysis of coal. Many researchers report on the Raman character of the natural organic matter in carbon-containing compounds, such as coal, and relate the Raman bands to the structural order of the amorphous carbons. The basis of most of these studies evolved around the assignment of the G (graphitic, ∼1580 cm −1 ) band to crystalline graphite and any other bands, called D bands, (disorder, various from 1100 to 1500 cm −1 ) to any type of structural disorder in the graphitic structure. Concerning coal analysis, the information gained by Raman investigations has been used to describe char evolution as a function of temperature, the presence of catalysts and different gasification conditions. In addition, researchers looked at maturation, grade, doppleritization and many more aspects of interest. One aspect that has, however, not been addressed by most of the researchers is the natural inorganic matter (NIM) in the carbon-containing compounds. Micro-Raman spectroscopy (MRS) has many advantages over other characterization tools, i.e. in situ analysis, nondestructive, no sample preparation, low detection limit, micrometer-scale characterization, versatility and sensitivity to many amorphous compounds. With the distinct advantages it has over that of other molecular characterization tools, such as powder X-ray diffraction (PXRD), Fourier-transform infrared spectrometry (FT-IR) and scanning electron microscopy with X-ray detection (SEM/EDS), it is surprising that it has not yet been fully exploited up to this point for the characterization of the NIM in coal and other amorphous carbons. This paper reviews the work published on the Raman characterization of the natural organic matter (NOM) of coals and reports on preliminary results of the NIM character of various South African coals, whereby various inorganic compounds and minerals in the coal have been characterized.

The determination of low-Z elements such as carbon, nitrogen, and oxygen in atmospheric aerosol particles is of interest in studying environmental pollution. Conventional electron probe microanalysis technique has a limitation for the determination of the low-Z elements, mainly because the Be window in an energy-dispersive X-ray (EDX) detector hinders the detection of characteristic X-rays from light elements. The feasibility of low-Z element determination in individual particles using a windowless EDX detector is investigated. To develop a method capable of identifying chemical species of individual particles, both the matrix and the geometric effects of particles have to be evaluated. X-rays of low-Z elements generated by an electron beam are so soft that important matrix effects, mostly due to X-ray absorption, exist even within particles in the micrometer size range. Also, the observed radiation, especially that of light elements, experiences different extents of absorption, depending on the shape and size of the particles. Monte Carlo calculation is applied to explain the variation of observed X-ray intensities according to the geometric and chemical compositional variation of individual particles, at different primary electron beam energies. A comparison is carried out between simulated and experimental data, collected for standard individual particles with chemical compositions as generally observed in marine and continental aerosols. Despite the many fundamental problematic analytical factors involved in the observation of X-rays from low-Z elements, the Monte Carlo calculation proves to be quite reliable to evaluate those matrix and geometric effects. Practical aspects of the Monte Carlo calculation for the determination of light elements in individual particles are also considered.