Abstract: The molecular character of atmospheric particulate matter is of prime importance when interpreting air pollution trends and its subsequent influence on environmental monitoring and preventative conservation. The known methods of estimating the molecular composition normally involve elemental analysis of particles (both as bulk and computer controlled analyses of single particles) with subsequent multivariate analyses to clusterise the elements in groups of elements that are closely related to each other. With this approach one can at best suggest associations. Evidently the application of molecular spectroscopy in addition to elemental concentration profiles would provide intimate information regarding the nature of the particles and consequently their fate. This paper gives an overview of research performed in our laboratory and describes the optimisation of experimental parameters to use scanning electron microscopy with energy-dispersive X-ray detection (SEM/EDX) or electron probe X-ray microanalysis (EPXMA) in parallel with micro-Raman Spectrometry (MRS) to investigate single environmental particles. The challenges associated with the two stand-alone techniques are revealed and consequently those posed with an interfaced approach are discussed. Preliminary results, of an initial investigation of the SEM/EDX interfaced with MRS to ultra-fine heterogeneous environmental particles, are given.

Abstract: The promotion of good indoor air quality in schools is of particular public concern for two main reasons: (1) school-age children spend at least 30% of their time inside classrooms and (2) indoor air quality in urban areas is substantially influenced by the outdoor pollutants, exposing tenants to potentially toxic substances. Two schools in Curitiba, Brazil, were selected to characterize the gaseous compounds indoor and outdoor of the classrooms. The concentrations of benzene, toluene, ethylbenzene, and the isomers xylenes (BTEX); NO2; SO2; O3; acetic acid (HAc); and formic acid (HFor) were assessed using passive diffusion tubes. BTEX were analyzed by gas chromatographyion trap mass spectrometry and other collected gasses by ion chromatography. The concentration of NO2 varied between 9.5 and 23 µg m−3, whereas SO2 showed an interval from 0.1 to 4.8 µg m−3. Within the schools, BTEX concentrations were predominant. Formic and acetic acids inside the classrooms revealed intermediate concentrations of 1.5 µg m−3 and 1.2 µg m−3, respectively.

Abstract: Iron (Fe) and other trace elements such as Zn, Mn, Ni and Cu are known as key-factors in marine biogeochemical cycles. It is believed that ocean primary productivity blooms in iron deficient regions can be triggered by iron in aeolian dust. Up to now, scarce aerosol elemental composition, based on measurements over sea at the Western South Atlantic (WSA), exist. An association between the Patagonian semi-desert dust/Fe and chlorophyll-a variability at the Argentinean continental shelf is essentially inferred from models. We present here experimental data of Fe enriched aerosols over the WSA between latitudes 22°S62°S, during 4 oceanographic campaigns between 2002 and 2005. These data allowed inferring the atmospheric Fe flux onto different latitudinal bands which varied from 30.4 to 1688 nmolFe m−2 day−1 (October 29thNovember 15th, 2003); 5.831586 nmolFe m−2 day−1 (February 15thMarch 6th, 2004) and 4.73586 nmolFe m−2 day−1(October 21stNovember 5th, 2005).

Abstract: Thoracic (PM10), fine thoracic (PM2.5) and sub-micrometer (PM1) airborne particulate matter was sampled during day and night. In total, about 100 indoor and outdoor samples were collected for each fraction at ten different office environments. Energy-dispersive X-ray fluorescence spectrometry and ion chromatography were applied for the quantification of some major and minor elements and ions in the collected aerosols. During daytime, mass concentrations were in the ranges: 1129, 8.124, and 6.618 μg m−3, with averages of 20 ± 1, 15.0 ± 0.9, and 11.0 ± 0.8 μg m−3, respectively. At night, mass concentrations were found to be significantly lower for all fractions. Indoor PM1 concentrations exceeded the corresponding outdoor levels during office hours and were thought to be elevated by office printers. Particles with diameters between 1 and 2.5 μm and 2.5 and 10 μm were mainly associated with soil dust elements and were clearly subjected to distinct periods of settling/resuspension. Indoor NO3 − levels were found to follow specific microclimatic conditions at the office environments, while daytime levels of sub-micrometer Cl− were possibly elevated by the use of Cl-containing cleaning products. Indoor carbon black concentrations were sometimes as high as 22 μg m−3 and were strongly correlated with outdoor traffic conditions.

Abstract: Marine aerosols have extensively been monitored in the framework of a research project to investigate the inorganic and organic nutrient fluxes of the atmospheric nitrogen input into the North Sea. As a part of this project bulk analysis was also performed by energy dispersive X-ray fluorescence (EDXRF) on a total of 366 samples in order to provide detailed elemental composition. Samples have been clustered per campaign and differences were related to backward trajectories. Elements as Cl, Si, and S appeared to be the best tracers for coastal aerosols. Therefore they have been chosen to represent each campaign and to map the seasonal variations. It is clear that Cl is an excellent tracer for oceanic trajectories, while a less clear correlation between the soil dust components and the air mass trajectories is found.

Abstract: Several specimens of Libyan desert glass (LDG), an enigmatic natural glass from Egypt, were subjected to investigation by micro-Raman spectroscopy. The spectra of inclusions inside the LDG samples were successfully measured through the layers of glass and the mineral species were identified on this basis. The presence of cristobalite as typical for high-temperature melt products was confirmed, together with co-existing quartz. TiO2 was determined in two polymorphic species rutile and anatase. Micro-Raman spectroscopy proved also the presence of minerals unusual for high-temperature glasses such as anhydrite and aragonite.

Abstract: The present paper synthesizes data obtained during a multidisciplinary cruise carried out in June 2004 at the continental margin of the northern Bay of Biscay. The data-set allows to describe the different stages of a coccolithophore bloom dominated by Emiliania huxleyi. The cruise was carried out after the main spring phytoplankton bloom that started in mid-April and peaked in mid-May. Consequently, low phosphate (PO4 < 0.2 μM) and silicate (DSi < 2.0 μM) concentrations, low partial pressure of carbon dioxide (pCO2) and high calcite saturation degree in surface waters combined with thermal stratification, probably favoured the blooming of coccolithophores. During the period of the year our cruise was carried out, internal tides induce enhanced vertical mixing at the continental shelf break leading to the injection of inorganic nutrients to surface waters that probably trigger the bloom. The bloom developed as the water-column stratified and as the water mass was advected over the continental shelf, following the general residual circulation in the area. The most developed phase of the bloom was sampled in a remote sensed high reflectance (HR) patch over the continental shelf that was characterized by low chlorophyll-a (Chl-a) concentration in surface waters (<1.0 μg L−1), high particulate inorganic carbon (PIC) concentration (not, vert, similar8 μmol L−1) and coccolithophore abundance up to 57 × 106 cells L−1. Transparent exopolymer particles (TEP) concentrations ranged between 15 and 75 μg C L−1 and carbon content of TEP represented up to 26% of the particulate organic carbon (POC; maximum concentration of 15.5 μmol L−1 in the upper 40 m). Integrated primary production (PP) ranged between 210 and 680 mg C m−2 d−1 and integrated calcification (CAL) ranged between 14 and 140 mg C m−2 d−1, within the range of PP and CAL values previously reported during coccolithophore blooms in open and shelf waters of the North Atlantic Ocean. Bacterial protein production (BPP) measurements in surface waters (0.30.7 μg C L−1 h−1) were much higher than those reported during early phases of coccolithophore blooms in natural conditions, but similar to those during peak and declining coocolithophorid blooms reported in mesocosms. Total alkalinity anomalies with respect to conservative mixing (ΔTA) down to −49 μmol kg−1 are consistent with the occurrence of biogenic precipitation of calcite, while pCO2 remained 15107 μatm lower than atmospheric equilibrium (372 μatm). The correlation between ΔTA and pCO2 suggested that pCO2 increased in part due to calcification, but this increase was insufficient to overcome the background under-saturation of CO2. This is related to the biogeochemical history of the water masses due to net carbon fixation by the successive phytoplankton blooms in the area prior to the cruise, hence, the investigated area remained a sink for atmospheric CO2 despite calcification.

Abstract: The results of Chemkar PM10, the first large scale chemical characterisation project of PM10 in Flanders are presented. Between September 2006 and September 2007 a total of 365 PM10 samples were collected by sampling every sixth day at six different sites in Flanders (Belgium) varying in character from urban background to rural. Samples were analysed for a series of elements, elemental and organic carbon, 13C/12C- and 15N/14N-isotopic ratios, and water-soluble ions. At three sites extra sampling was carried out to determine PAHs by means of a novel technique that uses sorption tubes consisting of polydimethylsiloxane (PDMS) foam, PDMS particles and a TENAX TA bed. Results showed that the most important fractions were secondary inorganic ions (nitrate, sulphate and ammonium): 41% (12.6 μg m−3), organic matter: 20% (6.1 μg m−3), crustal matter: 14% (4.3 μg m−3), sea salt: 8% (2.4 μg m−3) and elemental carbon: 4% (1.2 μg m−3). Although the general composition profile was rather similar for the six sites, substantial differences could be observed for some main components and for several trace metals such as chromium, copper, zinc, arsenic and lead. Although the average sum of the PAH 16 was quite variable between the three sites (between 132 and 248 ng m−3) the average sum of the PAH 7 was between 7 and 9 ng m−3 for the three sites. The largest relative differences between sites were found for elemental carbon and crustal matter, thereby indicating that there is some potential for local measures to reduce the concentrations of particulate matter by a few μg m−3. Both for carbon and nitrogen isotopic ratios significant differences in time were observed. Isotopic differences in location could only be detected for carbon.

Abstract: 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.