A combined chemical/size fractionation approach to study winter/summer variations, ageing and source strength of atmospheric particles.

We studied the size distribution of ions (Cl-, NO3-, SO4=, Na+, NH4+, K+, Mg++, Ca++) and elements (As, Ba, Cd, Co, Cs, Cu, Fe, Li, Mn, Ni, Pb, Rb, Sb, Se, Sn, Sr, Ti, Tl, V, Zn) during the winter and summer seasons of seven consecutive years (2008-2014) in an area of the Po Valley (Northern Italy) characterised by industrial, agricultural and urban settings. The study included the collection and analysis of 41 series of size-segregated samples (MOUDI sampler, 10 stages, cut sizes from 0.18 to 18 µm). Ions were analysed by ion chromatography; elemental analysis was carried out by ICP-MS, by applying a chemical fractionation method able to increase the selectivity of PM source tracers. Our results indicate that important winter/summer variations occurred in both the concentration and size distribution of most PM components. These variations were explained in terms of variations in the strength of the prevailing sources of each component. The contribution of biomass burning for domestic heating was highlighted by the well-known tracer K+ but also by the soluble fraction of Rb, Cs and Li. Biomass burning contribution to atmospheric PM was mostly contained in the fine fraction, with a broad size-distribution from 0.18 to 1.8 µm. This source also appreciably increased the concentration of other elements in fine PM (As, Cd, Co, Mn, Pb, Sb, Sn). A few PM components (tracers of sea-spray, brake lining and some industries) did not show marked seasonal variations in concentration and size distribution. However, during winter, for brake lining and industry tracers we observed an upward shift in the dimension of fine particles and a downward shift in the dimension of coarse particles, due to the ageing of the air masses.

Seasonal variations in the chemical composition of particulate matter: a case study in the Po Valley. Part I: macro-components and mass closure.

The seasonal variability in the mass concentration and chemical composition of atmospheric particulate matter (PM10 and PM2.5) was studied during a 2-year field study carried out between 2010 and 2012. The site of the study was the area of Ferrara (Po Valley, Northern Italy), which is characterized by frequent episodes of very stable atmospheric conditions in winter. Chemical analyses carried out during the study allowed the determination of the main components of atmospheric PM (macro-elements, ions, elemental carbon, organic matter) and a satisfactory mass closure was obtained. Accordingly, chemical components could be grouped into the main macro-sources of PM: soil, sea spray, inorganic compounds from secondary reactions, vehicular emission, organics from domestic heating, organics from secondary formation, and other sources. The more significant seasonal variations were observed for secondary inorganic species in the fine fraction of PM; these species were very sensitive to air mass age and thus to the frequency of stable atmospheric conditions. During the winter ammonium nitrate, the single species with the highest concentration, reached concentrations as high as 30 µg/m(3). The intensity of natural sources was fairly constant during the year; increases in natural aerosols were linked to medium and long-range transport episodes. The ratio of winter to summer concentrations was roughly 2 for combustion product, close to 3 for secondary inorganic species, and between 2 and 3 for organics. The winter increase of organics was due to poorer atmospheric dispersion and to the addition of the emission from domestic heating. A similar winter to summer ratio (around 3) was observed for the fine fraction of PM.

Determination of soluble ions and elements in ambient air suspended particulate matter: Inter-technique comparison of XRF, IC and ICP for sample-by-sample quality control.

In this paper, we describe a validation procedure for chemical fractionation analysis of elements (Al, As, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, S, Sb, Si, Sr, Ti and V) and soluble ions (Cl(-), NO(3)(-), SO(4)(2-), Na(+), NH(4)(+), Mg(2+), Ca(2+)) in suspended particulate matter (PM). The procedure applies three distinct measurement techniques (XRF, IC and ICP-OES) to the analysis of individual samples. The techniques used generate different outputs at different stages in the procedure. This makes it possible to identify the contributions of specific parameters to measurement uncertainty. On this basis, we propose a scheme for controlling the analytical quality of data from individual samples in which inter-technique comparisons is used in the same way many analytical methods use surrogates. We apply this scheme to about 310 samples of PM(10) and PM(2.5) identifying and assessing the main factors contributing to measurement uncertainty. This procedure successfully resolved a number of difficulties frequently encountered during the analysis of PM, including lack of appropriate reference materials and the low reliability of alternative techniques of quality control. The results demonstrate the critical importance of sample treatment prior to destructive analysis by IC and ICP.

Characterisation of gaseous and particulate atmospheric pollutants in the East Mediterranean by diffusion denuder sampling lines.

A field study aimed to characterize atmospheric pollutants in the gaseous and the particulate phases was conducted during the fall-winter of 2004 and the summer of 2005 in the Ashdod area, Israel. The site is influenced by both anthropogenic sources (power plants, refineries, chemical and metal industries, a cargo port, road traffic) and natural sources (sea-spray and desert dust). The use of diffusion lines--a series of annular diffusion denuders for sampling gaseous compounds followed by a cyclone and a filter pack for determining PM(2.5) composition--allowed a good daily characterization of the main inorganic compounds in both the gaseous (HCl, HNO(3), SO(2), NH(3)) and the particulate phase (Cl(-), NO(3)(-), SO(4)(=), NH(4)(+), and base cations). During the summer campaign two other activities were added: an intensive 3-h sampling period and the determination of PM(2.5) bulk composition. The results were interpreted on the basis of meteorological condition, especially the mixing properties of the lower atmosphere as determined by monitoring the natural radioactivity due to Radon progeny, a good proxy of the atmospheric ability to dilute pollutants. Several pollution episodes were identified and the predominance of different sources was highlighted (sea-spray, desert dust, secondary photochemical pollutants). During the summer period a considerable increase of nitric acid and particulate sulphate was observed. Secondary inorganic pollutants (nitrate, sulphate and ammonium) constituted, on the average, 57% of the fine particle fraction, organic compounds 20%, primary anthropogenic compounds 14%, natural components (sea-spray and crustal elements) 9%. The advantages of the diffusion lines in determining gaseous and particulate N- and S- inorganic compounds are discussed.

Inorganic constituents of urban air pollution in the Lazio region (Central Italy).

A field study was carried out at six locations in the Lazio region (Central Italy) aimed at characterising atmospheric particulate matter (PM10 and PM2.5) from the point of view of the chemical composition and grain size distribution of the particles, the mixing properties of the atmosphere, the frequency and relevance of natural events. The combination of four different analytical techniques (ion chromatography, X-ray fluorescence and ICP for inorganic components, thermo-optical analysis for carbon compounds) yielded sound results in terms of characterisation of the air masses. During the first three months of the study (October-December 2004), many pollution events of natural (sea-salt or desert dust episodes) or anthropogenic nature were identified and characterised. More than 90% of the collected mass was identified by chemical analysis. The central role played by the mixing properties of the lower atmosphere when pollution events occurred was highlighted. The results show a major impact of primary anthropogenic pollutants on traffic stations and a homogeneous distribution of secondary pollutants over the regional area. An evaluation of the sources of PM and an identification of possible reliable tracers were obtained using a chemical fractionation procedure.

Inorganic constituents of urban air pollution in the Lazio region (Central Italy).

A field study was carried out at six locations in the Lazio region (Central Italy) aimed at characterising atmospheric particulate matter (PM10 and PM2.5) from the point of view of the chemical composition and grain size distribution of the particles, the mixing properties of the atmosphere, the frequency and relevance of natural events. The combination of four different analytical techniques (ion chromatography, X-ray fluorescence and ICP for inorganic components, thermo-optical analysis for carbon compounds) yielded sound results in terms of characterisation of the air masses. During the first three months of the study (October-December 2004), many pollution events of natural (sea-salt or desert dust episodes) or anthropogenic nature were identified and characterised. More than 90% of the collected mass was identified by chemical analysis. The central role played by the mixing properties of the lower atmosphere when pollution events occurred was highlighted. The results show a major impact of primary anthropogenic pollutants on traffic stations and a homogeneous distribution of secondary pollutants over the regional area. An evaluation of the sources of PM and an identification of possible reliable tracers were obtained using a chemical fractionation procedure.