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Thermo-optical analysis is widely adopted for the quantitative determination of total, TC, organic, OC and elemental, EC, Carbon in aerosol samples collected on quartz fibre filters. Nevertheless, the methodology presents several issues in particular about the artefacts related to the formation of pyrolytic carbon. It is usually neglected the uncertainty due to the possible presence of brown carbon (BrC) in the sample under analysis, i.e. the optically active fraction of OC produced by biomass burning and with characteristics intermediate between OC and EC. We introduce here a novel correction to the standard thermo-optical protocol based on the determination of the fraction of the sample absorbance due to the (possible) presence of BrC. This is achievable thanks to the coupled use of the Multi Wavelength Absorbance Analyser (MWAA) of the University of Genoa and a standard Sunset Inc. EC/OC analyser. Our correction provides a firmer OC/EC separation as well as an operative quantification of the BrC mass. The methodology has been validated against independent determination of the levoglucosan content in the same filters sent to the Sunset analysis. Corrections up to 23% in the OC and EC values, determined via the standard and new thermo-optical analysis, have been found in a set of PM10 (i.e. Particulate Matter with aerodynamic diameter less than 10 μm) samples collected wintertime at a mountain site in Northern Italy.

In this paper, a new way to apportion the absorption coefficient (babs) of carbonaceous atmospheric aerosols starting from a multi-wavelength optical analysis is shown. This methodology can disentangle and quantify the contribution to total absorption of equivalent black carbon (EBC) emitted by wood burning (EBCWB) and fossil fuel (EBCFF) as well as brown carbon (BrC) due to incomplete combustion. The method uses the information gathered at five different wavelengths in a renewed and upgraded version of the approach usually referred to as Aethalometer model. Moreover, we present the results of an apportionment study of carbonaceous aerosol sources performed in a rural area and in a coastal city, both located in the North-West of Italy. Results obtained by the proposed approach are validated against independent measurements of levoglucosan and radiocarbon. At the rural site the EBCWB and EBCFF relative contributions are about 40% and 60% in winter and 15% and 85% in summer, respectively. At the coastal urban site, EBCWB and EBCFF are about 15% and 85% during fall. The OC contribution to the wood burning source at the rural site results approximately 50% in winter and 10% in summer and about 15% at the coastal urban site in fall. The new methodology also provides a direct measurement of the absorption Angstrom exponent of BrC (αBrC) which resulted αBrC = 3.95 ± 0.20.

Receptor and Chemical Transport Models are commonly used tools in source apportionment studies, even if different expertise is required. We describe an experiment using both approaches to apportion the PM2.5 (i.e., particulate matter with aerodynamic diameters below 2.5 μm) sources in the city of Genoa (Italy). A sampling campaign was carried out to collect PM2.5 samples daily for approximately six month during 2011 in three sites. The subsequent compositional analyses included the speciation of elements, major ions and both organic and elemental carbon; these data produced a large database for receptor modelling through Positive Matrix Factorisation (PMF). In the same period, a meteorological and air quality modelling system was implemented based on the mesoscale numerical weather prediction model WRF and the chemical transport model CAMx to obtain meteorological and pollutant concentrations up to a resolution of 1.1 km. The source apportionment was evaluated by CAMx over the same period that was used for the monitoring campaign using the Particulate Source Apportionment Technology tool. Even if the source categorisations were changed (i.e., groups of time-correlated compounds in PMF vs. activity categories in CAMx), the PM2.5 source apportionment by PMF and CAMx produced comparable results. The different information provided by the two approaches (e.g., real-world factor profile by PMF and apportionment of a secondary aerosol by CAMx) was used jointly to elucidate the composition and origin of PM2.5 and to develop a more general methodology. When studying the primary and secondary components of PM, the main anthropogenic sources in the area were road transportation, energy production/industry and maritime emissions, accounting for 40%–50%, 20%–30% and 10%–15%, of PM2.5, respectively.

The concentration of carbonates in atmospheric Particulate Matter (PM) is usually quite low. The surroundings of marble quarries are peculiar sites where the impact of carbonates in PM levels can be significant. We present here the results of a PM10 sampling campaign performed in Carrara (Italy). The town lies between the famous marble quarries and the harbour: about 1000 trucks per day transport marble blocks and debris from the quarries to the harbour passing through the town centre. PM10 was collected on daily basis on PTFE filters analyzed by Energy-Dispersive X-Ray Fluorescence (ED-XRF) and Ion-Chromatography (IC). Carbonate concentration was measured by a non-destructive Infrared Spectroscopy analysis (FT-IR). Time series of elemental (Na–Pb by ED-XRF), ionic (SO42−, NH4+ by ion-chromatography) and carbonate (by FT-IR) concentration values were merged in a unique data set and a PMF analysis singled out the major PM10 sources in the area. Marble transportation turned out to be the major pollution source in the town accounting to PM10 for about 36%; this corresponded to a CaCO3 average level of about 8 μg m−3 during working days. The FT-IR analysis was a crucial part of the work and an ad-hoc analytical procedure was specifically set up, calibrated, and tested as described in the text.

The particulate emissions near a large steel plant, located inside the town of Genoa (Italy) have been studied from May to December 1997. We have used two-stage continuous streaker samples and subsequent PIXE (particle-induced X-ray emission) analysis with hourly resolution, to follow both seasonal and daily trends. A first streaker sampler remained installed very close to the plant cokery and furnaces, while another sampler was moved to different locations in town. Samples were analysed by PIXE, deducing concentrations for elements from Na to Pb. We have always collected the PM10 fraction of the aerosol: during part of the campaign, the fine (PM2.5) and coarse (PM2.5–10) aerosol fractions have been also resolved. We have measured and analysed about 8500 PIXE spectra. The steel plant emissions have been identified and resolved from other aerosol sources using principal component analysis (PCA) and other statistical techniques. Finally, the impact of the steel smelter on its surrounding has been evaluated.