M. Giannoni

The use of levoglucosan for tracing biomass burning in PM2.5 samples in Tuscany (Italy)

Levoglucosan was present in all samples and its concentrations showed a pronounced annual cycle with maximum levels in the cold season. The annual percentage of ratios of levoglucosan to OC ranged from 0.04 to 9.75% evidencing a major contribution of biomass burning to the aerosol OC during the winter. In the urban-background site, OC was strongly correlated with EC in winter, suggesting that the major fraction of OC was generated as primary particles along with EC. A background levoglucosan component showed that biomass burning was continuously taking place in all the investigated sites. The biomass burning contribution to the Tuscany aerosol was made up of a background component and an additional component during winter probably due to wood burning for domestic heating.

The contribution of waste water treatment plants to PBDEs in ambient air

Air samples were collected at different sites in and around two wastewater treatment plants (WWTPs) located in central Italy to determine the concentrations, compositional profiles and contribution to ambient levels of eight polybrominated diphenyl ethers (PBDEs). The investigated WWTPs were selected as they treat industrial wastewater produced by local textile industries along with municipal wastewater. PBDE concentrations within the WWTPs were higher than those measured at reference sites located 4 and 5 km away with BDE-209 dominating the BDE congener composition in all air samples in 2008. Ambient PBDE concentrations measured in and around the WWTPs and estimates of emissions from aeration tanks suggest that WWTPs are sources of PBDEs to ambient air. Principal component analysis and Pearson correlations confirmed this result. The effect of distance from the plant and wind direction on atmospheric concentrations was also investigated. Although the primary fate of PBDEs in WWTPs will be partitioning to sewage sludge, this study suggests that plants can provide a measurable source of these compounds to local ambient air.

Biomass burning contributions estimated by synergistic coupling of daily and hourly aerosol composition records

Biomass burning (BB) is a significant source of particulate matter (PM) in many parts of the world. Whereas numerous studies demonstrate the relevance of BB emissions in central and northern Europe, the quantification of this source has been assessed only in few cities in southern European countries. In this work, the application of Positive Matrix Factorisation (PMF) allowed a clear identification and quantification of an unexpected very high biomass burning contribution in Tuscany (central Italy), in the most polluted site of the PATOS project. In this urban background site, BB accounted for 37% of the mass of PM10 (particulate matter with aerodynamic diameter<10 μm) as annual average, and more than 50% during winter, being the main cause of all the PM10 limit exceedances. Due to the chemical complexity of BB emissions, an accurate assessment of this source contribution is not always easily achievable using just a single tracer. The present work takes advantage of the combination of a long-term daily data-set, characterized by an extended chemical speciation, with a short-term high time resolution (1-hour) and size-segregated data-set, obtained by PIXE analyses of streaker samples. The hourly time pattern of the BB source, characterised by a periodic behaviour with peaks starting at about 6 p.m. and lasting all the evening-night, and its strong seasonality, with higher values in the winter period, clearly confirmed the hypothesis of a domestic heating source (also excluding important contributions from wildfires and agricultural wastes burning).

A comparison between thermal-optical transmittance elemental carbon measured by different protocols in PM2.5 samples

Although controlled procedures for the determination of carbonaceous fractions are of importance for any air quality measurements, currently no reference method for elemental carbon (EC) and organic carbon (OC) analysis is established yet in Europe. The implementation of the different thermal evolution protocols available in the literature, differing in temperature and duration of the heating ramps, affects the results and can result in a wide variation of EC and OC values. In this study three different protocols for thermal-optical-transmittance analysis of EC and OC were compared, namely He-870 (a variation of the NIOSH protocol), He-550 (a proxy of the IMPROVE protocol), and EUSAAR_2. Measurements were carried out on PM2.5 samples collected on Quartz fibre filters in three sites of different typology: urban background and urban traffic in Florence (Italy) and regional background in Livorno (Italy). The samples were analysed before and after a washing procedure to remove possible water-soluble organic compounds (WSOC), which may enhance the charring process, complicating the EC quantification. This study evidenced a very good agreement for TC measurement (at 2-3% level) and some discrepancies in EC measurement (up to 40%), as expected. WSOC and Pyrolitic Carbon (PyC) present a good correlation, independently of site typology, demonstrating that water soluble compound can be responsible of charring mechanism during the He phase.