Seasonal and Spatial Variations of the Oxidative Properties of Ambient PM2.5 in the Po Valley, Italy, before and during COVID-19 Lockdown Restrictions.

This study describes the chemical and toxicological characteristics of fine particulate matter (PM2.5) in the Po Valley, one of the largest and most polluted areas in Europe. The investigated samples were collected in the metropolitan area of Milan during the epidemic lockdown and their toxicity was evaluated by the oxidative potential (OP), measured using ascorbic acid (OPAA) and dithiothreitol (OPDTT) acellular assays. The study was also extended to PM2.5 samples collected at different sites in the Po Valley in 2019, to represent the baseline conditions in the area. Univariate correlations were applied to the whole dataset to link the OP responses with the concentrations of the major chemical markers of vehicular and biomass burning emissions. Of the two assays, OPAA was found mainly sensitive towards transition metals released from vehicular traffic, while OPDTT towards the PM carbonaceous components. The impact of the controlling lockdown restrictions on PM2.5 oxidative properties was estimated by comparing the OP values in corresponding time spans in 2020 and 2019. We found that during the full lockdown the OPAA values decreased to 80-86% with respect to the OP data in other urban sites in the area, while the OPDTT values remained nearly constant.

Seasonal and Spatial Variations of PM10 and PM2.5 Oxidative Potential in Five Urban and Rural Sites across Lombardia Region, Italy.

Oxidative potential (OP) of particulate matter (PM) is gaining strong interest as a promising health exposure metric. This study investigated OP of a large set of PM10 and PM2.5 samples collected at five urban and background sites near Milan (Italy), one of the largest and most polluted urban areas in Europe, afflicted with high particle levels. OP responses from two acellular assays, based on ascorbic acid (AA) and dithiothreitol (DTT), were combined with atmospheric detailed composition to examine any possible feature in OP with PM size fraction, spatial and seasonal variations. A general association of volume-normalized OP with PM mass was found; this association may be related to the clear seasonality observed, whereby there was higher OP activity in wintertime at all investigated sites. Univariate correlations were used to link OP with the concentrations of the major chemical markers of vehicular and biomass burning emissions. Of the two assays, AA was particularly sensitive towards transition metals in coarse particles released from vehicular traffic. The results obtained confirm that the responses from the two assays and their relationship with atmospheric pollutants are assay- and location-dependent, and that their combination is therefore helpful to singling out the PM redox-active compounds driving its oxidative properties.

Results of an interlaboratory comparison of analytical methods for quantification of anhydrosugars and biosugars in atmospheric aerosol.

An interlaboratory comparison was performed to evaluate the analytical methods for quantification of anhydrosugars - levoglucosan, mannosan, galactosan - and biosugars - arabitol, glucose and mannitol - in atmospheric aerosol. The performance of 10 laboratories in Italy currently involved in such analyses was investigated on twenty-six PM (particulate matter) ambient filters, three synthetic PM filters and three aqueous standard solutions. An acceptable interlaboratory variability was found, determined as the mean relative standard deviation (RSD%) of the results from the participating laboratories, with the mean RSD% values ranging from 25% to 46% and decreasing with increasing sugar concentration. The investigated methods show good accuracy, evaluated as the percentage error (ε%) related to mean values, since method biases ranged within ±20% for most of the analytes measured in the different laboratories. The detailed investigation (ANOVA analysis at p < 0.05) of the contribution of each laboratory to the total variability and the measurement accuracy shows that comparable results are generated by the different methods, despite the great diversity in terms of extraction conditions, chromatographic separation - more recent LC (liquid chromatography) and EC (exchange chromatography) methods compared to more widespread GC (gas chromatography) - and detection systems, namely PAD (pulsed amperometric detection) or mass spectrometry.