Characterisation of the correlations between oxidative potential and in vitro biological effects of PM10 at three sites in the central Mediterranean.

Atmospheric particulate matter (PM) is one of the major risks for global health. The exact mechanisms of toxicity are still not completely understood leading to contrasting results when different toxicity metrics are compared. In this work, PM10 was collected at three sites for the determination of acellular oxidative potential (OP), intracellular oxidative stress (OSGC), cytotoxicity (MTT assay), and genotoxicity (Comet assay). The in vitro tests were done on the A549 cell line. The objective was to investigate the correlations among acellular and intracellular toxicity indicators, the variability among the sites, and how these correlations were influenced by the main sources by using PMF receptor model coupled with MLR. The OPDTTV, OSGCV, and cytotoxicity were strongly influenced by combustion sources. Advection of African dust led to lower-than-average intrinsic toxicity indicators. OPDTTV and OSGCV showed site-dependent correlations suggesting that acellular OP may not be fully representative of the intracellular oxidative stress at all sites and conditions. Cytotoxicity correlated with both OPDTTV and OSGCV at two sites out of three and the strength of the correlation was larger with OSGCV. Genotoxicity was correlated with cytotoxicity at all sites and correlated with both, OPDTTV and OSGCV, at two sites out of three. Results suggest that several toxicity indicators are useful to gain a global picture of the potential health effects of PM.

Concentration and size distribution of atmospheric particles in southern Italy during COVID-19 lockdown period.

Many countries imposed lockdown (LD) to limit the spread of COVID-19, which led to a reduction in the emission of anthropogenic atmospheric pollutants. Several studies have investigated the effects of LD on air quality, mostly in urban settings and criteria pollutants. However, less information is available on background sites, and virtually no information is available on particle number size distribution (PNSD). This study investigated the effect of LD on air quality at an urban background site representing a near coast area in the central Mediterranean. The analysis focused on equivalent black carbon (eBC), particle mass concentrations in different size fractions: PM2.5 (aerodynamic diameter Da < 2.5 µm), PM10 (Da < 10 µm), PM10-2.5 (2.5 < Da < 10 µm); and PNSD in a wide range of diameters (0.01-10 µm). Measurements in 2020 during the national LD in Italy and period immediately after LD (POST-LD period) were compared with those in the corresponding periods from 2015 to 2019. The results showed that LD reduced the frequency and intensity of high-pollution events. Reductions were more relevant during POST-LD than during LD period for all variables, except quasi-ultrafine particles and PM10-2.5. Two events of long-range transport of dust were observed, which need to be identified and removed to determine the effect of LD. The decreases in the quasi-ultrafine particles and eBC concentrations were 20%, and 15-22%, respectively. PM2.5 concentration was reduced by 13-44% whereas PM10-2.5 concentration was unaffected. The concentration of accumulation mode particles followed the behaviour of PM2.5, with reductions of 19-57%. The results obtained could be relevant for future strategies aimed at improving air quality and understanding the processes that influence the number and mass particle size distributions.

Inter-annual variability of source contributions to PM10, PM2.5, and oxidative potential in an urban background site in the central mediterranean.

Airborne particulate matter (PM) is studied because of its effects on human health and climate change. PM long-term characterisation allows identifying trends and evaluating the outcomes of environmental protection policies. This work is aimed to study the inter-annual variability of PM2.5 and PM10 concentrations and chemical composition in an urban background site (Italy). A dataset of daily PM2.5 and PM10 was collected in the period 2016-2017, including the content of OC, EC, major water-soluble ions, main metals, and compared to a similar dataset collected in the period 2013-2014. Oxidative potential using DTT assay (dithiothreitol) was evaluated and expressed in DTTV as 0.39 nmol/min·m3 in PM10 and 0.29 in PM2.5 nmol/min·m3. PM source apportionment was computed using the EPA PMF5.0 model and source contributions compared with those of a previous dataset collected between 2013 and 2014. Multi linear regression analysis identified which source contributed (p < 0.05) to the oxidative potential of each size fraction. Inter-annual trends were more evident on PM2.5 with reductions of biomass burning contribution and increases in traffic contribution in the 2016-2017 period. Crustal contributions were similar for the two periods, in both size fractions. Carbonates were comparable in PM10 with a slight increase in PM2.5. Sea spray decreased in PM10. The DTTV of PM2.5 peaked during cold periods, while, the DTTV of the PM10-2.5 fraction peaked in summer, suggesting that different sources, with different seasonality, influence OP in the PM2.5 and PM10-2.5 fractions. Analysis showed that sea spray, crustal, and carbonates sources contribute ∼13.6% to DTTV in PM2.5 and ∼62.4% to DTTV in PM10-2.5. Combustion sources (biomass burning and traffic) contribute to the majority of DTTV (50.6%) in PM2.5 and contribute for ∼26% to DTTV in PM10-2.5. Secondary nitrate contributes to DTTV in both fine and coarse fraction; secondary sulphate contribute to DTTV in PM2.5 with negligible contributions to DTTV in PM10-2.5.

Characterization of airborne particulate fractions from the port city of Rijeka, Croatia.

The aim of this work was characterization of airborne particulates in the port city of Rijeka in order to evaluate impact of ship emissions on air quality. Samples of airborne particulates were collected with a ten stages cascade impactor during two campaigns: autumn and spring. A total of 16 weekly samples were analyzed on mass concentration, ions, metals and carbonaceous species (EC, OC, WSOC). Distribution of airborne fractions showed a bimodal distribution, with two maxima: one in coarse, and other in fine fraction. Source apportionment using PMF receptor model identified six sources of airborne particulates in Rijeka: crustal, biomass burning, sea salt, traffic/metal industry, combustion/SIA and HFO burning, i.e., ship emission (contribution 3%). The contribution of ship traffic to primary emission of particulate matter, using vanadium as tracer, indicated a twofold increase for PM10 and PM2.5 relative to 2012-14. An unusual desert dust event was registered in autumn campaign.

Inter-comparison of carbon content in PM10 and PM2.5 measured with two thermo-optical protocols on samples collected in a Mediterranean site.

Scientific interest is focusing on different approaches for characterising organic carbon (OC), elemental carbon (EC) and equivalent black carbon (eBC), although EUSAAR2 protocol has been established and frequently used in EU for regulatory purposes. Discrepancies are observed due to thermal protocols used for OC/EC determinations and the effect of the chemical-physical properties of aerosol using optical measurements for eBC. In this work, a long-term inter-comparison of carbon measurements with two widely used protocols (EUSAAR2 and NIOSH870) was performed on PM2.5 and PM10 samples. The influence of the protocol on the evaluation of secondary organic aerosol (SOC) and on the correlation between EC and eBC was investigated. An extensive check of repeatability gave typical uncertainties of ~ 5% for TC and OC, and ~ 10% for EC for both thermal protocols. Results show that OC is statistically comparable between the two protocols but EC is significantly higher with EUSAAR2, especially during the warm season. The ratio OC/EC is lower with EUSAAR2, also showing a seasonality (lower values in the warm season) not observed with NIOSH870. Despite the differences in OC/EC ratios, the contribution of SOC to OC (~ 50%), evaluated using the EC-tracer method, did not differ significantly between the two protocols and for both size fractions. Further, SOC/OC ratios were comparable in cold and warm periods. eBC/EC ratios larger than one for both protocols were obtained, 1.62 (EUSAAR2) and 1.92 (NIOSH870), and also correlated with the ratio OC/EC for both protocols, especially in the cold season.

Contribution of harbour activities and ship traffic to PM2.5, particle number concentrations and PAHs in a port city of the Mediterranean Sea (Italy).

In this work, an assessment of the impact of ship traffic and related harbour activities (loading/unloading of ships and hotelling in harbour) on PM 2.5 and particle number concentrations (PNC) separating the contribution associated to ship traffic from that of harbour-related activities is reported. Further, an assessment of the impact and environmental risks associated to polycyclic aromatic hydrocarbon (PAH) concentrations was performed. Results refer to the city of Brindisi (88,500 inhabitants) in the south-eastern part of Italy and its harbour (with yearly 9.5 Mt of goods, over 520,000 passengers and over 175,000 vehicles). PM2.5 and PNC concentrations show a clear daily pattern correlated with daily ship traffic pattern in the harbour. High temporal resolution measurements and correlations with wind direction were used to estimate the average direct contribution to measured concentrations of this source. The average relative contribution of ship traffic was 7.4% (±0.5%) for PM2.5 and 26% (±1%) for PNC. When the contribution associated to harbour-related activities is added, the percentages become 9.3% (±0.5%) for PM2.5 and 39% (±1%) for PNC. In the site analysed, air coming from the harbour/industrial sector was richer in PAHs (5.34 ng/m3) than air sampled from all directions (3.89 ng/m3). The major compounds were phenanthrene, fluoranthene and pyrene, but the congener profiles were different in the two direction sectors: air from the harbour/industrial sector was richer in phenanthrene and fluorene, which are the most abundant PAHs in ship emissions. Results showed that lighter PAHs are associated to the gas phase, while high molecular weight congeners are mostly present in the particulate phase. The impact on the site studied of the harbour/industrial source to PAHs was 56%(range, 29-87%).