Potential role of particulate matter in the spreading of COVID-19 in Northern Italy: first observational study based on initial epidemic diffusion.

OBJECTIVES: A number of studies have shown that the airborne transmission route could spread some viruses over a distance of 2 meters from an infected person. An epidemic model based only on respiratory droplets and close contact could not fully explain the regional differences in the spread of COVID-19 in Italy. On March 16th 2020, we presented a position paper proposing a research hypothesis concerning the association between higher mortality rates due to COVID-19 observed in Northern Italy and average concentrations of PM10 exceeding a daily limit of 50 µg/m3. METHODS: To monitor the spreading of COVID-19 in Italy from February 24th to March 13th (the date of the Italian lockdown), official daily data for PM10 levels were collected from all Italian provinces between February 9th and February 29th, taking into account the maximum lag period (14 days) between the infection and diagnosis. In addition to the number of exceedances of the daily limit value of PM10, we also considered population data and daily travelling information for each province. RESULTS: Exceedance of the daily limit value of PM10 appears to be a significant predictor of infection in univariate analyses (p<0.001). Less polluted provinces had a median of 0.03 infections over 1000 residents, while the most polluted provinces showed a median of 0.26 cases. Thirty-nine out of 41 Northern Italian provinces resulted in the category with the highest PM10 levels, while 62 out of 66 Southern provinces presented low PM10 concentrations (p<0.001). In Milan, the average growth rate before the lockdown was significantly higher than in Rome (0.34 vs 0.27 per day, with a doubling time of 2.0 days vs 2.6, respectively), thus suggesting a basic reproductive number R0>6.0, comparable with the highest values estimated for China. CONCLUSION: A significant association has been found between the geographical distribution of daily PM10 exceedances and the initial spreading of COVID-19 in the 110 Italian provinces.

Estimation of local and external contributions of biomass burning to PM2.5 in an industrial zone included in a large urban settlement.

A total of 85 PM2.5 samples were collected at a site located in a large industrial zone (Porto Marghera, Venice, Italy) during a 1-year-long sampling campaign. Samples were analyzed to determine water-soluble inorganic ions, elemental and organic carbon, and levoglucosan, and results were processed to investigate the seasonal patterns, the relationship between the analyzed species, and the most probable sources by using a set of tools, including (i) conditional probability function (CPF), (ii) conditional bivariate probability function (CBPF), (iii) concentration weighted trajectory (CWT), and (iv) potential source contribution function (PSCF) analyses. Furthermore, the importance of biomass combustions to PM2.5 was also estimated. Average PM2.5 concentrations ranged between 54 and 16 µg m-3 in the cold and warm period, respectively. The mean value of total ions was 11 µg m-3 (range 1-46 µg m-3): The most abundant ion was nitrate with a share of 44 % followed by sulfate (29 %), ammonium (14 %), potassium (4 %), and chloride (4 %). Levoglucosan accounted for 1.2 % of the PM2.5 mass, and its concentration ranged from few ng m-3 in warm periods to 2.66 µg m-3 during winter. Average concentrations of levoglucosan during the cold period were higher than those found in other European urban sites. This result may indicate a great influence of biomass combustions on particulate matter pollution. Elemental and organic carbon (EC, OC) showed similar behavior, with the highest contributions during cold periods and lower during summer. The ratios between biomass burning indicators (K+, Cl-, NO3-, SO42-, levoglucosan, EC, and OC) were used as proxy for the biomass burning estimation, and the contribution to the OC and PM2.5 was also calculated by using the levoglucosan (LG)/OC and LG/PM2.5 ratios and was estimated to be 29 and 18 %, respectively.

Particulate-bound polycyclic aromatic hydrocarbon sources and determinants in residential homes.

Human exposure to polycyclic aromatic hydrocarbons (PAHs) in indoor environments can be particularly relevant because people spend most of their time inside buildings, especially in homes. This study aimed to investigate the most important particle-bound PAH sources and exposure determinants in PM2.5 samples collected in 19 homes located in northern Italy. Complementary information about ion content in PM10 was also collected in 12 of these homes. Three methods were used for the identification of PAH sources and determinants: diagnostic ratios with principal component and hierarchical cluster analyses (PCA and HCA), chemical mass balance (CMB) and linear mixed models (LMMs). This combined and tiered approach allowed the infiltration of outdoor PAHs into indoor environments to be identified as the most important source in winter, with a relevant role played by biomass burning and traffic exhausts to be identified as a general source of PAHs in both seasons. Tobacco smoke exhibited an important impact on PAH levels in smokers' homes, whereas in the whole sample, cooking food and natural gas sources played a minor or negligible role. Nitrate, sulfate and ammonium were the main inorganic constituents of indoor PM10 owing to the secondary formation of ammonium sulfates and nitrates.

Small scale spatial gradients of outdoor and indoor benzene in proximity of an integrated steel plant.

Benzene is known as a human carcinogen, whose annual mean concentration exceeded the EU limit value (5 µg/m(3)) only in very few locations in Europe during 2012. Nevertheless 10% to 12% of the EU-28 urban population was still exposed to benzene concentrations above the WHO reference level of 1.7 µg/m(3). WHO recommended a wise choice of monitoring stations positioning in proximity of "hot spots" to define and assess the representativeness of each site paying attention to micro-scale conditions. In this context benzene and other VOCs of health concern (toluene, ethylbenzene, xylenes) concentrations have been investigated, with weekly passive sampling for one year, both in outdoor and indoor air in inhabited buildings in close proximity (180 m far up to 1100 m) of an integrated steel plant in NE of Italy. Even though the outdoor mean annual benzene concentration was below the EU limit in every site, in the site closest to the works the benzene concentration was above 5 µg/m(3) in 14 weeks. These events were related to a benzene over toluene ratio above one, which is diagnostic for the presence of an industrial source, and to meteorological factors. These information pointed at the identification of the coke ovens of the plant as the dominant outdoor source of benzene. Benzene gradients with the increasing distance from coke ovens have been found for both outdoor and indoor air. Linear models linking outdoor to indoor benzene concentrations have been then identified, allowing to estimate indoor exposure from ambient air benzene data. In the considered period, a narrow area of about 250 m appeared impacted at a higher degree than the other sites both considering outdoor and indoor air. Passive BTEX sampling permits to collect information on both ambient air and daily life settings, allowing to assemble a valuable data support for further environmental cost-benefit analyses.

High secondary aerosol contribution to particulate pollution during haze events in China.

Rapid industrialization and urbanization in developing countries has led to an increase in air pollution, along a similar trajectory to that previously experienced by the developed nations. In China, particulate pollution is a serious environmental problem that is influencing air quality, regional and global climates, and human health. In response to the extremely severe and persistent haze pollution experienced by about 800 million people during the first quarter of 2013 (refs 4, 5), the Chinese State Council announced its aim to reduce concentrations of PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 micrometres) by up to 25 per cent relative to 2012 levels by 2017 (ref. 6). Such efforts however require elucidation of the factors governing the abundance and composition of PM2.5, which remain poorly constrained in China. Here we combine a comprehensive set of novel and state-of-the-art offline analytical approaches and statistical techniques to investigate the chemical nature and sources of particulate matter at urban locations in Beijing, Shanghai, Guangzhou and Xi'an during January 2013. We find that the severe haze pollution event was driven to a large extent by secondary aerosol formation, which contributed 30-77 per cent and 44-71 per cent (average for all four cities) of PM2.5 and of organic aerosol, respectively. On average, the contribution of secondary organic aerosol (SOA) and secondary inorganic aerosol (SIA) are found to be of similar importance (SOA/SIA ratios range from 0.6 to 1.4). Our results suggest that, in addition to mitigating primary particulate emissions, reducing the emissions of secondary aerosol precursors from, for example, fossil fuel combustion and biomass burning is likely to be important for controlling China's PM2.5 levels and for reducing the environmental, economic and health impacts resulting from particulate pollution.

Comparison of wood smoke PM2.5 obtained from the combustion of FIR and beech pellets on inflammation and DNA damage in A549 and THP-1 human cell lines.

The aim of this study was to investigate the effect on the induction of interleukin-8 of particulate matter (PM) from fir and beech pellets burnt in domestic appliances on two human cells lines, namely the lung epithelial cell line A549 and the promyelocytic cell line THP-1. The effects of PM2.5 obtained from combustion of beech and fir pellets were compared to reference diesel exhaust particulates (DEP). In parallel, wood smoke PM-induced genotoxicity and oxidative stress were also investigated in A549 cells. Cells were treated for different times (3-72 h) with increasing concentrations of PM2.5 obtained from sequential combustions of fir and beech pellets or reference DEP. Cell viability was assessed by lactate dehydrogenase leakage, and the release of interleukin-8 or CXCL8 (IL-8) was measured to evaluate the pro-inflammatory effect. Oxidative stress was evaluated by the 5(6)-carboxy-2',7'dichlorofluorescein diacetate (DCFH-DA) assay and DNA damage by the alkaline comet assay and micronucleus frequency by flow cytometry. Both A549 and THP-1 cells responded in a dose- and time-related manner to wood smoke PM2.5 with IL-8 release, particles obtained from late combustions being the most active. THP-1 cells were more sensitive than A549 cells. On a mass base, similar effects were observed for both fir and beech PM2.5. However, the combustion of beech pellets generated approximately three times more PM2.5 than fir pellets. Regarding the mechanism of PM2.5 uptake, in both THP-1 and A549 cells, cytochalasin D prevented PM2.5-induced IL-8 mRNA expression and cytokine release, indicating a key role for actin polymerization in particles uptake and that the production of IL-8 correlated with particle phagocytosis. As signal transduction pathway involvement, in both THP-1 and A549 cells, PM2.5-induced IL-8 release could be completely blocked by the selective inhibitor SB203580, indicating a role of p38 MAPK activation. PM2.5 from both fir and beech pellets also induced modest DNA lesions dose related, measured as strand breaks, whereas no increase in the number of micronucleus was observed. Similar effects were observed with DEP, arguing against less dangerous effects of wood smoke particles than other categories of combustion-derived particles in the same size range. Overall, results suggest that combustion conditions can significantly affect the characteristics of particles and the consequent toxicity, and that different woods can generate different amounts of PM2.5.

Ionic profile of honey as a potential indicator of botanical origin and global environmental pollution.

Aim of this study was to determine by Ion Chromatography ions (Na(+), Ca(++), Mg(++), NH4(+), Cl(-), Br(-), SO4(2-), NO3(-), PO4(3-)) in honeys (honeydew and floral nectar honeys) from different Italian Regions and from countries of the Western Balkan area. The compositional data were processed by multivariate analysis (PCA and HCA). Arboreal honeydew honeys from the Western Balkans had higher concentrations (from two to three times) of some environmental pollutants (Br(-), SO4(2-) and PO4(3-) contents), due to industrial and agricultural activities, than those from Italian regions. The cationic profiles were very similar in both groups. Multivariate analysis indicated a clear difference between nectar honeys and arboreal/honeydew honeys (recognition of the botanical origin). These findings point to the potential of ionic constituents of honey as indicators of environmental pollution, botanical origin and authenticity.

Kinetic modeling of the formation and destruction of polychlorinated dibenzo-p-dioxin and dibenzofuran from fly ash native carbon at 300 °C.

The kinetics for the oxidative breakdown of native carbon in raw fly ash samples (RFA) and for the formation and destruction of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF), abbreviated PCDD/F, were investigated using a flow-over solid system in which the RFA samples were thermally treated at 300 °C under synthetic air. This study investigated the correlation between the disappearance of the reagent and the formation of the products to gain insight into the underlying mechanisms that govern these reactions at congener groups level. The detailed analyses of the experimental concentration-time data revealed significant differences in the behavior between the 2,3,7,8-substituted PCDD and the 2,3,7,8-substituted PCDF, non-2,3,7,8-substituted PCDD and PCDF. The chlorine balance for the former was always negative, that is, chlorine was released regardless of reaction time and primarily resulted from the dechlorination of the hepta- and octa-homologues. However, for the others, the balance was substantially positive up to approximately 240 min and became negative at longer intervals when the dechlorination reactions took over. The processes involving PCDD and PCDF in which the thermal destruction was only partial were found to increase the total equivalent toxicity (TEQ) levels rather than reduce them.

Optimisation of analytical procedures for the quantification of ionic and carbonaceous fractions in the atmospheric aerosol and applications to ambient samples.

In the last decade, our research group set up and optimised analytical techniques for the characterisation of the major components of atmospheric aerosol (i.e. secondary inorganic ions and carbonaceous material) and source markers (e.g. levoglucosan, carbonates). In this study, we present a complete overview on the most problematic aspects that can be encountered during the quantification of the two main components of aerosol, i.e. the ionic and carbonaceous fractions. More in detail, different liquid chromatographic approaches were set up for main ions and anhydrosugars determination. Quality assurance procedures (i.e. tests on data reliability) were applied during the set-up phase and they are presented in this work. As regards the carbonaceous component characterisation, two evolved gas analysis techniques were set up and applied: the thermogravimetric technique coupled to the Fourier transformed infrared spectroscopy (TGA/FTIR) and the thermal-optical transmittance method (TOT). A suitable protocol for organic and elemental carbon separation was set up for the TGA/FTIR system and a comparison with the results obtained by the TOT method was carried out. Studies on the impact of filter load, field blanks, and sample composition on OC/EC quantification by the TOT method were performed. Moreover, approaches for carbonate carbon quantification on different kinds of filters were developed. It was demonstrated that this approach allows to reach the ionic balance in samples impacted by carbonate compounds. The optimised methods have been applied for the analysis of thousands of PM filters allowing the obtainment of reliable results.

PM10 source apportionment in Milan (Italy) using time-resolved data.

In this work Positive Matrix Factorization (PMF) was applied to 4-hour resolved PM10 data collected in Milan (Italy) during summer and winter 2006. PM10 characterisation included elements (Mg-Pb), main inorganic ions (NH(4)(+), NO(3)(-), SO(4)(2-)), levoglucosan and its isomers (mannosan and galactosan), and organic and elemental carbon (OC and EC). PMF resolved seven factors that were assigned to construction works, re-suspended dust, secondary sulphate, traffic, industry, secondary nitrate, and wood burning. Multi Linear Regression was applied to obtain the PM10 source apportionment. The 4-hour temporal resolution allowed the estimation of the factor contributions during peculiar episodes, which would have not been detected with the traditional 24-hour sampling strategy.

Profile of nitric oxide (NO) metabolites (nitrate, nitrite and N-nitroso groups) in honeys of different botanical origins: nitrate accumulation as index of origin, quality and of therapeutic opportunities.

Besides dermoprotective activity, honey also has a strong gastroprotective effect, from salivary reduction of nitrate (NO(3)(-)) to nitrite (NO(2)(-)) and intragastric formation of nitric oxide (NO), this lastly involved in the preservation of the gastric mucosa capillaries and in boosting mucous production. Aim of this work is to profile the distribution of NO metabolites (NO(3)(-), NO(2)(-) and total N-nitroso-groups, N-NO) in a set of honeys (n=54) of different botanical origins, using a chemiluminescence based technique (NO-analyzer, NOA). All the honeys contained appreciable amounts of NO(3)(-) (from 1.63+/-0.04 to 482.98+/-5.34 mg/kg), the highest in honeydew honeys (10-40 times than in nectar honeys). Low levels of NO(2)(-) were found in all samples (0.01+/-0.00 to 0.56+/-0.01 mg/kg). N-NO groups, at trace levels in some nectar honeys, were higher in honeydew samples (from 0.01+/-0.00 to 0.29+/-0.01 mg/kg). Total phenol content (TP) and total protein (TProt) were comparable to those in literature. Multivariate analysis indicated that N-NO groups were significantly associated with NO(2)(-) and TP thus to suggest an in situ environmental nitrosation of specific nitrosable substrates (lysine, proline) favored by high reducing conditions. The bee-smoking process can be an alternative or complementary explanation for N-NO contamination. Hence NO(3)(-) rich honeys intake may exert beneficial effects against NSAIDs-induced gastric injury. Finally NO(3)(-) is a potential reliable marker of a honey's origin and quality.

4-hours resolution data to study PM10 in a "hot spot" area in Europe.

Nowadays, high-time resolved aerosol studies are mandatory to better understand atmospheric processes, such as formation, removal, transport, deposition or chemical reactions. This work focuses on PM10 physical and chemical characterisation with high-time resolution: elements (from Na to Pb), ions and OC/EC fractions concentration were determined during two weeks in summer and two in winter 2006 with 4-hours resolution. Further measurements aimed at hourly elemental characterisation of fine and coarse fractions and at the determination of particles number concentration in the 0.25-32 microm size range in 31 bins. The chemical mass closure was carried out in both seasons, enhancing intra-day differences in PM10 composition. In Milan, the highest contribution came from organic matter (34% and 33% in summer and winter, respectively); other important contributors were secondary inorganic compounds (16% and 24% in summer and winter, respectively) and, in summer, crustal matter (14%). Temporal trends showed strong variations in PM10 composition during contiguous time-slots and diurnal variations in different components contribution were identified. Moreover, peculiar phenomena, which would have hardly been detected with 24-hours samplings, were evidenced. Particles removal due to precipitations, aerosol local production and long range transport were studied in detail.