Burkholderia thailandensis E264 as a promising safe rhamnolipids' producer towards a sustainable valorization of grape marcs and olive mill pomace.

Within the circular economy framework, our study aims to assess the rhamnolipid production from winery and olive oil residues as low-cost carbon sources by nonpathogenic strains. After evaluating various agricultural residues from those two sectors, Burkholderia thailandensis E264 was found to use the raw soluble fraction of nonfermented (white) grape marcs (NF), as the sole carbon and energy source, and simultaneously, reducing the surface tension to around 35 mN/m. Interestingly, this strain showed a rhamnolipid production up to 1070 mg/L (13.37 mg/g of NF), with a higher purity, on those grape marcs, predominately Rha-Rha C14-C14, in MSM medium. On olive oil residues, the rhamnolipid yield of using olive mill pomace (OMP) at 2% (w/v) was around 300 mg/L (15 mg/g of OMP) with a similar CMC of 500 mg/L. To the best of our knowledge, our study indicated for the first time that a nonpathogenic bacterium is able to produce long-chain rhamnolipids in MSM medium supplemented with winery residues, as sole carbon and energy source. KEY POINTS: • Winery and olive oil residues are used for producing long-chain rhamnolipids (RLs). • Both higher RL yields and purity were obtained on nonfermented grape marcs as substrates. • Long-chain RLs revealed stabilities over a wide range of pH, temperatures, and salinities.

A quantitative structure-activity relationships approach to predict the toxicity of narcotic compounds to aquatic communities.

Species may vary markedly in terms of their sensitivity to toxicants, and such variation can be described through the species sensitivity distribution (SSD) approach. Using SSD cumulative functions, it is possible to calculate the hazardous concentration for 5% of the species (HC5), namely the contaminant concentration at which 5% of species will be affected. HC5 is often utilised to derive the predicted no-effect concentration, or the concentration at which a chemical will likely have no toxic effects on the different species present in an ecosystem. However, the lack of sufficient ecotoxicological data frequently obstructs the derivation of SSD curves and consequently the HC5. In the last 30 years, quantitative structure-activity relationship (QSAR) models have been widely used to predict the toxicity of chemicals to single species. The aim of this study was to evaluate the possibility of extending the applicability domain of these models from single species to the community level by predicting the HC5 values for aquatic communities and bypassing the need to derive SSD curves. This approach's practical advantage is that it would allow information on the toxicity of contaminants to be obtained on a hierarchical scale (aquatic community), which is ecologically more relevant than on the scale of single species, without the need for a robust toxicity data set. In the first part of the study, two simple QSAR models were developed for narcotic and polar narcotic compounds. Then, the QSAR model developed for narcotic compounds was utilised to define the baseline toxicity for aquatic communities and to calculate the toxicity ratios for various specifically acting compounds (insecticides and herbicides).

Biomonitoring of human activities recovery following lockdown in a highly touristic Mediterranean Island using Mytilus galloprovincialis.

Coastal waters face significant anthropogenic stress, particularly from tourism, exacerbating pollution, especially in areas like touristic islands. Ischia, the largest island in the Gulf of Naples and part of the Regno di Nettuno Marine Protected Area, suffers from pollution due to tourism and maritime traffic. During the initial SARS-CoV-2 lockdown from March to June 2020, Ischia was isolated, providing a unique opportunity to study pollutant release and its impact on coastal ecosystems. Adult Mytilus galloprovincialis mussels were transplanted to three sites on the island for active biomonitoring. Accumulation of chemicals in tissues and biomarkers related to metabolism, detoxification, and oxidative stress were measured. Results indicated that pollutants from daily activities entered the sea, affecting filter feeders. Translocated organisms showed modulated metabolic functions and biochemical changes, highlighting coastal vulnerability and calling for conservation efforts.

Conditioning factors in the spreading of Covid-19 - Does geography matter?

There is evidence in literature that the spread of COVID-19 can be influenced by various geographic factors, including territorial features, climate, population density, socioeconomic conditions, and mobility. The objective of the paper is to provide an updated literature review on geographical studies analysing the factors which influenced COVID-19 spreading. This literature review took into account not only the geographical aspects but also the COVID-19-related outcomes (infections and deaths) allowing to discern the potential influencing role of the geographic factors per type of outcome. A total of 112 scientific articles were selected, reviewed and categorized according to subject area, aim, country/region of study, considered geographic and COVID-19 variables, spatial and temporal units of analysis, methodologies, and main findings. Our literature review showed that territorial features may have played a role in determining the uneven geography of COVID-19; for instance, a certain agreement was found regarding the direct relationship between urbanization degree and COVID-19 infections. For what concerns climatic factors, temperature was the variable that correlated the best with COVID-19 infections. Together with climatic factors, socio-demographic ones were extensively taken into account. Most of the analysed studies agreed that population density and human mobility had a significant and direct relationship with COVID-19 infections and deaths. The analysis of the different approaches used to investigate the role of geographic factors in the spreading of the COVID-19 pandemic revealed that the significance/representativeness of the outputs is influenced by the scale considered due to the great spatial variability of geographic aspects. In fact, a more robust and significant association between geographic factors and COVID-19 was found by studies conducted at subnational or local scale rather than at country scale.

Effectiveness of the SARS-CoV-2 Vaccination in Preventing Severe Disease-Related Outcomes: A Population-Based Study in the Italian Province of Bolzano (South Tyrol).

Objective: To investigate the effectiveness of SARS-CoV2 vaccination in preventing ordinary or intensive care unit (ICU) admissions and deaths among cases registered during a variant transitional pandemic phase in the geographically and culturally unique territory of the Province of Bolzano (South Tyrol), an Italian region with low vaccination coverage. Methods: We collected data from 93,643 patients registered as positive for SARS-CoV-2 by health authorities during the winter of 2021-22. The data were analyzed retrospectively using descriptive statistics and multiple logistic regression. Results: 925 patients were hospitalized (0.99%), 89 (0.10%) were in intensive care, and 194 (0.21%) died. Vaccinated patients had a significantly lower risk of being hospitalized: adjusted Odds Ratio (aOR): 0.39; 95% CI: 0.33-0.46, ICU admission: aOR: 0.16; 95% CI: 0.09-0.29 and death: aOR: 0.41; 95% CI: 0.29-0.58. Similar risk reductions were also observed in booster-vaccinated patients, independent of sex, age, and predominant variant. Furthermore, the median length of stay (LoS) in the ICU was significantly longer for unvaccinated individuals compared to vaccinated subjects (9 vs. 6 days; p < 0.003). Conclusion: Primary series vaccination and ongoing campaign booster doses were effective in preventing all severe disease-related outcomes and in reducing ICU Length of Stay, even during a transitional pandemic phase and in a unique territorial context.

Silent Contamination: The State of the Art, Knowledge Gaps, and a Preliminary Risk Assessment of Tire Particles in Urban Parks.

Tire particles (TPs) are one of the main emission sources of micro- and nano-plastics into the environment. Although most TPs are deposited in the soil or in the sediments of freshwater and although they have been demonstrated to accumulate in organisms, most research has focused on the toxicity of leachate, neglecting the potential effects of particles and their ecotoxicological impact on the environment. In addition, studies have focused on the impact on aquatic systems and there are many gaps in the biological and ecotoxicological information on the possible harmful effects of the particles on edaphic fauna, despite the soil ecosystem becoming a large plastic sink. The aim of the present study is to review the environmental contamination of TPs, paying particular attention to the composition and degradation of tires (I), transport and deposition in different environments, especially in soil (II), the toxicological effects on edaphic fauna (III), potential markers and detection in environmental samples for monitoring (IV), preliminary risk characterization, using Forlanini Urban Park, Milan (Italy), as an example of an urban park (V), and risk mitigation measures as possible future proposals for sustainability (VI).

Glacier foreland insect uptake synthetic compounds: an emerging environmental concern.

Pesticides, synthetic fragrances and polycyclic aromatic hydrocarbons contaminated two glacier-fed streams (Amola, Mandrone) and one spring (Grostè) in the Italian Alps. Ten compounds (chlorpyrifos (CPY), chlorpyrifos-methyl (CPY-m), galaxolide (HHCB), tonalide (AHTN), fluorene (Flu), phenanthrene (Phen), anthracene (Ant), fluoranthene (Fl), pyrene (Pyr), benzo[a]anthracene (BaA)) accumulated in aquatic larvae of chironomids (Diamesa steinboecki, D. latitarsis, D. bertrami, D. tonsa, D. zernyi, Pseudokiefferiella parva, Orthocladiinae) and tipulids. Their tissue concentrations (detected by gas chromatography coupled with mass spectrometry) ranged from 1.1 ± 0.1 ng/g d.w. (= dry weight) (CPY-m in D. tonsa from Amola) to 68.0 ± 9.1 ng/g d.w. (Pyr in D. steinboecki from Mandrone). HHCB, AHTN, and CPY, with one exception, were accumulated by all aquatic insects. Six compounds (CPY, CPY-m, HHCB, AHTN, Fl, Pyr) also contaminated carabids (Nebria germarii, N. castanea, N. jockischii) predating adults of merolimnic insects. Their tissue concentrations ranged from 1.1 ± 0.3 ng/g d.w. (CPY-m in N. germarii from Mandrone) to 84.6 ± 0.3 ng/g d.w. (HHCB in N. castanea from Grostè). HHCB and AHTN were accumulated by all Nebria species. Intersite and interspecies differences were observed, which might be attributed to different environmental contamination levels. There was a stronger similarity between species from the same site than among the same species from different sites, suggesting that uptake is not species specific. At all sites, the concentration of xenobiotics was higher in larvae than in water and comparable or higher in carabids than in larvae from the same site, suggesting trophic transfer by emerging aquatic insects to their riparian predators.

Bioconcentration and cellular effects of emerging contaminants in sponges from Maldivian coral reefs: A managing tool for sustainable tourism.

Tourism is the main income source for the Maldives, but concurrently, it represents a growing threat to its marine ecosystem. Here, we monitored the bioaccumulation of 15 emerging contaminants (ECs) in the Maldivian reef sponges Spheciospongia vagabunda collected in two resort islands (Athuruga and Thudufushi, Ari Atoll) and an inhabited island (Magoodhoo, Faafu Atoll), and we analysed their impact on different sponge cellular stress biomarkers. Caffeine and the insect repellent DEET were detected in sponges of all the islands, whereas the antibiotic erythromycin and the UV filter 4-methylbenzylidene camphor were found in resort islands only. Although concentrations were approximately a few ng/g d.w., we quantified various induced cellular effects, in particular an increase of the levels of the enzyme glutathione S-transferase involved in cell detoxification. Our results highlight the importance to increase awareness on ECs pollution, promoting the use of more environmental friendly products to achieving the sustainable development goals.

Occurrence, sources, and ecological risks of polycyclic aromatic hydrocarbons (PAHs) in the Amazon river.

The Amazon is the largest river by discharge volume and one of the most biodiverse biomes in the world. Lately, there has been a rapid increase of the urban population in the region, which has been translated into a growing emission of organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) into surface water bodies. This study provides the most comprehensive evaluation of the PAH contamination levels in surface waters of the Amazon basin. We investigated the occurrence and potential sources of 16 priority PAHs and characterised their risks for freshwater ecosystems. For this, we took 40 water samples from different sites along the Brazilian part of the Amazon River, including three major tributaries, and smaller rivers crossing the main urban areas. The results of this study show that PAHs are widespread contaminants in rivers of the Brazilian Amazon. The sum of the total concentration of the 16 priority PAHs reached values of 134 ng L-1 in the Amazon River, and 163 ng L-1 near densely populated areas. On the other hand, the total PAH concentration was generally lower in the monitored tributaries. In most samples, the contamination pattern was dominated by high molecular weight PAHs, suggesting a major contribution of pyrogenic sources, although petrogenic contamination was also present in some locations near urban areas. We assessed ecological risks posed by PAH mixtures using a hazard index. The results indicated that PAH contamination is not likely to pose direct toxic effects for Amazonian freshwater organisms, however continued monitoring is recommended near densely populated areas.

Nanoplastics: Status and Knowledge Gaps in the Finalization of Environmental Risk Assessments.

Nanoplastics (NPs) are particles ranging in size between 1 and 1000 nm, and they are a form of environmental contaminant of great ecotoxicological concern. Although NPs are widespread across ecosystems, they have only recently garnered growing attention from both the scientific community and regulatory bodies. The present study reviews scientific literature related to the exposure and effects of NPs and identifies research gaps that impede the finalization of related environmental risk assessments (ERAs). Approximately 80 articles published between 2012 and 2021 were considered. Very few studies (eight articles) focused on the presence of NPs in biotic matrices, whereas the majority of the studies (62 articles) assessed the lethal and sublethal effects of NPs on aquatic and terrestrial organisms. Whilst many studies focused on nude NPs, only a few considered their association with different aggregates. Amongst NPs, the effects of polystyrene are the most extensively reported to date. Moreover, the effects of NPs on aquatic organisms are better characterized than those on terrestrial organisms. NP concentrations detected in water were close to or even higher than the sublethal levels for organisms. An ERA framework specifically tailored to NPs is proposed.

Diesel exhaust particulate emissions and in vitro toxicity from Euro 3 and Euro 6 vehicles.

Incomplete combustion processes in diesel engines produce particulate matter (PM) that significantly contributes to air pollution. Currently, there remains a knowledge gap in relation to the physical and chemical characteristics and also the biological reactivity of the PM emitted from old- and new-generation diesel vehicles. In this study, the emissions from a Euro 3 diesel vehicle were compared to those from a Euro 6 car during the regeneration of a diesel particulate filter (DPF). Different driving cycles were used to collect two types of diesel exhaust particles (DEPs). The particle size distribution was monitored using an engine exhaust particle sizer spectrometer and an electrical low-pressure impactor. Although the Euro 6 vehicle emitted particulates only during DPF regeneration that primarily occurs for a few minutes at high speeds, such emissions are characterized by a higher number of ultrafine particles (<0.1 µm) compared to those from the Euro 3 diesel vehicle. The emitted particles possess different characteristics. For example, Euro 6 DEPs exhibit a lower PAH content than do Euro 3 samples; however, they are enriched in metals that were poorly detected or undetected in Euro 3 emissions. The biological effects of the two DEPs were investigated in human bronchial BEAS-2B cells exposed to 50 µg/mL of PM (corresponding to 5.2 µg/cm2), and the results revealed that Euro 3 DEPs activated the typical inflammatory and pro-carcinogenic pathways induced by combustion-derived particles, while Euro 6 DEPs were less effective in regard to activating such biological responses. Although further investigations are required, it is evident that the different in vitro effects elicited by Euro 3 and Euro 6 DEPs can be correlated with the variable chemical compositions (metals and PAHs) of the emitted particles that play a pivotal role in the inflammatory and carcinogenic potential of airborne PM.

Ecological risk assessment of pesticides in urban streams of the Brazilian Amazon.

The use of pesticides in households and peri-urban areas of the Amazon has increased notably during the last years. Yet, the presence of these contaminants in Amazonian freshwater ecosystems remains unexplored. Here, we assessed the exposure to 18 pesticides and 5 transformation products in the Amazon River and in the urban streams of Manaus, Santarém, Macapá, and Belém (Brazil). Pesticide concentrations were analyzed by liquid and gas chromatography methods. Ecological risks were assessed following a two-tiered approach. First, hazard quotients and an overall hazard index were calculated using toxicity data for standard test species of primary producers, invertebrates, and fish. Second, the pesticides showing moderate-to-high ecological risks in the first tier were evaluated using Species Sensitivity Distributions (SSDs). Our study shows that pesticides are widespread in urban and peri-urban areas of the Brazilian Amazon. The frequency of detection was higher in urban streams than in the Amazon River, with some samples taken in Manaus, Santarém, and Belém containing up to 8 compounds. Most pesticides were measured at relatively low concentrations (ng L-1), except for malathion, carbendazim and the bulk concentration of chlorpyrifos, which were monitored at concentrations above 100 ng L-1. Based on the first-tier assessment, we found moderate-to-high risks for freshwater invertebrates for malathion, chlorpyrifos, and chlorpyrifos-methyl, and moderate risks for malathion to fish. The risk assessment performed with SSDs indicated high risks of malathion and chlorpyrifos-methyl in urban areas, with up to 15% and 5% of invertebrate species potentially affected, respectively. The bulk concentrations of chlorpyrifos resulted in high risks in some urban areas (14-22% of species affected) and in areas of the main river (32-44%) impacted by agriculture. We conclude that pesticide residues may contribute to a biodiversity impact in the Amazon and should be further monitored in urban and peri-urban areas, particularly after heavy rainfall events.

Sulfoxaflor and nutritional deficiency synergistically reduce survival and fecundity in bumblebees.

A range of anthropogenic factors are causing unprecedented bee declines. Among these drivers the usage of pesticides is believed to be crucial. While the use of key bee-harming insecticides, such as the neonicotinoids, has been reduced by regulatory authorities, novel, less studied substances have occupied their market niche. Understanding the threat of these chemicals to bees is, therefore, crucial to their conservation. Here we focus on sulfoxaflor, a novel insecticide, targeting the same neural receptor as the neonicotinoids. In stark contrast to the growing concerns around its negative impacts on bee health, a recent assessment has resulted in the extension of its authorisations across the USA. However, such assessments may underestimate risks by overlooking interactive impacts of multiple stressors. Here we investigated co-occurring, lethal and sublethal risks of sulfoxaflor and a dietary stress for bumblebees (Bombus terrestris), a key pollinator. Specifically, we employed a novel microcolony design, where, for the first time in bees, pesticide exposure mimicked natural degradation. We orally exposed workers to sulfoxaflor and a sugar-deficient diet in a fully factorial design. Field realistic, worst-case sulfoxaflor exposure caused a sharp increase in bee mortality. At sublethal concentrations, sulfoxaflor negatively affected bee fecundity, but not survival. Nutritional stress reduced bee fecundity and synergistically or additively aggravated impacts of sulfoxaflor on bee survival, egg laying and larval production. Our data show that non-mitigated label uses of sulfoxaflor may have major, yet severely neglected effects on bumblebee health, which may be exacerbated by nutritional stress. By unravelling mechanistic interactions of synergistic risks, our study highlights the need to overcome inherent limitations of Environmental Risk Assessment schemes, which, being based on a "single stressor paradigm", may fail to inform policymakers of the real risks of pesticide use.

Use of the Species Sensitivity Distribution Approach to Derive Ecological Threshold of Toxicological Concern (eco-TTC) for Pesticides.

The species sensitivity distribution (SSD) calculates the hazardous concentration at which 5% of species (HC5) will be potentially affected. For many compounds, HC5 values are unavailable impeding the derivation of SSD curves. Through a detailed bibliographic survey, we selected HC5 values (from acute toxicity tests) for freshwater aquatic species and 129 pesticides. The statistical distribution and variability of the HC5 values within the chemical classes were evaluated. Insecticides are the most toxic compounds in the aquatic communities (HC5 = 1.4 × 10-3 µmol L-1), followed by herbicides (HC5 = 3.3 × 10-2 µmol L-1) and fungicides (HC5 = 7.8 µmol L-1). Subsequently, the specificity of the mode of action (MoA) of pesticides on freshwater aquatic communities was investigated by calculating the ratio between the estimated baseline toxicity for aquatic communities and the HC5 experimental values gathered from the literature. Moreover, we proposed and validated a scheme to derive the ecological thresholds of toxicological concern (eco-TTC) of pesticides for which data on their effects on aquatic communities are not available. We proposed eco-TTCs for different classes of insecticides, herbicides, and fungicides with a specific MoA, and three eco-TTCs for those chemicals with unavailable MoA. We consider the proposed approach and eco-TTC values useful for risk management purposes.

Pharmaceuticals and other urban contaminants threaten Amazonian freshwater ecosystems.

Urban areas in the Brazilian Amazon have grown at an unprecedented rate during the last years. About 90% of the wastewater produced by these urban areas are discharged untreated into Amazonian freshwater ecosystems, constituting a potential environmental pathway for pharmaceuticals and other chemicals consumed by modern societies (e.g. psychostimulants, personal-care products, hormones). The distribution of these chemicals into the Amazon River and their potential risks for freshwater biodiversity have not been evaluated so far. Here, we show the results of the largest chemical monitoring campaign conducted in the Amazon region. We assessed exposure patterns for 43 pharmaceuticals and other urban contaminants in 40 sampling sites distributed along the Amazon River, three major tributaries (Negro, Tapajós and Tocantins Rivers), and four large cities of the Brazilian Amazon (Manaus, Santarém, Macapá, Belém). We assessed risks for freshwater biodiversity using species sensitivity distributions and mixture toxicity approaches. We found that urban areas constitute important hot-spots for chemical contamination, with mixtures containing up to 40 different compounds and exposure concentrations reaching the world's maxima for some of them. We show that chemical pollution can result in long-term effects for up to 50-80% of aquatic species next to urban areas. Moreover, we identified several ubiquitous compounds which can be used as tracers of anthropogenic pressure in the Amazon basin. We conclude that the chemical burden created by urbanization significantly contributes to a biodiversity loss in the region and should be further controlled.

Biological effects of combustion-derived particles from different biomass sources on human bronchial epithelial cells.

Combustion-derived particles (CDPs), in particular from traffic, are regarded as a central contributor for adverse health effects linked to air pollution. Recently, also biomass burning has been recognized as an important source for CDPs. Here, the effects of CDPs (PM10) originating from burning of pellet, charcoal and wood on key processes associated to lung carcinogenesis were explored. Human bronchial epithelial cells (HBEC3-KT) were exposed to 2.5 µg/cm2 of CDPs for 24 h and biological effects were examined in terms of cytotoxicity, inflammation, epithelial to mesenchymal transition (EMT)-related effects, DNA damage and genotoxicity. Reduced cell migration, inflammation and modulation of various PM-associated genes were observed mainly after exposure to wood and pellet. In contrast, only particles from pellet burning induced alteration in cell proliferation and DNA damage, which resulted in cell cycle alterations. Charcoal instead, appeared in general less effective in inducing pro-carcinogenic effects. These results illustrate differences in the toxicological profile due to the CDPs source. The different chemical compounds adsorbed on CDPs seemed to be central for particle properties, leading to an activation of various cellular signaling pathways involved in early steps of cancer progression.

First record of emerging contaminants in sponges of an inhabited island in the Maldives.

In the Maldivian islands, the lack of sewage wastewater treatment and an improper landfill enhance the potential hazard of emerging contaminants, including pharmaceuticals and personal care products. In order to analyze the occurrence of emerging contaminants in the marine biota, sponges were collected in two coral reef areas of Magoodhoo island (Faafu), one near the landfill and the other furthest from the island. Caffeine, fluoxetine and norfluoxetine were detected only in the proximity of the landfill, with caffeine showing the highest concentration (28.4 ng/g d.w.), followed by fluoxetine (6.00 ng/g d.w.). Norfluoxetine was below the limit of quantification of 10 ng/g d.w. Nitro xylene, N,N-Diethyl-meta-toluamide and galaxolide were found in both areas, with concentrations of 3.51/6.11/8.54 and

Chemically and size-resolved particulate matter dry deposition on stone and surrogate surfaces inside and outside the low emission zone of Milan: application of a newly developed "Deposition Box".

The collection of atmospheric particles on not-filtering substrates via dry deposition, and the subsequent study of the particle-induced material decay, is trivial due to the high number of variables simultaneously acting on the investigated surface. This work reports seasonally resolved data of chemical composition and size distribution of particulate matter deposed on stone and surrogate surfaces obtained using a new method, especially developed at this purpose. A "Deposition Box" was designed allowing the particulate matter dry deposition to occur selectively removing, at the same time, variables that can mask the effect of airborne particles on material decay. A pitched roof avoided rainfall and wind variability; a standardised gentle air exchange rate ensured a continuous "sampling" of ambient air leaving unchanged the sampled particle size distribution and, at the same time, leaving quite calm condition inside the box, allowing the deposition to occur. Thus, the "Deposition Box" represents an affordable tool that can be used complementary to traditional exposure systems. With this system, several exposure campaigns, involving investigated stone materials (ISMs) (Carrara Marble, Botticino limestone, Noto calcarenite and Granite) and surrogate (Quartz, PTFE, and Aluminium) substrates, have been performed in two different sites placed in Milan (Italy) inside and outside the low emission zone. Deposition rates (30-90 µg cm-2 month-1) showed significant differences between sites and seasons, becoming less evident considering long-period exposures due to a positive feedback on the deposition induced by the deposited particles. Similarly, different stone substrates influenced the deposition rates too. The collected deposits have been observed with optical and scanning electron microscopes and analysed by ion chromatography. Ion deposition rates were similar in the two sites during winter, whereas it was greater outside the low emission zone during summer and considering the long-period exposure. The dimensional distribution of the collected deposits showed a significant presence of fine particles in agreement with deposition rate of the ionic fraction. The obtained results allowed to point out the role of the fine particles fraction and the importance of making seasonal studies.