Effects of road dust suppressants on PM levels in a Mediterranean urban area.

The abatement of road dust emissions is currently a major challenge for sustainable transportation, causing exceedances of limits on particulate matter (PM) and high population exposures to mineral dust and metals. Mitigation measures have been proposed such as improved street cleaning and the use of dust suppressants. This study evaluated, for the first time, the effectiveness of calcium-magnesium acetate (CMA) and MgCl2 in reducing road dust emissions in a Mediterranean city. During a two-month campaign, a typical urban road in the city of Barcelona was sprayed, and changes in PMx levels and components were monitored at four traffic sites and one background monitoring sites. The integrated results indicate no statistically significant effectiveness of dust suppressants on PM10 and PM2.5-10 levels. Episodic reductions of Al, K, Mg, Cr, Li, Cu, and Zn were observed during CMA applications, but they were not systematically statistically significant over different stations and spreading days. MgCl2 days showed lower PM10 mean concentrations, but these reductions were not statistically significant and were not supported by significant drops in mineral and brake-wear metals. Based on our literature review, it can be postulated that the higher the road dust loading, the higher the dust suppressant effectiveness.

Concentrations and co-occurrence of 101 emerging and legacy organic pollutants in the ultrafine, fine and coarse fractions of airborne particulates associated with treatment of waste from electrical and electronic equipment.

Occupational exposure to airborne particles can increase the development of morbidity, also because of the chemical composition of particulate matter (PM). In workplace, where manual and mechanical disassembly of electric and electronic equipment (EEE) take place, there are evident risks of respiratory exposure to a great number of different toxic organic compounds present in the electrical and plastic materials of which the equipment is made. Airborne particles are numerous, cover a wide range of sizes and are rich in toxic organic compounds. In the present work, a sampling program was conducted and ultrafine, fine and coarse airborne particles were collected in three EEE waste treatment plants. Afterwards, the extraction and analysis of polycyclic aromatic hydrocarbons (PAHs), their nitro and oxygenated derivatives (nitroPAHs, oxyPAHs), organophosphorus compounds (OPEs), Brominated Flame Retardants (BFRs), polychlorinated biphenyls (PCBs), Polybrominated Diphenyl Ethers (PBDEs), and polyfluoralkyl substances (PFASs) was performed. The percentage ratio of the mass of organic compounds and the mass of the ultrafine fraction of PM (PM0.1) was higher than those of the fine and coarse fractions. Even with low concentrations, the co-occurrence of numerous potentially toxic compounds capable of easily reaching other organs passing by the lung vasculature, through the lymph makes the working environment unhealthy.

Saharan dust contribution to PM10, PM2.5 and PM1 in urban and suburban areas of Rome: a comparison between single-particle SEM-EDS analysis and whole-sample PIXE analysis.

From February 15th to April 15th 2009, a period characterised by two episodes of Saharan dust outbreaks in Italy, particulate matter (PM) samples were collected at two stations (urban and suburban) in Rome. Some samples were selected and analysed using the SEM-EDS technique to characterise PM, focussing especially on the mineral contribution. Samples were representative both of days affected by Saharan dust episodes and days without this contribution. Cluster analysis allowed the attribution of each of about 67,000 analysed particles to one of the seven main statistical groups based on their composition. Characteristics of the particulate components identified using SEM-EDS analysis were verified by PIXE analysis carried out on filters collected in a suburban area. Ultimately, the contribution of crustal particles was revealed to be consistently high, highlighting the importance of local and regional mineral contributions, as well as those of Saharan origin. Therefore, quantifying all mineral contributions to resuspended particulate could lead to significant reductions of the PM level also on days not influenced by Saharan dust, thus limiting conditions when PM10 daily limit value (DLV) established by European legislation is exceeded.

Characterization of aerosol sources in León (Spain) using Positive Matrix Factorization and weather types.

A one-year aerosol sampling campaign, between 2016 and 2017, was conducted in a suburban area of León city, Spain. An association between the Positive Matrix Factorization (PMF) results and air masses through circulation weather types was carried out, through the construction of linear models from the PM10 concentrations and its chemical composition. The aerosol sources, identified by PMF six-factor solution, were: traffic (29%), aged sea salt (26%), secondary aerosols (16%), dust (13%), marine aerosol (7%) and biomass burning (3%). Traffic and secondary factors showed the highest PM10 contribution in the hybrid cyclonic types with wind component from the first and second quadrant. Anticyclonic types with wind component from the first quadrant exhibited high values of secondary, aged sea salt and dust factors. The highest contributions of the dust factor were also associated with northerly types. The linear models built for estimating the source apportionment of PM10, from aerosol chemical composition and geostrophic flow, showed positive coefficients for: westerly flows (WF) in marine factor, southerly flows (SF) in secondary and traffic factors, and shear southerly vorticities (ZS) in dust factor. Negative dependences were observed for ZS in aged sea salt factor and for SF in dust factor. The PM10 mass concentration calculated by the linear models and by the PMF model were strongly correlated. This can be very useful to determine the contribution of a specific source to PM10 in León, only by knowing some meteorological and chemical variables.

Towards a model for aerosol removal by rain scavenging: The role of physical-chemical characteristics of raindrops.

A one-year study was carried out in León, Spain, in order to characterize physically and chemically the precipitation. With the aim of studying the scavenging process of atmospheric pollutants, scavenging ratio and removal coefficients were calculated through physical parameters of raindrops (obtained by disdrometer data) and through chemical properties of aerosols. Finally, linear models for the prediction of the chemical composition of rainwater and the efficiency of the removal effect were established. In general, the rainwater was dominated by NH4+ > SO42- > NO3- in all seasons. Higher ion concentrations and conductivity and lowest pH were observed in summer, due to the low volume of rain. In winter, the high values of Na+ and Cl- in the rainwater showed the contribution from marine sources, while in summer the high concentrations of Ca2+, Mg2+, SO42-, NH4+ and NO3- reflected the contribution from both crustal and anthropogenic sources. The linear models revealed that the amount of dissolved organic carbon and of the water-soluble ions in rain samples, Ca2+, SO42-, NO3-, increases with the volume swept by the falling drops. Insoluble carbon fraction has a negative dependence with the volume swept and positive with the diameter of the raindrop. Removal coefficients are affected by the concentration in the air of each species before precipitation, the duration of the event and the time elapsed between two precipitation events.

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.

Source apportionment of fine and coarse particles at a roadside and urban background site in London during the 2012 summer ClearfLo campaign.

London, like many major cities, has a noted air pollution problem, and a better understanding of the sources of airborne particles in the different size fractions will facilitate the implementation and effectiveness of control strategies to reduce air pollution. Thus, the trace elemental composition of the fine and coarse fraction were analysed at hourly time resolution at urban background (North Kensington, NK) and roadside (Marylebone Road, MR) sites within central London. Unlike previous work, the current study focuses on measurements during the summer providing a snapshot of contributing sources, utilising the high time resolution to improve source identification. Roadside enrichment was observed for a large number of elements associated with traffic emissions (Al, S, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Rb and Zr), while those elements that are typically from more regional sources (e.g. Na, Cl, S and K) were not found to have an appreciable increment. Positive Matrix Factorization (PMF) was applied for the source apportionment of the particle mass at both sites with similar sources being identified, including sea salt, airborne soil, traffic emissions, secondary inorganic aerosols and a Zn-Pb source. In the fine fraction, traffic emissions was the largest contributing source at MR (31.9%), whereas it was incorporated within an "urban background" source at NK, which had contributions from wood smoke, vehicle emissions and secondary particles. Regional sources were the major contributors to the coarse fraction at both sites. Secondary inorganic aerosols (which contained influences from shipping emissions and coal combustion) source factors accounted for around 33% of the PM10 at NK and were found to have the highest contributions from regional sources, including from the European mainland. Exhaust and non-exhaust sources both contribute appreciably to PM10 levels at the MR site, highlighting the continuing importance of vehicle-related air pollutants at roadside.

Polycyclic aromatic hydrocarbons and their derivatives (nitro-PAHs, oxygenated PAHs, and azaarenes) in PM2.5 from Southern European cities.

Atmospheric particulate matter (PM2.5) samples were collected over two one month periods during winter and summer in three Southern European cities (Oporto - traffic site, Florence - urban background, Athens - suburban). Concentrations of 27 polycyclic aromatic hydrocarbons (PAHs), 15 nitro-PAHs (NPAHs), 15 oxygenated-PAHs (OPAHs) and 4 azaarenes (AZAs) were determined. On average, the winter-summer concentrations of ΣPAHs were 16.3-5.60, 7.75-3.02 and 3.44-0.658ngm-3 in Oporto, Florence and Athens, respectively. The corresponding concentrations of ΣNPAHs were 15.8-9.15, 10.9-3.36 and 15.9-2.73ngm-3, whilst ΣOPAHs varied in the ranges 41.8-19.0, 11.3-3.10 and 12.6-0.704ngm-3. Concentrations of ΣAZAs were always below 0.5ngm-3. Irrespective of the city, the dominant PAHs were benzo[b+j+k]fluoranthene, retene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene. The most abundant OPAH in all cities was 1,8-naphthalic anhydride, whereas 5-nitroacenaphthene was the prevailing NPAH. The ΣOPAHs/ΣPAHs and ΣNPAHs/ΣPAHs were higher in summer than in winter, suggesting increasing formation of derivatives by photochemical degradation of PAHs. Molecular diagnostic ratios suggested that, after traffic, biomass burning was the dominant emission source. Apart from being influenced by seasonal sources, the marked differences between winter and summer may indicate that these diagnostic ratios are particularly sensitive to photodegradation, and thus should be applied and interpreted cautiously. The lifetime excess cancer risk from inhalation was, in part, attributable to PAH derivatives, acclaiming the need to include these compounds in regular monitoring programmes. On average, 206, 88 and 26 cancer cases per million people were estimated, by the World Health Organisation method, for the traffic-impacted, urban background and suburban atmospheres of Oporto, Florence and Athens, respectively.

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.

A one-year record of carbonaceous components and major ions in aerosols from an urban kerbside location in Oporto, Portugal.

PM2.5 aerosol samples were collected from January 2013 to January 2014 on the kerbside of a major arterial route in the city of Oporto, Portugal, and later analyzed for carbonaceous fractions and water soluble ions. The average concentrations of organic carbon (OC), elemental carbon (EC) and water soluble organic carbon (WSOC) in the aerosol were 6.2µg/m(3), 5.0µg/m(3) and 3.8µg/m(3), respectively, and fit within the range of values that have been observed close to major roads in Europe, Asia and North America. On average, carbonaceous matter accounted for 56% of the gravimetrically measured PM2.5 mass. The three carbon fractions exhibited a similar seasonal variation, with high concentrations in late autumn and in winter, and low concentrations in spring. SO4(2-) was the dominant water soluble ion, followed by NO3(-), NH4(+), Cl(-), Na(+), K(+), oxalate, Ca(2+), Mg(2+), formate, methanesulfonate and acetate. Some of these ions exhibited a clear seasonal trend during the study period. The average OC/EC ratio for the entire set of samples was 1.28±0.61, which was consistent with a significant influence of vehicle exhaust emissions on aerosol composition. On the other hand, the average WSOC/OC ratio was 0.67±0.23, reflecting the influence of other emitting sources. WSOC was highly correlated with nssK(+), a tracer of biomass combustion, and was not correlated with nssSO4(2-), a species associated with secondary processes, suggesting that the main source of WSOC was biomass burning. Most of the SO4(2-) was anthropogenic in origin and was closely associated with NH4(+), pointing to the formation of secondary aerosols. Na(+), Cl(-) and methanesulfonate were clearly associated with marine sources while NO3(-) was related with combustion of both fossil and non-fossil fuels. Mixed sources explained the occurrence of the other water soluble ions.

Oxidative potential and chemical composition of PM2.5 in office buildings across Europe - The OFFICAIR study.

In the frame of the OFFICAIR project, indoor and outdoor PM2.5 samples were collected in office buildings across Europe in two sampling campaigns (summer and winter). The ability of the particles to deplete physiologically relevant antioxidants (ascorbic acid (AA), reduced glutathione (GSH)) in a synthetic respiratory tract lining fluid, i.e., oxidative potential (OP), was assessed. Furthermore, the link between particulate OP and the concentration of the PM constituents was investigated. The mean indoor PM2.5 mass concentration values were substantially lower than the related outdoor values with a mean indoor/outdoor PM2.5 mass concentration ratio of 0.62 and 0.61 for the summer and winter campaigns respectively. The OP of PM2.5 varied markedly across Europe with the highest outdoor OP(AA) m(-3) and OP(GSH) m(-3) (% antioxidant depletion/m(3) air) values obtained for Hungary, while PM2.5 collected in Finland exhibited the lowest values. Seasonal variation could be observed for both indoor and outdoor OP(AA) m(-3) and OP(GSH) m(-3) with higher mean values during winter. The indoor/outdoor OP(AA) m(-3) and OP(GSH) m(-3) ratios were less than one with 4 and 17 exceptions out of the 40 cases respectively. These results indicate that indoor air is generally less oxidatively challenging than outdoors. Correlation analysis revealed that trace elements play an important role in determining OP, in particular, the Cu content. Indoor air chemistry might affect OP since weaker correlations were obtained for indoor PM2.5. Our findings also suggest that office workers may be exposed to health relevant PM constituents to a different extent within the same building.

Changes in chemical composition and oxidative potential of urban PM(2.5) between 2010 and 2013 in Hungary.

A comprehensive chemical characterization and oxidative potential (OP) assessment of PM2.5 was carried out at an urban site of Budapest between June 2010 and May 2013 to investigate the seasonal variability of particulate phase air pollutants and their oxidative activity. Chemical analyses included the determination of the concentration of trace elements, major water-soluble inorganic ions and carbonaceous fractions (total carbon, water-soluble organic carbon, organic carbon, elemental carbon). The OP of PM2.5 was assessed by antioxidant depletion using a synthetic respiratory tract lining fluid containing ascorbate, reduced glutathione and urate. The mean PM2.5 mass concentration (21.0 µg m(-3)) was just below the 25 µg m(-3) annual mean PM2.5 limit value set by the European Commission and showed a seasonal pattern with higher levels during winter. On average, 84% of the gravimetric mass could be reconstructed by the chemical measurements. Organic matter and secondary inorganic ions were the most dominant PM2.5 constituents contributing 40 and 29% of its mass, respectively. Changes in the yearly concentrations were not identified for the investigated compounds between 2010 and 2013. Temporal differences in both ascorbate and glutathione oxidation could be observed during the 3-year long sampling period; however, no clear seasonal trend was apparent. OP metrics were associated mainly with traffic-related trace elements; however, other PM sources (i.e., long-range transport, secondary aerosol formation) could also contribute to particulate OP in Budapest. The weak correlation between OP metrics and PM2.5 mass concentration suggests the possibility of using OP as an additional metric in epidemiology.

One-year study of the elemental composition and source apportionment of PM10 aerosols in Florence, Italy.

An extensive investigation was carried out for the characterisation of the air particulate composition in Florence. The aim was to determine the aerosol elemental concentrations, as well as to identify pollution sources. For our investigation, the external Particle-Induced X-Ray Emission-Particle-Induced gamma-Ray Emission beam facility of the Istituto Nazionale di Fisica Nucleare, Van de Graaff accelerator at the Physics Department of the Florence University was used. We report the results of the analysis of a long temporal series (approximately 1 yr) of PM10 particulate samples, collected on Millipore filters on a daily basis in three different sites (characterised by different urban settings). Daily concentrations of more than 20 elements were detected. The long sampling period (approximately 1 yr) allowed a comparison with the air quality recommended values and the identification of seasonal variations. Four main sources (traffic, oil-combustion, soil-dust, and wind transported sea-salt) were extracted with the help of Principal Component Analysis (PCA). An absolute PCA showed traffic to be the major source both in the high traffic site and in the urban background site.

High-time resolution and size-segregated elemental composition in high-intensity pyrotechnic exposures.

Typical of festivals in Eastern Spain, mascletàs are high-intensity pyrotechnic events where thousands of firecrackers are burnt in an intense, rapid episode that generates short-lived heavy aerosol clouds. High temporal resolution and size distribution characterisation of aerosol components were performed to evaluate the effects of the brief (<30 min) and acute exposure on the spectators present. Very high concentrations of firework specific elements, especially in the fine fraction, were reached during mascletàs, with values of about 500 µg/m(3) for K and 300 µg/m(3) for Cl. Sr, Al, Mg, Ba, Cu, Co, Zn, and Pb concentration increase factors of more than 100 (1000 for Sr and Ba) were observed in the fine fraction with respect to background levels. Crustal origin elements, like Ca, Fe, Si, Ti, also showed an important concentration rise (~10 times above background levels) but this is due to dust resuspension by pyrotechnic explosions. The crustal components are mainly in the coarse mode (>90% elemental mass), between 2 and 3 µm. Most firework related metals are concentrated in the submicrometric region (>80%) with a trimodal size distribution. This may be interesting to epidemiologists given the toxic effects that such fine, metal-rich particles can have on human health.

PM10 source apportionment in the surroundings of the San Vicente del Raspeig cement plant complex in southeastern Spain.

INTRODUCTION: The concentrations of trace metals, ionic species, and carbonaceous components in PM(10) (particulate matter with aerodynamic diameters smaller than 10 µm) were measured from samples collected near an industrial complex, primarily composed of cement plants, in southeastern Spain, from September 2005 to August 2006. MATERIALS AND METHODS: Positive matrix factorization and conditional probability function were applied to this data set to identify different types of sources. RESULTS: Six significant sources were identified: crustal matter, traffic, aged sea salt, industrial emissions, secondary aerosol, and sea salt. The difficulty of separating anthropogenic sources from those of natural origin is highlighted in this study; in particular, the crustal source can be connected with both natural (African outbreaks, wind resuspension) and man-made emissions, like fugitive emissions in an industrial environment.