Marco Pandolfi

Transport of desert dust mixed with North African industrial pollutants in the subtropical Saharan Air Layer

An analysis of chemical composition data of particulate matter samples (TSP, PM 10 and PM2.5) collected from 2002 to 2008 in the North Atlantic free troposphere at the Izãna Global Atmospheric Watch (GAW) observatory (Tenerife, Canary Islands) shows that desert dust is very frequently mixed with particulate pollutants in the Saharan Air Layer (SAL). The study of this data set with Median Concentrations At Receptor (MCAR) plots allowed the identification of the potential source regions of the dust and particulate pollutants. Areas located at the south of the southern slope of the Atlas mountains emerge as the most frequent source of the soil desert dust advected to the northern edge of the SAL in summer. Industrial emissions occurring in Northern Algeria, Eastern Algeria, Tunisia and the Atlantic coast of Morocco appear as the most important source of the nitrate, ammonium and a fraction of sulphate (at least 60 % of the sulphate<10 μm transported from some regions) observed in the SAL. These emissions are mostly linked to crude oil refineries, phosphate-based fertilizer industry and power plants. Although desert dust emissions appear as the most frequent source of the phosphorous observed in the SAL, high P concentrations are observed when the SAL is affected by emissions from open mines of phosphate and phosphate based fertilizer industry. The results also show that a significant fraction of the sulphate (up to 90 % of sulphate <10 μm transported from some regions) observed in the SAL may be influenced by soil emissions of evaporite minerals in well defined regions where dry saline lakes (chotts) are present. These interpretations of the MCAR plots are consistent with the results obtained with the Positive Matrix Factorization Correspondence to: S. Rodŕıguez (srodriguezg@aemet.es) (PMF2) receptor modelling. The results of this study show that North African industrial pollutants may be mixed with desert dust and exported to the North Atlantic in the Saharan Air Layer.

Child exposure to indoor and outdoor air pollutants in schools in Barcelona, Spain

Proximity to road traffic involves higher health risks because of atmospheric pollutants. In addition to outdoor air, indoor air quality contributes to overall exposure. In the framework of the BREATHE study, indoor and outdoor air pollution was assessed in 39 schools in Barcelona. The study quantifies indoor and outdoor air quality during school hours of the BREATHE schools. High levels of fine particles (PM2.5), nitrogen dioxide (NO2), equivalent black carbon (EBC), ultrafine particle (UFP) number concentration and road traffic related trace metals were detected in school playgrounds and indoor environments. PM2.5 almost doubled (factor of 1.7) the usual urban background (UB) levels reported for Barcelona owing to high school-sourced PM2.5 contributions: [1] an indoor-generated source characterised mainly by organic carbon (OC) from organic textile fibres, cooking and other organic emissions, and by calcium and strontium (chalk dust) and; [2] mineral elements from sand-filled playgrounds, detected both indoors and outdoors. The levels of mineral elements are unusually high in PM2.5 because of the breakdown of mineral particles during playground activities. Moreover, anthropogenic PM components (such as OC and arsenic) are dry/wet deposited in this mineral matter. Therefore, PM2.5 cannot be considered a good tracer of traffic emissions in schools despite being influenced by them. On the other hand, outdoor NO2, EBC, UFP, and antimony appear to be good indicators of traffic emissions. The concentrations of NO2 are 1.2 times higher at schools than UB, suggesting the proximity of some schools to road traffic. Indoor levels of these traffic-sourced pollutants are very similar to those detected outdoors, indicating easy penetration of atmospheric pollutants. Spatial variation shows higher levels of EBC, NO2, UFP and, partially, PM2.5 in schools in the centre than in the outskirts of Barcelona, highlighting the influence of traffic emissions. Mean child exposure to pollutants in schools in Barcelona attains intermediate levels between UB and traffic stations.

Variations in vanadium, nickel and lanthanoid element concentrations in urban air

The emission of trace metal pollutants by industry and transport takes place on a scale large enough to alter atmospheric chemistry and results in measurable differences between the urban background of inhalable particulate matter (PM) in different towns. This is particularly well demonstrated by the technogenic release into the atmosphere of V, Ni, and lanthanoid elements. We compare PM concentrations of these metals in large datasets from five industrial towns in Spain variously influenced by emissions from refinery, power station, shipping, stainless steel, ceramic tiles and brick-making. Increased La/Ce values in urban background inhalable PM, due to La-contamination from refineries and their residual products (fuel oils and petcoke), contrast with Ce-rich emissions from the ceramic related industry, and clearly demonstrate the value of this ratio as a sensitive and reliable tracer for many point source emissions. Similarly, anomalously high V/Ni values (>4) can detect the influence of nearby high-V petcoke and fuel oil combustion, although the use of this ratio in urban background PM is limited by overlapping values in natural and anthropogenic materials. Geochemical characterisation of urban background PM is a valuable compliment to the physical monitoring of aerosols widely employed in urban areas, especially given the relevance of trace metal inhalation to urban health issues.

A comprehensive assessment of PM emissions from paved roads: Real-world Emission Factors and intense street cleaning trials

Compliance with air quality standards requires control of source emissions: fine exhaust particles are already subject to regulation but vehicle fleets increase whilst the non-exhaust emissions are totally uncontrolled. Emission inventories are scarce despite their suitability for researchers and regulating agencies for managing air quality and PM reduction measures. Only few countries in Europe proposed street cleaning as a possible control measure, but its effectiveness is still far to be determined. This study offers first estimates of Real-world Emission Factors for PM(10) and brake-wear elements and the effect on PM(10) concentrations induced by intense street cleaning trials. A straightforward campaign was carried out in the city of Barcelona with hourly elemental composition of fine and coarse PM to detect any short-term effect of street cleaning on specific tracers of non-exhaust emissions. Samples were analyzed by Particle Induced X-Ray Emission. Real-world Emission Factor for PM(10) averaged for the local fleet resulted to be 97 mg veh(-1) km(-1). When compared to other European studies, our EF resulted higher than what found in UK, Germany, Switzerland and Austria but lower than Scandinavian countries. For brake-related elements, total EFs were estimated, accounting for the sum of direct and resuspension emissions, in 7400, 486, 106 and 86 microg veh(-1) km(-1), respectively for Fe, Cu, Sn and Sb. In PM(2.5)Fe and Cu emission factors were respectively 4884 and 306 microg veh(-1) km(-1). Intense street cleaning trials evidenced a PM(10) reduction at kerbside of 3 microg m(-3) (mean daily levels of 54 microg m(-3)), with respect to reference stations. It is important to remark that such benefit could only be detected in small time-integration periods (12:00-18:00) since in daily values this benefit was not noticed. Hourly PM elemental monitoring allowed the identification of mineral and brake-related metallic particles as those responsible of the PM(10) reduction.

2001–2012 trends on air quality in Spain

This study aims at interpreting the 2001-2012 trends of major air pollutants in Spain, with a major focus on evaluating their relationship with those of the national emission inventories (NEI) and policy actions. Marked downward concentration trends were evidenced for PM10, PM2.5 and CO. Concentrations of NO2 and NOx also declined but in a lesser proportion at rural and traffic sites. At rural sites O3 has been kept constant, whereas it clearly increased at urban and industrial sites. Comparison of the air quality trends and major inflection points with those from NEIs, the National Energy Consumption and the calendar of the implementation of major policy actions allowed us to clearly identify major benefits of European directives on power generation and industrial sources (such as the Large Combustion Plants and the Integrated Pollution Prevention and Control Directives). This, together with a sharp 2007-2008 decrease of coal consumption has probably caused the marked parallel decline of SO2, NOx and for PM2.5 concentrations. Also the effect of the EURO 4 and 5 vehicle emission standards on decreasing emissions of PM and CO from vehicles is noticeable. The smooth decline in NO2-NOx levels is mostly attributed to the low efficiency of EURO 4 and 5 standards in reducing real life urban driving NO2 emissions. The low NOx decrease together with the complexity of the reactions of O3 formation is responsible for the constant O3 concentrations, or even the urban increase. The financial crisis has also contributed to the decrease of the ambient concentration of pollutants; however this caused a major reduction of the primary energy consumption from 2008 to 2009, and not from 2007 to 2008 when ambient air PM and SO2 sharply decreased. The meteorological influence was characterized by a 2008-2012 period favorable to the dispersion of pollutants when compared to the 2001-2007.

Effect of fireworks events on urban background trace metal aerosol concentrations: is the cocktail worth the show?

We report on the effect of a major firework event on urban background atmospheric PM(2.5) chemistry, using 24-h data collected over 8 weeks at two sites in Girona, Spain. The firework pollution episode (Sant Joan fiesta on 23rd June 2008) measured in city centre parkland increased local background PM(2.5) concentrations as follows: Sr (x86), K (x26), Ba (x11), Co (x9), Pb (x7), Cu (x5), Zn (x4), Bi (x4), Mg (x4), Rb (x4), Sb (x3), P (x3), Ga (x2), Mn (x2), As (x2), Ti (x2) and SO(4)(2-) (x2). Marked increases in these elements were also measured outside the park as the pollution cloud drifted over the city centre, and levels of some metals remained elevated above background for days after the event as a reservoir of metalliferous dust persisted within the urban area. Transient high-PM pollution episodes are a proven health hazard, made worse in the case of firework combustion because many of the elements released are both toxic and finely respirable, and because displays commonly take place in an already polluted urban atmosphere.

Concentrations, sources and geochemistry of airborne particulate matter at a major European airport

Monitoring of aerosol particle concentrations (PM(10), PM(2.5), PM(1)) and chemical analysis (PM(10)) was undertaken at a major European airport (El Prat, Barcelona) for a whole month during autumn 2007. Concentrations of airborne PM at the airport were close to those at road traffic hotspots in the nearby Barcelona city, with means measuring 48 microg PM(10)/m(3), 21 microg PM(2.5)/m(3) and 17 microg PM(1)/m(3). Meteorological controls on PM at El Prat are identified as cleansing daytime sea breezes with abundant coarse salt particles, alternating with nocturnal land-sourced winds which channel air polluted by industry and traffic (PM(1)/PM(10) ratios > 0.5) SE down the Llobregat Valley. Chemical analyses of the PM(10) samples show that crustal PM is dominant (38% of PM(10)), followed by total carbon (OC + EC, 25%), secondary inorganic aerosols (SIA, 20%), and sea salt (6%). Local construction work for a new airport terminal was an important contributor to PM(10) crustal levels. Source apportionment modelling PCA-MLRA identifies five factors: industrial/traffic, crustal, sea salt, SIA, and K(+) likely derived from agricultural biomass burning. Whereas most of the atmospheric contamination concerning ambient air PM(10) levels at El Prat is not attributable directly to aircraft movement, levels of carbon are unusually high (especially organic carbon), as are metals possibly sourced from tyre detritus/smoke in runway dust (Ba, Zn, Mo) and from brake dust in ambient PM(10) (Cu, Sb), especially when the airport is at its most busy. We identify microflakes of aluminous alloys in ambient PM(10) filters derived from corroded fuselage and wings as an unequivocal and highly distinctive tracer for aircraft movement.

Spatiotemporally resolved black carbon concentration, schoolchildren's exposure and dose in Barcelona

Abstract At city level, personal monitoring is the best way to assess peoples exposure. However, it is usually estimated from a few monitoring stations. Our aim was to determine the exposure to black carbon (BC) and BC dose for 45 schoolchildren with portable microaethalometers and to evaluate the relationship between personal monitoring and fixed stations at schools (indoor and outdoor) and in an urban background (UB) site. Personal BC concentra‐tions were 20% higher than in fixed stations at schools. Linear mixed‐effect models showed low R 2 between personal measurements and fixed stations at schools (R 2 ≤ 0.28), increasing to R 2 ≥ 0.70 if considering only periods when children were at schools. For the UB station, the respective R 2 were 0.18 and 0.45, indicating the importance of the distance to the monitoring station when assessing exposure. During the warm season, the fixed stations agreed better with personal measurements than during the cold one. Children spent 6% of their time on commuting but received 20% of their daily BC dose, due to co‐occurrence with road traffic rush hours and the close proximity to the source. Children received 37% of their daily‐integrated BC dose at school. Indoor environments (classroom and home) were responsible for the 56% BC dose.

Effects of sources and meteorology on particulate matter in the Western Mediterranean Basin: An overview of the DAURE campaign

DAURE (Determination of the Sources of Atmospheric Aerosols in Urban and Rural Environments in the Western Mediterranean) was a multidisciplinary international field campaign aimed at investigating the sources and meteorological controls of particulate matter in the Western Mediterranean Basin (WMB). Measurements were simultaneously performed at an urban-coastal (Barcelona, BCN) and a rural-elevated (Montseny, MSY) site pair in NE Spain during winter and summer. State-of-the-art methods such as 14C analysis, proton-transfer reaction mass spectrometry, and high-resolution aerosol mass spectrometry were applied for the first time in the WMB as part of DAURE. WMB regional pollution episodes were associated with high concentrations of inorganic and organic species formed during the transport to inland areas and built up at regional scales. Winter pollutants accumulation depended on the degree of regional stagnation of an air mass under anticyclonic conditions and the planetary boundary layer height. In summer, regional recirculation and biogenic secondary organic aerosols (SOA) formation mainly determined the regional pollutant concentrations. The contribution from fossil sources to organic carbon (OC) and elemental carbon (EC) and hydrocarbon-like organic aerosol concentrations were higher at BCN compared with MSY due to traffic emissions. The relative contribution of nonfossil OC was higher at MSY especially in summer due to biogenic emissions. The fossil OC/EC ratio at MSY was twice the corresponding ratio at BCN indicating that a substantial fraction of fossil OC was due to fossil SOA. In winter, BCN cooking emissions were identified as an important source of modern carbon in primary organic aerosol.

An inter-comparison of PM10 source apportionment using PCA and PMF receptor models in three European sites.

Source apportionment of aerosol is an important approach to investigate aerosol formation and transformation processes as well as to assess appropriate mitigation strategies and to investigate causes of non-compliance with air quality standards (Directive 2008/50/CE). Receptor models (RMs) based on chemical composition of aerosol measured at specific sites are a useful, and widely used, tool to perform source apportionment. However, an analysis of available studies in the scientific literature reveals heterogeneities in the approaches used, in terms of “working variables” such as the number of samples in the dataset and the number of chemical species used as well as in the modeling tools used. In this work, an inter-comparison of PM10 source apportionment results obtained at three European measurement sites is presented, using two receptor models: principal component analysis coupled with multi-linear regression analysis (PCA-MLRA) and positive matrix factorization (PMF). The inter-comparison focuses on source identification, quantification of source contribution to PM10, robustness of the results, and how these are influenced by the number of chemical species available in the datasets. Results show very similar component/factor profiles identified by PCA and PMF, with some discrepancies in the number of factors. The PMF model appears to be more suitable to separate secondary sulfate and secondary nitrate with respect to PCA at least in the datasets analyzed. Further, some difficulties have been observed with PCA in separating industrial and heavy oil combustion contributions. Commonly at all sites, the crustal contributions found with PCA were larger than those found with PMF, and the secondary inorganic aerosol contributions found by PCA were lower than those found by PMF. Site-dependent differences were also observed for traffic and marine contributions. The inter-comparison of source apportionment performed on complete datasets (using the full range of available chemical species) and incomplete datasets (with reduced number of chemical species) allowed to investigate the sensitivity of source apportionment (SA) results to the working variables used in the RMs. Results show that, at both sites, the profiles and the contributions of the different sources calculated with PMF are comparable within the estimated uncertainties indicating a good stability and robustness of PMF results. In contrast, PCA outputs are more sensitive to the chemical species present in the datasets. In PCA, the crustal contributions are higher in the incomplete datasets and the traffic contributions are significantly lower for incomplete datasets.