María Cruz Minguillón

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.

Application of optimally scaled target factor analysis for assessing source contribution of ambient PM10

Abstract Speciated coarse particulate matter (PM10) data ob tained at three air quality monitoring sites in a highly industrialized area in Spain between 2002 and 2007 were analyzed for assessing source contribution of ambient particulate matter (PM). The source apportionment of PM in this area is an especially difficult task. There are industrial mineral dust emissions that need to be separately quantified from the natural sources of mineral PM. On the other hand, the diversity of industrial processes in the area results in a puzzling industrial emissions scenario. To solve this complex problem, a two-step methodology based on the possibilities of the Multilinear Engine was used. Application of positive matrix factorization to the dataset allowed the identification of nine factors relevant to the study area. This preliminary analysis permitted resolving two mineral factors. As a second step, a target rotation was implemented for transforming the mineral factors into experimentally characterized soil resuspension and industrial clay sources. In addition to improving the physical interpretation of these factors, the target rotation reduced the errors arising from the rotational freedom of the solution and the multicollinearity among sources. In this way, the main primary industrial emissions of PM in the zone were identified by this target factor analysis. A marked decrease was observed between 2002 and 2007 for the contributions of industrial sources coinciding with the implementation of mitigation measures in their processes. This study supports the utility of source apportionment methodologies for quantitatively evaluating the effectiveness of the abatement programs for air quality improvement.

Exposure to airborne particulate matter in the subway system.

The Barcelona subway system comprises eight subway lines, at different depths, with different tunnel dimensions, station designs and train frequencies. An extensive measurement campaign was performed in this subway system in order to characterise the airborne particulate matter (PM) measuring its concentration and investigating its variability, both inside trains and on platforms, in two different seasonal periods (warmer and colder), to better understand the main factors controlling it, and therefore the way to improve air quality. The majority of PM in the underground stations is generated within the subway system, due to abrasion and wear of rail tracks, wheels and braking pads caused during the motion of the trains. Substantial variation in average PM concentrations between underground stations was observed, which might be associated to different ventilation and air conditioning systems, characteristics/design of each station and variations in the train frequency. Average PM2.5 concentrations on the platforms in the subway operating hours ranged from 20 to 51 and from 41 to 91 μg m(-3) in the warmer and colder period, respectively, mainly related to the seasonal changes in the subway ventilation systems. The new subway lines with platform screen doors showed PM2.5 concentrations lower than those in the conventional system, which is probably attributable not only to the more advanced ventilation setup, but also to the lower train frequency and the design of the stations. PM concentrations inside the trains were generally lower than those on the platforms, which is attributable to the air conditioning systems operating inside the trains, which are equipped with air filters. This study allows the analysis and quantification of the impact of different ventilation settings on air quality, which provides an improvement on the knowledge for the general understanding and good management of air quality in the subway system.

Effect of ceramic industrial particulate emission control on key components of ambient PM10.

The relationship between specific particulate emission control and ambient levels of some PM(10) components (Zn, As, Pb, Cs, Tl) was evaluated. To this end, the industrial area of Castellón (Eastern Spain) was selected, where around 40% of the EU glazed ceramic tiles and a high proportion of EU ceramic frits are produced. The PM(10) emissions from the ceramic processes were calculated over the period 2000-2006, taking into account the degree of implementation of corrective measures throughout the study period. Abatement systems were implemented in the majority of the fusion kilns for frit manufacture in the area as a result of the application of the Directive 1996/61/EC, leading to a marked decrease in PM(10) emissions. By contrast, emissions from tile manufacture remained relatively constant because of the few changes in the implementation of corrective measures. On the other hand, ambient PM(10) levels and composition measurements were carried out from 2002 to 2006. A high correlation between PM(10) emissions from frit manufacture and ambient levels of Zn, As, Pb and Cs (R(2) from 0.61 to 0.98) was observed. On the basis of these results, the potential impact of the implementation of corrective measures to reduce emissions from tile manufacture was quantified, resulting in a possible decrease of 3-5 microg/m(3) and 2 microg/m(3) in ambient mineral PM(10) (on an annual basis) in urban and suburban areas, respectively. This relatively simple methodology allows us to estimate the direct effect of a reduction in primary particulate emissions on ambient levels of key particulate components, and to make a preliminary quantification of the possibilities of air quality improvement by means of further emission reduction. Therefore, it is a useful tool for developing future air quality plans in the study area and in other industrialised areas.

Factors controlling air quality in different European subway systems

Sampling campaigns using the same equipment and methodology were conducted to assess and compare the air quality at three South European subway systems (Barcelona, Athens and Oporto), focusing on concentrations and chemical composition of PM2.5 on subway platforms, as well as PM2.5 concentrations inside trains. Experimental results showed that the mean PM2.5 concentrations widely varied among the European subway systems, and even among different platforms within the same underground system, which might be associated to distinct station and tunnel designs and ventilation systems. In all cases PM2.5 concentrations on the platforms were higher than those in the urban ambient air, evidencing that there is generation of PM2.5 associated with the subway systems operation. Subway PM2.5 consisted of elemental iron, total carbon, crustal matter, secondary inorganic compounds, insoluble sulphate, halite and trace elements. Of all metals, Fe was the most abundant, accounting for 29-43% of the total PM2.5 mass (41-61% if Fe2O3 is considered), indicating the existence of an Fe source in the subway system, which could have its origin in mechanical friction and wear processes between rails, wheels and brakes. The trace elements with the highest enrichment in the subway PM2.5 were Ba, Cu, Mn, Zn, Cr, Sb, Sr, Ni, Sn, Co, Zr and Mo. Similar PM2.5 diurnal trends were observed on platforms from different subway systems, with higher concentrations during subway operating hours than during the transport service interruption, and lower levels on weekends than on weekdays. PM2.5 concentrations depended largely on the operation and frequency of the trains and the ventilation system, and were lower inside the trains, when air conditioning system was operating properly, than on the platforms. However, the PM2.5 concentrations increased considerably when the train windows were open. The PM2.5 levels inside the trains decreased with the trains passage in aboveground sections.

A new look at inhalable metalliferous airborne particles on rail subway platforms

Most particles breathed on rail subway platforms are highly ferruginous (FePM) and extremely small (nanometric to a few microns in size). High magnification observations of particle texture and chemistry on airborne PM₁₀ samples collected from the Barcelona Metro, combined with published experimental work on particle generation by frictional sliding, allow us to propose a general model to explain the origin of most subway FePM. Particle generation occurs by mechanical wear at the brake-wheel and wheel-rail interfaces, where magnetic metallic flakes and splinters are released and undergo progressive atmospheric oxidation from metallic iron to magnetite and maghemite. Flakes of magnetite typically comprise mottled mosaics of octahedral nanocrystals (10-20 nm) that become pseudomorphed by maghemite. Continued oxidation results in extensive alteration of the magnetic nanostructure to more rounded aggregates of non-magnetic hematite nanocrystals, with magnetic precursors (including iron metal) still preserved in some particle cores. Particles derived from steel wheel and rails contain a characteristic trace element chemistry, typically with Mn/Fe=0.01. Flakes released from brakes are chemically very distinctive, depending on the pad composition, being always carbonaceous, commonly barium-rich, and texturally inhomogeneous, with trace elements present in nanominerals incorporated within the crystalline structure. In the studied subway lines of Barcelona at least there appears to be only a minimal aerosol contribution from high temperature processes such as sparking. To date there is no strong evidence that these chemically and texturally complex inhalable metallic materials are any more or less toxic than street-level urban particles, and as with outdoor air, the priority in subway air quality should be to reduce high mass concentrations of aerosol present in some stations.

Origin of inorganic and organic components of PM2.5 in subway stations of Barcelona, Spain

The present work assesses indoor air quality in stations of the Barcelona subway system. PM2.5 concentrations on the platforms of 4 subway stations were measured during two different seasons and the chemical composition was determined. A Positive Matrix Factorization analysis was performed to identify and quantify the contributions of major PM2.5 sources in the subway stations. Mean PM2.5 concentrations varied according to the stations design and seasonal periods. PM2.5 was composed of haematite, carbonaceous aerosol, crustal matter, secondary inorganic compounds, trace elements, insoluble sulphate and halite. Organic compounds such as PAHs, nicotine, levoglucosan and aromatic musk compounds were also identified. Subway PM2.5 source comprised emissions from rails, wheels, catenaries, brake pads and pantographs. The subway source showed different chemical profiles for each station, but was always dominated by Fe. Control actions on the source are important for the achievement of better air quality in the subway environment.

PM sources in a highly industrialised area in the process of implementing PM abatement technology. Quantification and evolution.

Principal component analysis (PCA) coupled with a multilinear regression analysis (MLRA) was applied to PM(10) speciation data series (2002-2005) from four sampling sites in a highly industrialised area (ceramic production) in the process of implementing emission abatement technology. Five common factors with similar chemical profiles were identified at all the sites: mineral, regional background (influenced by the industrial estate located on the coast: an oil refinery and a power plant), sea spray, industrial 1 (manufacture and use of glaze components, including frit fusion) and road traffic. The contribution of the regional background differs slightly from site to site. The mineral factor, attributed to the sum of several sources (mainly the ceramic industry, but also with minor contributions from soil resuspension and African dust outbreaks) contributes between 9 and 11 microg m(-3) at all the sites. Source industrial 1 entails an increase in PM(10) levels between 4 and 5 microg m(-3) at the urban sites and 2 microg m(-3) at the suburban background site. However, after 2004, this source contributed less than 2 microg m(-3) at most sites, whereas the remaining sources did not show an upward or downward trend along the study period. This gradual decrease in the contribution of source industrial 1 coincides with the implementation of PM abatement technology in the frit fusion kilns of the area. This relationship enables us to assess the efficiency of the implementation of environmental technologies in terms of their impact on air quality.

The effect of ventilation protocols on airborne particulate matter in subway systems

As part of the European-funded IMPROVE LIFE project work programme experiments were performed in the Barcelona Metro system with the objective of better understanding the relationship between ventilation and air quality. The results demonstrate that tunnel ventilation plays an extremely important role in maintaining cleaner air and is capable of reducing both inhalable particulate matter (PM) mass and particle number concentration (>0.3μm) on platforms by over 50%, even in the presence of full-length platform screen doors. Another key influence on platform air quality is the chosen combination of fan power and forced air flow direction (impulsion of outdoor ambient air or extraction of subway indoor air): cleaner platform air was achieved using platform impulsion at higher power settings designed to ameliorate high summer temperatures underground. Reversing platform air flow from impulsion to extraction produced an immediate deterioration in PM air quality, most notably if the higher power setting was maintained, when an especially marked increase in numbers of very fine (submicron) particles was observed and attributed to tunnel air being drawn into the platform. At night, in the absence of trains and platform ventilation, platform air quality improves when tunnel fans are working at reduced power, whatever the flow direction (impulsion/extraction). Inside the air conditioned Barcelona Metro trains (where underground commuters spend most of their time) air quality is markedly better than on the platform, and unchanged A/C filters were observed capable of maintaining a similar reduction in inside train PM for at least three months.

Bioaerosols in the Barcelona subway system

Subway systems worldwide transport more than 100 million people daily; therefore, air quality on station platforms and inside trains is an important urban air pollution issue. We examined the microbiological composition and abundance in space and time of bioaerosols collected in the Barcelona subway system during a cold period. Quantitative PCR was used to quantify total bacteria, Aspergillus fumigatus, influenza A and B, and rhinoviruses. Multitag 454 pyrosequencing of the 16S rRNA gene was used to assess bacterial community composition and biodiversity. The results showed low bioaerosol concentrations regarding the targeted microorganisms, although the bacterial bioburden was rather high (104 bacteria/m3 ). Airborne bacterial communities presented a high degree of overlap among the different subway environments sampled (inside trains, platforms, and lobbies) and were dominated by a few widespread taxa, with Methylobacterium being the most abundant genus. Human-related microbiota in sequence dataset and ascribed to potentially pathogenic bacteria were found in low proportion (maximum values below 2% of sequence readings) and evenly detected. Hence, no important biological exposure marker was detected in any of the sampled environments. Overall, we found that commuters are not the main source of bioaerosols in the Barcelona subway system.