Yolanda González-Castanedo

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.

Contribution of mine wastes to atmospheric metal deposition in the surrounding area of an abandoned heavily polluted mining district (Rio Tinto mines, Spain)

The present study seeks to estimate the impact of abandoned mine wastes on the levels and chemical profile of total atmospheric deposition in one of the oldest and largest mining districts in Europe (Rio Tinto mines, Iberian Pyrite Belt), on the basis of a complete geochemical characterization of particulate matter samples periodically collected in five sampling stations located around the mining district between March 2009 and February 2011. The annual levels of total bulk deposition (soluble and insoluble fractions) registered in the Rio Tinto Mining District ranged between 18 and 43 g/m(2) depending on the distance from the sampling station with regard to the mine waste deposits. As a general pattern in the area, high mass levels of Zn and Cu were deposited in a range of 9-62 mg/m(2) not only in the insoluble but also in the soluble fraction. Other potentially toxic trace elements such as As, Sb, Ba, Pb, Sn and Bi showed greater deposition fluxes in the locations closest to the mine waste deposits. A principal component analysis with a Multilinear Regression Analysis certifies the presence of two common sources in the mining area: 1) a mineral factor composed mainly of elements derived from silicate minerals (Al, Ca, Sr, Ti, Li, Mg, Mn, K, Na and Fe), mixed with other anthropogenic species (NH4(+), SO4(2-), NO3(-)) within the village closest to the mine; and 2) a marine factor composed of Na, Cl, Mg, SO4(2-) and Sr. In addition, a mine waste factor made up of toxic elements (Cu, Zn, Ga, As, Sb, Ba, Pb, Sn, Cd and Bi) has been recognized in the sampling sites exposed to dust-bearing winds downwind of the mining area, suggesting that mine wastes are a relevant source of heavy-mineral particles with potentially adverse environmental effects to surrounding soils, plants and humans.

Characterization and origin of EC and OC particulate matter near the Doñana National Park (SW Spain).

In the South of Spain, major industrial estates (e.g. Huelva) exist alongside ecologically interesting zones (e.g. Doñana National Park). Between June 2005 and June 2006, PM10 and PM2.5 were measured, for total mass, organic carbon (OC) and elemental carbon (EC) chemical composition, at a station in an ecologically interesting area located near Doñana National Park and an urban background area with industrial influence. The mean OC concentration is higher in the urban background (3.5 microg m(-3)) than in the rural monitoring station (2.8 microg m(-3)) as a consequence of local emissions (e.g. traffic). A total of 82% of TC is OC in the rural station, while the urban background station reveals 70% and 73% of TC in the PM10 and PM2.5 mass, respectively. The study of air-mass origin and characterization of carbonaceous species in the course of simultaneous sampling in rural and urban background monitoring stations differentiated three long-range air-mass transports: a North-African dust outbreak, Atlantic Advection and Continental (N-NW) episodes, the origins of the first and last of which are more heavily influenced by the anthropogenic emissions from industrial estates located around the city of Huelva (Punta del Sebo and Nuevo Puerto). Higher values were measured for OC and EC in the study area during the North-African dust outbreak, similar to those obtained during the Continental episode (N-NW), which was clearly influenced by industrial emissions, followed by the Atlantic Advection episodes. The comparison of carbon species with air-mass origin can help to discriminate the origin and source of particulate matter, as well as to determine the urban impact on rural areas.

Levels and chemical composition of PM in a city near a large Cu-smelter in Spain

A long-term series (2001-2008) of chemical analysis of atmospheric particulate matter (PM(10) and PM(2.5)) collected in the city of Huelva (SW Spain) is considered in this study. The impact of emission plumes from one of the largest Cu-smelters in the world on air quality in the city of Huelva is evidenced by the high daily and hourly levels of As, other potentially toxic elements (e.g. Cu, Zn, Cd, Se, Bi, and Pb) in particulate matter, as well as the high levels of some gaseous pollutants (NO(2) and SO(2)). Mean arsenic levels in the PM10 fraction were higher than the target value set by European Directive 2004/107/EC (6 ngAs m(-3)) for 1(st) January 2013. Hourly peak concentrations of As and other metals and elements (Zn, Cu, P and Se) analyzed by PIXE can reach maximum hourly levels as high as 326 ngAs m(-3), 506 ngZn m(-3), 345 ngCu m(-3), 778 ngP m(-3) and 12 ngSe m(-3). The contribution of Cu-smelter emissions to ambient PM is quantified on an annual basis in 2.0-6.7 µg m(-3) and 1.8-4.2 µg m(-3) for PM(10) and PM(2.5), respectively. High resolution outputs of the HYSPLIT dispersion model show the geographical distribution of the As ambient levels into the emission plume, suggesting that the working regime of the Cu-smelter factory and the sea breeze circulation are the main factors controlling the impact of the Cu-smelter on the air quality of the city. The results of this work improve our understanding of the behaviour of industrial emission plumes and their impact on air quality of a city, where the population might be exposed to very high ambient concentrations of toxic metals during a few hours.

Urban NH3 levels and sources in six major Spanish cities.

A detailed spatial and temporal assessment of urban NH3 levels and potential emission sources was made with passive samplers in six major Spanish cities (Barcelona, Madrid, A Coruña, Huelva, Santa Cruz de Tenerife and Valencia). Measurements were conducted during two different periods (winter-autumn and spring-summer) in each city. Barcelona showed the clearest spatial pattern, with the highest concentrations in the old city centre, an area characterised by a high population density and a dense urban architecture. The variability in NH3 concentrations did not follow a common seasonal pattern across the different cities. The relationship of urban NH3 with SO2 and NOX allowed concluding on the causes responsible for the variations in NH3 levels between measurement periods observed in Barcelona, Huelva and Madrid. However, the factors governing the variations in A Coruña, Valencia and Santa Cruz de Tenerife are still not fully understood. This study identified a broad variability in NH3 concentrations at the city-scale, and it confirms that NH3 sources in Spanish urban environments are vehicular traffic, biological sources (e.g. garbage containers), wastewater treatment plants, solid waste treatment plants and industry. The importance of NH3 monitoring in urban environments relies on its role as a precursor of secondary inorganic species and therefore PMX. Further research should be addressed in order to establish criteria to develop and implement mitigation strategies for cities, and to include urban NH3 sources in the emission inventories.

Impact of abandoned mine waste on atmospheric respirable particulate matter in the historic mining district of Rio Tinto (Iberian Pyrite Belt).

This work documents for the first time the levels and composition of atmospheric particulate matter in the historic mining district of Rio Tinto (Spain) to estimate the contribution and impact of resuspended particles from hazardous mine waste on air quality. The resuspended mine waste dust contributes notably (32%) to the total concentrations of toxic trace metals (Bi, As, Cu, Pb, Cd, Zn and Sb) into the atmosphere, with the consequent impact on public health.

Characterization of a long range transport pollution episode affecting PM in SW Spain

A multidisciplinary study on aerosol characterization was performed at the regional background monitoring station of El Arenosillo, in SW Spain, between 28 June and 5 July 2006. The main aim of the Arenosillo aerosol measurement campaign 2006 was to compare the results of aerosol characterization obtained by different groups by measuring physical and chemical parameters using optical methods and in situ sampling. The campaign coincided with a long-range transport episode from Western Iberia, passing through the Gulf of Cadiz and the Straits of Gibraltar towards the study area. The results of the variability of PM levels and chemical composition of PM10, PM2.5 and PM1 at El Arenosillo and at three nearby regional and urban background sites were interpreted. Mean levels measured during the campaign reached 23, 15 and 12 microg m(-3) for PM10, PM2.5 and PM1, respectively, at El Arenosillo. PM during the Arenosillo campaign 2006 was dominated by the secondary inorganic aerosols (SIA, 24, 38 and 39% of PM10, PM2.5 and PM1 mass), carbonaceous aerosols (17, 21 and 23% of the mass), crustal material (13, 9 and 4%), and sea spray (10, 5 and 1%). These values are within the usual range of regional background sites of Southern Spain with the exception of the relatively low crustal load and the high SIA levels. Two major PM episodes were differentiated. The first one was characterized by high levels of Bi, As, Pb, Se, P and Zn, which are the main tracers of the industrial emissions near the town of Huelva. High concentrations of these elements were also recorded at the nearby sites. In the second episode, maximum levels of SO4(2-), V and coarse Cu as well as the bulk mass of PM1 were determined, tracing the polluted air mass transport from Western Iberia through the Straits of Gibraltar. These results underline the importance of the influence of long-range transport of pollutants on the levels and composition of regional background PM in SW Iberia, where local emissions may also play a role.

Modeling and evaluation of urban pollution events of atmospheric heavy metals from a large Cu-smelter.

Metal smelting and processing are highly polluting activities that have a strong influence on the levels of heavy metals in air, soil, and crops. We employ an atmospheric transport and dispersion model to predict the pollution levels originated from the second largest Cu-smelter in Europe. The model predicts that the concentrations of copper (Cu), zinc (Zn), and arsenic (As) in an urban area close to the Cu-smelter can reach 170, 70, and 30 ng m−3, respectively. The model captures all the observed urban pollution events, but the magnitude of the elemental concentrations is predicted to be lower than that of the observed values; ~300, ~500, and ~100 ng m−3 for Cu, Zn, and As, respectively. The comparison between model and observations showed an average correlation coefficient of 0.62 ± 0.13. The simulation shows that the transport of heavy metals reaches a peak in the afternoon over the urban area. The under-prediction in the peak is explained by the simulated stronger winds compared with monitoring data. The stronger simulated winds enhance the transport and dispersion of heavy metals to the regional area, diminishing the impact of pollution events in the urban area. This model, driven by high resolution meteorology (2 km in horizontal), predicts the hourly-interval evolutions of atmospheric heavy metal pollutions in the close by urban area of industrial hotspot.

Arsenic species in atmospheric particulate matter as tracer of the air quality of Doñana Natural Park (SW Spain).

Sampling and chemical analyses, including major compounds and trace elements, of atmospheric particulate matter (PM10 and PM2.5) have been performed during 2006-2007 in a regional background monitoring station located within the Doñana Natural Park (SW of Spain). This region is strategic for air quality and climate change studies, representing a meeting place of the European and African continents, and the Atlantic Ocean and Mediterranean Sea. The present study based on meteorological parameters demonstrated long-range transport and impact of industrial plumes on the Doñana Natural. Inorganic arsenic species (arsenate and arsenite) have been analyzed in particulate matter (PM) to characterize the impact of near Cu-smelter plumes and demonstrated the long-range transport of industrial pollutants. As(V) is the main specie of As and varies between 95% and 98% of total As in PM10 and 96-97% in PM2.5. The As(V)/As(III) ratio measured in emission plumes of a Cu-smelter are similar to the ratio found in the Doñana Natural Park. The application of Positive Matrix Factorization (PMF) to atmospheric particulate matter estimated the contributions and chemical profiles of natural and anthropogenic sources impacting the Natural Park, demonstrating the industrial origin of the As and other toxic elements in the air.

Antimony speciation as geochemical tracer for anthropogenic emissions of atmospheric particulate matter

The chemical composition of atmospheric particulate matter (PM) has been studied at the cities of Cordoba and Granada (South of Spain) between 2007 and 2013, considering urban background, traffic and industrial monitoring stations. The results of Principal Component Analysis (PCA) indicated that geochemical anomalies observed in the ambient air of Cordoba (mainly Cu, Zn, Pb and Cd) are closely related to the geochemical profile obtained from fugitive metallurgy emissions of brass industries. These findings have been confirmed performing an Sb speciation analysis of PM10 samples, which allowed to distinguish between Sb(III) and Sb(V). The percentage of Sb(V) in PM10 found in the traffic station of Granada was 64-69%. At Cordoba, the percentage of Sb(V) was found to be higher (73-77%) at both urban background and traffic stations, indicating a possible second source of Sb in the PM of this city. The PM10 samples from the industrial station of Cordoba showed a 85-86% of Sb(V). A similar percentage (84-88%) of Sb(V) was found for the fugitive emissions of the brass industries, confirming this industrial source of Sb. These results show that Sb speciation can be a useful geochemical tracer to identify anthropogenic sources (traffic and industrial) emissions of PM.