A.M. Sánchez de la Campa

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.

Size distribution and chemical composition of metalliferous stack emissions in the San Roque petroleum refinery complex, southern Spain

We demonstrate that there is great variation in the size range and chemical composition of metalliferous particulate matter (PM) present within petrochemical complex chimney stacks. Cascade impactor PM samples from seven size ranges (17, 14, 5, 2.5, 1.3, 0.67, and 0.33 μm) were collected from inside stacks within the San Roque complex which includes the largest oil refinery in Spain. SEM analysis demonstrates the PM to be mostly carbonaceous and aluminous fly ash and abundant fine metalliferous particles. The metals with the most extreme concentrations averaged over all size ranges were Ni (up to 3295 μg m(-3)), Cr (962 μg m(-3)), V (638 μg m(-3)), Zn (225 μg m(-3)), Mo (91 μg m(-3)), La (865 μg m(-3)), and Co (94 μg m(-3)). Most metal PM are strongly concentrated into the finest fraction (<0.33 μm), although emissions from some processes, such as purified terephthallic acid (PTA) production, show coarser size ranges. The fluid catalytic cracking stack shows high concentrations of La (>200 μg m(-3) in PM(0.67-1.3)), Cr and Ni in a relatively coarse PM size range (0.7-14 μm). Our unique database, directly sampled from chimney stacks, confirms that oil refinery complexes such as San Roque are a potent source of a variety of fine, deeply inhalable metalliferous atmospheric PM emissions.

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.

Health implications of the distribution of arsenic species in airborne particulate matter

Airborne particle samples were taken between 2001 and 2008 at an urban site (Huelva) in southwestern Spain. Arsenic was found in the samples due to the presence of a near-by copper smelter, sometimes at concentrations above the target value of 6 ng m(-3) proposed by EU regulations (annual means from 4.6 to 10.4 ng As m(-3) in PM10, and 3.0 to 9.1 ng As m(-3) in PM2.5). The results obtained by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) showed that arsenic accumulates preferentially (ca. 70-80%) in the particles with smaller diameter (PM2.5 versus PM10), representing a threat to human health due to the higher capacity of the finer particles to enter the organism through the respiratory system. Moreover, the toxicity of the inorganic arsenic species depends also on the oxidation state, As(III) being more toxic that As(V). The speciation analysis performed with High Performance Liquid Chromatography-Hydride Generation- Atomic Fluorescence Spectrometry (HPLC-HG-AFS) with samples collected between 2006 and 2008, showed that As(V) represented the main arsenic species, but As(III) was also found at significant concentration, representing a 5-10% of the total arsenic content. The results also indicate that the more toxic As(III) tends to concentrate preferentially in the finer fraction PM2.5 in comparison with As(V), thus representing an added health risk for the local population.

Modeling PM10 Originating from Dust Intrusions in the Southern Iberian Peninsula Using HYSPLIT

The Hybrid Single-Particle Lagrangian Integrated Trajectories (HYSPLIT) model has been applied to calculate the spatial and temporal distributions of dust originating from North Africa. The model has been configured to forecast hourly particulate matter #10 mm (PM10) dust concentrations focusing on the impacts over the southern Iberian Peninsula. Two full years (2008 and 2009) have been simulated and compared against surface background measurement sites. A statistical analysis using discrete and categorical evaluations is presented. The model is capable of simulating the occurrence of Saharan dust episodes as observed at the measurement stations and captures the generally higher levels observed in eastern Andalusia, Spain, with respect to the western Andalusia station. But the simulation tends to underpredict the magnitude of the dust concentration peaks. The model has also been qualitatively compared with satellite data, showing generally good agreement in the spatial distribution of the dust column.

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.

Mineralogy of atmospheric dust impacting the Rio Tinto mining area (Spain) during episodes of high metal deposition

Abstract This study is the first to investigate the mineral composition of the atmospheric particulate matter deposited at Rio Tinto, Spain, an historical mining district of world-class importance, with emphasis on metal-bearing particles and their environmental implications. The dustfall is composed of quartz, feldspars, phyllosilicates (mica, chlorite and/or kaolinite) and a variety of accessory heavy minerals, the most common being primary sulfides (pyrite, chalcopyrite with minor galena, sphalerite and bornite) and their oxidation products (notably goethite, hematite and jarosite). This mineral assemblage suggests a local source of wind-blown dust and it is consistent with the large deposition levels of sulfide-related elements (As, Bi, Cd, Cu, Pb, Sb and Zn) registered at the sampling site adjacent to the mine waste dumps. However, the generation of potentially harmful dust particles is not restricted to mine wastes. Anthropogenic metallic compounds arising from a nearby hazardous waste disposal centre can make a relevant additional contribution to the metal deposition, particularly for Fe, Ni, Cr and Mn. Atmospheric fallout is a major mechanism for metal input to soils and plants around or near the mining area.

Emissions from the combustion of eucalypt and pine chips in a fluidized bed reactor.

Interest in renewable energy sources has increased in recent years due to environmental concerns about global warming and air pollution, reduced costs and improved efficiency of technologies. Under the European Union (EU) energy directive, biomass is a suitable renewable source. The aim of this study was to experimentally quantify and characterize the emission of particulate matter (PM2.5) resulting from the combustion of two biomass fuels (chipped residual biomass from pine and eucalypt), in a pilot-scale bubbling fluidized bed (BFB) combustor under distinct operating conditions. The variables evaluated were the stoichiometry and, in the case of eucalypt, the leaching of the fuel. The CO and PM2.5 emission factors were lower when the stoichiometry used in the experiments was higher (0.33±0.1 g CO/kg and 16.8±1.0 mg PM2.5/kg, dry gases). The treatment of the fuel by leaching before its combustion has shown to promote higher PM2.5 emissions (55.2±2.5 mg/kg, as burned). Organic and elemental carbon represented 3.1 to 30 wt.% of the particle mass, while carbonate (CO3(2-)) accounted for between 2.3 and 8.5 wt.%. The particulate mass was mainly composed of inorganic matter (71% to 86% of the PM2.5 mass). Compared to residential stoves, BFB combustion generated very high mass fractions of inorganic elements. Chloride was the water soluble ion in higher concentration in the PM2.5 emitted by the combustion of eucalypt, while calcium was the dominant water soluble ion in the case of pine.