Ana M. Sánchez de la Campa

Identification and chemical characterization of industrial particulate matter sources in Southwest Spain

Abstract A detailed physical and chemical characterization of coarse particulate matter (PM10) and fine particulate matter (PM2.5) in the city of Huelva (in Southwestern Spain) was carried out during 2001 and 2002. To identify the major emission sources with a significant influence on PM10 and PM2.5, a methodology was developed based on the combination of: (1) real-time measurements of levels of PM10, PM2.5, and very fine particulate matter (PM1); (2) chemical characterization and source apportionment analysis of PM10 and PM2.5; and (3) intensive measurements in field campaigns to characterize the emission plumes of several point sources. Annual means of 37, 19, and 16 μg/m3 were obtained for the study period for PM10, PM2.5, and PM1, respectively. High PM episodes, characterized by a very fine grain size distribution, are frequently detected in Huelva mainly in the winter as the result of the impact of the industrial emission plumes on the city. Chemical analysis showed that PM at Huelva is characterized by high PO4 3− and As levels, as expected from the industrial activities. Source apportionment analyses identified a crustal source (36% of PM10 and 31% of PM2.5); a traffic-related source (33% of PM10 and 29% of PM2.5), and a marine aerosol contribution (only in PM10, 4%). In addition, two industrial emission sources were identified in PM10and PM2.5: (1) a petrochemical source, 13% in PM10 and 8% in PM2.5; and (2) a mixed metallurgical-phosphate source, which accounts for 11–12% of PM10 and PM2.5. In PM2.5 a secondary source has been also identified, which contributed to 17% of the mass. A complete characterization of industrial emission plumes during their impact on the ground allowed for the identification of tracer species for specific point sources, such as petrochemical, metallurgic, and fertilizer and phosphate production industries.

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.

Chemical and microbiological characterization of atmospheric particulate matter during an intense African dust event in Southern Spain.

This study presents the results of the physicochemical characterization of particulate matter associated with an important dust event from the Sahara area that occurred in the South of Spain in 2010. The chemical composition of the samples reflected the dominance of the crustal component of sand from the Sahara desert, although the presence of Mo, Ti, and V trace elements indicated that the dust contained industrial material; probably collected in its transport from Africa. Microbial biodiversity associated with the dust was low, but dominated by Firmicutes and Proteobacteria. Some Firmicutes (belonging to the genus Bacillus and Sporosarcina) were cultured on solid and liquid medium, which suggested that the transported microbes were alive or present as spores that germinated under favorable conditions. These cultivable microbes in the form of spores were highly resistant to desiccation, heat, and UV light.

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.

Physiological and transcriptomic characterization of a fliA mutant of Pseudomonas putida KT2440

Pseudomonas putida KT2440 encodes 23 alternative sigma factors. The fliA gene, which encodes σ(28) , is in a cluster with other genes involved in flagella biosynthesis and chemotaxis. Reverse transcriptase-PCR revealed that this cluster is comprised of four independent transcriptional units: flhAF, fleNfliA, cheYZA and cheBmotAB. We generated a nonpolar fliA mutant by homologous recombination and tested its motility, adhesion to biotic and abiotic surfaces, and responses to various stress conditions. The mutant strain was nonmotile and exhibited decreased capacity to bind to corn seeds, although its ability to colonize the rhizosphere of plants was unaffected. The mutant was also affected in binding to abiotic surfaces and its ability to form biofilms decreased by almost threefold. In the fliA mutant background expression of 25 genes was affected: two genes were upregulated and 23 genes were downregulated. In addition to a number of motility and chemotaxis genes, the fliA gene product is also necessary for the expression of some genes potentially involved in amino acid utilization or stress responses; however, we were unable to assign specific phenotypes linked to these genes since the fliA mutant used the same range of amino acids as the parental strain, and was as tolerant as the wild type to stress imposed by heat, antibiotics, NaCl, sodium dodecyl sulfate, H2 O2 and benzoate. Based on the sequence alignment of promoters recognized by FliA and genome in silico analysis, we propose that P. putidaσ(28) recognizes a TCAAG-t-N12 -GCCGATA consensus sequence located between -34 and -8 and that this sequence is preferentially associated with an AT-rich upstream region.

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.

Analytical approaches for arsenic determination in air : a critical review

This review describes the different steps involved in the determination of arsenic in air, considering the particulate matter (PM) and the gaseous phase. The review focuses on sampling, sample preparation and instrumental analytical techniques for both total arsenic determination and speciation analysis. The origin, concentration and legislation concerning arsenic in ambient air are also considered. The review intends to describe the procedures for sample collection of total suspended particles (TSP) or particles with a certain diameter expressed in microns (e.g. PM10 and PM2.5), or the collection of the gaseous phase containing gaseous arsenic species. Sample digestion of the collecting media for PM is described, indicating proposed and established procedures that use acids or mixtures of acids aided with different heating procedures. The detection techniques are summarized and compared (ICP-MS, ICP-OES and ET-AAS), as well those techniques capable of direct analysis of the solid sample (PIXE, INAA and XRF). The studies about speciation in PM are also discussed, considering the initial works that employed a cold trap in combination with atomic spectroscopy detectors, or the more recent studies based on chromatography (GC or HPLC) combined with atomic or mass detectors (AFS, ICP-MS and MS). Further trends and challenges about determination of As in air are also addressed.

Geochemical anomalies of toxic elements and arsenic speciation in airborne particles from Cu mining and smelting activities: influence on air quality.

A characterization of chemical composition and source contribution of PM10 in three representative environments of southwest Spain related to mining activities (mineral extraction, mining waste and Cu-smelting) has been performed. A study of geochemical anomalies was conducted in the samples collected at the three stations between July 2012 and October 2013. The influence of Cu-smelting processes was compared to other mining activities, where common tracers were identified. The Cu and As concentrations in the study area are higher than in other rural and urban stations of Spain, in which geochemical anomalies of As, Se, Bi, Cd, and Pb have been reported. The results of source contribution showed similar geochemical signatures in the industrial and mining factors. However, the contribution to PM10 is different according to the type of industrial activity. These results have been confirmed performing an arsenic speciation analysis of the PM10 samples, in which the mean extraction efficiency of arsenic depended on the origin of the samples. These finding indicate that the atmospheric particulate matter emitted from Cu-smelting has a high residence time in the atmosphere. This indicates that the Cu-smelter can impact areas of high ecological interest and considered as clean 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.

Short-term effects of ultrafine particles on daily mortality by primary vehicle exhaust versus secondary origin in three Spanish cities

BACKGROUND Evidence on the short-term effects of ultrafine particles (with diameter<100nm, UFP) on health is still inconsistent. New particles in ambient urban air are the result of direct emissions and also the formation of secondary UFP from gaseous precursors. We segregated UFP into these two components and investigated their impact on daily mortality in three Spanish cities affected by different sources of air pollution. METHODS We separated the UFP using a method based on the high correlation between black carbon (BC) and particle number concentration (N). The first component accounts for aerosol constituents emitted by vehicle exhaust (N1) and the second for the photochemical new particle formation enhancements (N2). We applied city-specific Poisson regression models, adjusting for long-term trends, temperature and population dynamics. RESULTS Mean BC levels were higher in Barcelona and Tenerife (1.8 and 1.2μg·m-3, respectively) than in Huelva (0.8μg·m-3). While mean UFP concentrations were similar in the three cities, from which N1 was 40% in Barcelona, 46% in Santa Cruz de Tenerife, and 27% in Huelva. We observed an association with N1 and daily mortality in Barcelona, by increasing approximately 1.5% between lags 0 and 2, per an interquartile increase (IQR) of 3277cm-3, but not with N2. A similar pattern was found in Santa Cruz de Tenerife, although none of the associations were significant. Conversely, in the industrial city of Huelva mortality was associated with N2 at lag 0, by increasing 3.9% per an IQR of 12,032·cm-3. CONCLUSION The pattern and origin of UFP determines their short-term effect on human health. BC is possibly the better parameter to evaluate the health effects of particulate vehicle exhaust emissions, although in areas influenced by domestic solid fuel combustion this should also be taken into account.