Jesús de la Rosa

Rayleigh fractionation of heavy rare earths and yttrium during metamorphic garnet growth

We present laser-ablation microprobe inductively coupled–mass spectrometry analyses of Y, Yb, Er, Dy, and Gd in garnet crystals from high-grade metamorphic and migmatitic rocks from the Sierras Pampeanas of Argentina. These rocks contain large garnet porphyroblasts (≥4 mm) that are compositionally zoned. Rare earth element concentrations in the rims are typically one order of magnitude lower than those in the cores. A notable feature of this zonation is the inversion of Yb/Er and Yb/Dy ratios, from >1 in the cores to <1 in the rims. We show quantitatively that the spatial distribution of these trace elements in garnet can be most simply and effectively explained as arising from Rayleigh fractionation during garnet growth. We also analyzed a small garnet crystal (<2 mm) representative of a garnet population that is associated with migmatitic leucosomes. This crystal displays uniformly low concentrations of all trace elements that are virtually identical in both absolute and relative magnitudes to those in the rims of the larger garnet porphyroblasts. The small crystals, and perhaps part of the porphyroblast rims, are likely to be peritectic products of incongruent melting reactions. We argue that melts formed from garnet-bearing sources may generally be unable to equilibrate with metamorphic garnet cores and may thus be more strongly depleted in heavy rare earth elements and Y than modeling based on bulk source-rock abundances of these elements would indicate.

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.

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.

A study of inherited zircons in granitoid rocks from the South Portuguese and Ossa-Morena Zones, Iberian Massif: support for the exotic origin of the South Portuguese Zone

Abstract Trace element and U–Pb isotopic analyses of inherited zircon cores from a sample of Gil Marquez granodiorite (South Portuguese Zone, SPZ) and Almonaster nebulite (Ossa-Morena Zone, OMZ, in the Aracena Metamorphic Belt) have been obtained using laser ablation-inductively coupled plasma-mass spectrometry. These data reveal differences in the age of deep continental crust in these two zones. Inherited zircon cores from the Ossa-Morena Zone range at 600±100 Ma, 1.7–2 Ga and 2.65–2.95 Ga, while those from the South Portuguese Zone range at 400–500 and 700–800 Ma. These data support the “exotic” origin of the South Portuguese Zone basement relative to the rest of Iberian Massif. The young ages of inherited zircon cores and Nd model ages of magmatic rocks of the South Portuguese Zone are comparable to results from granulite facies xenoliths and granitic rocks from the Meguma Terrane and Avalonia and support a correlation between the basement of the southernmost part of the Iberian Massif and the northern Appalachians.

Short-term effects of particulate matter constituents on daily hospitalizations and mortality in five South-European cities: results from the MED-PARTICLES project.

BACKGROUND Few recent studies examined acute effects on health of individual chemical species in the particulate matter (PM) mixture, and most of them have been conducted in North America. Studies in Southern Europe are scarce. The aim of this study is to examine the relationship between particulate matter constituents and daily hospital admissions and mortality in five cities in Southern Europe. METHODS The study included five cities in Southern Europe, three cities in Spain: Barcelona (2003-2010), Madrid (2007-2008) and Huelva (2003-2010); and two cities in Italy: Rome (2005-2007) and Bologna (2011-2013). A case-crossover design was used to link cardiovascular and respiratory hospital admissions and total, cardiovascular and respiratory mortality with a pre-defined list of 16 PM10 and PM2.5 constituents. Lags 0 to 2 were examined. City-specific results were combined by random-effects meta-analysis. RESULTS Most of the elements studied, namely EC, SO4(2-), SiO2, Ca, Fe, Zn, Cu, Ti, Mn, V and Ni, showed increased percent changes in cardiovascular and/or respiratory hospitalizations, mainly at lags 0 and 1. The percent increase by one interquartile range (IQR) change ranged from 0.69% to 3.29%. After adjustment for total PM levels, only associations for Mn, Zn and Ni remained significant. For mortality, although positive associations were identified (Fe and Ti for total mortality; EC and Mg for cardiovascular mortality; and NO3(-) for respiratory mortality) the patterns were less clear. CONCLUSIONS The associations found in this study reflect that several PM constituents, originating from different sources, may drive previously reported results between PM and hospital admissions in the Mediterranean area.

Volatile phase fluxed anatexis of metasediments during late Caledonian ophiolite obduction: evidence from the Sogneskollen Granitic Complex, west Norway

In the west Norwegian Caledonides minor granitic sheets were intruded during obduction of the c. 443 Ma Solund–Stavfjord Ophiolite Complex. The Sogneskollen Granitic Complex is the largest intrusive complex and consists of several minor lenses and one larger lens of granodiorite. The Sogneskollen Granitic Complex samples generally have high Ba, Sr and Na2O, very low Y values (<7 ppm), negative εNd420 Ma values (c. −7 to −10.1) and 87Sr/86Sr420 Ma ratios of 0.70437–0.70705. The REE patterns are strongly HREE depleted and La/Ybn varies from 0.3 to 36. Most samples display small positive Eu anomalies, but those that are most fractionated have small negative anomalies. The main part of the Sogneskollen Granitic Complex is a white composite granodiorite which is intruded by a suite of grey biotite-granite dykes. It is suggested that this, and other similar granitic sheets in the area, most probably formed by melting of sediments in the presence of a H2O-bearing volatile phase during obduction of the ophiolite. The quartzofeldspathic source sediments most probably contained detritus from long-term Rb-depleted lower continental crust and from an island arc. The sediments were deposited in large amounts in the marginal basin now represented by the Solund–Stavfjord Ophiolite Complex. During obduction the sediments were buried beneath the hot overriding Ophiolite Complex and the associated island-arc, and yielded granitic magmas during partial melting.

Physico-chemical characterisation of atmospheric aerosols in a rural area affected by the aznalcollar toxic spill, south-west Spain during the soil reclamation activities

High levels of atmospheric contamination due to the re-suspension of pyrite particles from the mining waste slurry were recorded in the Guadiamar valley (the Guadiamar is a tributary of the Guadalquivir river) after the toxic spill of Aznalcóllar, north of the Doñana Natural Park (SW Spain). Major high-particulate events occurred during the extraction of the pyrite-rich mud layer, which covered an extensive area of the valley downstream of the confluence of the Agrio and Guadiamar rivers. This study deals with the monitoring of the ambient air quality at two stations near the village of Aznalcázar in the central part of the flooded area. Although the Spanish legal limit for atmospheric particles and lead in environmental air were not exceeded, high daily levels of total suspended particles (TSP) and of some elements with an environmental significance (As, Cd, Cu, Mn, Ni, Pb, Sn, Tl and Zn) were recorded at Aznalcázar and in the Guadiamar valley during soil reclamation (July-August 1998). Despite a progressive decrease in TSP levels through September-October 1998, background was higher than the levels for the May-June period. Evolution of levels for most of the elements studied showed a similar trend. The exceptions were copper, which was partially increased by other emission sources such as fumigation activities, and sodium, which remained at relatively constant levels during the study period because of its marine origin. The physico-chemical characterisation of the atmospheric particulates allowed us to determine the major grain size modes of the pyrite related elements and the solubility of the potentially toxic elements, and to identify the major particulate types present in the atmosphere in the area. Secondary and tertiary aromatic amines (i.e. alkyldiphenylamines and phenylcarbazoles, respectively) were identified in the suspended particles and in the vapour phase collected at the same station as the TSP samples. As some of these aromatic amines had been previously identified in the pyrite sludge, it is assumed that fine sludge particles containing aromatic amines were re-suspended in the atmosphere. The highest concentrations of aromatic amines in the particulate phase were recorded in August 1998 during the pyrite slurry extraction in the proximity of the Aznalcázar sampling site. Despite a sharp drop in the suspended particles of the aromatic amine concentrations, a significant concentration was detected in the vapour phase (< 1.2 mm) during autumn, probably because of longer residence time in the atmosphere. Although health hazards associated with the presence of these aromatic amines are unknown, their acute toxicity exceeded that of urban aerosols.

Particulate matter and gaseous pollutants in the Mediterranean Basin: Results from the MED-PARTICLES project

Previous studies reported significant variability of air pollutants across Europe with the lowest concentrations generally found in Northern Europe and the highest in Southern European countries. Within the MED-PARTICLES project the spatial and temporal variations of long-term PM and gaseous pollutants data were investigated in traffic and urban background sites across Southern Europe. The highest PM levels were observed in Greece and Italy (Athens, Thessaloniki, Turin and Rome) while all traffic sites showed high NO2 levels, frequently exceeding the established limit value. High PM2.5/PM10 ratios were calculated indicating that fine particles comprise a large fraction of PM10, with the highest values found in the urban background sites. It seems that although in traffic sites the concentrations of both PM2.5 and PM10 are significantly higher than those registered in urban background sites, the coarse fraction PM2.5-10 is more important at the traffic sites. This fact is probably due to the high levels of resuspended road dust in sites highly affected by traffic, a phenomenon particularly relevant for Mediterranean countries. The long-term trends of air pollutants revealed a significant decrease of the concentration levels for PM, SO2 and CO while for NO2 no clear trend or slightly increasing trends were observed. This reduction could be attributed to the effectiveness of abatement measures and strategies and also to meteorological conditions and to the economic crisis that affected Southern Europe.

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.