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The concentration of rare earth elements together with Sc, Y, and U, as well as rare earth elements fractionation patterns, in the water of an affected acid mine drainage system were investigated. Significant dissolved concentrations of the studied elements were observed in the fluvial sector of this estuary system (Sc ~ 31 µg L-1, Y ~ 187 µg L-1, U - 41 µg L-1, Σ rare earth elements ~621 µg L-1), with pH values below 2.7. In the mixing zone of the estuary, concentrations are lower (Sc- 2.1 µg L-1; Y ~ 16.7 µg L-1; U ~ 4.8 µg L-1; Σ rare earth elements ~65.3 µg L-1) and show a strong longitudinal gradient. The largest rare earth elements removal occurs in the medium-chlorinity zone and it becomes extreme for heaw rare earth elements, as observed for Sc. Samples of the mixing zone show a North American Shale normalized pattern similar to the fluvial zone water, while the samples located in the zone with pH between 6.5 and 7.7 show a depletion of light rare earth elements relative to middle rare earth elements and heaw rare earth elements, similar to that observed in samples of the marine estuary. [ABSTRACT FROM AUTHOR]

The Tessier sequential extraction scheme (SES) was applied to sediments from the Odiel river catchment (Iberian Pyritic Belt, SW of Spain), one of the most acid rivers on Earth, to assess the chemical association (exchangeable, carbonatic, bound to manganese and iron oxides, bound to organic matter and residual mineral) of heavy metals (Zn, Cd, Pb, Cu, Cr, Mn, Ni, Fe, and Hg). Sediments are very heterogeneous in their textural characteristics, showing different grain size. Twenty-seven samples were studied from from areas along the Odiel River, from the source to the mouth, with special interest in the Odiel Marshes Natural Park due to its ecological significance. Samples were classified as sandy (especially at the river mouth with low iron oxide and organic matter content) and clay-silty (in the middle of the river catchment with high iron oxide content). The numerous sandy samples with low pH values explain the low levels of metals upstream, although potential metals contributions arise from mining and ore. However, the presence of sulfate in the mining area and carbonate at the mouth may explain the high presence of lead and iron in these sandy zones. Some percentage of mobile Ni, Cu, and Zn were detected in the mining area, but the elevated relative percentage of exchangeable Cd in the estuary is even more remarkable. The percentage of Zn bound to carbonate is considerable in the catchment but especially in the estuary. However, Cu is only detected in the carbonate phase downstream, in spite of the low concentration of carbonate, which represents a drawback in the application of the Tessier SES to these types of samples. Finally, relatively high percentages of residual, non-mobile, Hg and Pb were observed, in the estuarine and mining areas, respectively. Sand, lime, and clay fractions of representative samples from Areas I, II, and III were used in a metal speciation study. Mainly, the elements analyzed had accumulated in the non-residual fractions. In the mining area of the Pyrite Belt, the elements analyzed are mainly bound to Fe-Mn oxides (Fe + Mn + Cu + Cr + Pb + Mn ± Zn) and the organic matter/sulfide fraction (Ni + Zn + Hg ± Cd), independent of sediment grain size. In conclusion, we show that the results of the study of chemical speciation in sediments from acid rivers are independent of the sediment grain size considered. [ABSTRACT FROM AUTHOR]

Abstract: In this study, we present the levels and chemical composition of PM10 and PM2.5 from an urban background monitoring station to assess the impact of Cu-smelter emission plumes on the city of Huelva (south-western Spain). High concentrations of arsenic were measured in PM10 in 2005 (10.59ngm−3), compared to 2004 (4.67ngm−3), which was higher than the target value proposed by the EU as a recommended average value (6ngm−3 in PM10, European Commission, 2004). The PM2.5 arsenic fraction made up 85% of the total PM10 arsenic fraction. The increase in As concentration is synchronic with other metals such as Cu, Zn, Se and Bi, and is around 3–5 times higher than at other sites in Spain. The source relating to Cu-smelter emissions accounted for 8% of the bulk mass (3.2µgPM10 m−3). Although this source is one of the minor contributions to total PM10, most heavy metals of environmental interest (As, Se, Bi, Cu, Zn...) are included in it. Three meteorological scenarios were differentiated during episodes of Cu-smelter emission plumes impacting the city of Huelva, coinciding with third-quadrant wind directions. High concentrations of SO2 and metals in the urban environment air are tracers of the impact of Cu-smelter emission plumes. The methodology used in this study can help in air quality management, and can be used to support strategic plans to reduce the metal emissions from Cu-smelters in order to meet European Directives (e.g. EU, 1999; EU, 2004). [Copyright &y& Elsevier]

On 25 April 1998 the tailings dam of the Aznalcóllar mine burst, a great quantity of pyrite waste sludge and acid water was spilled reaching the vicinity of the Doñana National Park. In surface and ground water samples taken a week after dam breaking, metals, trace elements and Pb isotopic ratios (206Pb/207Pb and208Pb/206Pb) were analysed. In September 1998 a second sampling survey was carried out. The surface waters have a similar isotopic composition as the lead contained in the pyrite from the Aznalcóllar mine. The polluted groundwater of the Guadiamar aquifer also shows the influence of the mining origin of the lead. Lead isotope ratios (206Pb/207Pb and208Pb/206Pb) in the groundwater of the Almonte-Marismas are very low and they differ clearly from the rest of groundwater samples. A further group of wells has a lead isotope composition intermediate between the Aznalcóllar mine and the atmospheric aerosols of the Iberian Peninsula. [ABSTRACT FROM AUTHOR]

Abstract: Urban air quality impairment by ultrafine particles has become a matter of concern due to the adverse effects on human health. Most of the studies of ultrafine particles in urban air quality have focused on vehicle exhaust emissions. We studied how industrial emissions contribute to ultrafine particle concentrations in downwind urban ambient air. This research is based on experimental data collected in the ambient air of the industrial city of Huelva (SW Spain) over April 2008–December 2009 period (particle number, gaseous pollutants and black carbon concentrations and levels and chemical composition of PM10 and PM2.5 with daily and hourly resolution). This city is affected by emissions from the second largest Cu-smelter in Europe, phosphoric acid and fertilizer production plants and an oil refinery and petrochemical plant. Industrial emissions are the main cause of ultrafine particle episodes. When vehicle exhaust emissions are the main source, ultrafine particles typically show (24-h mean) concentrations within the range 14,700–5000 cm−3 (50th–1st), with 60% of these linked to this source and 30% to industrial emissions. In contrast, when daily mean levels of N are within the range 50,000–25,500 cm−3 (100th–70th), industrial and vehicle exhaust emissions accounted for 49 and 30%, respectively. High concentrations of toxic trace metals (As, Cu, Cd, Zn and Pb) were recorded when the study city suffered fumigations of the Cu-smelter plumes (e.g. 10–25 ng m−3 As, 1–2 ng m−3 Cd and >105 cm−3 of ultrafine particles). Because of these industrial emissions, ultrafine particle concentrations during daylight are about two times higher than those observed in other European cities. Recently, ultrafine particle emissions in vehicle exhausts have been subject to limit values in a recent stage of the EURO standards. Industrial emissions should also be considered. [Copyright &y& Elsevier]

Accessory minerals are thought to play a key role in controlling the behaviour of certain trace elements such as REE, Y, Zr, Th and U during crustal melting processes under high-grade metamorphic conditions. Although this is probably the case at middle crustal levels, when a comparison is made with granulite-facies lower crustal levels, differences are seen in trace element behaviour between accessory minerals and some major phases. Such a comparison can be made in Central Spain where two granulite-facies terranes have equilibrated under slightly different metamorphic conditions and where lower crustal xenoliths are also found. Differences in texture and chemical composition between accessory phases found in leucosomes and leucogranites and those of melanosomes and protholiths indicate that most of the accessory minerals in melt-rich migmatites are newly crystallized. This implies that an important redistribution of trace elements occurs during the early stages of granulite-facies metamorphism. In addition, the textural position of the accessory minerals with respect to the major phases is crucial in the redistribution of trace elements when melting proceeds via biotite dehydration melting reactions. In granulitic xenoliths from lower crustal levels, the situation seems to be different, as major minerals show high concentration of certain trace elements, the distribution of which is thus controlled by reactions involving final consumption of Al-Ti-phlogopite. A marked redistribution of HREE–Y–Zr between garnet and xenotime (where present) and zircon, but also of LREE between feldspars (K-feldspar and plagioclase) and monazite, is suggested. [Copyright &y& Elsevier]

A detailed analysis of the columnar optical aerosol properties has been carried out for data collected during the “El Arenosillo 2004 summer campaign”. These data are derived from a Cimel sun-photometer, as part of the PHOTONS-AERONET network at the El Arenosillo site in south-western Spain, over the period 1 June to 31 October 2004. Version 1 AERONET inversion products are used in the analysis. The aim of this campaign was to obtain a more complete set of data on aerosol particle microphysical, optical/radiative, absorbing and chemical properties for use in closure studies. In this paper we focus on the characterization of the aerosol optical depth (AOD)–alpha coefficients, and the particle size distribution together with their associated microphysical parameters, such as volume concentration, effective radius, etc., in order to define the features and ranges of these physical parameters associated with both fine and coarse particle modes. The requirement of high AOD values for using the inversion technique puts significant constraints on the estimation of the single scattering albedo (SSA) and refractive index, and thus requires great care in the analysis. As a result, only the characterizations of these parameters for desert dust events are considered reliable. Moreover, summer 2004 had the most frequent desert dust intrusions, including the most intense event (22–28 July and 31 July–2 August) ever recorded at the El Arenosillo site since the start of the measurements in February 2000. We summarize the results for the intensive summer campaign in terms of the range of values of the physical and optical parameters of the different aerosol types present in this area of Spain. [Copyright &y& Elsevier]

Despite their significant role in source apportionment analysis, studies dedicated to the identification of tracer elements of emission sources of atmospheric particulate matter based on air quality data are relatively scarce. The studies describing tracer elements of specific sources currently available in the literature mostly focus on emissions from traffic or large-scale combustion processes (e.g. power plants), but not on specific industrial processes. Furthermore, marker elements are not usually determined at receptor sites, but during emission. In our study, trace element concentrations in PM10 and PM2.5 were determined at 33 monitoring stations in Spain throughout the period 1995–2006. Industrial emissions from different forms of metallurgy (steel, stainless steel, copper, zinc), ceramic and petrochemical industries were evaluated. Results obtained at sites with no significant industrial development allowed us to define usual concentration ranges for a number of trace elements in rural and urban background environments. At industrial and traffic hotspots, average trace metal concentrations were highest, exceeding rural background levels by even one order of magnitude in the cases of Cr, Mn, Cu, Zn, As, Sn, W, V, Ni, Cs and Pb. Steel production emissions were linked to high levels of Cr, Mn, Ni, Zn, Mo, Cd, Se and Sn (and probably Pb). Copper metallurgy areas showed high levels of As, Bi, Ga and Cu. Zinc metallurgy was characterised by high levels of Zn and Cd. Glazed ceramic production areas were linked to high levels of Zn, As, Se, Zr, Cs, Tl, Li, Co and Pb. High levels of Ni and V (in association) were tracers of petrochemical plants and/or fuel-oil combustion. At one site under the influence of heavy vessel traffic these elements could be considered tracers (although not exclusively) of shipping emissions. Levels of Zn–Ba and Cu–Sb were relatively high in urban areas when compared with industrialised regions due to tyre and brake abrasion, respectively. [Copyright &y& Elsevier]

This work summarizes the results of a series of comprehensive studies on particulate matter (PM) carried out in Spain from 1999 to 2001. Monitoring sites were selected in accordance with different climatic and geographic conditions as well as anthropogenic influences, varying from rural background to urban curb-side sites. Measurements were carried out with gravimetric high-volume samplers and with automatic devices for different PM grain sizes, focusing on PM10 and PM2.5. A simultaneous meteorology study was performed to assess the influence of air masses and to detect long-range transport processes, especially African dust outbreaks, affecting the PM levels in the Iberian Peninsula and the Canary Islands. Mean values, chemical compositions and source apportionment analyses were obtained and discussed as a function of the different monitoring sites and during PM episodes. [Copyright &y& Elsevier]

Plastic pollution constitutes an environmental problem in the Canary Islands nowadays. Nevertheless, studies evaluating the impact of plastics on its avifauna are still scarce. Gastrointestinal tracts of 88 birds belonging to 14 species were studied for the presence of plastics. Moreover, their livers were analyzed for the determination of bromodiphenyl ethers (BDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs). Among Cory's shearwaters (n = 45), the frequency of occurrence of plastic ingestion was considerably high (88.89 %). This species had the highest mean value of items (7.22 ± 5.66) and most of them were compatible with lines derived from fishing gear. PCBs and PAHs were detected in all of the samples and OCPs in the great majority of them (98.86 %). Our results highlight the problems that plastic debris (mainly for seabirds) and organic pollutants pose to these species., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Trace element concentrations within PM10, gaseous pollutants (NO 2 and SO 2 ), and PM10 levels were studied during the Covid-19 lockdown at a regional level in Southern Spain (Andalusia). Pollutant concentrations were compared considering different mobility periods (pre-lockdown, lockdown, and relaxation) in 2020 and previous years (2013-2016). An acute decrease in NO 2 levels (<50%) was observed as a consequence of traffic diminution during the confinement period. Moreover, a lower reduction in PM10 levels and a non-clear pattern for SO 2 levels were observed. During the lockdown period, PM10 elements released from traffic emissions (Sn and Sb) showed the highest concentration diminution in the study area. Regarding the primary industrial sites, there were no significant differences in V, Ni, La, and Cr concentration reduction during 2020 associated with industrial activity (stainless steel and oil refinery) in Algeciras Bay. Similarly, concentrations of Zn showed the same behaviour at Cordoba, indicating that the Zn-smelter activity was not affected by the lockdown. Nevertheless, stronger reductions of Cu, Zn, and As in Huelva during the confinement period indicated a decrease in the nearby Cu-smelter emissions. Brick factories in Bailen were also influenced by the confinement measures, as corroborated by the marked decrease in concentrations of Ni, V, Cu, and Zn during the lockdown compared to that from previous years. This work has shown the baseline concentrations of trace elements of PM10, which is of great value to air quality managers in order to minimise pollution levels by applying the confinement of the population, affecting both traffic and industrial anthropogenic activities., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

We offer an overview of the COVID-19 -driven air quality changes across 11 metropolises in Spain with the focus on lessons learned on how continuing abating pollution. Traffic flow decreased by up to 80% during the lockdown and remained relatively low during the full relaxation (June and July). After the lockdown a significant shift from public transport to private vehicles (+21% in Barcelona) persisted due to the pervasive fear that using public transport might increase the risk of SARS-CoV-2 infection, which need to be reverted as soon as possible. NO 2 levels fell below 50% of the WHO annual air quality guidelines (WHOAQGs), but those of PM 2.5 were reduced less than expected due to the lower contributions from traffic, increased contributions from agricultural and domestic biomass burning, or meteorological conditions favoring high secondary aerosol formation yields. Even during the lockdown, the annual PM 2.5 WHOAQG was exceeded in cities within the NE and E regions with high NH 3 emissions from farming and agriculture. Decreases in PM 10 levels were greater than in PM 2.5 due to reduced emissions from road dust, vehicle wear, and construction/demolition. Averaged O 3 daily maximum 8-h (8hDM) experienced a generalized decrease in the rural receptor sites in the relaxation (June-July) with -20% reduced mobility. For urban areas O 3 8hDM responses were heterogeneous, with increases or decreases depending on the period and location. Thus, after canceling out the effect of meteorology, 5 out of 11 cities experienced O 3 decreases during the lockdown, while the remaining 6 either did not experience relevant reductions or increased. During the relaxation period and coinciding with the growing O 3 season (June-July), most cities experienced decreases. However, the O 3 WHOAQG was still exceeded during the lockdown and full relaxation periods in several cities. For secondary pollutants, such as O 3 and PM 2.5 , further chemical and dispersion modeling along with source apportionment techniques to identify major precursor reduction targets are required to evaluate their abatement potential., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

High severity wildfires cause a drastic alteration of soil carbon cycling - both oxidising and thermally altering soil organic matter (SOM) - and usually are followed by strong runoff and erosion events. To restore wildfire-degraded soils, SOM needs to be rebuilt while soil erosion is prevented. Post-fire straw mulching has been shown to mitigate soil erosion by providing a protective cover against rainsplash. However, SOM takes many decades or centuries to rebuilt naturally. Biochar, co-applied with straw to the soil surface can replace the SOM of the O-horizon, while the stabilised soil - by straw mulching - may gain in SOM naturally and by downward movement of biochar. We conducted a field study to test if straw-only and straw-biochar co-application could restore soils degraded by wildfire in one high burn severity (HBS) and one moderate burn severity (MBS) study area in southern Portugal and Spain, respectively, by monitoring erosion and SOM for the most intense rainfall period of the first post-fire year. Burned sites were characterized for soil and sediment physical properties, TOC content, SOM quality by thermogravimetry (DTG) and nuclear magnetic resonance (NMR 13 C) spectroscopy. Straw-biochar mulching significantly reduced soil erosion by 76% and 65% in the HBS and MBS sites, respectively, in both cases similar to the erosion reduction by straw-only mulching. DTG and NMR 13 C indicated that a relatively small proportion of the biochar eroded, i.e. 0.7%, indicating that co-application of straw with biochar may help restore the SOC lost in the wildfire in the medium term. The amount of SOM eroded was lower with straw-biochar mulching than in the untreated plots for both study areas. Straw-biochar mulching mitigates erosion of wildfire-degraded soils under extreme rainfall, while a relatively small proportion of the biochar is lost by erosion. Future studies need to monitor medium term effects., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The chemical evolution of brines resulting from an inactive phosphogypsum pond derived of fertilizer industry located in Huelva (Spain, SW Europe) has been studied based on a weekly sampling from 2014 to 2017. Long-range time variation of metals and ions concentrations in brines are expected to depend on environmental parameters such as rainfall and evaporation. The results show that brines are enriched in F - (1.7-2.0 g/l), Cl - (13-24 g/l), SO 4 2- (7.2-9.3 g/l), V (70-128 mg/l) and U (55-98 mg/l). A great variation of chemical concentrations has been found, due to dilution, recharge and evaporation processes. Most of the elements show peak concentrations in summer, coinciding with the lowest pH values (<1), high conductivity (>133 mS/cm), and high evaporation rates as expected. Nonetheless, F - shows an opposite behaviour, varying its concentrations between 0.9 g/l in summer and 3.7 g/l in the rainy season. According to the results, a future restoration plan for PG ponds should include the removal of brines and layered salts during summer in order to avoid the annual generation of brines and their impact on the environment., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study focuses on correlations between total number concentrations, road traffic emissions and noise levels in an urban area in the southwest of Spain during the winter and summer of 2009. The high temporal correlation between sound pressure levels, traffic intensity, particle number concentrations related to traffic, black carbon and NOx concentrations suggests that noise is linked to traffic emissions as a main source of pollution in urban areas. First, the association of these different variables was studied using PreFuRGe, a computational tool based on data mining and fuzzy logic. The results showed a clear association between noise levels and road-traffic intensity for non-extremely high wind speed levels. This behaviour points, therefore, to vehicular emissions being the main source of urban noise. An analysis for estimating the total number concentration from noise levels is also proposed in the study. The high linearity observed between particle number concentrations linked to traffic and noise levels with road traffic intensity can be used to calculate traffic related particle number concentrations experimentally. At low wind speeds, there are increases in noise levels of 1 dB for every 100 vehicles in circulation. This is equivalent to 2000 cm(-3) per vehicle in winter and 500 cm(-3) in summer. At high wind speeds, wind speed could be taken into account. This methodology allows low cost sensors to be used as a proxy for total number concentration monitoring in urban air quality networks., (Copyright © 2015 Elsevier B.V. All rights reserved.)

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.

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., (Copyright © 2011 Elsevier B.V. All rights reserved.)

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.

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.

The results of chemical analysis of PM(10) atmospheric dust samples collected between July 2001 and June 2002 in rural and urban background monitoring stations in Huelva (South-western Spain) are reported. In order to identify the sources and quantify their contribution to PM(10), principal component analysis and receptor modelling techniques were performed using independent variables of the complete series of concentrations of PM(10) contents. The Ria of Huelva is considered to be one of the high industrial estates in Spain, where several metallurgical, petrochemical and fertilizer industrial estates are located, surrounded by areas of a high ecological interest such as Doñana National Park. Annual means of 29-33 and 37 micro g PM(10)m(-3) were obtained for the study period in rural and urban monitoring stations, respectively. These values are below the mean annual limit value for 2005 and onwards from the Directive 1999/30/EC [EU, 1999. 1999/30/CE Council Directive relating to limit values for sulphur dioxide, nitrogen dioxide and oxide of nitrogen, particulate matter and lead in ambient air. The Council of the European Union]. High PM(10) episodes in rural and urban areas occurred during African dust events. Episodically, the emissions of plumes from industrial estates reach rural areas causing peak episodes of PO(4)(3-) Cu, Ti Pb and As. Anthropogenic particles arising from metallurgical emissions (pyrite, chalcopyrite and sphalerite) were observed in the rural sites. The annual mean As concentrations measured in PM(10) in the city of Huelva and surrounding rural areas (144 and 84-51mg Askg(-1) in PM(10), respectively) are several times high the concentrations obtained in other Spanish monitoring stations (7-57mg Askg(-1)). The source apportionment analyses allowed the quantification of the contribution to PM(10) of an industrial mixed source in the rural background.

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 microg/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 PM10 and 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.

This work analyses the spatial distribution, the origin, and the shale-normalised fractionation patterns of the rare earth elements (REE) in the alluvial aquifer of the Guadiamar River (south-western Spain). This river received notoriety in April 1998 for a spill that spread a great amount of slurry (mainly pyrites) and acid waters in a narrow strip along the river course. Groundwaters and surface waters were sampled to analyse, among other elements, the REEs. Their spatial distribution shows a peak close to the mining region, in an area with low values of pH and high concentrations of sulphates and other metals such as Zn, Cu, Co, Ni, Pb, and Cd. The patterns of shale-normalised fractionation at the most-contaminated points show an enrichment in the middle rare earth elements (MREE) with respect to the light (LREE) and heavy (HREE) ones, typical of acid waters. The Ce-anomaly becomes more negative as pH increases, due to the preferential fractionation of Ce in oxyhydroxides of Fe.

Background: Although conventional pressure ventilation (PSV) decreases the rate of intubation in acute respiratory failure, patient-ventilator dyssynchrony is a frequent cause of failure. In proportional assist ventilation (PAV), pressure is applied by the ventilator in proportion to the patient-generated volume and flow; therefore, there is automatic synchrony between the patient's effort and the ventilatory cycle., Objective: The aim of this study was to compare the effects of PSV and PAV during noninvasive ventilation in the treatment of acute respiratory failure., Design: Prospective randomised study., Setting: A multidisciplinary 24-bed intensive care unit of an acute-care teaching hospital in Alicante, Spain. PATIENTS. This study included 117 consecutive adult patients with acute respiratory failure randomised to noninvasive ventilation delivered by PSV ( n = 59) or PAV ( n = 58)., Measurements and Results: There were no statistically significant differences between patients assigned to each mode of ventilation with regard to baseline parameters and aetiological diagnoses of acute respiratory failure. With regard to outcome data, no significant differences were observed between PSV and PAV in the frequency of intubation (37% vs 34%), mortality rate (29% vs 28%), and mean length of stay. Subjective comfort (0-10 visual analogue scale) was rated higher and intolerance occurred less frequently (3.4% vs 15%, P = 0.03) in the PAV than in the PSV mode., Conclusions: Although PAV seems more comfortable and intolerance occurred less frequently, no major differences exist in terms of physiological improvement or in terms of outcomes when comparing PSV and PAV.

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.