Characterization and sources assignation of PM2.5 organic aerosol in a rural area of Spain

The results from a year-long study of the organic composition of PM2.5 aerosol collected in a rural area influenced by a highway of Spain are reported. The lack of prior information related to the organic composition of PM2.5 aerosol in Spain, concretely in rural areas, led definition of the goals of this study. As a result, this work has been able to characterize the main organic components of atmospheric aerosols, including several compounds of SOA, and has conducted a multivariate analysis in order to assign sources of particulate matter. A total of 89 samples were taken between April 2004 and April 2005 using a high-volume sampler. Features and abundance of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), alcohols and acids were separately determined using gas chromatography/mass spectrometry and high performance liquid chromatography analysis. The Σn-alkane and ΣPAHs ranged from 3 to 81 ng m^?3 and 0.1 to 6 ng m^?3 respectively, with higher concentrations during colder months. Ambient concentrations of Σalcohols and Σacids ranged from 21 to 184 ng m^?3 and 39 to 733 ng m^?3, respectively. Also, several components of secondary organic aerosol have been quantified, confirming the biogenic contribution to ambient aerosol. In addition, factor analysis was used to reveal origin of organic compounds associated to particulate matter. Eight factors were extracted accounting more than 83% of the variability in the original data. These factors were assigned to a typical high pollution episode by anthropogenic particles, crustal material, plant waxes, fossil fuel combustion, temperature, microbiological emissions, SOA and dispersion of pollutants by wind action. Finally, a cluster analysis was used to compare the organic composition between the four seasons.     

Assessing spatial variability of SO2 field as detected by an air quality network using Self-Organizing Maps,cluster, and Principal Component Analysis

In Bilbao (Spain), an air quality network measures sulphur dioxide levels at 4 locations. The objective of this paper is to develop a practical methodology to identify redundant sensors and evaluate a network's capability to correctly follow and represent SO₂ fields in Bilbao, in the frame of a continuous network optimization process.The methodology is developed and tested at this particular location, but it is general enough to be useable at other places as well, since it is not tied neither to the particular geographical characteristics of the place nor to the phenomenology of the air quality over the area.To assess the spatial variability of SO₂ measured at 4 locations in the area, three different techniques have been used: Self-Organizing Maps (SOMs), cluster analysis (CA) and Principal Component Analysis (PCA). The results show that the three techniques yield the same results, but the information obtained via PCA can be helpful not only for that purpose but also to throw light on the major mechanisms involved. This might be used in future network optimization stages. The main advantage of cluster analysis and SOMs is that they provide readily interpretable results. All the calculations have been carried out using the freely available software R.     

The stable carbon isotope composition of PM2.5 and PM10 in Mexico City Metropolitan Area air

The sources and distribution of carbon in ambient suspended particles (PM_2.5 and PM₁₀) of Mexico City Metropolitan Area (MCMA) air were traced using stable carbon isotopes (¹³C/¹²C). Tested potential sources included rural and agricultural soils, gasoline and diesel, liquefied-petroleum gas, volcanic ash, and street dust. The complete combustion of LP gas, diesel and gasoline yielded the lightest δ¹³C values (?27 to ?29‰ vs. PDB), while street dust (PM₁₀) represented the isotopically heaviest endmember (?17‰). The δ¹³C values of rural soils from four geographically separated sites were similar (?20.7 ± 1.5‰). δ¹³C values of particles and soot from diesel and gasoline vehicle emissions and agricultural soils varied between ?23 and ?26‰. Ambient PM samples collected in November of 2000, and March and December of 2001 at three representative receptor sites of industrial, commercial and residential activities had a δ¹³C value centered around ?25.1‰ in both fractions, resulting from common carbon sources. The predominant carbon sources to MCMA atmospheric particles were hydrocarbon combustion (diesel and/or gasoline) and particles of geological origin. The significantly depleted δ¹³C values from the industrial site reflect the input of diesel combustion by mobile and point source emissions. Based on stable carbon isotope mass balance, the carbon contribution of geological sources at the commercial and residential sites was approximately 73% for the PM₁₀ fraction and 54% for PM_2.5. Although not measured in this study, biomass-burning emissions from nearby forests are an important carbon source characterized by isotopically lighter values (?29‰), and can become a significant contributor (67%) of particulate carbon to MCMA air under the prevalence of southwesterly winds. Alternative sources of these ¹³C-depleted particles, such as cooking fires and municipal waste incineration, need to be assessed. Results show that stable carbon isotope measurements are useful for distinguishing between some carbon sources in suspended particles to MCMA air, and that wind direction has an impact on the distribution of carbon sources in this basin.     

Removal of an anionic dye (Acid Blue 92) by coagulation–flocculation using chitosan

Chitosan (a biopolymer) is an aminopolysaccharide that can be used for the treatment of colored solutions by coagulation–flocculation (as an alternative to more conventional processes such as sorption). Acid Blue 92 (a sulfonic dye) was selected as a model dye for verifying chitosan's ability to treat textile wastewater. A preliminary experiment demonstrated that chitosan was more efficient at color removal in tap water than in demineralized water, and that a substantially lower concentration of chitosan could be used with tap water. Dye removal reached up to 99% under optimum concentration; i.e., in terms of the acidic solutions and the stoichiometric ratio between the amine groups of the biopolymer and the sulfonic groups in the dye. The flocs were recovered and the dye was efficiently removed using alkaline solutions (0.001–1 M NaOH solutions) and the biopolymer, re-dissolved in acetic acid solution, was reused in a further treatment cycle.     

The whole relationship between environmental variables and firm performance: Competitive advantage and firm resources as mediator variables

The examination of the possible direct link between environmental protection and firm performance in the literature has generally produced mixed results. The present paper contributes to the literature by using the resource-based view as a mediating process in this relationship. The study specifically tests whether or not the resource-based view of the firm mediates the positive relationships of proactive environmental management and improved environmental performance with competitive advantage, which also has consequences for financial performance. We also check the possible link between the adoption of a pioneering approach and good environmental management practices. Our findings support that early investment timing and intensity in environmental issues impact on the adoption of a proactive environmental management, which in turn helps to improve environmental performance. The findings also show that a firm's resources and competitive advantage act as mediator variables for a positive relationship between environmental protection and financial performance. This contribution is original because the present paper develops a comprehensive whole picture of this path process, which has previously only been partially discussed in the literature. In addition, this study clarifies a relevant point in the literature, namely that the effect of environmental protection on firm performance is not direct and can vary depending on the sector considered. Whereas competitive advantage in relation to costs influences financial performance in the IPPC law sector, the relevant influence in the hotel sector comes from competitive advantage through differentiation.     

Determination of direct and fugitive PM emissions in a Mediterranean harbour by means of classic and novel tracer methods

Remodelling works are frequent in harbour areas, given that they must adapt to rapidly changing market requirements. Depending on their nature (construction, demolition, etc.), these works may be carried out during long periods of time and thus exert a significant impact on the air quality at the harbours and their surroundings. The air quality at the Valencia harbour was studied during an enlargement project. Four sampling stations aimed to cover the major dust-emitting activities in the harbour. In addition, a sampling campaign was carried out to collect dust materials at their emission sources (e.g., loading and unloading of clinker and petroleum coke, as well as the enlargement works). Differences obtained between PM levels at the monitoring sites were correlated with the distance between sampling stations and enlargement works and/or harbour operations, as well as with the preferential wind direction. In all cases, the days with the highest PM_10 levels were linked to wind directions coinciding with the location of the enlargement works or the clinker and petroleum coke stocks. Classic source apportionment methodologies (PCA and CMB) were applied to the data, but their interpretation was complex due to the similar chemical signatures of PM originating from direct and fugitive emissions from stocked materials (e.g., clinker), and the enlargement works. To overcome this difficulty, a novel non-statistical approach was used to obtain quantitative estimations of the contributions from sources (petroleum coke and clinker), based on the correlation between specific PM components (e.g., carbonaceous species) and source tracers (e.g., V). Finally, a qualitative test using phenolphthalein was devised to identify the presence of clinker on the filters, which provided positive results. This novel tracer approach is thus recommended for harbour authorities.     

Effects of dredging on benthic diatom assemblages in a lowland stream

The objective of this study was to assess the effects of dredging on the structure and composition of diatom assemblages from a lowland stream and to investigate whether the response of diatom assemblages to the dredging is also influenced by different water quality. Three sampling sites were established in Rodríguez Stream (Argentina); physico-chemical variables and benthic diatom assemblages were sampled weekly in spring 2001. Species composition, cell density, diversity and evenness were estimated. Diatom tolerance to organic pollution and eutrophication were also analyzed. Differences in physico-chemical variables and changes in benthic diatom assemblages were compared between the pre- and post-dredging periods using a t-test. Data were analyzed using Principal Components Analysis (PCA), non-metric multidimensional scaling (MDS) ordination and cluster analysis. The effects of dredging in the stream involve two types of disturbances: (i) in the stream bed, by the removal and destabilization of the substrate and (ii) in the water column, by generating chemical changes and an alteration of the light environment of the stream. Suspended solids, soluble reactive phosphorus and dissolved inorganic nitrogen were significantly higher in post-dredging periods. Physical and chemical modifications in the habitat of benthic diatoms produced changes in the assemblage; diversity and species numbers showed an immediate increase after dredging, decreasing at the end of the study period. Changes in the tolerance of the diatom assemblage to organic pollution and eutrophication were also observed as a consequence of dredging; in the post-dredging period sensitive species were replaced by either tolerant or most tolerant species. These changes were particularly noticeable in site 1 (characterized by its lower amount of nutrients and organic matter previous to dredging), which showed an increase in the amount of nutrients and oxygen demand as a consequence of sediment removal. However, these changes were not so conspicuous in sites 2 and 3, which already presented a marked water quality deterioration before the execution of the dredging works.     

Proposed methodology to delineate bodies of groundwater according to the European water framework directive. Application in a pilot Mediterranean river basin (Málaga,Spain)

The term “body of groundwater” represents a new administrative tool established by the water framework directive (WFD) in order to manage European groundwaters. Its practical application raises some difficulties due to unclear definitions and the large heterogeneity of European aquifers. In this work, a methodology is proposed to carry out the delineation of bodies of groundwater according to the requirements of the WFD. This methodology faces up to some of the major difficulties that can arise during the delineation, such as the identification of bodies of groundwater in multilayered aquifers, boundaries between superposed groundwater bodies, and delimitation in low permeability materials or in dismembered aquifers. In order to show its practical application, the proposed methodology is applied in a pilot Mediterranean river basin located in southern Spain. Results show that previous knowledge of the hydrogeological conditions is necessary to enable a correct delineation of groundwater bodies. Finally, alternative procedures are proposed for low permeability and small aquifers in order to reduce the number of groundwater bodies identified and simplify their overall management.     

Long-Term Changes in Game Species Over a Long Period of Transformation in the Iberian Mediterranean Landscape

Agricultural change has transformed large areas of traditional farming landscapes, leading to important changes in the species community assemblages in most European countries. We suspect that the drastic changes in land-use that have occurred in Andalusia (southern Spain) over recent decades, may have affected the distribution and abundance of game species in this region. This article compares the distribution of the main game species in Andalusia during the 1960s and 1990s, using data from maps available from the Mainland Spanish Fish, Game and National Parks Service and from recent datasets on hunting yield distributions, respectively. Big-game and small-game species were significantly segregated in southern Spain during the 1990s, as two clearly independent chorotypes (groups of species whose abundances are similarly distributed) were obtained from the classification analysis. In contrast, big-game and small-game species were not significantly segregated several decades ago, when there was only one chorotype consisting of small-game species and wild boar. The other three ungulates did not constitute a significant chorotype, as they showed positive correlations with some species in the group mentioned above. These changes seem to be a consequence of the transformations that have occurred in the Iberian Mediterranean landscape over the last few decades. The abandoning of traditional activities, and the consequent formation of dense scrubland and woodland, has led to an expansion of big-game species, and a decrease of small-game species in mountain areas. Moreover, agricultural intensification has apparently depleted small-game species populations in some agricultural areas. On the other hand, the increasingly intensive hunting management could be artificially boosting this segregation between small-game and big-game species. Our results suggest that the conservation and regeneration of traditional agricultural landscapes (like those predominating in the 1960s) should be a priority for the conservation of small-game species.     

Field Trial Assessment of Biological,Chemical, and Physical Responses of Soil to Tillage Intensity,Fertilization, and Grazing

Soil microbial populations can fluctuate in response to environmental changes and, therefore, are often used as biological indicators of soil quality. Soil chemical and physical parameters can also be used as indicators because they can vary in response to different management strategies. A long-term field trial was conducted to study the effects of different tillage systems (NT: no tillage, DH: disc harrow, and MP: moldboard plough), P fertilization (diammonium phosphate), and cattle grazing (in terms of crop residue consumption) in maize (Zea mays L.), sunflower (Heliantus annuus L.), and soybean (Glycine max L.) on soil biological, chemical, and physical parameters. The field trial was conducted for four crop years (2000/2001, 2001/2002, 2002/2003, and 2003/2004). Soil populations of Actinomycetes, Trichoderma spp., and Gliocladium spp. were 49% higher under conservation tillage systems, in soil amended with diammonium phosphate (DAP) and not previously grazed. Management practices also influenced soil chemical parameters, especially organic matter content and total N, which were 10% and 55% higher under NT than under MP. Aggregate stability was 61% higher in NT than in MP, 15% higher in P-fertilized soil, and also 9% higher in not grazed strips, bulk density being 12% lower in NT systems compared with MP. DAP application and the absence of grazing also reduced bulk density (3%). Using conservation tillage systems, fertilizing crops with DAP, and avoiding grazing contribute to soil health preservation and enhanced crop production.