David Elustondo

Ambient air levels of volatile organic compounds (VOC) and nitrogen dioxide (NO2) in a medium size city in Northern Spain

Ambient concentrations of volatile organic compounds (VOC) and nitrogen dioxide (NO2) were measured by means of passive sampling at 40 sampling points in a medium-size city in Northern Spain, from June 2006 to June 2007. VOC and NO2 samplers were analysed by thermal desorption followed by gas chromatography/mass-selective detector and by visible spectrophotometry, respectively. Mean concentrations of benzene, toluene, ethylbenzene, xylenes, propylbenzene, trimethylbenzenes, and NO(2) were 2.84, 13.26, 2.15, 6.01, 0.59, 1.32 and 23.17 microg m(-3) respectively, and found to be highly correlated. Their spatial distribution showed high differences in small distances and pointed to traffic as the main emission source of these compounds. The lowest levels of VOC and NO2 occurred during summer, owing to the increase in solar radiation and to lower traffic densities. Mean concentrations of benzene and NO2 exceeded the European limits at some of the monitored points.

Exposure to volatile organic compounds (VOC) in public buses of Pamplona, Northern Spain.

This study examines the exposure level of passengers and drivers to VOC in public buses in a medium-size metropolitan area (Northern Spain). In-vehicle monitoring was performed on different routes, on peak and non-peak hours, during January and February 2007. A total of 112 air samples were collected onto adsorbent tubes and analysed by thermal desorption (TD) and gas chromatography/mass selective detector (GC/MSD) technique. Statistical differences were found among route to route concentrations, with those routes with major prevalence in the commercial area of the city displaying higher values; differences between peak and non-peak hours were also observed. A decrease in VOC concentrations was also registered during the weekend. BTEX ratios were estimated and found to be related to traffic emissions and similar for all the surveyed routes. Correlations confirmed traffic as the main emission source for BTEX and trimethylbenzene, their concentrations being highly associated to changes in meteorological conditions.

Use of native mosses as biomonitors of heavy metals and nitrogen deposition in the surroundings of two steel works.

A biomonitoring survey using the moss species Hypnum cupressiforme Hedw. was conducted in the surroundings of two steel plants located in the North of Spain. Levels of V, Cr, Ni, Cu, Zn, As, Cd, Hg, Pb and N were determined. Very high concentrations in the areas of study were detected when compared to nearby unaffected regions. Similar trends were observed for all the elements in the differently orientated transects, showing an appreciable influence of the NW prevailing winds of the region in the dispersion of pollutants, as well as a clear decreasing gradient in the concentrations of metals in mosses within a distance of 1500 meters from the facilities. A differentiation between the elements emitted by the chimney as result of the industrial activity (V, Cr, Ni, Cu and As) and those with a high presence in steel slag deposits (Zn, Cd, Hg and Pb) was observed. The range of contamination was also established by means of the Contamination Factor, indicating a category 4 out of 6 categories, which shows the high levels reported in the areas of study. A different dynamic was registered for nitrogen regarding the rest of the heavy metals analysed except for Hg, probably due to the elevated volatility and mobility of both elements, as well as their high persistence in the atmosphere.

Ecological impacts of atmospheric pollution and interactions with climate change in terrestrial ecosystems of the mediterranean basin: Current research and future directions

Mediterranean Basin ecosystems, their unique biodiversity, and the key services they provide are currently at risk due to air pollution and climate change, yet only a limited number of isolated and geographically-restricted studies have addressed this topic, often with contrasting results. Particularities of air pollution in this region include high O3 levels due to high air temperatures and solar radiation, the stability of air masses, and dominance of dry over wet nitrogen deposition. Moreover, the unique abiotic and biotic factors (e.g., climate, vegetation type, relevance of Saharan dust inputs) modulating the response of Mediterranean ecosystems at various spatiotemporal scales make it difficult to understand, and thus predict, the consequences of human activities that cause air pollution in the Mediterranean Basin. Therefore, there is an urgent need to implement coordinated research and experimental platforms along with wider environmental monitoring networks in the region. In particular, a robust deposition monitoring network in conjunction with modelling estimates is crucial, possibly including a set of common biomonitors (ideally cryptogams, an important component of the Mediterranean vegetation), to help refine pollutant deposition maps. Additionally, increased attention must be paid to functional diversity measures in future air pollution and climate change studies to establish the necessary link between biodiversity and the provision of ecosystem services in Mediterranean ecosystems. Through a coordinated effort, the Mediterranean scientific community can fill the above-mentioned gaps and reach a greater understanding of the mechanisms underlying the combined effects of air pollution and climate change in the Mediterranean Basin.

Application of microwave digestion and ICP-MS to simultaneous analysis of major and trace elements in aerosol samples collected on quartz filters

A microwave digestion method in a closed vessel was developed for the simultaneous determination of trace and major elements, with the highest possible recoveries, in atmospheric aerosols using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). This method was developed to quantify the concentration of Na, Mg, Al, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Cd, Sb, Cs, Ba, La, Ce and Pb present in quartz filters containing particulate matter (PM10). The performance of the procedure was evaluated by analysis of the standard reference material NIST 1633b and CTA-FFA-1. Different combinations of nitric acid (HNO3), hydrogen peroxide (H2O2), hydrofluoric acid (HF) and hydrochloric acid (HCl) were tested to improve the recovery factors for the studied elements. The addition of a large amount (3 mL) of HF was required to fully dissolve the quartz filters. This fact made difficult the obtention of high recoveries for alkali (Rb, Cs), alkaline earth (Mg, Ca, Ba), and rare earth (La, Ce) elements, which showed the lowest recoveries. In this study three different digestion methods were assessed using a closed evaporation system, the addition of boric acid and a mixture of both procedures to minimize the effects of residual fluoride.

Carbon and nitrogen isotopes unravels sources of aerosol contamination at Caribbean rural and urban coastal sites

The constant increase of anthropogenic emissions of aerosols, usually resulting from a complex mixture from various sources, leads to a deterioration of the ambient air quality. The stable isotope compositions (δ13C and δ15N) of total carbon (TC) and nitrogen (TN) in both PM10 and emissions from potential sources were investigated for first time in a rural and an urban Caribbean costal sites in Cuba to better constrain the origin of the contamination. Emissions from road traffic, power plant and shipping emissions were discriminated by coupling their C and N contents and corresponding isotope signatures. Other sources (soil, road dust and cement plant), in contrast, presented large overlapping ranges for both C and N isotope compositions. δ13CPM10 isotope compositions in the rural (average of -25.4 ± 1.2‰) and urban (average of -24.8 ± 1.2‰) sites were interpreted as a mixture of contributions from two main contributors: i) fossil fuel combustion and ii) cement plant and quarries. Results also showed that this last source is impacting more air quality at the urban site. A strong influence from local wood burning was also identified at the rural site. These conclusions were comforted by a statistical analysis using a conditional bivariate probability function. TN and δ15N values from the urban site demonstrated that nitrogen in PM10 was generated by secondary processes through the formation of (NH4)2SO4. The exchange in the (NH4)2SO4 molecule between gaseous NH3 and particle NH4+ under stoichiometric equilibrium may control the observed 15N enrichment. At low nitrogen concentrations in the aerosols, representing PM10 with both the highest primary N and lowest secondary N proportions, comparison with the δ15N of potential sources indicate that emissions from diesel car and power plant emissions may represent the major vectors of primary nitrogen.

Eco-physiological response of Hypnum cupressiforme Hedw. to increased atmospheric ammonia concentrations in a forest agrosystem

Ammonia (NH3) emissions are linked to eutrophication, plant toxicity and ecosystem shifts from N to P limitation. Bryophytes are key components of terrestrial ecosystems, yet highly sensitive to N deposition. Hence, physiological responses of mosses may be indicative of NH3-related impacts, and thus useful to foresee future ecosystem damages and establish atmospheric Critical Levels (CLEs). In this work, samples of Hypnum cupressiforme Hedw. were seasonally collected along a well-defined NH3 concentration gradient in an oak woodland during a one-year period. We performed a comprehensive evaluation of tissue chemistry, stoichiometry, metabolic enzymes, antioxidant response, membrane damages, photosynthetic pigments, soluble protein content and N and C isotopic fractionation. Our results showed that all the physiological parameters studied (except P, K, Ca and C) responded to the NH3 gradient in predictable ways, although the magnitude and significance of the response were dependent on the sampling season, especially for enzymatic activities and pigments content. Nutritional imbalances, membrane damages and disturbance of cellular C and N metabolism were found as a consequence to NH3 exposure, being more affected the mosses more exposed to the barn atmosphere. These findings suggested significant implications of intensive farming for the correct functioning of oak woodlands and highlighted the importance of seasonal dynamics in the study of key physiological processes related to photosynthesis, mosses nutrition and responses to oxidative stress. Finally, tissue N showed the greatest potential for the identification of NH3-related ecological end points (estimated CLE=3.5μgm-3), whereas highly scattered physiological responses, although highly sensitive, were not suitable to that end.

Joining empirical and modelling approaches to estimate dry deposition of nitrogen in Mediterranean forests

In Mediterranean areas, dry deposition is a major component of the total atmospheric N input to natural habitats, particularly to forest ecosystems. An innovative approach, combining the empirical inferential method (EIM) for surface deposition of NO3- and NH4+ with stomatal uptake of NH3, HNO3 and NO2 derived from the DO3SE (Deposition of Ozone and Stomatal Exchange) model, was used to estimate total dry deposition of inorganic N air pollutants in four holm oak forests under Mediterranean conditions in Spain. The estimated total deposition varied among the sites and matched the geographical patterns previously found in model estimates: higher deposition was determined at the northern site (28.9 kg N ha-1 year-1) and at the northeastern sites (17.8 and 12.5 kg N ha-1 year-1) than at the central-Spain site (9.4 kg N ha-1 year-1). On average, the estimated dry deposition of atmospheric N represented 77% ± 2% of the total deposition of N, of which surface deposition of gaseous and particulate atmospheric N averaged 10.0 ± 2.9 kg N ha-1 year-1 for the four sites (58% of the total deposition), and stomatal deposition of N gases averaged 3.3 ± 0.8 kg N ha-1 year-1 (19% of the total deposition). Deposition of atmospheric inorganic N was dominated by the surface deposition of oxidized N in all the forests (means of 54% and 42% of the dry and total deposition, respectively). The relative contribution of NO2 to dry deposition averaged from 19% in the peri-urban forests to 11% in the most natural site. During the monitoring period, the empirical critical loads provisionally proposed for ecosystem protection (10-20 kg N ha-1 year-1) was exceeded in three of the four studied forests.

Assessment of Indexes for Heavy Metal Contamination in Remote Areas: A Case Study in a Pyrenean Forest, Navarra, Spain

The objective of the present work was to verify and compare the performance of different geochemical indices employed to identify the anthropogenic origin of selected heavy metals and other trace elements in soils. To that end, two background values, the upper continental crust and the metal content in the bed rock, were used and obtained from a forested basin of the western Pyrenees. The enrichment factor (EF), geo-accumulation index (Igeo), and contamination factor (Cif) were finally evaluated for their ability to determine anthropogenic contamination: Results indicate that an in-depth knowledge of the bed rock geochemistry and the geological background content is essential to distinguish between the natural variability of soils and any anthropogenic contribution of heavy metals. Although both EF and Cif show a similar ability to detect soil contamination, the latter is proposed as a more appropriate and sensitive marker given its ability for finding episodically elevated contamination levels.