The present work was carried out to assess the effect of atmospheric ammonia (NH3) on soil physicochemical properties, soil enzymatic activities (ß-glucosidase -ß-GLU-, nitrate reductase ¿NR-, urease ¿UR-, protease ¿PRO-, acid phosphatase ¿PHO-, dehydrogenase ¿DHA-), soil microbial biomass and soil respiration. The study was conducted along a NH3 gradient in a Q. pubescens Milld. forest in the vicinity of two livestock farms. Because of NHy (NHy: NH3 and NH4+) deposition, N saturation was detected up to 330 m from the farms. This excess of N led to a decrease in soil C:N and an increase in soil nitrification processes, which resulted in an accumulation of the heavy N isotope (15N) in the soil. N saturation was also reflected in the activity of NR enzyme, which was inhibited. On the other hand, while UR enzyme was inhibited close to the farms possibly due to the high amount of N-NH4+ resulting from the hydrolysis of NH3, PRO activity was stimulated by the presence of organic nitrogen compounds and the need of soil organisms to meet the C demand. In addition, the activity of PHO and ß-GLU enzymes was regulated by the relative amount of C and P that organisms need. Regarding biological variables, enhanced NH3 reduced soil microbial biomass and biomass respiratory efficiency. Finally, soil enzyme activities and soil microbial biomass have proved to be good biological indicators of soil quality.

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 = 3.5 mu g m(-3)), whereas highly scattered physiological responses, although highly sensitive, were not suitable to that end.

There is a significant lack of data in biomonitoring surveys from southern Europe and other Mediterranean biogeographic areas. This scarcity is mainly due to the impossibility of finding the commonly recommended species in a great portion of these dry environments. The present work was carried out with the aim of assessing the validity of the moss Pleurochaete squarrosa (Brid.) Lindb. (PS) as a feasible alternative in these regions. The study was developed in the Mediterranean area of Navarra, in northern Spain, where the response of PS to multiple atmospheric pollutants (N, Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Ti and Zn) was compared to that of Hypnum cupressiforme Hedw. (HC), an accepted and widely used species in biomonitoring surveys. Moreover, N isotopic signatures from both species were studied to evaluate their effectiveness when identifying nitrogen emission sources. The enrichment factor (EF) approach was used to evaluate the heavy metal uptake, showing a similar behaviour for both species: low EF for Al, As, Cr and Fe; intermediate for Mn, Ni, Pb and Sb; and high for Cd, Cr, Hg and Zn. Equally, both species depicted the same N deposition patterns across the study area. However, regarding ¿15N, PS gave a more congruent picture with the location of the main sources of N emissions in the area. These data suggest that PS may be a suitable biomonitor to fill the aforementioned gaps in Mediterranean biogeographic areas.

Deposition of dissolved organic nitrogen (DON) in both bulk precipitation (BD) and canopy throughfall (TF) has been measured for the first time in the western Mediterranean. The study was carried out over a year from 2012 to 2013 at four evergreen holm oak forests located in the Iberian Peninsula: two sites in the Province of Barcelona (Northeastern Spain), one in the Province of Madrid (central Spain) and the fourth in the Province of Navarra (Northern Spain). In BD the annual volume weighted mean (VWM) concentration of DON ranged from 0.25 mg l-1 in Madrid to 1.14 mg l-1 in Navarra, whereas in TF it ranged from 0.93 mg l-1 in Barcelona to 1.98 mg l-1 in Madrid. The contribution of DON to total nitrogen deposition varied from 34% to 56% in BD in Barcelona and Navarra respectively, and from 38% in Barcelona to 72% in Madrid in TF. Agricultural activities and pollutants generated in metropolitan areas were identified as potential anthropogenic sources of DON at the study sites. Moreover, canopy uptake of DON in Navarra was found in spring and autumn, showing that organic nitrogen may be a supplementary nutrient for Mediterranean forests, assuming that a portion of the nitrogen taken up is assimilated during biologically active periods.

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.

The concentrations of 15 selected polycyclic aromatic hydrocarbons (PAHs) were determined in daily PM10 samples collected at a rural site, an urban site and a traffic site in Navarra during 2009. PAHs were extracted by microwave-assisted extraction (MAE) from the corresponding quartz filters and later analyzed by gas chromatography/mass spectrometry (GC/MS). An intensive annual study was enabled with this analytical procedure as turnover is multiplied by 50 with MAE in comparison with the classical extraction technique (Soxhlet). The annual average total concentrations of the 15 target compounds ranged from 0.6 ng m(-3) to 1.2 ng m(-3) at the rural and traffic sampling stations respectively, showing up to four times higher PAHs concentrations in winter than in summer. When compared to other European cities, Pamplona registered significantly lower PAHs values. Other pollutants like NOx, CO and PM10 were found to be well correlated with PAHs, and O-3 presented a negative correlation. The results of diagnostic ratios and principal component analysis (PCA) revealed the high influence of diesel and gasoline emissions in the three studied areas, although, other main sources were also found.

The affinity of two widely used pesticides of diverse specificities, i.e., the fungicide Thiram and the herbicide Picloram, for lead ions has been studied by an electrochemical approach. The anodic stripping voltammetric profile of the studied metallic ion was significantly affected by the chemical nature of pesticide (ligand) used and new light has been shed on the nature, strength and possible stoichiometry of formed complexes. Thiram caused a pronounced effect on the stripping signals of Pb. Linearization algorithms of titration data with the metal allowed the conditional stability constant to be calculated for Thiram (log K' = 6.8) and Picloram (log K' = 6.0). It was found that both pesticides contribute to the formation of the respective 1:1 complexes with Pb in a high percentage (ca. 83%).

Recoge los principales resultados generados durante la realización del proyecto LIFE+RESPIRA, llevado a cabo en la ciudad de Pamplona (Navarra, España) por un equipo interdisciplinar constituido por más de 30 investigadores pertenecientes a la Universidad de Navarra, el Centro de Investigaciones Energéticas, Medioambientales y Tecnológicas (CIEMAT) y Gestión Ambiental de Navarra (GAN-NIK). El libro, que se ha publicado en castellano y en inglés, se ha dividido en 7 capítulos: 1. ¿Ciudades sostenibles? 2. Exposición de los ciudadanos a la contaminación atmosférica 3. Papel de la vegetación urbana en la calidad del aire 4. Modelos de alta resolución para evaluar la calidad del aire 5. Impactos de la contaminación urbana 6. Movilidad y sostenibilidad urbanas 7. Comunicación y educación ambiental. Este libro pretende ser una guía de utilidad para científicos, gestores y ciudadanos, aportando un conjunto de herramientas que permitan mejorar la calidad de vida de nuestras ciudades. Además, quiere rendir un homenaje a todos los voluntarios ciclistas que han participado en dicho proyecto y que son los verdaderos artífices del mismo, ya que gracias a su dedicación incondicional durante más de dos años, han proporcionado una cantidad ingente de datos sobre la calidad del aire de la ciudad de Pamplona.

This book collects the main outcomes that were generated during the implementation of the LIFE+RESPIRA project (LIFE13 ENV/ES/000417), carried out in the city of Pamplona, Navarra, Spain. The research was conducted by a cross-functional team made up of more than 30 researchers belonging to three entities: The University of Navarra, the Centre for Energy, Environmental and Technological Research (CIEMAT) and Environmental Management of Navarra (GAN-NIK).