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.

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).

Bulk/wet and throughfall fluxes of major compounds were measured from June 2011 to June 2013 at four Mediterranean holm-oak (Quercus ilex) forests in the Iberian Peninsula. Regression analysis between net throughfall fluxes and precipitation indicated that the best defined canopy process was leaching for K+ and uptake for NH4+ at all sites. A more variable response between sites was found for Na+, Ca2+, SO42- and Cl-, which suggests that the interplay of dry deposition, leaching and uptake at the canopy was different depending on site climate and air quality characteristics. A canopy budget model (CBM) was used to try to discriminate between the canopy processes and enable to estimate dry deposition and uptake fluxes at three of the sites that complied with the model specifications. To derive N uptake, an efficiency factor of NH4+ vs. NO3- uptake (xNH(4)) corresponding to moles of NH4+ taken up for each NO3- mol, has to be determined. Up to now, a value of 6 has been proposed for temperate forests, but we lack information for Mediterranean forests. Experimental determination of N absorption on Quercus ilex seedlings in Spain suggests efficiency factors from 1 to 6. Based on these values, a sensitivity analysis for xNH4 was performed and the NH4-N and NO3-N modeled dry deposition was compared with dry deposition estimated with independent methods (inferential modeling and washing of branches). At two sites in NE Spain under a milder Mediterranean climate, the best match was obtained for xNH(4) = 6, corroborating results from European temperate forests. Based on this value, total DIN deposition was 12-13 kg N ha(-1) y(-1) at these sites. However, for a site in central Spain under drier conditions, variation of the NH4+ efficiency factor had little effect on DD estimates (which ranged from 2 to 2.6 kg N ha(-1) y(-1) with varying xNH(4)); when added to wet deposition, this produced a total N deposition in the range 2.6-3.4 kg N ha(-1) y(-1). Dry deposition was the predominant pathway for N, accounting for 60-80% of total deposition, while for base cations wet deposition dominated (55-65%). Nitrogen deposition values at the northwestern sites were close to the empirical critical load proposed for evergreen sclerophyllous Mediterranean forests (15 -17 kg N ha(-1) y(-1)). When organic N deposition at these forests is added (3 kg N ha(-1) y(-1)), the total N input to the sites in NE Spain are close to the critical loads for Mediterranean evergreen oak forests. (

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 03 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. (c) 2017 Elsevier Ltd. All rights reserved.

To assess the impact of nitrogen (N) pollutants on forest ecosystems, the role of the interactions in the canopy needs to be understood. A great number of studies have addressed this issue in heavily N-polluted regions in north and central Europe. Much less information is available for the Iberian Peninsula, and yet this region is home to mountain forests and alpine grasslands that may be at risk due to excessive N deposition. To establish the basis for ecology-based policies, there is a need to better understand the forest response to this atmospheric impact. To fill this gap, in this study, we measured N deposition (as bulk, wet, and throughfall fluxes of dissolved inorganic nitrogen) and air N gas concentrations from 2011 to 2013 at four Spanish holm oak (Quercus ilex) forests located in different pollution environments. One site was in an area of intensive agriculture, two sites were influenced by big cities (Madrid and Barcelona, respectively), and one site was in a rural mountain environment 40 km north of Barcelona. Wet deposition ranged between 0.54 and 3.8 kg N ha-1 year-1 for ammonium (NH4+)-N and between 0.65 and 2.1 kg N ha-1 year-1 for nitrate (NO3-)-N, with the lowest deposition at the Madrid site for both components. Dry deposition was evaluated with three different approaches: (1) a canopy budget model based in throughfall measurements, (2) a branch washing method, and (3) inferential calculations.

Atmospheric organic nitrogen (ON) plays a key role in atmospheric chemistry, contributing significantly to N deposition, particle formation and long-distance transport of nitrogenous compounds. This review addresses the most relevant methodological aspects that should be taken into account for the study of the deposit of this fraction. Likewise, it provides information on the important contribution of ON at the global level, both in rainwater and aerosols, and the main sources where it can be formed. Finally, it shows evidence of the influence of ON on the biogeochemical cycles of N and C. The information gathered in this work shows that despite the advances made in recent years, our understanding of the chemical composition and the implications of the organic fraction on health and ecosystems is far from being complete.

Atmospheric nitrogen deposition is one of the main threats for biodiversity and ecosystem functioning. Measurement techniques like ion-exchange resin collectors (IECs), which are less expensive and time-consuming than conventional methods, are gaining relevance in the study of atmospheric deposition and are recommended to expand monitoring networks. In the present work, bulk and throughfall deposition of inorganic nitrogen were monitored in three different holm oak forests in Spain during two years. The results obtained with IECs were contrasted with a conventional technique using bottle collectors and with a literature review of similar studies. The performance of IECs in comparison with the conventional method was good for measuring bulk deposition of nitrate and acceptable for ammonium and total dissolved inorganic nitrogen. Mean annual bulk deposition of inorganic nitrogen ranged 3.09-5.43 kg N ha(-1) according to IEC methodology, and 2.42-6.83 kg N ha(-1) y(-1) using the conventional method. Intra-annual variability of the net throughfall deposition of nitrogen measured with the conventional method revealed the existence of input pulses of nitrogen into the forest soil after dry periods, presumably originated from the washing of dry deposition accumulated in the canopy. Important methodological recommendations on the IEC method and discussed, compiled and summarized.

Peri-urban vegetation is generally accepted as a significant remover of atmospheric pollutants, but it could also be threatened by these compounds, with origin in both urban and non-urban areas. To characterize the seasonal and geographical variation of pollutant concentrations and to improve the empirical understanding of the influence of Mediterranean broadleaf evergreen forests on air quality, four forests of Quercus ilex (three peri-urban and one remote) were monitored in different areas in Spain. Concentrations of nitrogen dioxide (NO2), ammonia (NH3), nitric acid (HNO3) and ozone (O3) were measured during 2 years in open areas and inside the forests and aerosols (PM10) were monitored in open areas during 1 year. Ozone was the only air pollutant expected to have direct phytotoxic effects on vegetation according to current thresholds for the protection of vegetation. The concentrations of N compounds were not high enough to directly affect vegetation but could be contributing through atmospheric N deposition to the eutrophization of these ecosystems. Peri-urban forests of Q. ilex showed a significant below-canopy reduction of gaseous concentrations (particularly NH3, with a mean reduction of 29-38%), which indicated the feasibility of these forests to provide an ecosystem service of air quality improvement.

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.

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).