Nitrogen (N) deposition has increased globally over the last 150 years and further increase is predicted for the future. Nitrogen is an important nutrient for lichens, involved in many processes in both photobiont and mycobiont.  However, N can be a stressor, causing many lichens and lichen communities to disappear with increased deposition. The objective of this thesis was to investigate the response of epiphytic lichens to increased N load. This was done by simulating an increased N deposition to lichens in a boreal forest with low background N, including both short term studies with transplanted lichens and long term studies of naturally established lichens. Alectoria sarmentosa was used as a model species for a N-sensitive lichens and Platismatia glauca as a relatively more N-tolerant lichen. Nitrogen deposition was simulated by daily spraying during the growing season with water and isotopically labeled ammonium nitrate (NH4NO3). In Paper I, I found that when N is supplied in realistic doses (equivalent to deposition of 0.6, 6, 12.5, 25 and 50 kg N ha-1), there were no significant differences in uptake of NO3- or NH4+ in either of the lichen species. The results in Paper II indicate that A. samentosa may be limited by phosphorous (P) and not N limited as expected. That study highlights the importance of P, when studying the effects of N deposition, since P can both mitigate and intensify the negative effects of N on epiphytic lichens. Paper III shows that four years of simulated N deposition caused an alteration of the epiphytic lichen community, since A. sarmentosa decreased in the highest N loads (25 and 50 kg ha-1 year-1), Bryoria spp. decreased to 12.5 kg N and higher loads and Hypogymnia physodes decreased over time for all treatments except in 12.5 kg ha-1, where it only decreased during the first treatment year and then increased after 2007.  The abundance of Platismatia glauca increased over time, independent of treatment. As hypothesized, responses to the treatments differed among species, reflecting their different N optima. In paper IV, the effects of N on carbon-based secondary compounds were studied. None of the studied species (P. glauca, A. sarmentosa, Lobaria scrobiculata and Xanthoria aureola) reduced their concentration of secondary compounds during the experimental period, but in P. glauca the concentration of all compounds were significantly lower in N treated thalli compared with control thalli. The results are consistent with a high degree of constitutive defence in three of the four studied lichens, and we conclude that all four studied lichens seem to have a robust chemical defence system despite considerable manipulation of the environmental conditions. However, we don't know if these lichens are able to keep up the high protection level over longer periods comprising a number of years when more new tissue is formed. In conclusion, long term experiments are necessary to understand lichen response to environmental changes.

Abstract Boreal urban forests are becoming more and more fragmented and, at the same time, are exposed to low-level but long-term nitrogen and sulphur deposition. Natural mid-boreal forests are dominated by few tree and shrub species, while herbs and grasses are rare. Soils in mid-boreal forests are rich in ectomycorrhizal (ECM) fungi, forming a symbiotic relationship with forest trees, which is important for the nutrient cycle especially in nutrient-poor ecosystems. Aims of this thesis were 1) to study differences between mid-boreal urban and rural forests in composition of macrofungi and structure of plant communities, 2) to explore whether responses of Scots pine seedlings to excess N are mediated via soil or via air, and 3) to study if partial removal of vegetation and humus layer alleviates the adverse effects of excess N on plant and fungal communities, and promotes performance and regeneration of Scots pine in urban forests. The growth responses of seedlings and their mycorrhizal colonization were studied in both field and greenhouse experiments. Peroxidase (POD) activity was used as a root stress indicator. Urban forests were poor in number of fruiting ECM fungal species, but rich in herbs and grasses in the field layer, as compared to rural forests. These differences were thought to result from changes in soil properties. ECM fungal colonization in Scots pine roots did not respond significantly to high nitrogen load in soil, but high root POD activity indicated changes in root physiology. ECM macrofungal diversity in urban forests was not markedly increased during a five-year survey after a partial humus removal treatment. On the other hand, fruiting of Cortinarius semisanguineus is a positive response to the treatment. Scots pine seedling emergence was poor due to rapid revegetation at the urban sites, but the treatment promoted both root and shoot growth of planted Scots pine seedlings in urban forests. Decreased root POD activity in Scots pine seedlings in the humus removal treatment possibly indicates lowered root stress. Soil manipulations may result in a risk of nutrient leakage, and a risk of invasion by non-typical plants. Also, small stand size with high recreation pressure causes a risk for tree regeneration in urban forest stands. These risks need to be considered when planning management of urban coniferous forests.

Afin d’appréhender l’impact des dépôts d’azote atmosphérique sur les écosystèmes,nous nous sommes intéressés à un écosystème d’intérêt patrimonial : les prairies acides duViolion caninae. Au sein de ces prairies, les objectifs étaient de (i) quantifier les variationsfloristiques temporelles et spatiales le long du domaine atlantique français et de déterminer siles variables de dépôts d’azote et du climat expliquaient ces patrons, (ii) comprendre lesprocessus mis en jeu lors de l’enrichissement en azote au niveau de la végétation et du sol, et(iii) examiner les moyens potentiels de conservation et de restauration.L’étude temporelle et spatiale des prairies acides a permis de mettre en évidence deschangements de composition à l’échelle locale du type de communautés mais également àl’échelle nationale du domaine atlantique français. A l’échelle locale et nationale, ceschangements ont pu être reliés à des changements climatiques d’augmentation de latempérature annuelle moyenne et de diminution de la disponibilité en eau du sol. Toutefois àl’échelle locale, les plus forts changements de végétation ont été perçus pour les sites soumiségalement aux plus forts dépôts chroniques d’azote depuis les 25 dernières années. Ceschangements de composition se sont produits au détriment des espèces de petites tailles, tellesque des dicotylédones, alors que les Poacées généralistes se sont maintenues en dominant lecouvert végétal. Ces changements sont visibles dès 10-15 kg N ha-1 an-1, déterminé comme lacharge critique d’azote pour les prairies acides.L’approche expérimentale a permis de souligner les processus mis en jeu dans ceshabitats acides lors d’un apport d’azote. Notamment, l’enrichissement en azote n’entraineraitpas de compétition pour la lumière au sein de la végétation. Ce type de milieu, principalementdéfini par son caractère oligotrophe et sa faible capacité à neutraliser l’acidité du sol,semblerait donc essentiellement affecté par des mécanismes de toxicité de l’ammonium voired’acidification du milieu à long terme.Enfin, les moyens de restauration étudiés ont montré la difficulté de conserver et derestaurer de tels habitats potentiellement affectés par les dépôts d’azote. En effet, l’utilisationde fauches répétées avec exportation de la biomasse a montré son inutilité dans un systèmequi n’est pas influencé par la compétition pour la lumière. De même, l’étude des banques degraines a montré que ce pool d’espèces ne pouvait pas représenter le seul moyen deconservation des espèces caractéristiques. Ces résultats révèlent l’importance de conserver lesprairies acides existantes, principalement dans des sites soumis à de faibles dépôts ambiants. / To assess the impact of atmospheric nitrogen deposition on ecosystems, we werefocused on a patrimonial interest ecosystem: acid grasslands of Violion caninae. Within thesegrasslands, we aimed to (i) characterise temporal and spatial variation in plant speciescomposition along the French Atlantic domain and determine if nitrogen deposition andclimate variables could explain these patterns, (ii) understand processes underlined bynitrogen addition on vegetation and soil, and (iii) examine the potential conservation andrestoration ways.Temporal and spatial approach of acid grasslands brought to light changes in speciescomposition at local scale of community type but also at the national French Atlantic domainscale. At both local and national scale, these changes were linked to climate change withincrease of mean annual temperature and decrease of soil water availability. However at localscale, the most changes in species composition were experienced on sites with climate changeand also the highest chronic nitrogen deposition since the last 25 years. These changes inspecies composition occurred at the expense of short stature species like forbs whereasgrasses species were persistent and dominated vegetation. These changes are visible from 10-15 kg N ha-1 an-1, determined as the critical load for nitrogen in acid grasslands.The experiment allowed to highlight processes underlined in acid grasslands afternitrogen addition. In particular, nitrogen enrichment did not lead to light competition invegetation. These grasslands, mainly defined by poor-nutrient and low capacity to bufferacidity in soil, were essentially affected by ammonium toxicity or even acidification on thelong range.Finally, the study of conservation ways showed the difficulty to conserve and restorethe grasslands affected by nitrogen deposition. Indeed, more frequent cuttings with biomassremoval were useless in a system not influenced by light competition within vegetation. Thestudy of seed banks showed also that conservation ways could not be based just on seed banksto maintain characteristic species. These results highlight the importance to conserve theexisting acid grasslands, mostly in region with low ambient nitrogen deposition.

Depuis des décennies, les dépôts atmosphériques azotés sont connus pour agir de manière sévère sur le fonctionnement des écosystèmes forestiers. Ils influent en effet la biogéochimie du sol, l’équilibre des éléments nutritifs et, en conséquence, la croissance des espèces végétales, la biodiversité végétale de sous-étage et plus globalement la santé des forêts. Dans le cadre de la convention internationale de Genève visant à limiter la pollution atmosphérique transfrontalière à longue distance, le concept de « Charges Critiques », défini à la fin des années 1980, a été retenu comme outil permettant d’évaluer la sensibilité d’un écosystème aux contaminants. Il permet d’estimer la quantité maximale de polluants atmosphériques acceptable par l’écosystème avant apparition de conséquences néfastes à son fonctionnement. De plus, en raison de l’impact des changements globaux sur les processus biogéochimiques régissant le fonctionnement des écosystèmes, l’influence des dépôts atmosphériques et du changement climatique doit être considéré de manière simultanée pour évaluer l’évolution de l’état des écosystèmes au cours du temps. Dès lors l’enjeu majeur est de pouvoir prédire l’effet combiné de ces facteurs sur les écosystèmes forestiers français. C’est l’objectif de ce travail de thèse. Des modèles dynamiques couplés biogéochimiques – écologiques, tels que les modèles ForSAFE-VEG ou PROPS, ou écologiques (basés sur la base de données EcoPlant) ont été développés ou adaptés à ces fins, et appliqués à différentes échelles locale, régionale et nationale, selon différents scénarios de dépôts et climatiques. L’application et la calibration du modèle couplé ForSAFE-VEG sur des placettes forestières permanentes du réseau RENECOFOR ont permis de prédire l’évolution de la composition biogéochimique de la solution du sol et en cascade de la composition floristique de trois sites, sous différents scénarios de dépôts atmosphériques et de changement climatique. Les principales évolutions des sites sont liées à leurs caractéristiques stationnelles. Si le changement climatique joue un rôle prédominant sur la réponse des espèces, les écosystèmes oligotrophes restent sensibles aux dépôts de N. A court terme, l’effet combiné des dépôts et du changement climatique sur le long terme est modulé par les effets de la gestion forestière. L’extrapolation du modèle couplé à plus large échelle nécessite une continuité dans la disponibilité des données d’entrée et de calibration de la réponse des espèces. Les données et scénarios de changement climatiques ont été complétés et actualisés à l’aide du modèle SAFRAN et des nouveaux scénarios RCP régionalisés. La calibration de la réponse des espèces végétales à l’échelle de la France a été réalisée à partir des mesures de la base de données phytoécologiques EcoPlant, par le développement de modèles de distribution d’espèces (SDM), en intégrant simultanément des variables climatiques, édaphiques, d’énergie et de nutrition. Le couplage entre le modèle ForSAFE et les SDM assure une modélisation robuste à l’échelle du territoire de la réponse des écosystèmes forestiers dans le temps, calibrée pour les conditions pédoclimatiques françaises. La modélisation des charges critiques d’acidité, d’eutrophisation et de biodiversité sur l’ensemble des sites RENECOFOR et la totalité des écosystèmes forestiers français montre des sensibilités variées aux dépôts de soufre et d’azote en fonction des écosystèmes, avec parmi les plus sensibles les Landes, la Sologne et le Massif Central. Des indices de qualité des habitats (HSi) ont été calculés à l’échelle de tous les écosystèmes par le modèle PROPS et les SDM. La sélection des espèces représentatives reste primordiale car elle conditionne la valeur finale de HSi. Ce paramètre est l’un des plus sensibles à prendre en compte dans la modélisation. Il est à mettre en relation avec les objectifs de protection des écosystèmes voulus par les gestionnaires. / For decades, it has been known that atmospheric nitrogen depositions have a severe impact on the operations of forest ecosystems. Indeed, they affect the soil biogeochemistry, the balance of the nutritive elements and consequently the plant species growth, the biodiversity of the understory vegetation and more globally the forest health. As part of the Geneva Agreement to limit the long-range transboundary air pollution, the concept of "critical loads", defined towards the end of the 1980s, was adopted as a tool to enable the assessment of the sensitivity of the ecosystems to contaminants. It can be used to estimate the maximal amount of atmospheric contaminants which can be accepted by the ecosystem before significant harmful effects on specified sensitive biological indicators appear. In addition, because of the impact of global warming on biogeochemical processes regulating the functioning of ecosystems, the influence of atmospheric depositions and climate change must be considered simultaneously to evaluate the evolution of ecosystem conditions over time. Since then, the major issue has been to be able to predict the combined effect of these factors on the French forest ecosystems. This is the aim of this PhD work. Coupled dynamic biochemical-ecological models, such as ForSAFE-VEG or PROPS models, or ecological (based on EcoPlant database) were developed or adapted for this purpose and applied to different local, regional and national scales against different deposition and climatic scenarios. The application and calibration of the coupled model ForSAFE-VEG on permanent forest plots from the RENECOFOR network enabled prediction of the evolution of the soil solution biogeochemical composition, as well as monitoring of the floristic composition of three sites, under different scenarios of atmospheric deposition and climate change. The principal site evolutions are related to their stational characteristics. If the climate change plays a primary role on a species’ response, the oligotrophic ecosystems remain sensitive to nitrogen depositions. On a short term basis, the combined effect of the deposits and long term climate change is modulated by forest management. The extrapolation of the coupled model on a larger scale requires continuity in the availability of input data and calibration of the species’ response. The data and climate changes scenarios were completed and updated with the SAFRAN model and new regionalised RCP scenarios. The calibration of the response of plant species throughout France was carried out using measurements of the phytoecological database EcoPlant, via development of species distribution models (SDM). The coupling between ForSAFE and the SDM ensures a robust global modelling of the forest ecosystems’ response over time, calibrated for the French pedoclimatic conditions. The modelling of the acidic, eutrophication and biodiversity critical loads, on all the RENECOFOR sites and French forest ecosystems, shows the various sensitivities to sulphur and nitrogen depositions depending on the ecosystem. Ecosystems located in the Landes, Sologne and Massif Central appear to be amongst the most sensitive ones. The Habitats Suitability Index (HSI) was calculated throughout all the ecosystems via PROPS models and the SDM. The selection of representative species remains pivotal as the final HSI value is conditional, depending on this factor. This parameter is one of the most sensitive factors to take into account with the model. It must be linked with forest managers' objectives for the protection of the ecosystems.

Litter decomposition is a key process for carbon and nutrient cycling in terrestrial ecosystems and is mainly controlled by environmental conditions, substrate quantity and quality as well as microbial community abundance and composition. In particular, the effects of climate and atmospheric nitrogen (N) deposition on litter decomposition and its temporal dynamics are of significant importance, since their effects might change over the course of the decomposition process. Within the TeaComposition initiative, we incubated Green and Rooibos teas at 524 sites across nine biomes. We assessed how macroclimate and atmospheric inorganic N deposition under current and predicted scenarios (RCP 2.6, RCP 8.5) might affect litter mass loss measured after 3 and 12 months. Our study shows that the early to mid-term mass loss at the global scale was affected predominantly by litter quality (explaining 73% and 62% of the total variance after 3 and 12 months, respectively) followed by climate and N deposition. The effects of climate were not litter-specific and became increasingly significant as decomposition progressed, with MAP explaining 2% and MAT 4% of the variation after 12 months of incubation. The effect of N deposition was litter-specific, and significant only for 12-month decomposition of Rooibos tea at the global scale. However, in the temperate biome where atmospheric N deposition rates are relatively high, the 12- month mass loss of Green and Rooibos teas decreased significantly with increasing N deposition, explaining 9.5% and 1.1% of the variance, respectively. The expected changes in macroclimate and N deposition at the global scale by the end of this century are estimated to increase the 12-month mass loss of easily decomposable litter by 1.1– 3.5% and of the more stable substrates by 3.8–10.6%, relative to current mass loss. In contrast, expected changes in atmospheric N deposition will decrease the mid-term mass loss of high-quality litter by 1.4–2.2% and that of low-quality litter by 0.9–1.5% in the temperate biome. Our results suggest that projected increases in N deposition may have the capacity to dampen the climate-driven increases in litter decomposition depending on the biome and decomposition stage of substrate.

No description available.

Espécies nitrogenadas vem sendo adicionadas ao meio ambiente de forma intensa desde o desenvolvimento do processo Haber-Bosch para transformação de N2 em NH3, alterando significativamente o ciclo biogeoquímico do nitrogênio no ambiente. Uma vez na atmosfera, o nitrogênio reativo é depositado de volta à superfície da Terra por processos de deposição úmida e seca. A importância de levar em conta as formas orgânicas de nitrogênio para estimar a deposição de nitrogênio atmosférico pela chuva (úmida) já é conhecida, no entanto, ainda há poucos trabalhos que avaliam essa fração devido às dificuldades e incertezas impostas pelos métodos analíticos disponíveis. Este trabalho traz o desenvolvimento de um novo método, simples e de baixo custo, para a determinação de nitrogênio orgânico (N-org) em água de chuva utilizando o processo foto-Fenton e um foto-reator construído de forma artesanal. Por meio da adição de solução de Fenton (50 µmol L-1 Fe2+ e 2 mmol L-1 H2O2) e 90 min de radiação UV (85 °C) foi possível obter em média 106 ± 8% de recuperação de nitrogênio para soluções contendo 50 µmol N L-1 das moléculas modelos: ureia, serina, glicina e histidina. No caso da arginina, 90 min de radiação foi suficiente para degradar soluções contendo 10 µmol N L-1. O reator comercial se mostrou mais eficiente na degradação dos compostos testados (30 min), no entanto, com um tempo de 75 min, o reator artesanal atingiu os mesmos resultados. Com o uso de 0,2 g L-1 TiO2 e 120 min de radiação UV, também foi possível obter resultados satisfatórios. Porém, esse método possuiu valores de branco elevados, havendo necessidade de filtrar as amostras irradiadas antes da análise, adicionando tempo e custo ao procedimento analítico. O método desenvolvido utilizando foto-Fenton foi aplicado para a determinação de N-org em amostras de água de chuva coletadas na cidade de Ribeirão Preto (SP) de 2013 a 2017. A concentração de N-org variou de 3,5 a 195 µmol N L-1 com concentração média ponderada pelo volume (MPV) de 17,7 ± 1,0 µmol N L-1 (n=236). Essa média foi maior que aquelas obtidas em água de chuva de várias partes do mundo, podendo ser atribuída a elevada queima de biomassa na região de estudo. As concentrações de aminoácidos livres dissolvidos (AA) representaram em média 15 ± 12% (n=144) em relação à fração orgânica de nitrogênio na chuva, enquanto as concentrações de ureia foram próximas ou inferiores ao limite de quantificação do método (0,5 µmol N L-1). Considerando toda série temporal iniciada no mesmo sítio amostral desde 2005, as concentrações MPV calculadas para os íons NH4+ foi de 22,2 ± 1,1 µmol L-1 (n=460), NO3- de 13,3 ± 0,6 µmol L-1 (n=466), sendo que a concentração de NO2- foi irrelevante. Foram obtidas concentrações significativamente mais elevadas (teste-t, P=0,05) de NH4+, NO3-, N-org e AA no período de safra da cana (seco) com relação à entressafra (chuvoso), para todos os anos avaliados. Apesar da colheita manual da cana ter sido drasticamente reduzida, o fato de manter a mesma tendência sazonal desde 2005, demonstra que a prática da queima de biomassa ainda é intensa na região. O uso de fogo para manejo na área rural ainda é comum, além de haver grandes áreas queimadas de forma acidental. A deposição úmida de nitrogênio (N-org + NH4+ + NO3-) para Ribeirão Preto foi de 10,5 kg (N) ha-1 ano-1, sendo que a fração orgânica representou 33% dessa deposição, demonstrando a importância de se determinar N-org para melhor estimar os fluxos atmosféricos de deposição. A massa estimada de nitrogênio depositada pela chuva é cerca de 16% do nitrogênio aplicado por meio de fertilizantes em culturas de cana. Somando as deposições de nitrogênio pelo material particulado, pela fase gasosa, e úmida, esta última representa 71% do fluxo atmosférico de nitrogênio. Nesse contexto, a fração orgânica corresponde a 24% da deposição total, sendo que este valor ainda pode estar sendo subestimado, pois as concentrações de N-org no material particulado não foram determinadas. A simplicidade e exatidão do método aqui proposto pode facilitar a aquisição de dados de N-org na chuva de outras partes do mundo, melhorando assim o conhecimento sobre o ciclo biogeoquímico global do nitrogênio. / Nitrogen species have been intensively added to the environment since the development of Haber-Bosch process for N2 transformation to NH3, significantly altering the biogeochemical cycle of nitrogen. Once in the atmosphere, reactive nitrogen is deposited back to the Earth\'s surface by wet and dry deposition processes. The importance of taking into account the organic forms of nitrogen to estimate atmospheric nitrogen deposition by rain is already known. However, few studies evaluated this fraction due to the difficulties and uncertainties imposed by the available analytical methods. This work presents the development of a new, simple and low-cost method for the determination of organic nitrogen (N-org) in rainwater using photo-Fenton process and a homemade photo-reactor. By adding Fenton solution (50 mol L-1 Fe2+ and 2 mmol L-1 H2O2) and keeping the reaction under UV radiation for 90 min (85 °C), it was possible to obtain an average of 106 ± 8% nitrogen recovery for solutions containing 50 mol N L-1 of the model molecules: urea, serine, glycine and histidine. In the case of arginine, 90 min of radiation was sufficient to degrade solutions containing 10 mol N L-1. A commercial reactor showed to be more efficient in degradation of the tested compounds (30 min). However, with a time of 75 min, the homemade reactor achieved the same results. With 0.2 g L-1 TiO2 and 120 min of UV radiation, it was also possible to obtain satisfactory results. Nevertheless, this method had high blank values, and filtration of irradiated samples before the analysis was necessary, which increased time and cost to the analytical procedure. The developed method using photo-Fenton was applied to determine N-org in rainwater samples collected in Ribeirão Preto city (SP) from 2013 to 2017. N-org concentrations ranged from 3.5 to 195 mol N L-1 with a volume-weighted mean concentration (VWM) of 17.7 ± 1.0 mol N L-1 (n = 236). This value was higher than those reported for rainwater from different parts of the world, and this fact can be attributed to the high biomass burning in the study region. Dissolved free amino acids (AA) mean concentrations represented 15 ± 12% (n = 144) of the organic nitrogen fraction in rain, while urea concentrations were close to or below the limit of quantification of the method (0.5 mol N L-1). Considering all temporal series, initiated in 2005 at the same sampling site, the VWM concentration calculated for NH4+ ions was 22.2 ± 1.1 mol L-1 (n = 460) and for NO3- was 13.3 ± 0.6 mol L-1 (n = 466), while NO2- mean concentration was irrelevant. Significantly higher concentrations (t-test, P = 0.05) of NH4+, NO3-, N-org and AA were obtained during the harvest period (dry season) in relation to the non-harvest one (rainy season), for all evaluated years. Although manual harvesting was drastically reduced, the fact that the same seasonal trend has been maintained since 2005 demonstrates that the practice of biomass burning is still intense in the region. In rural area, using fire for land management is still common, in addition to large areas burned by unintentional fires. Nitrogen deposition (N-org + NH4+ + NO3-) in Ribeirão Preto was 10.5 kg (N) ha-1 year-1, and the organic fraction represented 33% of this deposition, demonstrating the importance of determining N-org to better estimate the atmospheric deposition fluxes. The estimated mass of nitrogen deposited by rain represents approximately 16% of the nitrogen introduced by fertilizers in sugarcane crops. Summing up the nitrogen deposition by particulate matter, by gas phase, and by rain, the latter represents 71% of the atmospheric nitrogen flux. In this context, the organic fraction corresponds to 24% of the total deposition, and this value may still be underestimated, since N-org concentrations in particulate matter were not determined. The simplicity and accuracy of the method proposed here may facilitate acquisition of N-org data in rainwater from other parts of the world, thus improving the knowledge on the global biogeochemical cycle of nitrogen.

Espécies nitrogenadas vem sendo adicionadas ao meio ambiente de forma intensa desde o desenvolvimento do processo Haber-Bosch para transformação de N2 em NH3, alterando significativamente o ciclo biogeoquímico do nitrogênio no ambiente. Uma vez na atmosfera, o nitrogênio reativo é depositado de volta à superfície da Terra por processos de deposição úmida e seca. A importância de levar em conta as formas orgânicas de nitrogênio para estimar a deposição de nitrogênio atmosférico pela chuva (úmida) já é conhecida, no entanto, ainda há poucos trabalhos que avaliam essa fração devido às dificuldades e incertezas impostas pelos métodos analíticos disponíveis. Este trabalho traz o desenvolvimento de um novo método, simples e de baixo custo, para a determinação de nitrogênio orgânico (N-org) em água de chuva utilizando o processo foto-Fenton e um foto-reator construído de forma artesanal. Por meio da adição de solução de Fenton (50 µmol L-1 Fe2+ e 2 mmol L-1 H2O2) e 90 min de radiação UV (85 °C) foi possível obter em média 106 ± 8% de recuperação de nitrogênio para soluções contendo 50 µmol N L-1 das moléculas modelos: ureia, serina, glicina e histidina. No caso da arginina, 90 min de radiação foi suficiente para degradar soluções contendo 10 µmol N L-1. O reator comercial se mostrou mais eficiente na degradação dos compostos testados (30 min), no entanto, com um tempo de 75 min, o reator artesanal atingiu os mesmos resultados. Com o uso de 0,2 g L-1 TiO2 e 120 min de radiação UV, também foi possível obter resultados satisfatórios. Porém, esse método possuiu valores de branco elevados, havendo necessidade de filtrar as amostras irradiadas antes da análise, adicionando tempo e custo ao procedimento analítico. O método desenvolvido utilizando foto-Fenton foi aplicado para a determinação de N-org em amostras de água de chuva coletadas na cidade de Ribeirão Preto (SP) de 2013 a 2017. A concentração de N-org variou de 3,5 a 195 µmol N L-1 com concentração média ponderada pelo volume (MPV) de 17,7 ± 1,0 µmol N L-1 (n=236). Essa média foi maior que aquelas obtidas em água de chuva de várias partes do mundo, podendo ser atribuída a elevada queima de biomassa na região de estudo. As concentrações de aminoácidos livres dissolvidos (AA) representaram em média 15 ± 12% (n=144) em relação à fração orgânica de nitrogênio na chuva, enquanto as concentrações de ureia foram próximas ou inferiores ao limite de quantificação do método (0,5 µmol N L-1). Considerando toda série temporal iniciada no mesmo sítio amostral desde 2005, as concentrações MPV calculadas para os íons NH4+ foi de 22,2 ± 1,1 µmol L-1 (n=460), NO3- de 13,3 ± 0,6 µmol L-1 (n=466), sendo que a concentração de NO2- foi irrelevante. Foram obtidas concentrações significativamente mais elevadas (teste-t, P=0,05) de NH4+, NO3-, N-org e AA no período de safra da cana (seco) com relação à entressafra (chuvoso), para todos os anos avaliados. Apesar da colheita manual da cana ter sido drasticamente reduzida, o fato de manter a mesma tendência sazonal desde 2005, demonstra que a prática da queima de biomassa ainda é intensa na região. O uso de fogo para manejo na área rural ainda é comum, além de haver grandes áreas queimadas de forma acidental. A deposição úmida de nitrogênio (N-org + NH4+ + NO3-) para Ribeirão Preto foi de 10,5 kg (N) ha-1 ano-1, sendo que a fração orgânica representou 33% dessa deposição, demonstrando a importância de se determinar N-org para melhor estimar os fluxos atmosféricos de deposição. A massa estimada de nitrogênio depositada pela chuva é cerca de 16% do nitrogênio aplicado por meio de fertilizantes em culturas de cana. Somando as deposições de nitrogênio pelo material particulado, pela fase gasosa, e úmida, esta última representa 71% do fluxo atmosférico de nitrogênio. Nesse contexto, a fração orgânica corresponde a 24% da deposição total, sendo que este valor ainda pode estar sendo subestimado, pois as concentrações de N-org no material particulado não foram determinadas. A simplicidade e exatidão do método aqui proposto pode facilitar a aquisição de dados de N-org na chuva de outras partes do mundo, melhorando assim o conhecimento sobre o ciclo biogeoquímico global do nitrogênio. / Nitrogen species have been intensively added to the environment since the development of Haber-Bosch process for N2 transformation to NH3, significantly altering the biogeochemical cycle of nitrogen. Once in the atmosphere, reactive nitrogen is deposited back to the Earth\'s surface by wet and dry deposition processes. The importance of taking into account the organic forms of nitrogen to estimate atmospheric nitrogen deposition by rain is already known. However, few studies evaluated this fraction due to the difficulties and uncertainties imposed by the available analytical methods. This work presents the development of a new, simple and low-cost method for the determination of organic nitrogen (N-org) in rainwater using photo-Fenton process and a homemade photo-reactor. By adding Fenton solution (50 mol L-1 Fe2+ and 2 mmol L-1 H2O2) and keeping the reaction under UV radiation for 90 min (85 °C), it was possible to obtain an average of 106 ± 8% nitrogen recovery for solutions containing 50 mol N L-1 of the model molecules: urea, serine, glycine and histidine. In the case of arginine, 90 min of radiation was sufficient to degrade solutions containing 10 mol N L-1. A commercial reactor showed to be more efficient in degradation of the tested compounds (30 min). However, with a time of 75 min, the homemade reactor achieved the same results. With 0.2 g L-1 TiO2 and 120 min of UV radiation, it was also possible to obtain satisfactory results. Nevertheless, this method had high blank values, and filtration of irradiated samples before the analysis was necessary, which increased time and cost to the analytical procedure. The developed method using photo-Fenton was applied to determine N-org in rainwater samples collected in Ribeirão Preto city (SP) from 2013 to 2017. N-org concentrations ranged from 3.5 to 195 mol N L-1 with a volume-weighted mean concentration (VWM) of 17.7 ± 1.0 mol N L-1 (n = 236). This value was higher than those reported for rainwater from different parts of the world, and this fact can be attributed to the high biomass burning in the study region. Dissolved free amino acids (AA) mean concentrations represented 15 ± 12% (n = 144) of the organic nitrogen fraction in rain, while urea concentrations were close to or below the limit of quantification of the method (0.5 mol N L-1). Considering all temporal series, initiated in 2005 at the same sampling site, the VWM concentration calculated for NH4+ ions was 22.2 ± 1.1 mol L-1 (n = 460) and for NO3- was 13.3 ± 0.6 mol L-1 (n = 466), while NO2- mean concentration was irrelevant. Significantly higher concentrations (t-test, P = 0.05) of NH4+, NO3-, N-org and AA were obtained during the harvest period (dry season) in relation to the non-harvest one (rainy season), for all evaluated years. Although manual harvesting was drastically reduced, the fact that the same seasonal trend has been maintained since 2005 demonstrates that the practice of biomass burning is still intense in the region. In rural area, using fire for land management is still common, in addition to large areas burned by unintentional fires. Nitrogen deposition (N-org + NH4+ + NO3-) in Ribeirão Preto was 10.5 kg (N) ha-1 year-1, and the organic fraction represented 33% of this deposition, demonstrating the importance of determining N-org to better estimate the atmospheric deposition fluxes. The estimated mass of nitrogen deposited by rain represents approximately 16% of the nitrogen introduced by fertilizers in sugarcane crops. Summing up the nitrogen deposition by particulate matter, by gas phase, and by rain, the latter represents 71% of the atmospheric nitrogen flux. In this context, the organic fraction corresponds to 24% of the total deposition, and this value may still be underestimated, since N-org concentrations in particulate matter were not determined. The simplicity and accuracy of the method proposed here may facilitate acquisition of N-org data in rainwater from other parts of the world, thus improving the knowledge on the global biogeochemical cycle of nitrogen.

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Habitat degradation, fragmentation and loss are important factors causing loss in biodiversity and red listed species, and restoring habitats is essential in preventing this. However, there is a limited knowledge of the long term effects of restoration measures. This study focuses on analysing the long term restoration success of restoration measures carried out in a restoration program between the 1980's and early 2000's in locations of acidic fen, buffered fen, dry heather, wet heather, and wet grassland. The aim of the restoration program was to diminish the effects on ecosystems that were influenced by eutrophication, acidification, and dehydration. The locality species composition and Ellenberg values of nitrogen (EVN), moisture (EVM) and pH levels (EVpH) are analysed, by using previous and current restoration success scores from 54 locations in the province of Drenthe in the Netherlands. The dependence of restoration success score and Ellenberg values on change over time, habitat type, restoration method and EVN, EVM and EVpH are analysed. Restoration success depended on habitat type, with wet heather having significantly higher success compared to wet grasslands. The change in score over time, however, did not vary among habitats. Restoration success did not depend on restoration method(s), nor did change in restoration success. Ellenberg values varied among habitat types, and EVM changed significantly over time in dry heather, but was not significantly related to restoration success score. In conclusion, wet heather was shown to be doing quite well, but could benefit from additional restoration. Acidic fen, buffered fen, dry heather, and wet grassland have all shown poor long term restoration effects, indicating an overall need for further restoration measures. The results also highlight the importance of further studies into the effect of long term restorations, especially focused on finding successful restoration methods, and the importance of detailed data gathered in the field.