In Canada, more than 35 million kilograms of pesticide active ingredients are applied annually on agricultural land with about 84% of this mass applied in the Canadian Prairies Provinces. Pesticide residues may become airborne through post-volatilization losses from land, water or vegetative surfaces, via wind-eroded soil, and by spray drift during pesticide application. Once in the air, pesticides may be dispersed and transported as parent molecules or as degradation products. Currently used and legacy pesticide air concentrations were measured in the agricultural region of the Prairie Provinces and the northern subarctic and arctic regions of Canada in 2005 and 2007. More intensive air sampling was conducted across the province of Manitoba in 2008 and 2009. Separate wet versus dry atmospheric deposition samples and wetland water samples were also taken in these years. In general, pesticides were detected in the monitored environmental media as mixtures with the frequency and concentrations detected being largest for pesticides that were applied on-site. Although the most commonly used herbicides in western Canadian agriculture were frequently present in the air in the regions where they are applied, they appeared infrequently and at low levels in the Canadian Subarctic, Arctic, and remote sites far from agricultural pesticide applications. Results also indicated that the concentrations of legacy pesticides such as lindane (γ-HCH) and its manufacturing by-product prior to 1971 (α-HCH) continued to decrease over time in the Canadian environment. Air concentrations of pesticides in agricultural regions, and subsequent wet and dry atmospheric deposition, contaminated surface water following periods of pesticide application. Dry deposition contributed 12–51% of the total deposition. Calculations were performed to predict wetland water column pesticide concentrations based on total atmospheric deposits alone. The estimated concentrations were closest to actual concentrations for MCPA and predictions were also reasonable for a range of other herbicides, but a source other than atmospheric deposition was clearly relevant to the detection of clopyralid in the wetland water-column. Individual herbicide concentrations did not exceed Canadian water quality guidelines for the protection of aquatic life.

Les hydrocarbures aromatiques polycycliques (HAP) sont des polluants organiques persistants (POP) émis par les activités humaines suite à la combustion incomplète de la matière organique (industrie, chauffage, trafic routier...). En raison de leur faible taux de dégradation, de leur toxicité, de leur capacité à être transportés sur de longues distances et de leur bioaccumulation dans la matière organique, les HAP font l'objet d'une surveillance atmosphérique (directive cadre européenne 96/62/CE du 27 septembre 1996). Les bryophytes, plus communément appelées mousses, sont utilisées depuis une trentaine d'années pour la biosurveillance de la qualité de l'air. Leurs caractéristiques biologiques font de ces plantes terrestres d'excellents bioaccumulateurs des dépôts de polluants atmosphériques. Cependant, elles ont été peu utilisées pour la biosurveillance des HAP et pour des échelles spatiales et temporelles très limitées. Dans ce contexte, la thèse a pour objectif de valider l'utilisation de bryophytes comme outils pour la biosurveillance des retombées atmosphériques de HAP à différentes échelles spatio-temporelles. La première phase de ce travail a consisté en un développement analytique afin de valider l'analyse des HAP par chromatographie liquide associée à une détection par fluorescence (CLHP-FLD), l'extraction liquide-liquide des HAP contenus dans les dépôts totaux et l'extraction par liquide pressurisé (PLE) des HAP contenus dans les mousses. Cette dernière a été optimisée, grâce à la réalisation d'un plan d'expériences, et a été complétée par des tests de purification par extraction sur phase solide (SPE). Des études de terrain ont ensuite été réalisées afin d'évaluer les tendances temporelles à l'échelle saisonnière, annuelle et historique, ainsi que les tendances spatiales à l'échelle locale et régionale, des teneurs en HAP dans les mousses. Une étude menée sur des mousses d'herbier prélevées dans le Parc Naturel de Bertiz (Navarre, Espagne) entre 1879 et 2007 a permis d'identifier les sources historiques d'émission des HAP. Les bryophytes apparaissent comme de bons « témoins » de la contamination atmosphérique du passé. Une étude annuelle (2010-2011) de biosurveillance active menée à Bertiz a permis ensuite d'observer des tendances saisonnières des teneurs en HAP dans les mousses Hylocomium splendens (Hedw.) Schimp., liées aux variations des émissions atmosphériques et des conditions météorologiques, en particulier des précipitations. De plus, l'étude annuelle a révélé un fractionnement lors de l'accumulation par les mousses des HAP contenus dans les dépôts totaux, qui résulte d'une affinité des HAP pour les dépôts liée à leur solubilité et d'une affinité des HAP pour le végétal liée à leur propriété lipophile (KOW). Ainsi, le suivi des flux atmosphériques de HAP dans les dépôts totaux ne permet pas de prévoir a priori les teneurs de HAP dans les écosystèmes. Enfin, une analyse multivariée de la distribution spatiale des teneurs en HAP dans l'espèce Hypnum cupressiforme Hedw. prélevée en Espagne (Navarre), France (Île-de-France) et Suisse (Plateau Suisse et région de Bâle) a permis de caractériser les sources de contamination atmosphériques des régions étudiées et l'influence de paramètres environnementaux tels que l'altitude et la pluviométrie. / Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants (POPs) emitted by human activities during incomplete combustion of organic matter (industry, domestic heating, road traffic…). Due to their low degradation rates, toxicity, long-range transport and bioaccumulation in organic matter, PAHs are monitored in the atmosphere (Council Directive 96/62/EC of 27 September 1996). Bryophytes, more commonly called mosses, have been used during the past three decades for biomonitoring air quality. Because of their biological characteristics, these terrestrial plants are excellent bioaccumulators of airborne pollutants. However, few studies concern PAH biomonitoring and they are usually restricted to studies limited in time and space. In this context, the thesis aims to validate bryophytes as tools for biomonitoring atmospheric deposition of PAHs on various space-time scales. The first step of this work consisted in developing the analytical procedures in order to validate PAH analysis by liquid chromatography associated with fluorescence detection (HPLC-FLD), liquid-liquid extraction of PAHs from bulk deposition and pressurized liquid extraction (PLE) of PAHs from mosses. The latter was optimized with a factorial design and was completed by purification tests with solid phase extraction (SPE). Field studies were then carried out to evaluate temporal trends of PAH levels in mosses at seasonal, annual and historical scales, as well as spatial trends, at local and regional scales. A study undertaken on herbarium mosses sampled in Bertiz Natural Park (Navarra, Spain) between 1879 and 2007 leaded to the identification of PAH historical emission sources. Bryophytes appear as excellent “witnesses” of the past atmospheric contamination. An annual biomonitoring study (2010-2011) at Bertiz showed seasonal trends of PAH content in mosses Hylocomium splendens (Hedw.) Schimp., which are related to variations of PAH emissions and weather conditions, particularly precipitations. Moreover, the annual study revealed a fractionation of PAHs while they are transferred from total deposition to the mosses, as the affinity of PAHs for deposition samples was related with their solubility and their affinity for the plant was related to their lipophilic property (KOW). Thus, monitoring PAH fluxes in total deposition does not give an a priori estimation of PAH contents in the ecosystems. Finally, multivariate analysis of the spatial distribution of PAHs in the species Hypnum cupressiforme Hedw. sampled in Spain (Navarra), France (Île-de-France) and Switzerland (Swiss Plateau and Basel area) leaded to the characterization of the atmospheric contamination sources in the different areas and the influence of environmental parameters such as elevation and pluviometry.

No description available.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The goal of this study was to evaluate aspects of nutrients cycling in Eucalyptus dunnii by monitoring a stand throughout a year. This took place in Alegrete town, Rio Grande do Sul state, South Brazil, in an area of Stora Enso S/A, starting when stand was 16.5 months old. It was evaluated monthly rainfall and litterfall. Rainwater inside the stand was collected in 12 throughfall collectors and 12 stemflow collectors. The bulk precipitation was evaluated by two rainwater collectors located outside the stand. Assessing the litterfall, 16 collectors with 0.5 m² area were installed for the evaluation of leaves and miscellaneous (bark, reproductive material and branches - diameter less than or equal to 5 mm) fractions, plus the installation of 16 areas to collect thick branches (diameter greater than 5 mm). Rainwater and litterfall collectors were disposed in 4 blocks. Precipitation and litterfall were assessed for quantity, concentration of nutrients and input of these nutrients. Rainfall was 1586 mm y-1, with 7% interception by the stand. Throughfall accounted for 98% of effective precipitation, and the remaining 2% was stemflow. The concentration of ions in bulk precipitation was low, consistent with the rural areas of non-industrialized regions. Higher inputs occurred after the interaction of bulk precipitation with the forest canopy. It was fell 4.1 Mg ha-1 y-1 litterfall, where leaves corresponded to 93%, 6% of miscellaneous and 1% of thick branches. The higher concentration of macro and micronutrients was in general found in leaves fraction. The nutrient input was higher to litterfall, except for the macronutrient S. / O objetivo deste trabalho foi avaliar aspectos da ciclagem de nutrientes em Eucalyptus dunnii através do monitoramento de um povoamento durante o período de um ano, começando quando as árvores estavam com 16,5 meses de idade, no município de Alegrete, Rio Grande do Sul, em área pertencente à empresa Stora Enso S/A,. Foi avaliada, mensalmente, a deposição atmosférica dentro e fora do plantio, através de coletores de água da precipitação, e a deposição de serapilheira. A precipitação dentro do povoamento foi feita através de 12 coletores de precipitação interna e 12 coletores de solução decorrente do escorrimento pelo tronco. Já a precipitação global foi avaliada por dois coletores de precipitação instalados fora do povoamento e sem interferência do dossel. Para a amostragem da deposição de serapilheira foram instalados 16 coletores de 0,5 m² de área útil para avaliação das frações folhas e miscelânea (casca, material reprodutivo e galhos finos diâmetro menor ou igual a 5 mm), além da instalação de 16 áreas de coleta de galhos grossos (diâmetro maior que 5 mm). Tanto os coletores de precipitação dentro do plantio, quanto a deposição de serapilheira foram avaliadas em quatro parcelas. Precipitação e serapilheira foram avaliadas quanto à quantidade, à concentração de elementos e ao aporte dos mesmos. A precipitação global foi de 1586 mm ano-1, com 7% de interceptação pelo povoamento. A precipitação interna correspondeu a 98% da precipitação efetiva, sendo os 2% restantes relativos ao escorrimento pelo tronco. A concentração de íons, na precipitação global, foi baixa, condizente com áreas rurais de regiões não industrializadas. Ocorreu maior aporte de elementos após a interação da precipitação global com o dossel florestal. Foram depositados 4,1 Mg ha-1 ano-1 de serapilheira, sendo 93% de folhas, 6% de miscelânea e 1% de galhos grossos. A concentração de macro e micronutrientes foi, para a maioria dos elementos, encontrada na fração folhas. A devolução de nutrientes foi maior via deposição de serapilheira, com exceção para o macronutriente S.