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- Valerie McKenzie
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112 for each sample matrix s, n=5)
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116 A 0 EF - Grass-covered EF - Weeded EF - Composite top-soil EF - Reference EF (Cu/Fe) Cu - Grass-covered 65 Cu - Weeded 65 Cu - Composite top-soil 65 Cu - Reference Depth [cm] Cu B EF - Grass-covered EF - Weeded EF - Composite top-soil EF - Reference EF (Cu/Fe) Cu - Grass-covered 65 Cu - Weeded 65 Cu - Composite top-soil 65 Cu - Reference Depth [cm] Cu
117 ~ thatin the deepest soil horizon at site 1 ( This difference of ± ± ± ±±
118 ± ±
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122 Runoff SPM Dissolved Composite top-soil Site 1 Site 2 Bulk Silt Clay Fine clay Solution Bulk Silt Clay Fine clay Solution Bulk Silt Clay Fine clay Solution 65 Cu Fungicides Fe/Cu
123 5 Cu/Ca Al/Ca Al/Ca Silt Clay Fine clay 4 I mean [mm/h] y= x r 2 = Cu/Ca
124 18 Dissolved Cu Cu applied Cu applied [kg] May 18 May 25 May 1 Jun 8 Jun 15 Jun Time 22 Jun 29 Jun 6 Jul 13 Jul 20 Jul Dissolved Cu load [g]
125 Cu load SPM conc. SPM concentration [g/l] I max [mm/6min] SPM-bound Cu load [g] y= x r 2 =0.50
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154 Sorbed Cu Cu(I) log 1/Cu [log 1/(mg kg -1 )]
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248 Izabella BABCSÁNYI Le transport et le fractionnement isotopique du cuivre dans un agrosystème Résumé Depuis la fin du 19 ème siècle, le traitement des vignes par des fongicides cupriques a engendré une augmentation de la teneur en cuivre (Cu) dans les sols viticoles, ainsi que dans les écosystèmes aquatiques en aval. Cette thèse vise à mieux comprendre le devenir de ce Cu dans un agrosystème basé 65 Cu/ 63 Cu. Les résultats montrent que durant 4 à 5 décennies de culture de vignes, les sols en surface se sont enrichis en Cu de 9 à 28 fois par rapport au fond géochimique et que les minéraux argileux jouent un accumulation du Cu. Lors des événements pluvieux, ~1% du Cu appliqué est mobilisé, essentiellement lié à des argiles. en moyenne 68% du Cu dissous et plus de 92% du Cu particulaire. Les ratios isotopiques du Cu dans le bassin indiqueraient la sorption du Cu dissous dans les sédiments, ainsi que la réduction du Cu(II) in situ due à des processus biogéochimiques. Mots-clés: fongicides cupriques, biogéochimie, isotopes stables, vignes, sol, bassin versant, zone humide Résumé en anglais Since the end of the 19th century, the use of copper (Cu)-based fungicides has resulted in increased Cu concentrations in vineyard soils, but also in downstream aquatic ecosystems. The aim of the thesis was to better understand the fate of this Cu in an agrosystem based on assessing Cu isotope fractionation ( 65 Cu/ 63 Cu). The results have shown that the surface vineyard soils have become enriched in Cu from 9 to 28 times compared to the background level during 4 to 5 decades of vine-growing and that clay minerals were the major Cu sorbing phases in the soils. During rainfall, runoff mobilized ~1% of the applied Cu during the, mainly associated with clays. The stormwater wetland collecting the runoff retained in average 68% of the dissolved and more than 92% of particulate Cu. Cu isotope ratios measured in the wetland suggested dissolved Cu sorption to the sediments and in situ reduction of Cu(II) due to biogeochemical processes. Keywords: copper fungicides, biogeochemistry, stable isotopes, vineyard, soil, catchment, wetland
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