402 research outputs found

    Using Multiple Sources of Knowledge to Investigate Northern Environmental Change: Regional Ecological Impacts of a Storm Surge in the Outer Mackenzie Delta, N.W.T.

    Get PDF
    Field data, remote sensing, and Inuvialuit knowledge were synthesized to document regional ecological change in the outer Mackenzie Delta and to explore the timing, causes, and implications of this phenomenon. In September 1999, a large magnitude storm surge inundated low-lying areas of the outer Mackenzie Delta. The storm was among the most intense on record and resulted in the highest water levels ever measured at the delta front. Synthesis of scientific and Inuvialuit knowledge indicates that flooding during the 1999 storm surge increased soil salinity and caused widespread vegetation death. Vegetation cover was significantly reduced in areas affected by the surge and was inversely related to soil salinity. Change detection analysis, using remotely sensed imagery bracketing the 1999 storm event, indicates severe impacts on at least 13 200 ha of terrestrial vegetation in the outer delta. Inuvialuit knowledge identifying the 1999 surge as anomalous is corroborated by geochemical profiles of permafrost and by a recently published paleo-environmental study, which indicates that storm surge impacts of this magnitude have not previously occurred during the last millennium. Almost a decade after the 1999 storm surge event, ecological recovery has been minimal. This broad-scale vegetation change is likely to have significant implications for wildlife and must be considered in regional ecosystem planning and in the assessment and monitoring of the cumulative impacts of development. Our investigations show that Inuvialuit were aware of the 1999 storm surge and the environmental impacts several years before the scientific and regulatory communities recognized their significance. This study highlights the need for multidisciplinary and locally informed approaches to identifying and understanding Arctic environmental change.La synthĂšse des donnĂ©es d’exploitation et de tĂ©lĂ©dĂ©tection de mĂȘme que des connaissances des Inuvialuit a Ă©tĂ© effectuĂ©e afin de rĂ©pertorier les changements Ă©cologiques enregistrĂ©s dans la rĂ©gion extĂ©rieure du delta du Mackenzie et d’explorer la temporisation, les causes et les incidences de ce phĂ©nomĂšne. En septembre 1999, une onde de tempĂȘte de grande magnitude a inondĂ© les zones de faible Ă©lĂ©vation de l’extĂ©rieur du delta du Mackenzie. Il s’agit de la tempĂȘte la plus intense Ă  n’avoir jamais Ă©tĂ© enregistrĂ©e, ce qui s’est traduit par les niveaux d’eau les plus Ă©levĂ©s Ă  n’avoir jamais Ă©tĂ© mesurĂ©s Ă  la hauteur du delta. La synthĂšse des donnĂ©es scientifiques et des connaissances des Inuvialuit nous montre que l’inondation de 1999 a eu pour effet d’augmenter la salinitĂ© du sol et a entraĂźnĂ© la mort de la vĂ©gĂ©tation Ă  grande Ă©chelle. La couverture vĂ©gĂ©tale a Ă©tĂ© rĂ©duite considĂ©rablement dans les zones visĂ©es par l’onde et Ă©tait inversement reliĂ©e Ă  la salinitĂ© du sol. L’analyse des dĂ©tections de changement effectuĂ©e au moyen de l’imagerie tĂ©lĂ©dĂ©tectĂ©e dans le cas de la tempĂȘte de 1999 laisse entrevoir de fortes incidences sur au moins 13 200 hectares de vĂ©gĂ©tation terrestre dans l’extĂ©rieur du delta. Les connaissances des Inuvialuit, qui affirment que l’onde de 1999 Ă©tait anormale, sont corroborĂ©es par les profils gĂ©ochimiques du pergĂ©lisol ainsi que par une Ă©tude palĂ©oenvironnementale qui indique que des incidences de cette ampleur dĂ©coulant d’une onde de tempĂȘte ne se sont pas produites Ă  un autre moment donnĂ© du dernier millĂ©naire. PrĂšs d’une dĂ©cennie aprĂšs l’onde de tempĂȘte de 1999, le rĂ©tablissement Ă©cologique Ă©tait minime. Ce changement de vĂ©gĂ©tation Ă  grande Ă©chelle aura vraisemblablement d’importantes incidences sur la faune et doit entrer en considĂ©ration dans la planification de l’écosystĂšme rĂ©gional ainsi que dans l’évaluation et la surveillance des incidences cumulatives des travaux d’amĂ©nagement et de mise en valeur. Nos enquĂȘtes nous ont permis de constater que les Inuvialuit Ă©taient conscients des incidences environnementales de l’onde de tempĂȘte de 1999 plusieurs annĂ©es avant que les scientifiques et le personnel s’occupant de la rĂ©glementation ne reconnaissent leur importance. Cette Ă©tude fait ressortir la nĂ©cessitĂ© d’avoir des mĂ©thodes multidisciplinaires et de faire appel aux gens de la rĂ©gion pour dĂ©terminer et comprendre les changements environnementaux dans l’Arctique

    Sulfur K-Edge XAS Studies of the Effect of DNA Binding on the [Fe_4S_4] Site in EndoIII and MutY

    Get PDF
    S K-edge X-ray absorption spectroscopy (XAS) was used to study the [Fe_4S_4] clusters in the DNA repair glycosylases EndoIII and MutY to evaluate the effects of DNA binding and solvation on Fe–S bond covalencies (i.e., the amount of S 3p character mixed into the Fe 3d valence orbitals). Increased covalencies in both iron–thiolate and iron–sulfide bonds would stabilize the oxidized state of the [Fe_4S_4] clusters. The results are compared to those on previously studied [Fe_4S_4] model complexes, ferredoxin (Fd), and to new data on high-potential iron–sulfur protein (HiPIP). A limited decrease in covalency is observed upon removal of solvent water from EndoIII and MutY, opposite to the significant increase observed for Fd, where the [Fe_4S_4] cluster is solvent exposed. Importantly, in EndoIII and MutY, a large increase in covalency is observed upon DNA binding, which is due to the effect of its negative charge on the iron–sulfur bonds. In EndoIII, this change in covalency can be quantified and makes a significant contribution to the observed decrease in reduction potential found experimentally in DNA repair proteins, enabling their HiPIP-like redox behavior

    Biotransformation of polychlorinated biphenyls (PCBs) and bioformation of hydroxylated PCBs in fish

    Get PDF
    Abstract Hydroxylated PCBs (OH-PCBs) are a class of organic contaminants that have been found recently in the plasma of Great Lakes fish, the source of which is either bioformation from PCBs or accumulation from the environment. To address the potential for fish to biotransform PCBs and bioform OH-PCBs juvenile rainbow trout (Oncorhynchus mykiss; ∌80 g) were exposed to dietary concentrations of an environmentally relevant mixture of PCBs. Eight OH-PCBs were found in the plasma of rainbow trout after 30 days of exposure to the PCBs, the relative pattern of which was similar to those observed in wild lake trout (Salvelinus namaycush) from Lake Ontario. Hydroxylated-PCBs were not found (detection limit 0.02 pg/g) in the food or control (not PCB-exposed) fish. A curvilinear log t 1/2 -log K ow relationship for recalcitrant PCBs was found, similar to previously reported relationships, although t 1/2 values were longer and shorter than studies using smaller fish or cooler temperatures, respectively. A number of PCB congeners fell below the log t 1/2 -log K ow relationship providing the first estimates of non-chiral PCB biotransformation rates in fish. Enantioselective degradation of the chiral congeners PCBs 91 and 136, also indicated biotransformation. Biotransformation of PCBs was structure-dependent with greater biotransformation of PCBs with vicinal hydrogen atoms in the meta/para positions, suggesting CYP 2B-like biotransformation. Other chiral congeners with a meta/para substitution pattern showed no enantioselective degradation but were biotransformed based on the log t 1/2 -log K ow relationship. The results of this study demonstrate that laboratory held rainbow trout can biotransform a number of PCB congeners and that bioformation is likely an important source of OH-PCBs in wild salmonids of the Great Lakes

    Mechanism of selective benzene hydroxylation catalyzed by iron-containing zeolites

    Get PDF
    A direct, catalytic conversion of benzene to phenol would have wide-reaching economic impacts. Fe zeolites exhibit a remarkable combination of high activity and selectivity in this conversion, leading to their past implementation at the pilot plant level. There were, however, issues related to catalyst deactivation for this process. Mechanistic insight could resolve these issues, and also provide a blueprint for achieving high performance in selective oxidation catalysis. Recently, we demonstrated that the active site of selective hydrocarbon oxidation in Fe zeolites, named α-O, is an unusually reactive Fe(IV)=O species. Here, we apply advanced spectroscopic techniques to determine that the reaction of this Fe(IV)=O intermediate with benzene in fact regenerates the reduced Fe(II) active site, enabling catalytic turnover. At the same time, a small fraction of Fe(III)-phenolate poisoned active sites form, defining a mechanism for catalyst deactivation. Density-functional theory calculations provide further insight into the experimentally defined mechanism. The extreme reactivity of α-O significantly tunes down (eliminates) the rate-limiting barrier for aromatic hydroxylation, leading to a diffusion-limited reaction coordinate. This favors hydroxylation of the rapidly diffusing benzene substrate over the slowly diffusing (but more reactive) oxygenated product, thereby enhancing selectivity. This defines a mechanism to simultaneously attain high activity (conversion) and selectivity, enabling the efficient oxidative upgrading of inert hydrocarbon substrates
    • 

    corecore