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Browsing by Subject "Isotope geochemistry"
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Item Multiple sulfur isotopes fractionations associated with abiotic sulfur transformations in Yellowstone National Park geothermal springs(Springer Nature, 2014-05-28) Kamyshny, Alexey, Jr.; Druschel, Gregory; Mansaray, Zahra F.; Farquhar, James; Earth and Environmental Sciences, School of ScienceBackground: The paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling. Results: Water samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (<6 μmol L(-1)) in the pools with low pH due to fast disproportionation of thiosulfate. In the pools with higher pH, the concentration of thiosulfate varies, depending on different geochemical pathways of thiosulfate formation. The δ(34)S values of sulfate in four systems were close to those calculated using a mixing line of the model based on dilution and boiling of a deep hot parent water body. In two pools δ(34)S values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pH < 4. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur-polysulfide - hydrogen sulfide system. Triple sulfur isotope ((32)S, (33)S, (34)S) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in ∆(33)S among species and between pools are observed. Conclusions: The variation of sulfate isotopic composition, the origin of differences in isotopic composition of sulfide and zero-valent sulfur, as well as differences in ∆(33)S of sulfide and sulfate are likely due to a complex network of abiotic redox reactions, including disproportionation pathways.Item Ocean-atmosphere forcing of centennial hydroclimate variability in the Pacific Northwest(AGU, 2014-03-11) Steinman, Byron A.; Abbott, Mark B.; Mann, Michael E.; Ortiz, Joseph D.; Feng, Song; Pompeani, David P.; Stansell, Nathan D.; Anderson, Lesleigh; Finney, Bruce P.; Bird, Broxton W.; Earth Sciences, School of ScienceReconstructing centennial timescale hydroclimate variability during the late Holocene is critically important for understanding large-scale patterns of drought and their relationship with climate dynamics. We present sediment oxygen isotope records spanning the last two millennia from 10 lakes, as well as climate model simulations, indicating that the Little Ice Age was dry relative to the Medieval Climate Anomaly in much of the Pacific Northwest of North America. This pattern is consistent with observed associations between the El Niño–Southern Oscillation (ENSO), the Northern Annular Mode, and drought as well as with proxy-based reconstructions of Pacific and Atlantic ocean-atmosphere variations over the past 1000 years. The large amplitude of centennial variability indicated by the lake data suggests that regional hydroclimate is characterized by longer-term shifts in ENSO-like dynamics and that an improved understanding of the centennial timescale relationship between external forcing and drought is necessary for projecting future hydroclimatic conditions in western North America.