Molybdenum isotope fractionation and speciation in a euxinic lake-Testing ways to discern isotope fractionation processes in a sulfidic setting

The molybdenum (Mo) isotope composition in euxinic shales has been used as a proxy for the global distribution of anoxic conditions in ancient oceans, and since more recently also as a proxy for sulfide concentrations in depositional environments. However, there is currently no way to distinguish isotope fractionation at low bottom water sulfide concentrations in 'local' basins from 'global' secular isotope variations associated with changing seawater composition. This uncertainty is challenging the use of Mo isotopes for paleoceanographic reconstructions. To explore this further, we present new data from sediments deposited over the past similar to 9800 years in one of the best studied euxinic localities in the world: Lake Cadagno in Switzerland. The sample set allows us to test ways to discern isotope fractionation processes at play in a highly restricted euxinic basin. Most of our drill core samples (n = 18) show high delta Mo-98 values similar to previously studied shallow sediments, indicative of quantitative Mo removal from the water column (Dahl et al. 2010a). However, a few samples (n = 3) deposited between about 1200 and 3400 years ago carry low delta Mo-98 values and have been isotopically fractionated in the lake. Sedimentological and geochemical characterizations show that these delta(98)Mofractionated sediments formed during times of frequent injection of O-2-and sediment-rich river water into the deep sulfidic water column. A positive correlation between delta Mo-98 and sedimentary Mo contents suggests that isotope fractionation occurred during times of non-quantitative Mo removal, although Mn-oxide cycling at the chemocline might also contribute a subordinate proportion of (Mo-98-depleted) molybdenum into the sulfidic zone. Sedimentary Mo/U enrichments relative to oxic lake water further supports the hypothesis that a particulate Mo shuttle was most efficient during times of quantitative Mo removal. Therefore, periods with inefficient Mo capture are ascribed to incomplete conversion of molybdate to particle reactive Mo species when bottom water H2S levels were low or less stable than today. Using XAFS spectroscopy, we found that the two distinct Mo compounds predominating in the sediments (Mo-IV-S and Mo-VI-OS) are not diagnostic for isotope fractionation that has occurred in Lake Cadagno. Instead, we infer that delta Mo-98-fractionated products (forming via a low-sulfide Mo pathway) can be subsequently altered with little or no isotopic imprint during remobilization and re-precipitation (e.g., at higher sulfide levels in the sediments) as well as during post-depositional oxidation. Future work could investigate local delta Mo-98-fractionation processes expressed in other euxinic settings and explore other sedimentary metrics to constrain the steps involved in the euxinic burial pathway(s). One tantalizing prospect of this is to distinguish between local bottomwater sulfide levels and variations in the fraction of global seafloor anoxia from the Mo isotope composition in. ancient euxinic mudrocks.