Exploring the Effects of Residence Time on the Utility of Stable Isotopes and S/C Ratios as Proxies for Ocean Connectivity.

Various geochemical proxies have been developed to determine if ancient sedimentary strata were deposited in marine or nonmarine environments. A critical parameter for proxy reliability is the residence time of aqueous species in seawater, which is rarely considered for proxies relying on stable isotopes and elemental abundance ratios. Differences in residence time may affect our ability to track geologically short-lived alternations between marine and nonmarine conditions. To test this effect for sulfur and nitrogen isotopes and sulfur/carbon ratios, we investigated a stratigraphic section in the Miocene Oberpullendorf Basin in Austria. Here, previous work revealed typical seawater-like rare earth element and yttrium (REY) systematics transitioning to nonmarine-like systematics. This shift was interpreted as a brief transition from an open marine depositional setting to a restricted embayment with a reduced level of exchange with the open ocean and possibly freshwater influence. Our isotopic results show no discernible response in carbonate-associated sulfate sulfur isotopes and carbon/sulfur abundance ratios during the interval of marine restriction inferred from the REY data, but nitrogen isotopes show a decrease by several permil. This observation is consistent with the much longer residence time of sulfate in seawater compared with REY and nitrate. Hence, this case study illustrates that the residence time is a key factor for the utility of seawater proxies. In some cases, it may make geochemical parameters more sensitive to marine water influx than paleontological observations, as in the Oberpullendorf Basin. Particular care is warranted in deep time, when marine residence times likely differ markedly from the modern.

Contrasting nutrient availability between marine and brackish waters in the late Mesoproterozoic: Evidence from the Paranoá Group, Brazil.

Understanding the delayed rise of eukaryotic life on Earth is one of the most fundamental questions about biological evolution. Numerous studies have presented evidence for oxygen and nutrient limitations in seawater during the Mesoproterozoic era, indicating that open marine settings may not have been able to sustain a eukaryotic biosphere with complex, multicellular organisms. However, many of these data sets represent restricted marine basins, which may bias our view of habitability. Furthermore, it remains untested whether rivers could have supplied significant nutrient fluxes to coastal habitats. To better characterize the sources of the major nutrients nitrogen and phosphorus, we turned to the late Mesoproterozoic Paranoá Group in Brazil (~1.1 Ga), which was deposited on a passive margin of the São Francisco craton. We present carbon, nitrogen and sulphur isotope data from an open shelf setting (Fazenda Funil) and from a brackish-water environment with significant riverine input (São Gabriel). Our results show that waters were well-oxygenated and nitrate was bioavailable in the open ocean setting at Fazenda Funil; the redoxcline appears to have been deeper and further offshore compared to restricted marine basins elsewhere in the Mesoproterozoic. In contrast, the brackish site at São Gabriel received only limited input of marine nitrate and sulphate. Nevertheless, previous reports of acritarchs reveal that this brackish-water setting was habitable to eukaryotic life. Paired with previously published cadmium isotope data, which can be used as a proxy for phosphorus cycling, our results suggest that complex organisms were perhaps not strictly dependent on marine nutrient supplies. Riverine influxes of P and possibly other nutrients likely rendered coastal waters perhaps equally habitable to the Mesoproterozoic open ocean. This conclusion supports the notion that eukaryotic organisms may have thrived in brackish or perhaps even freshwater environments.

Highly Siderophile Elements and Coupled Fe-Os Isotope Signatures in the Temagami Iron Formation, Canada: Possible Signatures of Neoarchean Seawater Chemistry and Earth's Oxygenation History.

Banded iron formations (BIFs) were deposited before and concurrent with the Great Oxidation Event at ∼2.33 Ga. They provide useful archives that document the transformation of the Precambrian hydrosphere from anoxic to progressively oxygenated conditions. Their formation involves removal of oceanic Fe by either inorganic or biologically promoted Fe2+ oxidation, or both. To evaluate depositional settings, elemental sources that affect seawater chemistry, and oxidation pathways, we present the first combined highly siderophile element (HSE) and Fe-Os isotope study for the ∼2.7 Ga Temagami BIF, Abitibi Greenstone Belt, Ontario (Canada). HSE abundances and 187Os/188Os ratios show no systematic variation between alternating magnetite and (meta)chert bands of the Temagami BIF. Whereas HSE concentrations mostly resemble modern crustal values, present-day 187Os/188Os ratios range from ∼0.17 to ∼10.8. Magnetite samples define a regression line corresponding to an age of 2661 ± 126 Ma. A chondrite-like 187Os/188Os initial value is in agreement with earlier studies on Neoarchean marine sediments and is thought to reflect seawater composition, which, unlike modern oceans, is dominated by mantle-like 187Os inventory most likely derived from deep-sea hydrothermal vents. Our δ56Fe data vary from about +0.6‰ to +0.9‰ and define a sawtooth-like pattern between alternating magnetite and (meta)chert layers. Partial oxidation of hydrothermally sourced Fe(II) and a lack of microbially mediated dissimilatory iron reduction provide the most plausible explanation for the positive δ56Fe values. Notably, our δ56Fe data for Temagami are in accord with trends defined by literature results for other Algoma-type BIFs that were deposited throughout the Archean.