δ44/40\delta^{44/40}Ca-δ88/86\delta^{88/86}Sr multi-proxy constrains primary origin of Marinoan cap carbonates

The Neoproterozoic Earth experienced at least two global-scale glaciations termed Snowball Earth events. 'Cap carbonates' were widely deposited after the events, but controversy surrounds their origin. Here, we apply the novel $\delta^{44/40}$Ca-$\delta^{88/86}$Sr multi-proxy to two Marinoan (ca. 635 Ma) cap carbonate sequences from Namibia and show that the rocks archive primary environmental signals deriving from a combination of seawater-glacial meltwater mixing and kinetic isotope effects. In an outer platform section, dolostone $\delta^{44/40}$Ca and $\delta^{88/86}$Sr values define a line predicted for kinetic mass-dependent isotope fractionation. This dolostone mostly precipitated from meltwater. Moreover, stratigraphically higher samples exhibiting the fastest precipitation rates correlate with elevated 87Sr/86Sr ratios, consistent with long-held expectations that a rapid deglacial weathering pulse forced cap carbonate formation. An inner-platform dolostone shows greater effects from water-mass mixing but still reveals that precipitation rates increased up-section. Overlying limestones show the greatest Ca and Sr contributions from seawater. Amplification of local coastal processes during global ice sheet collapse offers a simple but sufficient proposition to explain the Ca isotope heterogeneity of cap carbonates. Detection of kinetic isotope effects in the rock record provides a basis for developing the $\delta^{44/40}$Ca-$\delta^{88/86}$Sr multi-proxy as an indicator of saturation state and $p$CO$_2$

Upper ocean oxygenation dynamics from I/Ca ratios during the Cenomanian-Turonian OAE 2

Author Posting. © American Geophysical Union, 2015. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 30 (2015): 510–526, doi:10.1002/2014PA002741.Global warming lowers the solubility of gases in the ocean and drives an enhanced hydrological cycle with increased nutrient loads delivered to the oceans, leading to increases in organic production, the degradation of which causes a further decrease in dissolved oxygen. In extreme cases in the geological past, this trajectory has led to catastrophic marine oxygen depletion during the so-called oceanic anoxic events (OAEs). How the water column oscillated between generally oxic conditions and local/global anoxia remains a challenging question, exacerbated by a lack of sensitive redox proxies, especially for the suboxic window. To address this problem, we use bulk carbonate I/Ca to reconstruct subtle redox changes in the upper ocean water column at seven sites recording the Cretaceous OAE 2. In general, I/Ca ratios were relatively low preceding and during the OAE interval, indicating deep suboxic or anoxic waters exchanging directly with near-surface waters. However, individual sites display a wide range of initial values and excursions in I/Ca through the OAE interval, reflecting the importance of local controls and suggesting a high spatial variability in redox state. Both I/Ca and an Earth System Model suggest that the northeast proto-Atlantic had notably higher oxygen levels in the upper water column than the rest of the North Atlantic, indicating that anoxia was not global during OAE 2 and that important regional differences in redox conditions existed. A lack of correlation with calcium, lithium, and carbon isotope records suggests that neither enhanced global weathering nor carbon burial was a dominant control on the I/Ca proxy during OAE 2.Z.L. thanks NSF OCE 1232620. J.D.O. is supported by an Agouron Postdoctoral Fellowship. T.W.L. acknowledges support from the NSF-EAR and NASA-NAI. A.R. thanks the support of NERC via NE/J01043X/1.2015-11-1

Redox‐controlled preservation of organic matter during “OAE 3” within the Western Interior Seaway

During the Cretaceous, widespread black shale deposition occurred during a series of Oceanic Anoxic Events (OAEs). Multiple processes are known to control the deposition of marine black shales, including changes in primary productivity, organic matter preservation, and dilution. OAEs offer an opportunity to evaluate the relative roles of these forcing factors. The youngest of these events—the Coniacian to Santonian OAE 3—resulted in a prolonged organic carbon burial event in shallow and restricted marine environments including the Western Interior Seaway. New high‐resolution isotope, organic, and trace metal records from the latest Turonian to early Santonian Niobrara Formation are used to characterize the amount and composition of organic matter preserved, as well as the geochemical conditions under which it accumulated. Redox sensitive metals (Mo, Mn, and Re) indicate a gradual drawdown of oxygen leading into the abrupt onset of organic carbon‐rich (up to 8%) deposition. High Hydrogen Indices (HI) and organic carbon to total nitrogen ratios (C:N) demonstrate that the elemental composition of preserved marine organic matter is distinct under different redox conditions. Local changes in δ13C indicate that redox‐controlled early diagenesis can also significantly alter δ13Corg records. These results demonstrate that the development of anoxia is of primary importance in triggering the prolonged carbon burial in the Niobrara Formation. Sea level reconstructions, δ18O results, and Mo/total organic carbon ratios suggest that stratification and enhanced bottom water restriction caused the drawdown of bottom water oxygen. Increased nutrients from benthic regeneration and/or continental runoff may have sustained primary productivity.Key PointsBottom water redox changes triggered carbon burial within the WIS during OAE 3Anoxia developed due to O2 drawdown in a stratified water columnRedox‐controlled changes in OM preservation altered primary δ13Corg signalsPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/112294/1/palo20210.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/112294/2/palo20210-sup-0001-SupportingInfo.pd

Geochemical data from the USGS #1 Portland core, Canon City, Colorado

During the Cretaceous, widespread black shale deposition occurred during a series of Oceanic Anoxic Events (OAEs). Multiple processes are known to control the deposition of marine black shales, including changes in primary productivity, organic matter preservation, and dilution. OAEs offer an opportunity to evaluate the relative roles of these forcing factors. The youngest of these events-the Coniacian to Santonian OAE 3-resulted in a prolonged organic carbon burial event in shallow and restricted marine environments including the Western Interior Seaway. New high-resolution isotope, organic, and trace metal records from the latest Turonian to early Santonian Niobrara Formation are used to characterize the amount and composition of organic matter preserved, as well as the geochemical conditions under which it accumulated. Redox sensitive metals (Mo, Mn, and Re) indicate a gradual drawdown of oxygen leading into the abrupt onset of organic carbon-rich (up to 8%) deposition. High Hydrogen Indices (HI) and organic carbon to total nitrogen ratios (C:N) demonstrate that the elemental composition of preserved marine organic matter is distinct under different redox conditions. Local changes in d13C indicate that redox-controlled early diagenesis can also significantly alter d13Corg records. These results demonstrate that the development of anoxia is of primary importance in triggering the prolonged carbon burial in the Niobrara Formation. Sea level reconstructions, d18O results, and Mo/total organic carbon ratios suggest that stratification and enhanced bottom water restriction caused the drawdown of bottom water oxygen. Increased nutrients from benthic regeneration and/or continental runoff may have sustained primary productivity