Organic carbon burial under greenhouse climate conditions: The regional expression of the Late Cretaceous Oceanic Anoxic Event 3 within the Western Interior Seaway.

The Cretaceous period (145−66 million years ago) was characterized by elevated atmospheric pCO2 and an equable, warm climate. High Cretaceous sea levels flooded continental areas producing extensive shallow seaways, including the Western Interior Seaway (WIS) in North America. The resulting sedimentary record of the WIS includes episodic deposition of organic carbon-rich black shales, during a series of Oceanic Anoxic Events (OAEs). Multiple processes control marine black shale deposition, including changes in primary productivity, organic matter preservation, and sedimentary dilution. OAEs offer an opportunity to evaluate the relative roles of these forcing factors on marine carbon burial. This dissertation centers on understanding the causes of enhanced organic carbon burial within the WIS during a particularly poorly studied OAE, the Coniacian-Santonian OAE 3 (~88−84 Ma). In Chapter 2, I use trace metal records from the USGS Portland core (drilled near Cañon City, Colorado) to reconstruct the degree of oxygenation before, during, and after OAE 3. These data are compared to bulk elemental and isotopic records of organic matter composition to demonstrate that oxygen depletion in pore and bottom waters provided a feedback to carbon burial, by triggering enhanced organic matter preservation within the WIS during OAE 3. In Chapter 3, I examine changes in organic carbon preservation in greater detail using biomarker and compound specific carbon isotope records. My results document distinct organic matter sources before, during, and after the OAE associated with varying degrees of bioturbation and therefore, oxygen exposure time. In Chapter 4, I explore the feedbacks associated with changing iron chemistry in the WIS. Sequential iron extractions, phosphorus, and sulfur results indicate that low reactive iron availability promoted phosphorus remineralization from sediments, illustrating the importance of internal nutrient recycling during and after OAE 3. In Chapter 5, trends and timing of organic carbon accumulation are examined on a larger spatial scale. Trace metal and foraminiferal records from western Alberta are compared to time equivalent records from the central seaway. The reconstructed seaway-wide patterns indicate that anoxic conditions and the resulting sedimentary elevated organic carbon accumulation closely follow the sea-level transgression and expanding influence of nutrient-rich Tethyan (equatorially-sourced) water.PhDGeologyUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/133431/1/atessin_1.pd

Lake Sediment Geochemical Changes in Response to Land Use Variations in the Catchments of Lakes Volvi and Koronia, Northern Greece

Lakes Koronia and Volvi, located within the Mygdonia Basin in northern Greece, comprise an internationally protected wetland. The lakes support major industrial and agricultural activities, and a population of 45,000. Consequently, both sites have been greatly impacted by the conversion of marshland to farmland, water losses to irrigation, and pollution discharges including raw sewage, agricultural run-off, and industrial wastes. Sediment chronology and accumulation rates have been determined in cores from multiple sites within the lakes using 210Pb dating techniques. Bulk sediment elemental composition (organic carbon content, C/N ratios, etc.) and trace metal concentrations have been measured to provide critical evidence for variations in land-use within watersheds. Stratigraphic variations in the carbon and nitrogen isotopic ratio of sedimented organic matter have been measured to determine changes in aquatic ecosystem productivity. The geochemical results will be compared to historical records to determine the relative importance of disturbances caused by urban, agricultural, and industrial activities

A changing Arctic Ocean

The Arctic is the fastest changing region on the planet. It is also intrinsically tied to global processes, whether they are climatic, environmental or socio-economic. The impacts of climate change on the vast and multiple interacting Arctic systems are inherently complex, although can be broadly summarised as an increase in temperature and the subsequent loss of sea-ice cover. This will ultimately result in the emergence of new physical and ecological statesNon peer reviewe

Benthic silicon cycling in the Arctic Barents Sea: a reaction–transport model study

Over recent decades the highest rates of water column warming and sea ice loss across the Arctic Ocean have been observed in the Barents Sea. These physical changes have resulted in rapid ecosystem adjustments, manifesting as a northward migration of temperate phytoplankton species at the expense of silica-based diatoms. These changes will potentially alter the composition of phytodetritus deposited at the seafloor, which acts as a biogeochemical reactor and is pivotal in the recycling of key nutrients, such as silicon (Si). To appreciate the sensitivity of the Barents Sea benthic system to the observed changes in surface primary production, there is a need to better understand this benthic–pelagic coupling. Stable Si isotopic compositions of sediment pore waters and the solid phase from three stations in the Barents Sea reveal a coupling of the iron (Fe) and Si cycles, the contemporaneous dissolution of lithogenic silicate minerals (LSi) alongside biogenic silica (BSi), and the potential for the reprecipitation of dissolved silicic acid (DSi) as authigenic clay minerals (AuSi). However, as reaction rates cannot be quantified from observational data alone, a mechanistic understanding of which factors control these processes is missing. Here, we employ reaction–transport modelling together with observational data to disentangle the reaction pathways controlling the cycling of Si within the seafloor. Processes such as the dissolution of BSi are active on multiple timescales, ranging from weeks to hundreds of years, which we are able to examine through steady state and transient model runs. Steady state simulations show that 60 % to 98 % of the sediment pore water DSi pool may be sourced from the dissolution of LSi, while the isotopic composition is also strongly influenced by the desorption of Si from metal oxides, most likely Fe (oxyhydr)oxides (FeSi), as they reductively dissolve. Further, our model simulations indicate that between 2.9 % and 37 % of the DSi released into sediment pore waters is subsequently removed by a process that has a fractionation factor of approximately −2 ‰, most likely representing reprecipitation as AuSi. These observations are significant as the dissolution of LSi represents a source of new Si to the ocean DSi pool and precipitation of AuSi an additional sink, which could address imbalances in the current regional ocean Si budget. Lastly, transient modelling suggests that at least one-third of the total annual benthic DSi flux could be sourced from the dissolution of more reactive, diatom-derived BSi deposited after the surface water bloom at the marginal ice zone. This benthic–pelagic coupling will be subject to change with the continued northward migration of Atlantic phytoplankton species, the northward retreat of the marginal ice zone and the observed decline in the DSi inventory of the subpolar North Atlantic Ocean over the last 3 decades

Bioactive Trace Metals and Their Isotopes as Paleoproductivity Proxies: An Assessment Using GEOTRACES-Era Data

86 pages, 33 figures, 2 tables, 1 appendix.-- Data Availability Statement: The majority of the dissolved data were sourced from the GEOTRACES Intermediate Data Products in 2014 (Mawji et al., 2015) and 2017 (Schlitzer et al., 2018), and citations to the primary data sources are given in the caption for each figure. Data sources for Figure 1 are given below. Figure 1: Iron: Conway & John, 2014a (Atlantic); Conway & John, 2015a (Pacific); Abadie et al., 2017 (Southern). Zinc: Conway & John, 2014b (Atlantic); Conway & John, 2015a (Pacific); R. M. Wang et al., 2019 (Southern). Copper: Little et al., 2018 (Atlantic); Takano et al., 2017 (Pacific); Boye et al., 2012 (Southern). Cadmium: Conway and John, 2015b (Atlantic); Conway & John, 2015a (Pacific); Abouchami et al., 2014 (Southern). Molybdenum: Nakagawa et al., 2012 (all basins). Barium: Bates et al., 2017 (Atlantic); Geyman et al., 2019 (Pacific); Hsieh & Henderson, 2017 (Southern). Nickel: Archer et al., 2020 (Atlantic); Takano et al., 2017 (Pacific); R. M. Wang et al., 2019 (Southern). Chromium: Goring-Harford et al., 2018 (Atlantic); Moos & Boyle, 2019 (Pacific); Rickli et al., 2019 (Southern). Silver: Fischer et al., 2018 (Pacific); Boye et al., 2012 (Southern)Phytoplankton productivity and export sequester climatically significant quantities of atmospheric carbon dioxide as particulate organic carbon through a suite of processes termed the biological pump. Constraining how the biological pump operated in the past is important for understanding past atmospheric carbon dioxide concentrations and Earth's climate history. However, reconstructing the history of the biological pump requires proxies. Due to their intimate association with biological processes, several bioactive trace metals and their isotopes are potential proxies for past phytoplankton productivity, including iron, zinc, copper, cadmium, molybdenum, barium, nickel, chromium, and silver. Here, we review the oceanic distributions, driving processes, and depositional archives for these nine metals and their isotopes based on GEOTRACES-era datasets. We offer an assessment of the overall maturity of each isotope system to serve as a proxy for diagnosing aspects of past ocean productivity and identify priorities for future research. This assessment reveals that cadmium, barium, nickel, and chromium isotopes offer the most promise as tracers of paleoproductivity, whereas iron, zinc, copper, and molybdenum do not. Too little is known about silver to make a confident determination. Intriguingly, the trace metals that are least sensitive to productivity may be used to track other aspects of ocean chemistry, such as nutrient sources, particle scavenging, organic complexation, and ocean redox state. These complementary sensitivities suggest new opportunities for combining perspectives from multiple proxies that will ultimately enable painting a more complete picture of marine paleoproductivity, biogeochemical cycles, and Earth's climate historyThis contribution grew (and grew) out of a joint workshop between GEOTRACES and Past Global Changes (PAGES) held in Aix-en-Provence in December 2018. The workshop was funded by the U.S. National Science Foundation (NSF) through the GEOTRACES program, the international PAGES project, which received support from the Swiss Academy of Sciences and NSF, and the French program Les Envelopes Fluides et l'Environnement. [...] T. J. Horner acknowledges support from NSF; S. H. Little from the UK Natural Environment Research Council (NE/P018181/1); T. M. Conway from the University of South Florida; and, J. R. Farmer from the Max Planck Society, the Tuttle Fund of the Department of Geosciences of Princeton University, the Grand Challenges Program of the Princeton Environmental Institute, and the Andlinger Center for Energy and the Environment of Princeton University. [...] With the institutional support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S

Arctic Continental Margin Sediments as Possible Fe and Mn Sources to Seawater as Sea Ice Retreats: Insights From the Eurasian Margin

Continental margins are hot spots for iron (Fe) and manganese (Mn) cycling. In the Arctic Ocean, these depositional systems are experiencing rapid changes that could significantly impact biogeochemical cycling. In this study, we investigate whether continental margin sediments north of Svalbard represent a source or sink of Fe and Mn to the water column and how climate change might alter these biogeochemical cycles. Our results highlight that sediments on the Yermak Plateau and Sofia Basin exhibit accumulations of Fe and Mn phases compared to average shale. Conversely, sediments from the Barents Sea slope exhibit lower enrichments of Fe and Mn compared to average shale, with the exception of enriched, near‐surface sediment layers. Pore waters from these slope sites provide evidence for Fe and Mn reduction and diffusion of Fe and Mn into near surface sediments, which are susceptible to physical or biogeochemical remobilization. These regional patterns are best explained by the spatial distribution of sea ice coverage and labile organic carbon fluxes to the seafloor. As sea ice continues to retreat and the Yermak Plateau becomes seasonally ice‐free, productivity is expected to increase, which would increase the flux of carbon to the sediments, thereby increasing oxidant demand, and the reduction of Fe and Mn mineral phases. Our results suggest that as sea ice continues to retreat, the Yermak Plateau and other Arctic continental margins could become sources of Fe and Mn to Arctic bottom waters

Stable silicon isotopes uncover a mineralogical control on the benthic silicon cycle in the Arctic Barents Sea

Biogeochemical cycling of silicon (Si) in the Barents Sea is under considerable pressure from physical and chemical changes, including dramatic warming and sea ice retreat, together with a decline in dissolved silicic acid (DSi) concentrations of Atlantic inflow waters since 1990. Associated changes in the community composition of phytoplankton blooms will alter the material comprising the depositional flux, which will subsequently influence recycling processes at and within the seafloor. In this study we assess the predominant controls on the early diagenetic cycling of Si, a key nutrient in marine ecosystems, by combining stable isotopic analysis (Si) of pore water DSi and of operationally defined reactive pools of the solid phase. We show that low biogenic silica (BSi) contents (0.26–0.52 wt% or 92–185 mol g dry wt−1) drive correspondingly low asymptotic concentrations of pore water DSi of 100 M, relative to biosiliceous sediments (20 wt% BSi) wherein DSi can reach 900 M. While Barents Sea surface sediments appear almost devoid of BSi, we present evidence for the rapid recycling of bloom derived BSi that generates striking transient peaks in sediment pore water [DSi] of up to 300 M, which is a feature that is subject to future shifts in phytoplankton community compositions. Using a simple isotopic mass balance calculation we show that at two of three stations the pore water DSi pool at 0.5 cm below the seafloor (+0.96 to +1.36 ‰) is sourced from the mixing of core top waters (+1.46 to +1.69 ‰) with the dissolution of BSi (+0.82 to +1.50 ‰), supplemented with a lithogenic Si source (LSi) (−0.89 0.16‰). Further, our sediment pore water Si profiles uncover a coupling of the Si cycle with the redox cycling of metal oxides associated with isotopically light Si (−2.88 0.17‰). We suggest that a high LSi:BSi ratio and apparent metal oxide influence could lead to a degree of stability in the annual background benthic flux of DSi, despite current pressures on pelagic phytoplankton communities. Coupled with supporting isotopic evidence for the precipitation of authigenic clays in Barents Sea sediment cores, our observations have implications for the regional Si budget

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

Global Ocean Sediment Composition and Burial Flux in the Deep Sea

Quantitative knowledge about the burial of sedimentary components at the seafloor has wide-ranging implications in ocean science, from global climate to continental weathering. The use of 230Th-normalized fluxes reduces uncertainties that many prior studies faced by accounting for the effects of sediment redistribution by bottom currents and minimizing the impact of age model uncertainty. Here we employ a recently compiled global data set of 230Th-normalized fluxes with an updated database of seafloor surface sediment composition to derive atlases of the deep-sea burial flux of calcium carbonate, biogenic opal, total organic carbon (TOC), nonbiogenic material, iron, mercury, and excess barium (Baxs). The spatial patterns of major component burial are mainly consistent with prior work, but the new quantitative estimates allow evaluations of deep-sea budgets. Our integrated deep-sea burial fluxes are 136 Tg C/yr CaCO3, 153 Tg Si/yr opal, 20Tg C/yr TOC, 220 Mg Hg/yr, and 2.6 Tg Baxs/yr. This opal flux is roughly a factor of 2 increase over previous estimates, with important implications for the global Si cycle. Sedimentary Fe fluxes reflect a mixture of sources including lithogenic material, hydrothermal inputs and authigenic phases. The fluxes of some commonly used paleo-productivity proxies (TOC, biogenic opal, and Baxs) are not well-correlated geographically with satellite-based productivity estimates. Our new compilation of sedimentary fluxes provides detailed regional and global information, which will help refine the understanding of sediment preservation