Biogeochemical effects of volcanic degassing on the oxygen-state of the oceans during the Cenomanian/Turonian Anoxic Event 2

ABSTRACT FINAL ID: PP11A-1769 Cretaceous anoxic events may have been triggered by massive volcanic CO2 degassing as large igneous provinces (LIPs) were emplaced on the seafloor. Here, we present a comprehensive modeling study to decipher the marine biogeochemical consequences of enhanced volcanic CO2 emissions. A biogeochemical box model has been developed for transient model runs with time-dependent volcanic CO2 forcing. The box model considers continental weathering processes, marine export production, degradation processes in the water column, the rain of particles to the seafloor, benthic fluxes of dissolved species across the seabed, and burial of particulates in marine sediments. The ocean is represented by twenty-seven boxes. To estimate horizontal and vertical fluxes between boxes, a coupled ocean–atmosphere general circulation model (AOGCM) is run to derive the circulation patterns of the global ocean under Late Cretaceous boundary conditions. The AOGCM modeling predicts a strong thermohaline circulation and intense ventilation in the Late Cretaceous oceans under high pCO2 values. With an appropriate choice of parameter values such as the continental input of phosphorus, the model produces ocean anoxia at low to mid latitudes and changes in marine δ13C that are consistent with geological data such as the well established δ13C curve. The spread of anoxia is supported by an increase in riverine phosphorus fluxes under high pCO2 and a decrease in phosphorus burial efficiency in marine sediments under low oxygen conditions in ambient bottom waters. Here, we suggest that an additional mechanism might contribute to anoxia, an increase in the C:P ratio of marine plankton which is induced by high pCO2 values. According to our AOGCM model results, an intensively ventilated Cretaceous ocean turns anoxic only if the C:P ratio of marine organic particles exported into the deep ocean is allowed to increase under high pCO2 conditions. Being aware of the uncertainties such as diagenesis, this modeling study implies that potential changes in Redfield ratios might be a strong feedback mechanism to attain ocean anoxia via enhanced CO2 emissions. The formation of C-enriched marine organic matter may also explain the frequent occurrence of global anoxia during other geological periods characterized by high pCO2 values

The physicochemical habitat of Sclerolinum sp., at Hook Ridge hydrothermal vent, Bransfield Strait, Antarctica

At Hook Ridge hydrothermal vent, a new species of Sclerolinum (Monilifera, Siboglinidae) was found at a water depth of 1,045 m. On the basis of investigations of multicores and gravity cores, the species habitat is characterized. Sclerolinum does not occur in sediments that are most strongly influenced by hydrothermal fluids, probably because of high temperature (up to 49°C) and precipitation of siliceous crusts. About 800 individuals m-2 occur in sediments that are only weakly exposed to hydrothermal flow and have the following characteristics: 20°C (15 cm sediment depth) to 21.5°C (bottom water), 18-40 cm yr-1 advection rates, pH 5.5, <25 µmol L-1 methane, <170 µmol L-1 sulfide, and <0.0054 mol m-2 yr-1 sulfide flux. Comparison with geochemical data from other reducing sediments indicates that the two groups of Siboglinidae, Monilifera and Frenulata, occur in sediments with low sulfide concentration and flux. In contrast, sulfurbased chemosynthetic organisms that typically occur at hydrothermal vents and cold seeps (e.g., Vestimentifera, vesicomyid clams, and bacterial mats) occur in sediments with higher sulfide availability; threshold values are around 500 µmol L-1 sulfide and 0.1 mol m-2 yr-1 sulfide fluxes. We did not find typical hydrothermal vent species at Hook Ridge hydrothermal vent, which might be explained by the unfavorable physicochemical habitat: At sites inhabited by Sclerolinum, sulfide availability appears to be too low, whereas at sites with higher sulfide availability, the temperatures might be too high, siliceous crust precipitation could preclude their occurrence, or both

Modeling benthic–pelagic nutrient exchange processes and porewater distributions in a seasonally hypoxic sediment: evidence for massive phosphate release by Beggiatoa?

This study presents benthic data from 12 samplings from February to December 2010 in a 28 m deep channel in the southwest Baltic Sea. In winter, the distribution of solutes in the porewater was strongly modulated by bioirrigation which efficiently flushed the upper 10 cm of sediment, leading to concentrations which varied little from bottom water values. Solute pumping by bioirrigation fell sharply in the summer as the bottom waters became severely hypoxic (< 2 μM O2). At this point the giant sulfide-oxidizing bacteria Beggiatoa was visible on surface sediments. Despite an increase in O2 following mixing of the water column in November, macrofauna remained absent until the end of the sampling. Contrary to expectations, metabolites such as dissolved inorganic carbon, ammonium and hydrogen sulfide did not accumulate in the upper 10 cm during the hypoxic period when bioirrigation was absent, but instead tended toward bottom water values. This was taken as evidence for episodic bubbling of methane gas out of the sediment acting as an abiogenic irrigation process. Porewater–seawater mixing by escaping bubbles provides a pathway for enhanced nutrient release to the bottom water and may exacerbate the feedback with hypoxia. Subsurface dissolved phosphate (TPO4) peaks in excess of 400 μM developed in autumn, resulting in a very large diffusive TPO4 flux to the water column of 0.7 ± 0.2 mmol m−2 d−1. The model was not able to simulate this TPO4 source as release of iron-bound P (Fe–P) or organic P. As an alternative hypothesis, the TPO4 peak was reproduced using new kinetic expressions that allow Beggiatoa to take up porewater TPO4 and accumulate an intracellular P pool during periods with oxic bottom waters. TPO4 is then released during hypoxia, as previous published results with sulfide-oxidizing bacteria indicate. The TPO4 added to the porewater over the year by organic P and Fe–P is recycled through Beggiatoa, meaning that no additional source of TPO4 is needed to explain the TPO4 peak. Further experimental studies are needed to strengthen this conclusion and rule out Fe–P and organic P as candidate sources of ephemeral TPO4 release. A measured C/P ratio of < 20 for the diffusive flux to the water column during hypoxia directly demonstrates preferential release of P relative to C under oxygen-deficient bottom waters. This coincides with a strong decrease in dissolved inorganic N/P ratios in the water column to ~ 1. Our results suggest that sulfide oxidizing bacteria could act as phosphorus capacitors in systems with oscillating redox conditions, releasing massive amounts of TPO4 in a short space of time and dramatically increasing the internal loading of TPO4 to the overlying water

Methanhydrate in arktischen Sedimenten – Einfluss auf Klima und Stabilität der Kontinentalränder

Methane hydrates in marine sediments – Impact on climate and stability of continental slopes: The Arctic Ocean increasingly gets into the focus of methane hydrate research with respect to Global Warming. In the cold Arctic Ocean, hydrates are stable at relatively shallow water depths, and due to rapidly increasing water temperatures this region is considered to become a major source of atmospheric methane in the near future. But many factors, which are essential to make solid predictions about the fate and consequences of hydrate-related methane in the Arctic, still remain unclear. Uncertainties range from the size of the Arctic methane hydrate inventory to the efficiency of microbes to consume methane that is liberated in sediments and migrating through the water column. A potential collateral impact of massive gas hydrate destabilization could be failures of Arctic continental slopes with resulting mass wasting and tsunami formation. Although the correlation between hydrates and mass wasting are still a matter of debate, historic events have been identified and their causes are part of ongoing research. This book chapter will provide an overview of most recent research and discussions about Arctic gas hydrates and its fate in the light of Global Warming

Silicate weathering in anoxic marine sediments

Two sediment cores retrieved at the northern slope of Sakhalin Island, Sea of Okhotsk, were analyzed for biogenic opal, organic carbon, carbonate, sulfur, major element concentrations, mineral contents, and dissolved substances including nutrients, sulfate, methane, major cations, humic substances, and total alkalinity. Down-core trends in mineral abundance suggest that plagioclase feldspars and other reactive silicate phases (olivine, pyroxene, volcanic ash) are transformed into smectite in the methanogenic sediment sections. The element ratios Na/Al, Mg/Al, and Ca/Al in the solid phase decrease with sediment depth indicating a loss of mobile cations with depth and producing a significant down-core increase in the chemical index of alteration. Pore waters separated from the sediment cores are highly enriched in dissolved magnesium, total alkalinity, humic substances, and boron. The high contents of dissolved organic carbon in the deeper methanogenic sediment sections (50–150 mg dm−3) may promote the dissolution of silicate phases through complexation of Al3+ and other structure-building cations. A non-steady state transport-reaction model was developed and applied to evaluate the down-core trends observed in the solid and dissolved phases. Dissolved Mg and total alkalinity were used to track the in-situ rates of marine silicate weathering since thermodynamic equilibrium calculations showed that these tracers are not affected by ion exchange processes with sediment surfaces. The modeling showed that silicate weathering is limited to the deeper methanogenic sediment section whereas reverse weathering was the dominant process in the overlying surface sediments. Depth-integrated rates of marine silicate weathering in methanogenic sediments derived from the model (81.4–99.2 mmol CO2 m−2 year−1) are lower than the marine weathering rates calculated from the solid phase data (198–245 mmol CO2 m−2 year−1) suggesting a decrease in marine weathering over time. The production of CO2 through reverse weathering in surface sediments (4.22–15.0 mmol CO2 m−2 year−1) is about one order of magnitude smaller than the weathering-induced CO2 consumption in the underlying sediments. The evaluation of pore water data from other continental margin sites shows that silicate weathering is a common process in methanogenic sediments. The global rate of CO2 consumption through marine silicate weathering estimated here as 5–20 Tmol CO2 year−1 is as high as the global rate of continental silicate weathering

Sediment release of dissolved organic matter in the oxygen minimum zone off Peru

In combination to sluggish ventilation by ocean currents, the nutrient upwelling and high surface productivity, followed by organic matter remineralization, leads to a pronounced oxygen minimum zone (OMZ) in the eastern tropical South Pacific (ETSP). There, oxygen concentrations drop below 1 �mol/kg at a water depth <80 m. The high productivity results in the supply of organic matter (OM) to the anoxic sediments and its utilization by heterotrophic communities. The microbial utilization of OM under anoxia leads to nitrogen loss processes, and an accumulation of sulphide and methane. The proximity of the OMZ to the ocean surface in the ETSP may lead to an active outgassing of climate relevant products of the anoxic OM remineralization. The degradation of OM in sediments is associated with production of dissolved organic matter (DOM) from organic particles (POM) that is further remineralized into inorganic nutrients and dissolved inorganic carbon, which then can be released back to the water column, fuelling productivity. Part of the DOM pool may be released to the overlying water column and serve as ligands for micronutrients, such as iron, or provide an additional substrate for microbial communities to respire, affecting overlying water column biogeochemistry. Despite the potential relevance for biogeochemical processes, the quality of the DOM in the pore waters that may be released to the overlying water column has been barely studied in the ETSP off Peru. High spatial resolution measurements of DOM fluorescence (FDOM) during the research cruise M93 (Feb-March 2013) indicated elevated intensities near the sediments in the ETSP off Peru. Those intensities were interpreted as a sediment release of DOM, the quantification of dissolved organic carbon (DOC) flux, however, was not possible at the time. To estimate DOM fluxes and DOM quality, DOC and DOM samples were collected from the sediment pore waters and from benthic incubation chambers from six stations along the 12°S transect in the Peruvian upwelling in 2017 (cruises M136, M137). Samples were collected using a multiple-corer and by Biogeochemical Observatories, respectively. Here, we evaluate DOC fluxes from the sediments and relate them to the measurements of FDOM. We evaluate the quality of DOM by Excitation Emission spectroscopy, followed by parallel factor analysis. The possible implications of the DOM release for water column biogeochemistry are discussed

Simple transfer functions for calculating benthic fixed nitrogen losses and C:N:P regeneration ratios in global biogeochemical models

Empirical transfer functions are derived for predicting the total benthic nitrate loss(LNO3) and the net loss of dissolved inorganic nitrogen (LDIN) in marine sediments,equivalent to sedimentary denitrification. The functions are dynamic vertically integratedsediment models which require the rain rate of particulate organic carbon to the seafloor(RRPOC) and a proposed new variable(O2-NO3)bw (bottom water O2 concentration minus NO3-concentration) as the only input parameters. Applied globally to maps of RRPOC and(O2-NO3)bw on a 1° x 1° spatial resolution, the models predict a NO3- drawdown of 196 Tg yr-1 (LNO3)of which 153 – 155 Tg yr-1 is denitrified to N2 (LDIN). This is in good agreement with previous estimates using very different methods. Our approach implicitly accounts for fixed N loss via anammox, such that our findings do not support the idea that the relatively recent discovery of anammox in marine sediments might require current estimates of the global benthic marine N budget to be revised. The continental shelf (0 – 200 m) accounts for >50% of global LNO3 and LDIN, with slope (200 – 2000 m) and deep-sea (>2000 m) sediments contributing ca. 30% and 20%, respectively. Denitrification in high-nitrate/low-oxygen regions such as oxygen minimum zones is significant (ca. 15 Tg N yr-1; 10% of global) despite covering only 1% of the seafloor. The data are used to estimate the net fluxes of nitrate (18 Tg N yr-1) and phosphate(27 Tg P yr-1) across the sediment-water interface. The benthic fluxes strongly deviate from Redfield composition, with globally averaged N:P, N:C and C:P values of 8.3, 0.067 and 122, respectively, indicating world-wide fixed N losses (by denitrification) relative to C and P. The transfer functions are designed to be coupled dynamically to general circulation models to better predict the feedback of sediments on pelagic nutrient cycling and dissolved O2 distributions