Beschreibung: A kinetic-bioenergetic reaction model for the anaerobic oxidation of methane (AOM) in coastal marine sediments is presented. The model considers a fixed depth interval of sediments below the zone of bioturbation (the window-of-observation), subject to seasonal variations of temperature and inputs of organic substrates and sulfate. It includes (1) nine microbially-mediated reaction pathways involved in CH4 production/consumption; (2) an explicit representation of five functional microbial groups; and (3) bioenergetic limitations of the microbial metabolic pathways. Fermentation of organic substrates is assumed to produce hydrogen (H2) and acetate (Ac) as key reactive intermediates. Competition among the metabolic pathways is controlled by the relative kinetic efficiencies of the various microbial processes and by bioenergetic constraints. Model results imply that the functional microbial biomasses within the window-of-observation undergo little variation over the year, as a result of kinetic and thermodynamic buffering of the seasonal forcings. Furthermore, the microbial processes proceed at only small fractions of their maximum potential rates. These findings provide a theoretical justification for the approximation of steady-state microbial biomasses, which is frequently used in diagenetic modeling. In contrast, AOM rates show a strong seasonal evolution: AOM only becomes spontaneous in winter, when hydrogenotrophic sulfate reduction (hySR) sufficiently reduces the local H2 concentration. The bioenergetic limitation of AOM is thus a critical factor modulating this process in seasonally-forced nearshore marine sediments. A global sensitivity analysis based on a 2-level factorial design reveals that AOM rates are most sensitive to the kinetic parameters describing hySR and acetotrophic methanogenesis (acME). The growth and substrate uptake kinetics of AOM are unimportant, whereas the threshold value of ATP energy conservation for AOM is the most sensitive thermodynamic parameter. These results confirm that anaerobic methane oxidizing microorganisms are metabolizing close to their thermodynamic limit, with the energetic balance being controlled by the relative rates of hySR and acME. The removal of Ac by acME primarily allows more sulfate (SO42−) to be utilized for H2 oxidation, thereby promoting AOM.

Beschreibung: The impact of oxygen on the preservation of organic matter in marine surface sediments is still controversial. We revisited this long-standing debate by determining the burial efficiency of sedimentary organic matter in the Black Sea, the largest anoxic and euxinic basin in the modern ocean. Surface sediments were sampled in the Danube paleodelta on the northwestern margin of the Black Sea at 420–1550 m water depth. Steady-state modeling of solid species (particulate organic carbon and nitrogen) and solutes (ammonium, sulfate, and total alkalinity) in sediments was performed to quantify rates of mass accumulation, particulate organic matter (POM) degradation, and POM burial. We develop a novel analytical model to quantify these rates applying an inverse modelling approach to down core data accounting for molecular diffusion, sediment burial and compaction. Our model results indicate that 56.7 ± 6.6 % of the particulate organic matter deposited in the study area is not degraded in surface sediments but accumulates below 10 cm sediment depth. This burial efficiency is substantially higher than those previously derived for seafloor areas underlying oxygenated bottom waters. Hence, our study confirms previous studies showing that euxinic bottom water conditions promote the preservation of particulate organic matter in marine sediments.

Beschreibung: The eastern tropical South Pacific (ETSP) represents one of the most productive areas in the ocean that is characterized by a pronounced oxygen minimum zone (OMZ). Particulate organic matter (POM) that sinks out of the euphotic zone is supplied to the anoxic sediments and utilized by microbial communities. The degradation of POM is associated with dissolved organic matter (DOM) production and reworking. The release of recalcitrant DOM to the overlying waters may represent an important organic matter escape mechanism from remineralization within sediments but received little attention in OMZ regions so far. Here, we combine measurements of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) with DOM optical properties in the form of chromophoric (CDOM) and fluorescent (FDOM) DOM from pore waters and near-bottom waters of the ETSP off Peru. We evaluate diffusion–driven fluxes and net in situ fluxes of DOC and DON in order to investigate processes affecting DOM cycling at the sediment–water interface along a transect 12° S. To our knowledge, these are the first data for sediment release of DON and pore water CDOM and FDOM for the ETSP off Peru. Pore-water DOC and DON accumulated with increasing sediment depth, suggesting an imbalance between DOM production and remineralization within sediments. High DON accumulation resulted in very low pore water DOC / DON ratios (〉 1) which could be caused by either an "imbalance" in DOC and DON remineralization, or to the presence of an additional nitrogen source. Diffusion driven fluxes of DOC and DON exhibited high spatial variability. They varied from 0.2–0.1 mmol m−2 d−1 to 2.52–1.3 mmol m−2 d−1 and from −0.042–0.02 mmol m−2 d−1 to 3.32–1.7 mmol m−2 d−1, respectively. Generally low net in situ DOC and DON fluxes as well as steepening of spectral slope (S) of CDOM and accumulation of humic-like FDOM at the near-bottom waters over time indicated active microbial DOM utilization at the sediment–water interface, potentially stimulated by nitrate (NO3−) and nitrite (NO2−). The microbial DOC utilization rates, estimated in our study, may be sufficient to support denitrification rates of 0.2–1.4 mmol m−2 d−1, suggesting that sediment release of DOM contributes substantially to nitrogen loss processes in the ETSP off Peru.

Beschreibung: The intraseasonal evolution of physical and biogeochemical properties during a coastal trapped wave event off central Peru is analysed using data from an extensive shipboard observational programme conducted between April and June 2017, and remote sensing data. The poleward velocities in the Peru–Chile Undercurrent were highly variable and strongly intensified to above 0.5 m s−1 between the middle and end of May. This intensification was likely caused by a first-baroclinic-mode downwelling coastal trapped wave, excited by a westerly wind anomaly at the Equator and originating at about 95∘ W. Local winds along the South American coast did not impact the wave. Although there is general agreement between the observed cross-shore-depth velocity structure of the coastal trapped wave and the velocity structure of first vertical mode solution of a linear wave model, there are differences in the details of the two flow distributions. The enhanced poleward flow increased water mass advection from the equatorial current system to the study site. The resulting shorter alongshore transit times between the Equator and the coast off central Peru led to a strong increase in nitrate concentrations, less anoxic water, likely less fixed nitrogen loss to N2 and a decrease of the nitrogen deficit compared to the situation before the poleward flow intensification. This study highlights the role of changes in the alongshore advection due to coastal trapped waves for the nutrient budget and the cumulative strength of N cycling in the Peruvian oxygen minimum zone. Enhanced availability of nitrate may impact a range of pelagic and benthic elemental cycles, as it represents a major electron acceptor for organic carbon degradation during denitrification and is involved in sulfide oxidation in sediments.

Beschreibung: Sediments in oxygen-depleted marine environments can be an important sink or source of bio-essential trace metals in the ocean. However, the key mechanisms controlling the release from or burial of trace metals in sediments are not exactly understood. Here, we investigate the benthic biogeochemical cycling of Fe and Cd in the oxygen minimum zone off Peru. We combine bottom water profiles, pore water profiles, as well as benthic fluxes determined from pore water profiles and in-situ from benthic chamber incubations along a depth transect at 12° S. In agreement with previous studies, both concentration-depth profiles and in-situ benthic fluxes indicate a Fe release from sediments into bottom waters. Diffusive Fe fluxes and Fe fluxes from benthic chamber incubations are roughly consistent (0.3–17.1 mmol m−2 y−1), indicating that diffusion is the main transport mechanism of dissolved Fe across the sediment-water interface. The occurrence of mats of sulfur oxidizing bacteria on the seafloor represents an important control on the spatial distribution of Fe fluxes by regulating hydrogen sulfide (H2S) concentrations and, potentially, Fe sulfide precipitation within the surface sediment. Removal of dissolved Fe after its release to anoxic bottom waters is rapid in the first 4 m away from the seafloor (half-life 〈 3 min) which hints to oxidative removal by nitrite or interaction with particles in the benthic boundary layer. Benthic flux estimates of Cd are indicative of a flux into the sediment within the oxygen minimum zone. Fluxes from benthic chamber incubations (up to 22.6 µmol m−2 y−1) exceed the diffusive fluxes (〈 1 µmol m−2 y−1) by a factor 〉 25, indicating that downward diffusion of Cd across the sediment-water interface is of subordinate importance for Cd removal from benthic chambers. As Cd removal in benthic chambers co-varies with H2S concentrations in the pore water of surface sediments, we argue that Cd removal is mediated by precipitation of CdS within the chamber. A mass balance approach, taking into account the contributions of diffusive fluxes and fluxes measured in benthic chambers as well as Cd delivery with organic material suggests that CdS precipitation in the near-bottom water could make an important contribution to the overall Cd mass accumulation in the sediment solid phase. According to our results, the solubility of trace metal sulfide minerals (Cd 〈〈 Fe) is a key-factor controlling trace metal removal and consequently the magnitude as well as the temporal and spatial heterogeneity of sedimentary fluxes. We argue that depending on their sulfide solubility, sedimentary source or sink fluxes of trace metals will change differentially as a result of declining oxygen concentrations and an associated expansion of sulfidic surface sediments. Such a trend could cause a change in the trace metal stoichiometry of upwelling water masses with potential consequences for marine ecosystems in the surface ocean.

Beschreibung: Microbial cells buried in subseafloor sediments comprise a substantial portion of Earth’s biosphere and control global biogeochemical cycles; however, the rate at which they use energy (i.e., power) is virtually unknown. Here, we quantify organic matter degradation and calculate the power utilization of microbial cells throughout Earth’s Quaternary-age subseafloor sediments. Aerobic respiration, sulfate reduction, and methanogenesis mediate 6.9, 64.5, and 28.6% of global subseafloor organic matter degradation, respectively. The total power utilization of the subseafloor sediment biosphere is 37.3 gigawatts, less than 0.1% of the power produced in the marine photic zone. Aerobic heterotrophs use the largest share of global power (54.5%) with a median power utilization of 2.23 × 10 −18 watts per cell, while sulfate reducers and methanogens use 1.08 × 10 −19 and 1.50 × 10 −20 watts per cell, respectively. Most subseafloor cells subsist at energy fluxes lower than have previously been shown to support life, calling into question the power limit to life.

Beschreibung: Phosphorus is essential for all living organisms, being a component of DNA and RNA and the energy carrier ATP. Phosphogenesis is a main sink of reactive phosphorus in the oceans. The present study reports the presence of intracellular dissolved inorganic phosphate (DIP) in benthic foraminifera from the Peruvian oxygen minimum zone (OMZ). The mean intracellular DIP concentration was 28 ± 3 mM; two to three orders-of-magnitude higher than in the ambient pore waters. The biological implications of the high intracellular phosphate enrichment may be related to the synthesis of polyphosphates or phospholipids for cell-membranes. The comparative genomics analysis of multiple species of foraminifera from different environments reveals that foraminifers encode the genes required for both phospholipid and polyphosphate metabolism. Rapid phosphogenesis and phosphorite formation associated with foraminiferal tests is hypothesized due to the pre-concentration of intracellular phosphate in these organisms. The results indicate that foraminifera may play a key and previously overlooked role in the global phosphorus cycle.

Beschreibung: Microbial degradation of organic carbon in marine sediments is a key driver of global element cycles on multiple time scales. However, it is not known to what depth microorganisms alter organic carbon in marine sediments or how microbial rates of organic carbon processing change with depth, and thus time since burial, on a global scale. To better understand the connection between the dynamic carbon cycle and life’s limits in the deep subsurface, we have combined a number of global data sets with a reaction transport model (RTM) describing first, organic carbon degradation in marine sediments deposited throughout the Quaternary Period and second, a bioenergetic model for microbial activity. The RTM is applied globally, recognizing three distinct depositional environments – continental shelf, margin and abyssal zones. The results include the masses of particulate organic carbon, POC, stored in three sediment-depth layers: bioturbated Holocene (1.7 × 10^17 g C), non-bioturbated Holocene (2.6 × 10^18 g C) and Pleistocene (1.4 × 1020 g C) sediments. The global depth-integrated rates of POC degradation have been determined to be 6.8 × 10^13, 1.2 × 10^14 and 1.2 × 10^14 g C yr-1 for the same three layers, respectively. A number of maps depicting the distribution of POC, as well as the fraction that has been degraded have also been generated. Using POC degradation as a proxy for microbial catabolic activity, total heterotrophic processing of POC throughout the Quaternary is estimated to be between 10^-11 – 10^-6 g C cm-3 yr-1, depending on the time since deposition and location. Bioenergetic modeling reveals that laboratory-determined microbial maintenance powers are poor predictors of sediment biomass concentration, but that cell concentrations in marine sediments can be accurately predicted by combining bioenergetic models with the rates of POC degradation determined in this study. Our model can be used to quantitatively describe both the carbon cycle and microbial activity on a global scale for marine sediments less than 2.59 million years old.

Beschreibung: In this study the sulfur cycle in the organic-rich mud belt underlying the highly productive upwelling waters of the Namibian shelf is quantified using a 1D reaction-transport model. The model calculates vertical concentration and reaction rate profiles in the top 500 cm of sediment which are compared to a comprehensive dataset which includes carbon, sulfur, nitrogen and iron compounds as well as sulfate reduction (SR) rates and stable sulfur isotopes (32S, 34S). The sulfur dynamics in the well-mixed surface sediments are strongly influenced by the activity of the large sulfur bacteria Thiomargarita namibiensis which oxidize sulfide (H2S) to sulfate () using sea water nitrate () as the terminal electron acceptor. Microbial sulfide oxidation (SOx) is highly efficient, and the model predicts intense cycling between and H2S driven by coupled SR and SOx at rates exceeding 6.0 mol S m−2 y−1. More than 96% of the SR is supported by SOx, and only 2–3% of the pool diffuses directly into the sediment from the sea water. A fraction of the produced by Thiomargarita is drawn down deeper into the sediment where it is used to oxidize methane anaerobically, thus preventing high methane concentrations close to the sediment surface. Only a small fraction of total H2S production is trapped as sedimentary sulfide, mainly pyrite (FeS2) and organic sulfur (Sorg) (∼0.3 wt.%), with a sulfur burial efficiency which is amongst the lowest values reported for marine sediments (〈1%). Yet, despite intense SR, FeS2 and Sorg show an isotope composition of ∼5 ‰ at 500 cm depth. These heavy values were simulated by assuming that a fraction of the solid phase sulfur exchanges isotopes with the dissolved sulfide pool. An enrichment in H2S of 34S towards the sediment-water interface suggests that Thiomargarita preferentially remove H232S from the pore water. A fractionation of 20–30‰ was estimated for SOx (εSOx) with the model, along with a maximum fractionation for SR (εSR–max) of 100‰. These values are far higher than previous laboratory-based estimates for these processes. Mass balance calculations indicate negligible disproportionation of autochthonous elemental sulfur; an explanation routinely cited in the literature to account for the large fractionations in SR. Instead, the model indicates that repeated multi-stepped sulfide oxidation and intracellular disproportionation by Thiomargarita could, in principle, allow the measured isotope data to be simulated using much lower fractionations for εSOx (5‰) and εSR (78‰).

Beschreibung: Ocean alkalinity enhancement (OAE) is an emerging strategy that aims to mitigate climate change by increasing the alkalinity of seawater. This approach involves increasing the alkalinity of the ocean to enhance its capacity to absorb and store carbon dioxide (CO2) from the atmosphere. This chapter presents an overview of the technical aspects associated with the full range of OAE methods being pursued and discusses implications for undertaking research on these approaches. Various methods have been developed to implement OAE, including the direct injection of alkaline liquid into the surface ocean; dispersal of alkaline particles from ships, platforms, or pipes; the addition of minerals to coastal environments; and the electrochemical removal of acid from seawater. Each method has its advantages and challenges, such as scalability, cost effectiveness, and potential environmental impacts. The choice of technique may depend on factors such as regional oceanographic conditions, alkalinity source availability, and engineering feasibility. This chapter considers electrochemical methods, the accelerated weathering of limestone, ocean liming, the creation of hydrated carbonates, and the addition of minerals to coastal environments. In each case, the technical aspects of the technologies are considered, and implications for best-practice research are drawn. The environmental and social impacts of OAE will likely depend on the specific technology and the local context in which it is deployed. Therefore, it is essential that the technical feasibility of OAE is undertaken in parallel with, and informed by, wider impact assessments. While OAE shows promise as a potential climate change mitigation strategy, it is essential to acknowledge its limitations and uncertainties. Further research and development are needed to understand the long-term effects, optimize techniques, and address potential unintended consequences. OAE should be viewed as complementary to extensive emission reductions, and its feasibility may be improved if it is operated using energy and supply chains with minimal CO2 emissions.