Abstract Controls on organic carbon preservation in marine sediments remain controversial but crucial for understanding past and future climate dynamics. Here we develop a conceptual-mathematical model to determine the key processes for the preservation of organic carbon. The model considers the major processes involved in the breakdown of organic carbon, including dissolved organic carbon hydrolysis, mixing, remineralization, mineral sorption and molecular transformation. This allows redefining of burial efficiency as preservation efficiency, which considers both particulate organic carbon and mineral-phase organic carbon. We show that preservation efficiency is almost three times higher than the conventionally defined burial efficiency and reconciles predictions with global field data. Kinetic sorption and transformation are the dominant controls on organic carbon preservation. We conclude that a synergistic effect between kinetic sorption and molecular transformation (geopolymerization) creates a mineral shuttle in which mineral-phase organic carbon is protected from remineralization in the surface sediment and released at depth. The results explain why transformed organic carbon persists over long timescales and increases with depth.
Abstract. 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 iron (Fe) and cadmium (Cd) in the oxygen minimum zone off Peru. We combine bottom water and pore water concentrations, as well as benthic fluxes determined from pore water profiles and from in situ 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 release of Fe from sediments to the bottom water. Diffusive Fe fluxes and Fe fluxes from benthic chamber incubations (−0.3 to −17.5 mmol m−2 yr−1) are broadly consistent at stations within the oxygen minimum zone, where the flux magnitude is highest, 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. Rapid removal of dissolved Fe after its release to anoxic bottom waters hints at oxidative removal by nitrite and interactions with particles in the near-bottom water column. Benthic flux estimates of Cd suggest a flux into the sediment within the oxygen minimum zone. Fluxes from benthic chamber incubations (up to 22.6 µmol m−2 yr−1) exceed diffusive fluxes (<1 µmol m−2 yr−1) by a factor of more than 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 covaries with H2S concentrations in the pore water of surface sediments, we argue that Cd removal is mediated by precipitation of cadmium sulfide (CdS) within the chamber water or directly at the sediment–water interface. A mass balance approach, taking the contributions of diffusive and chamber fluxes as well as Cd delivery with organic material into account, 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 and 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 the 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.
The benthic environment is a crucial component of marine systems in the provision of ecosystem services, sustaining biodiversity and in climate regulation, and therefore important to human society. With the contemporary increase in computational power, model resolution and technological improvements in quality and quantity of benthic data, it is necessary to ensure that benthic systems are appropriately represented in coupled benthic-pelagic biogeochemical and ecological modelling studies. In this paper we focus on five topical challenges related to various aspects of modelling benthic environments: organic matter reactivity, dynamics of benthic-pelagic boundary layer, microphytobenthos, biological transport and small-scale heterogeneity, and impacts of episodic events. We discuss current gaps in their understanding and indicate plausible ways ahead. Further, we propose a three-pronged approach for the advancement of benthic and benthic-pelagic modelling, essential for improved understanding, management and prediction of the marine environment. This includes: (A) development of a traceable and hierarchical framework for benthic-pelagic models, which will facilitate integration among models, reduce risk of bias, and clarify model limitations; (B) extended cross-disciplinary approach to promote effective collaboration between modelling and empirical scientists of various backgrounds and better involvement of stakeholders and end-users; (C) a common vocabulary for terminology used in benthic modelling, to promote model development and integration, and also to enhance mutual understanding.
Abstract. The forearc of the convergent margin offshore Costa Rica is a region characterized by strong advection of methane-charged fluids causing the formation of ubiquitous cold seeps (mounds). Presented here are the first measurements of microbial anaerobic oxidation of methane (AOM) and sulfate reduction (SR) rates in sediments from two mounds (11 and 12), applying radiotracer techniques in combination with numerical modelling. In addition, analysis of microbial, methane-dependent carbonate δ18O, δ13C, and 87Sr / 86Sr signatures constrained the origin of the carbonate-precipitating fluid. Average rates of microbial activities differed by a factor of ~5 to 6 between Mound 11 (AOM 140.71 (±40.84 SD) mmol m−2 d−1, SR 117.25 (±82.06 SD) mmol m−2 d−1) and Mound 12 (AOM 22.37 (±0.85 SD) mmol m−2 d−1, SR 23.99 (±5.79 SD) mmol m−2 d−1). Modelling results yielded upward fluid advection velocities of 200 cm yr−1 at Mound 11 and 15 cm yr−1 at Mound 12. Analysis of oxygen and carbon isotope variations of authigenic carbonates from the two locations revealed more enriched values for Mound 11 (δ18O : 3.18 to 6.15‰; δ13C: −14.14 to −29.56‰) compared to Mound 12 (δ18O : 3.09 to 4.48‰; δ13C : −39.53 to −48.98‰). The variation of carbonate 87Sr / 86Sr indicated considerable admixture of deep-source fluid at Mound 11, while seawater 87Sr / 86Sr characteristics prevailed at Mound 12 during precipitation. The present study is in accordance with previous work supporting considerable differences of methane flux between the two mounds. It also strengthens the hypothesis of a dominant deep fluid source with thermogenic methane at Mound 11 versus a shallow source of biogenic methane at Mound 12. The results demonstrate that measurements of methane-driven microbial activity in combination with numerical modelling are a valid tool for constraining recent methane fluxes in the study area. In addition, the analysis of methane-derived authigenic carbonates provides an independent line of evidence for long-term fluid contribution to the porewater chemistry of shallow sediments in the study area.
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