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The radiation of bioturbation during the Ediacaran–Cambrian transition has long been hypothesized to have oxygenated sediments, triggering an expansion of the habitable benthic zone and promoting increased infaunal tiering in early Paleozoic benthic communities. However, the effects of bioturbation on sediment oxygen are underexplored with respect to the importance of biomixing and bioirrigation, two bioturbation processes which can have opposite effects on sediment redox chemistry. We categorized trace fossils from the Ediacaran and Terreneuvian as biomixing or bioirrigation fossils and integrated sedimentological proxies for bioturbation intensity with biogeochemical modeling to simulate oxygen penetration depths through the Ediacaran–Cambrian transition. Ultimately, we find that despite dramatic increases in ichnodiversity in the Terreneuvian, biomixing remains the dominant bioturbation behavior, and in contrast to traditional assumptions, Ediacaran–Cambrian bioturbation was unlikely to have resulted in extensive oxygenation of shallow marine sediments globally.

 

Abstract. We introduce a time-dependent, one-dimensional model ofearly diagenesis that we term RADI, an acronym accounting for the mainprocesses included in the model: chemical reactions, advection, molecularand bio-diffusion, and bio-irrigation. RADI is targeted for study ofdeep-sea sediments, in particular those containing calcium carbonates(CaCO3). RADI combines CaCO3 dissolution driven by organic matterdegradation with a diffusive boundary layer and integrates state-of-the-artparameterizations of CaCO3 dissolution kinetics in seawater, thusserving as a link between mechanistic surface reaction modeling andglobal-scale biogeochemical models. RADI also includes CaCO3precipitation, providing a continuum between CaCO3 dissolution andprecipitation. RADI integrates components rather than individual chemicalspecies for accessibility and is straightforward to compare againstmeasurements. RADI is the first diagenetic model implemented in Julia, ahigh-performance programming language that is free and open source, and itis also available in MATLAB/GNU Octave. Here, we first describe thescientific background behind RADI and its implementations. Following this, we evaluateits performance in three selected locations and explore other potentialapplications, such as the influence of tides and seasonality on earlydiagenesis in the deep ocean. RADI is a powerful tool to study thetime-transient and steady-state response of the sedimentary system toenvironmental perturbation, such as deep-sea mining, deoxygenation, oracidification events. 

Ocean alkalinity plays a fundamental role in the apportionment of CO₂between the atmosphere and the ocean. The primary driver of the ocean's vertical alkalinity distribution is the formation of calcium carbonate (CaCO₃) by organisms at the ocean surface and its dissolution at depth. This so‐called “CaCO₃counterpump” is poorly constrained, however, both in terms of how much CaCO₃is exported from the surface ocean, and at what depth it dissolves. Here, we created a steady‐state model of global ocean alkalinity using Ocean Circulation Inverse Model transport, biogeochemical cycling, and field‐tested calcite and aragonite dissolution kinetics. We find that limiting CaCO₃dissolution to below the aragonite and calcite saturation horizons cannot explain excess alkalinity in the upper ocean, and that models allowing dissolution above the saturation horizons best match observations. Linking dissolution to organic matter respiration, or imposing a constant dissolution rate both produce good model fits. Our best performing models require export between 1.1 and 1.8 Gt PIC y⁻¹(from 73 m), but all converge to 1.0 Gt PIC y⁻¹export at 279 m, indicating that both high‐ and low‐export scenarios can match observations, as long as high export is coupled to high dissolution in the upper ocean. These results demonstrate that dissolution is not a simple function of seawater CaCO₃saturation (Ω) and calcite or aragonite solubility, and that other mechanisms, likely related to the biology and ecology of calcifiers, must drive significant dissolution throughout the water column.

 

Geochemical analyses of trace elements in the ocean water column have suggested that pelagic clay‐rich sediments are a major source of various elements to bottom‐waters. However, corresponding high‐quality measurements of trace element concentrations in porewaters of pelagic clay‐rich sediments are scarce, making it difficult to evaluate the contributions from benthic processes to global oceanic cycles of trace elements. To bridge this gap, we analyzed porewater and bulk sediment concentrations of vanadium, chromium, cobalt, nickel, copper, arsenic, molybdenum, barium and uranium, as well as concentrations of the major oxidants nitrate, manganese, iron, and sulfate in the top 30 cm of cores collected along a transect from Hawaii to Alaska. The data show large increases in porewater concentrations of vanadium, manganese, cobalt, nickel, copper, and arsenic within the top cm of the sediment, consistent with the release of these elements from remineralized organic matter. The sediments are a sink for sulfate, uranium, and molybdenum, even though conditions within the sampled top 30 cm remain aerobic. Porewater chromium concentrations generally increase with depth due to release from sediment particles. Extrapolated to the global aerial extent of pelagic clay sediment, the benthic fluxes in mol yr⁻¹are Ba 3.9 ± 3.6 × 10⁹, Mn 3.4 ± 3.5 × 10⁸, Co 2.6 ± 1.3 × 10⁷, Ni 9.6 ± 8.6 × 10⁸, Cu 4.6 ± 2.4 × 10⁹, Cr 1.7 ± 1.1 × 10⁸, As 6.1 ± 7.0 × 10⁸, V 6.0 ± 2.5 × 10⁹. With the exception of vanadium, calculated fluxes across the sediment–water interface are consistent with the variability in bottom‐water concentrations and ocean residence time of the studied elements.

 

The dissolution of CaCO 3 minerals in the ocean is a fundamental part of the marine alkalinity and carbon cycles. While there have been decades of work aimed at deriving the relationship between dissolution rate and mineral saturation state (a so-called rate law), no real consensus has been reached. There are disagreements between laboratory- and field-based studies and differences in rates for inorganic and biogenic materials. Rates based on measurements on suspended particles do not always agree with rates inferred from measurements made near the sediment–water interface of the actual ocean. By contrast, the freshwater dissolution rate of calcite has been well described by bulk rate measurements from a number of different laboratories, fit by basic kinetic theory, and well studied by atomic force microscopy and vertical scanning interferometry to document the processes at the atomic scale. In this review, we try to better unify our understanding of carbonate dissolution in the ocean via a relatively new, highly sensitive method we have developed combined with a theoretical framework guided by the success of the freshwater studies. We show that empirical curve fits of seawater data as a function of saturation state do not agree, largely because the curvature is itself a function of the thermodynamics. Instead, we show that models that consider both surface energetic theory and the complicated speciation of seawater and calcite surfaces in seawater are able to explain most of the most recent data.This new framework can also explain features of the historical data that have not been previously explained. The existence of a kink in the relationship between rate and saturation state, reflecting a change in dissolution mechanism, may be playing an important role in accelerating CaCO 3 dissolution in key sedimentary environments. 

We have designed, built, tested, and deployed a novel device to extract porewater from deep‐sea sediments in situ, constructed to work with a standard multicorer. Despite the importance of porewater measurements for numerous applications, many sampling artifacts can bias data and interpretation during traditional porewater processing from shipboard‐processed cores. A well‐documented artifact occurs in deep‐sea porewater when carbonate precipitates during core recovery as a function of temperature and pressure changes, while porewater is in contact with sediment grains before filtration, thereby lowering porewater alkalinity and dissolved inorganic carbon (DIC). Here, we present a novel device built to obviate these sampling artifacts by filtering porewater in situ on the seafloor, with a focus near the sediment–water interface on cm‐scale resolution, to obtain accurate porewater profiles. We document 1–10% alkalinity loss in shipboard‐processed sediment cores compared to porewater filtered in situ, at depths of 1600–3200 m. We also show that alkalinity loss is a function of both weight % sedimentary CaCO₃and water column depth. The average ratio of alkalinity loss to DIC loss in shipboard‐processed sediment cores relative to in situ porewater is 2.2, consistent with the signal expected from carbonate precipitation. In addition to collecting porewater for defining natural profiles, we also conducted the first in situ dissolution experiments within the sediment column using isotopically labeled calcite. We present evidence of successful deployments of this device on and adjacent to the Cocos Ridge in the Eastern Equatorial Pacific across a range of depths and calcite saturation states.

 

The isotopic composition of dissolved oxygen offers a family of potentially unique tracers of respiration and transport in the subsurface ocean. Uncertainties in transport parameters and isotopic fractionation factors, however, have limited the strength of the constraints offered by¹⁸O/¹⁶O and¹⁷O/¹⁶O ratios in dissolved oxygen. To improve our understanding of oxygen cycling in the ocean's interior, we investigated the systematics of oxygen isotopologues in the subsurface Pacific using new data and a 2‐D isotopologue‐enabled isopycnal reaction‐transport model. We measured¹⁸O/¹⁶O and¹⁷O/¹⁶O ratios, as well as the “clumped”¹⁸O¹⁸O isotopologue in the northeast Pacific, and compared the results to previously published data. We find evidence that oxygen consumption in the northeast Pacific follows different mass‐dependent fractionation exponents from those typically used in oceanographic studies. These fractionation factors imply that an elevated proportion of¹⁷O compared to¹⁸O in dissolved oxygen—that is, its triple‐oxygen isotope composition—may not uniquely reflect only gross primary productivity and mixing. For all oxygen isotopologues, transport, respiration, and photosynthesis comprise important parts of their respective budgets. Mechanisms of oxygen removal in the subsurface ocean are discussed.