The carbonate chemistry of Arctic Ocean seafloor and its vulnerability to ocean acidification remains poorly explored. This limits our ability to quantify how biogeochemical processes and bottom water conditions shape sedimentary carbonate chemistry, and to predict how climate change may affect such biogeochemical processes at the Arctic Ocean seafloor. Here, we employ an integrated model assessment that explicitly resolves benthic pH and carbonate chemistry along a S—N transect in the Barents Sea. We identify the main drivers of observed carbonate dynamics and estimate benthic fluxes of dissolved inorganic carbon and alkalinity to the Arctic Ocean. We explore how bottom water conditions and in-situ organic matter degradation shape these processes and show that organic matter transformation strongly impacts pH and carbonate saturation (Ω) variations. Aerobic organic matter degradation drives a negative pH shift (pH < 7.6) in the upper 2—5 cm, producing Ω < 1. This causes shallow carbonate dissolution, buffering porewater pH to around 8.0. Organic matter degradation via metal oxide (Mn/Fe) reduction pathways further increases pH and carbonate saturation state. At the northern stations, where Ω > 5 at around 10–25 cm, model simulations result in authigenic carbonate precipitation. Furthermore, benthic fluxes of dissolved inorganic carbon (12.5—59.5 µmol cm−2 yr−1) and alkalinity (11.3—63.2 µmol cm−2 yr−1) are 2—3-fold greater in the northern sites due to greater carbonate dissolution. Our assessment is of significant relevance to predict how changes in the Arctic Ocean may shift carbon burial and pH buffering into the next century.

Preservation of organic carbon (OC) in marine and terrestrial deposits is enhanced by bonding with reactive iron (FeR) phases. The association of OC with FeR (OC-FeR) provides physical protection and hinders microbiological degradation. Roughly 20% of all OC stored in unconsolidated marine sediments and 40% of all OC present in Quaternary terrestrial deposits is preserved as OC-FeR, but this value varies from 10 to 80% across depositional environments. In this work, we provide a new assessment of global OC-FeR burial rates in both marine and terrestrial environments, using published estimates of the fraction of OC associated with FeR, carbon burial, and probabilistic modelling. We estimate the marine OC-FeR sink at between 31 – 70 Mt C yr-1 (mean 52 Mt C yr-1), and the terrestrial OC-FeR sink at between 171 - 946 Mt C yr-1 (mean 472 Mt C yr-1). In marine environments, continental shelves (mean 17 Mt C yr-1) and deltaic/estuarine environments (mean 11 Mg C yr-1) are the primary locations of OC-FeR burial. On land, croplands (279 Mt C yr-1) and grasslands (121 Mt C yr-1) dominate the OC-FeR burial budget. Changes in the Earth system through geological time likely alter the OC-FeR pools, particularly in marine locations. For example, periods of intense explosive volcanism may lead to increased net OC-FeR burial in marine sediments. Our work highlights the importance of OC-FeR in marine carbon burial and demonstrates how OC-FeR burial rates may be an order of magnitude greater in terrestrial environments, those potentially most sensitive to anthropogenic impacts.

Volcanism is the dominant natural source of mercury (Hg) to the atmosphere, biosphere, ocean and sediments. In recent years, sedimentary Hg contents have emerged as a tool to reconstruct volcanic activity, and particularly activity of (subaerially emplaced) large igneous provinces (LIP) in geological deep time. More specifically, Hg has shown potential as a useful proxy to illuminate the previously elusive impact of such large-scale volcanism on marine and terrestrial paleo-environments. While Hg is now widely applied as volcanism tracer, non-volcanic factors controlling sedimentary Hg content are generally not well constrained. Part of this uncertainty stems from our inability to directly observe a natural unperturbed “steady-state” environment as a baseline, as the modern Hg cycle is heavily influenced by anthropogenic activity. Here we focus on the effects of ambient redox conditions in the water column and shallow sediments (early diagenesis), quantify their influence on the geological Hg record and thereby constrain their potential impact on the use of Hg as a proxy for deep-time volcanic activity. Constraining these factors is of critical importance for the application of Hg as a proxy. Many periods in the geological past for which records have been generated, such as the Mesozoic Oceanic Anoxic Events, are marked by a variety of high-amplitude environmental perturbations, including widespread deoxygenation and deposition of organic-rich sediments. We estimate the impact of redox changes and early diagenesis on the geological Hg record using a suite of (sub)recent–Pleistocene and Upper Cretaceous sediments representing oxic to euxinic marine conditions. Our sample set includes a transect through an oxygen minimum zone and cores that record transient shifts in oxygenation state, as well as post-depositional effects – all unrelated to volcanism, to the best of our knowledge. We find substantial alterations to the Hg record and the records of organic carbon and total sulfur, which are typically assumed to be the most common carrier phases of Hg in marine sediments. Moreover, these biases can lead to signal-alterations on a par with those interpreted to result from volcanic activity. Geochemical modifications are ubiquitous and their potential magnitude implies that the factors leading to biases in the geological record warrant careful consideration before interpretation. Factors of particular concern to proxy application are (1) the disproportionate loss of organic carbon and sulfur compounds relative to Hg during oxidation that strongly modulates normalized Hg records, (2) the evasion of Hg in anoxic and mildly euxinic sediments and (3) sharp focusing of Hg during post-depositional oxidation of organic matter.