Abstract. Estuarine regions are generally considered a major source of atmospheric CO2, as a result of the high organic carbon (OC) mineralization rates in their water column and sediments. Despite this, the intensity of anaerobic respiration processes in the sediments tempered by the reoxidation of reduced metabolites near the sediment–water interface controls the flux of benthic alkalinity. This alkalinity may partially buffer metabolic CO2 generated by benthic OC respiration in sediments. Thus, sediments with high anaerobic respiration rates could contribute less to local acidification than previously thought. In this study, a benthic chamber was deployed in the Rhône River prodelta and the adjacent continental shelf (Gulf of Lion, northwestern Mediterranean) in late summer to assess the fluxes of total alkalinity (TA) and dissolved inorganic carbon (DIC) from the sediment. Concurrently, in situ O2 and pH micro-profiles, voltammetric profiles and pore water composition were measured in surface sediments to identify the main biogeochemical processes controlling the net production of alkalinity in these sediments. Benthic TA and DIC fluxes to the water column, ranging between 14 and 74 and 18 and 78 mmol m−2 d−1, respectively, were up to 8 times higher than dissolved oxygen uptake (DOU) rates (10.4±0.9 mmol m−2 d−1) close to the river mouth, but their intensity decreased offshore, as a result of the decline in OC inputs. In the zone close to the river mouth, pore water redox species indicated that TA and DIC were mainly produced by microbial sulfate and iron reduction. Despite the complete removal of sulfate from pore waters, dissolved sulfide concentrations were low and significant concentrations of FeS were found, indicating the precipitation and burial of iron sulfide minerals with an estimated burial flux of 12.5 mmol m−2 d−1 near the river mouth. By preventing reduced iron and sulfide reoxidation, the precipitation and burial of iron sulfide increases the alkalinity release from the sediments during the spring and summer months. Under these conditions, the sediment provides a net source of alkalinity to the bottom waters which mitigates the effect of the benthic DIC flux on the carbonate chemistry of coastal waters and weakens the partial pressure of CO2 increase in the bottom waters that would occur if only DIC was produced.

The kinetics and mechanism of thiol oxidation by Mn oxides undergoing dynamic structural transformation under environmentally relevant conditions remain poorly understood. In this study, thiol/disulfide pair concentrations were simultaneously determined in situ using voltammetric microelectrodes during the interaction of four common thiols (cysteine, homocysteine, cysteamine, and glutathione) with fresh and aged δ-MnO 2 at pH 7.0. The reaction kinetics was first order with respect to thiol and zero order with respect to Mn oxides. A transient intermediate sulfur surface species observed during the reaction provides evidence for a mechanism involving two successive one-electron transfer steps. The reaction kinetics of fresh and aged δ-MnO 2 was investigated with cysteine and compared to that of manganite, a Mn(III) oxyhydroxide phase. The reactivity of aged δ-MnO 2 decreased as a result of structural transformation to cryptomelane but remained higher than that of manganite, suggesting the potential roles of transient Mn(III) surface intermediate in promoting the reduction of Mn(IV) in δ-MnO 2 and cryptomelane (compared to Mn(III) in manganite). This study demonstrates the importance of correlating Mn oxide mineral structure and redox reactivity and extends the potential for thiols commonly found in sedimentary environments to be utilized as electron shuttles during dissimilatory Mn reduction.

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Hypoxia and associated acidification are growing concerns for ecosystems and biogeochemical cycles in the coastal zone. The northern Gulf of Mexico (nGoM) has experienced large seasonal hypoxia for decades linked to the eutrophication of the continental shelf fueled by the Mississippi River nutrient discharge. Sediments play a key role in maintaining hypoxic and acidified bottom waters, but this role is still not completely understood. In the summer 2017, when the surface area of the hypoxic zone in the nGoM was the largest ever recorded, we investigated four stations on the continental shelf differentially influenced by river inputs of the Mississippi-Atchafalaya River System and seasonal hypoxia. We investigated diagenetic processes under normoxic, hypoxic, and nearly anoxic bottom waters by coupling amperometric, potentiometric, and voltammetric microprofiling with high-resolution diffusive equilibrium in thin-films (DET) profiles and porewater analyses. In addition, we used a time-series of bottom-water dissolved oxygen from May to November 2017, which indicated intense O2 consumption in bottom waters related to organic carbon recycling. At the sediment-water interface (SWI), we found that oxygen consumption linked to organic matter recycling was large with diffusive oxygen uptake (DOU) of 8 and 14 mmol m–2 d–1, except when the oxygen concentration was near anoxia (5 mmol m–2 d–1). Except at the station located near the Mississippi river outlet, the downcore pore water sulfate concentration decrease was limited, with little increase in alkalinity, dissolved inorganic carbon (DIC), ammonium, and phosphate suggesting that low oxygen conditions did not promote anoxic diagenesis as anticipated. We attributed the low anoxic diagenesis intensity to a limitation in organic substrate supply, possibly linked to the reduction of bioturbation during the hypoxic spring and summer.

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<p><strong>Abstract.</strong> Estuarine regions are generally considered a net source of atmospheric CO<sub>2</sub> as a result of the high organic carbon (OC) mineralization rates in the water column and their sediments. Yet, the intensity of anaerobic respiration processes in the sediments tempered by the reoxidation of reduced metabolites controls the net production of alkalinity from sediments that may partially buffer the metabolic CO<sub>2</sub> generated by OC respiration. In this study, a benthic chamber was deployed in the Rhône River prodelta and the adjacent continental shelf (Gulf of Lions, NW Mediterranean) to assess the fluxes of total alkalinity (TA) and dissolved inorganic carbon (DIC) from the sediment. Concurrently, <i>in situ</i> O<sub>2</sub> and pH microprofiles, electrochemical profiles, pore water and solid composition were measured in surface sediments to identify the main biogeochemical processes controlling the net production of alkalinity in these sediments. The benthic fluxes of TA and DIC, ranging between 14 and 74 mmol m<sup>−2</sup> d<sup>−1</sup> and 18 and 78 mmol m<sup>−2</sup> d<sup>−1</sup>, respectively, were up to 8 times higher than the DOU fluxes (10.4 ± 0.9 mmol m<sup>−2</sup> d<sup>−1</sup>) close to the river mouth, but their intensity decreased offshore, as a result of the decline in OC inputs. Low nitrate concentrations and strong pore water sulfate gradients indicated that the majority of the TA and DIC was produced by sulfate and iron reduction. Despite the complete removal of sulfate from the pore waters, dissolved sulfide concentrations were low due to the precipitation and burial of iron sulfide minerals (12.5 mmol m<sup>−2</sup> d<sup>−1</sup> near the river mouth), while soluble organic-Fe(III) complexes were concurrently found throughout the sediment column. The presence of organic-Fe(III) complexes together with low sulfide concentrations and high sulfate consumption suggests a dynamic system driven by the variability of the organic and inorganic particulate input originating from the river. By preventing reduced substances from being reoxidized, the precipitation and burial of iron sulfide decouples the iron and sulfur cycles from oxygen, therefore allowing a flux of alkalinity out of the sediments. In these conditions, the sediment provides a source of alkalinity to the bottom waters which mitigates the effect of the benthic DIC flux on the carbonate chemistry of coastal waters.</p>