Abstract. The Rhône River is the largest source of terrestrial organic and inorganic carbon for the Mediterranean Sea. A large fraction of this terrestrial carbon is either buried or mineralized in the sediments close to the river mouth. This mineralization follows aerobic and anaerobic pathways, with a range of impacts on calcium carbonate precipitation and dissolution in the sediment near the sediment-water interface. This study focuses on the production of dissolved inorganic carbon (DIC) and total alkalinity (TA) by early diagenesis, consequential pH variations and the effect on calcium carbonate precipitation or dissolution. The sediment porewater chemistry was investigated along a transect from the Rhône River outlet to the continental shelf. TA and concentrations of DIC, SO 2− 4 and Ca 2+ were analyzed on bottom waters and extracted sediment porewaters, whereas pH and oxygen concentrations were measured in situ using microelectrodes. The average oxygen penetration depth into the sediment was 1.7 ± 0.4 mm close to the river mouth and 8.2 ± 2.6 mm in the continental shelf sediments, indicating intense respiration rates. Diffusive oxygen fluxes through the sediment-water interface ranged between 3 and 13 mmol O 2 m −2 d −1 . In the first 30 cm of the sediment, TA and DIC porewater concentrations increased with depth up to 48 mmol L −1 near the river outlet and up to 7 mmol L −1 on the shelf as a result of aerobic and anaerobic mineralization processes. Due to aerobic processes, at all stations pH decreased by 0.6 pH units in the oxic layer of the sediment accompanied by a decrease of the saturation state regarding calcium carbonate. In the anoxic layer of the sediments, sulfate reduction was the dominant mineralization process and was associated with an increase of porewater saturation state regarding calcium carbonate.Ultimately anoxic mineralization of organic matter caused calcium carbonate precipitation demonstrated by a large decrease in Ca 2+ concentration with depth in the sediment. Carbonate precipitation decreased in the offshore direction, together with the carbon turnover and sulfate consumption in the sediments. The large production of porewater alkalinity characterizes these sediments as an alkalinity source to the water column, which may increase the CO 2 buffering capacity of these coastal waters. Estuarine sediments should therefore receive more attention in future estimations of global carbon fluxes.

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.

Abstract. Constraining the mechanisms controlling organic matter (OM) reactivity and, thus, degradation, preservation, and burial in marine sediments across spatial and temporal scales is key to understanding carbon cycling in the past, present, and future. However, we still lack a detailed quantitative understanding of what controls OM reactivity in marine sediments and, consequently, a general framework that would allow model parametrization in data-poor areas. To fill this gap, we quantify apparent OM reactivity (i.e. OM degradation rate constants) by extracting reactive continuum model (RCM) parameters (a and v, which define the shape and scale of OM reactivity profiles, respectively) from observed benthic organic carbon and sulfate dynamics across 14 contrasting depositional settings distributed over five distinct benthic provinces. We further complement the newly derived parameter set with a compilation of 37 previously published RCM a and v estimates to explore large-scale trends in OM reactivity. Our analysis shows that the large-scale variability in apparent OM reactivity is largely driven by differences in parameter a (10−3–107) with a high frequency of values in the range 100–104 years. In contrast, and in broad agreement with previous findings, inversely determined v values fall within a narrow range (0.1–0.2). Results also show that the variability in parameter a and, thus, in apparent OM reactivity is a function of the whole depositional environment, rather than traditionally proposed, single environmental controls (e.g. water depth, sedimentation rate, OM fluxes). Thus, we caution against the simplifying use of a single environmental control for predicting apparent OM reactivity beyond a specific local environmental context (i.e. well-defined geographic scale). Additionally, model results indicate that, while OM fluxes exert a dominant control on depth-integrated OM degradation rates across most depositional environments, apparent OM reactivity becomes a dominant control in depositional environments that receive exceptionally reactive OM. Furthermore, model results show that apparent OM reactivity exerts a key control on the relative significance of OM degradation pathways, the redox zonation of the sediment, and rates of anaerobic oxidation of methane. In summary, our large-scale assessment (i) further supports the notion of apparent OM reactivity as a dynamic ecosystem property, (ii) consolidates the distributions of RCM parameters, and (iii) provides quantitative constraints on how OM reactivity governs benthic biogeochemical cycling and exchange. Therefore, it provides important global constraints on the most plausible range of RCM parameters a and v and largely alleviates the difficulty of determining OM reactivity in RCM by constraining it to only one variable, i.e. the parameter a. It thus represents an important advance for model parameterization in data-poor areas.

<p><strong>Abstract.</strong> The Rhône River is the largest source of terrestrial organic and inorganic carbon for the Mediterranean Sea, and a large fraction thereof is buried or mineralized in the sediments close to the river mouth. The mineralization follows aerobic and anaerobic pathways with varying impacts on the carbonate chemistry in the sediment pore waters. This study focused on the production of dissolved inorganic carbon (DIC) and total alkalinity (TA) by early diagenesis at the sediment water-interface, consequential pH variations and the effect on calcium carbonate precipitation or dissolution. The sediment pore water chemistry was investigated during the DICASE cruise along a transect from the Rhône River outlet to the continental shelf. The concentrations of DIC, TA, SO<sub>4</sub><sup>2−</sup> and Ca<sup>2+</sup> were analyzed on bottom waters and extracted pore waters, whereas pH and oxygen concentrations were measured in situ using microelectrodes. The average oxygen penetration depth into the sediment was 1.7 ± 0.4 mm in the proximal domain and 8.2 ± 2.6 mm in the distal domain, indicating intense aerobic respiration rates. Diffusive oxygen fluxes through the sediment water interface range between 3 and 13 mmol O<sub>2</sub> m<sup>−2</sup> d<sup>−1</sup>. The DIC and TA concentrations increased with depth in the sediment pore waters up to 48 mmol L<sup>−1</sup> near the river outlet and up to 7 mmol L<sup>−1</sup> on the shelf as a result of aerobic and anaerobic mineralization processes. Due to oxic processes, the pH decreased by 0.6 pH units in the oxic layer of the sediment accompanied by a decrease of the saturation state regarding calcium carbonate. In the anoxic part of the sediments, sulfate reduction was seen to be the dominant mineralization process and was associated to an increase of pore water saturation state regarding calcium carbonate. Ultimately anoxic mineralization of organic matter caused calcium carbonate precipitation as shown by large decrease in Ca<sup>2+</sup> concentration with depth in the sediment. The saturation state and carbonate precipitation decreased in offshore direction, together with the carbon turnover and sulfate consumption in the sediments.</p>

Rivers are important links between continents and oceans by transporting terrestrial particulate organic matter (POM) to continental shelf regions through estuaries or deltas and the Mediterranean basin is a good example of this strong linkage. In the vicinity of river mouths, an important fraction of the terrestrial POM settles on the seafloor, sometimes mixed with marine POM, where both can be recycled or buried. In the Rhone River prodelta, previous studies have investigated the origin of the POM in the sediments. They pointed at the large fraction of terrestrial POM in the sediments and the transition to older POM fractions in offshore direction. These studies suggested that terrestrial POM could be an important food source for benthic heterotrophic organisms in this area. In this study, the d 13 C and D 14 C signatures of dissolved inorganic carbon (DIC) and DIC:NH 4 + ratio in sediment pore water have been measured along a nearshore-offshore transect. The data were compared with available datasets concerning isotopic signature and C:N of the POM in bottom waters and suspended particles from the Rhone River and sediments from its delta, in order to determine which fraction of the POM is actually mineralized. Our results show that a fraction of terrestrial POM corresponding to riverine plankton is preferentially mineralized. Indeed, 13 C-depleted riverine POM (d 13 C = À25 to À27‰) which is enriched with 14 C (D 14 C = +400 to +500‰) and shows a C:N < 8 gets mostly mineralized. This isotopic signature differs from that of sediment POM which highlights the selective mineralization already observed in other river deltas. In the Mediterranean context with large human influence in river watersheds such as dam building, our results highlight the importance of riverine primary production versus eroded organic matter in coastal carbon budgets.

Abstract. Constraining the mechanisms that control organic matter (OM) reactivity and, thus, degradation, preservation and burial in marine sediments across spatial and temporal scales is key to understanding carbon cycling in the past, present, and future. However, we still lack a quantitative understanding of what controls OM reactivity in marine sediments and, as a result, how to constrain it in global models. To fill this gap, we quantify apparent OM reactivity (i.e., model-derived estimates) by extracting reactive continuum model parameters (a and v) from observed benthic organic carbon and sulfate dynamics across 14 contrasting depositional settings distributed over five distinct benthic provinces. Our analysis shows that the large-scale range in apparent OM reactivity is largely driven by the wide variability in parameter a (10−3

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&lt;p&gt;&lt;strong&gt;Abstract.&lt;/strong&gt; Estuarine regions are generally considered a net source of atmospheric CO&lt;sub&gt;2&lt;/sub&gt; 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&lt;sub&gt;2&lt;/sub&gt; generated by OC respiration. In this study, a benthic chamber was deployed in the Rh&amp;#244;ne 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, &lt;i&gt;in situ&lt;/i&gt; O&lt;sub&gt;2&lt;/sub&gt; 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&amp;#8201;mmol&amp;#8201;m&lt;sup&gt;&amp;#8722;2&lt;/sup&gt;&amp;#8201;d&lt;sup&gt;&amp;#8722;1&lt;/sup&gt; and 18 and 78&amp;#8201;mmol&amp;#8201;m&lt;sup&gt;&amp;#8722;2&lt;/sup&gt;&amp;#8201;d&lt;sup&gt;&amp;#8722;1&lt;/sup&gt;, respectively, were up to 8 times higher than the DOU fluxes (10.4&amp;#8201;&amp;#177;&amp;#8201;0.9&amp;#8201;mmol&amp;#8201;m&lt;sup&gt;&amp;#8722;2&lt;/sup&gt;&amp;#8201;d&lt;sup&gt;&amp;#8722;1&lt;/sup&gt;) 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&amp;#8201;mmol&amp;#8201;m&lt;sup&gt;&amp;#8722;2&lt;/sup&gt;&amp;#8201;d&lt;sup&gt;&amp;#8722;1&lt;/sup&gt; 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.&lt;/p&gt;