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We present pore-fluid geochemistry and heat-flow data along the SWIM1 fault in the Horseshoe Abyssal Plain (northeastern Atlantic Ocean). The SWIM1 fault is part of the transcurrent plate boundary between Africa and Eurasia and cuts through as much as 5-km-thick sediments overlying >140 Ma oceanic lithosphere. In a number of places, restraining segments (as long as 15 km) of the SWIM1 fault generate anticlines (positive flower structures) that protrude as ∼100-m-high hills above the abyssal plain. Heat flow and gradients of dissolved constituents in pore water are enhanced at these seafloor highs. Transport-reaction modeling confirms that slow advection of deep-seated fluids, depleted in Mg and enriched in Sr and CH4, can explain the observations. The geochemical signature is similar to the one observed at deep-sea mud volcanoes located eastward on the SWIM1 fault. The upward-migrating fluids have interacted with carbonate rocks at maximum 5 km depth, which represent the oldest sedimentary unit on top of the basement. We argue that deep-rooted fluids can generally be mobilized and transported upward along flower structures that formed in restraining-bend segments of long strike-slip faults. Such tectonic settings represent largely unrecognized corridors for mass exchange between lithosphere and ocean.

Ratios of (un)reactive iron species, authigenic molybdenum contents (Moauth), and molybdenum isotope compositions (δ98Moauth) in sedimentary rocks are geochemical proxies that are widely used to reconstruct past marine redox states, which have been calibrated in modern marine settings covering oxic to euxinic conditions. However, syn- and postdepositional processes can result in alterations and ambiguities of proxy-derived redox signals that can challenge the validity of paleoreconstructions. We present new data from modern organic-rich sediments of two oxygen minimum zone settings in the Gulf of California and the Peruvian margin. The results show that Mo is fully immobilized shortly after deposition by reaction with hydrogen sulfide (H2S) produced during organoclastic sulfate reduction. Thus, any H2S produced deeper in the sediment (e.g., by sulfate reduction coupled to anaerobic methane oxidation) leaves the initially deposited Mo concentrations and δ98Mo signatures unaltered, which supports the robustness of Mo-based redox proxies. In contrast, the Fe speciation data reveal continued pyritization due to constant exposure of Fe minerals to H2S. Importantly, both Fe bound to oxides and carbonates (highly reactive Fe) and also poorly reactive Fe (e.g., sheet silicates) undergo pyritization during early diagenesis. This process generates Fe-based proxy signatures that falsely imply ferruginous or euxinic conditions.

It has been hypothesized that vanadium (V) isotopes have the potential to track sedimentary redox conditions due to multiple valence states occurring in nature, which might induce variable V isotope fractionation as a function of sedimentary redox state. These characteristica could make V isotopes a useful paleo-redox proxy. However, in order to understand the mechanisms driving V isotope fractionation, it is crucial to build a framework for the depositional and post-depositional controls on sedimentary V isotope records from a diverse set of sedimentary environments. This study, for the first time, investigates the V isotope variations of modern marine sediments deposited under a range of redox environments. Our results document that changes in local redox conditions impart a significant isotopic fractionation from seawater as recorded in the local sedimentary V isotopic signature. Importantly, there is a significant difference between the V isotope composition of sediments deposited in the open ocean setting with oxygen-deficient bottom waters compared to less reducing environments, whereby oxic sediments (benthic oxygen contents > 10 μΜ) exhibit Δoxic = −1.1 ± 0.3‰ and anoxic sediments exhibit Δanoxic = −0.7 ± 0.2‰. Combined with previous studies on seawater particulate and sediment pore fluid analysis, our results indicate that V is mainly delivered and enriched in anoxic sediments through settling particulates. Authigenic V isotope compositions in marine sediments are likely controlled by isotope fractionation between V species bound to particulates and dissolved in seawater, which likely varies with the speciation and adsorption properties of V that are strongly controlled by local redox conditions. In addition, the euxinic Cariaco Basin sediments exhibit distinctive Δeuxinic = −0.4 ± 0.2‰, which is likely influenced by the relationship between the seawater V removal rate and the seawater renewal rate. Our results highlight the direct link between authigenic marine sedimentary V isotope compositions and the overlying local redox conditions. This investigation of V isotopes in modern marine environments provides an initial framework for the utilization of V isotopes to reconstruct ancient redox fluctuations, which has the potential to track subtle redox variations of local oxygen-deficient to low oxygen environments.

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 ( 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 boundary layer plays a crucial role in the exchange of trace metals between surface sediments and the water column. So far it has been difficult to study dissolved–particulate interactions of trace metals in this highly reactive interface layer due to the lack of suitable sampling methods. We developed a new device, called Benthic Trace Profiler (BTP), which enables simultaneous sampling of near-bottom water and suspended particles in high depth resolution within the first 3 m above the seafloor. The device was tested successfully in the Baltic Sea. The concentrations of several trace metals (Co, Ni, Cu, Zn, and Cd) in the collected bottom waters overlapped with concentrations in water column samples above collected with conventional methods. This observation indicates that the sampling device and method is trace metal clean. The trace metals Fe and Mn showed concentration gradients within the benthic boundary layer indicating an upward diffusive flux. This observation is consistent with a diffusive benthic flux of these trace metals across the sediment–water interface, which was independently verified using pore-water profiles. Suspended particles can be used to study precipitation processes and to determine the carrier phases of trace metals. The BTP fulfilled all the intended requirements as it allowed a simultaneous, uncontaminating and oxygen-free sampling of seawater and suspended particles to gather high-resolution profiles of dissolved and particulate trace metal concentrations above the seafloor. The device closes the gap between water column and sediment sampling and helps researchers to better understand trace metal exchange processes across the ocean's lower boundary.

Climate change is expected to result in smaller fish size, but the influence of fishing has made it difficult to substantiate the theorized link between size and ocean warming and deoxygenation. We reconstructed the fish community and oceanographic conditions of the most recent global warm period (last interglacial; 130 to 116 thousand years before present) by using sediments from the northern Humboldt Current system off the coast of Peru, a hotspot of small pelagic fish productivity. In contrast to the present-day anchovy-dominated state, the last interglacial was characterized by considerably smaller (mesopelagic and goby-like) fishes and very low anchovy abundance. These small fish species are more difficult to harvest and are less palatable than anchovies, indicating that our rapidly warming world poses a threat to the global fish supply. Species shifts Our anthropogenically warmed climate will lead to a suite of organismal changes. To predict how some of these may occur, we can look to past warm (interglacial) periods. Salvatteci et al. used this approach and looked at a marine sediment record of the Humboldt Current system off the coast of Peru (see the Perspective by Yasuhara and Deutsch). They found that previous warm periods were dominated by small, goby-like fishes, whereas this ecosystem currently is dominated by anchovy-like fishes. Such a shift is not only relevant to ecosystem shifts but also to fisheries because anchovies are heavily fished as a food source and gobies are much less palatable than anchovies.

Extreme periods of global warming in Earth's history have been strongly associated with declining oxygen concentrations in the oceans, a scenario not unlike the evolution observed in the oceans in recent times. One of the most intense Phanerozoic deoxygenation events (so called Ocean Anoxic Events (OAE)) is the late Cretaceous OAE2 approximately 94 Ma ago. Although several studies have investigated the evolution of redox sensitive geochemical proxies during the OAE2 event, geochemical records that span the time period leading up to OAE2, in particular for molybdenum (Mo) and its isotopes are rare. Here, we investigate Mo cycling in the Tarfaya upwelling system in the Cretaceous proto-North Atlantic Ocean before and during OAE 2 throughout a 5 Ma record. The observed changes in sedimentary Mo isotope compositions can be explained by a mode of Mo cycling similar to that in modern oxygen minimum zones. Based on this interpretation we estimate the pre-OAE2 Mo isotope composition of seawater to be 1.6‰ indicating that late Cretaceous pre-OAE2 seawater had a lighter Mo isotope composition than the modern ocean. We suggest that Mo burial in oxic sediments was likely diminished under conditions of globally reduced oxygen concentrations. This allows us to model the Mo isotope composition of late Cretaceous pre-OAE2 seawater without lowering of the seawater Mo inventory (e.g., −55% oxic sink, + 40% anoxic sink). Previous estimations of the Mo seawater isotope composition during OAE2 are close to the signal observed pre-OAE here. The Mo isotope variation associated with the onset of OAE2 is therefore small, which is unexpected because strong expansion of anoxic sedimentation in OAE2 is indicated by e.g. sulfur isotopes. A further decrease of Mn burial rates in the open ocean during OAE2 could “buffer” the Mo seawater isotope signal during OAE2, to account for the small offset. Our findings emphasize that changes to the relative size of not only the anoxic sink but also the oxic sink are important considerations when interpreting paleo-Mo isotope data.

During the last glacial interval, marine sediments recorded reduced current ventilation within the ocean interior below water depths of approximately >1,500 m [B. A. Hoogakker et al., Nat. Geosci. 8, 40–43 (2015)]. The degree of the associated oxygen depletion in the different ocean basins, however, is still poorly constrained. Here, we present sedimentary records of redox-sensitive metals from the southwest African margin. These records show evidence of continuous bottom water anoxia in the eastern South Atlantic during the last glaciation that led to enhanced carbon burial over a prolonged period of time. Our geochemical data indicate that upwelling-related productivity and the associated oxygen minimum zone in the eastern South Atlantic shifted far seaward during the last glacial period and only slowly retreated during deglaciation times. While increased productivity during the last ice age may have contributed to oxygen depletion in bottom waters, especially on the upper slope, slow-down of the Late Quaternary deep water circulation pattern [Rutberg et al., Nature 405, 935–938 (2000)] appears to be the ultimate driver of anoxic conditions in deep waters.

Enrichments of highly reactive iron (Fe) (sum of Fe (oxyhydr)oxide, carbonate and sulfide minerals) in marine sediments and sedimentary rocks are commonly interpreted as an indication of anoxic conditions in the bottom water at the time of deposition. The model system for this proxy rationale is the semi-restricted Black Sea, where sediments underneath the anoxic and sulfidic (i.e., euxinic) deep-water are enriched in reactive Fe, which was mobilized from the surrounding shelf areas. To test whether such a shelf-to-basin Fe shuttle can operate in semi-restricted basins without euxinic deep water, we investigated sedimentary Fe speciation and Fe isotope compositions in sediments of the Guaymas Basin, Gulf of California. Sediments on the slope underneath the eastern equatorial Pacific oxygen minimum zone and sediments within the oxic deep basin are both enriched in reactive Fe, with reactive Fe making up 45 ± 11 % of the total Fe pool. The following mechanisms may contribute to these Fe enrichments: (1) Release of dissolved Fe from anoxic shelf and slope sediments followed by lateral transport of dissolved and/or particulate Fe in the water column; (2) preferential transport of fine-grained, terrigenous particles with a high reactive Fe content into the basin; (3) microbially mediated conversion of non-reactive silicate minerals to reactive Fe minerals during transport; (4) hydrothermal venting and lateral Fe transport within the deep water. The first process can explain reactive Fe enrichments in slope sediments, whereas all processes may contribute to sedimentary Fe enrichments in the deeper basin. The δ 56 Fe value of sediments increases from shelf to slope and decreases from the slope into the basin. This lateral pattern of δ 56 Fe, as well as the pattern of Fe enrichment, is similar to that observed in other marine systems with a Fe shuttle. However, the size of the Fe enrichment, and the range in δ 56 Fe (-0.06 to +0.16‰) is smaller. This difference is due to higher terrigenous sedimentation rates in the Guaymas Basin and, therefore, more intense dilution of shuttle-derived reactive Fe. We argue that, depending on the extent of bathymetric restriction and terrigenous background sedimentation, reactive Fe enrichments can form under a broad range of redox conditions and in diverse sedimentary environments. The concepts applied in this study can be used to identify those circumstances in the paleo-record.

Chromium (Cr) isotope fractionation is sensitive to redox changes and the Cr isotopic composition (δ 53 Cr) of sedimentary rocks has been used to reconstruct marine redox conditions and atmospheric oxygenation in the past. However, little is known about the behaviour of chromium isotopes across modern marine redox boundaries. We investigated Cr concentrations and δ 53 Cr variations in seawater and sediment across the Peruvian oxygen minimum zone (OMZ) to provide a better understanding of Cr cycling in the ocean. We found that seawater δ 53 Cr values ranged from 0.02 ± 0.16‰ to 0.59 ± 0.11‰ (2SD) and sediment values from 0.31 ± 0.07 to 0.92 ± 0.12‰. Neither Cr concentrations nor δ 53 Cr values in the water column revealed significant shifts across the oxic-anoxic boundaries. Instead, processes that operate at a local scale, such as Cr scavenging by Fe-rich particles and Cr release from reducing sediments, are identified as the main controls on Cr concentrations and isotope compositions in the water column. The δ 53 Cr values of sediments deposited in permanently anoxic waters (0.77 ± 0.19‰, n = 5) are significantly different from the δ 53 Cr values of sediments deposited in oxic bottom waters (0.46 ± 0.19‰, n = 4). This suggests that sediment Cr concentrations and δ 53 Cr values are to some extent influenced by water column redox (e.g. reductive dissolution and transport of Fe oxides) and/or early diagenetic (e.g. redistribution of Cr during phosphogenesis) processes as well as biologic activity. Our data demonstrate that local scale water column redox gradients and sediment exchange can lead to a large range of δ 53 Cr values in sediments, comparable to the range found in the entire geologic record to date. Given the increasing prominence of Cr isotope measurements in constraining atmospheric oxygenation in deep time, we argue that the processes influencing Cr cycling under different conditions and from the water column to the sediment need to be better resolved to verify the utility of such measurements as paleoenvironmental proxies.

Marine sediments are an important source and sink of bio-essential trace metals to the ocean. However, the different mechanisms leading to trace metal release or burial are not fully understood and the associated fluxes are not well quantified. Here, we present sediment, pore water , sequential extraction and benthic flux data of Mn, Co, Ni, Cu, Zn and Cd along a latitudinal depth transect across the Peruvian oxygen minimum zone at 12°S. Sediments are depleted in Mn and Co compared to the lithogenic background. Diffusive Mn fluxes from the sediments into the bottom water (−26 to −550 μmol m −2 y−1) are largely consistent with the rate of Mn loss from the solid phase (−100 to −1160 μmol m−2 yr−1 ) suggesting that 50% or more of the sedimentary Mn depletion is attributed to benthic efflux . In contrast, benthic Co fluxes (~ −3 μmol m −2 yr−1) are lower than the rate of Co loss from the solid phase (up to −120 μmol m−2 yr−1 ), implying Co dissolution in the water column. The trace metals Ni, Cu, Zn and Cd are enriched within the sediments with respect to the lithogenic background. Uptake of Ni by phytoplankton in the photic zone and delivery with organic matter to the sediment surface can account for up to 100% of the excess Ni accumulation (87 to 180 μmol m −2 y−1 ) in shelf sediments near the coast, whereas at greater water depth additional scavenging by Mn- and Fe-oxides may contribute to Ni accumulation. Up to 20% of excess Cu (33 to 590 μmol m −2 y−1) and generally less than 20% of excess Zn (58 to 2170 μmol m−2 y−1) and Cd (6 to 260 μmol m−2 y−1 ) can be explained by delivery with fresh organic matter. Sequential extraction data suggest that the discrepancies between the known sources of Cd (and Cu) and their excess accumulation may be driven by the delivery of allochthonous sulphide minerals precipitated from the water column. Additionally, Cu may be scavenged by downward sinking organic material. In contrast, precipitation of Zn sulphide chiefly takes place in the sediment. Diffusive Zn fluxes into the sediment (21 to 1990 μmol m −2 y−1 ) match the excess Zn accumulation suggesting that Zn delivery is mediated by molecular diffusion from bottom waters. Considering the diverse behavioural pattern of trace metals observed in this study, we argue that declining oxygen and increasing hydrogen sulphide concentrations in a future ocean will modify trace metal fluxes at the seafloor and the trace metal stoichiometry of seawater .

Iron is a key micronutrient controlling phytoplankton growth in vast regions of the global ocean. Despite its importance, uncertainties remain high regarding external iron source fluxes and interna...

Highlights • Geochemical analyses highlight multiple diagenesis processes occurring in the sediment. • Intense methane seepages and organic matter degradation contribute to the sulfate reduction. • Chemical of dissolved and mineral iron species indicate that iron is associated with clay minerals. • In response to seawater intrusion, ion exchange, dissolution and reverse weathering reactions change the composition of clay constituting the sediment. Abstract Pore water and sediment geochemistry in the western Black Sea were investigated on long Calypso piston core samples. Using this type of coring device facilitates the recovery of the thick sediment record necessary to analyze transport-reaction processes in response to the postglacial sea-level rise and intrusion of Mediterranean salt water 9 ka ago, and thus, to better characterize key biogeochemical processes and process changes in response to the shift from lacustrine to marine bottom water composition. Complementary data indicate that organic matter degradation occurs in the upper 15 m of the sediment column. However, sulfate reduction coupled with Anaerobic Methane Oxidation (AOM) is the dominant electron-accepting process and characterized by a shallow Sulfate Methane Transition Zone (SMTZ). Net silica dissolution, total alkalinity (TA) maxima and carbonate peaks are found at shallow depths. Pore water profiles clearly show the uptake of K+, Mg2+ and Na + by, and release of Ca2+ and Sr2+ from the heterogeneous lacustrine sediments, which is likely controlled by chemical reactions of silicate minerals and changes in clay mineral composition. Iron (Fe2+) and manganese (Mn2+) maxima largely coincide with Ca2+ peaks and suggest a close link between Fe2+, Mn2+ and Ca2+ release. We hypothesize that the Fe2+ maxima below the SMTZ result from deep Fe3+ reduction linked to organic matter degradation, either driven by DOC escaping from the shallow sulfate reduction zone or slow degradation of recalcitrant POC. The chemical analysis of dissolved and solid iron species indicates that iron is essentially associated with clay minerals, which suggests that microbial iron reduction is influenced by clay mineral composition and bioavailability of clay mineral-bound Fe(III). Overall, our study suggests that postglacial seawater intrusion plays a major role in shaping redox zonation and geochemical profiles in the lacustrine sediments of the Late Quaternary.

R/V Alkor Cruise AL543 was planned as a six-day cruise with a program of water column and sediment sampling in Kiel Bight and the western Baltic Sea. Due to restrictions related to the Covid-19 pandemic, the original plan had to be changed and the cruise was realized as six oneday cruises with sampling in Kiel Bight exclusively. The first day was dedicated to water column and sediment sampling for radionuclide analyses at Boknis Eck and Mittelgrund in Eckernförde Bay. On the remaining five days, water column, bottom water, sediment and pore water samples were collected at eleven stations covering different types of seafloor environment (grain size, redox conditions) in western Kiel Bight. The data and samples obtained on cruise AL543 will be used to investigate (i) the sedimentary cycling of bio-essential metals (e.g., nickel, zinc, and their isotopes) as a function of variable redox conditions, (ii) the impact of submarine groundwater discharge and diffusive benthic fluxes on the distribution of radium and radon as well as greenhouse gases (methane and nitrous oxide) in the water column, and (iii) to characterize and quantify the impact of coastal erosion on sedimentary iron, phosphorus and rare earth element cycling in Kiel Bight.

Highlights • next to organic matter degradation, bioirrigation and bottom water percolation through permeable surface sediments enhances benthic TPO43- and Fe2+ release • changes in bottom water oxygenation induce slight changes benthic TPO43- and Fe2+ release rates measured in 2011 and 2014 • deoxygenation experiments imply enhanced TPO43- and Fe2+ release at ongoing deoxygenation in the Mauritanian OMZ Abstract Benthic fluxes of total dissolved phosphate (TPO43-), dissolved iron (Fe2+), and dissolved inorganic carbon (DIC) were determined in situ using benthic chambers at nine stations along a depth transect between 47 and 1108 m water depth at 18 °N off Mauritania (NW Africa) during the upwelling season in 2014 (RV Meteor cruise M107). Bottom water oxygen (O2) concentrations were always ≥ 25 µM, and all fluxes (TPO43-, Fe2+, DIC) were consistently directed from the sediments into the bottom water. The highest benthic TPO43- release of 0.2 ± 0.07 mmol m2 d-1 was found at 47 m water depth (50 µM O2). The highest diffusive Fe2+ flux of 0.03 mmol m2 d-1, determined from porewater Fe2+ concentrations, occurred at 67 m water depth (27 µM O2). This was much lower than the detrital Fe supply as indicated by constant Fe/Al ratios along the depth transect. TPO43- release rates decreased concurrently with DIC flux and water depth. A difference of up to one order of magnitude between benthic chamber and diffusive TPO43- fluxes indicated that the total TPO43- release was strongly enhanced by bioirrigation. The observed fluxes were similar to those measured during an earlier cruise in 2011, generally indicating comparable release rates during both upwelling seasons. Furthermore, ex situ oxygen manipulation experiments showed an increase of the nutrient release (e.g. TPO43-, Fe2+) after seven days of anoxic bottom water conditions. The fluxes were enhanced by a factor of 1.4 for P and 7.3 for Fe compared to the measured release under natural conditions and reached values as high as those measured in the anoxic oxygen minimum zone off Peru. Our observations support the hypothesis that increasing deoxygenation of the oceans will likely enhance sedimentary TPO43- and Fe2+ release and thus contribute to a positive feedback mechanism with increasing nutrient levels and increased ocean productivity.

The sedimentary concentration and stable isotope composition of molybdenum (Mo) is widely used as a proxy for paleo redox conditions in the marine environment. However, the behavior of Mo during early diagenesis is still not fully understood, which complicates the application of the Mo proxy in ancient continental margin environments. Here, we present Mo concentrations and isotope compositions of sediment and pore water samples from the Guaymas Basin in the Gulf of California. Our sample set covers a broad range of depositional environments, including sediments from within the eastern equatorial Pacific oxygen minimum zone (OMZ), from a semi-restricted oxic graben, and from near a hydrothermal vent-field. By investigating Mo cycling in these different settings, we provide new insights into different modes of Mo fixation and the associated isotope fractionation. Sediments from the OMZ have authigenic Mo concentrations (Moauth) between 3.3 and 17.2 µg/g and δ98Mo between +1.64 and +2.13‰. A linear decrease in pore water Mo concentrations to the depth where hydrogen sulfide accumulates, along with sedimentary authigenic δ98Mo values (δ98Moauth) close to seawater, indicate diffusion of Mo from the bottom water into the sediment with little isotope fractionation during quantitative Mo removal. Sediments from the site with oxic bottom water within the basin reveal Moauth concentrations ranging from 1.2 to 14.7 µg/g and δ98Moauth signatures between –1.39 to +2.07‰. Pore water Mo concentrations are generally higher than ambient bottom water concentrations and the light δ98Mo signatures of the pore waters between +0.50 and +0.80‰ and δ98Moauth signatures of the sediments indicate continuous Mo exchange between the pore water and Mn and Fe oxides during early diagenesis. Sediment samples from the vent field mainly consist of black smoker debris and are characterized by Moauth concentrations ranging from 8.6 to 33.2 µg/g and δ98Moauth values as high as +2.20‰. The relatively high Mo concentrations and seawater-like δ98Mo can be explained by near-quantitative Mo scavenging from hydrothermal solutions with little isotope fractionation at high temperatures. Comparison of our new data for the OMZ sediments in the Gulf of California with previously published data for sediments from the Peruvian OMZ highlights that Mo isotope compositions in this kind of setting strongly depend on how Mo is delivered to the sediment. If diffusive Mo delivery from the bottom water into the sediment significantly contributes to Mo accumulation in the solid phase, as is the case in the Guaymas Basin, sedimentary Moauth concentrations are relatively low but the isotope values are close to the δ98Mo signal of seawater. If Mo is exclusively delivered by particles, like on the Peruvian shelf, much higher sedimentary Moauth concentrations can be attained. In the latter case, Moauth isotope values will be lighter because the sediments preserve the isotopic offset that was generated during adsorption or uptake of Mo by particles. Our findings de-emphasize the role of dissolved Mo speciation in pore waters but highlight the importance of the mode of Mo delivery for the Mo concentration and isotope composition preserved in the paleo-record.

Highlights • We present a 5 myr record of biogeochemical cycling in a Cretaceous upwelling area. • A novel quantitative approach for the evaluation of Fe speciation proxies was applied. • Ferruginous proxy signature reflects intense chemical weathering rather than anoxia. • Water column redox conditions evolved from oxic to nitrogenous to euxinic before OAE2. • Smaller seawater nitrate inventory facilitated sedimentary H2S release and euxinia. Abstract Oceanic Anoxic Events (OAEs) in Earth's history are regarded as analogues for current and future ocean deoxygenation, potentially providing information on its pacing and internal dynamics. In order to predict the Earth system's response to changes in greenhouse gas concentrations and radiative forcing, a sound understanding of how biogeochemical cycling differs in modern and ancient marine environments is required. Here, we report proxy records for iron (Fe), sulfur and nitrogen cycling in the Tarfaya upwelling system in the Cretaceous Proto-North Atlantic before, during and after OAE2 (∼93 Ma). We apply a novel quantitative approach to sedimentary Fe speciation, which takes into account the influence of terrigenous weathering and sedimentation as well as authigenic Fe (non-terrigenous, precipitated onsite) rain rates on Fe-based paleo-redox proxies. Generally elevated ratios of reactive Fe (i.e., bound to oxide, carbonate and sulfide minerals) to total Fe (FeHR/FeT) throughout the 5 million year record are attributed to transport-limited chemical weathering under greenhouse climate conditions. Trace metal and nitrogen isotope systematics indicate a step-wise transition from oxic to nitrogenous to euxinic conditions over several million years prior to OAE2. Taking into consideration the low terrigenous sedimentation rates in the Tarfaya Basin, we demonstrate that highly elevated FeHR/FeT from the mid-Cenomanian through OAE2 were generated with a relatively small flux of additional authigenic Fe. Evaluation of mass accumulation rates of reactive Fe in conjunction with the extent of pyritization of reactive Fe reveals that authigenic Fe and sulfide precipitation rates in the Tarfaya Basin were similar to those in modern upwelling systems. Because of a smaller seawater nitrate inventory, however, chemolithoautotrophic sulfide oxidation with nitrate was less efficient in preventing hydrogen sulfide release into the water column. As terrigenous weathering and sediment flux determine how much authigenic Fe is required to generate an anoxic euxinic or ferruginous proxy signature, we emphasize that both have to be taken into account when interpreting Fe-based paleo-redox proxies.

Periodic changes in sediment composition are usually ascribed to insolation forcing controlled by Earth’s orbital parameters. During the Cretaceous Thermal Maximum at 97–91 Myr ago (Ma), a 37–50-kyr-long cycle that is generally believed to reflect obliquity forcing dominates the sediment record. Here, we use a numerical ocean model to show that a cycle of this length can be generated by marine biogeochemical processes without applying orbital forcing. According to our model, the restricted proto-North Atlantic and Tethys basins were poorly ventilated and oscillated between iron-rich and sulfidic (euxinic) states. The Panthalassa Basin was fertilized by dissolved iron originating from the proto-North Atlantic. Hence, it was less oxygenated while the proto-North Atlantic was in an iron-rich state and better oxygenated during euxinic periods in the proto-North Atlantic. This redox see-saw was strong enough to create significant changes in atmospheric $$p_{\mathrm {CO}_2}$$ . We conclude that most of the variability in the mid-Cretaceous ocean–atmosphere system can be ascribed to the internal redox see-saw and its response to external orbital forcing. An internal redox see-saw between the Panthalassa Basin and the proto-North Atlantic can explain cyclic changes in the sediment record throughout the Cretaceous Thermal Maximum 97 to 91 million years ago, according to simulations with a numerical ocean model.

Highlights • Amazon shelf sediments take up seawater potassium (K) due to reverse weathering. • Amazon shelf sediments release terrigenous phosphorus (P) during resuspension. • Updated estimates of sedimentary K uptake and P release on Amazon shelf are presented. • Sedimentary K uptake on Amazon shelf corresponds to 13% of global riverine K input. • Sedimentary P release is ~5 times higher than dissolved P discharge of Amazon River. Abstract In this study, we identify and quantify processes that lead to sedimentary potassium (K) sequestration and phosphorus (P) release on the Amazon shelf. To this end, seven short sediment cores were recovered from the Amazon shelf during R/V Meteor cruise M147. All of the sediment cores investigated in this study are characterized by elevated K to aluminum (Al) ratios compared to Amazon riverine suspended matter, which indicates that seawater K+ is incorporated into the solid phase on the entire Amazon shelf. Pore water silica (Si) profiles are characterized by irregularly increasing concentrations and plateaus, thus, deviating from the asymptotic shape that is typically found in continental margin sediments. At one site, a dissolved Si plateau coincides with a K+ minimum suggesting that these solutes are incorporated into authigenic minerals, a process referred to as reverse weathering. Previous flux estimates for elements that participate in reverse weathering on the Amazon shelf were derived from pore water diffusive fluxes, reaction rates estimated from sediment incubations and solid phase extractions. In this study, we took an alternative approach, which is based on the concentration difference between shelf sediments and river suspended particles. The resulting K flux due to reverse weathering of 1.7 ∙ 1011 mol yr−1 is in agreement with previous estimates and corresponds to 13% of the global riverine dissolved K+ input. Previous studies demonstrated that Amazon riverine particulate P is partly solubilized on the Amazon shelf. However, these results are exclusively based on sediment data close to the river mouth and no distinction between terrestrial and marine sediment components was made. Here, we quantify P release from Amazon shelf sediments by comparing terrestrial P concentrations in shelf sediments with P concentrations in river suspended particles. The resulting solubilized P flux of 2.2 ∙ 1010 mol yr−1 is about five to six times higher than previous estimates and about seven times the Amazon riverine dissolved P discharge. The magnitudes of the presented fluxes imply that the alteration of riverine shelf sediments significantly affects the mean concentrations of dissolved K+ and P in the global ocean.

Highlights • Lusi crater waters represent a regional geochemical anomaly. • Erupted waters are the result of a complex mix of sedimentary and hydrothermal fluids. • Lusi is not a typical mud volcano but a sediment-hosted hydrothermal system. • The neighbouring volcanic complex feeds hydrothermal fluids for the Lusi eruption. Abstract The spectacular Lusi mud-eruption started in northeast Java the 29th of May 2006. Despite extensive research, the origin of the erupted water remains elusive and poorly constrained. Here we present a comprehensive study of the geochemistry of Lusi waters compared with those collected from surrounding areas, all collected between 2006 and 2013, including data from mud volcanoes and volcano-hosted hydrothermal springs. Within this broad context, the geochemical characteristics of the fluids expelled in the Lusi region suggest that we can classify the waters in three groups: 1) meteoric waters expelled in cold springs and artesian wells, 2) hydrothermal waters typically mixed with meteoric waters, and 3) formation water from marine sediments altered by diagenetic processes such as clay-mineral dehydration. Samples collected from the Lusi crater are Cl and Na dominated (up to 527 mM and 471.7 mM, respectively) similar to seawater indicating that altered sedimentary formation waters are predominant in this system. In addition they are enriched in Sr (up to 808.4 μM) and other elements commonly associated with hydrothermal systems, such as Li (up to 877.6 μM compared to 26 μM in seawater). Some of these elements are up to ten times enriched compared to seawater values. High-temperature fluid mineral interactions in the subsurface appear to have facilitated the transfer of Li and other mobile elements into the fluids. High temperature fluid-mineral interaction reactions are also supported by Si concentrations significantly higher compared to other sampled mud volcanoes in the island. Crater samples also show the highest δ18O values (+5‰ after correction for evaporation compared to +1‰ at the MV localities). 87Sr/86Sr ratios vary between of 0.7077 and 0.7083 and seem to reflect a general mixture of fluids from clay-mineral dehydration, carbonate recrystallization, alteration of volcanic rocks and hydrothermal imprint. Eight years of geochemical monitoring indicate that the composition of the deep-sourced Lusi fluids remain fairly constant through time. Thus our findings show that the Lusi crater waters represent a regional geochemical anomaly, and we suggest that a combination of high temperatures in the source region, and fluid-rock interactions with silicates and, possibly, carbonate-rich lithologies can explain the data. This is consistent with a model where the emitted gases migrate from a deep-seated (>4 km) source region, likely associated with the presence of hot igneous intrusions and/or high T reactions related to the presence of neighbouring active volcanoes.

Literature data on benthic dissolved iron (DFe) fluxes (µmol m−2 d−1), bottom water oxygen concentrations (O2BW, μM), and sedimentary carbon oxidation rates (COX, mmol m−2 d−1) from water depths ranging from 80 to 3700 m were assembled. The data were analyzed with a diagenetic iron model to derive an empirical function for predicting benthic DFe fluxes: inline image where γ (= 170 µmol m−2 d−1) is the maximum flux for sediments at steady state located away from river mouths. This simple function unifies previous observations that COX and O2BW are important controls on DFe fluxes. Upscaling predicts a global DFe flux from continental margin sediments of 109 ± 55 Gmol yr−1, of which 72 Gmol yr−1 is contributed by the shelf ( 2000 m) of 41 ± 21 Gmol yr−1 is unsupported by empirical data. Previous estimates of benthic DFe fluxes derived using global iron models are far lower (approximately 10–30 Gmol yr−1). This can be attributed to (i) inadequate treatment of the role of oxygen on benthic DFe fluxes and (ii) improper consideration of continental shelf processes due to coarse spatial resolution. Globally averaged DFe concentrations in surface waters simulated with the intermediate-complexity University of Victoria Earth System Climate Model were a factor of 2 higher with the new function. We conclude that (i) the DFe flux from marginal sediments has been underestimated in the marine iron cycle and (ii) iron scavenging in the water column is more intense than currently presumed.

Clones of Norway spruce (Picea abies L.) were grown for several years on an altitudinal gradient (1750 m, 1150 m and 800 m above sea level) to study the effects of environmental × genetic interactions on growth and foliar metabolites (protein, pigments, antioxidants). Clones at the tree line showed 4.3-fold lower growth rates and contained 60% less chlorophyll (per gram of dry matter) than those at valley level. The extent of growth reduction was clone-dependent. The mortality of the clones was low and not altitude-dependent. At valley level, but not at high altitude, needles of mature spruce trees showed lower pigment and protein concentrations than clones. In general, antioxidative systems in needles of the mature trees and young clones did not increase with increasing altitude. Needles of all trees at high altitude showed higher concentrations of dehydroascorbate than at lower altitudes, indicating higher oxidative stress. In one clone, previously identified as sensitive to acute ozone doses, this increase was significantly higher and the growth reduction was stronger than in the other genotypes. This clone also displayed a significant reduction in glutathione reductase activity at high altitude. These results suggest that induction of antioxidative systems is apparently not a general prerequisite to cope with altitude in clones whose mother plants originated from higher altitudes (about 650-1100 m above sea level, Hercycnic-Carpathian distribution area), but that the genetic constitution for maintenance of high antioxidative protection is important for stress compensation at the tree line.

We present iron (Fe) concentration and Fe isotope data for a sediment core transect across the Peru upwelling area, which hosts one of the ocean’s most pronounced oxygen minimum zones (OMZs). The lateral progression of total Fe to aluminum ratios (FeT/Al) across the continental margin indicates that sediments within the OMZ are depleted in Fe whereas sediments below the OMZ are enriched in Fe relative to the lithogenic background. Rates of Fe loss within the OMZ, as inferred from FeT/Al ratios and sedimentation rates, are in agreement with benthic flux data that were calculated from pore water concentration gradients. The mass of Fe lost from sediments within the OMZ is within the same order of magnitude as the mass of Fe accumulating below the OMZ. Taken together, our data are in agreement with a shuttle scenario where Fe is reductively remobilized from sediments within the OMZ, laterally transported within the anoxic water column and re-precipitated within the more oxic water below the OMZ. Sediments within the OMZ have increased 56Fe/54Fe isotope ratios relative to the lithogenic background, which is consistent with the general notion of benthic release of dissolved Fe with a relatively low 56Fe/54Fe isotope ratio. The Fe isotope ratios increase across the margin and the highest values coincide with the greatest Fe enrichment in sediments below the OMZ. The apparent mismatch in isotope composition between the Fe that is released within the OMZ and Fe that is re-precipitated below the OMZ implies that only a fraction of the sediment-derived Fe is retained near-shore whereas another fraction is transported further offshore. We suggest that a similar open-marine shuttle is likely to operate along many ocean margins. The observed sedimentary fingerprint of the open-marine Fe shuttle differs from a related transport mechanism in isolated euxinic basins (e.g., the Black Sea) where the laterally supplied, reactive Fe is quantitatively captured within the basin sediments. We suggest that our findings are useful to identify OMZ-type Fe cycling in the geological record.

Iodine and its radioisotope 129I have been successfully used to trace the origin of pore waters in submarine fluid escape structures because of their close association with organic material in deeply buried sediments. We report here halogen concentrations and 129I/I ratios for fluids of five mud volcanoes sampled along an E–W transect across the Gulf of Cadiz in the NE Atlantic Ocean. Concentrations of iodide and bromide increase consistently seaward accompanied by a decrease in 129I/I ratios from 6490 × 10− 15 to 663 × 10− 15. The exceptionally high 129I/I ratios at the near-shore locations reflect the presence of fissiogenic 129I, produced in situ by spontaneous fission of 238U within terrigenous sediments and released into pore water during clay mineral diagenetic processes. The observed 129I/I and halogen trends, together with similar changes in 87Sr/86Sr ratios, indicate a progressive seaward transition from inorganic-terrigenous to organic-marine fluid sources. Comparison of our results with literature data for varying geological settings reveals a general relationship between fissiogenic 129I, radiogenic 87Sr and the lithology or provenance of rocks and sediments, respectively. While 129I/I ratios in continental rock-hosted aquifers and terrigenous sedimentary systems are dominated by in situ production of fissiogenic 129I, iodine isotopes in oceanic settings or volcanogenic marine sediments reflect the release of ‘old’ iodine from deeply buried organic matter. The Gulf of Cadiz represents the full transition between these continental and oceanic 129I/I and 87Sr/86Sr end members. This is the first systematic investigation of fissiogenic 129I production in marine sedimentary environments.

In the oceans’ high-nitrate–low-chlorophyll regions, such as the Peru/Humboldt Current system and the adjacent eastern equatorial Pacific1, primary productivity is limited by the micronutrient iron. Within the Peruvian upwelling area, bioavailable iron is released from the reducing continental margin sediments2. The magnitude of this seafloor source could change with fluctuations in the extension or intensity of the oxygen minimum zones3, 4. Here we show that measurements of molybdenum, uranium and iron concentrations can be used as a proxy for sedimentary iron release, and use this proxy to assess iron release from the sea floor beneath the Peru upwelling system during the past 140,000 years. We observe a coupling between levels of denitrification, as indicated by nitrogen isotopes, trace metal proxies for oxygenation, and sedimentary iron concentrations. Specifically, periods with poor upper ocean oxygenation are characterized by more efficient iron retention in the sediment and a diminished iron supply to the water column. We attribute efficient iron retention under more reducing conditions to widespread sulphidic conditions in the surface sediment and concomitant precipitation of iron sulphides. We argue that iron release from continental margin sediments is most effective in a narrow redox window where neither oxygen nor sulphide is present. We therefore suggest that future deoxygenation in the Peru upwelling area would be unlikely to result in increased iron availability, whereas in weaker oxygen minimum zones partial deoxygenation may enhance the iron supply.

Benthic fluxes of dissolved ferrous iron (Fe2+) and phosphate (TPO4) were quantified by in situ benthic chamber incubations and pore-water profiles along a depth transect (11°S, 80–1000 m) across the Peruvian oxygen minimum zone (OMZ). Bottom-water O2 levels were < 2 µmol L-1 down to 500-m water depth, and increased to ~40 µmol L-1 at 1000 m. Fe2+ fluxes were highest on the shallow shelf (maximum 316 mmol m-2 yr-1), moderate (15.4 mmol m-2 yr-1) between 250 m and 600 m, and negligible at deeper stations. In the persistent OMZ core, continuous reduction of Fe oxyhydroxides results in depletion of sedimentary Fe :Al ratios. TPO4 fluxes were high (maximum 292 mmol m-2 yr-1) throughout the shelf and the OMZ core in association with high organic carbon degradation rates. Ratios between organic carbon degradation and TPO4 flux indicate excess release of P over C when compared to Redfield stoichiometry. Most likely, this is caused by preferential P release from organic matter, dissolution of fish debris, and/or P release from microbial mat communities, while Fe oxyhydroxides can only be inferred as a major P source on the shallow shelf. The benthic fluxes presented here are among the highest reported from similar, oxygen-depleted environments and highlight the importance of sediments underlying anoxic water bodies as nutrient sources to the ocean. The shelf is particularly important as the periodic passage of coastal trapped waves and associated bottom-water oxygenation events can be expected to induce a transient biogeochemical environment with highly variable release of Fe2+ and TPO4.

Lithium concentration and isotope data (δ7Li) are reported for pore fluids from 18 cold seep locations together with reference fluids from shallow marine environments, a sediment-hosted hydrothermal system and two Mediterranean brine basins. The new reference data and literature data of hydrothermal fluids and pore fluids from the Ocean Drilling Program follow an empirical relationship between Li concentration and δ7Li (δ7Li = −6.0(±0.3) · ln[Li] + 51(±1.2)) reflecting Li release from sediment or rocks and/or uptake of Li during mineral authigenesis. Cold seep fluids display δ7Li values between +7.5‰ and +45.7‰, mostly in agreement with this general relationship. Ubiquitous diagenetic signals of clay dehydration in all cold seep fluids indicate that authigenic smectite–illite is the major sink for light pore water Li in deeply buried continental margin sediments. Deviations from the general relationship are attributed to the varying provenance and composition of sediments or to transport-related fractionation trends. Pore fluids on passive margins receive disproportionally high amounts of Li from intensely weathered and transported terrigenous matter. By contrast, on convergent margins and in other settings with strong volcanogenic input, Li concentrations in pore water are lower because of intense Li uptake by alteration minerals and, most notably, adsorption of Li onto smectite. The latter process is not accompanied by isotope fractionation, as revealed from a separate study on shallow sediments. A numerical transport-reaction model was applied to simulate Li isotope fractionation during upwelling of pore fluids. It is demonstrated that slow pore water advection (order of mm a−1) suffices to convey much of the deep-seated diagenetic Li signal into shallow sediments. If carefully applied, Li isotope systematics may, thus, provide a valuable record of fluid/mineral interaction that has been inherited several hundreds or thousands of meters below the actual seafloor fluid escape structure.

Widespread mud volcanism across the thick ( 7000 between sites. Mixing of shallow biogenic and deep thermogenic gases cannot account for the observed compositions which instead result mainly from extensive migration of thermogenic gases in the deeply-buried sediments, possibly associated with biodegradation of C2+ homologues and secondary methane production at Captain Arutyunov and Carlos Ribeiro MVs. At the deep-water Bonjardim, Olenin and Carlos Ribeiro MVs, generation of C2+-enriched gases is probably promoted by high heat flux anomalies which have been measured in the western area of the wedge. At Porto MV, gases are highly enriched in CH4 having delta C-13-CH4 similar to -50 parts per thousand, as at most sites, but markedly lower delta H-2-CH4 Values < -250 parts per thousand, suggesting that it is not generated by thermal cracking of n-alkanes but rather that it has a deep Archaeal origin. The presence of petroleum-type hydrocarbons is consistent with a thermogenic origin, and at sites where CH4 is predominant support the suggestion that gases have experienced extensive transport during which they mobilized oil from sediments similar to 2-4 km deep. These fluids then migrate into shallower, thermally immature muds, driving their mobilization and extrusion at the seafloor. At Porto MV, the limited presence of petroleum in mud breccia sediments further supports the hypothesis of a predominantly deep microbial origin of CH4. (C) 2009 Elsevier B.V. All rights reserved.

The chemical and isotopic composition of pore fluids is presented for five deep-rooted mud volcanoes aligned on a transect across the Gulf of Cadiz continental margin at water depths between 350 and 3860 m. Generally decreasing interstitial Li concentrations and Sr-87/Sr-86 ratios with increasing distance from shore are attributed to systematically changing fluid sources across the continental margin. Although highest Li concentrations at the near-shore mud volcanoes coincide with high salinities derived from dissolution of halite and late-stage evaporites, clayey, terrigenous sediments are identified as the ultimate Li source to all pore fluids investigated. Light delta Li-7 values, partly close to those of hydrothermal vent fluids (delta Li-7: +11.9 parts per thousand), indicate that Li has been mobilized during high-temperature fluid/sediment or fluid/rock interactions in the deep sub-surface. Intense leaching of terrigenous clay has led to radiogenic Sr-87/Sr-86 ratios (similar to 0.7106) in pore fluids of the near-shore mud volcanoes. In contrast, non-radiogenic Sr-87/Sr-86 ratios (similar to 0.7075) at the distal locations are attributed to admixing of a basement-derived fluid component, carrying an isotopic signature from interaction with the basaltic crust. This inference is substantiated by temperature constraints from Li isotope equilibrium calculations suggesting exchange processes at particularly high temperatures (>200 degrees C) for the least radiogenic pore fluids of the most distal location.Advective pore fluids in the off-shore reaches of the Gulf of Cadiz are influenced by successive exchange processes with both oceanic crust and terrigenous, fine-grained sediments, resulting in a chemical and isotopic signature similar to that of fluids in near-shore ridge flank hydrothermal systems. This suggests that deep-rooted mud volcanoes in the Gulf of Cadiz represent a fluid pathway intermediate between mid-ocean ridge hydrothermal vent and shallow, marginal cold seep. Due to the thicker sediment coverage and slower fluid advection rates, the overall geochemical signature is shifted towards the sediment-diagenetic signal compared to ridge flank hydrothermal environments. (C) 2009 Elsevier Ltd. All rights reserved.

Highlights • A biogeochemical baseline of sediment geochemistry at potential offshore CCS sites. • Diagnostic indicators of CO2 leakage based on stoichiometry of porewater chemistry. • Porewater chemistry is modified by reverse weathering processes at Goldeneye site. Abstract Injection of carbon dioxide (CO2) into subseafloor reservoirs is gaining traction as a strategy for mitigating anthropogenic CO2 emissions to the atmosphere. Yet, potential leakage, migration and dissolution of externally-supplied CO2 from such reservoirs are a cause for concern. The potential impact of CO2 leakage on the biogeochemistry of sediments and overlying waters in the North Sea was studied during a controlled subsurface CO2 release experiment in 2019 at a potential carbon capture and storage site (Goldeneye). This study describes the natural (unperturbed) biogeochemistry of sediments. They are classified as muddy sand to sandy mud with low organic carbon content (∼0.6 %). Distributions of dissolved inorganic carbon (DIC) and total alkalinity (TA) in sediment porewaters are reported in addition to in situ benthic fluxes of dissolved nutrients and oxygen between the sediments and the overlying water. Oxygen fluxes into the sediment, measured using benthic chambers and eddy covariance, were 6.18 ± 0.58 and 5.73 ± 2.03 mmol m−2 d-1, respectively. Diagnostic indicators are discussed that could be used to detect CO2 enrichment of sediments due to reservoir leakage at CCS sites. These include the ratio TA and ammonium to sulfate in sediment porewaters, benthic fluxes and chloride-normalized cation distributions. These indicators currently suggest that the organic carbon at Goldeneye has an oxidation state below zero and is mainly degraded via sulfate reduction. Carbonate precipitation is apparently negligible, whereas decreases in Mg2+ and K+ point toward ongoing alteration of lithogenic sediments by reverse weathering processes.