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Association of organic carbon (OC) with reactive iron (FeR) represents an important mechanism by which OC is protected against remineralisation in soils and marine sediments. Recent studies indicate that the molecular structure of organic compounds and/or the identity of associated FeR phases exert a control on the ability of an OC–FeR complex to be extracted by the citrate–bicarbonate–dithionite (CBD) method. However, many variations of the CBD extraction are used, and these are often uncalibrated to each other, rendering comparisons of OC–FeR values extracted via the different methods impossible. Here, we created synthetic ferrihydrite samples coprecipitated with simple organic structures and subjected these to modifications of the most common CBD method. We altered some of the method parameters (reagent concentration, time of the extraction and sample preparation methods) and measured FeR recovery to determine which (if any) modifications affected the release of FeR from the synthetic sample. We provide an assessment of the reducing capacity of Na dithionite in the CBD method (the amount of Fe reduced by a fixed amount of dithionite) and find that the concentration of dithionite deployed can limit OC–FeR extractability for sediments with a high FeR content. Additionally, we show that extending the length of any CBD extraction offers no benefit in removing FeR. Moreover, we demonstrate that for synthetic OC–FeR samples dominated by ferrihydrite, freeze-drying samples can significantly reduce OC–FeR extractability; this appears to be less of an issue for natural marine sediments where natural ageing mechanisms may mimic the freeze-drying process for more stable Fe phases. While our study is not an all-inclusive method comparison and is not aimed at delivering the “perfect” extraction setup, our findings provide a collected summary of critical factors which influence the efficiency of the CBD extraction for OC–FeR. As such, we provide a platform from which OC–FeR values obtained under different methods can be interpreted and future studies of sediment carbon cycling can build upon.

Muds deposited in large-scale epicontinental seaways provide deep insights into palaeoclimates, biogeochemical cycles, sedimentation processes, and organic carbon burial during exceptionally warm periods throughout the Phanerozoic. Temporal changes can be monitored at single locations but the key, larger-scale oceanographical and related biogeochemical processes are likely to be more clearly revealed by comparisons between individual sub-basins within seaways. Here, we compare inorganic geochemical records from the Jurassic (upper Pectinatites wheatleyensis to lower Pectinatites pectinatus ammonite zones) of the Swanworth Quarry 1 Core from the Wessex Basin (Dorset, UK) to time-equivalent records from the Ebberston 87 Core in the Cleveland Basin (Yorkshire, UK), 400 km apart. Our synthesis shows that while the Dorset sediments were deposited in an energetically more dynamic setting than the Yorkshire sediments, the overarching climatic and oceanographical processes responsible for variations in organic carbon enrichment and sedimentation, were similar. Intervals of coeval organic carbon-rich sedimentation occurred in both basins, and a particulate shuttle was intermittently active in both basins. Consistent with recent climate simulations, we conclude that tropical climate conditions, associated with enhanced nutrient supply, were key drivers of sedimentation between the Jurassic Wessex and Cleveland Basins.

Pyrite oxidation in marine shales during weathering has been widely studied, however, the effects of this process on geochemical proxies commonly used to reconstruct ocean redox conditions, or the details of pyrite oxidation at the mineral grain scale, have not received much scientific attention. We conducted a four-week laboratory experiment designed to stimulate pyrite oxidation at shale outcrops, and to assess effects on the chemical phase of iron and sulphur in the samples both in bulk sediments (useful for comparison to palaeo-environmental geochemistry) and at a finer scale (to gain a better understanding of the nature of these changes). Geochemical and scanning electron microscopy (SEM) techniques provide evidence for pyrite oxidation, carbonate dissolution, and iron (oxyhydr)oxide formation during the experiment. The net effect of the experiment on the ratio of highly reactive iron phases (FeHR) to total iron (FeT) is minimal (≪0.03% difference), suggesting that this redox proxy behaves relatively conservatively during weathering. The effect of weathering on the ratio of pyrite-bound iron to highly reactive iron (FePY/FeHR), used to investigate the availability of sulphur, in contrast, is pronounced (up to 32.5% difference) due to the oxidation of pyrite and the precipitation of iron (oxyhydr)oxides in the shale samples. Electron microscopy provides evidence that iron (oxyhydr)oxides precipitated in situ as rims around cores of pyrite particles, “passivating” and protecting them from further oxidation. The quantification of these partly oxidised pyrite particles is now possible using a novel automated particle analysis method coupled to chemical mapping, developed in this study. We conclude that this method can be of wide use, both to quantify pyrite oxidation, and assess the significance of FePY/FeHR at measured in shale outcrop samples.

Burial of organic material in marine sediments represents a dominant natural mechanism of long-term carbon sequestration globally, but critical aspects of this carbon sink remain unresolved. Investigation of surface sediments led to the proposition that on average 10-20% of sedimentary organic carbon is stabilised and physically protected against microbial degradation through binding to reactive metal (e.g. iron and manganese) oxides. Here we examine the long-term efficiency of this rusty carbon sink by analysing the chemical composition of sediments and pore waters from four locations in the Barents Sea. Our findings show that the carbon-iron coupling persists below the uppermost, oxygenated sediment layer over thousands of years. We further propose that authigenic coprecipitation is not the dominant factor of the carbon-iron bounding in these Arctic shelf sediments and that a substantial fraction of the organic carbon is already bound to reactive iron prior deposition on the seafloor., Burial of organic material in marine sediments can sequester massive amounts of carbon, but the dynamics of this carbon sink are poorly understood. Here the authors investigate the so-called rusty carbon sink in Arctic shelf sediments, finding that organic carbon-iron associations are stable for 1000 s of years.

International audience; Fine-grained sedimentary successions contain the most detailed record of past environmental conditions. High-resolution analyses of these successions yield important insights into sedimentary composition and depositional processes and are, therefore, required to contextualise and interpret geochemical data which are commonly used as palaeoclimate proxies. The Kimmeridge Clay Formation (KCF) is a 500 m-thick mudstone succession deposited throughout the North Sea in the Late Jurassic and records environmental conditions through this time. Here, we present petrographic analyses (on 36 thin sections) on a 50 m section of a KCF core from the Cleveland Basin (Yorkshire, UK) to investigate controls on sedimentation in this region during the Tithonian, Late Jurassic. Facies descriptions demonstrate that deposition took place in a hydrodynamically variable environment in which the sediment origins, sediment dispersal mechanisms, and redox conditions fluctuated on the scale of thousands of years. Petrographic analyses show that the sediment comprises marine (algal macerals, calcareous fossils), detrital (quartz, clay, feldspar), and diagenetic (dolomite and authigenic kaolinite) components and that several sediment dispersal mechanisms influenced deposition and facilitated both the supply and preservation of terrestrial and marine organic material. This work provides a framework for the interpretation of geochemical palaeoclimate proxies and reinforces the importance of looking at the rock when interpreting whole-rock geochemical data.

The Arctic Ocean region is currently undergoing dramatic changes, which will likely alter the nutrient cycles that underpin Arctic marine ecosystems. Phosphate is a key limiting nutrient for marine life but gaps in our understanding of the Arctic phosphorus (P) cycle persist. In this study, we investigate the benthic burial and recycling of phosphorus using sediments and pore waters from the Eurasian Arctic margin, including the Barents Sea slope and the Yermak Plateau. Our results highlight that P is generally lost from sediments with depth during organic matter respiration. On the Yermak Plateau, remobilization of P results in a diffusive flux of P to the seafloor of between 96 and 261 µmol m −2 yr −1 . On the Barents Sea slope, diffusive fluxes of P are much larger (1736–2449 µmol m −2 yr −1 ), but these fluxes are into near-surface sediments rather than to the bottom waters. The difference in cycling on the Barents Sea slope is controlled by higher fluxes of fresh organic matter and active iron cycling. As changes in primary productivity, ocean circulation and glacial melt continue, benthic P cycling is likely to be altered with implications for P imported into the Arctic Ocean Basin. This article is part of the theme issue ‘The changing Arctic Ocean: consequences for biological communities, biogeochemical processes and ecosystem functioning’.

The Barents Sea is experiencing long-term climate-driven changes, e.g. modification in oceanographic conditions and extensive sea ice loss, which can lead to large, yet unquantified disruptions to ecosystem functioning. This key region hosts a large fraction of Arctic primary productivity. However, processes governing benthic and pelagic coupling are not mechanistically understood, limiting our ability to predict the impacts of future perturbations. We combine field observations with a reaction-transport model approach to quantify organic matter (OM) processing and disentangle its drivers. Sedimentary OM reactivity patterns show no gradients relative to sea ice extent, being mostly driven by seafloor spatial heterogeneity. Burial of high reactivity, marine-derived OM is evident at sites influenced by Atlantic Water (AW), whereas low reactivity material is linked to terrestrial inputs on the central shelf. Degradation rates are mainly driven by aerobic respiration (40–75%), being greater at sites where highly reactive material is buried. Similarly, ammonium and phosphate fluxes are greater at those sites. The present-day AW-dominated shelf might represent the future scenario for the entire Barents Sea. Our results represent a baseline systematic understanding of seafloor geochemistry, allowing us to anticipate changes that could be imposed on the pan-Arctic in the future if climate-driven perturbations persist. This article is part of the theme issue ‘The changing Arctic Ocean: consequences for biological communities, biogeochemical processes and ecosystem functioning’.

Continental margins are hot spots for iron (Fe) and manganese (Mn) cycling. In the Arctic Ocean, these depositional systems are experiencing rapid changes that could significantly impact biogeochemical cycling. In this study, we investigate whether continental margin sediments north of Svalbard represent a source or sink of Fe and Mn to the water column and how climate change might alter these biogeochemical cycles. Our results highlight that sediments on the Yermak Plateau and Sofia Basin exhibit accumulations of Fe and Mn phases compared to average shale. Conversely, sediments from the Barents Sea slope exhibit lower enrichments of Fe and Mn compared to average shale, with the exception of enriched, near‐surface sediment layers. Pore waters from these slope sites provide evidence for Fe and Mn reduction and diffusion of Fe and Mn into near surface sediments, which are susceptible to physical or biogeochemical remobilization. These regional patterns are best explained by the spatial distribution of sea ice coverage and labile organic carbon fluxes to the seafloor. As sea ice continues to retreat and the Yermak Plateau becomes seasonally ice‐free, productivity is expected to increase, which would increase the flux of carbon to the sediments, thereby increasing oxidant demand, and the reduction of Fe and Mn mineral phases. Our results suggest that as sea ice continues to retreat, the Yermak Plateau and other Arctic continental margins could become sources of Fe and Mn to Arctic bottom waters.

Calcareous and siliceous microorganisms are common components of mudrocks, and can be important in terms of stratigraphy and environmental interpretation. In addition, such microorganisms can have a significant &lsquo, after life&rsquo, through post-mortem alteration, and represent a potential source of additional information about the diagenetic and deformation history of the rock unit. Some examples of the latter are illustrated in this study from foraminifera within a Cretaceous black shale of Colombia. This includes foraminifera tests acting as understudied repositories of authigenic calcite cement, and of elements such as Ba, Zn, Fe and S through the formation of baryte, sphalerite and iron sulphides (pyrite, marcasite). Such repositories, within the body chambers of foraminiferal tests, can provide important windows into the diagenetic processes within mudstones. If calcite cement is not recognised or separated from biogenic calcite, the depositional calcite budget can be easily overestimated, skewing the application of mudrock classification schemes, and affecting environmental interpretation including that of productivity. The elements Ba, Zn and Fe (often in ratio with Al) are commonly utilised as geochemical proxies of environmental parameters (productivity, bottom water redox conditions, etc.). Therefore, the presence of significant amounts of baryte, sphalerite and pyrite-marcasite (within foraminifera) should be noted and their origins (source and timing) investigated based on their spatial relationships before making environmental deductions based on geochemical analysis alone. Additionally, commonly observed marginal shell damage of many of the observed foraminifera is reported. We interpret this damage, for the first time, as an indicator of lateral dissolution, brought about by horizontal foreshortening during orogenesis. This is also supported by the occurrence of microscale anastomosing horizontal to inclined baryte-filled fractures within the mudstone matrix.

The development and application of geochemical techniques to identify redox conditions in modern and ancient aquatic environments has intensified over recent years. Iron (Fe) speciation has emerged as one of the most widely used procedures to distinguish different redox regimes in both the water column and sediments, and is the main technique used to identify oxic, ferruginous (anoxic, Fe(II) containing) and euxinic (anoxic, sulfidic) water column conditions. However, an international sediment reference material has never been developed. This has led to concern over the consistency of results published by the many laboratories that now utilise the technique. Here, we report an interlaboratory comparison of four Fe speciation reference materials for palaeoredox analysis, which span a range of compositions and reflect deposition under different redox conditions. We provide an update of extraction techniques used in Fe speciation and assess the effects of both test portion mass, and the use of different analytical procedures, on the quantification of different Fe fractions in sedimentary rocks. While atomic absorption spectroscopy and inductively coupled plasma-optical emission spectrometry produced comparable Fe measurements for all extraction stages, the use of ferrozine consistently underestimated Fe in the extraction step targeting mixed ferrous–ferric minerals such as magnetite. We therefore suggest that the use of ferrozine is discontinued for this Fe pool. Finally, we report the combined data of four independent Fe speciation laboratories to characterise the Fe speciation composition of the reference materials. These reference materials are available to the community to provide an essential validation of in-house Fe speciation measurements. (Less)

The majority of organic carbon (OC) burial in marine sediments occurs on continental shelves, of which an estimated 10–20% is associated with reactive iron (FeR). The association of OC with FeR (OC-FeR) is thought to facilitate preservation of organic matter (OM) in sediments and therefore represents an important carbon sink. The citrate-bicarbonate-dithionite (CBD) method is used to quantify OC-FeR in marine sediments by reductively dissolving FeR, thereby releasing bound OC. While the CBD method is widely used, it may be less efficient at measuring OC-FeR than currently thought, due to the incomplete reduction of FeR, resulting from the neutral pH conditions required to prevent OM hydrolysis. Additionally, the typical range of values reported for OC-FeR in marine sediments is narrow, despite variation in OM and FeR inputs, OM source types and chemical compositions. This suggests a limitation exists on the amount of OC that can become associated with FeR, and/or that the CBD method is limited in the OC-FeR that it is able to quantify. In assessing the efficiency of the CBD method, we aimed to understand whether methodological errors or (mis)interpretation of these extraction results may contribute to the apparent limitation on OC-FeR values. Here, we synthesised OC-FeR composites with a known FeR phase and known OM moieties, varying in carboxyl content, at neutral pH. These were spiked into OC-free marine sediment, and subject to a CBD extraction to investigate i) the efficiency of CBD for OC extraction; ii) the efficiency of CBD for FeR extraction; ii) how the OC moiety affects the physical parameters of associated FeR minerals; and iii) the impact of OM moiety on OC and Fe release. We show that the CBD method results in only partial dissolution of the most susceptible FeR phase (ferrihydrite) and therefore incomplete removal of bound OC. While as little as ~20% of Fe is released from OC-free ferrihydrite, structural disorder of the mineral phase increases with the inclusion of more OC, resulting in greater losses of up to 62% Fe for carboxyl rich OC-FeR complexes. In addition, our results show that the NaCl control step performed in the CBD method is capable of removing weakly bound OC from FeR, such that inclusion of this OC in the total OC-FeR fraction may increase marine sediments OC-FeR estimates by ~33%. Finally, we suggest that the structure of OC involved in OC-FeR binding can affect quantification of the OC-FeR pool. Our results have important implications for assessing the FeR bound OC fraction in marine sediments and the fate of this OC in the global carbon cycle.

The formation of authigenic phosphate minerals in marine sediments is an important process for the burial and long-term storage of the bio-essential nutrient phosphorus (P). In this context, we report the composition of pore waters, bulk sediments, and the speciation of P in four sediment cores recovered on the continental margins off the Amazon, Rio de la Plata and Zambezi rivers. Here, pronounced sulphate-methane transitions (SMTs) occur between 4.5 and 6.5 m sediment depth where sulphate is consumed by the anaerobic oxidation of methane and free hydrogen sulphide builds up in the pore waters. This leads to the reductive dissolution of primary Fe (oxyhydr)oxides (FeOx) by hydrogen sulphide, and the subsequent liberation of FeOx-adsorbed phosphate into pore waters at the SMT. The released phosphate builds up to significant concentrations, making it available for the precipitation of authigenic minerals within and below the SMT. Using a sequential P extraction, we find consistently high contributions of carbonate fluorapatite (CFA) to the total P pool within the SMT, where it likely precipitates due to high local phosphate concentrations, high alkalinity and abundant dissolved Ca in the pore waters. PHREEQC calculations confirm these results, with highest saturation states with respect to authigenic apatite calculated at all SMTs. CFA authigenesis, however, is insufficient to completely consume pore water phosphate, leading to diffusive loss of phosphate from the SMT. While the upward decrease in phosphate above the SMT is relatively gentle, the significantly steeper phosphate gradient into underlying sediments suggests the formation of another authigenic mineral phase. Sequential P extraction and PHREEQC results clearly show that the dominant authigenic phase below the SMT is not CFA. Instead, geochemical conditions below the sulphidic zone at all four sites are favourable for the precipitation of Fe(II) phosphate minerals (e.g., vivianite). These conditions are summarized as the absence of sulphate and free hydrogen sulphide, but the presence of Fe2+ and phosphate in pore waters, and low calcium carbonate contents in the sediment. While we did not directly detect or quantify Fe(II) phosphate minerals, Fe-bound P clearly increases in the sediments below the sulphidic zones at all studied sites, and this is where highest pore water saturation states with respect to vivianite are calculated with PHREEQC. In addition, geochemical inverse models performed in PHREEQC show that vivianite formation is an important geochemical process controlling the observed patterns of dissolved P and Fe, pH and redox potential of the pore waters analysed below the SMT. We therefore argue that Fe(II) phosphate minerals are formed in these ocean margin sediments on a large scale, and pore water and sediment data indicate that this Fe-bound P largely originates from FeOx-adsorbed phosphate liberated within the sulphidic SMT. This study suggests that under specific but not unusual depositional conditions, SMTs are hotspots for biogeochemical P cycling in marginal marine sediments worldwide, with CFA precipitating within the SMT, and Fe(II) phosphates forming below it. It also adds to the growing evidence that Fe(II) phosphates may contribute significantly to the long-term burial of reactive P phases in Fe-rich, methanic marine sediments, and thus act as a previously underestimated sedimentary P sink.

Mudrocks are highly heterogeneous in a range of physical and chemical properties, including: porosity and permeability, fissility, colour, particle composition, size, orientation, carbon loading, degree of compaction, and diagenetic overprint. It is therefore important that the maximum information be extracted as efficiently and completely as possible. This can be accomplished through high-resolution analysis of polished thin sections by scanning electron microscopy (SEM), with the collection of large-area images and X-ray elemental map montages, and the application of targeted particle analysis. A workflow model, based on these techniques, for the digitization of mudrocks is presented herein. A range of the data that can be collected and the variety of analyses that can be achieved are also illustrated. Data collection is discussed in terms of inherent problems with acquisition, storage, transfer and manipulation, which can be time-consuming and non-trivial. Similar information and resolutions can be achieved through other techniques, such as QEMSCAN and infra-red (IR)/Raman spectroscopic mapping. These can be seen as complementary to the workflow described herein.

Accepted manuscript version. Published version available at https://doi.org/10.1130/G39904.1. Fertilization of the ocean by eolian dust and icebergs is an effective mechanism to enhance primary productivity. In particular, high-nutrient, low-chlorophyll (HNLC) areas where phytoplankton growth is critically iron-limited, such as the subarctic Pacific Ocean and the Southern Ocean, are proposed to respond to increases in bioavailable Fe supply with enhanced phytoplankton productivity and carbon export to the seafloor. While Fe-fertilization from dust is widely acknowledged to explain a higher export production during glacial periods in the Southern Ocean, paleoceanographic records supporting links between productivity and eolian dust and/or icebergs in the North Pacific are scarce. By combining independent proxies indicative of ice-sheet dynamics and ocean productivity from a single marine sedimentary record (Integrated Ocean Drilling Program [IODP] Site U1417), we present a comprehensive data set of phytoplankton response to different fertilization mechanisms in the subarctic northeast Pacific between 1.5 and 0.5 Ma, including the Mid Pleistocene Transition. Importantly, the timing of the fertilization events is more strongly controlled by local ice-sheet extent than by glacial-interglacial climate variability. Our findings indicate that fertilization by glacigenic debris results in productivity events in HNLC areas adjacent to ice sheets, and that this mechanism may represent an important, yet rarely considered, driver of phytoplankton growth.

Visual inspection (optical microscope point counting) and silica abundance show that laminated shale from the Late Cretaceous of Colombia contains high levels of detrital quartz silt and sand particles. Closer examination using the charge contrast imaging (CCI) technique, however, illustrates that much of the quartz is authigenic micro-quartz, and thus not exclusively of detrital origin. In addition, many "sand" grains that otherwise appear to represent simple detrital quartz particles are actually of biogenic origin, representing the tests of agglutinated foraminifera, formed from cemented silt-sized quartz particles. Finally, CCI shows that original detrital grains have undergone authigenic modification, with both syntaxial overgrowths and micro-quartz. Without recognition of these features, the relative proportion of detrital quartz (sand) would otherwise be greatly overestimated, with important implications for environmental interpretation. Furthermore, the recognition of biogenic structures, including agglutinated foraminifera, provides additional environmental information that otherwise could be easily overlooked.

The Kimmeridge Clay Formation (KCF) is a laterally extensive, total organic carbon-rich succession deposited throughout Northwest Europe during the Kimmeridgian–Tithonian (Late Jurassic). Here we present a petrographic and geochemical dataset for a 40 metre-thick section of a well-preserved drill core recovering thermally-immature deposits of the KCF in the Cleveland Basin (Yorkshire, UK), covering an interval of approximately 800 kyr. The new data are discussed in the context of depositional processes, sediment source and supply, transport and dispersal mechanisms, water column redox conditions, and basin restriction. Armstrong et al. (2016) recently postulated that an expanded Hadley Cell, with an intensified but alternating hydrological cycle, heavily influenced sedimentation and total organic carbon (TOC) enrichment, through promoting the primary productivity and organic matter burial, in the UK sectors of the Boreal Seaway. Consistent with such climate boundary conditions, petrographic observations, total organic carbon and carbonate contents, and major and trace element data presented here indicate that the KCF of the Cleveland Basin was deposited in the distal part of the Laurasian Seaway. Depositional conditions alternated between three states that produced a distinct cyclicity in the lithological and geochemical records: lower variability mudstone intervals (LVMIs) which comprise of clay-rich mudstone, TOC-rich sedimentation, and carbonate-rich sedimentation. The lower variability mudstone intervals dominate the studied interval but are punctuated by three ~ 2–4 m thick intervals of alternating TOC-rich and carbonate-rich sedimentation (here termed higher variability mudstone intervals, HVMIs). During the lower variability mudstone intervals, conditions were quiescent with oxic to sub-oxic bottom water conditions. During the higher variability mudstone intervals, highly dynamic conditions resulted in repeated switching of the redox system in a way similar to the modern deep basins of the Baltic Sea. During carbonate-rich sedimentation, oxic conditions prevailed, most likely due to elevated depositional energies at the seafloor by current/wave action. During TOC-rich sedimentation, anoxic-euxinic conditions led to an enrichment of redox sensitive/sulphide forming trace metals at the seafloor and a preservation of organic matter, and an active Mn-Fe particulate shuttle delivered redox sensitive/sulphide forming trace metals to the seafloor. In addition, based on TOC–S–Fe relationships, organic matter sulphurisation appears to have increased organic material preservation in about half of the analysed samples throughout the core, while the remaining samples were either dominated by excess Fe input into the system or experienced pyrite oxidation and sulphur loss during oxygenation events. New Hg/TOC data do not provide evidence of increased volcanism during this time, consistent with previous work. Set in the context of recent climate modelling, our study provides a comprehensive example of the dynamic climate-driven depositional and redox conditions that can control TOC and metal accumulations in the distal part of a shallow epicontinental sea, and is therefore key to understanding the formation of similar deposits throughout Earth's history.

Manganese (Mn) and cerium (Ce) are known as reactive metals sensitive to marine redox conditions, and can therefore serve as useful proxies for paleoceanographic environments. Quaternary sedimentary records in the Arctic Ocean show a consistent cyclicity of Mn enrichments, but Mn sources, transportation and deposition patterns, and relationship to paleoclimatic conditions are not well understood. Sediment core ARC3-B85D from the Alpha Ridge with the estimated stratigraphy covering ~350 kyr is used to investigate a coupled distribution of Mn and Ce in Quaternary Arctic Ocean sediments. By analyzing Mn and Ce distribution patterns in the core and surface sediments from the western Arctic Ocean and adjacent shelves, we investigate the conditions and dynamics of concurrent metal enrichments. Stratigraphic Ce and Mn patterns follow inferred glacial-interglacial cycles, with enrichments generally occurring during interglacial-type conditions with high sea levels. However, the relationships involved are not straightforward as highest Mn and Ce enrichments seem to occur closer to the end of interglacial/major interstadial periods, when sea levels were lowering from their highest positions. We conclude that the enrichment patterns are primarily defined by sediment dynamics controlling resuspension and transportation of reactive metals and their deposition in the central Arctic Ocean after diagenetic preconditioning on the shelves. We further infer that major transportation agents are sea-level affected cross-shelf and mid-depth ocean currents rather than sea ice as has been proposed earlier. Comprehending this coupled geochemical and sedimentary system is important for improving the chronostratigraphic framework for Quaternary deposits in the Arctic Ocean.

Petroleum source rocks are strongly enriched in organic carbon (OC), and their trace metal (TM) contents often reach low-grade ore levels. The mechanisms leading to these coenrichments are important for understanding how extreme environmental conditions support the formation of natural resources. We therefore studied organic-rich Eocene marls and limestones (oil shale) from the central Jordan Amzaq-Hazra subbasin, part of a Cretaceous–Paleogene shelf system along the southern Neo-Tethys margin. Geochemical analyses on two cores show highly dynamic depositional conditions, consistent with sedimentological and micropaleontological observations. Maximum and average contents, respectively, in OC (~26 and ~10 wt%), sulfur (~7 and ~2.4 wt%), phosphorus (~10 and ~2 wt%), molybdenum (>400 and ~130 ppm), chromium (>500 and ~350 ppm), vanadium (>1600 and ~550 ppm) and zinc (>3800 and ~900 ppm) are exceptional, in particular without any indication of hydrothermal or epigenetic processes. We propose a combination of two processes: physical reworking of OC- and metal-rich 30 material from locally exposed Cretaceous–Paleogene sediments (as supported by reworked nannofossils), and high marine productivity fueled by chemical remobilization of nutrients and metals on land that sustained anoxic-sulfidic conditions. Burial of high-quality organic matter (hydrogen index 600–700 mgHC/gOC) was related to strongly reducing conditions, punctuated by only short-lived oxygenation events, and to excess H2S, promoting organic matter sulfurization. These processes likely caused the OC and TM coenrichments in a high-energy shallow-marine setting that contradicts common models for black shale formation, but may explain similar geochemical patterns in other black shales.

Dark brown sediment layers are a potential stratigraphic tool in Quaternary Arctic Ocean sediments. They are rich in Mn, Fe, and trace metals scavenged from the water column and were most likely deposited during interglacial intervals. In this study, we combine sediment and pore water data from sediment cores taken in different parts of the Arctic Ocean to investigate the influence of early diagenetic processes on sediment geochemistry. In most studied cores, Mn, Co, and Mo are released into the pore waters from Mn oxide dissolution in deeper (>1.5 m) sediment layers. The relationship between sedimentary Mn, Co, and Mo contents in excess of the lithogenic background (elementxs) shows thatCoxs/Moxs values are a diagnostic tool to distinguish between layers with diagenetic metal addition from the pore waters (Coxs/Moxs 10), and unaffected layers (Coxs/Moxs from 1 to 10). Steady-state calculations based on current pore water profiles reveal that in the studied cores, the diagenetic addition of these metals from the pore water pool alone is not sufficient to produce the sedimentary metal enrichments. However, it seems evident that dissolution of Mn oxides in the Mn reduction zone can permanently alter the primary geochemical signature of the dark brown layers. Therefore, pore water data and Coxs/Moxs values should be considered before core correlation when this correlation is solely based on Mn contents and dark sediment color. In contrast to the mostly nonlithogenic origin of Mn in the dark brown layers, sedimentary Fe consists of a large lithogenic (80%) and a small non-lithogenic fraction (20%). Our pore water data show that diagenetic Fe remobilization is not currently occurring in the sediment. The dominant Fe sources are coastal erosion and river input. Budget calculations show that Fe seems to be trapped in the modern Arctic Ocean and accumulates in shelf and basin sediments. The Fe isotopic signal δ56Fe of the solid phase is positive (~0.2 to 0.3‰) in samples defined as the lithogenic background without significant Fe enrichments. With increasing non-lithogenic Fe contents in the sediment, δ56Fe becomes more negative, which indicates a shelf-to-basin export of an isotopically lighter Fe fraction. We assume that the same transport process is true for Mn.

During Expedition 323 of the Integrated Ocean Drilling Program to the Bering Sea (July 5–September 4, 2009), three sites were drilled along the Bering Sea northeastern continental margin [U1343 down to 745 meters below sea floor (mbsf), U1344 (745 mbsf), U1345 (150 mbsf)]. Diagenetic carbonates are present at all sites within the clayey, diatom-rich oozes of the Bering Sea, where pore waters are also characterized by extremely high methane concentrations. We here present mineralogical, elemental and isotopic data obtained from the authigenic carbonate-rich intercalations within the clay-rich Pleistocene sediments deposited along the Bering Sea continental margin. The mineralogy of the authigenic carbonates is generally represented by composite mixtures of very small crystals of magnesian calcite, dolomite, and iron-rich carbonates, with the latter phases occurring below 260 mbsf at Site U1343, below 200 mbsf at Site U1344, and below 130 mbsf at Site U1345. Element geochemistry shows that Ca, Mg, Fe, Ba, Mn, Sr and U are enriched in the carbonate-rich intercalations relative to the background sediments due to their incorporation into the carbonates and into other authigenic phases (e.g., barite and pyrite). The oxygen and carbon isotopic compositions of the authigenic carbonate minerals show that they were sequentially precipitated from pore waters at different temperatures (i.e., different burial depths) and with different isotopic compositions of dissolved inorganic carbon (DIC). The authigenic Mg-calcite precipitated early during diagenesis and shallow burial from a 13 C-depleted DIC pool, whereas dolomite and Fe-rich carbonates formed during later diagenesis and deeper burial from a 13 C-enriched DIC pool. These authigenic carbonate occurrences are interpreted as resulting from microbial sulfate reduction combined with anaerobic oxidation of methane, and methanogenesis that was intimately linked to the alteration of silicates, especially iron-rich clay minerals.

The water column of Lake Baikal (Siberia) is pervasively oxic and O2 penetrates several cm into the sediment, followed by distinct layers of Fe/Mn oxide that undergo reductive-dissolution/oxidative-precipitation cycles. Uranium (U) contents of the oxic surface sediment layers were ~ 15 μg g− 1, which is unparalleled in oxygenated lakes. To understand the processes leading to this enrichment we investigated the geochemical composition of the particulate matter and pore water of four sediment cores from different locations in the lake and performed mass balance calculations based on sediment mass accumulation rates and published loads from major tributaries. The comparison of loads and export of U in Lake Baikal suggested that current estimates of loads are too low by a factor of about 3 compared to sediment mass accumulation rates. Peak loads during spring ice melt in tributaries that are difficult to monitor and quantify might be the main cause for the deviation. The high U concentrations in the lake sediments originated from the scavenging of U in the water column through association with settling organic particles and particulate Fe(III)- and, to a lesser extent, Mn(IV)-oxides. We outline the hypothesis that two distinct U phases, lithogenic and non-lithogenic U reach the lake sediment and that authigenic U is subsequently formed under reducing conditions within the sediment. In some cores we found that most U was remobilized during the degradation of organic matter, in particular within the top oxygenated layer of the sediment. Significant enrichments prevailed due to U adsorption to and/or co-precipitation with Fe-oxides. When Fe-oxides and, to a lesser extent, Mn-oxides were reductively dissolved, they released U to the pore water, leading to peak dissolved U concentrations in the anoxic sediment, which in turn, precipitated as authigenic U under predominantly sulphate-reducing conditions. The onset of the accumulation of authigenic U coincided with the formation of distinct Fe/Mn oxide layers above. We argue that the resilience of Fe-oxides (especially crystalline goethite and hematite), in association with phosphate, even within reducing (but non-sulfidic) sediments support the burial of substantial amounts of U.

Sediment samples from the Gulf of Alaska (GOA, IODP Expedition 341, Site U1417) have been analyzed to understand present and past diagenetic processes that overprint the primary sediment composition. No Sulfate-Methane Transition Zone (SMTZ) was observed at the zone of sulfate depletion, but a >200 m thick sulfate- and methane-free sediment interval occurred between the depth of sulfate depletion (~200 m) and the onset of methanogenesis (~440 m). We suggest that this apparent gap in biogeochemical processing of organic matter is caused by anaerobic oxidation of methane fueled by sulfate which is released during dissolution of barites at the upper boundary of the methane rich layer. Beneath the methanogenic zone, at ~650 m depth, pore-water sulfate concentrations increase again, indicating sulfate supply from greater depth feeding into a deep, inverse SMTZ. A likely explanation for the availability of sulfate in the deep sub-seafloor at U1417 is the existence of a deep aquifer related to plate bending fractures, which actively transports sulfate-rich water to, and potentially along, the interface between sediments and oceanic crust. Such inverse diagenetic zonations have been previously observed in marine sediments, but have not yet been linked to subduction-related plate bending. With the discovery of a deep inverse SMTZ in an intra-oceanic plate setting and the blocking of upward methane diffusion by sulfate released from authigenic barite dissolution, Site U1417 provides new insights into sub-seafloor pore-fluid and gas dynamics, and their implications for global element cycling and the deep biosphere.

Reactive iron (Fe) oxides and sheet silicate-bound Fe in reservoir rocks may affect the subsurface storage of CO_{2} through several processes by changing the capacity to buffer the acidification by CO_{2} and the permeability of the reservoir rock: (1) the reduction of three-valent Fe in anoxic environments can lead to an increase in pH, (2) under sulphidic conditions, Fe may drive sulphur cycling and lead to the formation of pyrite, and (3) the leaching of Fe from sheet silicates may affect silicate diagenesis. In order to evaluate the importance of Fe-reduction on the CO_{2} reservoir, we analysed the Fe geochemistry in drill-cores from the Triassic Stuttgart Formation (Schilfsandstein) recovered from the monitoring well at the CO_{2} test injection site near Ketzin, Germany. The reservoir rock is a porous, poorly to moderately cohesive fluvial sandstone containing up to 2-4 wt% reactive Fe. Based on a sequential extraction, most Fe falls into the dithionite-extractable Fe-fraction and Fe bound to sheet silicates, whereby some Fe in the dithionite-extractable Fe-fraction may have been leached from illite and smectite. Illite and smectite were detected in core samples by X-ray diffraction and confirmed as the main Fe-containing mineral phases by X-ray absorption spectroscopy. Chlorite is also present, but likely does not contribute much to the high amount of Fe in the silicate-bound fraction. The organic carbon content of the reservoir rock is extremely low (

In this study, we reconstruct the recent environmental evolution of the inner Cadiz Bay using sedimentary records reaching back as far as AD 1700. We report lithological descriptions of the sediments and extensive mineralogical and geochemical analyses. An extraction technique that identifies different Fe phases provides an assessment of diagenetic alteration, which allows an estimation of the original organic matter inputs to the inner Cadiz Bay. Downcore variations in Corg/N ratios, δ13Corg and δ15N are related to changes in organic matter sources and the trophic state of the water column. The downcore records of selected trace metals (e.g. Pb, Zn and Cu) are interpreted to reflect changes in heavy metal pollution in the bay, while records of other elements (e.g. Mn and P) are likely overprinted by diagenetic alteration. Major environmental shifts took place during the 20th century, when the population around Cadiz Bay increased exponentially. Increases in sediment accumulation rates, organic matter inputs and heavy metal contents, in parallel with increases in δ13Corg and δ15N over this period, are interpreted as direct effects of the increasing anthropogenic influence in the area. The results of this study suggest that multiproxy approaches and detailed consideration of diagenetic overprinting are required to reconstruct past environmental conditions from coastal sediments.

We present inorganic geochemical analyses of pore waters and sediments of two Late Quaternary sediment cores from the western Arctic Ocean (southern Mendeleev Ridge, RV Polarstern Expedition ARK-XXIII/3), focussing on the composition and origin of distinct, brown-colored, Mn-rich sediment layers. Carbonate enrichments occur in association with these layers as peaks in Ca/Al, Mg/Al, Sr/Al and Sr/Mg, suggesting enhanced input of both ice-rafted and biogenic carbonate. For the first time, we show that the Mn-rich layers layers are also consistently enriched in the scavenged trace metals Co, Cu, Mo and Ni. Distinct bioturbation patterns, specifically well-defined brown burrows into the underlying sediments, suggest these metal enrichments formed close to the sediment–water interface. The geochemical signature of these metal- and carbonate-rich layers most probably documents formation under warmer climate conditions with an intensified continental hydrological cycle and only seasonal sea ice cover. Both rivers and sea ice delivered trace metals to the Arctic Ocean, while enhanced seasonal productivity exported reactive organic matter to the sea floor. The coeval deposition of organic matter, Mn (oxyhydr)oxides and trace metals triggered intense diagenetic Mn cycling at the sediment–water interface. These processes resulted in the formation of Mn and trace metal enrichments, and the degradation of labile organic matter. With the onset of cooler conditions, reduced riverine runoff and/or a solid sea ice cover terminated the input of riverine trace metal and fresh organic matter, resulting in deposition of grayish-yellowish, metal-poor sediments. Oxygen depletion of Arctic bottom waters under these cooler conditions is not supported by our data, and did not cause the sedimentary Mn distribution. While the original composition and texture of the brown layers resulted from specific climatic conditions and corresponding diagenetic processes, pore water data show that diagenetic Mn redistribution is still affecting the organic-poor deeper sediments. Given persistent steady state conditions, purely authigenic Mn-rich brown layers may form, while others may be partly or completely dissolved. The degree of diagenetic Mn redistribution largely depends on the depositional environment, the Mn and organic matter availability, and apparently affected the Co/Mo ratios of Mn-rich layers. Thus, brown Arctic layers are not necessarily synchronous features, and should not be correlated across the Arctic Ocean without additional age control.

Two independent analytical approaches, palynology and inorganic geochemistry, were applied to identify potential oxygen “burn-down” events in the Late Jurassic Kimmeridge Clay Formation (KCF). The KCF interval of the rotunda ammonite zone, spanning 121.82–122.72 m depth was sampled from the Swanworth Quarry 1 borehole (Dorset, UK) at 2.5–5.0 cm resolution. Samples were analysed for total organic carbon (TOC), concentrations of elements that are known to be productivity- and/or nutrient-related (e.g. Cu, P), detrital (e.g. Al, Ti, Zr) and redox-sensitive/sulphide-forming (e.g. V, Mo, Fe, Mn, S), and palynofacies components including analysis of organic-walled dinoflagellate cysts (dinocysts) on a species level. The TOC contents generally exceed 2 wt.%, with a maximum of 8.8 wt.% at 122.37 cm depth and elevated values in the central part of the investigated interval. This interval of relatively higher TOC values correlates well with the maximum recovery of marine palynomorphs and low Al values, suggesting that the TOC is primarily of marine organic matter (OM). Changes in V/Al, Mo/Al, Fe/Al, Mn/Al and S patterns at 122.37 m depth mark a shift from anoxic conditions in the lower part of the studied interval to more oxic conditions in its upper part. Such a shift could explain the relatively high TOC and marine palynomorph concentrations in the lower part of the studied interval as a result of better preservation, and the subsequent decrease as an effect of a post-depositional “burn-down”, i.e. OM oxidation. As the amount of marine palynomorphs and TOC content diminishes from the middle part of the section upwards, species-specific changes in dinocyst assemblages can be observed. In particular, concentrations of Circulodinium spp., Cyclonephelium spp., Sirmiodinium grossi, Senoniasphaera jurassica and Systematophora spp. decrease rapidly in comparison to other species, such as Glossodinium dimorphum and Cribroperidinium sp. 1, which may suggest selective degradation of dinocysts due to oxidation. We suggest that post-depositional oxygenation of bottom and pore waters within the sediment was most probably the cause for decreasing TOC values and reduced recovery of marine palynomorphs towards the top of the studied interval in comparison to high TOC and marine palynomorph values in the central part of the studied interval due to anoxic conditions.

Organic carbon-rich shales deposited during the Coniacian–Santonian Oceanic Anoxic Event 3 were drilled during ODP Leg 207 at Demerara Rise. We present integrated high-resolution geochemical records of core intervals from ODP Sites 1259 and 1261 both from nannofossil biozone CC14. Our results reveal systematic variations in marine and detrital sediment contribution, depositional processes, and bottom water redox conditions during black shale formation at two locations on Demerara Rise in different paleo-water depths. A combination of redox proxies (Fe/S, P/Al, C/P, redox-sensitive/sulfide-forming trace metals Mn, Cd, Mo, Ni, V, Zn) and other analytical approaches (bulk sediment composition, P speciation, electron microscopy, X-ray diffraction) evidence anoxic to sulfidic bottom water and sediment conditions throughout the deposition of black shale. These extreme redox conditions persisted and were periodically punctuated by short-termed periods with less reducing bottom waters irrespective of paleo-water depth. Sediment supply at both sites was generally dominated by marine material (carbonate, organic matter, opal) although relationships of detrital proxies as well as glauconitic horizons support some influence of turbidites, winnowing bottom currents and/or variable detritus sources, along with less reducing bottom water at the proposed shallower location (ODP Site 1259). At Site 1261, located at greater paleo-depth, redox fluctuations were more regular, and steady hemipelagic sedimentation sustained the development of mostly undisturbed lamination in the sedimentary record. Strong similarities of the studied deposits exist with the stratigraphic older Cenomanian–Turonian OAE2 black shale sections at Demerara Rise, suggesting that the primary mechanisms controlling continental supply and ocean redox state were time-invariant and kept the western equatorial Atlantic margin widely anoxic over millions of years.

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian–Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (∼15–20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe–P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ∼15–25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ∼90–100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ∼15–20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic–anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS− production.

High-resolution sedimentary records of major and minor elements (Al, Ba, Ca, Sr, Ti), total organic carbon (TOC), and profiles of pore water constituents (View the MathML sourceSO42-, CH4, Ca2+, Ba2+, Mg2+, alkalinity) were obtained for two gravity cores (core 755, 501 m water depth and core 214, 1686 m water depth) from the northwestern Black Sea. The records were examined in order to gain insight into the cycling of Ba in anoxic marine sediments characterized by a shallow sulfate–methane transition (SMT) as well as the applicability of barite as a primary productivity proxy in such a setting. The Ba records are strongly overprinted by diagenetic barite (BaSO4) precipitation and remobilization; authigenic Ba enrichments were found at both sites at and slightly above the current SMT. Transport reaction modeling was applied to simulate the migration of the SMT during the changing geochemical conditions after the Holocene seawater intrusion into the Black Sea. Based on this, sediment intervals affected by diagenetic Ba redistribution were identified. Results reveal that the intense overprint of Ba and Baxs (Ba excess above detrital average) strongly limits its correlation to primary productivity. These findings have implications for other modern and ancient anoxic basins, such as sections covering the Oceanic Anoxic Events which Ba is frequently used as a primary productivity indicator. Our study also demonstrates the limitations concerning the use of Baxs as a tracer for downward migrations of the SMT: due to high sedimentation rates at the investigated sites, diagenetic barite fronts are buried below the SMT within a relatively short period. Thus, ‘relict’ barite fronts would only be preserved for a few thousands of years, if at all.

The Zambezi deep-sea fan, the largest of its kind along the east African continental margin, is poorly studied to date, despite its potential to record marine and terrestrial climate signals in the southwest Indian Ocean. Therefore, gravity core GeoB 9309-1, retrieved from 1219 m water depth, was investigated for various geophysical (magnetic susceptibility, porosity, colour reflectance) and geochemical (pore water and sediment geochemistry, Fe and P speciation) properties. Onboard and onshore data documented a sulphate/methane transition (SMT) zone at ~ 450–530 cm sediment depth, where the simultaneous consumption of pore water sulphate and methane liberates hydrogen sulphide and bi-carbonate into the pore space. This leads to characteristic changes in the sediment and pore water chemistry, as the reduction of primary Fe (oxyhydr)oxides, the precipitation of Fe sulphides, and the mobilization of Fe (oxyhydr)oxide-bound P. These chemical processes also lead to a marked decrease in magnetic susceptibility. Below the SMT, we find a reduction of porosity, possibly due to pore space cementation by authigenic minerals. Formation of the observed geochemical, magnetic and mineralogical patterns requires a fixation of the SMT at this distinct sediment depth for a considerable time—which we calculated to be ~ 10 000 years assuming steady-state conditions—following a period of rapid upward migration towards this interval. We postulate that the worldwide sea-level rise at the last glacial/interglacial transition (~ 10 000 years B.P.) most probably caused the fixation of the SMT at its present position, through drastically reduced sediment delivery to the deep-sea fan. In addition, we report an internal redistribution of P occurring around the SMT, closely linked to the (de)coupling of sedimentary Fe and P, and leaving a characteristic pattern in the solid P record. By phosphate re-adsorption onto Fe (oxyhydr)oxides above, and formation of authigenic P minerals (e.g. vivianite) below the SMT, deep-sea fan deposits may potentially act as long-term sinks for P.