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International audience; The Upper Cretaceous sedimentary sequence at International Ocean Discovery Program Site U1512 in the Ceduna Sub-basin of the Great Australian Bight represents a continuous, > 690 m thick interval of black silty clay and claystone spanning the lower Turonian through Lower Campanian (~10 million years). Sediments were deposited in an elongate, ~E-W oriented, ~2500 km long rift system that developed between Australia and Antarctica with an open-ocean connection to the west and a continental bridge to the east. Site U1512 cores provide a unique, continuous record of Late Cretaceous deposition in the Ceduna Sub-basin on the hanging wall of the Wallaroo Fault Zone. Study of U1512 samples could provide both an important high-latitude, southern hemisphere perspective on climatic evolution during the peak and demise of the Cretaceous hothouse and an offshore record of the sedimentation history in the basin during the Late Cretaceous portion of the Gondwanan breakup. The Upper Cretaceous sequence at Site U1512 is notable for its lithologic uniformity. Burrow-mottled to massive claystone and silty claystone make up the majority of the almost 700 m section, while rare (n = 28) isolated, 2 to 21 cm thick medium to fine sandstone beds are a minor lithology. Macrofossils present include common inoceramids and rare occurrences of other bivalves and ammonites. Microfossils include common occurrences of calcareous nannofossils, agglutinated and calcareous benthic foraminifera, radiolaria and organic-walled dinoflagellate cysts as well as rare small, surface dwelling planktonic foraminifera. Carbonate (

nternational Ocean Discovery Program Expedition 369 drilled four sites on the southwestern Australian continental margin, in the deep water Mentelle Basin (MB) and on the neighboring Naturaliste Plateau (NP). The drillsites are located on continental crust that continued rifting after seafloor spreading began further north on the Perth Abyssal Plain (PAP) between magnetochrons M11r and M11n (133–132 Ma), ending when spreading began west of the NP between chrons M5n and M3n (126–124 Ma). Drilling recovered the first in situ samples of basalt flows overlying the breakup unconformity on the NP, establishing a magnetostratigraphically constrained eruption age of >131–133 Ma, and confirming a minimal late Valanginian age for the breakup unconformity (coeval with the onset of PAP seafloor spreading). Petrogenetic modeling indicates the basalts were generated by 25% melting at 1.5 GPa and a potential temperature of 1380°C–1410°C, consistent with proximity of the Kerguelen plume during breakup. Benthic foraminiferal fossils indicate that the NP remained at upper bathyal or shallower depths during the last 6 Myr of rifting and for 3–5 Myr after breakup between India and Australia. The limited subsidence is attributed to heat from the nearby Kerguelen plume and PAP spreading ridge. The margin subsided to middle bathyal depths by Albian time and to lower bathyal (NP) or greater (MB) depths by late Paleogene time. Periods of rapid sedimentation accompanied a westward jump of the PAP spreading ridge (108 Ma), rifting on the southern margin (100–84 Ma), and opening of the southern seaway between Australia and Antarctica (60–47 Ma).

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.

During seawater circulation in permeable intertidal sands, organic matter degradation alters the composition of percolating fluids and remineralization products discharge into surficial waters. Concurrently, coastal seawater nutrient and organic matter composition change seasonally due to variations in pelagic productivity. To assess seasonal changes in organic matter degradation in the intertidal zone of a high energy beach (Spiekeroog Island, southern North Sea, Germany), we analyzed shallow pore waters for major redox constituents (oxygen [O-2], manganese [Mn], and iron [Fe]) and inorganic nitrogen species (nitrite [NO2-], nitrate [NO3-], and ammonium [NH4+]) in March, August, and October. Surface water samples from a local time series station were used to monitor seasonal changes in pelagic productivity. O-2 and NO3- were the dominating pore water constituents in March and October. Dissolved Mn, Fe, and NH4+ were more widely distributed in August. Seasonal changes in seawater temperature as well as organic matter and nitrate supply by seawater were assumed to affect microbial rates and degradation pathways. Pore water and seawater variability led to seasonally changing constituent effluxes to surface waters. Mn, Fe, and NH4+ effluxes are minimal in March and reached their maximum in August. Furthermore, the intertidal sands switched from a net dissolved inorganic nitrogen sink in March to a net source in August. In conclusion, seasonal effects on intertidal pore water biogeochemistry affect constituent fluxes across the sediment-water interface. The seasonality of the beach bioreactor must be considered when fluxes are extrapolated to annual timescales. Plain Language Summary Beach sands are biologically active environments. Seawater is circulated through the sandy beach (e.g., via waves or tides) as are nutrients and algal remains - organic matter. Subsurface microbes start to break down organic matter and change the pore water chemistry before it is reintroduced into the ocean. This so called bioreactor is affected by seasonal changes in temperature and algal activity controlling seawater nutrient and organic matter content. This affects the rates of organic matter break down. Microbes are adapted to break down organic matter using various pathways and energy sources. The seasonality determines how fast microbes exhaust their energy source, for example, oxygen. The respective reaction pathways influence the release of pore water nutrients and trace metals. For example, beach sands of Spiekeroog are a sink for nitrogen in winter and early spring and retain nitrate from North Sea waters. In contrast, the beach is a nitrogen source to ocean water in summer: Nitrogen from algal biomass is recycled by microbes and resupplied to the coastal ocean. This is crucial, because during summer, nitrogen is a limiting factor for algal growth. Especially when coastal nutrient and metal budgets are being calculated, seasonal dynamics need to be considered. Key Points Seasonal changes in temperature and seawater composition affect the succession of organic matter degradation within intertidal beach sands Aerobic and nitrate reducing conditions dominate pore waters in cold seasons, but Mn and Fe reduction are more important in warm seasons Intertidal sands change from dissolved inorganic nitrogen sink to source from cold to warm seasons but release Mn and Fe all the year

The Pialli Level in the Umbria-Marche Basin (central Italy) correlates with the lowermost part of the positive carbon isotopic excursion characterizing the late Albian–early Cenomanian Oceanic Anoxic Event 1d (OAE 1d). High-resolution litho-, bio- and chemostratigraphic data from the Monte Petrano and Le Brecce sections allow for a bed-by-bed comparison of the two successions, and discriminate local from basin-scale signals. We present new X-ray fluorescence, ICP-MS and TOC data for both the limestones and the Pialli Level shales integrated with available carbonate carbon isotopes and nannofossil temperature and nutrient indices. Data indicate a homogenous background sedimentation dominated by pelagic carbonates, biogenic silica with little contribution by clays. The limited variation in lithogenic elements points to an essentially homogeneous detrital source area with limited fluvial terrigenous input. Higher Mn concentrations coupled with low enrichments in redox-sensitive elements, such as U, Fe, S, Re, Mo, Ag, suggest that the Pialli Level shales represent temporary suboxia without reaching anoxia. Furthermore, P, authigenic Ba, Cd and Ni enrichments, together with nannofossil nutrient index indicate generally low primary productivity conditions along the entire succession, with only minor increases for some of the black-to-dark grey shales of the Pialli Level. The nannofossil temperature index highlights a warm climate during the OAE 1d, with the warmest conditions experienced during the deposition of the Pialli Level shales. During the late Albian, the warm and humid climate was interrupted by brief episodes of relatively warmer and less saline surface waters ensuring slower rates of bottom water renewal and producing temporary suboxic conditions. Such paleoceanographic dynamics would be the continuation of episodic warmer and humid pulses characterizing the late Albian interval in the Umbria-Marche Basin. As such, the Pialli Level can be considered the result of a last episode closing a cycle before the establishment of a steadier climate during the early Cenomanian.

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.

In this study, Arctic Ocean patterns of deep water circulation and sediment provenance during the Last Glacial (LG) were compared with the recent situation by investigating the Nd and Sr isotopic composition ( 143 Nd/ 144 Nd, expressed as e Nd , 87 Sr/ 86 Sr) of the leachable and lithogenic sediment fractions as well as the elemental composition (Mn, Ca, Mg, total inorganic carbon (TIC)) on a spatially extended scale encompassing 11 sediment cores from several Arctic Ocean basins and ridges. The leachable, authigenic signature of the surface sediments implies a North Atlantic deep water source and a late Holocene circulation regime that leads to well-mixed, mostly uniform, e Nd values of − 10.9 to − 10.3. Sediments from the LG have overall more variable authigenic e Nd values (− 13.9 to − 7.4). Lower values specifically occur in the Amerasian and Amundsen Basins, documenting an enhanced flow of deep waters from the Makarov Basin to the Amundsen Basin probably via the Lomonosov Ridge intra-basin. In terms of detrital provenance areas, the lithogenic material deposited at the core locations cannot be unambiguously assigned to distinct source areas based on its radiogenic isotope composition, but represents a diverse mixture. Nevertheless, the Nd and Sr isotope signatures of surface sediments from the Amerasian Basin are dominated by western Arctic sources (e Nd = − 12.8 to − 11.0; 87 Sr/ 86 Sr = 0.7214 to 0.7251), while Eurasian Basin surface sediments are dominated by Eurasian sources (e Nd = − 10.9 to − 9.7, 87 Sr/ 86 Sr = 0.7178 to 0.7299), which is in agreement with previous studies. Bulk element patterns (Ca, Mg, TIC) of the studied sediments support these differences in provenance. The LG samples show the same trends with low e Nd (− 16.1 to − 13.7) and high 87 Sr/ 86 Sr (0.7294) in the Canada Basin, and higher e Nd (− 12.6 to − 8.8) and lower 87 Sr/ 86 Sr (0.7154 to 0.7249) in the Eurasian Basin sediments. However, LG samples have mostly lower and more heterogenous e Nd and 87 Sr/ 86 Sr values than the surface samples. Our geochemical study shows that the overall circulation pattern of the deep water masses during the LG was locally influenced by brine formation but was generally similar to today. The isotopic composition of the lithogenic material from the LG is different from modern times, presumably due to shorter transport pathways of lithogenic material to the Arctic Ocean because of a lower sea level and exposed shelves during the LG. Nevertheless, the lithogenic fraction still represents a mixture from several sources.

Early diagenetic processes play an important role in the environmental cycling of silicic acid (H4SiO4), one of the most important macronutrients in the ocean. Here, we present the first compilation of silicic acid concentrations in sediment pore water sampled in various parts of the Central Arctic Ocean. Based on these data, we calculate benthic fluxes of silicic acid from the sediments to Arctic bottom waters and interpret the pore water profiles in terms of silica dissolution–precipitation reactions deeper within the sediments. Silicic acid concentrations are very low in Arctic pore waters to sediment depths of ~ 8 m, with maxima ranging from 30 μmol/L on the Mendeleev Ridge to 300 μmol/L on the Alpha Ridge. These values are 1–2 orders of magnitude lower than silicic acid pore water concentrations in Atlantic, Indian, and Pacific Ocean sediments, reflecting the low biosilica productivity in the oligotrophic, seasonally ice-covered Arctic Ocean. Low silicic acid pore water concentrations translate into equally low benthic silicic acid fluxes, ranging between 1 and 15 mmol m− 2 a− 1 (1 ∗ 109 to 1.5 ∗ 1010 μmol km− 2 a− 1) at most study sites. With increasing sediment depth, asymptotic patterns typically observed in marine sediments occur at only five of twelve study sites. Deviations from this asymptotic shape at the other sites most likely reflect specific sediment intervals with elevated rates of biosilica dissolution (potentially from underlying Eocene-Cretaceous strata) in association with iron oxide dissolution, or with the consumption of silicic acid by neo-formation of authigenic clay minerals.

Inorganic geochemical investigations were performed on three Arctic surface sediment cores (PS72/408-4, PS72/410-2 and PS72/422-4) recovered during RV Polarstern expedition ARK-XXIII/3 on a transect across the Mendeleev Ridge. Dark brown layers are geochemically characterized by elevated Mn/Al and Fe/Al ratios and trace metal enrichments. Trace metals, such as As, Co, Cu, Mo and Ni, seem to be adsorbed onto Mn/Fe oxyhydroxide surfaces due to scavenging from the water column. Similar enrichment patterns of Mn, Co, Mo and Ni suggest that these trace metals are predominantly bound to Mn, whereas different patterns for Fe, As and Cu reveal that these trace metals are most probably mainly bound to other sediment phases like Fe-oxyhydroxides or clay minerals. Calculating Mn and Fe excess amounts reveals that the dark brown color of the layers, which so far has predominantly been attributed to enhanced Mn oxyhydroxide contents alone, may as well result from a higher Fe-oxyhydroxide contribution. In the investigated surface sediments Mn-rich layers seem to originate primarily from particulates formed within the water column. This implies that the composition of brown layers may be spatially variable even at short distances. A diagenetic overprint is not necessarily required, putting constraints on the large-scale correlation of brown layers across Arctic Basins. The Mn enrichments are presumably related to both Siberian river discharge and coastal erosion. Material input related to ice rafted debris is documented in Ca/Al, Mg/Al and TIC patterns indicating the occurrence of dolomite from the Canadian Archipelago. This material is transported via the Beaufort Gyre and shows decreasing abundance towards the west along the transect. A more basaltic component, presumably originating from the East Siberian hinterland, is characterized by low Si/Al and K/Al records. Cabio and Srxs patterns may serve as additional indicators for biogenic carbonate input and glacial/interglacial changes.

[1] Intergrated Ocean Drilling Program Expedition 323 recovered a sediment record covering the last ~4.3 Ma from the Bering Sea (Integrated Ocean Drilling Program Site U1341, Bowers Ridge, 2177 m water depth). To resolve Pliocene-Pleistocene paleoenvironmental changes in this marginal basin, ~190 sediment samples were analyzed for their bulk element composition. Aluminium contents in Bowers Ridge sediments are variable but overall higher toward younger sediments, probably related to the intensification of the Northern Hemispheric Glaciation and increasing sea ice transport in the Bering Sea. The gradual increase of terrigenous input is mirrored by decreasing SiO2 and excess Si (Sixs) contents, but the overall Si enrichment of the deposits reflects continuous opal deposition since the Pliocene at Bowers Ridge. Unlike in the North Pacific, the Sixs record at Site U1341 does not support a dramatic decrease in opal export following the onset of the Northern Hemispheric Glaciation around 2.7 Ma, but SiO2xs have higher accumulation rates (up to ~8 g/cm2/ka) between ~2.6 and ~1.8 Ma BP. During this period, the major oceanic opal deposition centers shifted globally from open marine high latitude regions to upwelling areas. We here discuss how the onset of North Pacific stratification at ~2.7 Ma BP may have caused leakage of nutrient-rich deep/intermediate North Pacific water into the Bering Sea via the deep Kamtchatka Strait, leading to increased opal deposition—and likely reactive organic matter export—at Bowers Ridge. As a result, magnetic and geochemical records were overprinted by intensified diagenesis, significantly affecting their applications as paleoceanographic proxies.

Distinct brown-coloured Mn-rich layers are common features in Quaternary sediments of the central Arctic Ocean, but their paleoenvironmental significance is disputed. Glacial–interglacial changes in bottom water ventilation, variable riverine input, and diagenetic processes have all been suggested to cause the cyclicity in optical and geochemical parameters in these deposits. To better assess the nature and origin of these sediment intervals and their implications for nutrient cycles, we applied bulk geochemical analyses and a sequential Fe extraction scheme to a sediment record covering the last ~ 130 ka on the southern Mendeleev Ridge. All brown layers in this core are enriched in Mn, but also in Fe (oxyhydr)oxides (e.g., ferrihydrite, lepidocrocite, goethite) that contribute to the characteristic sediment colour. Phosphorus and several trace metals (As, Co, Cu, Mo, Ni) are also enriched, indicating that both Mn and Fe (oxyhydr)oxides adsorbed P and trace metals from the water column. The metal enrichments are most probably caused by a combination of enhanced Mn and Fe input from Arctic rivers and/or the erosion of shelf deposits, coupled with early diagenetic processes leading to precipitation of authigenic Mn and Fe (oxyhydr)oxides close to the sediment–water interface. Both primary supply and diagenetic recycling of metals should have been enhanced by a more intense hydrological cycle under warmer climate conditions, combined with seasonal increases in productivity and reactive organic matter export during ice-free conditions in the Central Arctic Ocean. Consequently, the studied metal (oxyhydr)oxide-rich layers were formed under interglacial/interstadial climatic conditions. In contrast, sheet silicate-bound Fe (e.g., chlorite), a second major Fe pool in these sediments (15–35% of total Fe), is enriched between the oxide-rich layers. Thus, the delivery of Fe-rich sheet silicates from the East Siberian hinterland or the Bering Sea, and subsequent deposition on the Mendeleev Ridge, was enhanced by more intense physical weathering during glacial/stadial periods. These contrasts in Fe speciation between the brown layers and the adjacent sediments document the direct response of biogeochemical element cycles to glacial–interglacial variations in river input, weathering regime, and sea level in the Arctic Ocean.

A decade of studies of metal and nutrient inputs to the back-barrier area of Spiekeroog Island, NW German Wadden Sea, have concluded that pore water discharge provides a significant source of the enrichments of many components measured in the tidal channels during low tide. In this paper we add studies of radium isotopes to help quantify fluxes into and out of this system. Activities of radium isotopes in surface water from tidal channels in the back-barrier area exhibit pronounced changes in concert with the tide, with highest activities occurring near low tide. Other dissolved components: silica, total alkalinity (TA), manganese, and dissolved organic carbon (DOC) exhibit similar changes, with patterns matching the Ra isotopes. Uranium follows a reverse pattern with highest concentrations at high tide. Here we use radium isotope measurements in water column and pore water samples to estimate the fluxes of pore waters that enter the tidal channels during low tide. Using a flushing time of 4 days and the average activities of 224Ra, 223Ra, and 228Ra measured in the back-barrier surface and pore waters, we construct a balance of these isotopes, which is sustained by a deep pore water flux of (2–4) × 108 L per tidal cycle. This flux transports Ra and the other enriched components to the tidal channels and causes the observed low tide enrichments. An independent estimate of pore water recharge is based on the depletion of U in the tidal channels. The U-based recharge is about two times greater than the Ra-based discharge; however, other sinks of U could reduce the recharge estimate. The pore waters have wide ranges of enrichment in silica, alkalinity, manganese, DOC, and depletion of U with depth. We estimate concentrations of these components in pore water from the depth expected to contribute the majority of the pore water flux, 3.5 m, to determine fluxes of these components to the tidal channels. Samples from this depth have minimum concentrations of silica, alkalinity, manganese, and DOC. We also estimate the exports of these components (and import of U) due to mixing based on average measured concentrations in the tidal creeks and the 4-day flushing time. A comparison of these estimates reveals that the exports (negative in the case of U) equal or exceed the pore water fluxes. By using values slightly higher than the minimum concentrations at 3.5 m to calculate inputs, the two estimates could be forced to match. We conclude that pore water drainage is the major factor regulating fluxes of Ra isotopes, silica, alkalinity, manganese, DOC, and uranium in this system.

To date, North Sea tidal-flat sediments have been intensively studied down to a depth of 5 m below seafloor (mbsf). However, little is known about the biogeochemistry, microbial abundance, and activity of sulfate reducers as well as methanogens in deeper layers. In this study, two 20 m-long cores were retrieved from the tidal-flat area of Spiekeroog Island, NW Germany. The drill sites were selected with a close distance of 900 m allowing to compare two depositional settings: first, a paleo-channel filled with Holocene sediments and second, a mainly Pleistocene sedimentary succession. Analyzing these cores, we wanted to test to which degree the paleo-environmental imprint is superimposed by present processes. In general, the numbers of bacterial 16S rRNA genes are one to two orders of magnitude higher than those of Archaea. The abundances of key genes for sulfate reduction and methanogenesis (dsrA and mcrA) correspond to the sulfate and methane profiles. A co-variance of these key genes at sulfate-methane interfaces and enhanced ex situ AOM rates suggest that anaerobic oxidation of methane may occur in these layers. Microbial and biogeochemical profiles are vertically stretched relative to 5 m-deep cores from shallower sediments in the same study area, but still appear compressed compared to deep sea sediments. Our interdisciplinary analysis shows that the microbial abundances and metabolic rates are elevated in the Holocene compared to Pleistocene sediments. However, this is mainly due to present environmental conditions such as pore water flow and organic matter availability. The paleo-environmental imprint is still visible but superimposed by these processes.

Salt marshes form part of the widely distributed intertidal landscape. The salt marshes of the East Frisian barrier island Langeoog (NW Germany) belong to the barrier-connected salt marsh type and were protected by a summer dike that was removed in 2004. In this study, pore water and sediment data were combined to investigate the effects of the de-embankment along a transect including sites on seawater-influenced grassland, high and low salt marsh, and transition zone tidal flat–low salt marsh. Pore waters were sampled with in situ pore water samplers for 13 mo and analysed for trace metals (Fe, Mn), nutrients (NH4+, PO43−), dissolved organic carbon, and sulphate. Additionally, on site measurements of pH and salinity were carried out. Pore water ultrafiltration experiments with 5000 Da MWCO (molecular weight cut off) complemented the water analyses. Sediment samples were taken from hammer corings and were analysed for bulk parameters (total carbon [TC], total inorganic carbon [TIC], total organic...

Salt marsh succession after de-embankment was monitored on the East Frisian barrier island Langeoog by investigating permanent plots. Seventy years after embankment salt marsh plants were once again influenced mainly by the tidal regime. From 2002 to 2004 the former high marsh and glycophytic vegetation died out and was replaced by species of lower salt marsh zones. Nitrophytic halophytes like Suaeda maritima, Atriplex prostrata and Artemisia maritima established first because of the high nutrient content in the soil, a direct result of former vegetation decay. With decreasing nitrogen afterwards other species became more competitive. Until 2007 Atriplex portulacoides became more dominant in the lower marsh and Elymus athericus reached dominance in areas where grazing has been abandoned in the high marsh. The dynamics in the study area is much lower than in natural marshes due to the still existing drainage system. Therefore vegetation units with low species diversity are widespread.

The crystal structure of Al4B2O9, synthesized from Al(NO)(3)center dot 9H(2)O and B(OH)(3) via a sol-gel process, is studied and characterized by Rietveld refinements and grid search analyses combined with (11) B and Al-27 MAS NMR spectroscopy. The aluminum borate with a unit-cell composition of Al32B16O72 is closely related to the boralsilite (Al32B12Si4O74) Structure with Si replaced by B and to mullite (Al4+2xSi2-2xO10-x) It crystallizes in the monoclinic space group C2/m, a = 14.8056(7) angstrom, b = 5.5413(2) angstrom, c = 15.0531(6) angstrom, beta = 90.913(2)degrees, Z = 8 for Al4B2O9. The main structural units are isolated chains of edge-sharing AlO6-octahedra running parallel to b that is a characteristic feature of the mullite-type crystal structures. The octahedral chains are crosslinked by AlO4, AlO5, BO3, and BO4 groups with two B atoms and one O atom (O5') disordered on interstitial positions. Al-27 and B-11 NMR studies confirm the presence of sixfold (octahedral), fivefold, and fourfold (tetrahedral) coordinated Al (sixfold: [fourfold + fivefold] =similar to 50%:50%) and of threefold and fourfold coordinated B (similar to 80%:20%).

The sulfur isotopic composition of dissolved seawater sulfate is a basic parameter in quantification of fluxes in the global sulfur cycle. It has changed during Earth history but is generally assumed to be constant at a given time due to the long residence time of sulfate in the ocean. Past measurements in the modern ocean, however, have shown an unexpected variability. Since the known marine sedimentary record essentially reflects continental margin processes, we have investigated for the first time the isotopic composition of dissolved sulfate of a marginal sea, the North Sea by means of stable-isotope-ratio-monitoring mass spectrometry. Sampling took place in the water column at 30 stations during two seasons (early spring 1996 and summer 1997). Stable isotope results are compared to measurements of salinity, temperature, and phytoplankton biomass. Except for one profile, the isotopic composition was found to be essentially constant at both the spring ( δ 34 S = + 20.9 ± 0.13‰; n = 131; versus V-CDT) and the summer campaign ( δ 34 S = + 21.1 ± 0.13‰; n = 59). The mean composition of North Sea water sulfate of δ 34 S = + 21‰ is within 0.2‰ of δ 34 S values found for essentially unpolluted coastal waters collected at different stations worldwide (Atlantic and Pacific Ocean) and the water column of the modern open ocean.

A geochemical and stable isotope geochemical study was carried out on sediments and pore waters from the Strait of Sicily at the connection between the western and the eastern Mediterranean Sea (ODP Site 963). Organic-matter-rich layers (ORLs), which are proposed to be time-equivalent to eastern Mediterranean sapropels, only occur in sediments older than 550 kyr, most likely because of a strong dilution of late Pleistocene and Holocene sediments by terrigenous material. The ORLs have total organic carbon (TOC) contents of up to 1.6% and are enriched in pyrite and trace metals. TOC/pyrite ratios indicate the at least temporary presence of an anoxic water column during sediment formation, which is in agreement with the observed sulfur isotope discrimination. These conditions induced the enrichment in sulfide-forming and redox-sensitive trace elements. Trace metal enrichment is lower than at other sites in the Mediterranean Sea, which may be attributed to a less reducing or a less stable anoxic environment that was less favorable for the accumulation of redox-sensitive trace elements and organic matter. However, during sapropel events sedimentary conditions in the Strait of Sicily, based on manganese and barium geochemistry, must have been largely similar to those at other sites in the Mediterranean Sea. According to elemental, Rock-Eval, and stable carbon isotope analyses the organic matter in the ORLs is mainly of marine origin, which appears to have been overprinted significantly during diagenesis. A significant part of the organic matter in sediments from ODP Site 963 may also originate from uplifted land sections eroded during weathering and may primarily also be of marine origin. The results of pore water analyses illustrate the presence of an active deep biosphere in the sediments of Site 963, reflected for example by sulfate, methane and iodine concentrations. A brine, probably originating from underlying Messinian evaporites, was detected, but is only of minor influence.

A distinct Pliocene eastern Mediterranean sapropel (i-282), recovered from three Ocean Drilling Program (ODP) Leg 160 Sites, has been investigated for its organic and inorganic composition. This sapropel is characterized by high organic carbon (Corg) and trace element contents, and the presence of isorenieratene derivatives. The latter suggests that the base of the photic zone was sulphidic during formation of the sapropel. Combined with evidence of bottom water anoxia (preservation of laminae, high redox-sensitive trace element contents, and the abundance and isotopic composition of pyrite) this leads to the tentative conclusion that almost the entire water column may have been anoxic. This anoxia resulted from high productivity and not from stagnation, because an approximation of the trace element budget during sapropel formation shows that water exchange with the western Mediterranean is needed. Entire water column anoxia has been suggested earlier for several black shales. With regard to the depositional environment and the Corg content, however, only the Cenomanian/Turonian Boundary Event (CTBE) black shales appear to be comparable to this sapropel. The proposed trace element removal mechanism of scavenging and (co-)precipitation in an anoxic water column, is thought to be similar for both types of deposits. The ultimate trace element source for the sapropel, however, is seawater, whereas it is hydrothermal and fluvial input for CTBE black shales (because they have a larger temporal and spatial distribution). Nonetheless, the Corg-rich eastern Mediterranean Pliocene sapropel discussed here may be considered to be a younger analogue of CTBE black shales.

[1] Integrated Ocean Drilling Program (IODP) Expedition 302 (Arctic Coring Expedition, ACEX) recovered a unique sediment record from the central Arctic Ocean, revealing that this region underwent major environmental fluctuations since the Late Cretaceous. Major and trace element composition of 1,300 samples were determined using X-ray fluorescence (XRF). The results show significant compositional variability of the sediments with depth that can be attributed to changes in (a) provenance and pathways of detrital material, (b) paleoenvironmental conditions and depositional processes, and (c) diagenetic overprint of the primary record. In addition to existing lithological units, we introduce new geochemical units for a more process-related approach interpreting the ACEX record. In detail, via the geochemical signature of Siberian flood basalts we are able to reconstruct the discontinuous rifting and deepening of the central Lomonosov Ridge during the Paleogene, accompanied by changing current regimes and the onset of sea ice. Eocene biosiliceous sedimentation took place in a relatively shallow setting under predominantly anoxic bottom water conditions, causing a positive anoxia-productivity feedback, although water column stratification was repeatedly interrupted by ventilation events. Anoxic to sulfidic conditions were even more extreme after biosilica production ceased, and significant amounts of pyrite were deposited on the Lomonosov Ridge. Especially in organic matter-rich Paleogene deposits, diagenetic processes obscured the paleoenvironmental signals. Fundamental environmental changes occurred in the Middle Eocene, but geochemical and micropaleontological proxies point not to the identical sediment depth. After approximately 26 Ma of non-deposition or erosion, the Middle Miocene record shows the transition to dominantly oxic bottom water conditions, although suboxic diagenesis seemingly affected these deposits.

Drilling results from the Integrated Ocean Drilling Program’s Arctic Coring Expedition (ACEX) to the Lomonosov Ridge (LR) document a 26 million year hiatus that separates freshwater-influenced biosilica-rich deposits of the middle Eocene from fossil-poor glaciomarine silty clays of the early Miocene. Detailed micropaleontological and sedimentological data from sediments surrounding this mid-Cenozoic hiatus describe a shallow water setting for the LR, a finding that conflicts with predrilling seismic predictions and an initial postcruise assessment of its subsidence history that assumed smooth thermally controlled subsidence following rifting. A review of Cenozoic tectonic processes affecting the geodynamic evolution of the central Arctic Ocean highlights a prolonged phase of basin-wide compression that ended in the early Miocene. The coincidence in timing between the end of compression and the start of rapid early Miocene subsidence provides a compelling link between these observations and similarly accounts for the shallow water setting that persisted more than 30 million years after rifting ended. However, for much of the late Paleogene and early Neogene, tectonic reconstructions of the Arctic Ocean describe a landlocked basin, adding additional uncertainty to reconstructions of paleodepth estimates as the magnitude of regional sea level variations remains unknown.

The Cenozoic record of the Lomonosov Ridge (central Arctic Ocean) recovered during Integrated Ocean Drilling Program (IODP) Expedition 302 revealed an unexpected 26 Ma hiatus, separating middle Eocene (�44.4 Ma) from lower Miocene sediments (�18.2 Ma). To elucidate the nature of this unconformity, we performed a multiproxy palynological (dinoflagellate cysts, pollen, and spores), micropaleontological (siliceous microfossils), inorganic, and organic (Tetra Ether Index of lipids with 86 carbon atoms (TEX86) and Branched and Isoprenoid Tetraether (BIT)) geochemical analysis of the sediments from �5 m below to �7 m above the hiatus. Four main paleoenvironmental phases (A–D) are recognized in the sediments encompassing the unconformity, two below (A–B) and two above (C–D): (A) Below the hiatus, proxies show relatively warm temperatures, with Sea Surface Temperatures (TEX86-derived SSTs) of about 8�C and high fresh to brackish water influence. (B) Approaching the hiatus, proxies indicate a cooling trend (TEX86-derived SSTs of �5�C), increased freshwater influence, and progressive shoaling of the Lomonosov Ridge drilling site, located close to or at sea level. (C) The interval directly above the unconformity contains sparse reworked Cretaceous to Oligocene dinoflagellate cysts. Sediments were deposited in a relatively shallow, restricted marine environment. Proxies show the simultaneous influence of both fresh and marine waters, with alternating oxic and anoxic conditions. Pollen indicates a relatively cold climate. Intriguingly, TEX86-derived SSTs are unexpectedly high, �15–19�C. Such warm surface waters may be partially explained by the ingression of warmer North Atlantic waters after the opening of the Fram Strait during the early Miocene. (D) Sediments of the uppermost interval indicate a phase of extreme oxic conditions, and a well-ventilated environment, which occurred after the complete opening of the Fram Strait. Importantly, and in contrast with classical postrifting thermal subsidence models for passive margins, our data suggest that sediment erosion and/or nondeposition that generated the hiatus was likely due to a progressive shoaling of the Lomonosov Ridge. A shallow water setting both before and after the hiatus suggests that the Lomonosov Ridge remained at or near sea level for the duration of the gap in the sedimentary record. Interacting sea level changes and/or tectonic activity (possibly uplift) must be invoked as possible causes for such a long hiatus.

[1] The Late Jurassic to Early Cretaceous (Volgian-Ryazanian) was a period of a second-order sea-level low stand, and it provided excellent conditions for the formation of shallow marine black shales in the NorwegianGreenland Seaway (NGS). IKU Petroleum Research drilling cores taken offshore along the Norwegian shelf were investigated with geochemical and microscopic approaches to (1) determine the composition of the organic matter, (2) characterize the depositional environments, and (3) discuss the mechanisms which may have controlled production, accumulation, and preservation of the organic matter. The black shale sequences show a wide range of organic carbon contents (0.5–7.0 wt %) and consist of thermally immature organic matter of type II to II/III kerogen. Rock-Eval pyrolysis revealed fair to very good petroleum source rock potential, suggesting a deposition in restricted shallow marine basins. Well-developed lamination and the formation of autochthonous pyrite framboids further indicate suboxic to anoxic bottom water conditions. In combination with very low sedimentation rates it seems likely that preservation was the principal control on organic matter accumulation. However, a decrease of organic carbon preservation and an increase of refractory organic matter from the Volgian to the Hauterivian are superimposed on short-term variations (probably reflecting Milankovitch cycles). Various parameters indicate that black shale formation in the NGS was gradually terminated by increased oxidative conditions in the course of a sea-level rise. INDEX TERMS: 1055 Geochemistry: Organic geochemistry; 4802 Oceanography: Biological and Chemical: Anoxic environments; 9609 Information Related to Geologic Time: Mesozoic; 8105 Tectonophysics: Continental margins and sedimentary basins (1212); KEYWORDS: black shale formation, depositional environment, Norwegian-Greenland Seaway, Mesozoic, organic petrography Citation: Langrock, U., R. Stein, M. Lipinski, and H.-J. Brumsack, Late Jurassic to Early Cretaceous black shale formation and paleoenvironment in high northern latitudes: Examples from the Norwegian-Greenland Seaway, Paleoceanography, 18(3), 1074, doi:10.1029/2002PA000867, 2003.

The paleoclimatology and paleoceanology of the Late Jurassic and Early Cretaceous are of special interest because this was a time when large amounts of marine organic matter were deposited in sediments that have subsequently become petroleum source rocks. However, because of the lack of outcrops, most studies have concentrated on low latitudes, in particular the Tethys and the “Boreal Realm,” where information has been based largely on material from northwest Germany, the North Sea, and England. These areas were all south of 40°N latitude during the Late Jurassic and Early Cretaceous. We have studied sediment samples of Kimmeridgian (∼154 Ma) to Barremian (∼121 Ma) age from cores taken at sites offshore mid-Norway and in the Barents Sea that lay in a narrow seaway connecting the Tethys with the northern polar ocean. During the Late Jurassic-Early Cretaceous these sites had paleolatitudes of 42–67°N. The Late Jurassic-Early Cretaceous sequences at these sites reflect the global sea-level rise during the Volgian-Hauterivian and a climatic shift from warm humid conditions in Volgian times to arid cold climates in the early Hauterivian. The sediments indicate orbital control of climate, reflected in fluctuations in the clastic influx and variations in carbonate and organic matter production. Trace element concentrations in the Volgian-Berriasian sediments suggest that the central part of the Greenland-Norwegian Seaway might have had suboxic bottom water beneath an oxic water column. Both marine and terrigenous organic matter are present in the seaway sediments. The Volgian-Berriasian strata have unusually high contents of organic carbon and are the source rocks for petroleum and gas fields in the region. The accumulation of organic carbon is attributed to restricted conditions in the seaway during this time of low sea level. It might be that the Greenland-Norwegian segment was the deepest part of the transcontinental seaway, bounded at both ends by relatively shallow swells. The decline in organic matter content of the sediments in the Valanginian-Hauterivian indicates greater ventilation and more active flow through the seaway as the sea level rose. The same benthic foraminifera assemblages are encountered throughout the seaway. Endemic assemblages of arenaceous foraminifera in the Volgian-Berriasian give way to more diverse and cosmopolitan Valanginian-Hauterivian benthic communities that include calcareous species. The foraminiferal assemblages also suggest low oxygen content bottom waters during the earlier Cretaceous, changing to more fully oxygenated conditions later. The calcareous nannoplankton, particularly Crucibiscutum salebrosum, which is rare at low latitudes and abundant in high latitudes, reflect the meridional thermal gradient. They indicate that the Greenland-Norwegian segment of the seaway was north of a subtropical frontal zone that acted as a barrier between the Tethyan and Boreal Realms. This implies the existence of stable climatic belts during the early Valanginian and Hauterivian, significant meridional temperature gradients, and moderate “ice house” conditions.