The evolution of early diagenetic processes at the Mozambique margin during the last glacial-interglacial transition

The Mozambique continental margin experienced large variations in sedimentation rates, primarily due to re-routing of sediment deposition from the Zambezi River during the last glacial-Holocene transition. As changes in sediment accumulation and organic matter deposition impose a strong control on the formation of authigenic minerals in the sediment, the distribution of these minerals may reflect the regional paleoenvironmental and paleoclimatic evolution. Combining geochemical analyses of porewaters and sediments with a reactive transport modeling approach, we reconstruct the depositional history and its effect on pyrite formation and other biogeochemical transformations at a site on the Mozambique margin over the past 27 kyr. Fitting the model to match the observed geochemical patterns, most importantly authigenic pyrite, allowed for the reconstruction of past sulfate-methane transition zone depth, which migrated in response to changes in the sediment accumulation and organic matter deposition. Changes in sediment deposition quickly affected organoclastic sulfate reduction and associated pyrite formation, but the effect on anaerobic methane oxidation and subsequent pyrite formation occurred with a lag on the order of thousands of years. Model results reveal a transition from high diagenetic reaction rates representative of near-shore depositional environments during the late glacial maximum, to a setting typical of offshore sediments with low reaction rates at the present day. Notably, the remnants of methane and dissolved iron pools produced in the past still shape the diagenetic processes at and below the sulfate-methane transition zone today. Since deglacial shelf-flooding and corresponding changes in sediment deposition occurred along continental margins worldwide, our analysis highlights the important role of non-steady state diagenesis in continental margin sediments and its relevance for paleoceanographic interpretation of sediment cores experiencing strong variations in sediment input

Millennial scale persistence of organic carbon bound to iron in Arctic marine sediments

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

Data for: Reconstructing oxygen deficiency in the glacial Gulf of Alaska: Combining biomarkers and trace metals as paleo-redox proxies

BHT-x biomarker and redox sensitive trace element data related to the article: Zindorf et al., Reconstructing oxygen deficiency in the glacial Gulf of Alaska: Combining biomarkers and trace metals as paleo-redox proxie

Data for: Deep Sulfate-Methane-Transition and sediment diagenesis in the Gulf of Alaska (IODP Site U1417)

Supplemental Data to Zindorf et al., Deep Sulfate-Methane-Transition and sediment diagenesis in the Gulf of Alaska (IODP Site U1417

Data for: Reconstructing oxygen deficiency in the glacial Gulf of Alaska: Combining biomarkers and trace metals as paleo-redox proxies

BHT-x biomarker and redox sensitive trace element data related to the article: Zindorf et al., Reconstructing oxygen deficiency in the glacial Gulf of Alaska: Combining biomarkers and trace metals as paleo-redox proxiesTHIS DATASET IS ARCHIVED AT DANS/EASY, BUT NOT ACCESSIBLE HERE. TO VIEW A LIST OF FILES AND ACCESS THE FILES IN THIS DATASET CLICK ON THE DOI-LINK ABOV

Data for: Deep Sulfate-Methane-Transition and sediment diagenesis in the Gulf of Alaska (IODP Site U1417)

Supplemental Data to Zindorf et al., Deep Sulfate-Methane-Transition and sediment diagenesis in the Gulf of Alaska (IODP Site U1417)THIS DATASET IS ARCHIVED AT DANS/EASY, BUT NOT ACCESSIBLE HERE. TO VIEW A LIST OF FILES AND ACCESS THE FILES IN THIS DATASET CLICK ON THE DOI-LINK ABOV

Reconstructing oxygen deficiency in the glacial Gulf of Alaska: Combining biomarkers and trace metals as paleo-redox proxies

Marine anaerobic oxidation of ammonium (anammox) plays a central role in the nitrogen cycle of modern Oxygen Deficient Zones (ODZs). The newly developed bacteriohopanetetrol stereoisomer (BHT-x) biomarker for anammox, which is largely unaffected by early diagenesis, allows for the reconstruction of the presence and dynamics of past ODZs from the sedimentary record of continental margins. In this study, we investigate the development and dynamics of the ODZ in the Gulf of Alaska (GOA) between 60 and 15 cal ka BP using records of redox sensitive trace metals (TM) and the BHT-x anammox biomarker from IODP Site U1419 (~700 m water depth). The biomarker record indicates that the ODZ in the GOA was in concert with global climate fluctuations in the late Pleistocene. Anammox was more pronounced during warmer periods and diminished during cooler periods, as indicated by correlation with the δ18O signal obtained by the North Greenland Ice core Project (NGRIP). Trace metal enrichments, however, do not match the trend in BHT-x. Systematic metal enrichments in intervals where biomarkers point to more intense water column deoxygenation are not observed. We suggest that this proxy discrepancy was caused by environmental factors, other than water column redox conditions, with opposing effects on the TM and biomarker records. Two of the most widely used redox indicators, Mo and U, are not significantly enriched throughout the sediment record at Site U1419. Site U1419 experienced some of the highest sedimentation rates (100–1000 cm ka−1) ever reported for late Pleistocene continental margin sediments, leading to a continuous and rapid upward migration of the sediment-water interface. We suggest that despite water column and seafloor oxygen depletion, significant sedimentary enrichments of these redox sensitive trace metals were prevented by a limited time for their diffusion across the sediment-water interface and subsequent enrichment as authigenic phases. Thus, depositional conditions were ideal for biomarker preservation but prevented significant authigenic trace metal accumulations. Similar discrepancies between organic and inorganic redox proxies could exist in other high sedimentation rate environments, potentially putting constraints on paleo-redox interpretations in such settings if they are based on trace metal enrichments alone

Deep Sulfate-Methane-Transition and sediment diagenesis in the Gulf of Alaska (IODP Site U1417)

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