Description: The here presented sample set is from three cores from the Guaymas Basin (Gulf of California), covering a broad range of depositional environments. This includes sediments from the oxygen minimum zone, from a semi-restricted oxic graben, and from near a hydrothermal vent field. Cores were taken with a multiple corer.

Description: The here presented sample set is from three cores from the Guaymas Basin (Gulf of California), covering a broad range of depositional environments. This includes sediments from the oxygen minimum zone, from a semi-restricted oxic graben, and from near a hydrothermal vent field. Cores were taken with a multiple corer.

Description: The Neoarchean-Paleoproterozoic Transvaal Supergroup in South Africa contains the well-preserved stromatolitic Campbellrand-Malmani carbonate platform, which was deposited in shallow seawater shortly before the 2.40–2.32 Ga Great Oxidation Event (GOE). This platform is composed of alternating stromatolitic carbonates and mudstones and is a prominent candidate for (isotope-) geochemical mapping to investigate the appearance of very small amounts of free oxygen that accumulated in shallow waters preceding the GOE. Mo isotopes in sedimentary archives are widely used as a proxy for redox-changes in modern and ancient environments and recent evidence suggests that oxy-molybdate (MoO42−) is directly transferred from ocean water to inorganic carbonates with negligible fractionation, thus reflecting oceanic Mo isotope signatures. In this study we analyzed major and trace element compositions as well as Mo isotopic compositions of carbonate and mudstone samples from the KMF-5 drill core. Geochemical indicators, such as Fe and Mn concentrations and Fe-to-Mn abundance ratios reveal the preservation of some geochemical indicators despite the widespread silicification and dolomitization of the platform. Heavy δ30Si values of silicified carbonates between 0.53 and 2.35‰ point to Si precipitation from surface water during early diagenesis rather than to a later hydrothermal overprint. This assessment is supported by the frequent observation of rip-up structures of silica (chert) layers within the entire sedimentary succession. The δ98Mo values of whole rock samples throughout the Malmani-Campbellrand platform range between −0.82 and +1.40‰, similar to values reported for deeper slope carbonates from the Griqualand West area, but variations are independent from lithology or depositional water depth. These large variations in δ98Mo values indicate molybdenum redox cycling and thus the presence of free oxygen in the atmosphere-ocean system at that time, in agreement with earlier Mo isotopic studies on Campbellrand carbonates and shales. A similar range in δ98Mo values for carbonates between +0.40 and +0.87‰, however, was also found on the hand specimen scale, indicating the danger of a sample bias on the Mo isotopic stratigraphy of this carbonate platform. Results of previously unpublished adsorption experiments of Mo on CaCO3 clearly indicate that the Mo inventory of Malmani-Campbellrand carbonates was not only influenced by primary adsorption from seawater, but to a much larger degree by secondary processes during early diagenesis, which also affected the Mo isotopic composition of the samples on a local scale. Our results indicate that Mo concentrations and isotopic compositions in ancient stromatolitic carbonates were subject to redox changes within microbial mats and within the soft sediment during early diagenesis and later lithification, and as such cannot be used to quantitatively reconstruct the amount of free atmospheric oxygen or its fluctuations through Earth's history. Nevertheless, we interpret our heavy Mo isotopic signatures from carbonates as a minimum value for Neoarchean seawater and reinforce the assumption that free atmospheric oxygen built up a heavy oceanic Mo reservoir at that time.

Description: Molybdenum (Mo) concentrations and isotope compositions in sediments and shales are commonly used as proxies for anoxic and sulfidic (i.e., euxinic) conditions in the water column of paleo-marine systems. A basic assumption underlying this practice is that the proxy signal extracted from the geological record is controlled by long-term (order of decades to millennia) Mo scavenging in the euxinic water column rather than Mo deposition during brief episodes or events (order of weeks to months). To test whether this assumption is viable we studied the biogeochemical cycling of Mo and its isotopes in sediments of the intermittently euxinic Gotland Deep in the central Baltic Sea. Here, multiannual to decadal periods of euxinia are occasionally interrupted by inflow events during which well‑oxygenated water from the North Sea penetrates into the basin. During these events manganese (Mn) (oxyhydr)oxide minerals are precipitated in the water column, which are known to scavenge Mo. We present sediment and pore water Mo and Mo isotope data for sediment cores which were taken before and after a series of inflow events between 2014 and 2016. After seawater inflow, pore water Mo concentrations in anoxic surface sediments exceed the salinity-normalized concentration by more than two orders of magnitude and coincide with transient peaks of dissolved Mn. A fraction of the Mo liberated into the pore water is transported by diffusion in a downward direction and sequestered by organic matter within the sulfidic zone of the sediment. Diffusive flux calculations as well as a mass balance that is based on the sedimentary Mo isotope composition suggest that about equal proportions of the Mo accumulating in the basin are delivered by Mn (oxyhydr)oxide minerals during inflow events and Mo scavenging with hydrogen sulfide during euxinic periods. Since the anoxic surface sediment where Mo is released from Mn (oxyhydr)oxides are separated by several centimeters from the deeper sulfidic layers where Mo is removed, the solid phase record of Mo concentration and isotope composition would be misinterpreted if steady state Mo accumulation was assumed. Based on our observations in the Gotland Deep, we argue that short-term redox fluctuations need to be considered when interpreting Mo-based paleo-records.

Description: Highlights • Carbon cycle of Neoarchean carbonate platform and potential oxygen oasis. • Carbon isotopes reveal a shift to aerobic biosphere and increasing oxidation state. • Rare earth element patterns reveal decrease in open ocean water influx. • Rimmed margin architecture was crucial for evolution of aerobic ecosystems. Abstract The evolution of oxygenic photosynthesis is widely seen as the major biological factor for the profound shift from reducing to slightly oxidizing conditions in Earth’s atmosphere during the Archean-Proterozoic transition period. The delay from the first biogenic production of oxygen and the permanent oxidation of Earth’s atmosphere during the early Paleoproteorozoic Great Oxidation Event (GOE) indicates that significant environmental modifications were necessary for an effective accumulation of metabolically produced oxygen. Here we report a distinct temporal shift to heavier carbon isotope signatures in lagoonal and intertidal carbonates (δ13Ccarb from -1.6 to +0.2 ‰, relative to VPDB) and organic matter (δ13Corg from about -40 to -25 ‰, relative to VPDB) from the 2.58–2.50 Gy old shallow–marine Campbellrand-Malmani carbonate platform (South Africa). This indicates an increase in the burial rate of organic matter caused by enhanced primary production as well as a change from an anaerobic to an aerobic ecosystem. Trace element data indicate limited influx of reducing species from deep open ocean water into the platform and an increased supply of nutrients from the continent, both supporting primary production and an increasing oxidation state of the platform interior. These restricted conditions allowed that the dissolved inorganic carbon (DIC) pool in the platform interior developed differently than the open ocean. This is supported by coeval carbonates from the marginal slope setting, which had a higher interaction with open ocean water and do not record a comparable shift in δ13Ccarb throughout the sequence. We propose that the emergence of stable shallow-water carbonate platforms in the Neoarchean provided ideal conditions for the evolution of early aerobic ecosystems, which finally led to the full oxidation of Earth’s atmosphere during the GOE.

Description: The deposition of large amounts of mixed-valence Fe minerals in iron formations during the Archean and Paleoproterozoic indicates that the Fe(II)aq (aqueous) content of coeval anoxic seawater was likely several hundred μM, compared to ca. 1 to 20 nM of the modern oxygenated ocean. It has been suggested that oxygen production along shallow marine continental shelves, which probably started several hundred million years before the rise of atmospheric oxygen, effectively oxidized Fe(II)aq from deeper seawater and removed it as Fe(III)ppt (poorly soluble precipitates). However, the reconstruction of the marine Fe cycle during the Archean is still incomplete, partly because of diagenetic redox processes that challenge the interpretation of Fe concentration and isotope signatures of sedimentary archives. In this study, we present new Fe concentrations and isotope compositions of carbonate and mudrock samples from the Neoarchean Campbellrand-Malmani carbonate platform (CMCP) in South Africa. These samples are from the shelf facies of the CMCP and in combination with previously published data of Czaja and others (2012) from carbonates and mudrocks of the slope facies, we show that different depositional settings and conditions resulted in different data distributions. Coupled δ56Fe values (−3.685 to +0.083 ‰) and iron concentrations (861–27672 μg g−1) of pure carbonates deposited during open marine conditions, can be explained by partial Fe(II) oxidation between ferruginous deeper water and oxygenated shallow water, leaving the residual Fe(II)aq pool isotopically light, although Fe(II) oxidation by anoxygenic phototrophy cannot be ruled out. Pure carbonates deposited in a peritidal setting, with less exposure to open ocean water, show a smaller Fe isotope variability with δ56Fe values of −1.207 to −0.204 permil and Fe concentration range from 388 to 5413 μg g−1, respectively. We propose that the Fe systematics of peritidal carbonates were dominated by early diagenetic Fe cycling between carbonates and adjacent mudrocks. Synchrotron based X-ray adsorption spectroscopy reveals a change in Fe speciation, where Fe(II)-bearing ankerite and Fe-sulfide dominate the carbonates in the lower part of the CMCP, whereas carbonates of the upper part of the CMCP mainly contain Fe(III)-(oxyhydr)oxides. The fact that Fe(III) phases are still preserved argues for a higher oxidation state on the shelf of the upper CMCP. This is likely because of a lower content of reductants in those settings, in particular organic carbon, sulfide species, as well as restricted influx of reducing species from the anoxic open ocean due to the formation of a rimmed margin. Nevertheless, more studies of similar carbonate settings are necessary to verify our model. We propose that unfractionated Fe(II)aq in seawater was about two to three times lower on the shelf (30–310 μM) than along the slope (61–928 μM), which implies that Fe(II)aq was removed from the water column closer to the continent, likely by oxidation and precipitation. Overall, the Fe isotope composition and Fe speciation of CMCP sediments support the presence of molecular oxygen in the shallow-marine system and emphasize the utility of Ca-Mg carbonates as proxies for iron cycling in the aqueous environment.

Description: Cruise M135 was a contribution to the DFG Collaborative Research Project (SFB) 754: “Climate-Biogeochemistry Interactions in the Tropical Ocean” with the main goal to better understand the the role of diffusive and advective pathways connecting water within the bottom boundary layer (i.e. the water directly affected by sediment processes) to the pelagic and surface ocean. To achieve this, we have injected a conservative tracer (CF3SF5) within the bottom boundary layer at three different sites along the Peruvian coast at a depth of about 300 m in October 2015 that was mapped during M135. Tracer sampling was carried out by measuring water samples from the CTD-rosette water bottles. In total 144 CTD casts were carried out. From 132 CTD profiles 2828 samples for CF3CF5 investigations were gained and on most stations the tracer could be found. In addition 48 trace metal CTD’s were recorded and trace metal and chemical samples taken from the rosette bottles. On 166 of the CTD profiles oxygen samples were taken and on 94 CTD profiles nutrient samples were collected. Microstructure measurements were made on 24 stations and 2 gliders were deployed. For geological investigations at 5 locations multicorer and long gravity cores were taken. Continuous underway measurements of CO2,N2O and CO as well as continuous ADCP and thermosalinograph recording was made on 37 days. The cruise M135 was very successful; most systems on METEOR worked well and all planned objectives were reached.

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

Description: Enrichments of highly reactive iron (Fe) (sum of Fe (oxyhydr)oxide, carbonate and sulfide minerals) in marine sediments and sedimentary rocks are commonly interpreted as an indication of anoxic conditions in the bottom water at the time of deposition. The model system for this proxy rationale is the semi-restricted Black Sea, where sediments underneath the anoxic and sulfidic (i.e., euxinic) deep-water are enriched in reactive Fe, which was mobilized from the surrounding shelf areas. To test whether such a shelf-to-basin Fe shuttle can operate in semi-restricted basins without euxinic deep water, we investigated sedimentary Fe speciation and Fe isotope compositions in sediments of the Guaymas Basin, Gulf of California. Sediments on the slope underneath the eastern equatorial Pacific oxygen minimum zone and sediments within the oxic deep basin are both enriched in reactive Fe, with reactive Fe making up 45 ± 11 % of the total Fe pool. The following mechanisms may contribute to these Fe enrichments: (1) Release of dissolved Fe from anoxic shelf and slope sediments followed by lateral transport of dissolved and/or particulate Fe in the water column; (2) preferential transport of fine-grained, terrigenous particles with a high reactive Fe content into the basin; (3) microbially mediated conversion of non-reactive silicate minerals to reactive Fe minerals during transport; (4) hydrothermal venting and lateral Fe transport within the deep water. The first process can explain reactive Fe enrichments in slope sediments, whereas all processes may contribute to sedimentary Fe enrichments in the deeper basin. The δ56Fe value of sediments increases from shelf to slope and decreases from the slope into the basin. This lateral pattern of δ56Fe, as well as the pattern of Fe enrichment, is similar to that observed in other marine systems with a Fe shuttle. However, the size of the Fe enrichment, and the range in δ56Fe (-0.06 to +0.16‰) is smaller. This difference is due to higher terrigenous sedimentation rates in the Guaymas Basin and, therefore, more intense dilution of shuttle-derived reactive Fe. We argue that, depending on the extent of bathymetric restriction and terrigenous background sedimentation, reactive Fe enrichments can form under a broad range of redox conditions and in diverse sedimentary environments. The concepts applied in this study can be used to identify those circumstances in the paleo-record.