Sulfur concentrations and isotope ratios in sediments from Kiel Bay, western Baltic Sea

The isotope-ratios of sulfur-components in several sedimentologically different cores of recent marine sediments from Kiel Bay (Baltic Sea) were investigated. In addition, quantitative determinations were made on total sulfur, sulfate, sulfide, chloride, organic carbon, iron and watercontent in the sediment or in the pore-water solution. The investigations gave the following results: 1. The sulfur in the sediment (about 0.3 -2 % of the dry sample) was for the most part introduced into the sediment after sedimentation. This confirms the results of Kaplan et al. (1963, doi:10.1016/0016-7037(63)90074-7). The yield of Sulfur from organic material is very small (in our samples about 5-10% of the total sulfur in the sediment). 2. The sulfur bound in the sediment is taken from the sulfate of the interstitial water. During normal sedimentation, the exchange of sulfate by diffusion significant for changes in the sulfur-content goes down to a sediment depth of 4-6 cm. In this way the sulfate consumed by reduction and formation of sulfide or pyrite is mostly replaced. The uppermost layer of the sediment is an partly open system for the sulfur. The diagenesis of the sulfur is allochemical. 3. The isotope-values of the sediment-sulfur are largely influenced by the sulfur coming into the sediment by diffusion and being bound by bacteriological reduction. Due to the prevailing reduction of 32S and reverse-diffusion of sulfate into the open sea-water, an 32S enrichment takes place in the uppermost layer of the sediment. delta34S-values in the sediment range between -15 and -35 ? while seawater-sulfate has +20 ?. No relationship could be established between sedimentological or chemical changes and isotope-ratios. In the cores, successive sandy and clayly layers showed no change in the delta-values. The sedimentation rate, however, seems to influence isotope-ratios. In one core with low sedimentationrates the delta34S-values varied between -29 and -33 ?, while cores with higher sedimentationrates showed values between -17 and -24 ?. 4. As sediment depth increases, the pore-water sulfate shows decreasing concentrations (in a depth of 30-40 cm we found between 20 and 70 % of the seawater-values), and increasing delta 34S-values (in one case reaching more than +60 ?). The concentration of sulfide in the pore-water increases with sediment-depth (reaching 80 mg S/l in one case). The (delta34S-values of the pore-water-sulfide in all cores show increases paralleling the sulfate sulfur, with a nearly constant delta-distance of 50-60 ? in all cores. This seems to confirm the genetic relationship between the two components.

Geochemistry at DSDP Leg 55 Holes

The tops of the Emperor chain guyots, which were drilled during Leg 55, lie above the carbonate compensation depth (CCD), as well as above the foraminiferal dissolution level, i.e., lysocline. They are therefore the sites of accumulation of pelagic foraminiferal nannofossil ooze, such accumulation having taken place here since the moment of the seamounts' subsidence and the termination of shallow-water carbonate accumulation which was formerly developed on their tops. But the existence of strong bottom currents over the tops and slope scarps limits, and at some places reduces to zero, sedimentation of any pelagic particles. At such areas there are formed thick iron-manganese crusts. The seamounts drilled on Leg 55 are within the northern (Boreal) belt of biogenic silica accumulation, which existed in the northern Pacific throughout the Neogene. This circumstance presupposes a possible enrichment of the relatively fine-grained sediments with biogenic silica - diatoms and radiolarians.

(Table 1) Elemental mean values of the upper Paleocene and lower Eocene in IODP Hole 302-M0004A

We reconstruct the latest Paleocene and early Eocene (~57-50 Ma) environmental trends in the Arctic Ocean and focus on the Paleocene-Eocene thermal maximum (PETM) (~55 Ma), using strata recovered from the Lomonosov Ridge by the Integrated Ocean Drilling Program Expedition 302. The Lomonosov Ridge was still partially subaerial during the latest Paleocene and earliest Eocene and gradually subsided during the early Eocene. Organic dinoflagellate cyst (dinocyst) assemblages point to brackish and productive surface waters throughout the latest Paleocene and early Eocene. Dinocyst assemblages are cosmopolitan during this time interval, suggesting warm conditions, which is corroborated by TEX86'-reconstructed temperatures of 15°-18°C. Inorganic geochemistry generally reflects reducing conditions within the sediment and euxinic conditions during the upper lower Eocene. Spectral analysis reveals that the cyclicity, recorded in X-ray fluorescence scanning Fe data from close to Eocene thermal maximum 2 (~53 Ma, presence confirmed by dinocyst stratigraphy), is related to precession. Within the lower part of the PETM, proxy records indicate enhanced weathering, runoff, anoxia, and productivity along with sea level rise. On the basis of total organic carbon content and variations in sediment accumulation rates, excess organic carbon burial in the Arctic Ocean appears to have contributed significantly to the sequestration of injected carbon during the PETM.

Geochemistry and P and Fe fractionation in anoxic sediments

We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (~94 Ma) and the Paleocene-Eocene thermal maximum (?55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO3 contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO3 can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.

Geomicrobiology, bulk sediment characteristics and pore water chemistry of sediment cores from Laguna Potrok Aike, southern Patagonia

Authigenic minerals can form in the water column and sediments of lakes, either abiotically or mediated by biological activity. Such minerals have been used as paleosalinity and paleoproductivity indicators and reflect trophic state and early diagenetic conditions. They are also considered potential indicators of past and perhaps ongoing microbial activity within sediments. Authigenic concretions, including vivianite, were described in late glacial sediments of Laguna Potrok Aike, a maar lake in southernmost Argentina. Occurrence of iron phosphate implies specific phosphorus sorption behavior and a reducing environment, with methane present. Because organic matter content in these sediments was generally low during glacial times, there must have been alternative sources of phosphorus and biogenic methane. Identifying these sources can help define past trophic state of the lake and diagenetic processes in the sediments. We used scanning electron microscopy, phosphorus speciation in bulk sediment, pore water analyses, in situ ATP measurements, microbial cell counts, and measurements of methane content and its carbon isotope composition (d13C CH4) to identify components of and processes in the sediment. The multiple approaches indicated that volcanic materials in the catchment are important suppliers of iron, sulfur and phosphorus. These elements influence primary productivity and play a role in microbial metabolism during early diagenesis. Authigenic processes led to the formation of pyrite framboids and revealed sulfate reduction. Anaerobic oxidation of methane and shifts in pore water ion concentration indicated microbial influence with depth. This study documents the presence of active microbes within the sediments and their relationship to changing environmental conditions. It also illustrates the substantial role played by microbes in the formation of Laguna Potrok Aike concretions. Thus, authigenic minerals can be used as biosignatures in these late Pleistocene maar sediments.

Geochemical analysis at ODP Site 207-1261 from the Demerara Rise in the western equatorial Atlantic

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.

Geochemical analysis at ODP Site 207-1259 from the Demerara Rise in the western equatorial Atlantic

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.

In-situ Iron isotope measurements and mineral compositions from ODP Hole 206-1256D and IODP Hole 335-U1256D

In-situ Fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the Fe isotopic composition of Fe-Ti-oxides and Fe-sulfides of the different lithologies of the drilled rocks from IODP Hole 1256D (eastern equatorial Pacific; 15 Ma crust formed at the East Pacific Rise). Most igneous rocks normally have a very restricted range in their 56Fe/54Fe ratio. In contrast, Fe isotope compositions of hot fluids (> 300 °C) from mid-ocean-ridge spreading centers define a narrow range that is shifted to lower delta 56Fe values by 0.2 per mil - 0.5 per mil as compared to igneous rocks. Therefore, it is expected that mineral phases that contain large amounts of Fe are especially affected by the interaction with a fluid that fractionates Fe isotopes during exsolution/precipitation of those minerals. We have used a femtosecond UV-Laser ablation system to determine mineral 56Fe/54Fe ratios of selected samples with a precision of < 0.1 per mil (2 sigma level) at micrometer-scale. We have found significant variations of the delta 56Fe (IRMM-014) values in the minerals between different samples as well as within samples and mineral grains. The overall observed scale of delta 56Fe (magnetite) in 1256D rocks ranges from - 0.12 to + 0.64 per mil, and of delta 56Fe (ilmenite) from - 0.77 to + 0.01 per mil. Pyrite in the lowermost sheeted dike section is clearly distinguishable from the other investigated lithological units, having positive delta 56Fe values between + 0.29 and + 0.56 per mil, whereas pyrite in the other samples has generally negative delta 56Fe values from - 1.10 to - 0.59 permil. One key observation is that the temperature dependent inter-mineral fractionations of Fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values, while synthesized, well equilibrated magnetite-ilmenite pairs are compatible with the theoretical predictions. Theoretical considerations including beta-factors of different aqueous Fe-chlorides and Rayleigh-type fractionations in the presence of a hydrous, chlorine-bearing fluid can explain this observation. The disagreement between observed and theoretical equilibrium fractionation, the fact that magnetite, in contrast to ilmenite shows a slight downhole trend in the delta 56Fe values, and the observation of small scale heterogeneities within single mineral grains imply that a general re-equilibration of the magnetite-ilmenite pairs is overprinted by kinetic fractionation effects, caused by the interaction of magnetite/ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling, or incomplete re-equilibration at low temperatures. Furthermore, the observation of significant small-scale variations in the 56Fe/54Fe ratios of single minerals in this study highlights the importance of high spatial-resolution-analyses of stable isotope ratios for further investigations.