Geochemistry of sediment cores from METEOR cruise M76/1b

Marine sediments are the main sink in the oceanic phosphorus (P) cycle. The activity of benthic microorganisms is decisive for regeneration, reflux, or burial of inorganic phosphate (Pi), which has a strong impact on marine productivity. Recent formation of phosphorites on the continental shelf and a succession of different sedimentary environments make the Benguela upwelling system a prime region for studying the role of microbes in P biogeochemistry. The oxygen isotope signature of pore water phosphate (d18OP) carries characteristic information of microbial P cycling: Intracellular turnover of phosphorylated biomolecules results in isotopic equilibrium with ambient water, while enzymatic regeneration of Pi from organic matter produces distinct offsets from equilibrium. The balance of these two processes is the major control for d18OP. Our study assesses the importance of microbial P cycling relative to regeneration of Pi from organic matter from a transect across the Namibian continental shelf and slope by combining pore water chemistry (sulfate, sulfide, ferrous iron, Pi), steady-state turnover rate modeling, and oxygen isotope geochemistry of Pi. We found d18OP values in a range from 12.8 per mill to 26.6 per mill, both in equilibrium as well as pronounced disequilibrium with water. Our data show a trend towards regeneration signatures (disequilibrium) under low mineralization activity and low Pi concentrations, and microbial turnover signatures (equilibrium) under high mineralization activity and high Pi concentrations. These findings are opposite to observations from water column studies where regeneration signatures were found to coincide with high mineralization activity and high Pi concentrations. It appears that preferential Pi regeneration in marine sediments does not necessarily coincide with a disequilibrium d18OP signature. We propose that microbial Pi uptake strategies, which are controlled by Pi availability, are decisive for the alteration of the isotope signature. This hypothesis is supported by the observation of efficient microbial Pi turnover (equilibrium signatures) in the phosphogenic sediments of the Benguela upwelling system.

Geochemistry of karst headwaters

This study investigated CO2 degassing and related carbon isotope fractionation effects in the Wiesent River that drains a catchment in the karst terrain of the Fraconian Alb, Southern Germany. The river was investigated by physico-chemical and stable isotope analyses of water and dissolved inorganic carbon during all seasons in 2010 along 65 km long downstream transects between source and mouth. This data set contains the results of field and solute parameters (temperature, conductivity, pH, total alkalinity, total CO2, and pCO2) and stable isotope analyses (d2H-H2O, d18O-H2O, d13C-DIC) for the Wiesent River and major tributaries.

Geochemistry on core 202-1240A

The modern Eastern Equatorial Pacific (EEP) Ocean is a large oceanic source of carbon to the atmosphere1. Primary productivity over large areas of the EEP is limited by silicic acid and iron availability, and because of this constraint the organic carbon export to the deep ocean is unable to compensate for the outgassing of carbon dioxide that occurs through upwelling of deep waters. It has been suggested that the delivery of dust-borne iron to the glacial ocean could have increased primary productivity and enhanced deep-sea carbon export in this region, lowering atmospheric carbon dioxide concentrations during glacial periods. Such a role for the EEP is supported by higher organic carbon burial rates documented in underlying glacial sediments but lower opal accumulation rates cast doubts on the importance of the EEP as an oceanic region for significant glacial carbon dioxide drawdown. Here we present a new silicon isotope record that suggests the paradoxical decline in opal accumulation rate in the glacial EEP results from a decrease in the silicon to carbon uptake ratio of diatoms under conditions of increased iron availability from enhanced dust input. Consequently, our study supports the idea of an invigorated biological pump in this region during the last glacial period that could have contributed to glacial carbon dioxide drawdown. Additionally, using evidence from silicon and nitrogen isotope changes, we infer that, in contrast to the modern situation, the biological productivity in this region is not constrained by the availability of iron, silicon and nitrogen during the glacial period. We hypothesize that an invigorated biological carbon dioxide pump constrained perhaps only by phosphorus limitation was a more common occurrence in low-latitude areas of the glacial ocean.

Sedimentology and geochemistry on core Co1204

Lakes Prespa and Ohrid, in the Balkan region, are considered to be amongst the oldest lakes in Europe. Both lakes are hydraulically connected via karst aquifers. From Lake Ohrid, several sediment cores up to 15 m long have been studied over the last few years. Here, we document the first long sediment record from nearby Lake Prespa to clarify the influence of Lake Prespa on Lake Ohrid and the environmental history of the region. Radiocarbon dating and dated tephra layers provide robust age control and indicate that the 10.5 m long sediment record from Lake Prespa reaches back to 48 ka. Glacial sedimentation is characterized by low organic matter content and absence of carbonates in the sediments, which indicate oligotrophic conditions in both lakes. Holocene sedimentation is characterized by particularly high carbonate content in Lake Ohrid and by particularly high organic matter content in Lake Prespa, which indicates a shift towards more mesotrophic conditions in the latter. Long-term environmental change and short-term events, such as related to the Heinrich events during the Pleistocene or the 8.2 ka cooling event during the Holocene, are well recorded in both lakes, but are only evident in certain proxies. The comparison of the sediment cores from both lakes indicates that environmental change affects particularly the trophic state of Lake Prespa due to its lower volume and water depth.

Geochemistry of pockmark sediments from the inner Oslofjord

Pockmarks are geological features that are found on the bottom of lakes and oceans all over the globe. Some are active, seeping oil or methane, while others are inactive. Active pockmarks are well studied since they harbor specialized microbial communities that proliferate on the seeping compounds. Such communities are not found in inactive pockmarks. Interestingly, inactive pockmarks are known to have different macrofaunal communities compared to the surrounding sediments. It is undetermined what the microbial composition of inactive pockmarks is and if it shows a similar pattern as the macrofauna. The Norwegian Oslo Fjord contains many inactive pockmarks and they are well suited to study the influence of these geological features on the microbial community in the sediment. Here we present a detailed analysis of the microbial communities found in three inactive pockmarks and two control samples at two core depth intervals. The communities were analyzed using high-throughput amplicon sequencing of the 16S rRNA V3 region. Microbial communities of surface pockmark sediments were indistinguishable from communities found in the surrounding seabed. In contrast, pockmark communities at 40 cm sediment depth had a significantly different community structure from normal sediments at the same depth. Statistical analysis of chemical variables indicated significant differences in the concentrations of total carbon and non-particulate organic carbon between 40 cm pockmark and reference sample sediments. We discuss these results in comparison with the taxonomic classification of the OTUs identified in our samples. Our results indicate that microbial surface sediment communities are affect by the water column, while the 40 cm communities are affect by local conditions within the sediment.

Extractable hydrocarbon and carbon isotope geochemistry of Lower Cretaceous sediments of the Exmouth Plateau

The organic geochemical character of rocks selected from Aptian, Valanginian, and Berriasian clay stone and siltstone sequences encountered in Ocean Drilling Program (ODP) Holes 762C and 763C on the Exmouth Plateau was determined by means of a variety of analytical procedures. These sequences represent distal portions of the Mesozoic Barrow delta, in which petroleum source rocks and reservoirs exist on the Australian continent. The organic matter at the ODP sites is thermally immature type III material. Biomarker hydrocarbon compositions are dominated by long-chain, waxy n-alkanes and by C29 steranes, which reflect the land-plant origin of organic matter. Organic carbon d13C values ranged from -26 per mil to -28 per mil, consistent with a C3 land-plant source. Kerogen pyrolysate compositions and hopane isomerization ratios revealed progressively larger contributions of recycled organic matter as the depth of the deltaic sedimentary layers became greater.

(Appendix) Bulk inorganic chemistry at DSDP Leg 77 Holes

Clay mineralogic and inorganic geochemical investigations of Cretaceous and Cenozoic sediments of the western Gulf of Mexico lead to the following main conclusions. (1) Transition of lowermost Cretaceous continental to marine sedimentation is marked by a clay evaporitic stage, north of the Campeche Escarpment. (2) Existence of combined mineralogic and geochemical stratigraphy allows us to propose correlations between Sites 535 and 540, especially for the Albian. (3) Predominance of detrital clay assemblages is indicative of hot and variably humid continental climate until the early late Cenozoic. (4) Tectonic destabilization of the margins of Gulf of Mexico occurred at different periods, especially until the middle Cretaceous, with a mixed erosion of rocks and soils and temporary oxidized conditions of deposition. (5) Successive developments of confined perimarine basins occurred from the earliest Cretaceous until the Miocene, chiefly in the Florida area. The sources of inorganic materials were chiefly situated on the east of the studied area until the late Tertiary and after that in the Mississippi River basin. (6) Occasionally, volcanic activity influenced the clay mineralogy and mainly the geochemistry, and possibly contributed to the rather strong magnesian character of the deposition until the late Paleogene. (7) The argillaceous diagenesis is weak; variability of the carbonate diagenesis is marked by the relation Sr = f(CaO) and chiefly depends on the depth of burial, the clay content, the porosity, and the geologic age.

Geochemistry of tropical Atlantic sediments of Marine Isotope Stage 4

Antarctic Intermediate Water (AAIW) and Subantarctic Mode Water (SAMW) are the main conduits for the supply of dissolved silicon (silicic acid) from the deep Southern Ocean (SO) to the low-latitude surface ocean and therefore have an important control on low-latitude diatom productivity. Enhanced supply of silicic acid by AAIW (and SAMW) during glacial periods may have enabled tropical diatoms to outcompete carbonate-producing phytoplankton, decreasing the relative export of inorganic to organic carbon to the deep ocean and lowering atmospheric pCO2. This mechanism is known as the "silicic acid leakage hypothesis" (SALH). Here we present records of neodymium and silicon isotopes from the western tropical Atlantic that provide the first direct evidence of increased silicic acid leakage from the Southern Ocean to the tropical Atlantic within AAIW during glacial Marine Isotope Stage 4 (~60-70 ka). This leakage was approximately coeval with enhanced diatom export in the NW Atlantic and across the eastern equatorial Atlantic and provides support for the SALH as a contributor to CO2 drawdown during full glacial development.

Organic geochemistry of interstitial waters at DSDP Holes 64-474 and 64-479

Studies of the nature and amount of dissolved organic matter (DOM) in pore-water solutions have been confined mostly to recent sediments (Henrichs and Farrington, 1979; Krom and Sholkovitz, 1977; Nissenbaum et al., 1972). The analyses of organic constituents in interstitial waters have not been extended to sediment depths of more than 15 meters (Starikova, 1970). Large fluctuations in organic contents of near-bottom interstitial fluids suggest that organic compounds may provide insight into the chemical and biological processes occurring in the sedimentary column. Gradients in inorganic ion concentrations have been used as indicators of diagenesis of organic matter in deep sediments and interstitial waters. Shishkina (1978) attributed the occurrence of iodine and Cl/Br ratios that deviated from the value of seawater to the breakdown of organic matter and the liberation of bromide during mineralization. Sulfate depletion and maxima in ammonia concentrations were interpreted to be a consequence of sulfate reduction reactions in pore fluids, even at depths of more than 400 meters (Miller et al., 1979; Manheim and Schug, 1978).The purpose of this chapter is to study organic carbon compounds dissolved in interstitial waters of deep sediments at Sites 474 and 479.

Geochemistry on water profiles from the Kara Sea

As a part of the Russian-German project "Siberian River-Runoff (SIRRO)" the major element composition of the dissolved load and the major and trace element composition of particulate load and bottom sediment of the Yenisei River and Estuary were analyzed and examined in context of the basin lithology and climate. In addition, the processes controlling the transformation of the river load in the estuarine mixing zone were investigated. The chemical composition of the dissolved and particulate load of the Yenisei fluvial endmember is generally comparable to that of other major world rivers. The dissolved load is chiefly controlled by carbonate weathering and the chemical composition of the river suspended particulate matter (SPM) is similar to that of the North American Shale Composite (NASC), which represents the weathering product of the upper continental crust. The Chemical Index of Alteration (CIA) of the Yenisei SPM amounts to 71, which indicates moderate chemical weathering. With regard to the SPM geochemistry, the Yenisei occupies an intermediate position between the adjacent rivers Khatanga and the Lena. Drastic changes in the composition of the river load are seen in the mixing zone between fresh and salt water. While dissolved Na, Ca, Mg, K, CI, S04, F, Br, Sr and HC03 behave conservatively, dissolved Fe is completely removed from solution at very low salinities. Particulate Mn exhibits a pronounced mid-salinity minimum concomitant with a maximum of dissolved Mn, which is probably related to suboxic conditions in the area of the so-called "marginal filter", where highest turbidities are found. The Mn-minimum in SPM is paralleled by depletions of the elements Ba, Zn, Cd, Ni, Cu and V, which can be associated with manganese particles. The estuarine bottom sediments are composed of mud and sand and the sedimentological parameters of the bottom sediments have to be considered for the interpretation of the bulk geochemical data. The chemical composition of the mud is comparable to the SPM, whereas the sand is relatively enriched in Si/Al, Ba/Al, Zr/Al and Sr/Al ratios and depleted in transition metals.

Sulphur geochemistry of interstitial waters and squeeze cake samples of ODP Leg 181 sites

Seventy-nine interstitial water samples from six sites (Ocean Drilling Program Sites 1119-1124) from the southwestern Pacific Ocean have been analyzed for stable isotopes of dissolved sulfate (34S), along with major and minor ions. Sulfate from the interstitial fluids (34S values between +20.7 and +57.5 vs. the Vienna-Canyon Diablo troilite standard) was enriched in 34S with respect to modern seawater (34S +20.6), indicating that differing amounts of microbial sulfate reduction took place at all investigated sites. Microbial sulfate reduction was found at all sites, the intensity depending on the availability of organic matter, which is controlled by paleosedimentation conditions (e.g., sedimentation rate and presence of turbidites). In addition, total reduced inorganic sulfur (essentially pyrite) as a product of microbial sulfate reduction was quantified in selected sediments from Site 1119.