Chemical composition of phosphorites from the Peru and Chile shelves

Recent and Late Quaternary shelf phosphorites have low Fe, Ti and Al contents. These elements enter the phosphorites with terrigenous impurities and organic detritus. Ti, Al, and some Fe are removed when the phosphorites are lithified, whereas remaining iron settles in the phosphorites as sulfides. Ti/Fe, Al/Fe and Ti/Al ratios are used as examples of difference between behavior of Fe and that of Ti and Al.

Geochemistry and petrography of organic matter at DSDP Hole 77-535

Organic geochemical and organic petrographic methods were used to study three Lower to middle Cretaceous sediment samples from Hole 535 in the southeastern Gulf of Mexico for organic matter contents and origin and level of maturation. All three samples contain mixed kerogen Type II/III organic matter with a maturity corresponding to about 0.4% vitrinite reflectance. The marine component increases with stratigraphic age, and microbial reworking of the organic matter is significant in each age. The lower two samples of Hauterivian to Valanginian age appear to be impregnated (or contaminated) with soluble polar organic compounds, but there is only a weak indication for the presence of more mature, nonindigenous hydrocarbons.

Dissolved phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2003)

This data set contains measurements of dissolved phosphorus (total dissolved nitrogen: TDP, dissolved inorganic phosphorus: PO4P and dissolved organic phosphorus: DOP) in samples of soil water collected in 2003 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 mm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled bi-weekly, in 2003 at the 07.03.2003; 24.03.2003; 07.04.2003; 22.04.2003; 07.05.2003; 20.05.2003; 03.06.2003; 28.07.2003; 12.09.2003; 22.09.2003; 07.10.2003; and 21.10.2003, and analyzed for dissolved inorganic P (PO4P) and total dissolved phosphorus (TDP). Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (CFA SAN++, Skalar [Breda, The Netherlands]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. Total dissolved P in soil solution was analyzed by irradiation with UV and oxidation with K2S2O8 followed by reaction with ammonium molybdate (Skalar catnr. 503-553w/r). As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.02 mg P l-1 (CFA, Skalar). Dissolved organic P (DOP) in soil solution was calculated as the difference between TDP and PO4P. In a low number of samples, TDP was equal to or smaller than PO4P; in these cases, DOP was assumed to be zero.

Dissolved phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2004)

This data set contains measurements of dissolved phosphorus (total dissolved nitrogen: TDP, dissolved inorganic phosphorus: PO4P and dissolved organic phosphorus: DOP) in samples of soil water collected in 2004 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled bi-weekly, in 2004 at the 15.01.2004; 30.01.2004; 12.02.2004; 27.02.2004; 09.03.2004; 25.03.2004; 21.04.2004; 07.05.2004; and 24.05.2004, and analyzed for dissolved inorganic P (PO4P) and total dissolved phosphorus (TDP). Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (for samples collected until spring 2004: CFA SAN++, Skalar [Breda, The Netherlands]; for samples collected later: CFA Autoanalyzer [Bran&Luebbe, Norderstedt, Germany]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. Total dissolved P in soil solution was analyzed by irradiation with UV and oxidation with K2S2O8 followed by reaction with ammonium molybdate (Skalar catnr. 503-553w/r). As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.02 mg P l-1 (CFA, Skalar) and 0.04 mg P l-1 (Autoanalyzer, Bran&Luebbe). Dissolved organic P (DOP) in soil solution was calculated as the difference between TDP and PO4P. In a low number of samples, TDP was equal to or smaller than PO4P; in these cases, DOP was assumed to be zero.

Organic geochemistry of deep sea sediments from the Nankai Trough and the Southwest Japan forearc region

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

Calcium carbonate, organic carbon, d13C and C/N composition of ODP Sites 186-1150 and 186-1151

Past changes in sea-surface productivity in the Oyashio Current are evaluated on the basis of abundances of biological constituents in sediments from Leg 186 sites. Organic carbon contents at Sites 1150 and 1151 are moderate (0.5 to 1.5 wt%) and have an algal origin as indicated by low C/N ratios (<10) and by carbon isotopic compositions ranging from -23.4 to -21.3. A decreasing trend in organic carbon contents, carbon isotope ratios, and C/N ratios occurs with depth at both sites, probably as a consequence of diagenetic degradation of organic matter. Mass accumulation rates (MARs) determined for organic carbon and carbonates at Sites 1150 and 1151 show an abrupt increase between ~5 and 7 Ma. Similar results have been reported for sites in the Indian Ocean and the Pacific Ocean for the same time interval. As it has been previously suggested, the observed increase in MAR for both carbonate and organic carbon at Leg 186 sites probably resulted from augmented nutrient supply either from continental sources or from a more vigorous ocean circulation.

(Table 1) Composition of bottom sediments and pore waters from the West Africa shelf

Organic and mineral phosphorus (P_org and P_min) have been determined in pore waters of terrigenous, biogenous, as well as weakly phosphatic and phosphatic sediments from the shelf of the West Africa (in 30 samples). Concentrations of P_min in the pore waters have been examined in close relation to grain size and chemical composition (amounts of P and N_org) of solid phase of the sediments. It has been demonstrated that among sands and coarse silts, maximum concentrations of P_min (up to 1.7 mg/l) in the pore waters have been observed in weakly phosphatic and phosphatic sediments rich in organic matter of the highly productive shelf of the Southwest Africa. Concentrations of P_min in the pore waters are most clearly associated with contents of N_org in the solid phase of the sediments (correlation coefficient R = 0.71) and P_org in the pore waters (R = 0.78).

Major element and cadmium contents in phosphorites from Pacific seamounts

Cadmium contents in studied rocks from Pacific seamounts usually lower than both in biogenic-diagenetic shelf phosphorites and in pelagic sedimentatary-diagenetic Fe-Mn nodules. In general, the behavior of Cd in phosphorites, phosphatized rocks and iron-manganese-phosphate crusts from the seamounts shows that phosphorus, iron, and manganese are apparently of normal sedimentary origin.

X-ray fluorescence scanning of discrete samples on the Schwalbenberg II loess-paleosol sequence, raw data, magnetic susceptibility, organic carbon and U-ratio as grainsize index

The Schwalbenberg II loess-paleosol sequence (LPS) denotes a key site for Marine Isotope Stage (MIS 3) in Western Europe owing to eight succeeding cambisols, which primarily constitute the Ahrgau Subformation. Therefore, this LPS qualifies as a test candidate for the potential of temporal high-resolution geochemical data obtained X-ray fluorescence (XRF) scanning of discrete samplesproviding a fast and non-destructive tool for determining the element composition. The geochemical data is first contextualized to existing proxy data such as magnetic susceptibility (MS) and organic carbon (Corg) and then aggregated to element log ratios characteristic for weathering intensity [LOG (Ca/Sr), LOG (Rb/Sr), LOG (Ba/Sr), LOG (Rb/K)] and dust provenance [LOG (Ti/Zr), LOG (Ti/Al), LOG (Si/Al)]. Generally, an interpretation of rock magnetic particles is challenged in western Europe, where not only magnetic enhancement but also depletion plays a role. Our data indicates leaching and top-soil erosion induced MS depletion at the Schwalbenberg II LPS. Besides weathering, LOG (Ca/Sr) is susceptible for secondary calcification. Thus, also LOG (Rb/Sr) and LOG (Ba/Sr) are shown to be influenced by calcification dynamics. Consequently, LOG (Rb/K) seems to be the most suitable weathering index identifying the Sinzig Soils S1 and S2 as the most pronounced paleosols for this site. Sinzig Soil S3 is enclosed by gelic gleysols and in contrast to S1 and S2 only initially weathered pointing to colder climate conditions. Also the Remagen Soils are characterized by subtle to moderate positive excursions in the weathering indices. Comparing the Schwalbenberg II LPS with the nearby Eifel Lake Sediment Archive (ELSA) and other more distant German, Austrian and Czech LPS while discussing time and climate as limiting factors for pedogenesis, we suggest that the lithologically determined paleosols are in-situ soil formations. The provenance indices document a Zr-enrichment at the transition from the Ahrgau to the Hesbaye Subformation. This is explained by a conceptual model incorporating multiple sediment recycling and sorting effects in eolian and fluvial domains.

Geochemistry of Cretaceous sediments from Argo and Gascoyne Abyssal Plains

The accumulation of organic matter, ferrous and pyrite iron, and the ratios of organic carbon/total sulfur and organic carbon/total phosphorus in the Lower Cretaceous sediments from the Argo and Gascoyne abyssal plains have been used as indicators of both the source and reactivity of organic matter in the sediments and the depositional environment. Total sulfur, used as an indicator of pyrite sulfur, is more abundant in sediments from the Gascoyne Abyssal Plain than in those from the Argo Abyssal Plain. Sulfur positively correlates with TOC at both sites (although poorly at the Argo Abyssal Plain site, R = 0.48), with an extension of the line of best-fit through the origin, indicating that pyrite (TOC <2 wt%) is diagenetic and deposited from normal marine conditions. The average ratio of C/S for samples of TOC <2 wt% is 5.4 at Argo Abyssal Plain (compared to the modern normal marine value of 2.8) indicating deposition of organic matter probably of mixed terrestrial and oxidized marine sources that is unreactive to the sulfate-reducing bacteria. One sample from the Aptian sediments is rich in TOC (5.1 wt%) and has a C/S ratio of 0.5. The average C/S ratio in Gascoyne Abyssal Plain sediments is 0.8 (R = 0.97), which indicates the formation of abundant pyrite in addition to burial and preservation of relatively fresh organic matter that is reactive to the sulfate-reducing bacteria. Organic carbon to phosphorus ratios (C/P) in the sediments indicate preferential remobilization of organic carbon over phosphorus with increasing water depth. Estimates of the degree of pyritization (DOP) increase with increasing TOC at both sites, indicating iron is not limiting and pyrite is formed diagenetically. The one sample with a TOC content of 5.1 wt%, from the Argo Abyssal Plain near the Barremian-Aptian boundary, is composed mostly of framboidal pyrite, finely laminated and not bioturbated, and hence may have been deposited during a brief period of anoxia in the overlying waters.

Benthic oxygen and nitrogen fluxes at different time series sites in the southern North Sea, 2012 to 2014

Benthic oxygen and nitrogen fluxes were quantified within the years 2012 to 2014 at different time series sites in the southern North Sea with the benthic lander NuSObs (Nutrient and Suspension Observatory). In situ incubations of sediments, in situ bromide tracer studies, sampling of macrofauna and pore water investigations revealed considerable seasonal and spatial variations of oxygen and nitrogen fluxes. Seasonal and spatial variations of oxygen fluxes were observed between two different time series sites, covering different sediment types and/or different benthic macrofaunal communities. On a sediment type with a high content of fine grained particles (<63 µm) oxygen fluxes of -15.5 to -25.1 mmol/m**2/d (June 2012), -2.0 to -8.2 mmol/m**2/d (March 2013), -16.8 to -21.5 mmol/m**2/d (November 2013) and -6.1 mmol/m**2/d (March 2014) were measured. At the same site a highly diverse community of small species of benthic macrofauna was observed. On a sediment type with a low content of fine grained particles (<63 µm) high oxygen fluxes (-33.2 mmol/m**2/d August 2012; -47.2 to -55.1 mmol/m**2/d November 2013; -16.6 mmol/m**2/d March 2014) were observed. On this sediment type a less diverse benthic macrofaunal community, which was dominated by the large bodied suspension feeder Ensis directus, was observed. Average annual rain rates of organic carbon and organic nitrogen to the seafloor of 7.44 mol C/m**2/y and 1.34 mol N/m**2/y were estimated. On average 79% of the organic bound carbon and 95% of the organic bound nitrogen reaching the seafloor are recycled at the sediment-water interface.

Biogeochemistry of mesocosm experiments in the tropical Pacific and Atlantic Ocean

Oxygen-deficient waters in the ocean, generally referred to as oxygen minimum zones (OMZ), are expected to expand as a consequence of global climate change. Poor oxygenation is promoting microbial loss of inorganic nitrogen (N) and increasing release of sediment-bound phosphate (P) into the water column. These intermediate water masses, nutrient-loaded but with an N deficit relative to the canonical N:P Redfield ratio of 16:1, are transported via coastal upwelling into the euphotic zone. To test the impact of nutrient supply and nutrient stoichiometry on production, partitioning and elemental composition of dissolved (DOC, DON, DOP) and particulate (POC, PON, POP) organic matter, three nutrient enrichment experiments were conducted with natural microbial communities in shipboard mesocosms, during research cruises in the tropical waters of the southeast Pacific and the northeast Atlantic. Maximum accumulation of POC and PON was observed under high N supply conditions, indicating that primary production was controlled by N availability. The stoichiometry of microbial biomass was unaffected by nutrient N:P supply during exponential growth under nutrient saturation, while it was highly variable under conditions of nutrient limitation and closely correlated to the N:P supply ratio, although PON:POP of accumulated biomass generally exceeded the supply ratio. Microbial N:P composition was constrained by a general lower limit of 5:1. Channelling of assimilated P into DOP appears to be the mechanism responsible for the consistent offset of cellular stoichiometry relative to inorganic nutrient supply and nutrient drawdown, as DOP build-up was observed to intensify under decreasing N:P supply. Low nutrient N:P conditions in coastal upwelling areas overlying O2-deficient waters seem to represent a net source for DOP, which may stimulate growth of diazotrophic phytoplankton. These results demonstrate that microbial nutrient assimilation and partitioning of organic matter between the particulate and the dissolved phase are controlled by the N:P ratio of upwelled nutrients, implying substantial consequences for nutrient cycling and organic matter pools in the course of decreasing nutrient N:P stoichiometry.